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Middle distillate hydrocarbons are produced from feed mixtures of carbon monoxide and hydrogen by contacting said feed at elevated temperature and pressure in a first stage with certain impregnated catalysts and contacting at least the middle distillate fraction of the product of the first stage in

Middle distillate hydrocarbons are produced from feed mixtures of carbon monoxide and hydrogen by contacting said feed at elevated temperature and pressure in a first stage with certain impregnated catalysts and contacting at least the middle distillate fraction of the product of the first stage in the presence of hyrogen with a catalyst containing at least one metal having hydrogenation activity supported on a porous carrier.

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1. A process for the preparation of a hydrocarbon mixture, a major proportion of which is middle distillates boiling in the temperature range between about 140° and about 370° C., from a feed mixture of carbon monoxide and hydrogen, which comprises contacting an H 2 - and CO-containing feed in a fir

1. A process for the preparation of a hydrocarbon mixture, a major proportion of which is middle distillates boiling in the temperature range between about 140° and about 370° C., from a feed mixture of carbon monoxide and hydrogen, which comprises contacting an H 2 - and CO-containing feed in a first stage at a temperature in the range of 125°-350° C. and pressure in the range of 1-150 bar with a first stage fixed bed catalyst (Co-impregnation catalyst) containing 10-40 parts by weight of cobalt and 0.25-5 parts by weight of zirconium, titanium or chromium per 100 parts by weight of silica, said first stage catalyst having been prepared by impregnating a silica carrier with one or more aqueous solutions of salts of cobalt and zirconium, titanium or chromium, followed by drying the composition, calcining at 350°-700° C. and reducing at 200°-350° C., with the proviso that if the feed has an H 2 /CO molar ratio of less than 1.5, water is added to said feed and that in said first stage the Co-impregnation catalyst is used in combination with a CO-shift catalyst, and contacting at least a suitable distillate fraction of the reaction product of the first stage in a second stage in the presence of hydrogen at an elevated temperature and pressure with a fixed bed catalyst containing at least one metal with hydrogenation activity supported on a porous carrier. 2. A process as in claim 1 wherein water is added to the H 2 - and CO-containing mixture feed to the first stage, and first contacts a CO-shift catalyst and then contacts a Co-impregnation catalyst without CO having been removed. 3. A process as in claim 1 wherein said H 2 - and CO-containing feed mixture to which water has been added is contacted in the first stage with a catalyst bed which is either built up on several alternating layers of consecutively a CO-shift catalyst and a Co-impregnation catalyst, or said bed is a physical mixture of a CO-shift catalyst and a Co-impregnation catalyst. 4. A process as in claim 1 wherein the first stage is carried out at a temperature of 175°-275° C. and a pressure of 5-100 bar. 5. A process as in claim 1 wherein the second stage catalyst contains one or more noble metals of Group VIII supported on a carrier. 6. A process as in claim 5 wherein in the second stage a catalyst contains 0.1-2% by weight of one or more noble metals of Group VIII supported on a carrier comprising 13-15% by weight of alumina, the remainder consisting of silica. 7. A process as in claim 1 wherein the second stage is carried out at a temperature of 175°-400° C., a hydrogen partial pressure of 10-250 bar, a space velocity of 0.1-5 kg.l -1 ·h -1 and a hydrogen/oil ratio of 100-5000 Nl·kg -1 . 8. A process as in claim 1 wherein said feed for the first stage comprises an H 2 - and CO-containing fraction which has been separated from a reaction product from a prior reaction, said prior reaction comprising contacting an H 2 /CO mixture having an H 2 /CO molar ratio of less than 2.0 with a bifunctional catalyst combination containing one or more metal components with catalytic activity for the conversion of an H 2 /CO mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydrocarbons and a crystalline silicate, which silicate possesses the following properties after one hour's calcination in air at 500° C.: (a) thermally stable to a temperature above 600° C., (b) an X-ray powder diffraction pattern containing the four lines stated in Table A in the specification as strongest lines, (c) in the formula representing the composition of the silicate expressed in moles of oxides and containing in addition to oxides of hydrogen, alkali metal and/or alkaline earth metal and silicon, one or more oxides of a trivalent metal A chosen from the group consisting of aluminum, iron, gallium, rhodium, chromium and scandium, the SiO 2 /A 2 O 3 molar ratio is more than 10, with the proviso that if the H 2 /CO feed mixture has an H 2 /CO molar ratio of less than 1.5, a trifunctional catalyst combination is used contained one or more metal components with catalytic activity for the conversion of an H 2 /CO mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydrocarbons, one or more metal components with CO-shift activity and the crystalline silicate. 9. A process as in claim 8 wherein said crystalline silicate is selected from the group consisting of aluminum, iron or gallium silicates. 10. A process as in claim 8 wherein the trifunctional catalyst combination is composed of two separate catalysts X and Y, catalyst X possessing activity for the conversion of an H 2 /CO mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydrocarbons as well as CO-shift activity and catalyst Y is the crystalline silicate. 11. A process as in claim 8 wherein as catalyst X is capable of converting an H 2 /CO mixture into mainly methanol and/or dimethyl ether. 12. A process as in claim 8 wherein catalyst X contains 30-75 parts by weight of iron and 5-40 parts by weight of magnesium per 100 parts by weight of alumina and is prepared by impregnating an alumina carrier with one or more aqueous solutions of salts of iron and magnesium, followed by drying the composition, calcining at a temperature of 700°-1200° C. and, finally reducing. 13. A process as in claim 8 wherein catalyst X contains 10-40 parts by weight of iron and 0.25-10 parts by weight of chromium per 100 parts by weight of silica and is prepared by impregnating a silica carrier with one or more aqueous solutions of salts of iron and chromium, followed by drying the composition, calcining and reducing at a temperature of 350°-750° C. 14. A process as in claim 8 wherein said prior reaction is carried out at a temperature of 200°-500° C., a pressure of 1-150 bar and a space velocity of 50-5000 Nl of gas/l of catalyst/h. 15. A process as in claim 1 wherein said feed for the first stage comprises an H 2 - and CO-containing fraction which has been separated from a reaction product of a prior reaction, said prior reaction comprising contacting an H 2 /CO mixture having an H 2 /CO molar ratio of less than 1.0 with an iron-containing bifunctional catalyst or catalyst combination possessing CO-shift activity in addition to activity for the conversion of an H 2 /CO mixture into substantially hydrocarbons. 16. A process as in claim 15 wherein said prior reaction is carried out at a temperature of 200°-350° C., a pressure of 10-70 bar and a space velocity of 500-5000 Nl of gas/l of catalyst/h. 17. A process as in claim 8 wherein the H 2 /CO feed mixture to said prior reaction are prepared by steam-gasification of coal at a temperature of 700°-1500° C. and a pressure of 10-1000 bar. 18. A process as in claim 1 wherein at least about 60 percent by weight of the hydrocarbon mixture product is middle distillates boiling in the temperature range between about 150° and about 360° C.