JPS6019730A - Preparation of chlorinated hydrocarbon - Google Patents

Abstract

PURPOSE:To obtain a chlorinated hydrocarbon, by chlorinating a hydrocarbon oxidatively by the use of a catalyst having extremely high suppressing action on NH3 combustion prepared by adding at least one of Co, Mn, and Cr to a system comprising a copper oxide such as copper chloride as a main catalyst. CONSTITUTION:In oxychlorination in a gaseous phase to produce a chlorinated hydrocarbon by reacting a hydrocarbon such as ethylene, propylene, etc. with an oxygen-containing gas by the use of ammonium chloride as a chlorine source, a catalyst used is obtained by adding at least one selected from Co, Mn, and Cr and their compounds as a cocatalyst component to copper metal or its chloride as a catalyst [especially a ratio of Cu to the cocatalyst is preferably (10:0.1)- (0.1:10) (atom ratio)], followed by supporting the catalyst on a carrier. The reaction temperature is 200-600 deg.C, especially 250-500 deg.C, and the contact time with the catalyst is preferably about 0.5-60sec.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for sulfur chlorination of hydrocarbons.

More specifically, ammonium chloride (hereinafter N) I, 01
) is used as a chlorine source in 17. Hydrocarbons such as ethylene and propylene, NTT, 01, and an oxygen-containing gas are reacted in the presence of a solid catalyst with a new composition to produce chlorinated hydrocarbons. Relating to a gas phase oxychlorination method.

Conventionally, the method of oxidatively chlorinating hydrocarbons, such as ethylene, propylene, benzene, etc., with hydrogen chloride (hereinafter referred to as H01) in the presence of a catalyst mainly consisting of a copper compound is widely known as the oxychlorination method. There is. Instead of this HOI,
The oxychlorination method using NH,01 as the chlorine source is also called the ammonium chloride oxychlorination method (hereinafter referred to as "ammonium oxy").
It is known that similar catalysts can be used. For example, in Japanese Patent Publication No. 42-9924, in the presence of a catalyst in the conventional oxychlorination method containing copper chloride as the main component,
A method of carrying out ammonium oxychloride at temperatures between 0 and 400<0>C is disclosed. With ammonium oxychloride, NH, which is a chlorine source, is present in the reaction system.
, 01 (hereinafter referred to as NT-) coexists. Normally, this NH, is extremely combustible in the reaction system. Therefore, not only does it cause economic loss, but ammonium chloride also generates nitrogen in addition to the reaction heat of oxychlorination.
This results in the combustion heat of H, resulting in an extremely large calorific value. As a result, serious problems arise in industrial operations, such as control of reaction temperature and efficiency of equipment. Historically, when the combustion rate of NETs coexisting in the reaction system increases, the amount of available oxygen used in the oxychlorination reaction decreases, resulting in a decrease in the reaction rate of oxychlorination. Therefore.

It is necessary to increase the amount of acid lA to be supplied to the reaction system, which causes the problem that the raw material mixed gas enters the explosive range.

As described above, conventional oxychlorination catalysts cause a serious problem of combustion of NH, which coexists in the reaction system, in the case of ammonium chloride oxy, and therefore attempts have been made to improve the catalysts. For example, Japanese Patent Publication No. 47-14082 states that the use of a catalyst containing iron chloride and copper chloride in a specific ratio improves the reaction rate of hydrocarbons and effectively suppresses the combustion of NH. However, the recovery rate of NH is less than 70%, which is not a satisfactory result. Special Public Service 50-19
According to Publication No. 523, (mr41.np04.l4
A copper compound catalyst for oxychlorination added with a phosphorus compound such as poS is added to this catalyst system for the purpose of suppressing catalyst volatilization and imparting low-temperature activity, etc. KCI, Na(:], NaH8
O4゜KI'1804. ) to add a salt such as TT S04 and/or MR, Li,.

It is said that catalysts in combination with metals or compounds such as rare earth elements are advantageously used. However, the typical catalyst system of this reference is CuO], 2-K(1!1-(rir(I), n
Even when using pq or T+61'O, the recovery rate of NH is extremely small at 45 or less. The effects of other additive element compounds are not exemplified. KCsb(o)i)a) in Special Publication No. 50-19524
Catalysts based on copper compounds to which antimony compounds are added have been proposed. According to this reference, salts similar to those in the above-mentioned Japanese Patent Publication No. 50-19523 are combined with the basic catalyst system for the purpose of suppressing volatilization of the catalyst, imparting low-temperature activity, etc. e, Co.

Old, MPI, I, 1. 0uC1□-KOl, -K(sb
(on), ) are used, but the recovery rate of Na is extremely low at 40 or less. No effect has been shown on the addition of other additive elements, such as compounds such as ljθ and CO.

Thus, a catalyst that can sufficiently suppress combustion in the ammonium chloride method has not yet been found.

