Desulfurization of Carbon Dioxide-containing Gases

Abstract

Sulfur-containing compounds are removed from crude CO.sub.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.sub.2S 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.sub.2 and a recycle gas comprising at least one sulfur-containing compound which is recycled to the Claus process. Some H.sub.2S 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.sub.2S and any other residual sulfur-containing impurities by the physical separation or the chemical reaction steps.

Claims

1. A method for desulfurization of crude carbon dioxide (CO.sub.2) gas comprising hydrogen sulfide (H.sub.2S) and optionally at least one other sulfur-containing impurity comprising: feeding crude CO.sub.2 gas comprising H.sub.2S to a Claus process to convert H.sub.2S in the presence of oxygen (O.sub.2) gas to elemental sulfur and produce Claus tail-gas comprising CO.sub.2, residual H.sub.2S 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.sub.2S in the presence of hydrogen (H.sub.2) and produce H.sub.2S-enriched CO.sub.2 tail-gas; cooling said H.sub.2S-enriched CO.sub.2 tail gas and removing condensed water to produce cooled H.sub.2S-enriched CO.sub.2 tail gas; compressing said cooled H.sub.2S-enriched CO.sub.2 tail-gas, or an impure CO.sub.2 gas comprising H.sub.2S derived therefrom, to produce compressed impure CO.sub.2 gas comprising H.sub.2S; removing H.sub.2S and any other sulfur-containing impurities from said compressed impure CO.sub.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.sub.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.

2. The method according to claim 1 further comprising: generating H.sub.2 in a hydrogen generation process; and feeding said H.sub.2 to said hydrogenation process.

3. The method according to claim 1 further comprising: recovering CO.sub.2 and H.sub.2S from said H.sub.2S-enriched CO.sub.2 tail-gas by non-selective amine absorption to produce said impure CO.sub.2 gas for compression, together with a waste gas comprising CO.sub.2 and at least one non-condensable gas.

4. The method according to claim 1 wherein said H.sub.2S-enriched CO.sub.2 tail-gas is compressed directly to produce said compressed impure CO.sub.2 gas comprising H.sub.2S.

5. The method according to claim 1 further comprising: feeding said purified CO.sub.2 to a further purification unit to produce further purified CO.sub.2 and a second recycle gas comprising CO.sub.2 and H.sub.2; and recycling said second recycle gas, or a H.sub.2-enriched gas derived therefrom, to said hydrogenation process, wherein a portion of said second recycle gas, or of said H.sub.2-enriched gas derived therefrom, is purged.

6. The method according to claim 5 comprising recovering H.sub.2 gas from said second recycle gas in a membrane separation process to produce said H.sub.2-enriched gas for recycle to said hydrogenation process, together with a waste gas comprising CO.sub.2 and at least one non-condensable gas.

7. The method according to claim 1 further comprising: recovering H.sub.2S from said H.sub.2S-enriched CO.sub.2 tail-gas by selective amine absorption to produce H.sub.2S-depleted CO.sub.2 tail-gas and recovered H.sub.2S; recycling said recovered H.sub.2S to said Claus process to convert said recovered H.sub.2S to elemental sulfur; and recovering CO.sub.2 and residual H.sub.2S from said H.sub.2S-depleted CO.sub.2 tail-gas by non-selective amine absorption to produce said impure CO.sub.2 gas for compression, together with waste gas comprising CO.sub.2 and at least one non-condensable gas, wherein said H.sub.2S-depleted CO.sub.2 tail-gas is compressed directly to produce said compressed impure CO.sub.2 gas.

8. The method according to claim 7 further comprising: feeding said purified CO.sub.2 to a further purification unit to produce further purified CO.sub.2 and a second recycle gas comprising CO.sub.2 and H.sub.2; and recycling said second recycle gas, or a H.sub.2-enriched gas derived therefrom, to said hydrogenation process, wherein a portion of said second recycle gas, or of said H.sub.2-enriched gas derived therefrom, is purged.

9. The method according to claim 8 further comprising recovering H.sub.2 gas from said second recycle gas in a membrane separation process to produce said H.sub.2-enriched gas, together with a waste gas comprising CO.sub.2 and at least one non-condensable gas.

10. The method according to claim 1 wherein H.sub.2S and any other sulfur-containing impurities are removed from said compressed impure CO.sub.2 gas by said chemical reaction with at least one solid metal oxide to form solid metal sulfide(s) and subsequent oxidative regeneration.

11. The method according to claim 1 wherein H.sub.2S and any other sulfur-containing impurities are removed from said compressed impure CO.sub.2 gas by selective adsorption as said physical separation, wherein said selective adsorption involves removing H.sub.2S and any other sulfur-containing compounds in the compressed impure CO.sub.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.sub.2 and, after desorption with a regeneration gas, a spent regeneration gas comprising said H.sub.2S and any other sulfur-containing compounds from the compressed impure CO.sub.2 gas as said first recycle gas.

12. The method according to claim 11, further comprising drying the purified CO.sub.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.sub.2 gas feed to the selective adsorption unit comprises water.

13. The method according to claim 1 wherein H.sub.2S and any other sulfur-containing impurities are removed from said compressed impure CO.sub.2 gas by passing said impure CO.sub.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.sub.2; and regenerating the bed using a regeneration gas comprising O.sub.2 to produce a spent regeneration gas comprising sulfur dioxide (SO.sub.2) as said first recycle gas.

14. The method according to claim 13 wherein the regeneration gas comprises water in an amount that is insufficient to hydrolyze other sulfur-containing compounds.

15. The method according to claim 13, further comprising drying the purified CO.sub.2 gas downstream of the bed comprising said at least one solid metal oxide; wherein said compressed impure CO.sub.2 gas feed to said reactor comprises water.

16. A method comprising: removing H.sub.2 and any other non-condensable gases from a compressed impure CO.sub.2 gas by distillation and/or partial condensation with phase separation to produce H.sub.2S-enriched CO.sub.2 fluid and H.sub.2-enriched CO.sub.2 gas; recycling said H.sub.2-enriched CO.sub.2 gas, or a further H.sub.2-enriched CO.sub.2 gas derived therefrom, as a second recycle gas to a hydrogenation process; and separating said H.sub.2S-enriched CO.sub.2 fluid by distillation and/or partial condensation with phase separation to produce a purified CO.sub.2 as overhead gas and a H.sub.2S-enriched bottoms liquid; vaporizing said H.sub.2S-enriched bottoms liquid to produce H.sub.2S-enriched gas as said first recycle gas; wherein a portion of said second recycle gas, or of said H.sub.2-enriched gas derived therefrom, is purged.

17. The method according to claim 16, further comprising recovering H.sub.2 gas from said second recycle gas in a membrane separation process to produce said further H.sub.2-enriched CO.sub.2 gas for recycle, together with a waste gas comprising CO.sub.2 and at least one non-condensable gas.

18. The method according to claim 16, wherein said purified CO.sub.2 overhead gas comprises one or more residual sulfur-containing compounds.

19. The method of claim 18, further comprising: removing H.sub.2S and any other sulfur-containing impurities from said purified CO.sub.2 overhead gas by selective adsorption or by chemical reaction with at least one solid metal oxide to form solid metal sulfide(s) and subsequent oxidative regeneration, to produce further purified CO.sub.2 and a third recycle gas comprising at least one sulfur-containing compound; and recycling said third recycle gas to said Claus process to convert said sulfur-containing compound(s) into elemental sulfur.

20. A system comprising: a Claus unit for removing H.sub.2S from crude CO.sub.2 gas, said Claus unit comprising: a first inlet for oxidant gas comprising O.sub.2; a second inlet for said crude CO.sub.2 gas; a first outlet for Claus tail-gas comprising CO.sub.2, residual H.sub.2S and at least one other sulfur-containing impurity; and a second outlet for elemental sulfur; a source of oxidant gas comprising O.sub.2 in fluid flow communication with the first inlet of the Claus unit; a source of crude CO.sub.2 gas in fluid flow communication with the second inlet of the Claus unit; a hydrogenation unit for converting said at least one other sulfur-containing impurity in said Claus tail-gas into H.sub.2S, said hydrogenation unit comprising: a first inlet in fluid flow communication with the first outlet of said Claus unit; a second inlet for H.sub.2; and a first outlet for H.sub.2S-enriched CO.sub.2 tail-gas; a source of H.sub.2 in fluid flow communication with the second inlet of said hydrogenation unit; a cooling unit for cooling H.sub.2S-enriched CO.sub.2 tail gas, said cooling unit comprising: a first inlet in fluid communication with said first outlet of said hydrogenation unit; a first outlet for cooled H.sub.2S-enriched CO.sub.2 tail gas; and a second outlet for condensed water; a compression unit for compressing cooled H.sub.2S-enriched CO.sub.2 tail-gas or impure CO.sub.2 gas comprising H.sub.2S derived therefrom, said compression device comprising: an inlet in fluid flow communication with the first outlet of said cooling unit; and an outlet for compressed impure CO.sub.2 gas; and a purification unit for removing H.sub.2S and any other sulfur-containing impurities from compressed impure CO.sub.2 gas by physical separation or by chemical reaction with at least one metal oxide to form solid metal sulfide(s) and subsequent oxidative regeneration, said purification unit comprising: a first inlet in fluid flow communication with the outlet of said compression unit; a first outlet for purified CO.sub.2; and a second outlet for a first recycle gas comprising at least one sulfur-containing compound, wherein the second outlet of said purification unit is in fluid communication with said Claus unit.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0071] Preferred embodiments of the present invention will now be described with reference to the drawings in which:

[0072] FIG. 1 is a simplified flowsheet depicting an embodiment of the invention in which tail gas from a Claus plant is treated by hydrogenation and selective amine absorption (to remove H.sub.2S) in a tail gas treatment unit before CO.sub.2 is recovered by non-selective amine absorption and purified in a selective adsorption unit (or a reactor);

[0073] FIG. 2 is a simplified flowsheet depicting an alternative to the embodiment of the invention depicted in FIG. 1 in which impure CO.sub.2 gas from the tail gas treatment unit is compressed and then purified first in a selective adsorption unit (or reactor) and then either by distillation or by partial condensation and phase separation;

[0074] FIG. 3 is a simplified flowsheet depicting a modified version of the process depicted in FIG. 1 without the selective amine absorption step;

[0075] FIG. 4 is a simplified flowsheet depicting a modified version of the process depicted in FIG. 2 without the selective amine absorption step;

[0076] FIG. 5 is a simplified flowsheet of an alternative embodiment of the invention in which the purification unit has a first stage comprising a CPU and a second stage comprising a distillation unit;

[0077] FIG. 6 is a simplified flowsheet depicting a modified version of the process depicted in FIG. 5 with sulfur removal (unit 50) on stream 107 from CPU unit 56; and

[0078] FIG. 7 is a simplified flowsheet depicting embodiments in which the tail gas treatment processes of FIGS. 1 to 5 may be integrated with a SUPERCLAUS process and/or a EUROCLAUS process.

DETAILED DESCRIPTION OF THE INVENTION

[0079] The first aspect of the present invention is a method for desulfurization of crude CO.sub.2 gas comprising H.sub.2S and optionally at least one other sulfur-containing impurity. The method comprises feeding crude CO.sub.2 gas comprising H.sub.2S to a Claus process to convert H.sub.2S in the presence of O.sub.2 gas into elemental sulfur and produce Claus tail-gas comprising CO.sub.2, residual H.sub.2S and at least one sulfur-containing impurity. The Claus tail-gas is fed to a hydrogenation process to convert the other sulfur-containing impurity (or impurities) into H.sub.2S in the presence of H.sub.2 and produce H.sub.2S-enriched CO.sub.2 tail-gas. The H.sub.2S-enriched CO.sub.2 tail-gas is cooled to knock-out water and the resultant cooled H.sub.2S-enriched tail gas (or an impure CO.sub.2 gas comprising H.sub.2S derived therefrom) is compressed to produce compressed impure CO.sub.2 gas comprising H.sub.2S. H.sub.2S and any other sulfur-containing impurities are removed from the compressed gas by physical separation or by chemical reaction with solid metal oxide(s) to form solid metal sulfide(s) which are converted back to the metal oxide(s) by oxidative regeneration to produce purified CO.sub.2 and a first recycle gas comprising at least one sulfur-containing compound. The first recycle gas is recycled to said Claus process to convert the at least one sulfur-containing compound into elemental sulfur.

[0080] Embodiments of the present invention improve the recovery and/or purity of CO.sub.2 from crude CO.sub.2 comprising H.sub.2S and optionally any other sulfur-containing impurities.

[0081] The Claus process may be a conventional air-Claus process or an oxy-Claus process as described above but in either case typically comprises a thermal stage and at least one, e.g., from one to four, preferably two or three, catalytic stages. Recycle gas(es) may be recycled either to the feed to the Claus process or to an interstage location, i.e., between two stages within the process, or both.

[0082] The Claus process may alternatively be a SUPERCLAUS process or a EUROCLAUS process, or a combination of the two Claus processes.

