Patent GB-458035-A (GB)
Title: Improvements in the reaction of oxides of carbon with hydrogen
IPC: C08G61/04
Filed: 1935-06-11
Abstract: The conversion of oxides of carbon with hydrogen into hydrocarbons or their oxygen-containing derivatives is carried out in an apparatus in which the conversion is catalytically promoted by the internal surfaces of the apparatus itself, which at the parts coming into contact with the gas mixture comprise an etched metal, particularly iron.  Preferably, no other catalyst is present.  Suitable metals include ingot steel, iron, special steels, nickel, cobalt, copper and their alloys and metals coated with zinc, nickel or cobalt, e.g. by electrolysis, burning or soldering.  The surfaces may be etched by means of acids, particularly nitric, acetic, lactic, formic or picric acids, and compounds of uranium, alkali metals, copper, silver, magnesium, mercury, manganese, or chromium, especially uranyl nitrate, copper nitrate, magnesium nitrate or potassium nitrate may be added to the acids &c. as activators for the catalyst.  The etching may also be performed by means of alkalis or ammonia in the case of zinc and iron; electrolysis; salts, e.g. alkali nitrates, ammonium chloride or copper sulphate; gases, e.g. hydrogen chloride or oxides of nitrogen or fused substances.  Various methods may also be used simultaneously or successively.  A suitable catalyst comprises a spiral tube of etched ingot steel through which a heating or cooling medium is passed, or a bundle of narrow tubes, the heating or cooling medium flowing through or around them.  The tubes may be ribbed if desired.  Suitable heating or cooling agents are gases, superheated or saturated steam, water, oils or fused metals or salts. The conversion is effected at temperatures above 150 DEG  C., preferably between 200--450 DEG  C., and at pressures from atmospheric up to 100 or more atmospheres.  For example, the outer surface of a steel tubular spiral, of Mannesmann-S II ingot steel, and lined with copper, is etched with a solution of glacial acetic acid, uranyl nitrate and potassium nitrate.  Superheated steam at a temperature between 200--400 DEG  C. is passed through the spiral at 12 atmospheres as a heating and cooling medium.  Hydrogen is first led through the reaction chamber past the spiral followed by a mixture of equal parts of carbon monoxide and hydrogen under a pressure of 100 atmospheres and at a temperature of 368--412 DEG  C. The product consists of oil and readily volatile hydrocarbons and a gas containing methane, ethane, and homologues.ALSO:The conversion of oxides of carbon with hydrogen into hydrocarbons or their oxygen-containing derivatives is carried out in an apparatus in which the conversion is catalytically promoted by the internal surfaces of the apparatus itself, which at the parts coming into contact with the gas mixture comprise an etched metal, particularly iron.  Preferably no other catalyst is present.  Suitable metals include ingot steel, iron, special steels, nickel, cobalt, copper and their alloys and metals coated with zinc, nickel or cobalt, e.g. by electrolysis, burning or soldering.  The surfaces may be etched by means of acids, particularly nitric, acetic, lactic, formic or picric acids, and compounds of uranium, alkali-metals, copper, silver, magnesium, mercury, manganese or chromium, especially uranyl nitrate, copper nitrate, magnesium nitrate or potassium nitrate may be added to the acids &c. as activators for the catalyst.  The etching may also be performed by means of alkalis or ammonia in the case of zinc and iron; electrolysis; salts, e.g. alkali nitrates, ammonium chloride or copper sulphate; gases, e.g. hydrogen chloride or oxides of nitrogen, or fused substances.  Various methods may also be used simultaneously or successively.  A suitable catalyst comprises a spiral tube of etched ingot steel through which a heating or cooling medium is passed, or a bundle of narrow tubes, the heating or cooling medium flowing through or around them.  The tubes may be ribbed if desired. Suitable heating or cooling agents are gases, superheated or saturated steam, water, oils or fused metals or salts.  The conversion is effected at temperatures above 150 DEG  C., preferably between 200--450 DEG  C., and at pressures from atmospheric up to 100 or more atmospheres.  For example, the outer surface of a steel tubular spiral, of Mannesmann--SII ingot steel, and lined with copper, is etched with a solution of glacial acetic acid, uranyl nitrate and potassium nitrate.  Superheated steam at a temperature between 200--400 DEG  C. is passed through the spiral at 12 atm. as a heating and cooling medium.  Hydrogen is first led through the reaction chamber past the spiral followed by a mixture of equal parts of carbon monoxide and hydrogen under a pressure of 100 atmospheres, and at a temperature of 368--412 DEG  C.  The product consists of oil and readily volatile hydrocarbons and a gas containing methane, ethane, and homologues.