JPH061726A - Method for hydrogenation - Google Patents

Abstract

PURPOSE:To hydrogenate an organic compound containing sulfur compounds as impurities at a high hydrogenation rate. CONSTITUTION:An organic compound containing sulfur compounds as impurities is hydrogenated using, as catalyst, a group VIII-5 or 6 metal (so called platinum metal) or compound, in the presence of at least one kind of oxide of a metal selected from iron, cobalt, nickel, copper and zinc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for hydrogenating organic compounds. More specifically, it relates to a method for hydrogenating an organic compound containing sulfur as an impurity.

[0002]

2. Description of the Related Art Hydrogenation reaction of organic compounds is an industrially important technique and is used as a synthetic method for various functional compounds. Examples include synthesis of cyclic paraffins by hydrogenation of aromatic rings, synthesis of saturated fatty acids or saturated alcohols by hydrogenation of unsaturated double bonds, synthesis of amines from nitro compounds, and alcohol synthesis from carboxylic acids. Generally, Pt, Pd,
Noble metals such as Ru and Rh and metals such as Ni, Cu and Fe are used.However, if the raw material contains a small amount of sulfur, the catalyst is poisoned and the reaction is suppressed. The reaction does not proceed at all. Therefore, usually performs desulfurization treatment prior to hydrogenation, for example _{Co-Mo / Al 2 O 3} , Ni-
When a hydrodesulfurization catalyst such as Mo / Al ₂ O ₃ is used, not only the reaction conditions are high temperature and high pressure but the cost of the apparatus is high, and the organic compound itself as a raw material may be hydrolyzed. For example, it is as described in Vol. 67, No. 1, page 28 of "Fuel Association Magazine".

The sulfur content can also be removed by using sodium metal, Raney nickel, etc., but in the former case, the organic compound as a raw material may be deteriorated, and in the latter case, the cost is high. Have difficulty. For desulfurization with metallic sodium, "Aromatics" Vol. 32 1
Although it is described on page 6 of the publication, alteration of organic substances other than sulfur compounds is suggested. Further, it is difficult to remove the sulfur content up to a level that does not affect the hydrogenation reaction, for example, to the ppm order by other separation methods.

[0004] As examples of the removal of sulfur in naphthalene, which is a typical aromatic compound, a crystallization method from methanol (Japanese Patent Publication No. 47-47020) and a method by adding aluminum chloride (Japanese Patent Publication No. 47-47021). ), A fractional crystallization and a white clay treatment combined use method (Japanese Patent Publication No. 47-47023), and a method utilizing the reaction with hydrogen peroxide (JP-A-54-812).
47) and the like are known, but none of them can satisfy the sulfur removal rate. Also, an extractive distillation in which an alcohol amine is added is shown (JP-A-62-149).
No. 633), the sulfur content is reduced to 10 ppm, but this method can be applied only to the removal of benzothiophene in naphthalene, and for other systems, it is necessary to search for an applicable combination each time.

[0005]

The object of the present invention is to prevent the deterioration of catalyst performance due to sulfur as much as possible in hydrogenating an organic compound containing a sulfur compound as an impurity,
To obtain a high hydrogenation rate.

[0006]

Means for Solving the Problems As a result of intensive studies on the reaction of a hydrogenation catalyst and a metal oxide with a sulfur compound in order to solve the above problems, the present inventor has found that a specific hydrogenation catalyst and a metal oxide are reacted. It was found that the hydrogenation of an organic compound containing a sulfur compound as an impurity is possible by using the substances in combination. That is, in the present invention, when hydrogenating an organic compound containing a sulfur compound as an impurity, one or more metal groups selected from Group VIII, Group 5 and Period 6 of the Periodic Table or a compound thereof is used as a catalyst,
Further, it is a method for hydrogenating an organic compound, characterized in that one or a mixture of two or more of oxides of iron, cobalt, nickel, copper and zinc is made to coexist.

The sulfur compounds as impurities contained in the organic compounds targeted by the present invention include mercaptans such as methyl mercaptan, ethyl mercaptan and thiophenol, sulfides such as dimethyl sulfide, diethyl sulfide and methyl ethyl sulfide, diethyl. Disulfides such as disulfide and dibutyl disulfide,
Examples thereof include thiophenes such as thiophene, methylthiophene, benzothiophene, dibenzothiophene and the like. The content of the sulfur compound is not particularly limited, but if it is too small, the present invention is not necessary, and if it is too large, the amount of the metal oxide added becomes too large and the handling becomes difficult. Preferably, the sulfur content is in the range of 10 ppm to 10,000 ppm.

The organic compound to be hydrogenated by the method of the present invention may be one having a site which undergoes a hydrogenation reaction. For example, an olefin bond, an acetylene bond, an aromatic ring, an aldehyde group, a ketone group, a nitrile group, a nitro group, a carboxyl group, an organic compound having an ester bond, specifically, naphthalene, methylnaphthalene, indene, styrene, Phenol, cresol, xylenol, benzaldehyde, dinitronaphthalene, acetic acid and acetic acid ester, benzoic acid and benzoic acid ester, terephthalic acid and terephthalic acid ester, naphthoic acid and naphthoic acid ester, naphthalenedicarboxylic acid and naphthalenedicarboxylic acid ester, C ₅ and C ₉ petroleum resin,
Examples thereof include indene-coumarone resin and terpene resin.

The catalyst used in the present invention may be used as a so-called noble metal black as it is as a metal, or may be used as a compound such as an oxide or a hydroxide. Most commonly, activated carbon or silica is used. , Alumina, titania, zirconia, chromia, magnesia, diatomaceous earth, etc. It may also be used as a colloid catalyst. The metals used for these catalysts may be used alone or in combination of two or more. In addition, if it contains a metal of Group VIII Group 5 and 6 of the Periodic Table as the main component,
Other active ingredients may be included as adjunct ingredients. The catalyst may be in the form of powder or a molded product.