[0083] The SUPERCLAUS process consists of a thermal stage followed by a minimum three catalytic reaction stages, with sulfur removed between stages by condensers. The first reactors are filled with standard Claus catalyst such as activated alumina, promoted alumina and/or titania (TiO.sub.2), while the final reactor is filled with a selective oxidation catalyst such as iron oxide and/or chromium oxide (or other metal oxides) on alpha alumina or silica. In the thermal stage, the acid gas is burned with a sub-stoichiometric amount of controlled combustion air (or pure O.sub.2 or O.sub.2-enriched air), such that the tail gas leaving the last Claus reactor contains typically 0.8 to 1.0 vol. % H.sub.2S. The selective oxidation catalyst in the final reactor oxidizes the H.sub.2S to sulfur at an efficiency of more than 85%. A third Claus reactor stage could be installed upstream of the selective oxidation reactor if a sulfur recovery rate of more than 99% is required.

[0084] The EUROCLAUS process consists of a thermal stage followed by three or four catalytic reaction stages, with sulfur removed between stages by condensers. The final Claus reactor is filled with a layer of hydrogenation catalyst such as CoMo catalyst (cobalt & molybdenum oxides on alumina), followed by a reactor filled with selective oxidation catalyst such as iron oxide and/or chromium oxide (or other metal oxides) on alpha alumina or silica. In the thermal stage, the acid gas is burned with a sub-stoichiometric amount of controlled combustion air, and the tail gas leaving the last Claus reaction typically contains 0.8 to 1.0 vol. % H.sub.2S and 100 to 200 ppmv SO.sub.2. This low SO.sub.2 content is obtained with a hydrogenation catalyst that converts SO.sub.2 to H.sub.2S in the last Claus reactor. The selective oxidation catalyst in the final reactor oxidizes the H.sub.2S to sulfur at an efficiency of more than 85%. Total sulfur recovery efficiency up to 99.3% can be obtained with three reactor stages, and up to 99.5% can be achieved with four stages.

[0085] The crude CO.sub.2 gas may be fed to the Claus process at a temperature from about 10 C. to about 70 C., e.g., about 45 C., and at a pressure in a range from about 0.3 bar gauge (g) to about 30 bar g, e.g., from about 0.3 bar g to about 1.8 bar g, e.g., about 0.9 bar g.

[0086] The hydrogenation process requires H.sub.2 as the reducing gas. The H.sub.2 may generated in a H.sub.2 generation process such as the partial oxidation of natural gas with sub-stoichiometric air/oxygen in a reducing gas generator, and then fed to the hydrogenation process. However, the demand for fresh H.sub.2, or make-up H.sub.2, from the H.sub.2 generation process may be reduced or even eliminated entirely by recycling H.sub.2 from another point in the process (see below).

[0087] The Claus tail-gas may be fed to the hydrogenation process at a temperature in a range from about 120 C. to about 200 C., e.g., about 130 C., and at a pressure in a range from about 0.2 bar g to about 30 bar g, e.g., from about 0.2 bar g to about 1.8 bar g, e.g., about 0.3 bar g. The pressure and/or temperature of the Claus tail gas may be adjusted as required using conventional means prior to being fed to the hydrogenation process although, in preferred embodiments, the tail gas is fed to the hydrogenation process without adjustment in this way.

[0088] The H.sub.2S-enriched CO.sub.2 tail gas from the hydrogenation process is cooled. Any suitable cooling process may be used but, in preferred embodiments, the H.sub.2S-enriched CO.sub.2 tail gas is quenched by direct contact with liquid water. After removal of condensed water, the cooled H.sub.2S-enriched CO.sub.2 tail gas is compressed to form compressed impure CO.sub.2 gas comprising H.sub.2S.

[0089] The cooled H.sub.2S-enriched CO.sub.2 tail gas may be fed to a compression unit at a temperature in a range from about 10 C. to about 70 C., e.g., about 45 C., and at a pressure in a range from about 0.3 bar g to about 1.8 bar g, e.g., about 1 bar g. The compression unit compresses the gas to a pressure in a range from about 1 bar g to about 120 bar g, e.g., about 30 bar g.

[0090] The content of H.sub.2S and any other sulfur-containing impurities in the compressed impure CO.sub.2 gas is reduced significantly, in some embodiments to a level below 100 ppm, either by physical separation or by chemical reaction with at least one solid metal oxide to form solid metal sulfide(s) and subsequent oxidative regeneration to produce purified CO.sub.2, together with a first recycle gas comprising at least one sulfur-containing compound which is recycled to the Claus process.

[0091] Physical separation may be by selective adsorption or by distillation and/or partial condensation with phase separation.

[0092] In embodiments using selective adsorption, the method involves removing H.sub.2S and any other sulfur-containing compounds in the compressed impure CO.sub.2 gas by adsorption on a bed of at least one adsorbent material selective for sulfur-compounds in a selective adsorption unit to produce the purified CO.sub.2 and, after desorption, a spent regeneration gas comprising H.sub.2S and any other sulfur-containing compounds from the compressed impure CO.sub.2 gas as the first recycle gas.

[0093] Such adsorbent materials include silica gel, molecular sieves (e.g., 4A or 5A zeolites), activated alumina and activated carbons (e.g., Calgon Cu material and Cu-impregnated carbons). The sulfur-containing compounds are adsorbed reversibly on a bed of the solid selective adsorbent(s) and then desorbed, preferably once the solid adsorbent is saturated with the sulfur-containing compound(s). The adsorption process may operate any suitable cycle including PSA, vacuum swing adsorption (VSA) or temperature swing adsorption (TSA). Specific examples include TSA with silica gel; PSA or VSA with silica gel; TSA with zeolites (e.g., 4A, 5A); and TSA with Cu-impregnated carbons.

[0094] Compressed impure CO.sub.2 gas may be fed to a selective adsorption unit at a temperature in a range from about 10 C. to about 70 C., e.g., about 50 C.

[0095] The adsorbent bed of the selective adsorption unit is suitably regenerated using purified (or further purified) CO.sub.2 generated in the process. The temperature and/or pressure of the regeneration gas may be adjusted as required using conventional means depending on the temperature and/or pressure of the CO.sub.2 gas at the location at which it is removed from the process and the type of cycle being used, e.g., TSA, VSA or PSA, etc. In embodiments using solid metal oxide(s) to purify the compressed impure CO.sub.2 gas, the method comprises passing the compressed gas through a bed comprising at least one solid metal oxide in a reactor. The H.sub.2S and any other sulfur-containing impurities in the gas convert the metal oxide(s) in the bed to the corresponding metal sulfide(s), thereby removing the impurities from the gas and producing the purified CO.sub.2. The metal oxide(s) in the bed is/are regenerated oxidatively by passing a regeneration gas comprising O.sub.2 through the bed, usually in a direction countercurrent to the gas when the bed is on feed, which drives off the sulfur from the bed in the form of SO.sub.2. The spent regeneration gas comprising SO.sub.2 is then recycled to the Claus process as the first recycle gas.

[0096] In embodiments in which H.sub.2S is removed by chemical reaction with at least one solid metal oxide, suitable solid metal oxides include zinc (II) oxide (ZnO), iron (Ill) oxide (Fe.sub.2O.sub.3), aluminum (Ill) oxide (Al.sub.2O.sub.3) and Group II metal oxides such as calcium oxide (CaO), magnesium oxide (MgO) and barium oxide (BaO). A single metal oxide may be used but, in some embodiments, a mixture of metal oxides (i.e., a mixed metal oxide) is used. In some embodiments, the mixture of solid metal oxides comprises from about 40 wt % to about 60 wt %, e.g., about 50 wt %, of ZnO.

[0097] An example of a suitable mixed metal oxide is disclosed in U.S. Pat. No. 4,044,114 and comprises from about 20 wt % to about 85 wt %, preferably from about 25 wt % to about 80 wt %, of zinc oxide (calculated as ZnO), from about 0.9 wt % to about 50 wt % of alumina (calculated as Al.sub.2O.sub.3), and from about 2 wt % to about 45 wt % of an oxide of a Group II metal, preferably calcium (calculated as oxide) with or without additional elements.

[0098] Compressed impure CO.sub.2 gas may be fed to the reactor at a temperature in a range from about 300 C. to about 800 C., or from about 300 C. to about 700 C., e.g., from about 400 to about 550 C.

[0099] After compression, the temperature of the compressed gas may be adjusted as required using conventional means prior to being fed to the reactor containing the solid metal oxide(s).

[0100] The mixed metal oxide bed of the reactor is suitably regenerated using an oxygen-containing gas, such as purified (or further purified) CO.sub.2 generated in the process to which O.sub.2 is added in an amount in a range from about 1 to about 5 mol. %, e.g., about 2 mol. %, oxygen. The temperature and/or pressure of the regeneration gas may be adjusted as required using conventional means depending on the temperature and/or pressure of the CO.sub.2 gas at the location at which it is removed from the process.

[0101] The first recycle gas may be recycled to the Claus process at a temperature in a range from about 10 C. to about 70 C., e.g., about 50 C. and at a pressure in a range from about 0.3 bar g to 30 bar g, or from about 0.3 bar g to about 1.8 bar g, e.g., about 1 bar g. In embodiments in which the temperature and/or pressure of the first recycle gas leaving the purification process is not appropriate in view of the operating conditions of the Claus unit, then the temperature and/or the pressure of the first recycle gas will be adjusted by conventional means as appropriate.

[0102] The compressed impure CO.sub.2 gas being fed to the selective adsorption unit or to the reactor containing the solid metal oxide(s) will typically contain water. In such cases, the water may be removed by adsorption on at least one adsorbent material selective for water located downstream of either the adsorbent material(s) selective for sulfur-containing compounds or the solid metal oxides. Suitable water selective adsorbent materials include those materials identified above as sulfur-selective adsorbent materials. The water selective adsorbent material(s) may be located in the same vessel as the sulfur-selective adsorbent material(s) or metal oxides, e.g., in a separate layer, or in a separate vessel.

[0103] Alternatively, the water may be removed by absorption in a separate vessel, e.g. a glycol unit, located downstream of either the selective adsorption unit or the reactor.

[0104] Whether the sulfur-containing impurities are removed by selective adsorption or chemical reaction with solid metal oxide(s), the regeneration gas may contain a small amount of water. However, if water is present, the amount of water is not sufficient to hydrolyze any sulfur-containing compounds being driven off the bed that is being regenerated. In this regard, the regeneration gas typically comprises less than 5 mol. %, preferably less than 2 mol. %, more preferably less than 1 mol. % water. Such an amount of water would be considered in the art to be a de minimis amount.

[0105] The H.sub.2S-enriched tail gas may be fed directly to a compression unit for compression to produce the compressed impure CO.sub.2. However, in some embodiments, the method comprises recovering H.sub.2S from the H.sub.2S-enriched CO.sub.2 tail-gas by selective amine absorption to produce H.sub.2S-depleted CO.sub.2 tail-gas and recovered H.sub.2S; and recycling the recovered H.sub.2S to the Claus process to convert the recovered H.sub.2S to elemental sulfur.

[0106] The H.sub.2S-enriched CO.sub.2 tail-gas may be fed to a selective amine absorption unit at a temperature from about 10 C. to about 70 C., e.g., about 50 C. and at a pressure from about 0.05 bar g to about 30 bar g, e.g., from about 0.05 bar g to about 1.8 bar g, e.g., about 0.1 bar g.

[0107] Conventional selective amine absorption processes using, for example, methyldiethanolamine (MDEA) as the selective amine, are suitable for use in these embodiments of the present invention.

[0108] The H.sub.2S-depleted CO.sub.2 tail gas may be fed directly to a compression unit for compression to produce the compressed impure CO.sub.2. However, in some embodiments, the method comprises recovering CO.sub.2 and residual H.sub.2S from the H.sub.2S-depleted CO.sub.2 tail-gas by non-selective amine absorption to produce the impure CO.sub.2 gas comprising H.sub.2S, together with waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0109] The H.sub.2S-depleted CO.sub.2 tail gas may be fed to a non-selective amine absorption unit at a temperature from about 10 C. to about 70 C., e.g., about 50 C. and at a pressure from about 0.01 bar g to about 30 bar g, e.g., from about 0.01 bar g to about 1.8 bar g, e.g., about 0.1 bar g.

[0110] Conventional non-selective amine absorption processes using, for example, monoethanolamine (MEA), activated methyldiethanolamine (aMDEA) or diethanolamine (DEA) as the non-selective amine, are suitable for use in these embodiments of the present invention.

[0111] Depending on the composition, any waste gas produced in the present invention may be vented or fed to a thermal oxidizer where it is combusted to produce a flue gas conforming to local emissions standards, and optionally steam. If the waste gas contains a significant amount of H.sub.2, then the waste gas itself may be used as a fuel or H.sub.2 may be recovered from the waste gas.

[0112] As indicated above, the purified CO.sub.2 may contain less than 100 ppm of sulfur-containing impurities in which case further purification is typically not required for CCS. However, in embodiments in which the amount of the impurities exceeds this threshold, further purification is typically required.

