Patent GB-347208-A (GB)
Title: Improvements in or relating to methods for the production of nickel carbonyl
IPC: C01G53/02
Filed: 1930-01-16
Abstract: In a process for the formation of nickel carbonyl by passing carbon monoxide over nickel or a process for extraction of nickel as nickel carbonyl from reduced ores, mattes, &c., the rate of formation of nickel carbonyl is increased by the presence of a compound containing sulphur, selenium or tellurium in "active form," while avoiding the introduction of any substance in sufficient quantity to have a deleterious effect upon the carbonyl formation.  The presence of active sulphur in the reaction chamber is brought about by adding to the matte &c. or to the reduced metal a sulphur-containing compound in the form of a solid, liquid, solution, wet mixture, or suspension; if added before or during reduction it must consist of nickel sulphide or a sulphide capable of reduction by carbon monoxide to yield carbon oxysulphide or a substance which will be reduced under the prevailing conditions to one of the said sulphides or will react or decompose under the prevailing conditions to yield hydrogen sulphide, sulphur dioxide, or sulphur trioxide, while, if the sulphur-containing compound is added after the reduction, it must be nickel sulphide or a sulphide reducable by carbon monoxide to yield carbon oxysulphide.  Alternatively, the presence of active sulphur is brought about by introducing small quantities of sulphur-containing gases during the reaction or by bringing such gases into contact with the matte &c. at a previous stage of the process; or by allowing to remain or only partially removing sulphates or other sulphur-containing compounds formed in the matte &c. prior to the reduction thereof but not originally present in the matte &c. Selenium or tellurium compounds which have a similar chemical behaviour to the above-mentioned sulphur compounds, may also be employed.  Sulphides originally present in the matte &c. and allowed to remain as such up to the stage of carbonyl formation are not suitable forms of sulphur.  The mixture of matte &c. and added sulphur-containing compound must not be subjected to temperatures causing sintering of the matte, that is about 500 DEG  C. and the reduction of the matte alone must not take place at over 500 DEG  C. if the sulphus compounds are added subsequently.  The solid compounds which may be employed include the sulphides of nickel, sodium, cobalt, iron, zinc, cadmium, mercury, calcium, copper (cupric), antimony, manganese, barium, arsenic, phosphorus, selenium, and tellurium, the sulphates of nickel, zinc, aluminium, cadmium, mercury, iron (ferric), copper, and chromium, thiosulphates, and thionates.  The gaseous or vaporous sulphur compounds include hydrogen sulphide, particularly when employed after reduction at temperatures below 150 DEG  C., sulphur dioxide particularly when employed during reduction, a slight further reduction following the treatment, carbon oxysulphide, carbon disulphide, thiophene, sulphur vapour, sulphur chloride, allyl isothiocyanate, benzene sulphonic acid, benzene sulphonic chloride, and thioacetic acid.  When sulphates are formed by a calcination of the matte, the latter is preferably wetted so as to distribute the sulphates throughout the matte, which is then dried.  Sulphates may also be introduced by moistening the matte with sulphuric acid.  Suitable selenium and tellurium compounds include the selenides of nickel and hydrogen and nickel telluride.  Specification 334,190, [Class 1 (ii), Inorganic compounds, other than &c.], is referred to.