Desulfurization of carbon dioxide-containing gases
Sulfur-containing compounds are removed from crude CO 2 by conversion to elemental sulfur in a Claus process and subsequently by hydrogenation of the Claus tail gas to convert residual sulfur-containing compounds into H 2 S which, after cooling to knock out water and then compressing, is removed, together with any other sulfur-containing impurities, either by physical separation or by chemical reaction with a solid metal oxide to form solid metal sulfide with subsequent oxidative regeneration to produce purified CO 2 and a recycle gas comprising at least one sulfur-containing compound which is recycled to the Claus process. Some H 2 S in the Claus tail gas may be removed initially by selective and/or non-selective amine absorption(s) in a tail gas treatment unit prior to removal of residual H 2 S and any other residual sulfur-containing impurities by the physical separation or the chemical reaction steps.
1 . A method for desulfurization of crude carbon dioxide (CO 2 ) gas comprising hydrogen sulfide (H 2 S) and optionally at least one other sulfur-containing impurity comprising:
feeding crude CO 2 gas comprising H 2 S to a Claus process to convert H 2 S in the presence of oxygen (O 2 ) gas to elemental sulfur and produce Claus tail-gas comprising CO 2 , residual H 2 S and at least one other sulfur-containing impurity;
feeding said Claus tail-gas to a hydrogenation process to convert said at least one other sulfur-containing impurity into H 2 S in the presence of hydrogen (H 2 ) and produce H 2 S-enriched CO 2 tail-gas;
cooling said H 2 S-enriched CO 2 tail gas and removing condensed water to produce cooled H 2 S-enriched CO 2 tail gas;
compressing said cooled H 2 S-enriched CO 2 tail-gas, or an impure CO 2 gas comprising H 2 S derived therefrom, to produce compressed impure CO 2 gas comprising H 2 S;
removing H 2 S and any other sulfur-containing impurities from said compressed impure CO 2 gas by physical separation or by chemical reaction with at least one solid metal oxide to form at least one solid metal sulfide and subsequent oxidative regeneration, to produce purified CO 2 and a first recycle gas comprising at least one sulfur-containing compound;
recycling said first recycle gas to said Claus process to convert said at least one sulfur-containing compound into elemental sulfur;
feeding said purified CO 2 to a further purification unit to produce further purified CO 2 and a second recycle gas comprising CO 2 and H 2 ; and
recycling said second recycle gas, or a H 2 -enriched gas derived therefrom, to said hydrogenation process,
wherein a portion of said second recycle gas, or of said H 2 -enriched gas derived therefrom, is purged.
2 . The method according to claim 1 further comprising:
generating H 2 in a hydrogen generation process; and
feeding said H 2 to said hydrogenation process.
3 . The method according to claim 1 further comprising:
recovering CO 2 and H 2 S from said H 2 S-enriched CO 2 tail-gas by non-selective amine absorption to produce said impure CO 2 gas for compression, together with a waste gas comprising CO 2 and at least one non-condensable gas.
4 . The method according to claim 1 wherein said H 2 S-enriched CO 2 tail-gas is compressed directly to produce said compressed impure CO 2 gas comprising H 2 S.
5 . The method according to claim 1 comprising recovering H 2 gas from said second recycle gas in a membrane separation process to produce said H 2 -enriched gas for recycle to said hydrogenation process, together with a waste gas comprising CO 2 and at least one non-condensable gas.
6 . The method according to claim 1 wherein H 2 S and any other sulfur-containing impurities are removed from said compressed impure CO 2 gas by said chemical reaction with at least one solid metal oxide to form solid metal sulfide(s) and subsequent oxidative regeneration.
7 . The method according to claim 1 wherein H 2 S and any other sulfur-containing impurities are removed from said compressed impure CO 2 gas by passing said impure CO 2 gas through a bed comprising said at least one solid metal oxide in a reactor to convert the at least one solid metal oxide to at least one metal sulfide and produce said purified CO 2 ; and
regenerating the bed using a regeneration gas comprising O 2 to produce a spent regeneration gas comprising sulfur dioxide (SO 2 ) as said first recycle gas.
8 . The method according to claim 7 wherein the regeneration gas comprises water in an amount that is insufficient to hydrolyze other sulfur-containing compounds.
9 . The method according to claim 7 , further comprising drying the purified CO 2 gas downstream of the bed comprising said at least one solid metal oxide; wherein said compressed impure CO 2 gas feed to said reactor comprises water.