[0113] In embodiments where further purification is required, the method may comprise feeding the purified CO.sub.2 to a further purification process to produce further purified CO.sub.2 and a second recycle gas comprising CO.sub.2 and H.sub.2; and recycling the second recycle gas, or a H.sub.2-enriched gas derived therefrom, to the hydrogenation process. A portion of the second recycle gas, or of said H.sub.2-enriched gas derived therefrom, is typically purged to prevent a build-up of H.sub.2 (if it is in excess), or N.sub.2 and/or Ar non-condensable contaminants gas within the process.

[0114] The further purification process for further purifying CO.sub.2 may involve distillation such as the process disclosed in U.S. Ser. No. 10/254,042 and/or partial condensation with phase separation such as the process disclosed in U.S. Pat. No. 7,819,951, both of which the inventors have realized may be adapted as appropriate for integration with the present invention.

[0115] Both distillation and partial condensation of CO.sub.2 require a temperature in a range from the critical temperature of CO.sub.2 (i.e., about +31 C.) to the triple point temperature of CO.sub.2 (i.e., about 57 C.). In some embodiments, the distillation and/or partial condensation with phase separation take(s) place at a low (or sub-ambient) temperatures, typically in the range from about +15 C. to about 55 C. In other embodiments, the distillation and/or partial condensation with phase separation take(s) place at a temperature in the range from about 0 C. to 30 C., particularly for H.sub.2S distillation from CO.sub.2.

[0116] The purified CO.sub.2 is typically at a temperature from about 10 C. to about 70 C., e.g., about 50 C. and at a pressure from about 10 bar g to about 120 bar g, e.g., about 30 bar g. Thus, in embodiments in which further purification is required, the purified CO.sub.2 is typically cooled, e.g., by heat exchange with a refrigerant, to a suitable temperature as described above before being further purified. Additionally or alternatively, the purified CO.sub.2 would be further compressed if the pressure of the gas is not sufficient for the further purification.

[0117] Recycling H.sub.2 to the hydrogenation process enables a reduction in the amount of additional H.sub.2 that needs to be generated to meet demand in that process, thereby reducing the size of or even eliminating the hydrogenation unit required which in turn saves capital and operational costs. Where demand is only partially met by the recycled H.sub.2, additional H.sub.2 can be produced in a H.sub.2 generation process as discussed above. However, in some embodiments, the amount of H.sub.2 recycled to the hydrogenation process is sufficient to meet the demand for H.sub.2 in that process, eliminating the need for a H.sub.2 generation process entirely.

[0118] Recycling CO.sub.2 to the hydrogenation process enables an increase in overall CO.sub.2 recovery. It may however be desirable or advantageous to reduce the amount of CO.sub.2 being recycled to the hydrogenation unit in the second recycle gas, for example to reduce the size of the hydrogenation unit. In such cases, the method may comprise recovering H.sub.2 gas from a recycle gas being fed to the hydrogenation process in a membrane separation process to produce a H.sub.2-enriched gas which is recycled to the hydrogenation unit, together with a waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0119] Conventional membrane separation units may be used to recover H.sub.2 gas from recycle gas being recycled to the hydrogenation process. The membranes may be spiral wound, hollow fiber membranes made from polymers such as polysulfone, polyimide or cellulose acetate. An example of a suitable membrane separation process is disclosed in US2010/126180A which the Inventors have realized may be adapted as appropriate for integration with the present invention.

[0120] In embodiments in which H.sub.2S-enriched CO.sub.2 tail-gas is compressed directly to produce the compressed impure CO.sub.2 gas comprising H.sub.2S, the method may comprise feeding the purified CO.sub.2 to a further purification process as described above to produce further purified CO.sub.2 and a second recycle gas comprising CO.sub.2 and H.sub.2; and recycling the second recycle gas, or a H.sub.2-enriched gas derived therefrom, to the hydrogenation process. A portion of the second recycle gas, or of said H.sub.2-enriched gas derived therefrom, is typically purged to prevent the build-up of H.sub.2 (if it is in excess), or N.sub.2 and/or Ar in the process.

[0121] As mentioned above, purification by physical separation may be by distillation and/or partial condensation with phase separation.

[0122] In these embodiments, the method typically comprises removing H.sub.2 and any non-condensable gases from the compressed impure CO.sub.2 by distillation and/or partial condensation with phase separation to produce H.sub.2S-enriched CO.sub.2 fluid (which may be a liquid, a gas or two-phase) and H.sub.2-enriched CO.sub.2 gas, recycling the H.sub.2-enriched CO.sub.2 gas, or a further H.sub.2-enriched CO.sub.2 gas derived therefrom, as a second recycle gas to the hydrogenation process; separating the H.sub.2S-enriched CO.sub.2 fluid by distillation and/or partial condensation with phase separation to produce the purified CO.sub.2 as overhead gas and a H.sub.2S-enriched bottoms liquid; and vaporizing the H.sub.2S-enriched bottoms liquid to produce H.sub.2S-enriched gas as the first recycle gas. A portion of the second recycle gas, or of said H.sub.2-enriched gas derived therefrom, is usually purged to avoid a build-up of H.sub.2 (if it is in excess), or N.sub.2 and/or Ar in the process.

[0123] As mentioned above, suitable CO.sub.2 purification processes in this context are disclosed in U.S. Ser. No. 10/254,042 and U.S. Pat. No. 7,819,951 which the Inventors have realized may be adapted as appropriate for integration with the present invention.

[0124] In embodiments in which the purified CO.sub.2 comprises at least one residual sulfur-containing impurity, said method may comprise further purifying said purified CO.sub.2 by selective adsorption or by chemical reaction with at least one solid metal oxide to form solid metal sulfide(s) and subsequent oxidative regeneration, to produce further purified CO.sub.2 and a further recycle gas comprising at least one sulfur-containing compound; and recycling said further recycle gas to said Claus process to convert said sulfur-containing compound(s) into elemental sulfur.

[0125] Alternatively, in embodiments in which the purified CO.sub.2 overhead gas comprises one or more residual sulfur-containing compounds as impurities, the method may comprise removing H.sub.2S and any other sulfur-containing impurities from said purified CO.sub.2 overhead gas by selective adsorption or by chemical reaction with at least one solid metal oxide to form solid metal sulfide(s) and subsequent oxidative regeneration, to produce further purified CO.sub.2 and a third recycle gas comprising at least one sulfur-containing compound. The third recycle gas may be recycled to the Claus process to convert the sulfur-containing compound(s) into elemental sulfur.

[0126] The second aspect of the present invention is apparatus for desulfurizing crude CO.sub.2 gas comprising H.sub.2S and optionally at least one other sulfur-containing impurity, typically in accordance with the method of the first aspect.

[0127] The apparatus comprises a Claus unit for removing H.sub.2S from crude CO.sub.2 gas. The Claus unit comprises a first inlet for oxidant gas comprising O.sub.2, a second inlet for the crude CO.sub.2 gas, a first outlet for Claus tail-gas comprising CO.sub.2, residual H.sub.2S and at least one sulfur-containing impurity; and a second outlet for elemental sulfur. An example of a suitable Claus unit is described in US2010/0126180A.

[0128] The apparatus also comprises a source of oxidant gas comprising O.sub.2 in fluid flow communication with the first inlet of the Claus unit. For units operating an air-Claus process, the source may simply be a blower with a small filter whereas, for units operating an oxy-Claus process, the source may be a vacuum swing adsorption (VSA) unit or an air separation unit (ASU), optionally in combination with a back-up system such as a liquid oxygen tank and vaporizer.

[0129] In addition, the apparatus comprises a source of crude CO.sub.2 gas in fluid flow communication with the second inlet of the Claus unit. Such sources include natural gas sweetening units which use amine absorption processes/units, membrane separation systems/units and/or low temperature purification processes/units to generate acid gas streams.

[0130] The apparatus further comprises a hydrogenation unit for converting the at least one sulfur-containing impurity in the Claus tail-gas into H.sub.2S. The hydrogenation unit comprises a first inlet in fluid flow communication with the first outlet of the Claus unit, a second inlet for H.sub.2 and a first outlet for H.sub.2S-enriched CO.sub.2 tail-gas. An example of a suitable hydrogenation unit is described in US2010/0126180A.

[0131] The apparatus also comprises a source of H.sub.2 in fluid flow communication with the second inlet of the hydrogenation unit. The source may be a unit generating H.sub.2 as described above.

[0132] In addition, the apparatus comprises a cooling unit for cooling H.sub.2S-enriched CO.sub.2 tail gas which is either separate from or integrated with the hydrogenation unit. The cooling unit comprises a first inlet in fluid communication with the first outlet of the hydrogenation unit, a first outlet for cooled H.sub.2S-enriched CO.sub.2 tail gas, and a second outlet for condensed water. The cooling unit may be a heat exchanger using indirect heat exchange with a coolant but is usually a direct contact cooler comprising a second inlet for cooling water. The cooling unit may be a separate unit or may be integrated with the hydrogenation unit.

[0133] Further, the apparatus comprises a compression unit for compressing H.sub.2S-enriched CO.sub.2 tail-gas or impure CO.sub.2 gas comprising H.sub.2S derived therefrom. The compression unit must therefore be inherently suitable for handling sour gases.

[0134] The compression unit comprises an inlet in fluid flow communication with the outlet of the first outlet of the cooling unit; and an outlet for compressed impure CO.sub.2 gas. The compression unit may comprise one or more centrifugal or reciprocating compressor and/or may be a multistage compressor with associated intercooler(s) and aftercooler(s). In particular, the compression unit may be an integrally geared or inline centrifugal compressor.

[0135] Furthermore, the apparatus comprises a purification unit for removing H.sub.2S and any other sulfur-containing impurities from compressed impure CO.sub.2 gas by physical separation or chemical reaction with solid metal oxide(s). The purification unit comprises a first inlet in fluid flow communication with the outlet of said compression unit, a first outlet for purified CO.sub.2; and a second outlet for a first recycle gas comprising at least one sulfur-containing compound. The second outlet of the purification unit is in fluid communication with the Claus unit. In this regard, the second outlet may be in fluid flow communication with the second inlet of the Claus unit or with a third inlet on the Claus unit which is typically dedicated for recycle gas.

[0136] Throughout the specification, the term in fluid flow communication is used to refer to different units (or parts of units such as inlets/outlets) being connected by conduits, pipes and/or ducting as appropriate in such a manner to allow the flow of fluid, e.g., gas, between units. The term is intended to include associated flow control devices such as the necessary sensors and/or valves to ensure operational control of the apparatus. Unless stated otherwise, the term is intended to cover both direct and indirect fluid flow communication. Direct fluid (or gas) flow communication means that no other fluid (or gas) processing unit (not including flow control apparatus) is provided in the line between the units so connected. Indirect fluid (or gas) flow communication is to be interpreted accordingly, i.e., one or more other fluid (or gas) processing units are provided in the line between the units so connected.

[0137] In some embodiments, the apparatus comprises a H.sub.2 generation unit comprising an outlet for H.sub.2 in fluid communication with the second inlet of the hydrogenation unit.

[0138] The purification unit in some embodiments is or comprises a selective adsorption unit comprising at least one vessel having an upstream end and a downstream end, and the or each vessel comprises an adsorbent bed comprising at least one layer of adsorbent material(s) selective for sulfur-containing compounds, a first inlet for compressed impure CO.sub.2 gas at the upstream end of the or each vessel, a first outlet for purified CO.sub.2 at the downstream end of the or each vessel, a second inlet for regeneration gas at the downstream end of the or each vessel; and a second outlet for spent regeneration gas at the upstream end of the or each vessel. The first inlet is in fluid flow communication with the outlet of the compression unit and the second outlet is in fluid flow communication with the Claus unit. In this regard, the second outlet may be in fluid flow communication with the second inlet of the Claus unit or with a third inlet on the Claus unit which is typically dedicated for recycle gas.

[0139] In other embodiments, the purification unit comprises a reactor comprising at least one vessel having an upstream end and a downstream end. The or each vessel comprises a bed comprising at least one solid metal oxide, a first inlet for compressed impure CO.sub.2 gas at the upstream end of the or each vessel, a first outlet for purified CO.sub.2 at the downstream end of the or each vessel; a second inlet for regeneration gas at the downstream end of the or each vessel; and a second outlet for spent regeneration gas at the upstream end of the or each vessel. The first inlet is in fluid flow communication with the outlet of the compression device and the second outlet is in fluid flow communication with the Claus unit. In this regard, the second outlet may be in fluid flow communication with the second inlet of the Claus unit or with a third inlet on the Claus unit which is typically dedicated for recycle gas.

[0140] The Inventors have realized that an example of a suitable reactor that may be adapted for integration with these embodiments is disclosed in U.S. Pat. No. 4,797,268.

[0141] The bed in the or each vessel of the selective adsorption unit or the reactor may comprise at least one layer of adsorbent material(s) selective for water downstream of at least one layer of adsorbent material(s) selective for sulfur-containing compound(s) or the solid metal oxide(s) respectively.

[0142] Alternatively, the purification unit may comprise a separate drier unit downstream of either the selective adsorption unit of the reactor. The drier unit may be a further selective adsorption unit or an absorption unit such as a glycol unit. Either way, the drier unit typically comprises an inlet in fluid communication with the first outlet of the selective adsorption unit or the reactor as appropriate, and an outlet for dried and purified CO.sub.2.

