CN115501746A - Method and system for carrying out decarburization and cooperative conversion on refinery flue gas - Google Patents
Method and system for carrying out decarburization and cooperative conversion on refinery flue gas Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 74
- 239000003546 flue gas Substances 0.000 title claims abstract description 39
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000005261 decarburization Methods 0.000 title claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 137
- 239000003054 catalyst Substances 0.000 claims abstract description 116
- 239000002250 absorbent Substances 0.000 claims abstract description 91
- 230000002745 absorbent Effects 0.000 claims abstract description 91
- 239000000047 product Substances 0.000 claims abstract description 57
- 238000003860 storage Methods 0.000 claims abstract description 48
- 239000007787 solid Substances 0.000 claims abstract description 41
- 238000010521 absorption reaction Methods 0.000 claims abstract description 40
- 238000002407 reforming Methods 0.000 claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 20
- 238000006057 reforming reaction Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 47
- 239000001257 hydrogen Substances 0.000 claims description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000005262 decarbonization Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/82—Solid phase processes with stationary reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention discloses a method for the decarburization and cooperative conversion of refinery flue gas, which comprises the following steps: s1, CO 2 In the gathering stage, carbon-containing flue gas tail gas of an oil refinery enters CO 2 Absorption unit from solid CO 2 Absorbent with CO 2 Carbonation reaction is carried out, and decarbonized refinery tail gas and solid CO are obtained at an outlet 2 The carbonating reaction product of the absorbent proceeds to step S2; s2, a refinery gas reforming stage, namely feeding the carbonation reaction product in the step S1 into a reforming device, introducing refinery gas, and performing a reforming reaction on the carbonation reaction product by calcining the carbonation reaction product and the refinery gas under the condition of a first catalyst to generate H 2 And CO, and returning the calcined product of the carbonation reaction product after the calcination to the CO in the step S1 2 The absorption unit participates in the carbonation reaction. The invention also discloses a system for the oil refinery flue gas decarburization and the cooperative conversion of the oil refinery gas, which comprises CO 2 An absorption device, a reforming device and a corresponding reaction product storage tank. The invention can realize zero carbon emission of oil refineries, and can realize high value-added conversion and CO of refinery gases 2 The resource utilization of the method is realized.
Description
Technical Field
The invention relates to a method and a system for converting and utilizing refinery gas, in particular to a method and a system for converting refinery gas by decarbonizing and cooperating with refinery gas.
Background
The oil refining industry is the major CO in the world 2 One of the emission sources, CO 2 Trapping, sequestration and utilization technologies are the only accepted ways to achieve the carbon abatement goal in the short term. Wherein based on solid CO 2 Absorbent (MeO/MeCO) 3 ) The cyclic calcination/carbonation process of (CO) is a highly attractive CO 2 The emission reduction process mainly comprises the following steps: solid CO 2 Absorbent (MeCO) 3 ) Calcining in a calcining reactor to decompose MeO and CO 2 So that CO with high concentration and available for subsequent sealing or utilization can be obtained at the outlet of the calcination reactor 2 (ii) a The generated MeO enters a carbonating reactor and is mixed with CO in the flue gas of the incoming flow 2 Reaction is carried out to realize CO in the flue gas 2 Removal of (2), formation of MeCO 3 And returning the calcined product to the calcination reactor for calcination regeneration.
Refineries produce large quantities of refinery gases during the oil production process. Refinery gases are usually composed of H 2 、CH 4 、N 2 、O 2 、CO、CO 2 、C 2 H 6 And the like. For example, catalytic dry gases consisting essentially of H 2 (25％)、CH 4 (28％)、N 2 (18％)、C 2 H 4 (13％)、C 2 H 6 (10%) and CO 2 (3%), and the like; the coking dry gas is mainly composed of H 2 (12％)、CH 4 (53％)、C 2 H 6 (27%) and C 2 H 4 (4%) and the like. For refinery gas with high hydrogen concentration, a refrigeration method, a separation membrane method and a pressure reduction adsorption process can be adopted to directly separate and recover hydrogen in the refinery gas. Aiming at refinery gas with lower hydrogen concentration, the hydrogen concentration in the refinery gas is improved by adopting a catalytic conversion method at present, and the specific process comprises the following steps: removing olefin or saturating and hydrogenating olefin to generate alkane, and then preparing hydrogen through adsorption enhanced steam alkane reforming reaction.
