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    • 专利摘要:
    METHOD FOR TREATMENT OF A SUPPLY GAS CURRENT CONTAINING AT LEAST CARBON DIOXIDE AND HYDROGEN SULFIDE TO RECOVER A PURIFIED CO2 GAS CURRENT. The invention relates to a method for treating a hydrocarbon feed gas stream containing CO2 and H2S to recover a purified CO2 gas stream (vii), comprising: a. separating said feed gas stream into a sweetened gas stream (i), and an acid gas stream (ii); B. Introduce stream (ii) to a Claus unit in which an oxygen-rich stream is used as a combustible agent in the Claus furnace, thereby recovering a liquid elemental sulfur stream (iii) and a residual gas stream (iv ) ; ç. Introduce the current (iv) into a Waste Gas Treatment Unit (TGTU), thus separating said waste gas stream into a gas stream enriched in CO2 (v), and a stream enriched in sulfur compounds (vi); d. Compress the current (v) leaving the TGTU; and. Pass the compressed CO2 enriched gas through a CO2 purification unit, thus recovering a CO2 gas stream(...).
    公开号:BR112015000151B1
    申请号:R112015000151-3
    申请日:2013-06-13
    公开日:2021-06-08
    发明作者:Claire Weiss；Kamlesh Ghodasara；Frédéric POUSSE；Wolfgang Nehb；Eckhard Jüngst；Stefan Fraenkle；Sandeep Karode；Sylvain Gerard；Nicolas Chambron
    申请人:Total Sa；L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude；
    IPC主号:
    专利说明:

    field of invention
    [0001] The present invention relates to the removal of sulfur components and carbon dioxide contained in a hydrocarbon feed stream in order to recover the native carbon dioxide in a purified stream. More specifically, the present invention relates to a process for recovering native CO2 from a sour gas that contains CO2, H2S and other sulfur compounds, so that the recovered CO2 can then be sequestered or used for oil recovery enhanced (EOR) . Furthermore, the present invention relates to an installation for implementing such a process. Fundamentals
    [0002] Natural gas or gases associated with oil productions produced from geological reservoirs, or acidic refinery gases generally contain acidic contaminants such as carbon dioxide and/or hydrogen sulfide and/or other sulfur compounds such as mercaptans, COS, CS2, S. For most applications of these gas streams, acidic contaminants need to be removed, either partially or almost completely, depending on the application and the type of contaminant.
    [0003] Methods to remove carbon dioxide and/or hydrogen sulfide and/or other sulfur compounds from a hydrocarbon stream are known in the prior art.
    [0004] A common approach to removing acidic contaminants involves the use of solvents such as chemical solvent (amine-based solvent), hybrid solvent or physical solvent. These solvents have been widely disclosed in the art. However, if noticeable levels of sulfur compounds are present in the acid gas, the most common process to eliminate hydrogen sulfide is to convert said hydrogen sulfide to a non-hazardous product such as elemental sulfur, sending it to a recovery unit. of sulfur ("SRU").
    [0005] The Claus process is a known type of sulfur recovery process that allows the conversion of hydrogen sulfide into elemental sulfur. In a first step of said Claus process, hydrogen sulfide is partially burned with air in a Claus furnace to form sulfur dioxide which will react, in a second step, with hydrogen sulfide to form elemental sulfur according to the following reactions: (1) 2 H2S + 3 O2 ^ 2 SO2 + 2 H2O (2) 2 H2S + SO2 θ 3 S + 2 H2O
    [0006] In some embodiments, traces of remaining H2S are captured in a Waste Gas Treatment Unit (TGTU), positioned at the exit of the Claus unit to significantly increase sulfur recovery.
    [0007] At the output of TGTU, native CO2 is diluted by a large amount of nitrogen that comes from the air used for Claus combustion. To recover a purified CO2 stream, solvent-based CO2 capture technologies (eg, an amine-based solvent such as methylethanolamine (MEA) can be used. However, as CO2 is diluted in a large volume of nitrogen , the amine-based CO2 capture unit requires oversized equipment, thus impacting both CAPEX and OPEX.
    [0008] Additionally, an incinerator is generally connected to the output of the amine-based CO2 capture unit in order to continuously incinerate the remaining traces of sulfur compounds, hydrogen, carbon monoxide and hydrocarbons. It leads to significant fuel gas consumption and important gaseous CO2 emissions, which is a major disadvantage of such methods known in the art.
    [0009] Therefore, there is a need for a method that allows to recover native CO2 from a hydrocarbon feed gas stream that contains acidic compounds such as CO2, H2S and other sulfur compounds, with better yields, lower investments, lower CO2 emissions and reduced energy consumption compared to prior art processes.
    [00010] The present invention satisfies all these needs by providing a method in which:-a purified CO2 stream comprising at least 90% CO2 can be recovered,-an oxygen rich stream is used as a fuel agent for the Claus unit , thereby reducing the size and cost of equipment, -hydrogen can be efficiently separated from the CO2 stream and recovered, -a continuously working incinerator is not necessary, thus reducing system energy consumption and emission of carbon dioxide into the atmosphere, part of the CO2 stream can be recycled in the Claus furnace to cool it and facilitate oxygen-rich operations.