[0143] In some embodiments, the apparatus comprises a selective amine absorption unit for recovering H.sub.2S from H.sub.2S-enriched CO.sub.2 tail gas. The selective amine absorption unit typically comprises an inlet in fluid flow communication with the first outlet of the cooling unit, a first outlet for H.sub.2S-depleted CO.sub.2 tail-gas and a second outlet for recovered gas comprising H.sub.2S in fluid flow communication with the Claus unit. In this regard, the second outlet may be in fluid flow communication with the second inlet of the Claus unit or with a third inlet on the Claus unit which is typically dedicated for recycle gas. An example of a suitable selective amine absorption unit which the Inventors have realized may be adapted for use in this context is disclosed in WO93/10883A.

[0144] In some embodiments, the first outlet of the selective amine adsorption unit is in direct fluid flow communication with the inlet of the compression unit.

[0145] In other embodiments, the apparatus may further comprise a non-selective amine absorption unit for recovering CO.sub.2 and residual H.sub.2S from H.sub.2S-depleted CO.sub.2 tail-gas. The non-selective amine absorption unit typically comprises an inlet in fluid flow communication with the first outlet of the selective amine absorption unit, a first outlet for impure CO.sub.2 gas, and a second outlet for waste gas comprising CO.sub.2 and at least one non-condensable gas. The apparatus usually includes a vent for the waste gas, optionally with a thermal oxidizer comprising an inlet in fluid flow communication with the second outlet of the non-selective amine absorption unit, and an outlet for vent gas in fluid communication with the atmosphere via the vent.

[0146] In embodiments of the present invention in which the content of the sulfur-containing impurities in the purified CO.sub.2 gas even after passage through a selective adsorption unit or a reactor as described above is still above the required threshold, e.g., above 100 ppm, then the apparatus may further comprise a further purification unit, such as a distillation unit and/or a partial condensation with phase separation unit (or CPU), for further purifying purified CO.sub.2.

[0147] In these embodiments, the further purification unit comprises an inlet for purified CO.sub.2 in fluid flow communication with the first outlet of the purification unit, a first outlet for further purified CO.sub.2, and a second outlet for a second recycle gas comprising CO.sub.2 and H.sub.2 in fluid flow communication with either the hydrogenation unit and/or the Claus unit, and a purge line in fluid flow communication with the second outlet of said further purification unit.

[0148] For these and other embodiments involving the use of a further purification unit, the second outlet of the further purification unit may be in fluid flow communication with the first or second inlet of the hydrogenation unit or with a third inlet on the hydrogenation unit which is typically dedicated for recycle gas. The second outlet of the CPU may additionally or alternatively be in fluid communication with the first or second inlet of the Claus unit or with a third inlet on the Claus unit which is typically dedicated for recycle gas. Further, the purge line may be in direct fluid communication with a vent to the atmosphere, or with a thermal oxidizer. Alternatively, fluid from the purge line could be used as a fuel or for H.sub.2 recovery.

[0149] The inventors have realized that the CPU described in FIG. 1B of U.S. Ser. No. 10/254,042 may be used (after suitable adaptation as appropriate) as the further purification unit of the present invention.

[0150] These embodiments may further comprise a membrane separation unit for recovering H.sub.2 gas from second recycle gas. The membrane separation unit typically comprises an inlet for second recycle gas in fluid flow communication with the second outlet of the further purification unit, a first outlet for H.sub.2-enriched gas in direct fluid flow communication with the hydrogenation unit and/or the Claus unit, and a second outlet for waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0151] These embodiments of the apparatus usually include a vent for the waste gas, optionally with a thermal oxidizer comprising an inlet in fluid flow communication with the second outlet of the membrane separation unit, and an outlet for vent gas in fluid communication with the vent.

[0152] In addition, the second outlet of the membrane separation unit may be in fluid flow communication with the second inlet(s) of the hydrogenation unit and/or the Claus unit or with a third inlet(s) on the hydrogenation unit and/or Claus unit which is typically dedicated for recycle gas. In this regard, extra H.sub.2 can be fed to the Claus unit for combustion/disposal if not required elsewhere.

[0153] In other embodiments, the first outlet of the hydrogenation unit is in direct fluid flow communication with the inlet of the compression unit.

[0154] In these embodiments, the apparatus may comprise a further purification unit for further purifying purified CO.sub.2. The further purification unit typically comprises an inlet for purified CO.sub.2 in fluid flow communication with the first outlet of the purification unit, a first outlet for further purified CO.sub.2, and a second outlet for a second recycle gas comprising CO.sub.2 and H.sub.2 in fluid flow communication with the hydrogenation unit, and a purge line in fluid flow communication with the second outlet of the further purification unit. The second outlet of the further purification unit may be in fluid flow communication with an inlet of the hydrogenation unit (and/or the Claus unit), or with an inlet on the hydrogenation unit (and/or the Claus unit) which is typically dedicated for recycle gas.

[0155] These embodiments may further comprise a membrane separation unit for recovering H.sub.2 gas from second recycle gas. The membrane separation unit typically comprises an inlet for second recycle gas in fluid flow communication with the second outlet of the further purification unit, a first outlet for H.sub.2-enriched gas in direct fluid flow communication with the hydrogenation unit, and a second outlet for waste gas comprising CO.sub.2 and at least one non-condensable gas. The H.sub.2-enriched gas is typically taken from the permeate side of the membrane(s) and the waste gas is typically taken from the retentate side of the membrane(s).

[0156] These embodiments of the apparatus usually include a vent for the waste gas, optionally with a thermal oxidizer comprising an inlet in fluid flow communication with the second outlet of the membrane separation unit, and an outlet for vent gas in fluid communication with the vent.

[0157] In addition, the second outlet of the membrane separation unit may be in fluid flow communication with the second inlet(s) of the hydrogenation unit and/or the Claus unit or with a third inlet(s) on the hydrogenation unit and/or on the Claus unit which is typically dedicated for recycle gas.

[0158] In some embodiments, the apparatus comprises a non-selective amine absorption unit for recovering CO.sub.2 and H.sub.2S from H.sub.2S-enriched CO.sub.2 tail-gas. The non-selective amine absorption unit comprises an inlet in direct fluid flow communication with the outlet of the cooling unit, a first outlet for impure CO.sub.2 gas in direct fluid flow communication with the inlet of the compression unit, and a second outlet for waste gas comprising CO.sub.2 and at least one non-condensable gas. These embodiments of the apparatus usually include a vent for the waste retentate gas, optionally with a thermal oxidizer comprising an inlet in fluid flow communication with the second outlet of the membrane separation unit, and an outlet for vent gas in fluid communication with the vent.

[0159] The purification unit may be a single stage unit. In these embodiments, the purification unit comprises an inlet for compressed impure CO.sub.2 in fluid flow communication with the outlet of said compression unit; a first outlet for H.sub.2S-enriched CO.sub.2 fluid; and a second outlet for H.sub.2-enriched CO.sub.2 gas in fluid flow communication with an inlet of the hydrogenation unit (and/or with an inlet of the Claus unit).

[0160] In these embodiments, the apparatus may further comprise a selective adsorption unit comprising at least one vessel having an upstream end and a downstream end in which the or each vessel comprises an adsorbent bed, said adsorbent bed comprising at least one layer of adsorbent material(s) selective for sulfur-containing compound(s); a first inlet for H.sub.2S-enriched CO.sub.2 fluid at said upstream end of the or each vessel; a first outlet for purified CO.sub.2 at said downstream end of the or each vessel; a second inlet for regeneration gas at said downstream end of the or each vessel; and a second outlet for spent regeneration gas at said upstream end of the or each vessel. The first inlet of the selective adsorption vessel is in fluid flow communication with the first outlet of the single stage purification unit and the second outlet is in fluid flow communication with the Claus unit.

[0161] Alternatively, the apparatus may comprise a reactor comprising at least one vessel having an upstream end and a downstream end in which the or each vessel comprises a bed comprising at least one solid metal oxide; a first inlet for H.sub.2S-enriched CO.sub.2 fluid at said upstream end of the or each vessel; a first outlet for purified CO.sub.2 at said downstream end of the or each vessel; a second inlet for regeneration gas at said downstream end of the or each vessel; and a second outlet for spent regeneration gas at said upstream end of the or each vessel. The first inlet of the reactor is in fluid flow communication with the first outlet of the single stage purification unit and the second outlet is in fluid flow communication with the Claus unit.

[0162] In still further embodiments of the apparatus, the purification unit comprises a first stage, e.g., a CPU, and a second stage, e.g., a distillation unit.

[0163] The first stage comprises an inlet for compressed impure CO.sub.2 in fluid flow communication with the outlet of compression unit, a first outlet for H.sub.2S-enriched CO.sub.2 fluid, and a second outlet for H.sub.2-enriched CO.sub.2 gas in fluid flow communication with an inlet of the hydrogenation unit (and/or with an inlet of the Claus unit).

[0164] The second stage comprises an inlet for H.sub.2S-enriched CO.sub.2 fluid in fluid flow communication with the first outlet of first stage, a first outlet for purified CO.sub.2 gas, and a second outlet for H.sub.2S-enriched gas in fluid flow communication with the third inlet of the Claus unit. These embodiments of the apparatus further comprise a purge line in fluid flow communication with the second outlet of the first stage of the purification unit.

[0165] The Inventors have realized that FIG. 2 of U.S. Ser. No. 10/254,042 depicts an arrangement of integrated first and second stages that would be suitable for use as the purification unit according to these embodiments of the present invention.

[0166] These embodiments may further comprise a membrane separation unit for recovering H.sub.2 gas from H.sub.2-enriched CO.sub.2 gas. The membrane separation unit typically comprises an inlet for H.sub.2-enriched CO.sub.2 gas in fluid flow communication with the second outlet of the first stage of the purification unit, a first outlet for H.sub.2-enriched gas in direct fluid flow communication with an inlet of hydrogenation unit (and/or with an inlet of the Claus unit) and a second outlet for waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0167] These embodiments of the apparatus usually include a vent for the waste gas, optionally with a thermal oxidizer comprising an inlet in fluid flow communication with the second outlet of the membrane separation unit, and an outlet for vent gas in fluid communication with the vent.

[0168] In addition, the second outlet of the membrane separation unit may be in fluid flow communication with the second inlet(s) of the hydrogenation unit and/or of the Claus unit, or with a third inlet(s) on the hydrogenation unit and/or on the Claus unit which is typically dedicated for recycle gas.

[0169] If the amount of sulfur-containing components in the purified CO.sub.2 gas is still above the required threshold, e.g. above 100 ppm, then these embodiments may further comprise a further purification unit selected from a selective adsorption unit and a reactor comprising a bed of solid metal oxide(s) as described above.

[0170] A selective adsorption unit in this context typically comprises at least one vessel having an upstream end and a downstream end. The or each vessel comprises an adsorbent bed comprising at least one layer of adsorbent material(s) selective for sulfur-containing compound(s), a first inlet for purified CO.sub.2 at the upstream end of the or each vessel, a first outlet for further purified CO.sub.2 at the downstream end of the or each vessel, a second inlet for regeneration gas at the downstream end of the or each vessel, and a second outlet for spent regeneration gas at the upstream end of the or each vessel. In these embodiments, the first inlet of the further purification unit is in fluid flow communication with the first outlet of the second stage of the purification unit and the second outlet is in fluid flow communication with the Claus unit. In this regard, the second outlet of the or each vessel may be in fluid flow communication with the second inlet of the Claus unit or with a third inlet on the Claus unit which is typically dedicated for recycle gas.

[0171] A reactor in this context typically comprises at least one vessel having an upstream end and a downstream end. The or each vessel comprises at least one solid metal oxide, a first inlet for purified CO.sub.2 at the upstream end of the or each vessel, a first outlet for further purified CO.sub.2 at the downstream end of the or each vessel, a second inlet for regeneration gas at the downstream end of the or each vessel, and a second outlet for spent regeneration gas at the upstream end of the or each vessel. In addition, the first inlet of the further purification unit is in fluid flow communication with the first outlet of the second stage of the purification unit and the second outlet is in fluid flow communication with the Claus unit. In this regard, the second outlet of the or each vessel may be in fluid flow communication with the second inlet of the Claus unit or with a third inlet on the Claus unit which is typically dedicated for recycle gas.

[0172] Turning now to the figures, in FIG. 1, a stream 100 of crude CO.sub.2 gas comprising H.sub.2S is taken from an acid gas recovery unit 4 and fed to a Claus unit 6 where H.sub.2S is converted to a stream 102 of elemental sulfur. A sub-stoichiometric amount of oxygen from a stream 101 of air is used to oxidize sufficient H.sub.2S in the crude CO.sub.2 gas feed to produce a mixture of H.sub.2S and SO.sub.2 in the appropriate proportions to react and produce elemental sulfur. The Claus unit 6 typically converts from 92 mol. % to 99.5 mol. % of the H.sub.2S in the crude CO.sub.2 gas feed into elemental sulfur, depending on the type of Claus process. The residual sulfur compounds leave the Claus unit 6 in a stream 103 of Claus tail-gas comprising CO.sub.2 which is fed to a tail gas treatment unit 14 comprising a hydrogenation unit 16 and a selective amine absorption unit 20.