The existing refinery gas hydrogen preparation process of the refinery must include olefin removal steps (physical removal or saturated hydroconversion), which causes additional energy consumption and hydrogen consumption. Meanwhile, the decarbonization and the hydrogen production in the oil refinery are two independent processes at present, and CO is not realized yet 2 The direct resource utilization of the method is realized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for the decarbonization and cooperative conversion of refinery flue gas into refinery gas, so that the energy consumption and the hydrogen consumption caused by the olefin removal step in the hydrogen production process of the refinery gas are solved, and zero carbon emission of a refinery, high value-added conversion of the refinery gas and CO are realized 2 The resource utilization is realized. The invention also aims to provide a system for the synergistic conversion of refinery gas through the decarbonization of the refinery gas.
The technical scheme of the invention is as follows: a method for the decarbonization and the cooperative conversion of refinery flue gas comprises the following steps: s1, CO 2 A trapping stage, introducing carbon-containing flue gas into CO in the oil refinery 2 Absorption apparatus of said CO 2 Solid CO in the absorption device 2 Absorbent with CO 2 A carbonation reaction takes place, the solid CO 2 The carbonating reaction product of the absorbent enters the step S2 to participate in the reaction, and the CO 2 Obtaining decarbonized tail gas of the oil refinery at the outlet of the absorption device; s2, a refinery gas reforming stage, namely, the solid CO in the step S1 2 Sending the carbonated reaction product of the absorbent into a reforming device, introducing refinery gas and solid CO 2 The carbonated reaction product of the absorbent is subjected to a calcination reaction to produce CO 2 The gas and the refinery gas are subjected to reforming reaction under the action of a first catalyst to generate H 2 And CO, and mixing the solid CO 2 The calcined product of the carbonated reaction product of the absorbent after calcination is sent back to the CO in the step S1 2 The absorption device participates in the carbonation reaction.
Further comprising a step S3 of obtaining H and a hydrogen-rich stage, wherein the H is obtained in the step S2 2 Feeding the mixed gas product of the CO and the CO into a hydrogen enrichment device, introducing water vapor and part of the solid CO in the step S2 2 The calcined product of the absorbent is subjected to water gas reaction under the action of a second catalyst to prepare and obtain hydrogen, and the solid CO is used 2 The calcined product of the absorbent is sent back to the reforming device in the step S2 for calcination reaction after the carbonation reaction in the hydrogen enrichment device.
Further, the solid CO 2 The absorbent is CaO or CaO/Ca (OH) 2 /CaCO 3 Or Li 4 SiO 4 。
Further, the first catalyst is a nickel-based, copper-based, manganese-based, iron-based, cobalt-based, ruthenium-based, or platinum-based catalyst.
Further, the second catalyst is a nickel-based, copper-based, manganese-based, iron-based, cobalt-based, ruthenium-based, or platinum-based catalyst.
Further, the CO is 2 The reaction temperature in the absorption device is 500-750 ℃, the reaction pressure is 0.1-10 MPa, the reaction temperature in the reforming device is 500-900 ℃, and the reaction pressure is normal pressure.
Further, the reaction temperature in the hydrogen enrichment device is 400-700 ℃, the reaction pressure is normal pressure, and the volume ratio of the introduced water vapor to the CO is 1-10.
A system for decarbonizing and CO-converting refinery flue gas includes CO 2 Absorption plant and reformer, and CO 2 The absorption device is provided with a flue gas inlet, a tail gas outlet, an absorbent inlet and an absorbent outlet, the flue gas inlet is used for introducing carbon-containing flue gas of an oil refinery, the tail gas outlet is used for discharging decarbonized tail gas, and the reforming device is provided with a flue gas inlet, a tail gas outlet, an absorbent inlet and an absorbent outletThe device comprises a refinery gas inlet, a mixed gas outlet, an absorbent inlet and an absorbent outlet, wherein the refinery gas inlet is used for introducing refinery gas, and the mixed gas outlet is used for discharging H 2 And CO, said CO 2 The absorbent outlet of the absorber device is connected to the carbonator/catalyst storage tank, the outlet of the carbonator/catalyst storage tank is connected to the absorbent inlet of the reformer, the absorbent outlet of the reformer is connected to the calcine/catalyst storage tank, and the outlet of the calcine/catalyst storage tank is connected to the CO 2 An absorbent inlet of the absorption unit, the calcine/catalyst storage tank being used for storing solid CO 2 A calcined absorbent product after carbonation and a first catalyst, the carbonated product/catalyst storage tank for storing solid CO 2 An absorbent carbonation reaction product and a first catalyst for a reforming reaction within the reformer.