The kinds of oxides of iron, cobalt, nickel, copper and zinc are not particularly limited, but practically, for example, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , CoO,
Co ₂ O ₃ , Co ₃ O ₄ , NiO, CuO, Cu ₂ O,
Oxides such as ZnOFeO are preferred. These may be used alone or in combination of two or more. The form may be a powder or a molded product. The amount to be added varies depending on the amount of sulfur contained in the raw material, but is usually 5 to 50 times the amount of sulfur. It is also present separately from the catalyst. If it is present in the catalyst, the activity cannot be prevented from decreasing.

The hydrogenation reaction conditions differ depending on the target organic compound, but the temperature is 50 to 350 ° C. and the pressure is 5 to 300.
The range of kg / cm ² is preferred. In the present invention, the catalyst can be used repeatedly, but when it is used repeatedly, it is necessary to remove the added metal oxide. This can be performed by sedimentation separation or the like in the liquid utilizing the difference in specific gravity. In particular, when iron oxide is used, it can be easily separated by using a magnet.

[0012]

In the present invention, it is presumed that hydrogen sulfide is first produced by the reaction of the sulfur compound in the raw material with the catalytic metal, and the produced hydrogen sulfide is fixed as the metal sulfide by the reaction with the metal oxide. . Periodic Table Group VIII Group 5 and 6
Periodic metals, so-called platinum group elements, have very high hydrogen activating ability and strong interaction with sulfur, so they have great hydrodesulfurization activity, but hydrogen sulfide generated by desulfurization is generated on the metal surface. Adsorbs strongly and inhibits catalytic activity.
Therefore, it is not possible to use these metal catalysts for the hydrogenation of organic compounds which normally contain sulfur. on the other hand,
It is known that oxides of iron, cobalt, nickel, copper, and zinc react with hydrogen sulfide at high temperature to form sulfides, but in hydrogen atmosphere, the actions of the two cooperate and the oxides It is quite astonishing that the presence of the compound does not hinder the hydrogenation activity of the catalyst metal, and as a result, hydrogenation of an organic compound containing a sulfur compound as an impurity, which has been impossible in the past, is possible.

[0013]

EXAMPLES The present invention will be described in detail below with reference to examples. Example 1 Naphthalene (sulfur content: 2,000 ppm) 50 g, 1 wt% Pt / alumina 5 in a 0.2 l autoclave
g and zinc oxide (ZnO) 2 g were charged, hydrogen was introduced under pressure, and the reaction was performed for 3 hours under the conditions of a reaction pressure of 50 kg / cm ² and a temperature of 250 ° C. After the reaction was completed, the catalyst and zinc oxide were separated by filtration and the product was analyzed by gas chromatography. As a result, the total amount of naphthalene was converted to decalin.

EXAMPLE 2 Coumaron-indene resin (softening point 103 ° C., sulfur content 1,500 ppm) 50 in a 0.2 l autoclave
g, 50 g of ethylcyclohexane, 5 g of 1 wt% Pt / alumina were charged, and 1.5 g of zinc oxide (ZnO) was added.
And the reaction pressure is 100 kg / cm ² , and the temperature is 290 ° C.
The reaction was carried out for 8 hours under the conditions. After the reaction was completed, the catalyst and zinc oxide were separated by filtration, the solvent ethylcyclohexane was removed by distillation under reduced pressure, and the amount of aromatic hydrogen in the produced resin was adjusted to ¹ H-NM.
It was 95.5% when the hydrogenation rate of the aromatic ring represented by the following formula was calculated by measuring with R. (Hydrogenation rate calculation formula) Hydrogenation rate (%) = (A−B) / A × 100 A: Amount of aromatic hydrogen of raw material resin B: Amount of aromatic hydrogen of produced resin

Example 3 2 wt% P in place of 1 wt% Pt / alumina of Example 2
The same operation as in Example 2 was performed except that d / alumina was used. The hydrogenation rate of the aromatic ring was 94.8%.

Example 4 Ferrous tetroxide (Fe ₃ O ₄ ) was used in place of zinc oxide in Example 2.
The same operation as in Example 2 was performed except that was used. The hydrogenation rate of the aromatic ring was 94.0%. Example 5 The same operation as in Example 2 was carried out except that copper oxide (CuO) was used instead of zinc oxide in Example 2. The hydrogenation rate of the aromatic ring was 70.2%.

Comparative Example 1 The same operation as in Example 1 was carried out except that zinc oxide was not added in Example 1. As a result of analyzing the product, naphthalene 95
%, Tetralin 5%, and decalin which is a complete hydride was not produced. Comparative Example 2 The same operation as in Example 2 was performed except that zinc oxide was not added in Example 2. The hydrogenation rate of the aromatic ring was 1.3%.

[0018]

According to the present invention, a high hydrogenation rate can be obtained by directly hydrogenating an organic compound containing, as an impurity, a sulfur compound which is difficult to hydrogenate. Further, it is not necessary to desulfurize the raw material to be hydrogenated until the sulfur content becomes a trace amount or less.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C07C 7/163 13/50 9280-4H // C07B 61/00 300

Claims (1)

[Claims] 1. When hydrogenating an organic compound containing a sulfur compound as an impurity, one or more metals selected from Groups VIII and 5 of the periodic table or a compound thereof is used as a catalyst, And iron, cobalt, nickel,
A hydrogenation method comprising coexisting one or more metal oxides selected from the group of copper and zinc.