[0173] The residual sulfur compounds are converted in the hydrogenation unit 16 in the presence of H.sub.2 gas produced in a reducing gas generation unit 18, into H.sub.2S to produce a stream 104 of H.sub.2S-enriched CO.sub.2 tail-gas which, after quenching with water in a direct contact cooler (shown as integrated with the hydrogenation unitsee stream (of water) leaving hydrogenation unit 16), is then fed to the selective amine absorption unit 20 which selectively absorbs H.sub.2S to produce a stream 105 of H.sub.2S-depleted CO.sub.2 tail-gas and recovered H.sub.2S which is recycled back to the Claus unit 6 as part of stream 110. The H.sub.2S-depleted CO.sub.2 tail-gas from the tail-gas treatment unit 14 contains mainly CO.sub.2, N.sub.2, H.sub.2 and small quantities of sulfur compounds, and is saturated with water.

[0174] In the absence of a CO.sub.2 capture unit, stream 105 would typically be oxidized in a thermal oxidizer. In this case, however, the CO.sub.2 is intended for capture and storage.

[0175] The H.sub.2S-depleted CO.sub.2 tail-gas 105 from tail gas treatment unit 14 is fed to a non-selective amine absorption unit 26 in which most of the CO.sub.2 and sulfur compounds are captured and recovered non-selectively to produce a stream 107 of impure CO.sub.2 gas, together with a stream 115 of waste gas comprising CO.sub.2 and the non-condensable gases, N.sub.2 and H.sub.2, together with water which is either vented directly or fed to a thermal oxidizer 42 before being vented, depending on its composition.

[0176] Stream 107 is mostly CO.sub.2 but contains sulfur compounds which may not be acceptable for CO.sub.2 sequestration or further use. Stream 107 is therefore fed to compression device 32 where it is compressed to form a stream 108 of compressed impure CO.sub.2 gas which is then purified using a selective adsorption unit (or reactor) 36 according to the present invention to remove the sulfur compounds and produce a stream 111 of purified CO.sub.2 for sequestration and a stream 109 of spent regeneration gas (or purge gas) comprising desorbed sulfur compound(s) which is recycled to the Claus unit 6.

[0177] Water may be removed from the compressed impure CO.sub.2 gas in the selective adsorption unit (or reactor) 36 by including at least one layer of water adsorbent material downstream of the layer(s) of sulfur-selective adsorbent material(s) or of the solid metal oxide(s), e.g., ZnO. Alternatively, the stream 111 of purified CO.sub.2 may be fed to a drier unit (not shown) prior to sequestration.

[0178] The flowsheet depicted in FIG. 2 is an alternative to that depicted in FIG. 1. Unless otherwise indicated, common features between the two flowsheets have been given the same reference numerals. The following is a discussion of the features that distinguish FIG. 2 over FIG. 1.

[0179] Instead of air as used in FIG. 1, the process of FIG. 2 uses a stream 101 of O.sub.2 or O.sub.2-enriched air as the oxidant feed the Claus unit 6 for the conversion of the required amount of H.sub.2S into SO.sub.2 for the Claus reaction to produce elemental sulfur.

[0180] In addition, stream 105 of H.sub.2S-depleted CO.sub.2 tail-gas is taken from the tail gas treatment unit 14 and fed directly to a compression device 46 where it is compressed. Water is knocked out of the compressed gas in one or more intercoolers and/or an aftercooler (not shown). A stream 106 of compressed impure CO.sub.2 gas is then purified using a selective adsorption unit (or reactor) 50 according to the present invention to remove the sulfur-containing compound(s) and produce a stream 107 of purified CO.sub.2 gas and a stream 109 of spent regeneration gas (or purge gas) comprising sulfur-containing compound(s) which is recycled to the Claus unit 6.

[0181] Water may be removed from the compressed impure CO.sub.2 gas in the selective adsorption unit (or reactor) 50 by including at least one layer of water-adsorbent material downstream of the layer(s) of sulfur-selective adsorbent material(s) or of the solid metal oxide(s), e.g., ZnO. Alternatively, the stream 111 of purified CO.sub.2 may be fed to a drier unit (not shown) prior to sequestration.

[0182] Stream 107 of purified CO.sub.2 gas is then fed to a further purification unit 56 where CO.sub.2 is further purified by distillation and/or by partial condensation and phase separation to produce a stream 111 of further purified CO.sub.2 for sequestration or other use, and a stream 108 of a waste gas comprising CO.sub.2 and H.sub.2.

[0183] Stream 108 can be recycled directly to the hydrogenation unit 16. However, it may be desirable to reduce the amount of CO.sub.2 that is recycled to the hydrogenation unit 16. In such cases, stream 108 may be fed to a membrane unit 62 for H.sub.2 recovery to produce a stream 112 of H.sub.2-enriched gas and a stream 115 of waste gas.

[0184] Stream 112 is recycled to the hydrogenation unit 16. Recycling of this stream in this way has the benefit of reducing or even eliminating the need for fresh H.sub.2 from a reducing gas generation unit (not shown) to feed the hydrogenation unit 16.

[0185] The stream 115 of waste gas may be vented directly or fed to a thermal oxidizer 70 before being vented, depending on its composition.

[0186] The flowsheet depicted in FIG. 3 is a modified version of that depicted in FIG. 1 without the selective amine adsorption unit 20. Unless otherwise indicated, common features between the two flowsheets have been given the same reference numerals. The following is a discussion of the features that distinguish FIG. 3 over FIG. 1.

[0187] Stream 104 of H.sub.2S-enriched CO.sub.2 tail-gas is fed directly from the hydrogenation unit 16 to the non-selective amine absorption unit 26 in which most of the CO.sub.2 and sulfur-containing compounds are captured and recovered non-selectively to produce stream 107 of impure CO.sub.2 gas, together with a stream 115 of waste gas which is either vented directly or fed to a thermal oxidizer 42 before being vented, depending on its composition.

[0188] The flowsheet depicted in FIG. 4 is a modified version of that depicted in FIG. 2 without the selective amine adsorption unit 20. Unless otherwise indicated, common features between the two flowsheets have been given the same reference numerals. The following is a discussion of the features that distinguish FIG. 4 over FIG. 2.

[0189] In this arrangement, the stream 101 of O.sub.2 or O.sub.2-rich air for the Claus unit 6 is generated in an air separation unit 72 either by vacuum swing adsorption (VSA) or cryogenic air separation (in an air separation unit or ASU).

[0190] Stream 104 of impure CO.sub.2 tail-gas is fed directly from the hydrogenation unit 16 to the compression device 46 where it is compressed to form stream 106 of compressed impure CO.sub.2 gas which is then fed to the selective adsorption unit (or reactor) 50 where H.sub.2S (optionally, together with water) is removed from the gas.

[0191] In this arrangement, sufficient H.sub.2 may be recovered in the membrane separation unit 62 and recycled to the hydrogenator 16 that a reducing gas generator (not shown) is not required to provide additional H.sub.2.

[0192] The flowsheet depicted in FIG. 5 is a modified version of that depicted in FIG. 4 in which the purification unit comprises a selective adsorption unit (or reactor) to further purify the CO.sub.2. Unless otherwise indicated, common features between the two flowsheets have been given the same reference numerals. The following is a discussion of the features that distinguish FIG. 5 over FIG. 4.

[0193] The purification unit has a first stage and a second stage. Regarding the first stage, stream 106 of compressed impure CO.sub.2 gas is fed to a first stage 56 where CO.sub.2 is purified, e.g., by partial condensation with phase separation, to produce H.sub.2S-enriched CO.sub.2 liquid, and a stream 108 of a waste gas comprising CO.sub.2 and H.sub.2 for recycling to the hydrogenation unit 16, optionally after passage through a membrane separation unit 62 to recover H.sub.2.

[0194] A stream 107 of H.sub.2S-enriched CO.sub.2 liquid (or gas if vaporised) is fed to a distillation column system 74 where CO.sub.2 and H.sub.2S are separated in the second stage to generate purified CO.sub.2 as overhead gas and H.sub.2S-enriched bottoms liquid which is vaporised prior to recycling to the Claus unit 6 in stream 110.

[0195] The stream 111 of purified CO.sub.2 may be suitable for sequestration. However, if the total amount of sulfur-containing compounds in the purified CO.sub.2 is too high, e.g., over 100 ppm, then the purified CO.sub.2 may be further purified in a selective adsorption unit (or reactor) 50 to produce a stream 120 of further purified CO.sub.2 for sequestration or further use, and a stream 118 of spent regeneration gas (or purge gas) comprising desorbed sulfur-containing compounds which is recycled to the Claus unit 6.

[0196] The flowsheets depicted in FIGS. 2, 4 and 5 all involve a membrane separation unit 62 for recovering H.sub.2 from waste gas generated in a purification unit. In these embodiments, a purge stream may be taken from the recycle stream 112 to control the build-up of H.sub.2 (if it is in excess), or N.sub.2 and/or Ar in the processes.

[0197] The flowsheet depicted in FIG. 6 is a modified version of that depicted in FIG. 5 in which the purification unit comprises a single stage and a selective adsorption unit (or reactor) may be used to further purify the CO.sub.2. Unless otherwise indicated, common features between the two flowsheets have been given the same reference numerals. The following is a discussion of the features that distinguish FIG. 6 over FIG. 5.

[0198] The purification unit has a single stage (unit 56). Stream 106 of compressed impure CO.sub.2 gas is fed to unit 56 where CO.sub.2 is purified, e.g., by partial condensation with phase separation or distillation, to produce H.sub.2S-enriched CO.sub.2 liquid, and a stream 108 of a waste gas comprising CO.sub.2 and H.sub.2 for recycling to the hydrogenation unit 16, optionally after passage through a membrane separation unit 62 to recover H.sub.2.

[0199] The level of sulfur-containing compounds in stream 107 of H.sub.2S-enriched CO.sub.2 gas, typically over 2 mol. %, is far too high for CCS. However, rather than purifying the CO.sub.2 by distillation (as in FIG. 5), the stream may be fed from unit 56 to the selective adsorption unit (or reactor) 50 to produce a stream 111 of purified CO.sub.2 for sequestration or further use, and a stream 110 of spent regeneration gas (or purge gas) comprising desorbed sulfur-containing compounds which is recycled to the Claus unit 6.

[0200] The flowsheet in FIG. 7 depicts how a SUPERCLAUS process and/or a EUROCLAUS process (unit 6*) may be integrated with the tail gas treatment processes depicted in FIGS. 1 to 5. In this regard, unit 26** represents the CCS block, which includes the specific combination of selective amine absorption unit, non-selective amine absorption unit, compression unit, selective adsorption unit, reactor unit, membrane separation unit and/or purification unit depicted in one of FIGS. 1 to 5. The H.sub.2S-containing recycle stream(s) is fed to the Claus unit 6*, the purified CO.sub.2 is removed as stream 111 and the waste gas is sent via stream 115 to the thermal oxidizer unit 42.

Aspects of the Invention

[0201] #1. A method for desulfurization of crude CO.sub.2 gas comprising H.sub.2S and optionally at least one other sulfur-containing impurity, said method comprising: [0202] feeding crude CO.sub.2 gas comprising H.sub.2S to a Claus process to convert H.sub.2S in the presence of O.sub.2 gas to elemental sulfur and produce Claus tail-gas comprising CO.sub.2, residual H.sub.2S and at least one other sulfur-containing impurity; [0203] feeding said Claus tail-gas to a hydrogenation process to convert said at least one other sulfur-containing impurity into H.sub.2S in the presence of H.sub.2 and produce H.sub.2S-enriched CO.sub.2 tail-gas; [0204] cooling said H.sub.2S-enriched CO.sub.2 tail gas and removing condensed water to produce cooled H.sub.2S-enriched CO.sub.2 tail gas; [0205] compressing said cooled H.sub.2S-enriched CO.sub.2 tail-gas, or an impure CO.sub.2 gas comprising H.sub.2S derived therefrom, to produce compressed impure CO.sub.2 gas comprising H.sub.2S; [0206] removing H.sub.2S and any other sulfur-containing impurities from said compressed impure CO.sub.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.sub.2 and a first recycle gas comprising at least one sulfur-containing compound; and [0207] recycling said first recycle gas to said Claus process to convert said at least one sulfur-containing compound into elemental sulfur.

[0208] #2. A method according to #1 comprising: [0209] generating H.sub.2 in a hydrogen generation process; and [0210] feeding said H.sub.2 to said hydrogenation process.

[0211] #3. A method according to #1 or #2 wherein said H.sub.2S-enriched CO.sub.2 tail gas is cooled by direct contact with water.

[0212] #4. A method according to any of #1 to #3 wherein H.sub.2S and any other sulfur-containing impurities are removed from said compressed impure CO.sub.2 gas by selective adsorption as said physical separation.

[0213] #5. A method according to #4 wherein said selective adsorption involves removing H.sub.2S and any other sulfur-containing compounds in the compressed impure CO.sub.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.sub.2 and, after desorption with a regeneration gas, a spent regeneration gas comprising said H.sub.2S and any other sulfur-containing compounds from the compressed impure CO.sub.2 gas as said first recycle gas.