Further, the device comprises a hydrogen enrichment device, wherein the hydrogen enrichment device is provided with a mixed gas inlet, a water vapor inlet, an absorbent outlet and a hydrogen enrichment gas outlet, the absorbent outlet of the hydrogen enrichment device is connected to the carbonated product/catalyst storage tank, the mixed gas outlet of the reforming device is connected to the mixed gas inlet of the hydrogen enrichment device, and the outlets of the calcined product/catalyst storage tank are respectively connected to the CO inlets 2 An absorbent inlet of the absorption device and an absorbent inlet of the hydrogen enrichment device, the calcined product/catalyst storage tank being used for storing solid CO 2 A calcined product after absorbent carbonation, a first catalyst and a second catalyst, the carbonated product/catalyst storage tank is used for storing solid CO 2 An absorbent carbonation reaction product, a first catalyst, and a second catalyst for a water gas reaction within the hydrogen enrichment device.
Further, the CO is 2 And heat exchangers are arranged between the absorbent outlet of the absorption device and the carbonated product/catalyst storage tank, between the absorbent outlet of the reforming device and the calcined product/catalyst storage tank and at the mixed gas outlet of the reforming device.
Compared with the prior art, the invention has the advantages that:
the method of the invention converts CO in the tail gas of the oil refinery 2 By solid CO 2 Absorbing the absorbent by carbonation reaction, then calcining and releasing in a reformer, and respectively utilizing CO 2 Reforming reaction with alkanes (e.g. methane and ethane in coker dry gas) and alkenes (e.g. ethylene in coker dry gas) to synthesis gas (H) 2 And CO); in addition, the solid CO is carbonated 2 The calcined product of the absorbent can be reused for absorbing CO 2 Not only can realize zero carbon emission of an oil refinery, but also can realize high value-added conversion (namely production of synthesis gas) and CO of refinery gas 2 The resource utilization is realized. Still further, the solid CO is combined by water gas reaction after obtaining the synthesis gas 2 Absorbent pair CO 2 Can increase the H content of the finally prepared hydrogen-rich gas 2 Concentration, absorbed CO 2 Can be used by reforming reaction with refinery gas, and controls CO while obtaining hydrogen-rich gas 2 Is discharged.
Drawings
Fig. 1 is a schematic structural diagram of a system for decarbonizing and co-converting refinery flue gas in an oil refinery according to embodiment 1 of the present invention.
Fig. 2 is a schematic structural diagram of a system for the co-decarbonization and co-conversion of refinery flue gas in an oil refinery in example 2 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example 1:
referring to FIG. 1, a system for decarbonizing refinery flue gas and CO-converting refinery flue gas includes CO 2 An absorption device 101, a reforming device 102, a first check valve 103, a second check valve 104, a third check valve 105, a fourth check valve 106, a first heat exchanger 107, a second heat exchanger 108, and a third heat exchanger 109.CO 2 2 The absorption apparatus 101 and the reforming apparatus 102 are both fluidized bed reactors.
