SU667231A1 - Catalyst for isomerisation of cyclohexane into methylcyclopentane - Google Patents

Description

This invention relates to the manufacture of catalysts for melt cyclohexene isomerization to methylcyclopentane. A known catalyst for this iipo process, consisting of a Lot -deciated Dealuminated type Y zeolite on alumina. At 4OO C, the yield of methipcyclopentane is 66-77%, however, when the temperature drops to 325 C, the product yield drops to 62% l. The closest to the invention in terms of the composition and the result achieved is a catalyst for isomerization of cytohexene to methylcyclopentane, which is a LOI -decination type X or Y-21 zeolite, Disadvantage; The known catalyst is its low activity and selectivity (the yield of methylcyclopentane is not more than 10-30%). The aim of the invention is to increase the activity and selectivity of the catalyst. This goal is achieved by the fact that the catalyst contains La -decathione t Bath zeolite tapa V and magnesium aluminosilicate in the following ratio of components, wt.%: Ca - decationized zeolite of type Y10-4О Magnesium aluminate 6 0-90 A distinctive feature of the invention is the additional introduction catalyst magnesium aluminum silicate. At the same time, this difference allows to obtain an active and selective catalyst, which provides a yield of methylcyclopentane up to 91.6%. The catalyst is obtained by precipitating magnesium, aluminum and silicon hydroxides from aqueous solutions of their salts by the action of ammonia, followed by adding 30% to them in the form of an aqueous suspension. concentration of a deactivated type U zeolite and calcining the precipitate at. The catalyst has high thermal stability, activity, and selectivity as the reaction temperature drops to / 325 ° C. The side reactions are minimized. Preparation of magnesium aluminum silicate. To a 5% aqueous solution of sodium silicate (307.905 g NagSlO X XHENCO in 234 O ml of water), acidified -. 5% HNO (2700 ml) to pH-1, 5% aqueous solutions of magnesium nitrate salts (31.800 g MeSMOZUbNaO in 340 ml of water) and aluminium 1220.590 gAe (NG) g-9H20 are added. at. 2 2 86 m of water), then light an oily ammonia solution (l: l) to pH-12 at. intensive mixing. After precipitation, the mixture of three hydroxides is stirred for another 30 minutes and left for 1 day. on ripening. After the indicated period, the mixture is washed with bidistille tom with the addition of ammonia droplets (pH 7–8) to the nonshifter before the disappearance of diphenylamine N0 ions in the filtrate. The filtered mass is divided by weight into 5 equal parts (67Og). Preparation of L a-decationized zeolite Tina U. Air-dry powdered Nay zeolite with a ratio of Si, 4 containing about 23% of water, processed -. once with oxalic acid 0.25 at the end of the preparation for 1 hour at room temperature in the ratio of zeopite:; 1: 5 solution. The ratio of S-tOj. should be no more than 5.0-6.1. The zeolite is then stirred into a Bccner funnel and rinsed with bidistillate until the denier is warm. the COOH anion, a zeolig, is dried at 110 ° C in a drying cabinet, and then ion exchanged with a pa-i tail of lanthanum nitrate of 0.02 M concentration for 4 hours at room temperature and the ratio of zeolite: S solution is 1:20. Wire t processing zeolite twice with this solution. The degree of mixing of No to Ua should be at least 50-52%. The resulting L a is a decationized form; zeolite containing I, 6-i, 8 mg.eq./g, treated with a solution of ammonium chloride 1 n, the concentration at the rate of 6 ml of solution per 1 g of zeolite. The zeolite is treated seven times with a single solution. The residual content is not an assumption to exceed 0.1–0.2 mg vv / g. The zeopite is placed in a Buchner funnel and washed with double-distilled water to a negative ion pressure in the filtrate, dried at 110 ° C in an oven, and ammonium ion in air at 55 ° C for 2-3 hours. Preparation of the catalyst. Example,. The catalyst having the chemical composition: 90% magnesium aluminum silicate (5% Sch + 65% SiO -f 30% Atj 0h) + 10% UaHY, is prepared as follows. To 1/5 hr, Alumino-aluminosilicate (67Og), Nationium by the method described above, is added with vigorous stirring in the form of an aqueous suspension of 30% concentration 2, g of C-decateonated zeolite Y -52%, with a SiOg: AE20 ratio of 5.0–5.1), and stirred for 1 hour. The filtered mass is sewn under the air and formed into granules of 2-3 mm, which are then dried for 20 hours at room temperature. temperature, 3 hours at 120 ° C and calcined for 4 hours at 400 ° C. A and M e r 2. A catalyst having a chemical composition: 80% magnesium aluminum and jarajfcara (5% Mg0 + 65% SiO + 3O% Aif)) + + 20% UaHy, is prepared as follows. To 1/5 h of the mixture of hydroxides obtained by iabix by co-precipitation over the above methyde: di, ye, 5,000 g of La-decationated zeolite Y in the form of an aqueous suspension of 30% - "oh concentration" are added with vigorous stirring. The resulting suspension is stirred for 1 h and. the same operations are repeated as in Example 1. P and M 3. The catalyst having. chemical composition: 7O% (5% MgO + 65% SiO, (+ 30%) + 30% Ua NU, prepared as follows: To 1/5 part of the carrier. Obtained by the above method, add 8.571 g of zeolite Y in The la-decationized form in, in the form of an aqueous suspension of 30% concentration, is stirred for 1 hour and the operations are repeated as in Example 1, for example, for a catalyst having a chemical composition: 60% ( 5% MgfO + + 65% SiOj, + 30% At2 Oz) + 40% LaHY, are prepared as follows: To 1/5 part of the carrier obtained by the above method, add 13.333 g of type Y zeolite in a "cation" cation form in Water suspension si 30% - "th concentration, peremets1ivat for 1 h, filtered and then repeat all the operations, as in example 1.