    [00011] Unless otherwise indicated, all percentages mentioned in this patent application are expressed as molar percentages. Summary of the inventionMethod
    [00012] An object of the present invention is a method for treating a hydrocarbon feed gas stream containing at least carbon dioxide and hydrogen sulfide to recover a purified CO2 gas stream (vii), said process comprising the following steps :The. Separating said hydrocarbon feed gas stream into a sweetened hydrocarbon gas stream (i), and an acidic gas stream (ii) comprising at least carbon dioxide and hydrogen sulfide; b. Introducing said acid gas stream (ii) to a Claus unit, in which an oxygen-rich stream is used as a combustible agent in the Claus furnace, thereby recovering a liquid elemental sulfur stream (iii) and a stream of tail gas (iv) comprising mainly carbon dioxide, hydrogen and sulfur compounds; c. Introduce the outgoing waste gas stream (iv) into a Waste Gas Treatment Unit (TGTU) thereby separating said waste gas stream into a gas stream enriched in CO2 also containing hydrogen and sweetened in sulfur compounds (v) , and a gas stream enriched in sulfur compounds (vi); d. Compress the CO2 enriched gas stream (v) exiting the TGTU;e. Pass the compressed CO2 enriched gas stream through a CO2 purification unit thereby recovering a purified CO2 gas stream (vii).
    [00013] In one embodiment, the combustible agent used in the Claus furnace of the Claus unit is an oxygen-rich stream, wherein the amount of nitrogen does not exceed 50%, is preferably less than 40%, more preferably less than 20%, and more preferably less than 10%.
    [00014] In one embodiment, the waste gas stream (iv), the CO2 enriched gas stream (v) and the purified CO2 gas stream (vii) also contain nitrogen.
    [00015] In one embodiment, the sour gas stream (ii) is enriched in H2S by a sour gas enrichment unit located upstream of the Claus unit.
    [00016] In one embodiment, the TGTU comprises an in-line burner or a waste gas heater, a hydrogenation reactor, a cooling contactor and optionally an absorber unit, in particular an amine-based absorber unit.
    [00017] In one embodiment, a CO2-enriched gas stream exiting the compression unit is dehydrated before entering the CO2 purification unit.
    [00018] In one embodiment, the CO2 purification unit is a cryogenic separation unit producing a purified CO2 gas stream (vii) and a lean CO2 stream (viii) .
    [00019] In one embodiment, the CO2 purification unit is a membrane unit producing a purified CO2 gas stream (vii) on the residue side and a lean CO2 stream (viii) on the permeate side.
    [00020] In one embodiment, the CO2 purification unit is an adsorption unit producing a purified CO2 gas stream (vii) and a lean CO2 stream (viii) .
    [00021] In one embodiment, the CO2 purification unit is an absorption unit producing a purified CO2 gas stream (vii) and a lean CO2 stream (viii) .
    [00022] In one embodiment, the CO2 purification unit is a combination of CO2 purification units.
    [00023] In one embodiment, part of the Claus tail gas stream (iv) is recycled to the Claus furnace prior to introduction into the TGTU.
    [00024] In one embodiment, part of the gas stream within the Claus unit is recycled to the Claus furnace by internal recycling.
    [00025] In one embodiment, part of the gas stream exiting the TGTU's cooling tower is recycled to the Claus furnace prior to introduction into the absorber unit.
    [00026] In one embodiment, part of the purified CO2 gas stream (vii) leaving the CO2 purification unit is recycled to Claus's furnace.
    [00027] In one embodiment, part of the lean CO2 stream (viii) exiting the CO2 purification unit is recycled upstream of or directly into the Claus furnace.
    [00028] In one embodiment, part of the lean CO2 stream (viii) leaving the CO2 purification unit is recycled between the Claus unit and the TGTU hydrogenation reactor.
    [00029] In one modality, step d) is eliminated. Device
    [00030] The present invention also relates to a device for carrying out the method as described above.
    [00031] The device of the present invention comprises in the direction of flow:- an acid gas removal unit providing a stream of acid gas; - a Claus unit operated with an oxygen-rich current; - a Waste Gas Treatment Unit that removes sulfur compounds; - a compression device; and- a CO2 purification device.
    [00032] In one embodiment, the Waste Gas Treatment unit comprises an in-line burner or a waste gas heater, a hydrogenation reactor, a cooling contactor and optionally an absorber unit, in particular an absorber unit with base into an amine.
    [00033] In one embodiment, the device further comprises an acid gas enrichment unit located upstream of the Claus unit.
    [00034] In one embodiment, the device further comprises a dehydrating device.
    [00035] In one embodiment, the CO2 depurification device is a cryogenic separation unit.
    [00036] In one embodiment, the CO2 depurification device is a membrane unit.
