Recovery of chlorine values from iron chloride by-produced in chlorination of ilmenite and the like

In the process comprising chlorinating, in the presence of carbon or a carbon-containing reducing agent, a titaniferous material containing more than 5 percent by weight iron oxide to obtain as a by-product iron chloride, and separating the iron chloride from the titaniferous material, the improvement comprising:

• (a) partially dechlorinating the ferric chloride obtained from oxidation stage (b) plus any ferric chloride in the iron chloride separated from the titaniferous material in the presence of a reducing agent selected from the group consisting of sulfur and chlorine polysulfides wherein the ratio of sulfur to chlorine is greater than 1, to form ferrous chloride and a sulphur monochloride;
• (b) oxidizing the ferrous chloride produced in the dechlorinating stage (a) plus any ferrous chloride in the iron chloride separated from the titaniferous material in the presence of an oxidizing agent, selected from the group consisting of oxygen and oxygen-containing gases at a temperature of between about 300.degree. C. and about 1200.degree. C. to produce ferric chloride and ferric oxide, passing the ferric chloride on to the dechlorination stage (a) and removing the ferric oxide from the system;
• and
• (c) recovering the chlorine values from the sulphur monochloride produced in stage (a) in a form suitable for recycle to the titaniferous chlorination stage.

In the process comprising chlorinating, in the presence of carbon or a carbon-containing reducing agent, a titaniferous material containing more than 5 percent by weight iron oxide to obtain iron chloride as a by-product and separating the iron chloride from the titaniferous material, the improvement comprising:

• (a) partially dechlorinating the ferric chloride from oxidation stage (b) plus any ferric chloride in the iron chloride separated from the titaniferous material, in the presence of carbon disulfide to form ferrous chloride, carbon tetrachloride and sulphur monochloride;
• (b) oxidizing the ferrous chloride produced in the dechlorinating stage (a) plus any ferrous chloride in the iron chloride separated from the titaniferous material, in the presence of an oxidizing agent selected from the group consisting of oxygen and oxygen-containing gases, at a temperature of between about 300.degree. C. and about 1200.degree. C. to produce ferric chloride and ferric oxide, passing the ferric chloride on to the dechlorination stage (a) and removing the ferric oxide from the system;
• and
• (c) recovering the chlorine values from the sulphur monochloride produced in stage (a) in a form suitable for recycle to the titaniferous chlorination stage.

In the process comprising chlorinating a titaniferous material containing more than 5 percent by weight iron oxide to obtain iron chloride as a by-product and separating the iron chloride from the titaniferous material, the improvement comprising:

• (a) partially dechlorinating the ferric chloride obtained from oxidation stage (b) plus any ferric chloride in the iron chloride separated from the titaniferous material in the presence of a reducing agent selected from the group consisting of unsaturated hydrocarbons which readily undergo addition reactions with chlorine to form ferrous chloride and chlorinated hydrocarbon, and passing the ferrous chloride on to stage (b);
• and
• (b) oxidizing the ferrous chloride produced in the dechlorinating stage (a) plus any ferrous chloride in the iron chloride in the presence of an oxidizing agent selected from the group consisting of oxygen and oxygen-containing gases, at a temperature in the range of between about 300.degree. C. and about 1200.degree. C. to produce ferric chloride and ferric oxide;
• passing the ferric chloride on to the dechlorination stage (a) and removing the ferric oxide from the reaction system;
• whereby the chlorine value in the iron chloride is regained as the chlorinated hydrocarbon.

In the process comprising chlorinating, a titaniferous material containing more than 5 percent by weight iron oxide to obtain an iron chloride by-product, and separating the iron chloride by-product from the titaniferous material, the improvement comprising:

• (a) partially dechlorinating the ferric chloride obtained from the oxidation stage (b) plus any ferric chlroide in the iron chloride by-product in the presence of carbon bisulfide plus a second reducing agent selected from the group consisting of sulfur and chlorine polysulfide, wherein the ratio of sulfur to chlorine is greater than 1, to form ferrous chloride, and carbon tetrachloride and sulfur monochloride, the carbon tetrachloride being directly, and the sulfur monochloride being indirectly, after further reaction, suitable for recycle to the titaniferous material chlorination process, and passing the ferrous chloride on to stage (b);
• (b) oxidizing the ferrous chloride produced in the dechlorinating stage (a) plus any ferrous chloride in the iron chloride by-product in the presence of an oxidizing agent comprising elemental oxygen at a temperature of between about 300.degree. C. and about 1200.degree. C. to produce ferric chloride and ferric oxide, passing the ferric chloride back to the dechlorination stage (a) and removing the ferric oxide from the system;
• whereby the chlorine value of the iron chloride by-product is recovered as material which directly or indirectly is suitable for recycle to the titaniferous chlorination stage.