METHOD OF PROCESSING MIXTURE OF HYDROGEN AND CARBON OXIDES (VERSIONS) Russian patent published in 2009 - IPC C10G2/00 C07C1/04 C07C41/09 C07C43/04 

FIELD: chemistry.

SUBSTANCE: method is proposed for processing a mixture of hydrogen and carbon oxides at high temperature and excess pressure (three versions) by bringing the mixture into contact with a catalyst at the first stage, where the catalyst consists of a methanol synthesis catalyst and a solid acid catalyst, and bringing products of the first stage into contact with a zeolite-containing catalyst at the second stage. One of the versions of the method is characterised by that, the initial mixture has volume ratios (H₂-CO₂)/(CO+CO₂)=1-3 and CO/CO₂=0-100 and on both stages, the process is carried out with separate recirculation of gas streams. The first contacting stage is carried out at pressure from 20 to 80 atm, bulk speed of supplying the initial mixture of 500 to 10000 h^-1, circulation ratio of 3 to 20. The methanol synthesis catalyst and the acid catalyst can be placed in form of a mixture in one reaction zone and the process is carried out at temperature from 200 to 320°C or these catalysts can be placed separately in different reaction zones and in the zone of the methanol synthesis catalyst, the process is carried out at temperature from 200 to 320°C, and in the zone with the acid catalyst the process is carried out at temperature from 200-400°C. Reaction products from the first stage are cooled and separated into a liquid fraction and a gas stream, which contains dimethyl ether and unconverted components of the initial mixture. The liquid fraction is separated by rectification with extraction of CO₂-containing gas, dimethyl ether, water-methanol solution and water; the gas stream of the products of the first stage is fed into a washing column being washed with water-methanol solution, after which it is divided into two streams, one of which is directed in form of a recycle for mixing with the initial mixture, and the other is either bled-off or directed to the second stage of the process, and the enriched water-methanol solution coming from the washing column is taken for rectification together with liquid products from the first stage, after which the extracted water-methanol solution is partially directed into the washing column, and the other part is taken to the second stage of the process, where at pressure from 1 to 40 atm, temperature from 320 to 460 °C, mass flow rate from 0.5 to 10 h^-1, it is brought into contact with a catalyst while recirculating gaseous products from the second stage with circulation ratio of 1 to 10. Products from the second stage are separated with extraction of a high-octane benzene fraction or aromatic hydrocarbons and a light benzene fraction, water and fraction(s) of hydrocarbon gases, including propane, butane fraction, part of which is used in form of a recycle for the second stage. Components of the solid acid catalyst at the first stage are aluminium oxide and/or crystalline silico aluminophosphate and/or zeolite with ZSM-5 or ZSM-11 structure, with molar ratio SiO₂/Al₂O₃ not greater than 200, and/or zeolite of the type β (beta), L, erionite, mordenite, and the catalyst at the second stage contains zeolite with ZSM-5 or ZSM-11 structure, with molar ratio SiO₂/Al₂O₃ not greater than 200.

EFFECT: wider assortment of desired products and increased versatility of the process, as well as increased output of C₃₊ hydrocarbons in terms of total amount of hydrocarbons.

3 cl, 8 ex, 7 dwg