    [00037] In one embodiment, the CO2 depurification device is an adsorption unit.
    [00038] In one embodiment, the CO2 depurification device is an absorption unit.
    [00039] In one embodiment, the CO2 purification device is a combination of CO2 purification units.
    [00040] In one embodiment, the device further comprises a recycling line to collect part of the gas stream between the Claus unit and the TGTU and inject it into the Claus furnace.
    [00041] In one embodiment, the device further comprises a recycling line to collect part of the gas stream inside the Claus unit and inject it into the Claus furnace by internal recycling.
    [00042] In one embodiment, the device further comprises a recycling line to collect part of the gas stream between the cooling tower and the TGTU absorber unit and inject it into the Claus oven.
    [00043] In one embodiment, the device additionally comprises a recycling line to collect part of the purified CO2 gas stream (vii) that leaves the CO2 purification unit and inject it into Claus's oven.
    [00044] In one embodiment, the device further comprises a recycle line to collect part of the lean CO2 stream (viii) leaving the CO2 purification unit and inject upstream of or directly into the Claus oven.
    [00045] In one embodiment, the device additionally comprises a recycling line to collect part of the lean CO2 stream (viii) that leaves the CO2 purification unit and inject between the Claus unit and the TGTU hydrogenation reactor. Brief description of the figures
    [00046] Figure 1 is a schematic view of a classic native CO2 recovery unit as known in the prior art.
    [00047] Figure 2 is a schematic view of the native CO2 recovery unit to carry out the method of the present invention.
    [00048] Figure 3 is a schematic view of the native CO2 recovery unit for carrying out the method of the present invention, in which the CO2 purification uses a membrane unit.
    [00049] Figure 4 is a schematic view of the native CO2 recovery unit to carry out the method of the present invention, in which the CO2 purification uses a cryogenic separation unit. Detailed description of the invention
    [00050] The process according to the invention applies to the treatment of a hydrocarbon gas stream containing acidic contaminants, such as a natural gas stream or refinery gas stream. Acidic contaminants are mainly composed of carbon dioxide and hydrogen sulfide. However, the gas stream may also contain other acidic contaminants such as sulfur compounds, in particular mercaptans.
    [00051] Typically, the hydrocarbon feed gas stream may contain (on a dry basis) from 1% to 70% of CO2, in particular from 2% to 40% of CO2, more particularly from 3% to 20% of CO2 and from 0.5% to 50% of H2S, in particular from 0.5% to 40% of H2S, more particularly from 0.5% to 20% of H2S.
    [00052] According to step a) of the method of the invention, the hydrocarbon feed gas stream is separated into a sweetened hydrocarbon gas stream (i), and an acid gas stream (ii) comprising at least dioxide of carbon and hydrogen sulfide.
    [00053] By "sweetened hydrocarbon gas stream" is meant a hydrocarbon gas stream containing less acidic contaminants than the hydrocarbon feed gas stream. The acid gas stream (ii), on the other hand, is enriched in acidic contaminants compared to the hydrocarbon feed gas stream.
    [00054] Methods for obtaining a sweetened hydrocarbon gas stream (i) and acid gas stream (ii) from a hydrocarbon feed gas stream containing acid contaminants are well known to the person skilled in the art. Any sweetening method can be used to carry out step a) of the present invention. Such methods include solvent treatment such as chemical solvent treatment, in particular amine based solvent treatment, hybrid solvent treatment or physical solvent treatment.
    [00055] Typically, the acid gas stream (ii) contains (on a dry basis) from 10% to 90% of CO2, in particular from 25% to 75% of CO2 and from 10% to 90% of H2S, in particular from 25% to 75% H2S.
    [00056] According to step b) of the method of the invention, the acid gas stream (ii) is then introduced to a Claus unit in which an oxygen rich stream (also called "oxygen or oxygen plus air") is used as a combustible agent in the Claus furnace (also called the combustion furnace), thereby recovering (iii) an elemental sulfur liquid stream (iii) and a residual gas stream (iv) comprising mainly carbon dioxide, hydrogen and sulfur compounds.
    [00057] In one embodiment, the sour gas stream (ii) is enriched in a sour gas enrichment unit located upstream of the Claus unit to increase the H2S content in the sour gas stream (ii).
    [00058] As explained earlier, a Claus unit allows the conversion of hydrogen sulfide into elemental sulfur according to the following reactions: (1) 2 H2S + 3 O2 ^ 2 SO2 + 2 H2O(2) 2 H2S + SO2 θ 3S + 2 H2O.
    [00059] In a Claus unit, air is generally used as a fuel agent for the conversion of hydrogen sulfide to sulfur dioxide. However, since air contains about 80% nitrogen and 20% oxygen, the use of air as a combustible agent results in a large volume of nitrogen in the process gas stream, which in turn requires large equipment. .
    [00060] According to the present invention, an oxygen rich stream is used as a combustible agent, instead of air, in order to reduce the process gas volume. By "oxygen rich stream" is meant a stream containing an amount of oxygen from 20% to 100%, preferably from 70% to 100% and more preferably from 97% to 100%. The balanced components can be CO2, N2, Ar, Xe, H2, H2O, etc.