In view of the above circumstances, the present inventors conducted extensive research on the catalysts of the ammonium chloride method, and found that at least one of the elements cobal l-, manganese, and chromium was added to a system containing a copper compound such as copper chloride as the main catalyst. It was discovered that the catalyst to which 1.5% was added significantly suppressed the combustion of Nl- coexisting in the reaction system, and that oxychlorination could proceed efficiently.12. That is, in the case of the ammonium chloride oxycatalyst in the method of the present invention, the activity (for example, the yield of dichloroethane) decreases by 6%, but even when the reaction is carried out at a high temperature of about 400°C, the combustion rate of NII remains 1
It has become clear that it can be suppressed to less than 0% J''J, which is advantageous as an industrial technology.

Note that the use of a cobalt compound as a component of an ammonium chloride oxycatalyst is described in the cited Japanese Patent Publication No. 50-19524, but the possibility of its use is only suggested when used in combination with an antimony compound. However, it has not been found that an extremely high NH 2 combustion suppressing effect is exhibited as in the present invention.

As described above, the present invention was completed based on the discovery of a new catalyst, in which hydrocarbons, NT (C1) and oxygen or an oxygen-containing gas are selected from the group consisting of a copper compound and the elements cobalt, manganese and chromium. The present invention provides a method for producing chlorinated hydrocarbons by reacting them in the presence of a catalyst containing at least one component containing chlorinated hydrocarbons.

The present invention will be explained in detail below.

The present invention relates to a method for gas phase chlorination of hydrocarbons using ammonium chloride.
f: Any material to which an oxychlorination method using a chlorine source can be applied is acceptable, and ethylene and propylene are preferable.

Particularly preferably, this method is advantageously adopted as a method for producing dichloroethane from ethylene.

The catalyst used in the present invention contains at least one member selected from the group consisting of cobalt, manganese, and chromium metals or compounds thereof as a promoter component to copper metal or compounds such as chlorides and oxides. It was added.

The compound of the promoter element is not particularly limited, but it may usually be selected from halides, oxides, nitrates, organic carboxylates, and the like. The amount of these promoter elements added to the copper element serving as the main catalyst is 1, Cu/M=10/Q, 1
It may be selected from the range of 0.1/10 to 0.1/10 (atomic ratio, M represents a promoter element). Generally, if the promoter component is small, the combustion rate of NHB will be high as a natural result, and the object of the present invention will not be achieved. On the other hand, when the amount of the co-catalyst increases, the activity for the oxychlorination reaction tends to be suppressed. Preferably, Ou/LI=10/1 to 2/8.

The catalyst of the present invention also contains additives, namely Na11, K, (3), which are conventionally used in oxychlorine method catalysts for the purpose of preventing volatilization of the main catalyst copper compound, improving activity, etc.

Alkali and alkaline earth metal chlorides such as OaO], MgO], bisulfates such as Na, 11O,, KH, O21, K, PO, etc.

(NH4), HT)04. Phosphate compounds such as H and P can be used in appropriate combinations. It is usually preferable to use these additives. Of course, platinum,
Metals such as palladium and rare earth elements or their chlorides.

It is also possible to use compounds such as oxides in combination with conventional oxychlorination catalysts.

On the other hand, the catalyst component of the present invention is preferably supported on a carrier and used as a catalyst, such as silica, alumina, silica-alumina, and silica-magnesia.

There is no particular restriction as long as it is a material that is normally used as a catalyst carrier, such as activated carbon or diatomaceous earth 1. At this time, the main catalyst steel component is prepared in the carrier by a known method such as an immersion method or a coprecipitation method so that the concentration range is usually 1 to 20 wt%.

When carrying out ammonium oxychloride using the catalyst of the present invention, the chlorine source NH,01 is not particularly limited, and usually,
It is convenient to use one produced by the ammonia soda method, which is easily available in large quantities. In addition, NT (,C!1
There is no problem in substituting a part of the MCI with the MCI, but from the point of view of the present invention, no particular advantage is recognized. Although oxygen is additionally required, a pure gas of oxygen or an oxygen-containing gas such as air may be employed. The raw materials of hydrocarbon, NT(,01, and oxygen) are introduced onto the catalyst of the present invention as a mixed gas. Usually, NH,011 is determined per mole of raw material hydrocarbon.
~5.0 mol, and 111 to 2.0 mol of oxygen. In particular, the oxygen partial pressure greatly influences the oxychlorination reaction rate, but a large excess amount of oxygen is not very desirable because it increases the combustion of NT- coexisting in the reaction system. Therefore, the raw material mixed gas, preferably in the range of α2 to 1.0 mol, is diluted with a gas inert to the oxychlorination reaction, such as nitrogen, helium, argon, water vapor, etc., when introduced into the reactor. I don't mind if you ask me.

