SU695998A1 - Method of preparing saturated cyclic hydrocarbons - Google Patents

Description

I

The present invention relates to a process for producing {w saturated cyclic hydrocarbons from aromatic hydrocarbons.

The known method of hydrogenation of aromatic hydrocarbons into diclohexane row hydrocarbons in two stages in the presence of catalyst of Group VIII of the periodic system, used without a carrier or on a carrier 1, as a catalyst. The disadvantage of this method is the need for the process (the possibility of carrying out the process in two stages.

The closest in technical essence is the method of producing nascent cyclic hydrocarbons by liquid phase hydrogenation of aromatic hydrocarbons with a catalyst containing Group VIII metals, mainly in the form of a metal. In the case of obtaining saturated cyclic hydrocarbons containing less than 500 parts per million of impurities, the product is hydrogenated in the gas phase in contact with a catalyst containing Group VIII metals as oxides 2). The disadvantage of this method is the two-stage process.

The purpose of the present invention is to simplify the process: 1.

The goal is achieved by the described method of obtaining a saturated cyclic hydrocarbon by liquid phase hydrogenation of aromatic hydrocarbons in the presence of catalyst of metals of group VIII and cocatalyst - titanium (IV) or molybdenum (V) or vanadium (IV) cocatalyst, at the following ratio of components, wt.%: Titanium 0.5 - 1 or molybdenum 0.2-0.5, or vanadium 0.25-0.4, oxidized coal the rest in the amount of 5-35 weight. h. cocatalyst for 1 wt. h. catalyst.

Below are examples of the synthesis of catalysts and components of catalytic systems; examples of better saturated cyclic derivatives from aromatic hydrocarbons. Oxidized activated carbons from CKJ coal (TU D2 GU31460) were obtained according to the following method: SKT coal (TU D2 TU31460)

placed in a glass, poured acid | 4 with a specific ratio of 1.4 and heated in a water bath at a temperature of 80 ° C for 6 hours. After cooling, the coal was washed by decanting the liter water several times, transferred to a porous filter and washed with distilled water until the filtrate was neutral. Dried coal in a dry cabinet at 105 ° C to a constant weight. The total amount of acidic content plants was determined by T1 | thshev of a certain amount of 0.1 NbOH coal.

i Hereinafter, carbonated carbon-based oxidized carrier will be designated Y-0. The separation of the products of benzene and xylene hydrogenation was performed on a Chromium-3 chromatograph, n4polish1 chromosorb W, gaddka phase — nylacetylene glycol adipate, gas- arsenic-argon. The identification of anthracene products was carried out using the spectrums of spectrophotometer Specord in atanol solution.

Preparation of U-O-- T transfer catalyst | C 1 3 6 g of oxidized coal obtained by the above procedure, with a NaOH capacity of 5–6 mg-qsv / g, were boiled with 40 ml of TiCi4 per atmosphere at a rate of dry nitrogen for 4 hours The adsorbionic TiCU was thoroughly washed with dry benzene with 1 × hexane in an N2 atmosphere with a primary lecture, then with a porous (}) filter until used, -. IY in the filtrate traces) i.

The U-0-TiClg cyjHii thus obtained in a pacoule gun at day xy; 1nly in a vacuum desiccator. The amount of applied Ti was 70-80 mg per 1 g of coal.

Getting katschchizator-carrier U-O- -TiCtn (ОЯ) z- “

n 1,2, R CjHs.

1.8 g of U-O-T1C 3, prepared according to the described procedure, was boiled in 50 ml of ethanol for 4 hours under dry W2 atmosphere, filtered in a stream of N3 and washed with ethanol to a negative reaction with Ti-HOit todike). Thus obtained U-O-TiCI (OR) 2 sushi-7SH in a vacuum pistol. When treating the U-O-T C1 3 zl-anol at a comm ual temperature, U-O-TiC 2 (OR) was obtained. The amount of titanium applied was 57.5 mg per 1 g of coal.

All experiments on hydrofluorics were carried out in a thermostated duck vessel at 22 ° C and a hydrogen pressure of 1 atm.

Preparation of a non-carrier catalyst U-O-MoCl4 1 g of oxidized carbon brand SKT with Naon mg-SQV / g placed; n1 in 50 ml of absolute benzene, N2 was blown and then 0.5 g of MoClj was added, the mass was heated to boiling in a flow} more than 4 hours, after cooling, the coal was washed several times with decantation of dry benzene, filtered in an inert atmosphere and dried under vacuum. 1 g of coal contained 0.19 10 mol (Mo).

Preparation of U-0-VCI3 transfer catalyst 1.2 g of oxidized carbon grade E 5.5 mg-qsv / g were placed in 50 ml of CCI4, N2 was purged and then 0.7 g was heated to boiling for 5 hours, after cooling, the coal was washed} several times by decantation with dry benzene, filtered in an inert atmosphere and dried under vacuum. 1 g of coal contained 1.4510 mol (U).

Example 1. 112.5 are loaded into a duck

х1 (G mol CgHg; 2,21СГ metallic Pt catalyst, 0.2 g У-О-Т (Сзз 4.5210 mol (Ti). 119.4-10 mol was absorbed in 8.5 hours 2. The reaction product was absorbed by cyclohexane Conversion of benzene - 31.2%. Specific catalyst activity - 1 mol / g-at.min. Spread rate 63.5 catalytic cycles per hour.

.. Example 2. A duck load is 112.10 mol of CgHg 1.7510 mol of mTallic; Pt catalyst, 0.134 g U-0-T C12 (OR).

During 5.36 hours, 40-10 mol H2 was absorbed. The reaction product is cyclohexane. Benzene conversion - 11.9%. The specific ac7T1 of the catalyst is 0.72 mol / g-at.min. The rate of hydrogenation is 42.9 catalysts of 1.1 cycles per hour.

Example 3. 94-lCr mol of SBS5SNz, 2.210 mol of metallic Pt catalyst, 0.2 g of U-0-T | C1z mol of H2 are loaded into a duck. Pro; .tukt reaction - M.tetil1D klogeksai. Toluene conversions - 23,869s. Catalyst specificity

0.43 mol / g-at. Lshn. The rate of saturation is 25.6 catalytic cycles per hour.

Example 4. A duck was charged with an iron of 82.9 (G mol o-SbP4 (SPZ) 2, 2.2 ICT mol of metallic Ft catalyst, 0.2 g U-0-T1C1z 4.52-10 mol (Ti) For 8.48 h, 25 iCT mol H2 was consumed. The reaction product was dimethylcyclohexane. The o-xylene conversion was 10.05%.

The specific activity of the catalyst is 0.223 mol / g –at.min. Hydrogen rate of 13.6 catalytic in 1 h.

Example 5. 8110 mol of “-SbN4 (SPZ) 2, 2.2 ICf. Mole of metal are loaded into a duck

Ft catalyst, 0.2 g U-O-T1C1z 4.52-10 mol (Ti). For 7.48 hours, 49-1 was absorbed (D mol P2. The product of the reaction was dimethyl cyclohexane. Conversion of α-xylene — 20.2%. Specific catalyst activity — 0.5 mol / g-at. Min. Speed

hydrogenation of 30 kata; plastics cycles in 1 hour. 6. To the duck is charged 112.5i h of MSH, 1.8-10 mol of L of catalyst, 0.2 g of yO TiCl3, t4.52ia-mol (T1). 3a 17 h was absorbed 118.6-1СГ mol H2. Product