Hydrogen-assisted adsorption of sulphur compounds from olefin mixtures

A process for purifying hydrocarbon mixtures, in which a contaminated hydrocarbon mixture comprising olefins is at least partly freed of sulphur-containing contaminants by contacting the contaminated hydrocarbon mixture with a solid sorbent in the presence of hydrogen, wherein the contaminated hydrocarbon mixture, immediately prior to the contacting with the solid sorbent, contains hydrogen in a concentration, based on the total mass of the contaminated hydrocarbon mixture, between 1 ppm by weight and 10 000 ppm by weight, wherein the contaminated hydrocarbon mixture is exclusively in the liquid state during the contacting with the solid sorbent wherein the contaminated hydrocarbon mixture comprises 1-butene and the contacting with the solid sorbent converts less than 5% by weight of the 1-butene in the contaminated hydrocarbon mixture, wherein the solid sorbent has the following composition that adds up to 100% by weight:

• copper oxide:
• 10% by weight to 60% by weight calculated as CuO;
• zinc oxide:
• 10% by weight to 60% by weight calculated as ZnO;
• aluminium oxide:
• 10% by weight to 30% by weight calculated as Al2O3;
• and
• other substances:
• 0% by weight to 5% by weight,
• wherein the solid sorbent has a copper oxide surface area of at least 50 m2/g,
• and wherein the contaminated hydrocarbon mixture fulfills one of the following specifications A, B, C and D, each of which adds up to 100% by weight, the stated proportions by weight each being based on the total weight of the contaminated hydrocarbon mixture:
• Specification A:
• isobutane 15% to 45% by weight;
• n-butane 5% to 18% by weight;
• 1-butene 5% to 20% by weight;
• isobutene 12% to 25% by weight;
• 2-butenes 9% to 40% by weight;
• 1,3-butadiene 0% to 3% by weight;
• water 0% to 1% by weight;
• sulphur-containing impurities less than 0.5% by weight;
• and
• hydrogen less than 1 ppm by weight;
• Specification B:
• isobutane 0.5% to 15% by weight;
• n-butane 0.5% to 20% by weight;
• 1-butene 9% to 25% by weight;
• isobutene 10% to 35% by weight;
• 2-butenes 3% to 15% by weight;
• 1,3-butadiene 25% to 70% by weight;
• water 0% to 1% by weight;
• sulphur-containing impurities less than 0.5% by weight;
• and
• hydrogen less than 1 ppm by weight;
• Specification C:
• isobutane 0.5% to 18% by weight;
• n-butane 0.5% to 25% by weight;
• 1-butene 9% to 40% by weight;
• isobutene 10% to 55% by weight;
• 2-butenes 3% to 25% by weight;
• 1,3-butadiene 0% to 5% by weight;
• water 0% to 1% by weight;
• sulphur-containing impurities less than 0.5% by weight;
• and
• hydrogen less than 1 ppm by weight;
• and
• Specification D:
• isobutane 0% to 20% by weight;
• n-butane 10% to 35% by weight;
• 1-butene 0.2% to 45% by weight;
• 2-butenes 35% to 85% by weight;
• water 0% to 1% by weight;
• sulphur-containing impurities less than 0.5% by weight;
• and
• hydrogen less than 1 ppm by weight.