56

The catalyst was tested in an isonon reaction, which was filled with cyclohexene triethy- peneration at a temperature of glycolic butyric ester on

325 С, atmospheric pressure, bulk zeolite, and also according to IR spectra of 0.5 h of speed, Before the start of test-stripes of methyl cylopentane

Neither the catalyst was activated for 2-3 h in s (MCP) 534, 84§, YuvTsm. air flow at a temperature of experience. Resulgates tested akgivnrdti

The reaction products were analyzed gas-proposed catalyst in comparison

Mathematical chromatographic media with known catalysts are given.

Raf LHM-8MTS using KCW in the table.

Comparative data on the testing of the activity of known and proposed catalysts {temperature 325 С, volumetric rate 0.5 h)

: ji, Wij,. -

66,723 I:

9O% (5% M O + 65% Traces 37.228, O Si02 + 3O% P1O% LaH.Y Traces 77.012, O 80% (5% SHO + 65% + 30% ACO3) + + 20% UHY 3.4 91 , 6No 8O%. (5% Mg04 € 5% SiO2 + 30% + 20% LaHY 6.878.27.6 7O% (5 Mg 0 + 65% S Oj + 30% Lez Oz) + 43O% LaHY 9.376.75, 2 60% (5% MdO + 65% siOj + zo% Ae203) + + 40% LaHY Footprints, 51.4 23.5 2.2 No 77.1

(C) 1.5 7O, O. 53.1 4.3 2.3 95.6 8O, 5 5, O No lOO91.6 3.5 No 96.1 81.4 5.2 No 96.479.6 66.5

667231

As can be seen from the table, the preparatory catalyst has a higher linearity and selectivity in comparison with the known catalysts. The yield of methylcyclopentane is 777S wt.% With a process selectivity of 81% and a decrease in the reaction temperature from 400 to.

The catalyst with a composition of 20% LAH + 80% (5% A O + 65% S-i02 + 30% AEgOg) gives a maximum yield of MORP of 91.6% by weight at 36O C. The reaction by-product yield is minimal and is no more than 7%. ten%.

Catalyst synthesis is pretty simple

and does not row the cost of expensive reagents and special equipment for

Claims (2)

1. Forward number 2318975/04, t5 cl. In OIJ 11 / 4O, 1976, according to which a decision was made to issue an author's certificate. 2. A. A. Kubasov, et al. The transformation of cyclohexene by octationized zeolites20 so Y. Vestnik Moskovskogo Universiteta. Chemistry, № 4, 1970, p. .406.