SU641982A1 - Catalyst for isomerisation of carbons having double links - Google Patents

Description

I

This invention relates to the manufacture of catalysts for the isomerization of hydrocarbons containing double bonds.

A known catalyst for this process contains cyclopentadienyl titanium trichloride l in combination with apium hydride.

The immediate solution of the problem is a catalyst containing an organic or non-granular iron salt or iron pentacarbonate and an aluminum organic compound of the general formula A, 1R 3, M dHHX where R is an alkyl radical,

X - hapoid 2.

A disadvantage of the known catalyst is its low activity.

Thus, isomerization of vinylnorbornene into ethylidenenorbornene under the action of iron acetyltonone and triisobutypaluminium at 144 ° C takes 2 hours, while the conversion of the initial hydrocarbon does not exceed 12%.

The aim of the invention is to increase the activity of the catalyst.

The chain is achieved by the fact that a catalyst comprising an organic or inorganic salt of iron or iron pentacarbonium and an organoaluminum compound contains, as the latter, a compound of the general formula

MSODS

where alkaline or shchepochno-land metal,

R is a hydrocarbon radical with a carbon number of 2-6,

N 1 or 2

in this case, per 1 mol of the iron compound, the catalyst contains 0, O1-1O mol) of the organoaluminum compound.

Potassium, sodium, calcium and other alkali and pinch-earth metals are used as an aluminiumorganic compound. Benzoate, oxalate, acetyl-Petonate are used as iron compounds.

chloride, bromide, ferrous sulfate, and iron pentacarbonyl

Example 1. A glass ampoule of 5 cm in nitrogen ioKe is loaded with 1 MP (0.00739 g mol) of Vilnorbornene, 0.223 g {0.000 296 GMop di-butylbenoate of iron and 1.4 ml (O, O01776 GMO) a toluene solution of KOAv (i-).

The molar ratio of the components of the catalyst is tert-C H) with HgCoo 2 e: coAe (i -) 1: 6.

The ampoule is sealed and kept in a thermostat at 140 ° C for 30 minutes. At the end of the reaction, the ampoule is cooled, opened and the composition of the products is determined by GLC (LCM-8MD chromatograph, flame ionization detector, 45m capillary column, apion-stationary phase - L temperature is 90 ° C.) The content of ethyl denorbornene is 21.1% by weight.

When using triisobutyl aluminum A1 (i - CdH) as the organoaluminum compound, (under the same conditions, the ethylidene norbornane content in the reaction products is 12%

Example 2. The experiment was carried out as described in example 1. Iron pentacarbonyl was used as an iron compound. The ethylidene norbornane content in the reaction products, depending on the ratio of the catalyst components, is given in the table.

Isomerization of vneshnorbornene (0.00739 g. Mole) in ethylidene norbornene b in the presence of iron pentacarbonyl (O, OOO 296 g mop) and COLE. (,) at 14 ° C for 6 ° min.

Example 3 The test is carried out as described in Example 2. NaOAK (i-CgHj) is used as the organoaluminum compound.

the molar ratio of the components of Fe (CO); : NaOAe (1: 0,

The content of typedinorboripep in the product of isomerization of vinylnorbornene aa in 2 hours is 73.6%,

Example 4 Opton is carried out as described in Example 2. As the organoaluminum compound

NII use (i-SDN) 2 The molar ratio of the components fe (CaCOAe (i - ,,) J И -0.5. The ethylidene norbornene content in the vinyl norbornene isomerization product is 67.3% for 1.5 hours. Example 5. In a steel reactor with a volume of 30 see 7.5 ml (0.0938 mol mol) of 1-butene, 1.26 ml (p, 00938 g-mol) of iron pentacarbonyl and 14.7 ml (0.00938 mol) of a toluene solution of diisopropyl aluminate potassium KOAf (-) .. Reactor r rinsed with nitrogen and sealed. The mixture was stirred at 100 ° C for 2 hours. According to GLC (column temperature 30 ° C) conversion of butene-1 to butene-2 is 66.6%When using iron pentacarbonyl without diizopropipalyuminata potassium 2-butene content in the reaction products as a component of the catalyst is 22%

Example 6 The test was carried out as described in example 5. For isomerization, 1O g (0.119 gmol) of hexene-2, 7.8 g (0, O048 gmol) of ferric chloride and 10 ml (0.028 gmol) of toluene were taken. AAgr / OAS (t-SdN / Molar ratio of the components of the catalyst FeCl: Mgr CAB (i 3 2 1: 6

The mixture is heated at 2 ° C for 50 minutes. Conversion of hexene-2 to hexene-3 is 22.4%

Example 7 The experiment was carried out as described in Example 5, 6g (0, O7 g. Mol) 2-methylpentene-1, O, 96 ml (O, O07) pentacarbonyl gas and 14 mp (O, OO36 g-mol) are taken for isomerization. kopuolny solution of a mixture of KOAe (-C) and KOAB (t -C,) 2. The mixture is heated at 1 ° C to 18 ° C for 1 hour, the conversion of 2-methylpentene-1 to 2-metipentene-2 is 75.2%

From the data given in examples 1-7, it follows that the use of the general formula M () as an organoaluminum compound can significantly increase the activity of the catalyst and, thereby, increase the yield of the target product

The output of etipene9 .2 norbornene, wt.%

Claims (2)

1. US patent Ns 3535395, cl. 26O-666, 197O, 2. US patent number 3586726, cl. 26O-666 a, 1971.