[0214] #6. A method according to #5, wherein said regeneration gas comprises water in an amount that is insufficient to hydrolyze the other sulfur-containing compounds.

[0215] #7. A method according to #5 or #6, wherein said compressed impure CO.sub.2 gas feed to the selective adsorption unit comprises water, said method comprising drying the purified CO.sub.2 gas downstream of said adsorbent material(s) selective for sulfur-containing compound(s).

[0216] #8. A method according to #1 to #3 wherein H.sub.2S and any other sulfur-containing impurities are removed from said compressed impure CO.sub.2 gas by said chemical reaction with at least one solid metal oxide to form solid metal sulfide(s) and subsequent oxidative regeneration.

[0217] #9. A method according to #8 comprising: [0218] passing said compressed impure CO.sub.2 gas through a bed comprising said at least one solid metal oxide in a reactor to convert the metal oxide(s) to metal sulfide(s) and produce said purified CO.sub.2; and [0219] regenerating the bed using a regeneration gas comprising O.sub.2 to produce a spent regeneration gas comprising SO.sub.2 as said first recycle gas.

[0220] #10. A method according to #9 wherein said regeneration gas comprises water in an amount that is insufficient to hydrolyze the other sulfur-containing compounds.

[0221] #11. A method according to #9 or #10, wherein said compressed impure CO.sub.2 gas feed to said reactor comprises water, said method comprising drying the purified CO.sub.2 gas downstream of the bed comprising said solid metal oxide(s).

[0222] #12. A method according to any of #1 to #11 comprising: [0223] recovering H.sub.2S from said H.sub.2S-enriched CO.sub.2 tail-gas by selective amine absorption to produce H.sub.2S-depleted CO.sub.2 tail-gas and recovered H.sub.2S; and [0224] recycling said recovered H.sub.2S to said Claus process to convert said recovered H.sub.2S to elemental sulfur.

[0225] #13. A method according to #12 comprising recovering CO.sub.2 and residual H.sub.2S from said H.sub.2S-depleted CO.sub.2 tail-gas by non-selective amine absorption to produce said impure CO.sub.2 gas for compression, together with waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0226] #14. A method according to #12, wherein said H.sub.2S-depleted CO.sub.2 tail-gas is compressed directly to produce said compressed impure CO.sub.2 gas.

[0227] #15. A method according to #14 comprising: [0228] feeding said purified CO.sub.2 to a further purification process to produce further purified CO.sub.2 and a second recycle gas comprising CO.sub.2 and H.sub.2; and [0229] recycling said second recycle gas, or a H.sub.2-enriched gas derived therefrom, to said hydrogenation process,

[0230] wherein a portion of said second recycle gas, or of said H.sub.2-enriched gas derived therefrom, is purged.

[0231] #16. A method according to #15 wherein the amount of H.sub.2 recycled to said hydrogenation process is sufficient to meet demand in that process.

[0232] #17. A method according to #15 or #16 comprising recovering H.sub.2 gas from said second recycle gas in a membrane separation process to produce said H.sub.2-enriched gas, together with a waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0233] #18. A method according to any of #1 to #3 wherein said H.sub.2S-enriched CO.sub.2 tail-gas is compressed directly to produce said compressed impure CO.sub.2 gas comprising H.sub.2S.

[0234] #19. A method according to any of #1 to #18 comprising: [0235] feeding said purified CO.sub.2 to a further purification process to produce further purified CO.sub.2 and a second recycle gas comprising CO.sub.2 and H.sub.2; and [0236] recycling said second recycle gas, or a H.sub.2-enriched gas derived therefrom, to said hydrogenation process,

[0237] wherein a portion of said second recycle gas, or of said H.sub.2-enriched gas derived therefrom, is purged.

[0238] #20. A method according to #19 wherein the amount of H.sub.2 recycled to said hydrogenation process is sufficient to meet demand in that process.

[0239] #21. A method according to #19 or #20 comprising recovering H.sub.2 gas from said second recycle gas in a membrane separation process to produce said H.sub.2-enriched gas for recycle, together with a waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0240] #22. A method according to any of #1 to #3 comprising recovering CO.sub.2 and H.sub.2S from said H.sub.2S-enriched CO.sub.2 tail-gas by non-selective amine absorption to produce said impure CO.sub.2 gas for compression, together with a waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0241] #24. A method according to #1 to #3, wherein said H.sub.2S and any other sulfur-containing impurities are removed from said compressed impure CO.sub.2 gas by distillation and/or partial condensation with phase separation as said physical separation.

[0242] #25. A method according to #24, wherein said purified CO.sub.2 comprises at least one residual sulfur-containing impurity, said method comprising: [0243] further purifying said purified CO.sub.2 by selective adsorption or by chemical reaction with at least one solid metal oxide to form solid metal sulfide(s) and subsequent oxidative regeneration, to produce further purified CO.sub.2 and a further recycle gas comprising at least one sulfur-containing compound; and [0244] recycling said further recycle gas to said Claus process to convert said sulfur-containing compound(s) into elemental sulfur.

[0245] #26. A method according to #25, comprising: [0246] removing H.sub.2 and any other non-condensable gases from said compressed impure CO.sub.2 gas by distillation and/or partial condensation with phase separation to produce H.sub.2S-enriched CO.sub.2 fluid and H.sub.2-enriched CO.sub.2 gas; [0247] recycling said H.sub.2-enriched CO.sub.2 gas, or a further H.sub.2-enriched CO.sub.2 gas derived therefrom, as a second recycle gas to said hydrogenation process; and [0248] separating said H.sub.2S-enriched CO.sub.2 fluid by distillation and/or partial condensation with phase separation to produce said purified CO.sub.2 as overhead gas and a H.sub.2S-enriched bottoms liquid; [0249] vaporizing said H.sub.2S-enriched bottoms liquid to produce H.sub.2S-enriched gas as said first recycle gas;

[0250] wherein a portion of said second recycle gas, or of said H.sub.2-enriched gas derived therefrom, is purged.

[0251] #27. A method according to #26 wherein the amount of H.sub.2 recycled to said hydrogenation process is sufficient to meet demand in that process.

[0252] #28. A method according to #26 or #27 comprising recovering H.sub.2 gas from said second recycle gas in a membrane separation process to produce said further H.sub.2-enriched CO.sub.2 gas for recycle, together with a waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0253] #29. A method according to #26 to #28, wherein said purified CO.sub.2 overhead gas comprises one or more residual sulfur-containing compounds, said method comprises: [0254] removing H.sub.2S and any other sulfur-containing impurities from said purified CO.sub.2 overhead gas by selective adsorption or by chemical reaction with at least one solid metal oxide to form solid metal sulfide(s) and subsequent oxidative regeneration, to produce further purified CO.sub.2 and a third recycle gas comprising at least one sulfur-containing compound; and [0255] recycling said third recycle gas to said Claus process to convert said sulfur-containing compound(s) into elemental sulfur.

[0256] #30. Apparatus for desulfurizing crude CO.sub.2 gas comprising H.sub.2S and optionally at least one other sulfur-containing impurity, said apparatus comprising: [0257] a Claus unit for removing H.sub.2S from crude CO.sub.2 gas, said Claus unit comprising: [0258] a first inlet for oxidant gas comprising O.sub.2; [0259] a second inlet for said crude CO.sub.2 gas; [0260] a first outlet for Claus tail-gas comprising CO.sub.2, residual H.sub.2S and at least one other sulfur-containing impurity; and [0261] a second outlet for elemental sulfur; [0262] a source of oxidant gas comprising O.sub.2 in fluid flow communication with the first inlet of the Claus unit; [0263] a source of crude CO.sub.2 gas in fluid flow communication with the second inlet of the Claus unit; [0264] a hydrogenation unit for converting said at least one other sulfur-containing impurity in said Claus tail-gas into H.sub.2S, said hydrogenation unit comprising: [0265] a first inlet in fluid flow communication with the first outlet of said Claus unit; [0266] a second inlet for H.sub.2; and [0267] a first outlet for H.sub.2S-enriched CO.sub.2 tail-gas; [0268] a source of H.sub.2 in fluid flow communication with the second inlet of said hydrogenation unit; [0269] a cooling unit for cooling H.sub.2S-enriched CO.sub.2 tail gas, said cooling unit comprising: [0270] a first inlet in fluid communication with said first outlet of said hydrogenation unit; [0271] a first outlet for cooled H.sub.2S-enriched CO.sub.2 tail gas; and [0272] a second outlet for condensed water; [0273] a compression unit for compressing cooled H.sub.2S-enriched CO.sub.2 tail-gas or impure CO.sub.2 gas comprising H.sub.2S derived therefrom, said compression device comprising: [0274] an inlet in fluid flow communication with the first outlet of said cooling unit; and [0275] an outlet for compressed impure CO.sub.2 gas;

[0276] and [0277] a purification unit for removing H.sub.2S and any other sulfur-containing impurities from compressed impure CO.sub.2 gas by physical separation or by chemical reaction with at least one metal oxide to form solid metal sulfide(s) and subsequent oxidative regeneration, said purification unit comprising: [0278] a first inlet in fluid flow communication with the outlet of said compression unit; [0279] a first outlet for purified CO.sub.2; and [0280] a second outlet for a first recycle gas comprising at least one sulfur-containing compound,

[0281] wherein the second outlet of said purification unit is in fluid communication with said Claus unit.

[0282] #31. Apparatus according to #30 wherein said source of H.sub.2 is an H.sub.2 generation unit comprising an outlet for H.sub.2 in fluid communication with said second inlet of said hydrogenation unit.

[0283] #32. Apparatus according to #30 or #31 wherein said cooling unit is a direct contact cooler further comprising a second inlet for cooling water.

[0284] #33. Apparatus according to #30 wherein said purification unit comprises a selective adsorption unit comprising: [0285] at least one vessel having an upstream end and a downstream end, the or each vessel comprising: [0286] an adsorbent bed, said adsorbent bed comprising at least one layer of adsorbent material(s) selective for sulfur-containing compounds; [0287] a first inlet for compressed impure CO.sub.2 gas at said upstream end of the or each vessel; [0288] a first outlet for purified CO.sub.2 at said downstream end of the or each vessel; [0289] a second inlet for regeneration gas at said downstream end of the or each vessel; and [0290] a second outlet for spent regeneration gas at said upstream end of the or each vessel,

[0291] wherein said first inlet of said selective adsorption unit is in fluid flow communication with the outlet of said compression unit and wherein said second outlet is in fluid flow communication with said Claus unit.

[0292] #34. Apparatus according to #33 wherein said adsorbent bed in the or each vessel comprises at least one layer of adsorbent material(s) selective for water downstream of said at least one layer of adsorbent material(s) selective for sulfur-containing compound(s).

[0293] #35. Apparatus according to #33 or #34 comprising a drier unit downstream of said selective adsorption unit, said drier unit comprising: [0294] an inlet in fluid flow communication with the first outlet of said selective adsorption unit; and [0295] an outlet for dry purified CO.sub.2 in fluid flow communication with the inlet of said compression unit.

[0296] #36. Apparatus according to Claim #30 wherein said purification unit comprises a reactor comprising: [0297] at least one vessel having an upstream end and a downstream end, the or each vessel comprising: [0298] a bed comprising at least one solid metal oxide; [0299] a first inlet for compressed impure CO.sub.2 gas at said upstream end of the or each vessel; [0300] a first outlet for purified CO.sub.2 at said downstream end of the or each vessel; [0301] a second inlet for regeneration gas at said downstream end of the or each vessel; and [0302] a second outlet for spent regeneration gas at said upstream end of the or each vessel,

[0303] wherein said first inlet of said reactor is in fluid flow communication with the outlet of said compression device and wherein said second outlet is in fluid flow communication with said Claus unit.

[0304] #37. Apparatus according to #36 wherein the or each vessel comprises at least one layer of adsorbent material(s) selective for water downstream of the bed comprising said solid metal oxide(s).

[0305] #38. Apparatus according to #36 or #37 comprising a drier unit downstream of said reactor, said drier unit comprising: [0306] an inlet in fluid communication with the first outlet of said reactor; and [0307] an outlet for dry purified CO.sub.2 in fluid flow communication with said compression unit.

[0308] #39. Apparatus according to any of #30 to #38 comprising: [0309] a selective amine absorption unit for recovering H.sub.2S from H.sub.2S-enriched CO.sub.2 tail gas, said selective amine absorption unit comprising: [0310] an inlet in fluid flow communication with the first outlet of said cooling unit; and [0311] a first outlet for H.sub.2S-depleted CO.sub.2 tail-gas in fluid flow communication with the inlet of said compression unit; and [0312] a second outlet for recovered H.sub.2S in fluid flow communication with said Claus unit.

[0313] #40. Apparatus according to #39 comprising: [0314] a non-selective amine absorption unit for recovering CO.sub.2 and residual H.sub.2S from H.sub.2S-depleted CO.sub.2 tail-gas, said non-selective amine absorption unit comprising: [0315] an inlet in fluid flow communication with the first outlet of said selective amine absorption unit; [0316] a first outlet for impure CO.sub.2 gas in direct fluid flow communication with the inlet of said compression unit; and [0317] a second outlet for waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0318] #41. Apparatus according to #39 wherein the first outlet of said selective amine adsorption unit is in direct fluid flow communication with the inlet of said compression unit.