10 . A method for desulfurization of crude carbon dioxide (CO 2 ) gas comprising hydrogen sulfide (H 2 S) and optionally at least one other sulfur-containing impurity comprising:
feeding crude CO 2 gas comprising H 2 S to a Claus process to convert H 2 S in the presence of oxygen (O 2 ) gas to elemental sulfur and produce Claus tail-gas comprising CO 2 , residual H 2 S and at least one other sulfur-containing impurity;
feeding said Claus tail-gas to a hydrogenation process to convert said at least one other sulfur-containing impurity into H 2 S in the presence of hydrogen (H 2 ) and produce H 2 S-enriched CO 2 tail-gas;
cooling said H 2 S-enriched CO 2 tail gas and removing condensed water to produce cooled H 2 S-enriched CO 2 tail gas;
compressing said cooled H 2 S-enriched CO 2 tail-gas, or an impure CO 2 gas comprising H 2 S derived therefrom, to produce compressed impure CO 2 gas comprising H 2 S;
removing H 2 S and any other sulfur-containing impurities from said compressed impure CO 2 gas by physical separation or by chemical reaction with at least one solid metal oxide to form at least one solid metal sulfide and subsequent oxidative regeneration, to produce purified CO 2 and a first recycle gas comprising at least one sulfur-containing compound; and
recycling said first recycle gas to said Claus process to convert said at least one sulfur-containing compound into elemental sulfur;
recovering H 2 S from said H 2 S-enriched CO 2 tail-gas by selective amine absorption to produce H 2 S-depleted CO 2 tail-gas and recovered H 2 S;
recycling said recovered H 2 S to said Claus process to convert said recovered H 2 S to elemental sulfur; and
recovering CO 2 and residual H 2 S from said H 2 S-depleted CO 2 tail-gas by non-selective amine absorption to produce said impure CO 2 gas for compression, together with waste gas comprising CO 2 and at least one non-condensable gas,
wherein said H 2 S-depleted CO 2 tail-gas is compressed directly to produce said compressed impure CO 2 gas.
11 . The method according to claim 10 further comprising:
feeding said purified CO 2 to a further purification unit to produce further purified CO 2 and a second recycle gas comprising CO 2 and H 2 ; and
recycling said second recycle gas, or a H 2 -enriched gas derived therefrom, to said hydrogenation process,
wherein a portion of said second recycle gas, or of said H 2 -enriched gas derived therefrom, is purged.
12 . The method according to claim 11 further comprising recovering H 2 gas from said second recycle gas in a membrane separation process to produce said H 2 -enriched gas, together with a waste gas comprising CO 2 and at least one non-condensable gas.
13 . A method for desulfurization of crude carbon dioxide (CO 2 ) gas comprising hydrogen sulfide (H 2 S) and optionally at least one other sulfur-containing impurity comprising:
feeding crude CO 2 gas comprising H 2 S to a Claus process to convert H 2 S in the presence of oxygen (O 2 ) gas to elemental sulfur and produce Claus tail-gas comprising CO 2 , residual H 2 S and at least one other sulfur-containing impurity;
feeding said Claus tail-gas to a hydrogenation process to convert said at least one other sulfur-containing impurity into H 2 S in the presence of hydrogen (H 2 ) and produce H 2 S-enriched CO 2 tail-gas;
cooling said H 2 S-enriched CO 2 tail gas and removing condensed water to produce cooled H 2 S-enriched CO 2 tail gas;
compressing said cooled H 2 S-enriched CO 2 tail-gas, or an impure CO 2 gas comprising H 2 S derived therefrom, to produce compressed impure CO 2 gas comprising H 2 S;
removing H 2 S and any other sulfur-containing impurities from said compressed impure CO 2 gas by physical separation or by chemical reaction with at least one solid metal oxide to form at least one solid metal sulfide and subsequent oxidative regeneration, to produce purified CO 2 and a first recycle gas comprising at least one sulfur-containing compound; and
recycling said first recycle gas to said Claus process to convert said at least one sulfur-containing compound into elemental sulfur;
wherein H 2 S and any other sulfur-containing impurities are removed from said compressed impure CO 2 gas by selective adsorption as said physical separation,
wherein said selective adsorption involves removing H 2 S and any other sulfur-containing compounds in the compressed impure CO 2 gas by adsorption on a bed comprising at least one adsorbent material selective for sulfur-containing compound(s) in a selective adsorption unit to produce said purified CO 2 and, after desorption with a regeneration gas, a spent regeneration gas comprising said H 2 S and any other sulfur-containing compounds from the compressed impure CO 2 gas as said first recycle gas.
14 . The method according to claim 13 , further comprising drying the purified CO 2 gas downstream of said adsorbent material(s) selective for sulfur-containing compound(s), wherein said regeneration gas comprises water in an amount that is insufficient to hydrolyze said other sulfur-containing compounds, and wherein said compressed impure CO 2 gas feed to the selective adsorption unit comprises water.