CO 2 The absorption device 101 is provided with a flue gas inlet 101a and a tail gas outlet101b, an absorbent inlet 101c and an absorbent outlet 101d, wherein the flue gas inlet 101a is used for introducing carbon-containing flue gas from an oil refinery, the tail gas outlet 101b is used for discharging decarbonized tail gas, the reforming device 102 is provided with a refinery gas inlet 102a, a mixed gas outlet 102b, an absorbent inlet 102c and an absorbent outlet 102d, the refinery gas inlet 102a is used for introducing refinery gas, and the mixed gas outlet 102b is connected with a third heat exchanger 109 and used for discharging H 2 And CO. CO 2 2 The absorbent outlet 101d of the absorber 101 is connected to the first heat exchanger 107 via a first check valve 103 and then to the carbonated product/catalyst storage tank 110, the outlet of the carbonated product/catalyst storage tank 110 is connected to the absorbent inlet 102c of the reformer 102 via a second check valve 104, the absorbent outlet 102d of the reformer 102 is connected to the second heat exchanger 108 via a third check valve 105 and then to the calcined product/catalyst storage tank 111, the outlet of the calcined product/catalyst storage tank 111 is connected to the CO via a fourth check valve 106 2 The absorbent inlet 101c of the absorption device 101. Calcined product/catalyst storage tank 111 for storing solid CO 2 Absorbent, first catalyst and solid CO 2 Calcination product of absorbent after carbonation, solid CO 2 The absorbent can be CaO or CaO/Ca (OH) 2 /CaCO 3 Natural mineral or waste as main ingredient, or Li 4 SiO 4 Or with Li 4 SiO 4 As the main component of natural minerals or wastes, caO is selected as solid CO in this example 2 An absorbent. Carbonated product/catalyst storage tank 110 for storing solid CO 2 The absorbent carbonating reaction product, i.e. CaCO 3 And a first catalyst, which is used for the reforming reaction in the reforming apparatus 102, and is typically a metal-based catalyst, such as nickel-based, copper-based, manganese-based, iron-based, cobalt-based, ruthenium-based, or platinum-based catalyst, and may be natural minerals or waste containing these metal-based catalysts, and the nickel-based catalyst is selected in this embodiment.
The method for the co-conversion of refinery gas by decarbonization of refinery flue gas of this example is as follows:
(1) In CO 2 A gathering stage, the tail gas of the carbon-containing flue gas of the oil refinery enters CO 2 Absorption ofThe apparatus 101, caO in the calcine/catalyst tank 111 and the nickel-based catalyst are introduced together into the CO through the fourth check valve 106 2 The absorption means 101.CO 2 2 The absorption device 101 is internally provided with CaO and CO 2 The following carbonation reaction takes place to form CaCO 3 To realize CO in the tail gas 2 Is removed from
CO 2 The reaction temperature in the absorption apparatus 101 is 500 to 750 ℃ and the reaction pressure is 0.1 to 10MPa, and in this example, the temperature is controlled to 650 ℃ and the pressure is 0.1MPa. CaCO 3 After passing through the first check valve 103 along with the nickel-based catalyst, heat is recovered by the first heat exchanger 107 and enters the carbonated product/catalyst storage tank 110. Decarbonized refinery off gas from CO 2 The off-gas outlet 101b of the absorption device 101.
(2) CaCO stored in the carbonated product/catalyst storage tank 110 during the refinery gas reforming stage 3 After passing through the second check valve 104, the nickel-based catalyst enters the reformer 102, and the refinery gas also enters the reformer 102 at the same time 3 Calcining reaction at high temperature to generate CaO and CO 2
Simultaneously, under the action of a nickel-based catalyst, the main components of methane, ethane and ethylene in the refinery gas are respectively mixed with CO 2 The reforming reaction takes place and the reaction is carried out,
the reaction temperature in the reforming apparatus 102 is 500 to 900 ℃ and the reaction pressure is normal pressure, and in this example, the reforming reaction temperature is 850 ℃ and the pressure is normal pressure, and high-concentration H is generated 2 And CO, and the mixture gas is discharged after heat is recovered from the mixture gas outlet 102b of the reformer 102 by the third heat exchanger 109. CaO generated by the calcination reaction and the nickel-based catalyst pass through the third one-way valve 105, then pass through the second heat exchanger 108 to recover heat, and are stored in the calcined product/catalyst storage tank 111. The heat source of the reformer 102 can be obtained by burning refinery-related gas, and the tail gas from the combustion of refinery-related gas can be decarbonized in step (1).
Example 2:
referring to FIG. 2, a system for decarbonizing refinery flue gas and converting refinery gas includes CO 2 An absorption device 201, a reforming device 202, a hydrogen enrichment device 203, a first check valve 204, a second check valve 205, a third check valve 206, a fourth check valve 207, a fifth check valve 208, a sixth check valve 209, a first heat exchanger 210, a second heat exchanger 211, a third heat exchanger 212, a fourth heat exchanger 213, and a fifth heat exchanger 214.CO 2 2 The absorption device 201, the reforming device 202, and the hydrogen enrichment device 203 are all fluidized bed reactors.
