JPS5872531A - Preparation of carbonyl compound - Google Patents

Abstract

PURPOSE:To prepare a carbonyl compound in high yield and high space time yield, even from butene, by the vapor-phase reaction of an olefin and oxygen (- containing gas) in the presence of water using a catalyst obtained by supporting a rhodium salt and an element of III-VI group of the periodic table. CONSTITUTION:A carbonyl compound is prepared by reacting an olefin with oxygen (-containing gas) in the presence of water, using a catalyst obtained by supporting a rhodium salt (e.g. rhodium chloride, rhodium nitrate, etc.) and a typical element of the III-VI group of the periodic table (e.g. boron, aluminum, gallium, etc.) to a carrier (silica, alumina, silica-alumina, etc. having a specific surface area of >=30m<2>/g). The amount of the rhodium salt is 0.1-10wt%, preferably 0.4-5wt% of the carrier in terms of metal, and that of the III-VI group element is 0.2-10pts., preferably 0.4-5pts. per 1 pt. of the metallic rhodium. The reaction temperature is 50-250 deg.C, preferably 100-180 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing carbonyl compounds from olefins, and more particularly to a method for efficiently producing carbonyl compounds by oxidizing olefins in the presence of a specific catalyst.

Conventionally, the Hoechst-Wanker method is the most well-known method for producing the corresponding carbonyl compound from olefins, and has already been used industrially for ethylene and propylene. Hoechst Wat in general
It is well known that the catalyst binding used in the Kerr method uses an aqueous solution of palladium chloride and cupric chloride, and that the reaction proceeds as follows.

02H4+ H,, O+ Pd(J2−+ 0H3CH
O+Pd +2HaePd+2Cu(J −+
PdC4□+ 20uCM2CuCJ+ 2HCI+
802 →2 CucJ2 +H20 However, as is clear from the above equation, in this reaction, if cupric chloride as a reoxidation catalyst is not present in the reaction system, the reaction will stop when palladium chloride or metal palladium or radium is reached. However, only a stoichiometric product (acetaldehyde) can be obtained. Therefore, in order to progress the oxidation of olefins in a catalytic manner, it is necessary to use a large amount of chloride as a reoxidation catalyst.
Not only does it require the use of copper, which results in the production of chlorides and other complex purification processes, but it is also extremely corrosive, requiring equipment made of expensive materials such as titanium and glass. There are many problems with driving, and there are many problems.

Furthermore, the Hoechst-Wanker method has not been industrialized due to various obstacles in the production of higher olefins such as butene, which have lower reactivity than ethylene and propylene, and in particular, it has not been widely used by oxidizing butene. There are drawbacks that make it inapplicable to the production of methyl ethyl ketone with

As a production method that overcomes these drawbacks, carbonyl compounds can be converted from olene and yne substantially without using a reoxidizing agent by using a catalyst in which palladium and/or rhodium salts are adsorbed on activated carbon under specified conditions. A manufacturing method has been proposed (Japanese Patent Publication No. 115-576S, Japanese Patent Publication No. 117-172gg).

However, like the Hoechst-Wanker method, this method also has the drawback that it is difficult to apply to olefins with low reactivity such as butene. Moreover, the performance of the catalyst used here varies considerably depending on its preparation conditions, and the catalyst strength is not sufficient, so that many of the problems of the Hoechst-Wanker method have not yet been solved.

The present inventors have conducted intensive research on various catalysts and supports for a method for producing methyl ethyl ketone by catalytic oxidation of butene, which has few problems as an industrial production method and has low reactivity. It has already been discovered that methyl ethyl ketone can be efficiently produced without the need for a reoxidizing agent by using a catalyst in combination with a carrier of
.

The present invention aims to improve the above-mentioned method and provide an even better method for producing carbonylated compound 1, which consists of a rhodium salt and m-th compound of the periodic table.
This is a carbonyl method characterized by reacting an olefin with oxygen or an oxygen-containing gas in the presence of water using a catalyst comprising a typical element of group (1), (v) or (2) supported on a carrier.

The catalyst used in the method of the present invention supports catalyst components. Here, as a carrier, various types of supports,
It may be selected as appropriate depending on the purpose, etc., but usually silica,
Alumina, silica-alumina, zeolite, activated carbon, etc. are used, and the specific surface area is 30 m2/ψ or more, especially 30 to 1000 m2/? Preferably. on the other hand,
The catalyst component to be supported on the carrier is a rhodium salt and a typical element of Groups 1, IV, V or II of the periodic table.

Here, as the rhodium salt, any salt of an inorganic acid or an organic acid that can be dissolved in water, an aqueous solution such as an acid, or an organic solvent such as an alcohol can be used. For example, rhodium chloride and bromide.

Inorganic salts such as sulfates, nitrates, chlorates, organic acid salts such as formates, acetates, monochloroacetates, naphthenates, or mixtures thereof; Chlorides are preferred. Typical elements of group ■+IQ+■ or group ■ of the periodic table include boron, aluminum, gallium, thallium, and germanium.

Sy: + Lead + ') N, antimony, bismuth, tellurium, etc. Among them, thallium and germanium.