    [00061] In one embodiment, the combustible agent used in the Claus furnace of the Claus unit is an oxygen-rich stream, wherein the amount of nitrogen does not exceed 50%, is preferably less than 40%, more preferably less than 20%, and more preferably less than 10%.
    [00062] The oxygen-rich stream can be obtained from atmospheric air using an air separation unit (ASU) that separates atmospheric air into its primary components: mostly nitrogen and oxygen, and sometimes also argon and other gases rare inerts. Any suitable method of separation can be used in the process of the invention, for example, cryogenic distillation.
    [00063] The Claus reactions described above are quite exothermic. Typically, the pressure in the Claus furnace is 0.17 to 0.19 MPa (1.7 to 1.9 bar) and the temperature must be maintained between 900 °C and 1450 °C. Hot gas from the combustion chamber passes through the reaction and condensation steps to produce liquid elemental sulfur (iii).
    [00064] The use of an oxygen-rich current when a combustible agent in the Claus furnace promotes side reactions that result in the formation of hydrogen. The residual gas stream (iv) downstream of the Claus unit thus contains smaller amounts of hydrogen.
    [00065] Thus, according to the invention, the waste gas stream (iv) recovered at the Claus unit outlet mainly contains carbon dioxide and water, but also contains a certain amount of hydrogen, nitrogen and possibly carbon monoxide, as well as trace amounts of sulfur compounds such as hydrogen sulfide and sulfur dioxide.
    [00066] Depending on the CO2 purification technology, the nitrogen content in the oxygen rich stream can be adjusted depending on the nitrogen content that can be accepted in the purified CO2 stream.
    [00067] The waste gas stream (iv) leaving the Claus unit generally contains (on a dry basis) at least 40% CO2, preferably from 50% to 90% CO2. Balanced components can be H2, N2, H2S, SO2, CO, Air, COS, etc.
    [00068] According to step c) of the method of the invention, the waste gas stream (iv) leaving the Claus unit is introduced into a Waste Gas Treatment Unit (TGTU), thus separating said stream from tail gas (iv) in a gas stream enriched in CO2 (v) containing hydrogen and sweetened in sulfur compounds, and a gas stream enriched in sulfur compounds (vi).
    [00069] The TGTU allows the conversion of sulfur compounds from the waste gas stream (iv) into H2S.
    [00070] In one embodiment, the TGTU comprises four main equipment in the flow direction: - a burner in the feed line or a waste gas heater to heat the waste gas stream (iv), - a hydrogenation reactor to convert the sulfur compounds from the tail gas stream (iv) into H2S, - a cooling contactor which removes extra water from the gas stream, and - an absorber unit (based on amine) to separate the sulfur compounds (mainly H2S) from the other constituents of the residual gas stream (iv) .
    [00071] TGTU includes Waste Gas Treatment Units based on amine or residual gas treatment below dew point or Waste Gas Treatment Units based on direct oxidation. The TGTU used to implement the method of the invention is not limited to these TGTUs. Any type of TGTU can be suitable to implement the method of the invention.
    [00072] As a result, two streams are recovered at the output of the TGTU: a gas stream enriched in CO2 containing hydrogen (v) , and a gas stream enriched in sulfur compounds (vi) (ie containing more sulfur compounds than the residual gas (iv)) on the other hand.
    [00073] Typically, the gas stream enriched in sulfur compounds (vi) is introduced into the Claus unit.
    [00074] The in-line burner/or waste gas heater positioned upstream of the hydrogenation reactor provides the heat and the hydrogenation or heat.
    [00075] The hydrogenation reactor typically comprises a catalyst bed where sulfur compounds such as SO2, S, COS and CS2 are converted into H2S. The hydrogenated stream is then passed through a cooling contactor, preferably a water cooling tower, in order to reduce the temperature and remove extra water.
    [00076] The gas stream at the cooling outlet leaving the cooling tower is then passed through an absorber unit, in which sulfur compounds, mainly H2S, are absorbed through an absorption solution. Preferably, the absorber unit is amine based. A gas stream enriched in CO2 (v) thus is recovered from the absorber unit, which contains less than 500 ppm of H2S, preferably less than 100 ppm of H2S. The sulfur-containing stream is separated from the absorption solution and recycled back to the Claus furnace.
    [00077] Alternatively, the recovered gas stream in the cooling outlet may not be passed through the absorber unit if the H2S content in the CO2 stream is less than the required H2S specification in the purified CO2 stream. In this case, the TGTU only comprises an in-line burner or a waste gas heater, a hydrogenation reactor and a cooling contactor.
    [00078] At the outlet of the TGTU, the gas stream enriched with CO2 (v) generally contains (on a dry basis) at least 40% carbon dioxide, preferably from 50% to 90% carbon dioxide.
    [00079] In one embodiment, the gas stream enriched with CO2 (v) also comprises nitrogen due to the presence of nitrogen in the oxygen rich stream used as a combustible agent.
    [00080] In other embodiments, according to step d) of the method of the invention, the gas stream enriched with CO2 (v) leaving the TGTU is compressed, preferably at a pressure of 1 to 10 MPa (10 bar to 100 bar), more preferably from 2 to 6 MPa (20 bar to 60 bar). Of course, the compression step can be eliminated if the purification technology does not require it.
    [00081] In one embodiment, the compressed CO2 enriched gas stream is passed through a dehydration unit in order to complete the removal of water contained in the CO2 stream. Preferably, the dehydration unit is a glycol unit or an adsorption unit, but any other suitable technique can be used.
    [00082] According to step e) of the method of the invention, the compressed CO2 enriched gas stream is then passed through a CO2 purification unit, such as the CO2/H2 separation unit, thus recovering a purified CO2 gas stream (vii) on the one hand and a lean CO2 stream (viii) on the other side, which comprises hydrogen.
    [00083] Any suitable CO2 purification unit can be used. Preferably, the CO2 purification unit is a cryogenic separation unit, a membrane unit, an adsorption unit, an absorption unit or a combination thereof.
    [00084] The cryogenic separation unit produces a purified CO2 gas stream (vii) and a non-condensable stream (viii) containing H2, CO2, N2, Ar, etc. so it can be retrieved for further use.
    [00085] As for membrane separation, the CO2 recovery rate in general is lower than that of cryogenic separation. However, as the membrane permeate comprises a large amount of carbon dioxide, it can be advantageously recycled to the Claus furnace in order to facilitate oxygen-rich operations. In the case of membrane separation, the CO2 recovery rate can be increased by recycling all or part of the membrane permeate into the Claus furnace.
    [00086] In case of low CO2 content in the compressed CO2 enriched gas stream, a combination of CO2 purification units can be implemented advantageously to increase CO2 recovery.
    [00087] The CO2 stream may be needed to control the temperature of the Claus furnace and recycled at different stages of the process. Preferably, the recycled CO2 stream is collected as far upstream as possible in order to reduce the volume of gas to be treated by the downstream units.
    [00088] In one embodiment, part of the gas stream exiting the TGTU's cooling tower is recycled to the Claus furnace prior to introduction into the absorber unit.
    [00089] In one embodiment, part of the gas stream (iv) exiting the Claus unit is recycled to the Claus furnace prior to introduction into the TGTU.
    [00090] In one embodiment, part of the gas stream within the Claus unit is recycled to the Claus furnace by internal recycling.
    [00091] In one embodiment, part of the purified CO2 gas stream (vii) leaving the CO2 purification unit is recycled to Claus's furnace.
    [00092] In one embodiment, part of the lean CO2 stream (viii) leaving the CO2 purification unit is recycled between the Claus unit and the TGTU hydrogenation reactor.
    [00093] In one embodiment, part of the lean CO2 stream (viii) exiting the CO2 purification unit is recycled upstream of or directly into the Claus furnace.
    [00094] A combination of these recycles can also be performed.
    [00095] The purified CO2 stream (vii) obtained by the method of the invention may contain from 90% to 100% of CO2, preferably from 97% to 99.9% of CO2. Then it can be sequestered or used for enhanced oil recovery (EOR).
    [00096] In one embodiment, the purified CO2 gas stream (vii) also contains nitrogen due to the presence of nitrogen in the oxygen-rich stream used as a combustible agent.
    [00097] As mentioned above, the purity of the CO2 stream obtained by the method of the invention will depend on the type of combustible agent used in Claus furnace, TGT technology and CO2 purification technology. To obtain a CO2 stream with high purity (98% or more), it is preferable to use oxygen rich stream with high purity (for Claus oven) . However, for a lower purity of the CO2 rich stream produced, a lower purity of the oxygen rich stream (for the Claus oven) may be preferable as it is cheaper to implement.
    [00098] Another object of the present invention is a device for carrying out the method of the invention as described above, said device comprising in the flow direction: - an acid gas removal unit providing a stream of acid gas; - a Claus unit operated with an oxygen-rich current; - a Waste Gas Treatment Unit that removes sulfur compounds; - a compression device; and- a CO2 purification device.
    [00099] The sour gas removal unit can be a unit that performs a classic sweetening method such as by chemical solvent, hybrid solvent or physical solvent. For example, it could be an amine wash unit. Amine solutions are well known to the person skilled in the art. According to the desired specification, amine solutions can include DEA (diethanolamine), MDEA (methyl diethanolamine) or activated MDEA or any other solution.
    [000100] As mentioned earlier, the combustible agent for the Claus unit can be an oxygen-rich stream. The oxygen rich current can be produced by an air separation unit. In addition, part of the purified CO2 stream (vii) can be recycled to the Claus unit to facilitate oxygen-rich operations.
    [000101] In one embodiment, the device further comprises a sour gas enrichment unit located between the sour gas removal unit and the Claus unit to increase the content of H2S in the stream.
    [000102] In one embodiment, the Waste Gas Treatment unit (TGTU) comprises in the flow direction an in-line burner or a waste gas heater, a hydrogenation reactor, a cooling contactor and optionally an absorber unit, in particular an amine-based absorber unit. As explained above, it may not be necessary to include an absorber unit in the TGTU if the H2S content in the CO2 stream at the output of the hydrogenation reactor is less than the required specification in the purified CO2 stream. In this case, the TGTU only comprises an in-line burner or a waste gas heater, a hydrogenation reactor and a cooling contactor.
    [000103] In one embodiment, TGTU includes waste gas treatment below dew point or Waste Gas Treatment Units based on direct oxidation. The TGTU used to implement the method of the invention is not limited to these TGTUs. Any type of TGTU can be suitable to implement the method of the invention.
    [000104] In one embodiment, the device further comprises a dehydration device located upstream of the CO2 purification device. Depending on the compression setting, dehydration can be located between two stages of compression. Preferably, the CO2 purification device is a cryogenic separation unit, a membrane unit, an adsorption unit or an absorption unit.
    [000105] In one embodiment, the CO2 purification device is a combination of CO2 purification technologies.
    [000106] The device may additionally comprise one or several recycle lines as follows:- a recycle line to collect part of the gas stream (iv) between the Claus unit and the TGTU and inject into the Claus furnace;- a recycle line to collect part of the gas stream inside the Claus unit is recycled to the Claus furnace,- a recycle line to collect part of the gas stream between the TGTU cooling tower and the absorber unit and inject into the furnace from Claus, - a recycle line to collect part of the purified CO2 gas stream (vii) leaving the CO2 purification unit and inject it into the Claus furnace, - a recycle line to collect part of the lean CO2 stream (viii ) that leaves the CO2 purification unit and inject between the Claus unit and the TGTU hydrogenation reactor, - a recycle line to collect part of the lean CO2 stream (viii) that leaves the CO2 purification unit and inject upstream from or directly in the Claus oven.
    [000107] The invention is further described in figures 1, 2, 3 and 4. These examples are offered to illustrate the invention and should in no way be seen as limiting the invention.
    [000108] Figure 1 provides a schematic view of a classic CO2 recovery unit, as known in the prior art.
    [000109] In Figure 1, a sour gas stream is introduced into an acid gas removal unit (AG U), thus providing a fresh gas stream and an acid gas stream containing 48% carbon dioxide and 43 % hydrogen sulfide. The acid gas stream then enters a Claus unit at a pressure of 0.1 to 0.2MPa (1 to 2 bar). In the Claus unit hydrogen sulfide is converted to elemental sulfur using arc containing 20% oxygen and 80% nitrogen as a fuel agent, thus leading to the dilution of carbon dioxide with nitrogen. This mixture then enters a Waste Gas Treatment Unit (TGTU) to remove traces of remaining sulfur compounds, leading to a waste gas stream mixture composed of 60% nitrogen, 30% carbon dioxide and 10% Water. At the exit of the TGTU, said mixture is then contacted with an amine-based solvent in order to capture the carbon dioxide, thereby separating the remaining carbon dioxide from nitrogen.
    [000110] Typically, MethylEthanolamine (MEA) is used as the most common amine solvent to capture CO2 from the TGT purge gas. After the absorption step, the carbon dioxide-enriched chemical amine solvent is sent to a regenerator operating at a pressure ranging from 0.1 to 0.2 MPa (1 to 2 bar) to recover the depleted amine solvent in carbon dioxide and to provide a stream of carbon dioxide gas saturated with water. After the compression and dehydration steps (typically using a TEG unit), a stream composed of about 99.9% carbon dioxide and 600 ppm hydrogen sulfide is obtained.
    [000111] The remaining mixture leaving the CO2 capture absorber comprising 87% nitrogen, 4% carbon dioxide, 6% water and 3% hydrogen is sent to the incinerator.
    [000112] As a result, the typical native CO2 recovery from such capture is about 90%.
    [000113] Figure 2 provides a schematic view of the native CO2 recovery unit to perform the method of the present invention.
    [000114] In Figure 2, a sour gas stream is introduced into an acid gas removal unit (AGRU), thus providing a sweet gas stream (i) and an acid gas stream (ii) containing 48% dioxide carbon and 43% hydrogen sulfide. A classic sweetening method using a chemical solvent, a hybrid solvent or a physical solvent is used as an acid gas removal unit (AGRU) . The acid gas stream (ii) then enters a Claus unit using oxygen-rich stream at a pressure of 0.17 to 0.19 MPa (1.7 to 1.9 bar). In fact, hydrogen sulfide is transformed into elemental sulfur in the Claus unit using oxygen-rich stream as a combustible agent. Two streams exit the Claus unit: an elemental sulfur stream (iii) and a waste gas stream (iv) comprising mainly CO2, H2 and sulfur compounds. Then, the waste gas stream (iv) enters a Waste Gas Treatment Unit (TGTU) in order to remove traces of remaining sulfur compounds, thus producing a gas effluent (v) composed of 85% carbon dioxide , 10% hydrogen, 5% water and 100 ppm hydrogen sulfide. Then, this gas effluent (v) enters the compression unit, then a CO2 purification unit, thus forming, on the one hand, a stream of purified carbon dioxide (vii) and, on the other hand, a stream of lean carbon dioxide (viii) comprising carbon dioxide and hydrogen.
    [000115] The composition of the purified carbon dioxide stream (vii) and lean CO2 stream (viii) will depend on the type of separation technology.
    [000116] One or several recycle lines can be included in the process: - recycle line (1), in which part of the gas stream leaving the cooling tower is recycled to the Claus furnace before introduction into the absorber unit, - recycle line (2), in which part of the gas stream (iv) leaving the Claus unit is recycled to the Claus furnace before introduction into the TGTU, - recycle line (3), in which part of the stream gas inside the Claus unit is recycled to the Claus furnace by internal recycling, - recycling line (4), in which part of the purified CO2 gas stream (vii) leaving the CO2 purification unit is recycled to the Claus furnace, - recycling line (5), in which part of the lean CO2 stream (viii) leaving the CO2 purification unit is recycled between the Claus unit and the TGTU hydrogenation reactor, - recycling line (6), in which part of the lean CO2 stream (viii) leaving the CO2 purification unit is recycled upstream of or directly in Claus' oven.
    [000117] Figure 3 provides a schematic view of the native CO2 recovery unit to carry out the method of the present invention, in which the CO2 purification unit is a membrane.
    [000118] In Figure 3, a sour gas stream is introduced into an acid gas removal unit (AGRU), thus providing a sweet gas stream (i) and an acid gas stream (ii) containing 48% dioxide carbon and 43% hydrogen sulfide. A classic sweetening method using a chemical solvent, a hybrid solvent or a physical solvent is used as an acid gas removal unit (AGRU) . The acid gas stream (ii) then enters a Claus unit using oxygen rich stream as a combustible agent in the Claus furnace at a pressure of 0.17 to 0.19 MPa (1.7 to 1.9 bar ) . Two streams exit the Claus unit: an elemental sulfur stream (iii) and a waste gas stream (iv) comprising mainly CO2, H2 and sulfur compounds. Then, the waste gas stream (iv) enters a Waste Gas Treatment Unit (TGTU), the so-called TGTU which is an amine-based technology, thus producing a gas effluent (v) composed of 85% of carbon dioxide, 8% hydrogen, 7% water and 100 ppm hydrogen sulfide. Then, this effluent gas (v) enters a compression unit and a dehydration unit, then a membrane unit for CO2 purification, thus forming a purified carbon dioxide residue and a permeate stream containing carbon dioxide. carbon and hydrogen.
    [000119] The purified carbon dioxide waste stream (vii), at a pressure close to the discharge pressure of the compression unit, is composed of 98% carbon dioxide, 1.7% hydrogen, 0.3% of carbon monoxide and less than 100 ppm of hydrogen sulfide. The permeate stream (viii), at about 0.2 MPa (2 bar) is composed of approximately 70% carbon dioxide and 30% hydrogen. Said membrane permeate stream (viii) is totally or partially recycled upstream of or directly in the Claus unit. As a result of total recycling, typical native CO2 recovery from this process scheme is about 100%.
    [000120] Figure 4 provides a schematic view of the native CO2 recovery unit to carry out the method of the present invention, in which the CO2 purification unit is a cryogenic unit.
    [000121] In Figure 4, a sour gas stream is introduced into an sour gas removal unit (AGRU), thus providing a sweet gas stream (i) and a sour gas stream (ii) containing 18% of carbon dioxide and 73% hydrogen sulfide. A classic sweetening method using a chemical solvent, a hybrid solvent or a physical solvent is used as an acid gas removal unit (AGRU) . The acid gas stream (ii) then enters a Claus unit using oxygen rich stream as a combustible agent in the Claus furnace at a pressure of 0.17 to 0.19 MPa (1.7 to 1.9 bar ). Two streams exit the Claus unit: an elemental sulfur stream (iii) and a waste gas stream (iv) comprising mainly CO2, H2 and sulfur compounds. Then, the waste gas stream (iv) enters a Waste Gas Treatment Unit (TGTU), the so-called TGTU which is an amine-based technology. Part of the gas stream after the cooling tower is recycled to the Claus furnace, with a composition of 59% CO2, 20% H2 and 4% H2S. Downstream of the TGT amine, an effluent gas (v) is produced, composed of 58% carbon dioxide, 23% hydrogen, 15% water and 500 ppm hydrogen sulfide. Then, this effluent gas (v) enters a compression unit and a dehydration unit, then a cryogenic unit for CO2 purification, thus forming a purified carbon dioxide product (vii) and a lean CO2 stream. (viii) containing hydrogen and adding carbon dioxide.