CO 2 The absorption device 201 is provided with a flue gas inlet 201a, a tail gas outlet 201b, an absorbent inlet 201c and an absorbent outlet 201d, wherein the flue gas inlet 201a is used for introducing carbon-containing flue gas of an oil refinery, the tail gas outlet 201b is used for discharging decarbonized tail gas, the reforming device 202 is provided with a refinery gas inlet 202a, a mixed gas outlet 202b, an absorbent inlet 202c and an absorbent outlet 202d, the refinery gas inlet 202a is used for introducing refinery gas, and the mixed gas outlet 202b is connected with a third heat exchanger 212 and used for discharging H 2 And CO. CO 2 2 The absorbent outlet of the absorption unit 201 is connected to the first heat exchanger 210 via a first check valve 204 and to the carbonated product/catalyst storage tank 215, and the outlet of the carbonated product/catalyst storage tank 215 is connected to the absorbent inlet 202c of the reforming unit 202 via a second check valve 205, and the absorbent is then fed to the first heat exchanger 210 via a second check valve 205The absorbent outlet 202d of the whole device 202 is connected to the second heat exchanger 211 via a third check valve 206 and then to the calcined product/catalyst storage tank 216, and the outlet of the calcined product/catalyst storage tank 216 is connected to the CO via a fourth check valve 207 2 The absorbent inlet of the absorption device 201. The hydrogen enrichment device 203 is provided with a mixed gas inlet 203a, a water vapor inlet 203b, an absorbent inlet 203c, an absorbent outlet 203d and a hydrogen enrichment gas outlet 203e, the absorbent outlet 203d of the hydrogen enrichment device 203 is connected with the fourth heat exchanger 213 through the fifth one-way valve 208 and then connected with the carbonated product/catalyst storage tank 215, the mixed gas outlet 202b of the reforming device 202 is directly connected with the mixed gas inlet 203a of the hydrogen enrichment device 203 after passing through the third heat exchanger 212, and the outlet of the calcined product/catalyst storage tank 216 except for the CO 2 The absorber 201 is also connected to an absorber inlet 203c of the hydrogen enriching device 203 through a sixth check valve 209. Calcined product/catalyst storage tank 216 for storing solid CO 2 Absorbent, first catalyst, second catalyst and solid CO 2 Calcination product of absorbent carbonation reaction, solid CO 2 The absorbent can be CaO or CaO/Ca (OH) 2 /CaCO 3 Natural mineral or waste as main ingredient, or Li 4 SiO 4 Or with Li 4 SiO 4 Natural minerals or wastes as main components, caO is used as solid CO in this example 2 An absorbent. Carbonated product/catalyst storage tank 215 for storing solid CO 2 The absorbent carbonating reaction product, i.e. CaCO 3 And a first catalyst and a second catalyst, the first catalyst is used for the reforming reaction in the reforming apparatus 202, and is generally a metal-based catalyst such as nickel-based, copper-based, manganese-based, iron-based, cobalt-based, ruthenium-based, platinum-based, etc., and may be natural minerals or waste containing these metal-based catalysts, and the ruthenium-based catalyst is selected in this embodiment. The second catalyst is used for the water gas reaction in the hydrogen enrichment device 203, and is generally a metal-based catalyst such as a nickel-based catalyst, a copper-based catalyst, a manganese-based catalyst, an iron-based catalyst, a cobalt-based catalyst, a ruthenium-based catalyst, a platinum-based catalyst, and the like, and may be natural minerals or waste containing the metal-based catalysts, and the nickel-based catalyst is selected in this embodiment.