Particularly preferred are tin, lead, phosphorus, tellurium, bismuth, and the like. These typical elements are usually supported in the form of various compounds containing these elements. When the typical element is used in the form of an oxide, it is preferable to add a small amount of hydrochloric acid.

The amount of the catalyst component supported on the carrier is not particularly limited and varies depending on various conditions and cannot be unambiguously determined, but it is usually 0.7 to 10% of the amount of rhodium salt as metal to the carrier.
It should be % by weight, preferably % by weight. Further, regarding the typical elements of groups ① to ② of the periodic table, 0.2 to 70 times, preferably 0.2 to 70 times, the metal rhodium of the above rhodium salt. It should be selected within the range of ~S times.

There are no particular restrictions on the method of supporting these catalyst components on the carrier, such as a method of supporting them using a normal impregnation method or an adsorption method, or a method of adding an aqueous solution of the catalyst components and colloidal silica or alumina, concentrating and solidifying and then shaping. can be adopted. Further, in supporting the catalyst component on the carrier, a one-stage method may be used in which the rhodium salt and the above-mentioned typical elements are simultaneously supported on the carrier, or a method may be employed in which the catalyst components are supported in two or more stages.

After drying, the carrier supporting the catalyst component has a temperature of 10θ to Sθ0°C,
A highly active and stable catalyst can be obtained by calcining for 7 to 70 hours, preferably at a temperature of 150 to 00°C, in an atmosphere of air, nitrogen, inert gas such as argon, or chlorine gas.

By using the catalyst prepared as described above, carbonyl compounds corresponding to each olefin can be efficiently produced from sprout refin. Examples of olefins that can be used are ethylene, propylene,
n-butene/.

Aliphatic linear olefins such as n-butene-, 2,n-hexene; 3-methylbutene-/, 3-methylpe/thene-
Diolefins such as /, 3-detadiene, cyclohexazoene, and alicyclic olefins such as cyclopentene and cyclohexene can be cited as examples of these olefins. mixtures such as n-butene-/, n-putenoco,
Furthermore, a mixture of saturated hydrocarbons such as n-butane and isobutane and nitrogen can also be used.

The method of producing a carbonyl compound from a raw material olefin in the present invention involves mixing the raw material olefin with oxygen or an oxygen-containing gas, usually in the presence of water vapor, at a temperature of 5θ to 230°.
C1 The carbonyl compound is produced by contacting with the above catalyst at a temperature of preferably 10θ to gθ°C.

As for the reaction method, any of fixed bed, fluidized bed, and moving bed can be used. The reaction is carried out using a gas phase method, a gas-liquid mixing method, or a liquid phase method, although the reaction differs depending on the raw material olefin, and is preferably carried out in a flow system during the gas phase reaction. In particular, it is advantageous to employ a gas phase reaction in terms of separation and purification of the product. In addition, there is no particular restriction on the reaction pressure, and 50
It is carried out below atmospheric pressure.

Further, as the oxygen-containing gas, air or a mixed gas of oxygen and an inert gas (such as nitrogen) is suitable, and water is vaporized through the preheating layer and introduced into the reaction system as water vapor.

The mixing ratio of olefin, oxygen or oxygen-containing gas, and water vapor is arbitrarily determined depending on the type of raw material olefin, reaction conditions, and the like. For example, when producing methyl ethyl ketone using n-butene, an appropriate mixing ratio (volume ratio) of n-butene:oxygen or oxygen-containing gas:steam =/:/~coθ:/~20 is appropriate. be. Further, the contact time between these mixed gases and the catalyst is about 3 to 3θ seconds, preferably 5-N2θ seconds.

As described above, according to the method of the present invention, useful carbonyl compounds such as acetaldehyde, acetone, and methyl ethyl ketone can be efficiently produced. In particular, the ability to effectively produce methyl ethyl ketone from olefins with low reactivity such as butene is a major feature not found in the Hoechst-Wanker process or conventional techniques using activated carbon carriers. Moreover, the method of the present invention does not cause corrosion due to chlorides, which is a major problem in the Hoechst-Wanker method, and together with the strength and stability of the catalyst, it makes it possible to provide an industrially excellent production method. It is.

In addition, in the method of the present invention, since the catalyst used is one in which not only a rhodium salt but also typical elements of Groups 1 to 2 of the periodic table are supported on a carrier, only a rhodium salt can be used as a carrier. Compared to methods using supported catalysts, this method provides a higher reaction yield of carbonyl compounds and better STY (space-time yield).

Example SnC'-M465HzOO939? was dissolved in Sθml of water and impregnated onto a γ-Ai203 molded carrier (3mmφ x 3mm, specific surface area: θom27y->tyθ2, and then calcined at Sθθ°C under air circulation for a period of 2 hours.
3H20 was dissolved in Sθml of water, impregnated into the supported catalyst, and then calcined for 3 hours at λθθ°C under air circulation to obtain a supported catalyst with a Ph of 7% by weight + sn of θ, and a left weight ratio.

39 ml of the obtained catalyst was packed into a glass tubular reactor with a diameter of 25 m, containing 77.5% of butylene and S% of oxygen.

A mixed gas consisting of 7.5% nitrogen and 70% water (volume composition) was flowed at /3S0C2 normal pressure and for a contact time of 9 seconds to obtain the results shown in the table.

Comparative Example / /2 RhCJV, 3.3H20 was dissolved in 3θml of water, and γ-A1□03 molded carrier (311IIIφ×311
IK, specific surface area (θOm2/1) II After impregnating with θ1, the catalyst was calcined at 20θ°C for 3 hours under air circulation to prepare a catalyst in which Rh was supported by weight, and the results were reacted in the same manner as in Example/. - Shown in /.

Example 1 Example 2 Sn (J4-5H20-θ,!; 9 ff and Rh
(J3-3H20/P was dissolved in 3θml of water, and γ-
M203 molded carrier (31φX3101. Specific surface area 20θ
m2/P) 'Iθ? After impregnation, under air circulation, 20
Calcinate at 0℃ for 3 hours, Rh is 7% by weight + Sn is θ,
A catalyst supported at a weight of 5 was prepared and reacted in the same manner as in Example 1. The results are shown in Table 2.

Example 3~S A catalyst was prepared in the same manner as in Example 3, except that the supported amounts of Rh and Sn were changed, and the reaction results are shown in Table 1.

Examples 6-g 0.3 P, 04. f, /-2't
(7) Bi (J3 dissolved in 3Qml of water, γ-A
1°03 shaped carrier (3Mn<6-X31EIl, specific surface area; toom27y, same below).

After being impregnated to 1iot, it was baked at 1looo C. for 9 hours under air circulation. Then /1 Rhcz3-3 H2O was added to 3θm
After dissolving in 1 of water and impregnating the above supported catalyst,
A catalyst was prepared by firing at 00° C. for 3 hours, and the results of the reaction are shown in Table 1.

Example 9~/θ 5n (J4-5 H20θ, 0.25 instead of S Wag
P.

The procedure in Example 1 was followed except that 0.51 T e O2 was dissolved in 3θml of concentrated hydrochloric acid. The results are shown in Table-/.

Example /l ・0.73t town po, (8 degrees g5%) and /1 R
The operation was carried out according to Example 1, except that hCl3.3H20 was used. The results are shown in Table-/.

Example/2 0.3 g t GeCA4! r Omlノ'7
Seton K i solution L, r-A! After impregnating 1 lot of 203 molded carrier, it was baked at 20θ°C for 3 hours under air circulation. Thereafter, operations were performed according to Example/. The results are shown in Table-/.

Example/, 3, /1I SnCJ-4・5 H20θ,! ; instead of 9 ff, θ, 23 P (7) T-eCJ3.0, respectively
．． 2 A? +7) The operation was carried out according to Example/, except that Pb (J□) was used.The results are shown in Table-
/ Shown in /.

Comparative Example Korg S, 0acf2 + RhCl instead of nCl-4
The operation was carried out in accordance with Example/, except that 2'*KCJ was used.

The results are shown in Table-/.

Comparative Example 5 Rh (using J3-3H20 and CucJV, 2,
Rh 7% by weight, C! u2. ! ; After impregnating γ-8 into 203 molded carrier, under air circulation 20
A catalyst was prepared by calcining at 0° C. for 9 hours, and the following reaction was carried out according to Example. The results are shown in Table-2.

Comparative Example Using Otsu pact□ and CucJ 2, a γ-A1□0 roll-formed carrier was impregnated with 7% by weight of Pd, 7% by weight of OniCu l, and then baked at 200°C under air circulation for 9 hours. A catalyst was prepared, and the following reaction was carried out according to Example. The results are shown in Table C.

Table-2 Comparative example A46.0 4B, 7 22.4
*1 of 2 indicates methyl ethyl keto/.

$2 In Comparative Example 5.4 above, an oily substance was observed in the product, and the result of Ganu chromatography analysis was C3.
It was C4 chloride.

Continued from page 1 0 Inventor Yoshio Hironaka Procedural amendment (spontaneous) November 27, 1980 Haruki Shimada, Commissioner of the Japan Patent Office 1 Keiji patent application 171548 1982 2 Name of the invention Manufacture of carbonyl compounds Method 5 Relationship with the case of the person making the amendment Patent applicant Idemitsu Kosan Co., Ltd. Representative Agent Address: 1-10 Kyobashi, Chuo-ku, Tokyo 104 4th amendment in the detailed description of the invention in the specification to be amended r Ph Jt [ph
Correct to J.

Claims (1)

[Claims] 1 Rhodium salt and periodic table m, ■, v or ■
1. A method for producing a carbonyl compound, which comprises reacting an olefin with oxygen or an oxygen-containing gas in the presence of water using a catalyst comprising a typical element of the group supported on a carrier. 2. The production method according to claim 1, wherein the reaction is carried out in the gas phase in the presence of water. 3. The carrier is silica with a specific surface area of 30 m2/f or more. The manufacturing method according to claim 1, which is alumina, silica-alumina, zeolite or activated carbon.