    [000122] The purified carbon dioxide stream (vii), around 1MPa (10 bar), is composed of 99.9% carbon dioxide and less than 0.1% hydrogen sulfide. The low-CO2 stream (viii) rich in hydrogen (viii), at about 0.13 MPa (1.3 bar) is composed of approximately 72% hydrogen and 14% carbon dioxide, the remaining components being argon , carbon monoxide, nitrogen.
    权利要求:
    Claims (16)
    [0001]
    1. A method of treating a hydrocarbon feed gas stream containing at least carbon dioxide and hydrogen sulfide to recover a purified CO2 gas stream (vii), said method comprising the following steps: a. separating said hydrocarbon feed gas stream into a sweetened hydrocarbon gas stream (i), and an acidic gas stream (ii) comprising at least carbon dioxide and hydrogen sulfide; b. introducing said acid gas stream (ii) to a Claus unit, wherein an oxygen-rich stream is used as a combustible agent in the Claus furnace, thereby recovering a liquid elemental sulfur stream (iii) and a stream of tail gas (iv) comprising mainly carbon dioxide, hydrogen and sulfur compounds; c. introduce the outgoing waste gas stream (iv) into a Waste Gas Treatment Unit (TGTU) thereby separating said waste gas stream into a gas stream enriched in CO2 also containing hydrogen and sweetened in sulfur compounds (v) , and a stream enriched in sulfur compounds (vi);d. compress the CO2 enriched gas stream (v) leaving the TGTU; and is. pass the compressed CO2 enriched gas through a CO2 purification unit thereby recovering a purified CO2 gas stream (vii), characterized by the fact that the oxygen rich stream used as a combustible agent in Claus's furnace contains a quantity of oxygen from 70% to 100% and an amount of nitrogen not exceeding 50% and the pressure in the Claus furnace is 1.7 to 1.9 bar and the temperature is between 900 °C 1450 °C during step b .
    [0002]
    2. Method according to claim 1, characterized in that the waste gas stream (iv), the CO2 enriched gas stream (v) and the purified CO2 gas stream (vii) also contain nitrogen.
    [0003]
    3. Method according to claim 1 or 2, characterized in that the acid gas stream (ii) is enriched in H2S by an acid gas enrichment unit located upstream of the Claus unit.
    [0004]
    4. Method according to any one of claims 1 to 3, characterized in that the TGTU comprises an in-line burner or a waste gas heater, a hydrogenation reactor, a cooling contactor and optionally an absorber unit , in particular an amine-based absorber unit.
    [0005]
    5. Method according to any one of claims 1 to 4, characterized in that the gas stream enriched with CO2 leaving the compression unit is dehydrated before entering the CO2 purification unit.
    [0006]
    6. Method according to any one of claims 1 to 5, characterized in that the CO2 purification unit is a cryogenic separation unit producing a purified CO2 gas stream (vii) and a lean CO2 stream (viii ).
    [0007]
    7. Method according to any one of claims 1 to 5, characterized in that the CO2 purification unit is a membrane unit producing a purified CO2 gas stream (vii) on the waste side and a CO2 stream poor (viii) on the permeate side.
    [0008]
    8. Method according to any one of claims 1 to 5, characterized in that the CO2 purification unit is an adsorption unit producing a purified CO2 gas stream (vii) and a lean CO2 stream (viii) .
    [0009]
    9. Method according to any one of claims 1 to 5, characterized in that the CO2 purification unit is an absorption unit producing a purified CO2 gas stream (vii) and a lean CO2 stream (viii) .
    [0010]
    10. Method according to any one of claims 1 to 9, characterized in that the CO2 purification unit is a combination of CO2 purification units.
    [0011]
    11. Method according to any one of claims 1 to 10, characterized in that part of the gas stream leaving the Claus unit is recycled to the Claus furnace before introduction into the TGTU.
    [0012]
    12. Method according to any one of claims 1 to 11, characterized in that part of the gas stream inside the Claus unit is recycled to the Claus furnace by internal recycling.
    [0013]
    13. Method according to any one of claims 1 to 12, characterized in that part of the gas stream leaving the cooling tower is recycled to the Claus oven before introduction into the absorber unit.
    [0014]
    14. Method according to any one of claims 1 to 13, characterized in that part of the purified CO2 gas stream (vii) leaving the CO2 purification unit is recycled to Claus's furnace.
    [0015]
    15. Method according to any one of claims 1 to 14, characterized in that part of the lean CO2 stream (viii) leaving the CO2 purification unit is recycled upstream of or directly into the Claus furnace.
    [0016]
    16. Method according to any one of claims 1 to 15, characterized in that part of the lean CO2 stream (viii) leaving the CO2 purification unit is recycled between the Claus unit and the hydrogenation reactor of the TGTU.
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-03| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-03-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |
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    US201261668689P| true| 2012-07-06|2012-07-06|
    US61/668,689|2012-07-06|
    PCT/EP2013/062250|WO2014005817A1|2012-07-06|2013-06-13|Integrated process for native co2 recovery from a sour gas comprising h2s and co2|
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