[0319] #42. Apparatus according to #41 wherein said purification unit is a selective adsorption unit or a reactor, said apparatus further comprising: [0320] a further purification unit for further purifying purified CO.sub.2, said further purification unit comprising: [0321] an inlet for purified CO.sub.2 in fluid flow communication with said first outlet of said selective adsorption unit or said reactor; [0322] a first outlet for further purified CO.sub.2; and [0323] a second outlet for a second recycle gas comprising CO.sub.2 and H.sub.2 in fluid flow communication with said hydrogenation unit,

[0324] and [0325] a purge line in fluid flow communication with the second outlet of said further purification unit.

[0326] #43. Apparatus according to #42 comprising: [0327] a membrane separation unit for recovering H.sub.2 gas from second recycle gas, said membrane separation unit comprising: [0328] an inlet for second recycle gas in fluid flow communication with the second outlet of said further purification unit; [0329] a first outlet for H.sub.2-enriched gas in direct fluid flow communication with said hydrogenation unit; and [0330] a second outlet for waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0331] #44. Apparatus according to any of #30 to #32 wherein the first outlet of said hydrogenation unit is in direct fluid flow communication with the inlet of said compression unit.

[0332] #45. Apparatus according to #44 wherein said purification unit is a selective adsorption unit or a reactor, said apparatus further comprising: [0333] a further purification unit for further purifying purified CO.sub.2, said further purification comprising: [0334] an inlet for purified CO.sub.2 in fluid flow communication with said first outlet of said selective adsorption unit or said reactor; [0335] a first outlet for further purified CO.sub.2; and [0336] a second outlet for a second recycle gas comprising CO.sub.2 and H.sub.2 in fluid flow communication with said hydrogenation unit,

[0337] and [0338] a purge line in fluid flow communication with the second outlet of said further purification unit.

[0339] #46. Apparatus according to #45 comprising: [0340] a membrane separation unit for recovering H.sub.2 gas from second recycle gas, said membrane separation unit comprising: [0341] an inlet for second recycle gas in fluid flow communication with the second outlet of said further purification unit; [0342] a first outlet for H.sub.2-enriched permeate gas in direct fluid flow communication with an inlet of said hydrogenation unit; and [0343] a second outlet for waste retentate gas comprising CO.sub.2 and at least one non-condensable gas.

[0344] #47. Apparatus according to any of #30 to #32 comprising: [0345] a non-selective amine absorption unit for recovering CO.sub.2 and H.sub.2S from H.sub.2S-enriched CO.sub.2 tail-gas, said non-selective amine absorption unit comprising: [0346] an inlet in direct fluid flow communication with the outlet of said cooling unit; [0347] a first outlet for impure CO.sub.2 gas in direct fluid flow communication with the inlet of said compression unit; and [0348] a second outlet for waste gas comprising CO.sub.2 and at least one non-condensable gas.

[0349] #48. Apparatus according to any of #30 to #32 wherein said purification unit is a single stage purification unit comprising: [0350] an inlet for compressed impure CO.sub.2 in fluid flow communication with the outlet of said compression unit; [0351] a first outlet for H.sub.2S-enriched CO.sub.2 fluid; [0352] a second outlet for H.sub.2-enriched CO.sub.2 gas in fluid flow communication with an inlet of said hydrogenation unit;

[0353] said apparatus comprising a selective adsorption unit comprising: [0354] at least one vessel having an upstream end and a downstream end, the or each vessel comprising: [0355] an adsorbent bed, said adsorbent bed comprising at least one layer of adsorbent material(s) selective for sulfur-containing compound(s); [0356] a first inlet for H.sub.2S-enriched CO.sub.2 fluid at said upstream end of the or each vessel; [0357] a first outlet for purified CO.sub.2 at said downstream end of the or each vessel; [0358] a second inlet for regeneration gas at said downstream end of the or each vessel; and [0359] a second outlet for spent regeneration gas at said upstream end of the or each vessel,

[0360] wherein said first inlet of said selective adsorption vessel is in fluid flow communication with the first outlet of said single stage purification unit and wherein said second outlet is in fluid flow communication with said Claus unit.

[0361] #49. Apparatus according to any of #30 to #32 wherein said purification unit is a single stage purification unit comprising: [0362] an inlet for compressed impure CO.sub.2 in fluid flow communication with the outlet of said compression unit; [0363] a first outlet for H.sub.2S-enriched CO.sub.2 fluid; [0364] a second outlet for H.sub.2-enriched CO.sub.2 gas in fluid flow communication with an inlet of said hydrogenation unit;

[0365] said apparatus comprising a reactor comprising: [0366] at least one vessel having an upstream end and a downstream end, the or each vessel comprising: [0367] a bed comprising at least one solid metal oxide; [0368] a first inlet for H.sub.2S-enriched CO.sub.2 fluid at said upstream end of the or each vessel; [0369] a first outlet for purified CO.sub.2 at said downstream end of the or each vessel; [0370] a second inlet for regeneration gas at said downstream end of the or each vessel; and [0371] a second outlet for spent regeneration gas at said upstream end of the or each vessel,

[0372] wherein said first inlet of said reactor is in fluid flow communication with the first outlet of said single stage purification unit and wherein said second outlet is in fluid flow communication with said Claus unit.

[0373] #50. Apparatus according to any of #30 to #32 wherein said purification unit comprises a purification unit comprising a first stage and a second stage; [0374] said first stage comprising: [0375] an inlet for compressed impure CO.sub.2 in fluid flow communication with the outlet of said compression unit; [0376] a first outlet for H.sub.2S-enriched CO.sub.2 fluid; [0377] a second outlet for H.sub.2-enriched CO.sub.2 gas in fluid flow communication with an inlet of said hydrogenation unit; [0378] said second stage comprising: [0379] an inlet for H.sub.2S-enriched CO.sub.2 fluid in fluid flow communication with the first outlet of said first stage; [0380] a first outlet for purified CO.sub.2 gas; [0381] a second outlet for H.sub.2S-enriched gas in fluid flow communication with said Claus unit

[0382] and [0383] a purge line in fluid flow communication with the second outlet of said first stage of said purification unit.

[0384] #51. Apparatus according to #50 comprising: [0385] a membrane separation unit for recovering H.sub.2 gas from H.sub.2-enriched CO.sub.2 gas, said membrane separation unit comprising: [0386] an inlet for H.sub.2-enriched CO.sub.2 gas in fluid flow communication with the second outlet of said first stage of said purification unit; [0387] a first outlet for H.sub.2-enriched permeate gas in direct fluid flow communication with an inlet of said hydrogenation unit; and [0388] a second outlet for waste retentate gas comprising CO.sub.2 and at least one non-condensable gas.

[0389] #52. Apparatus according to #51 comprising a selective adsorption unit comprising: [0390] at least one vessel having an upstream end and a downstream end, the or each vessel comprising: [0391] an adsorbent bed, said adsorbent bed comprising at least one layer of adsorbent material(s) selective for sulfur-containing compound(s); [0392] a first inlet for purified CO.sub.2 at said upstream end of the or each vessel; [0393] a first outlet for further purified CO.sub.2 at said downstream end of the or each vessel; [0394] a second inlet for regeneration gas at said downstream end of the or each vessel; and [0395] a second outlet for spent regeneration gas at said upstream end of the or each vessel,

[0396] wherein said first inlet of said selective adsorption unit is in fluid flow communication with the first outlet of said second stage of said purification unit and wherein said second outlet is in fluid flow communication with said Claus unit.

[0397] #53. Apparatus according to #51 comprising a reactor comprising: [0398] at least one vessel having an upstream end and a downstream end, the or each vessel comprising: [0399] a bed comprising at least one solid metal oxide; [0400] a first inlet for purified CO.sub.2 at said upstream end of the or each vessel; [0401] a first outlet for further purified CO.sub.2 at said downstream end of the or each vessel; [0402] a second inlet for regeneration gas at said downstream end of the or each vessel; and [0403] a second outlet for spent regeneration gas at said upstream end of the or each vessel,

[0404] wherein said first inlet of said reactor is in fluid flow communication with the first outlet of said second stage of said purification unit and wherein said second outlet is in fluid flow communication with said Claus unit.

EXAMPLES

[0405] Particular embodiments of the invention will now be illustrated by computer modelling in the following examples.

Example 1

[0406] The process depicted in the flow sheet of FIG. 1 in which unit 36 is a reactor comprising a bed of mixed metal oxides of the type disclosed in U.S. Pat. No. 4,797,268, was modelled by computer using Aspen Plus (version 10) and the heat and mass balance data for key streams is provided in Table 1.

TABLE-US-00001 TABLE 1 100 101 102 103 104 105 Vapor Vapor Liquid Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Temper- C. 46.0 28.0 135.0 130.0 50.0 50.0 ature Pres- barg 0.8 0.8 0.5 0.3 0.1 0.1 sure Mole kmol/hr 1000.0 375.5 400.0 1785.2 1701.1 1824.7 Flows Mole Fractions CO.sub.2 0.6500 0.0000 0.0000 0.3585 0. 0.2515 H.sub.2S 0.4000 0.0000 0.0000 0.00 0.0134 0.0001 SO 0.0000 0.0000 0.0000 0.0017 0.0000 0.0000 H O 0.0500 0.0000 0.0000 0.237 0.11 0.1135 Sulfur 0.0000 0.0000 1.0000 0.001 0.0000 0.0 0 H.sub.2 0.0000 0.0000 0.0000 0.023 0.0272 0.0395 N.sub.2 0.0000 0.7800 0.0000 0.3880 0. 84 O.sub.2 0.0000 0.2100 0.0000 0.0000 0.0000 0.0000 107 108 109 110 111 112 Vapor Vapor Vapor Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Temper- 45.0 50.0 50.0 52.1 50.0 50.0 ature Pres- 1.0 30.0 30.0 1.0 35.0 0.0 sure Mole 541.0 518.2 8.8 85.9 500.7 1083.0 Flows Mole Fractions CO.sub.2 0.9487 0.8912 0.6 0. 1.0000 0.0527 H.sub.2S 0.0002 0.0002 0.0000 0.2 0.0000 0.0000 SO 0.0000 0.0000 0.0110 0.0012 0.0000 0.0000 H O 0.0511 0.0082 0. 0.11 0.0000 0.1447 Sulfur 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 H.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0427 N.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.7856 O.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 indicates data missing or illegible when filed

[0407] This example illustrates an overall CO.sub.2 recovery of 92.5 mol. % at a purity of 100 mol. %, i.e., complete removal of residual H.sub.2S (and water) from impure CO.sub.2.

Example 2

[0408] The process depicted in the flow sheet of FIG. 2 in which unit 50 is a reactor having a bed of mixed metal oxides of the type disclosed in U.S. Pat. No. 4,797,268 and unit 56 is a CPU of the type disclosed in U.S. Pat. No. 7,819,951, was modelled by computer using Aspen Plus (version 10) and the heat and mass balance data for key streams is provided in Table 2. In the model, the purge stream had zero flow.

TABLE-US-00002 TABLE 2 100 101 102 103 104 105 106 Vapor Vapor Liquid Vapor Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Phase Temper- C. 45.0 25.0 130.0 50.0 50.0 50.0 ature Pres- barg 0.5 0.5 0.5 2.3 0.1 0.1 sure Mole kmol/hr 1000.0 188.3 400.0 1078.7 745.2 3.5 Flows Mole Fractions CO.sub.2 0.0000 H.sub.2S 0.4030 0.0000 0.0083 SO 0.0000 0.0000 0.00 H O 0.0000 0.0000 0. Sulfur 0.0000 0.0024 H.sub.2 0.0000 0.0083 N.sub.2 .0000 O.sub.2 .0000 0.0000 107 108 109 110 111 112 113 Vapor Vapor Vapor Vapor Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Phase Temper- 50.5 30.0 50.0 42.3 20.0 26.0 28.8 ature Pres- 32.0 30.0 30.0 14.0 35.0 29. sure Mole 7.2 20.7 75 529.4 13.8 53.5 Flows Mole Fractions CO.sub.2 0.5953 H.sub.2S SO H O Sulfur H.sub.2 N.sub.2 O.sub.2 indicates data missing or illegible when filed

[0409] This example illustrates an overall CO.sub.2 recovery of 95.8 mol. % at a purity of 99.5 mol. % with the remainder being H.sub.2, i.e., complete removal of residual H.sub.2S (and water) from impure CO.sub.2.

Example 3

[0410] The process depicted in the flow sheet of FIG. 3 in which unit 36 is a reactor having a bed of mixed metal oxide of the type disclosed in U.S. Pat. No. 4,797,268 was modelled by computer using Aspen Plus (version 10) and the heat and mass balance data for key streams is provided in Table 3.