The reaction temperature must be within a range in which the reaction raw materials and products can maintain their gaseous states, and is generally selected appropriately depending on the type of raw material hydrocarbon, the composition of the raw material mixed gas, the catalyst, and the like. Normally, the range is 200 to 600°C, but as the reaction temperature increases, the combustion of NH increases, and at low temperatures, the rate of the oxychlorination reaction decreases, so it is preferably 250°C.
A range from °C to 500 °C is adopted.

There is no particular restriction on the reaction pressure, and the reaction may normally be carried out at around normal pressure.

The contact time between the raw material mixed gas and the catalyst can be selected from a relatively wide range depending on the reaction conditions. Usually, about 0.5 to 60 seconds is sufficient, but the reaction rate of oxychlorination + NIET
Considering the influence of (a) on the combustion rate, etc., a range of 1 to 20 seconds is preferable.

The method of the present invention is implemented in a fixed bed.

Any method such as a fluidized bed or a moving bed may be used. Furthermore, since ammonium chloride oxy is an exothermic reaction, α
- The reaction can also be carried out by diluting the catalyst with alumina, silicon carbide, catalyst carrier, etc. and filling the reactor with the diluted catalyst.

Thus, the reaction mixture obtained by the method of the invention is
The target chlorinated hydrocarbon, unreacted raw materials, by-products, etc. are separated and recovered by a known method. Of course, the recovered raw materials are reused in the reaction by appropriately separating each component or adjusting the composition.

Next, examples of the present invention will be described in more detail, but the present invention is not limited thereby.

Examples 1-4 Dried silica gel (diameter 75-150 μm).

Specific surface area 275. On? /g) 509, (NHl)
Aqueous solution 250II+7 in which t+u'04α969 was dissolved
and then dried at 90°C. 1 for this dry powder
0 wt% copper chloride (cuc4) and Ou, O], equimolar potassium chloride (KCl,) and the same (0wO1, equimolar potassium chloride (KCl)) as cocatalysts.
4) + Impregnation with either manganese chloride (MnC14) or cobalt chloride (Coolω) as an aqueous solution, followed by evaporation and drying. Prepared in this way (!uc!
1.2 MX KOI (NQ)zHP04(MX-O
Samples containing rOl, a, MnO, or Cool were all pressed, refined, and made into 28 to 60 meshes and used as catalysts.

The reaction was carried out using an atmospheric pressure fixed bed flow reactor made of Pyrex glass and having an inner diameter of 1.3 crn. That is, the catalyst 1.32! ; If filled with argon gas (Ar)
It was heated to the set temperature under circulation. Then C2H410
A gas having a composition (molar ratio) of 2/NI (, CF, /Ar = 2/1/4/6.8) was introduced onto the catalyst so that the contact time was 3 seconds.The reaction product gas was After assimilating and separating unreacted NI (C1ff) in a trap heated to ℃, the liquid and gaseous substances were analyzed by gas chromatography. The results are shown in Table 1.

Comparative Examples 1 to 4 In the same manner as in Example 1, 0uO1,-KO was added to silica gel.
I-(No, ), HpO4 (Comparative Examples 1-3) and Ou
, C1,-KOI (Comparative Example 4) to OuO], is 10
A catalyst supported at wt% was prepared. Next, a reaction was carried out under the same conditions as in Example 1, and the results shown in Table 1 were obtained.

Examples 5 to 7 In a catalyst consisting of OuC], -Cool, -KCl, the supported amount of OuO] was 10 wt% and KOI was
Equimolar to ol1, C! uo1. and Oo 01. Catalysts with different molar ratios (atomic ratio of Ou and Cof') were prepared in the same manner as in Example 1.

Next, a reaction was carried out under the same conditions as in Example 5, and the results shown in Table 2 were obtained.

Comparative Example 5 In Example 5, a catalyst supporting only Co014 and KOI in an equimolar amount with Cool4 was used in Example 1.
Prepared in the same manner. Next, the entire reaction was carried out under the same conditions as in Example 5, and the results shown in Table 2 were obtained.

Table 1 1) Dichlorinated ethane yield: Production rate of dichloroethane based on supplied ethylene 2) N% combustion rate; Ratio of combustible NH (mol%) relative to supplied NH401 Table 2 Implementation Example 8 A reaction was carried out using the same catalyst and reaction conditions as in Example 5, except that ethylene was changed to pyrene. As a result, 1.
Yield of 2-dichloropropane: 11.4%.

1. Yield of 3-dichloropropane! 5.7chi, N
The combustion rate a1qID was 1-111.

Patent applicant: Toyo Soda Kogyo Co., Ltd.

Claims (1)

[Claims] (1) A copper oxychloride compound catalyst containing at least one component selected from the group consisting of cobalt, manganese, and chromium metals or their compounds using hydrocarbon, ammonium chloride, and oxygen or an oxygen-containing gas as a cocatalyst. React in the presence of 1. A method for producing chlorinated hydrocarbons, characterized by: