JPS59216846A - Production of benzophenone - Google Patents

Abstract

PURPOSE:To produce the titled substance useful as a fixer of perfumes, etc., economically, in high yield, by the catalytic vapor-phase oxidation of a diphenylmethane derivative with an O2-containing gas in the presence of a catalyst composed of specific two kinds of oxide components. CONSTITUTION:The objective compound is produced by the catalytic vapor- phase oxidation of a diphenylmethane derivative of formula (R is either of the substituent 1-3C alkyl groups bonded to m- and/or p-positions; m and n are 0- 3) with an O2-containing gas in the presence of a catayst comprising an oxide composition composed of (A) a lead oxide and (B) one or more oxides selected from the group of titanium oxide, zirconium oxide, tin oxide and cerium oxide. Preferably, the catalyst is composed of 1-90wt% of the component (A) in terms of PbO and 99-10wt% of the component (B) in terms of TiO and/or ZrO, SnO2 and CeO2.

Description

[Detailed description of the invention] The present invention relates to a method for producing benzophenone.

To be more specific, the present invention provides a method for producing benzophenone by catalytic gas phase oxidation of a diphenylmethane derivative, and more specifically, a diphenylmethane derivative represented by the following general formula (1) (wherein R is meta and / or represents any substituent of an alkyl group having 1 to 3 carbon atoms bonded to the para position, and m and n are each 0 to 3.
Represents the number of 3 identical or different substituents. ) to produce benzophenone by catalytic gas phase oxidation with a molecular oxygen-containing gas, lead oxide as component A,
Provided is a method for producing benzophenone, characterized by using a catalyst containing as a catalytically active substance at least one selected from the group consisting of titanium oxide, zirconium oxide, tin oxide and cerium oxide as component B. .

The present inventors previously disclosed in Japanese Patent Application No. 57-227457 a method for producing benzophenone, which is characterized in that a catalyst containing a lead compound is used as a catalytically active substance when producing benzophenone from the above-mentioned raw materials. However, the above catalysts still have the disadvantage of low activity and yield, so the inventors conducted further intensive studies and found that
The production method disclosed in the present invention has significantly improved activity and yield, and is therefore disclosed herein.

Benzophenone is a substance useful as a perfume fixative, a polymerization inhibitor, an ultraviolet absorber, a photopolymerization initiator, and the like.

Conventionally, benzophenone has been obtained by the reaction of benzoyl chloride and benzene, benzene and phosgene, or benzene and carbon tetrachloride, but all of these methods consume equimolar amounts of anhydrous aluminum chloride and are expensive raw materials. However, it has the disadvantage of being difficult to handle.

The raw material diphenylmethane derivative used in the present invention is represented by the above general formula (1), and when it has a substituted alkyl group, examples of R include a methyl group, an ethyl group, and a propyl group. Compounds without group (R) include diphenylmethane, or when R is present, for example, when R is a methyl group, 3-methyl or 4-
Methyldiphenylmethane, still 4,4'-dimethyl or dimethyl-substituted diphenylmethane, such as 3,4'-dimethyl or 3,4-dimethyldiphenylmethane, or 3,4.5-)dimethyl still 3,4°3'-trimethyl Trimethyl-substituted diphenylmethane, such as diphenylmethane, or tetramethyl-substituted diphenylmethane, such as 3,4,5,3'-tetramethyl or 3,5,3',5'-tetramethyldiphenylmethane, still 3,4,5,3' , 5'-pentamethyldiphenylmethane, pentamethyl-substituted diphenylmethane, or 3 y 41513', 4'y 5'-hexamethyldiphenylmethane. Similarly, compounds in which R is a plurality of different types of ethyl, propyl, methyl, ethyl, and propyl groups may also be targeted.

The above raw material diphenylmethane derivatives are supplied onto the catalyst as a single compound or as a mixture of two or more.

The action of the catalyst disclosed in the present invention when producing benzophenone by catalytic gas phase oxidation of the diphenylmethane derivative disclosed in the present invention using a molecular oxygen-containing gas is surprising.

For example, from diphenylmethane derivatives having no substituted alkyl group at the ortho position of the benzene nucleus shown in the general formula (1) above, to benzophenone mainly having no substituted alkyl group, regardless of the presence or absence of substituted alkyl groups at the meta and/or para positions. is incorrect.

Another unique catalytic action of the catalyst disclosed in the present invention is that the product contains no or very little oxidation by-products such as maleic acid and benzoic acid.

These newly discovered unique catalytic actions lead to an industrially advantageous production method for producing benzophenone in terms of inexpensive acquisition of raw materials and/or product purification.

Until now, the use of lead oxide as a catalyst in a method for producing benzophenone by catalytic gas phase oxidation of a diphenylmethane derivative with a molecular oxygen-containing gas was first disclosed in the above-mentioned Japanese Patent Application No. 57-227457. Moreover, the catalyst disclosed in the present invention, which is an improvement over the above-mentioned prior invention, that is, lead oxide as the A component and titanium oxide as the B component,
It is novel that a catalyst containing at least one member selected from the group consisting of zirconium oxide, tin oxide and cerium oxide as a catalytically active substance is used for the production of benzophenone according to the present invention.

The present inventors have conducted intensive studies on methods for producing benzophenone by catalytic gas phase oxidation using various diphenylmethane derivatives as starting materials. As a result, when using an oxidation catalyst containing each element as described above, the invention of the earlier application The present inventors have newly discovered that the yield and activity are dramatically improved compared to the method disclosed in 1999, and that benzophenone can be produced industrially advantageously, leading to the present invention.

That is, the present invention is specified as follows.

(1) Diphenylmethane derivatives represented by the following general formula (I) (wherein R represents any substituent among the alkyl groups having 1 to 3 carbon atoms bonded to the meta and/or bara position, m and Each number represents the number of the same or different substituents. 1. A method for producing benzophenone, which comprises using a catalyst containing at least one component selected from the group consisting of titanium oxide, zirconium oxide, tin oxide, and cerium oxide as a catalytically active substance.

(2) Component A is 1 to 90% by weight as PbO, component B is TiO2 and/or ZrO2 and/or 8n
The method according to (1) above, wherein the content of Ogura and/or CeO2 is 10 to 99% by weight.

The present invention will be explained in more detail below.

All of the raw material diphenylmethane derivatives used in the present invention can be obtained by known methods.

The catalyst used in the present invention is specified as an oxide catalyst containing each element as described above, and there are no particular limitations on the type of catalyst raw materials, the shape of the catalyst, the presence or absence of a co-catalyst, the presence or absence of a support, and the manufacturing method. . In other words, the lead compound that is an active component of the catalyst is not limited to oxides such as lead monoxide, dilead trioxide, dilead tetroxide, or lead dioxide, but also lead metals, sulfides, inorganic salt compounds, and organic salts. Substances that change into oxides by heating or other treatment, such as compounds, organic compounds, or complex compounds, can be used.

Examples of the above-mentioned inorganic salt compounds include lead fluoride, lead chloride, lead bromide, lead iodide, lead carbonate, lead sulfate, lead hydroxide, and lead hydroxy carbonate. Examples of organic salt compounds include lead acetate, lead propionate, lead oxalate,
Examples include lead citrate, lead stearate, or lead benzoate. Examples of organic compounds include tetramethyl lead, tetraethyl lead, tetrapropyl lead, tetraphenyl lead, and tetraxyl lead. Examples of the complex compound include ammonium hexachloropate and the like.

On the other hand, to name the metal compounds that serve as component B, titanium oxide represented by TiO2, zirconium oxide represented by ZrO, tin oxide represented by 8n02, and cerium oxide represented by CeO1 are not limited to oxides, but each element ammonium salts, sulfates, nitrates, halides,
It can be suitably selected from substances that change into the above-mentioned oxides upon heating, such as organic acid salts and hydroxides. These may be used alone or as a mixture in any proportion. When used as a mixture, the catalyst may be a composite oxide of each element of titanium, zirconium, tin, and cerium.

At least a portion of the catalytically active material is a composite oxide, such as lead titanate (PbSnO3, PbTi307, etc.),
Lead zirconate (PbZr0B etc.), lead stannate (PbSn
Preferable results can also be obtained by using lead zirconate (PbTi, Zr1-102.0<x<1, etc.).

In the catalyst of the present invention, the above-mentioned catalytically active composition further includes bulkari metals such as lithium, sodium, potassium, rubidium, and cesium, alkaline earth metals such as magnesium, calcium, strontium, and barium, boron, aluminum, and gallium. ,indium,
thallium, silicon, germanium, phosphorus, arsenic, antimony, bismuth, selenium, tellurium, copper, silver, gold, zinc,
Cadmium, (Nadium, Niobium, Tantalum, Chromium, Molybdenum, Tungsten, Manganese, Iron, Conogult, Nickel, Ruthenium, Rhodium,) (Radium,
Rare earth elements such as uranium or lanthanum, samarium (
(excluding cerium) may be contained as a co-catalyst component. The above-mentioned additional elements can be, for example, their respective oxides, salts or composite oxides with lead and/or titanium, zirconium, tin, cerium, etc. in the final catalyst.

