SU727211A1 - Catalyst for hydrogenation of benzene - Google Patents

Description

one

The invention relates to catalysts, in particular to a catalyst for the hydrogenation of benzene based on skeletal nickel.

On the industrial scale, a sulfide catalyst (4O% Nis + 60% we) is known, the vapor phase hydrogenation process at 27O kgf / cm n ZOO325 C with bulk velocity O, 5 0, 6 h l.

A nickel catalyst is known that conducts hydrogenation of benzene at 1OO kgf / cm, and 220-420 0 2. Under these conditions, isomerization and cleavage products can be formed.

Lime catalysts based on Rene nickel with the addition of chromium fij and 4j. The complete cessation of benzene in cyclohexane with the indicated catalysts is achieved, respectively, in ISO and 100 - 228 minutes, in addition, on the nickel-chromium catalyst, hydrogenation is carried out at 110 kgf / cm and.

The closest to the invention is a catalytic agent for hydrogenation of benzene based on a leached n-aluminum alloy with a content of 5 O Bec.% Ni and 50 wt.% A in the starting alloy 5. The activity of this catalyst expressed by the reaction rate or hourly productivity product in a batch reactor is 3.8 ° C or 228

The disadvantage of the known catalyst is relatively low activity and low stability (conversion of benzene to cyclohexane after the b-th test is only 68.3%).

In order to increase the activation and stability of the catalyst, a catalyst for the hydrogenation of benzene based on a leached ns el – / hyuminium alloy containing a pre-sary samarium is proposed, with the following content of ingredients, wt.%: Samarium 0.5-5.0 Nickel45.0 -49.5 Aluminum Else The distinguishing features of the invention are the additional content in the starting samarium alloy and the indicated content of ingredients. The rate of hydrogenation of benzene in the presence of the proposed catalyst reaches 4.21 - 5.52 gN / gW lb. The catalyst according to the invention also has an increased stability compared to the known catalyst, so the proposed catalyst practically does not lose seryu initial activity during six repeated SIELOS The yield of cyclohexane is 98.6-100%. Alloys with the composition of nickel-aluminum samaria and catalysts based on them are prepared according to. following method described in example 1.;. . EXAMPLE 1. To obtain a SO of an alloy having the composition N: ACrSor49, 0: 50: 1.0, 52.0 g of aluminum in the form of 3–5 mm pieces are loaded into a quartz crucible and heated in a high-frequency melting furnace. marks 6KB-802b to I6O-120O ° C. Then, 49.0 g of nickel and 1, O g of samarium are introduced into the molten aluminum. With this, the pace of paTyiia exothermically rises to 170 ° –180 ° C and is maintained for 5 minutes. Then the furnace is turned off and the casting is performed in a graphite mold with its subsequent cooling in air to 2 ° C. Then the resulting alloy is ground into a mortar, sieved through a No. 6O sieve (O, 25 mm), the particles of the required size are separated and subjected to idf leaching 20% -4 € water races

Skeletal Nickel-Samarium Catalysts Activity in Benzode Hydrogenation Reactions

727211

i Table 1 with caustic soda in a boiling water bath for 1 hour. The resulting catalyst mass is washed with distilled water until neutral in phenopthalein and then with ethyl alcohol for. remove traces of moisture; Thus, the prepared catalyst is used to hydrogenate benzene. . Example 2. Other compositions of alloys and catalysts containing 0.5; 3.0; 5.0 wt% samarium is prepared as described in Example 1. The activity and stability of the catalysts are tested. Example 3. The experiments were carried out in an autoclave of the LenNIIHimmash system with vigorous stirring. ; For the hydrogenation, take 200 ml of a mark ash bottle; (t. ksh, 77.6 ° C, - 0.879, the content of thiophene is 0.0001%). The hydrogenation temperature is 160 ° C, the hydrogen pressure is 40 kgf / cm, the amount of catalyst is 0.5 g or 0.2V% by weight of the initial benzene. The hydrogenation products of the analyzer are t-gas by gas chromatography on an LCM-8M-D chromatograph. Gas carrier argb, solid carrier — BiK resorb (O, 25–0.375 mm), stationary. Liquid phase — polyethylene glycol adipate, column length: 2 m. g) obtained on 1.0 g of catalyst for 1 h (or min). The results of the hydrogenation of benzene on skeletal nickel-samarium (5O% Af) catalysts are given in Table 1.

 Hi skeleton

(SO% N) (known)

Nl-SrtV (O, 5% Sm)

Ni-Sn, (1, oW)

3.82

4.21

## 5.52 The amount of catalyst is 0.28%, “100% yield of cyclohexane to 100% yield of cyclohexane to From the data table. As can be seen in Fig. 1, hydrophenization of benzene on nickel-samarium catalysts at 40 kg / cm proceeds with the formation of cyclohexane without the formation of isomerization products and cleavage. Samarium additives (0.5–5.0 wt.% With respect to nickel) increase the activity of skeletal nickel by 1.1–1.5 times. KoriTisKT exhibits the highest catalytic activity with 1.0 V8c.% Samarium, the rate is g | 1 drifting, which is almost 1.5 times higher than that of skeletal nickel without an additive. Samarite additives to skeletal nickel help speed up the process, at its optimal composition its 1OO% cyclohexane yield is reached in 66 minutes, while on skeletal nickel without additives 1OO% conversion of benzene to cyclohexane occurs after 110 minutes of hydrogenation. In addition, the chromatographic data show that the catalyst obtained contains cyclohexane and unreacted benzene. This indicates the high selectivity of nickel – sa- rium catalysts. Along with high activity and selectivity, skeletal and nickel-sodium catalysts exhibit high stability in the benzyl hydrogenation reaction. Example 4. The stability of the nickel-samar catalyst (l, O% Sn), 49, ONI is studied by repeated hydrogenation of benzene at 160 ° C and 40 kgf / cm on the same sample of catalyst. Comparison of the activity of the known and proposed catalyst are according to the data of six repeated experiments. A portion of the catalyst is taken twice as large (1, O g) than in the benzo benzene 2OO ml. for but min hydrogenation for 66 minutes of hydrogenation. e 3 (Q, 5 g), which provides 100% cyclohexane yield for short m of hydrogenation. Comparative data on the stability of nickel – samarium and nickel (50% M) catalysts are given in Table. 2. Table 2 Stability of catalysts in the process of hydrogenation of benzene. The amount of catalyst is 0.5–6%, the amount of benzene is 2OO ml: g40 kgf-cm, temperature 160H. The duration of the experiment 5O minutes The duration of the experiment 30 minutes

Claims (5)

1. Karzhev V. I, and others. Sat. Research and application of hydrogenation presesses in the oil refining industry. M., INIITEnefhekhim, 1966, p. eight. 2. Kalechits I. V, and others. Proceedings of the East-Siberian branch of the Academy of Sciences of the USSR, 3, 1955, p. 94-98. 3. USSR author's certificate No. 276912, B 01 J 25/02, 1970. 4. USSR author's certificate N9 245057, B01 325/02, 1969. 5. Dufoo F.A., Eftchara F., NaaZE A.C.ThOKon G.H.Chem. Ena. Progr. 60 No. 0 9.43, 969 (nPOTOTWi.