TABLE-US-00003 TABLE 3 100 101 102 103 104 107 108 110 111 115 Vapor Vapor Liquid Vapor Vapor Vapor Vapor Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Phase Phase Phase Phase Temper- C. 45.0 28.0 135.0 130.0 50.0 45.0 50.0 27.1 50.0 50.0 ature Pres- barg 0.9 0.8 0.5 0.3 0.1 1.0 30.0 1.0 30.0 0.0 sure Mole kmol/hr 1000.0 734.3 400.0 1667.7 1570.8 507.2 585. 103.1 5 3.7 963. Flows Mole Fractions CO.sub.2 0.5500 0.0000 0.0000 0.3634 0.3359 0.9218 0.9555 0.5428 1.0000 0.0645 H.sub.2S 0.4000 0.0000 0.0000 0.0093 0.0135 0.0349 0.0361 0.0000 0.0000 0.0000 SO 0.0000 0.0000 0.0000 0.0019 0.0000 0.0000 0.0000 0.2052 0.0000 0.0000 H O 0.0500 0.0000 0.0000 0.2521 0.1118 0.0434 0.0082 0.2520 0.0000 0.1549 Sulfur 0.0000 0.0000 1.0000 0.0015 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 H.sub.2 0.0000 0.0000 0.0000 0.0240 0.0261 0.0000 0.0000 0.0000 0.0000 0.0458 N.sub.2 0.0000 0.4900 0.0000 0.3478 0.4508 0.0000 0.0000 0.0000 0.0000 0.7348 O.sub.2 0.0000 0.2100 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 indicates data missing or illegible when filed

[0411] This example illustrates an overall CO.sub.2 recovery of 91.5 mol. % at 100 mol. % purity, i.e., complete removal of residual H.sub.2S (and water) from impure CO.sub.2.

Example 4

[0412] The process depicted in the flow sheet of FIG. 4 in which unit 50 is a reactor having a bed of mixed metal oxide of the type disclosed in U.S. Pat. No. 4,797,268 was modelled by computer using Aspen Plus (version 10) and the heat and mass balance data for key streams is provided in Table 4.

TABLE-US-00004 TABLE 4 100 101 102 103 104 106 Vapor Vapor Liquid Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Temper- C. 45.0 28.0 135.0 130.0 50.0 50.0 ature Pres- barg 0.9 0.8 0.5 0.3 0.1 30.0 sure Mole kmol/hr 1000.0 153.7 400.0 1085.1 754.8 675.8 Flows Mole Fractions CO.sub.2 0.5500 0.0000 0.0000 0.5838 0.8185 0.8120 H.sub.2S 0.4000 0.0000 0.0000 0.0005 0.0180 0.0201 SO 0.0000 0.0000 0.0000 0.0017 0.0000 0.0000 H O 0.0500 0.0000 0.0000 0.3870 0.1117 0.0052 Sulfur 0.0000 0.0000 1.0000 0. 0.0000 0.0000 H.sub.2 0.0000 0.0000 0.0000 0.369 0.535 0.0598 N.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 O.sub.2 0.0000 1.0000 0.0000 0.0000 0.0000 0.0000 107 108 110 111 112 115 Vapor Vapor Vapor Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Temper- 50.0 30.0 27.5 20.0 30.0 29.8 ature Pres- 30.0 30.0 1.0 14.0 25.0 23.5 sure Mole 595.0 65.7 94.63 529.3 13.4 52.3 Flows Mole Fractions CO.sub.2 0.9321 0.4221 0.5638 0.9854 0.3877 0.4350 H.sub.2S 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 SO 0.0000 0.0000 0.1440 0.0000 0.0000 0.0000 H O 0.0000 0.0000 0.2025 0.0000 0.0000 0.0000 Sulfur 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 H.sub.2 0.0679 0.5779 0.0000 0.0046 0.8323 0.5540 N.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 O.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 indicates data missing or illegible when filed

[0413] This example illustrates an overall CO.sub.2 recovery of 95.8 mol. % at a purity of 99.5 mol. % with the remainder being H.sub.2, i.e., complete removal of residual H.sub.2S (and water) from impure CO.sub.2.

Example 5

[0414] The process depicted in the flow sheet of FIG. 5 in which the purification unit 56 & 74 is of the type disclosed in FIG. 2 of U.S. Ser. No. 10/254,042A was modelled by computer using Aspen Plus (version 10) and the heat and mass balance data for key streams is provided in Table 5.

TABLE-US-00005 TABLE 5 100 101 102 103 104 106 Vapor Vapor Liquid Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Temper- C. 45.0 28.0 135.0 130.0 50.0 50.0 ature Pres- barg 0.9 0.3 0.5 0. 0.1 30.0 sure Mole kmol/hr 1000.0 1 3.3 399.9 1045.6 717.9 537.5 Flows Mole Fractions CO.sub.2 0.5500 0.0000 0.0000 0.5525 0.8114 0.9134 H.sub.2S 0.4000 0.0000 0.0000 0.0088 0.0189 0.0212 SO 0.0000 0.0000 0.0000 0.0015 0.0000 0.0000 H O 0.0500 0.0000 0.0000 0.3850 0.1117 0.0000 Sulfur 0.0000 0.0000 1.0000 0.0025 0.0000 0.0000 H.sub.2 0.0000 0.0000 0.0000 0.0255 0.0500 0.0553 N.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 O.sub.2 0.0000 1.0000 0.0000 0.0000 0.0000 0.0000 107 108 110 111 112 115 Vapor Vapor Vapor Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Temper- 20.0 30.0 30.0 20.0 30.0 29.5 ature Pres- 14.0 30.0 1.0 14.0 25.0 29.5 sure Mole 569.3 58.3 41.2 528.1 13.4 54.9 Flows Mole Fractions CO.sub.2 0.5718 0.4265 0.5719 0.5952 0. 21 0.439 H.sub.2S 0.0238 0.0000 0.3261 0.0001 0.0000 0.0000 SO 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 H O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 Sulfur 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 H.sub.2 0.0044 0.5735 0.0000 0.0047 0.0279 0.5603 N.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 O.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 indicates data missing or illegible when filed

[0415] This example illustrates an overall CO.sub.2 recovery of 95.6 mol. % at a purity of 99.5 mol. %. The product CO.sub.2 also contains about 0.5 mol. % H.sub.2 and no more than 100 ppm H.sub.2S which meets the required specification of H.sub.2S for sequestration.

Example 6

[0416] The process depicted in the flow sheet of FIG. 1 in which unit 36 is a selective adsorption unit of the type disclosed in WO2021130530A was modelled by computer using Aspen Plus (version 10) and the heat and mass balance data for key streams is provided in Table 6.

TABLE-US-00006 TABLE 6 100 101 102 103 104 105 Vapor Vapor Liquid Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Temper- C. 45.0 28.0 125.0 120.0 50.0 50.0 ature Pres- barg 0.5 0.5 0.5 0.3 0.1 0.1 sure Mole kmol/hr 1000.0 989.3 400.9 1942.7 1783.9 1582.5 Flows Mole Fractions CO.sub.2 0.5500 0.0000 0.0000 0.3582 0.3832 0.3585 H.sub.2S 0.4000 0.0000 0.0000 0.0084 0.0119 0.0001 SO 0.0000 0.0000 0.0000 0.0017 0.0000 0.0000 H O 0.0500 0.0000 0.0000 0.2301 0.1118 0.14 Sulfur 0.0000 0.0000 1.0000 0.0014 0.0000 0.0000 H.sub.2 0.0000 0.0000 0.0000 0.02 0.0282 0.0275 N.sub.2 0.0000 0.7300 0.0235 0.3774 0.4 0.4852 O.sub.2 0.0000 0.2100 0.0000 0.0000 0.0000 0.0000 107 108 109 110 111 115 Vapor Vapor Vapor Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Temper- 45.0 50.0 50.0 52.1 50.0 50.0 ature Pres- 1.0 29.5 30.0 1.0 30.0 0.0 sure Mole 5 .5 534.3 50.7 141.8 503.7 1034.4 Flows Mole Fractions CO.sub.2 0.9511 0.5617 0.5224 0.7768 1.0000 0.0550 H.sub.2S 0.0002 0.0002 0.0017 0.14 0.0000 0.0000 SO 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 H O 0.0437 0.0083 0.0759 0.0742 0.0000 0.1495 Sulfur 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 H.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0423 N.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.7624 O.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 indicates data missing or illegible when filed

[0417] This example illustrates an overall CO.sub.2 recovery of 91.6 mol. % at a purity of 100 mol. %, i.e., complete removal of residual H.sub.2S (and water) from impure CO.sub.2 using a selective adsorbent unit 36 (including the layer of water-adsorbent material).

Example 7

[0418] The process depicted in the flow sheet of FIG. 6 in which the purification unit 56 is of the type disclosed as the first stage in FIG. 1B of U.S. Ser. No. 10/254,042A was modelled by computer using Aspen Plus (version 10) and the heat and mass balance data for key streams is provided in Table 7.

TABLE-US-00007 TABLE 7 100 101 102 103 104 106 Vapor Vapor Vapor Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Temper- C. 45.0 28.0 135.0 130.0 50.0 50.0 ature Pres- barg 0.9 0.8 0.5 0.3 0.1 29.5 sure Mole kmol/hr 1000.0 163.6 400.0 1076.3 750.3 666.3 Flows Mole Fractions CO.sub.2 0.5500 0.0000 0.0000 0.5651 0.8173 0.9201 H.sub.2S 0.4000 0.0000 0.0000 0.0085 0.0181 0.0204 SO 0.0000 0.0000 0.0000 0.0017 0.0000 0.0000 H O 0.0500 0.0000 0.0000 0.3850 0.1117 0.0000 SULFU-01 0.0000 0.0000 1.0000 0.0024 0.0000 0.0000 H.sub.2 0.0000 0.0000 0.0000 0.0372 0.0529 0.0595 N.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 O.sub.2 0.0000 1.0000 0.0000 0.0000 0.0000 0.0000 107 108 110 111 112 115 Vapor Vapor Vapor Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Temper- 60.0 30.0 26.3 60.0 30.0 29.6 ature Pres- 29.5 30.0 1.0 29.5 25.0 29.5 sure Mole 598.4 57.9 85.4 526.5 12.9 55.1 Flows Mole Fractions CO.sub.2 0.9733 0.4512 0.6816 0.9955 0.3973 0.4638 H.sub.2S 0.0227 0.0000 0.0000 0.0000 0.0000 0.0000 SO 0.0000 0.0000 0.1592 0.0000 0.0000 0.0000 H O 0.0000 0.0000 0.1592 0.0000 0.0000 0.0000 SULFU-01 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 H.sub.2 0.0040 0.5458 0.0000 0.0045 0.6027 0.5362 N.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 O.sub.2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 indicates data missing or illegible when filed

[0419] This example illustrates an overall 002 recovery of 95.3 mol % at a purity of 99.5 mol. %. The product CO.sub.2 also contains less than 0.5 mol. % H.sub.2 and no H.sub.2S which meets the required specification of H.sub.2S for sequestration.

Example 8

[0420] The process depicted in the flow sheet of FIG. 7 (in which unit 26** represents the specific combination of units 26, 32 and 36 from FIG. 1) was modelled by computer using Aspen Plus (version 10) and the heat and mass balance data for key streams is provided in Table 8.

TABLE-US-00008 TABLE 8 100 101 102 103 104 110 111 115 Vapor Vapor Vapor Vapor Vapor Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Phase Temper- C. 45.0 28.0 135.0 130.0 50.0 23.4 50.0 50.0 ature Pres- barg 0.9 0.8 0.5 0.3 0.1 1.0 30.0 0.0 sure Mole kmol/hr 1000.0 838.0 400.0 1229.7 1652.6 68.7 503.7 1051.1 Flows Mole Fractions CO.sub.2 0.5500 0.0000 0.0000 0.3503 0.3763 0.8149 1.0000 0.0586 H.sub.2S 0.4000 0.0000 0.0000 0.0005 0.0024 0.0001 0.0000 0.0000 SO 0.0000 0.0000 0.0000 0.0003 0.0000 0.0587 0.0000 0.0000 H O 0.0500 0.0000 0.0000 0.2415 0.1118 0.1263 0.0000 0.1479 SULFU-01 0.0000 0.0000 1.0000 0.015 0.0000 0.0000 0.0000 0.0000 H.sub.2 0.0000 0.0000 0.0000 0.0231 0.0314 0.0000 0.0000 0.0490 N.sub.2 0.0000 0.7900 0.0000 0.3827 0.4780 0.0000 0.0000 0.7445 O.sub.2 0.0000 0.2100 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 indicates data missing or illegible when filed

[0421] This example illustrates an overall CO.sub.2 recovery of 91.6 mol. % at a purity of 1005 mol. %. Thus, while CO.sub.2 recovery is less than in other embodiments, the purity of the 002 is higher in this embodiment.

[0422] It will be appreciated that the invention is not restricted to the details described above with reference to the preferred embodiments but that numerous modifications and variations can be made without departing from the spirit and scope of the invention as defined in the following claims.

[0423] In this specification, unless expressly otherwise indicated, the word or is used in the sense of an operator that returns a true value when either or both of the stated conditions are met, as opposed to the operator exclusive or which requires only that one of the conditions is met. The word comprising is used in the sense of including rather than to mean consisting of.

[0424] All prior teachings above are hereby incorporated herein by reference. No acknowledgement of any prior published document herein should be taken to be an admission or representation that the teaching thereof was common general knowledge in Australia or elsewhere at the date thereof.