The composition ratio of each component of the above-mentioned catalytically active substance is not particularly limited, but as a preferred composition ratio, lead as component A is calculated as lead monoxide (pbo) in an amount of 05 to 95% by weight based on the total amount of the catalytically active substance. , preferably 1 to 90% by weight, titanium oxide, zirconium oxide as component B,
At least one selected from the group consisting of tin oxide and cerium oxide is selected from each oxide (Tie, ZrO2, 5n0
An amount of 5 to 995% by weight, divided by 2 and Cent), or 10 to 99% by weight, is used.

When adding component C, at least one compound selected from the group consisting of the above-mentioned elements is calculated as its highest valence oxide, and 30 times i is added to the total of components A and B.
Amounts up to % may be used.

Examples of methods for producing a catalyst using the above-mentioned catalyst raw materials include suspending powder of component B such as titanium oxide or zirconium oxide in an aqueous lead compound solution, concentrating the slurry, and then molding; is sprayed onto a heated carrier, and then heated to a high temperature (400 to 800℃) in the presence of molecular oxygen.
) to make a catalyst. Alternatively, after mixing the above-mentioned lead compound and the above-mentioned B component compound such as titanium or zirconium, the mixture is heated at high temperature (
After firing at a temperature of 400 to 1,300°C, the catalyst is pulverized into an appropriate size and molded, or supported on a carrier to form a catalyst. Alternatively, a coprecipitate is obtained by a known method from a homogeneous aqueous solution of the above-mentioned A and B components, filtered, dried and then molded, or supported on a carrier and then calcined at a high temperature (400 to SOO℃) to form a catalyst. shall be. All suitable catalysts can be produced by the methods described above, but are not limited thereto.

In addition, the above-mentioned catalytically active substance may be used as a powdered or shaped catalyst by itself or together with a powder such as silicon carbide, alumina, iron oxide, silica or silicates such as magnesium or barium, or in some cases, the above-mentioned inert It is used by supporting it on a carrier made of a substance.

Even better results can be obtained by incorporating rice into the above-mentioned catalyst composition as a supporting or shaping aid. The following points can be praised as effects of adding whiskers. That is, since the catalyst becomes porous, the activity and/or selectivity are improved, and furthermore, in the case of a supported catalyst, the supported small droplet υ is improved, and mechanical strength such as peel strength and drop strength is improved. Even in the case of shaped catalysts, mechanical strengths such as drop strength, crush strength, and peel strength can be dramatically improved.

Examples of whisker materials that can be used include metal whiskers such as tungsten, iron, and nickel, and silicon carbide, silicon nitride, aluminum oxide, titanium oxide, beryllium oxide, boron carbide, titanium carbide, potassium titanate, and calcium phosphate. Their shape preferably has an average diameter of 5 microns or less, more preferably 1 micron or less, and a length of 1000 microns or less, more preferably 500 microns or less. The suitable amount of whiskers to be used varies depending on the raw materials, composition, form, manufacturing method, etc. of the catalyst, but preferably an amount in the range of 1 to 50 inches (by weight) based on the amount of the catalytically active substance is sufficient to achieve the above effects. Demonstrated. Particularly, when at least a part of the catalytically active substance is previously formed into a composite oxide such as lead titanate, lead zirconate, or lead stannate, and then the composite oxide is molded or supported on a carrier, the above-mentioned effect of whisker addition is remarkable.

The reaction conditions for catalytic gas phase oxidation of the diphenylmethane derivatives described above using the catalysts described above are set as follows.

That is, the reaction temperature is 250 to 600°C, preferably 2
80~550℃, space velocity 100~10,000Hr
-1 (S, T, P, ), preferably 200 to 6,00
0 Hr-1 (S, T, P, ), the gas concentration in the conduction gas of the diphenylmethane derivative that is the raw material is 0.04 ~
2 volume, preferably 0.08 to 1.0 volume, and air or molecular oxygen-containing gas is used as the conduction gas, preferably the oxygen gas concentration in the conduction gas is 5 to 40 volume. Furthermore, 0 to 20 volumes of water vapor may be added to the conduction gas. Also, the reaction pressure is normal pressure or 10k
It is also possible to pressurize at g/crIG''!.

Next, the present invention will be explained in more detail with reference to Examples.

In the examples, selectivity refers to molar selectivity with respect to reacted raw materials.

Example 1 (a) Production of catalyst Titanium oxide powder (anatase type, specific surface area 18.5 m'/y) 200ml of water in which lead nitrate 2971 was dissolved
y was added and suspended. This suspension was sprayed onto a spherical silicon carbide carrier with an average diameter of 3U and then heated to 520"C.
A catalyst was produced by calcining with The catalyst composition at this time was PbO
: TiO2 = 50:50 (weight ratio), and the supported amount is 15.8r/100m7 carrier.

