DE921930C - Process for converting carbon monoxide with hydrogen - Google Patents

Description

Process for the conversion of carbon monoxide with hydrogen The for the Conversion of carbon oxide with hydrogen to multi-membered hydrocarbons, optionally in addition to liquid or solid oxygen-containing hydrocarbon derivatives Metals of the iron group (iron, nickel or cobalt) containing catalysts used are mostly prepared in such a way that one of these hydroxides or carbonates Metals precipitates from solutions of their salts, optionally together with activating Additives and hzw. or on carriers brought into the precipitation solution, and the precipitated substances are then optionally reduced with sintering. When using Iron as an effective catalyst component is also often used as what are known as melt catalysts by using iron alone or together with activating substances in a stream of oxygen melts and the melt solidified by cooling is crushed and with hydrogen reduced.

It has now been found that the implementation mentioned is very advantageous such catalysts can be used, which can be done in a much simpler manner produces naturally occurring iron ores, which are predominantly oxidic in nature or can be converted into oxides by roasting or heating alone, in the latter case after such roasting or heating without the addition of alkalis with reducing gases, preferably hydrogen, at temperatures over 300 to 3500 treated. The main oxidic iron ores are magnetite and Usable hematite. Also sulphidic and especially carbonatic ores such as siderite, are after roasting (the last also by heating) and subsequent reduction suitable for use as catalysts. The ore is expedient before the reduction crushed to the desired grain size; for example, grain sizes are set from 6 to 15 mm, in some cases also those under 2 mm or finely ground powder here.

In addition to hydrogen, there are also hydrogen-rich technical gases for the reduction very suitable. In these, however, the content of carbon dioxide and Methane doesn't have to be too high to avoid carbon sequestration, which is for the effectiveness of the catalysts is disadvantageous. The reducing effect will favored by adding small amounts of ammonia. The reduction temperature depends on the nature of the ore being treated. Generally it is below 6500) In some cases, however, temperatures up to 7000 or higher (up to to about 850'0) into consideration.

The catalysts produced in this way are used to carry out the synthesis in a liquid medium, e.g. B. the so-called own (Sl (i.e. the one at the Synthesis formed liquid product), or a fraction of the same is used. You can use a lumpy catalyst filled into the reaction space or with a suspension of the finely divided catalyst in the liquid Work medium and, if necessary, circulate the suspension.

The suitability of the catalysts prepared in the manner described1 is surprising because it is well known that the ores mentioned are always in more or less in large quantities they contain various impurities which are involved in the Treatment with hydrogen could not be removed and was therefore to be feared. that these impair the catalytic effectiveness considerably.

The treatment of the iron oxide with hydrogen or other reducing agents Gassing can take place at ordinary, increased or reduced pressure. Advantageous one passes the hydrogen with a sufficient flow rate, z. B. from 50 to 1000 1 per hour of oxide, over this, so that the water formed is diverted as quickly as possible away from the oxide. The withdrawing hydrogen can then be returned again. The freshly supplied hydrogen is advantageous dried, as is the water content of the rice course by means of intermediate cooling and / or adsorption or the like. Removed.

The ores can be reduced in the synthesis furnace itself or in a special facility take place. In the latter case, it is during transfer to the synthesis furnace ensure that the catalytic converter is protected from burning by using it protected from the entry of air or oxygen.

However, it can also be used temporarily without prejudice to its effectiveness into the air, if its pyrophoricity is eliminated by suitable measures was e.g. B. by treatment with carbon dioxide after it has been brought to temperatures below so'O, preferably below 400, has been cooled.

The catalyst can also be soaked in oil or stored in oil, before it is brought into the conversion furnace.

With the iron catalysts prepared in the manner described can the reaction of the carbon oxide with the hydrogen in the usual for this Conditions, d. H. at ordinary or advantageously elevated pressure, e.g. B. at 5 up to 35 at, and at temperatures between ISO up to 4000. The pressure but can also be higher, e.g. B. 100 to 200 at and even more.

Example A magnetic iron ore containing 1.4% / o silicon, 0.19% / o Aluminum, 66.77% iron, 0.12% copper, 0.028% nickel, 0.28% vanadium, 0.037% manganese, 0.50% titanium, 0.67% calcium, 0.73% magnesium, 0.046% Sulfur, 0.024 ovo phosphorus, o, o8 for potassium, o, oS 0/0 sodium, 0.26 0/0 carbon and contains detectable traces of lead and tin, becomes pieces of 5 to 8 mm Crushed diameter and then treated with hydrogen, the hourly The amount of hydrogen per kilogram of ore is 0.2 Ncbm.

The catalyst produced in this way is placed in a 2.35 m high pressure pipe from where mm diameter filled, whereupon a synthesis gas into this from bottom to top, which contains carbon oxide and hydrogen in a volume ratio of 55:45, in cocurrent with part of that formed in a previous operation and then condensed Synthesis product (the treatment takes place in the liquid phase) under Maintaining a temperature of 260 to 2800 and a pressure of about 25 at will. For each passage of the gas through the furnace, 50% of the carbon dioxide-hydrogen mixture is added implemented. The gases and vapors leaving the furnace are released along with the cycle oil cooled to 120-3; some of the condensate obtained is returned to the furnace returned.

For each Ncbm converted carbon oxide-hydrogen mixture, 120 g of multi-membered Hydrocarbons are formed which boil to about 60% in the boiling range of gasoline and about 30 to 35% gaseous hydrocarbons of 3 and 4 carbon atoms are.

Claims (1)

PATENT CLAIM Process for converting carbon oxide with hydrogen to multi-membered hydrocarbons, optionally in addition to liquid or solid oxygen-containing hydrocarbon derivatives, in the presence of iron catalysts in the liquid phase, thereby indicates that there are catalysts that are made by treating naturally occurring iron ores predominantly oxidic in nature or obtained by roasting or heating alone Iron ores converted into oxides without the addition of alkalis with reducing gases. Cited publications: German Patent No. 906 931; french U.S. Patent No. 871,536; Russian Patent Specification No. 42 060 (published in Chem. Zentralblatt, 1935, II, p. 396I) and 54 392 (published in Chem. Zentralblatt, I939, II, p.3917).