(b) The catalyst 90r obtained in (a) of Oxidation Reaction Example 1 was packed into a tubular reaction tube with an inner diameter of 21 mm, and the tube wall temperature was adjusted to 460"C. Next, a mixture of diphenylmethane J, 92 and air 1201 (1) was charged. space velocity (8V)-1500hr-'(8,T,P
, ) into the reaction tube. The raw material gas concentration at this time is 0.
It is about 2 moles.

The unreacted raw materials and condensable products discharged from the reaction tube were collected by cooling and dissolved in a solvent, and each component was analyzed by gas chromatography, and the following results were obtained.

Conversion rate: 99.2 Benzophore selectivity: 876% The by-products were mostly fluorenone and carbon dioxide gas, with no benzoic acid or maleic acid observed.

Examples 2 to 5 The ratio and supported amount of pbo and TiO2 in Example 1(a) and the tube wall temperature in Example 1(b) are shown in the table below.
Example 1 was carried out in the same manner as in Example I, except that the raw material gas concentration was changed as shown in Table 1 to 0.4 volume, and the results shown in Table 1 below were obtained.

Examples 6 to 8 Zr0 instead of TiO2 powder in Example 1(a)
2 (specific surface area 22.8 y7r'/t: Example 6
), 8n02 (specific surface area 20.77H'/'
t: Example 7) or Cent (specific surface area 18.4
trl/t: Example 8) The same procedure as in Example 1 was carried out except that powder was used, and the results shown in Table 2 below were obtained.

Example 9 (a) Production of catalyst In Example 1 (a), ammonium metavanadate 0.052F was added to the TiOtM suspension in an oxalic acid aqueous solution (oxalic acid 008
PbO: TiO2: V, 0. =50:5
A catalyst having a composition of 0:0.1 (weight ratio) was produced.

The supported amount at this time was 17.3 f/100d carrier.

(b) Oxidation reaction Example 1(b) was carried out in the same manner as in Example 1(b) except that the raw material gas concentration was changed to 0.4 molar ratio, and the results shown in Table 2 below were obtained.

Example 10 (a) Production of catalyst A homogeneous aqueous solution containing 10 moles of lead nitrate and 10 moles of titanyl nitrate was added under stirring to an aqueous solution containing 22 moles of oxalic acid kept at 80°C to form a suspension of lead titanyl oxalate. I got it. After removing water from this suspension by filtration and drying,
The powder was fired to obtain lead titanate powder. The above lead titanate powder 3632 and silicon carbide whiskers (fiber diameter 0.05 to 0.0
．． The average fiber diameter is 0.2 μm, the fiber length is 5 to 50 μm, and the average fiber length is 20 μm.
n') was added and suspended.

This suspension was sprayed onto a rotating silicon carbide carrier having an average diameter of 3 V heated to 150 to 400 DEG C. to obtain a lead titanate supported catalyst. The catalyst composition at this time is expressed as PbO and TiO2, pbo:Ti02=73.6:
26.4 (weight ratio). Further, the content of whiskers was 20% by weight based on the supported composition. Note that when whiskers were not added, lead titanate powder could not be supported and a usable catalyst could not be obtained.

(b) Oxidation reaction The same procedure as in Example 9(b) was conducted to obtain the results shown in Table 2 below.

Example 11 (a) Production of catalyst In Example 1 (a), silicon nitride whiskers (fiber diameter O62-0.5 μm, fiber length 50 μm) were added to the titanium oxide suspension.
P
A catalyst with a composition of bO:TiO2:whiskers of 45:45:10 (weight ratio) and a supported amount of 26.2 r/100 ml of carrier was obtained.

(b) Oxidation reaction The reaction was carried out in the same manner as in Example 9(b), and the results shown in Table 2 below were obtained.

Example 12 Example 1 except that the raw material in Example 1(b) was changed to 4-methyldiphenylmethane and the tube wall temperature was changed to 440°C.
The same procedure was carried out and the results shown below were obtained.

Conversion rate: 954% Benzophonate selectivity: 60.2% 4-methylbenzophenone, fluorenone, and carbon dioxide gas were mostly by-products.

Patent applicant: Nippon Shokubai Chemical Co., Ltd. 23- 281-

Claims (2)

[Claims] (1) °Diphenylmethane derivative (R) represented by the following general formula (I) (R)rL (wherein, R is any alkyl group having 1 to 3 carbon atoms bonded to the meta and/or para position , and m and l each represent the number of the same or different substituents (from 0 to 3). Production of benzophenone characterized by using a catalyst containing lead oxide as a catalytically active substance and at least one selected from the group consisting of titanium oxide, zirconium oxide, tin oxide and cerium oxide as a component B. Method. (2) Component A is 1 to 90% by weight as PbO, component B is Tie, and/or still ZrO2 and/or 8nO
7 and/or 10 to 99% by weight as Cent.