The method for the refinery flue gas decarburization and the cooperative conversion of the refinery flue gas in the embodiment is as follows:
(1) In CO 2 In the gathering stage, carbon-containing flue gas tail gas of an oil refinery enters CO 2 The CaO and ruthenium-based catalyst, nickel-based catalyst in the absorber 201, the calcine/catalyst storage tank 216 are introduced together into the CO through the fourth check valve 207 2 The absorption device 201.CO 2 2 The absorption device 201 is internally provided with CaO and CO 2 The following carbonation reaction takes place to form CaCO 3 To realize CO in the tail gas 2 Is removed from
CO 2 The reaction temperature in the absorption apparatus 201 is 500 to 750 ℃ and the reaction pressure is 0.1 to 10MPa, and in this example, the temperature is controlled to 650 ℃ and the pressure is 3MPa. CaCO 3 After passing through the first check valve 204 together with the ruthenium-based catalyst and the nickel-based catalyst, heat is recovered by the first heat exchanger 210 and enters the carbonated product/catalyst storage tank 215. Decarbonized refinery off gas from CO 2 The off-gas outlet of the absorber 201.
(2) CaCO stored in the carbonated product/catalyst storage tank 215 during the refinery gas reforming stage 3 Enters the reforming device 202 together with ruthenium-based catalyst and nickel-based catalyst after passing through the second one-way valve 205, and refinery gas also enters the reforming device 202 at the same time 3 Calcining reaction at high temperature to generate CaO and CO 2
Simultaneously, under the action of ruthenium-based catalyst, the main components of methane, ethane and ethylene in refinery gas are respectively mixed with CO 2 The reforming reaction takes place and the reaction is carried out,
the reaction temperature in the reforming apparatus 202 is 500 to 900 ℃ and the reaction pressure is normal pressure, and in this example, the reforming reaction temperature is 850 ℃ and the pressure is normal pressure, and high-concentration H is generated 2 And the mixed gas of CO, and the mixed gas is discharged from the mixed gas outlet of the reforming device 202 through heat exchange of the third heat exchanger 212. The CaO generated by the calcination reaction, together with the ruthenium-based catalyst and the nickel-based catalyst, passes through the third check valve 206, and then passes through the second heat exchanger 211 to recover heat and store in the calcined product/catalyst storage tank 216.
(3) In the hydrogen-rich stage, the mixed gas outlet 202b of the reformer 202 discharges a high concentration H 2 The mixed gas of the CO and the CaO is sent to the hydrogen enriching device 203 after the temperature of the mixed gas is adjusted by the third heat exchanger 212, the water vapor is sent to the hydrogen enriching device 203 through the water vapor inlet 203b, the CaO, the ruthenium-based catalyst and the nickel-based catalyst which are stored in the carbonating product/catalyst storage tank 215 simultaneously enter the reforming device 202 through the sixth one-way valve 209, and the water vapor and the CO generate water gas reaction to generate CO under the action of the nickel-based catalyst 2 And H 2 ，
CaO and CO 2 Carbonation reaction to CaCO 3 The reaction temperature in the hydrogen enrichment device 203 is 500-700 ℃, the reaction pressure is normal pressure, the dimension of the water gas reaction in the embodiment is 650 ℃, the pressure is normal pressure, and the generated CaCO 3 With the ruthenium-based catalyst, the nickel-based catalyst, after heat recovery from the fourth heat exchanger 213 through the fifth check valve 208, is stored in the carbonated product/catalyst storage tank 215 by removing CO 2 The water gas reaction moves towards the hydrogen production direction, and the concentration of the hydrogen is further improved. With high concentration of hydrogenThe hydrogen-rich gas is discharged from the hydrogen-rich gas outlet 203e after heat is recovered by the fifth heat exchanger 214.
Claims (10)
1. A method for carrying out decarburization and cooperative conversion on refinery flue gas is characterized by comprising the following steps: s1, CO 2 A trapping stage, introducing carbon-containing flue gas into CO in the oil refinery 2 Absorption apparatus of said CO 2 By solid CO in the absorption unit 2 Absorbent with CO 2 A carbonation reaction takes place, the solid CO 2 The carbonating reaction product of the absorbent enters the step S2 to participate in the reaction, and the CO 2 Obtaining the decarbonized tail gas of the oil refinery at the outlet of the absorption device; s2, a refinery gas reforming stage, namely, the solid CO in the step S1 2 Sending the carbonated reaction product of the absorbent into a reforming device, introducing refinery gas and solid CO 2 The carbonatation reaction product of the absorbent is subjected to a calcination reaction to generate CO 2 The gas and the refinery gas are subjected to reforming reaction under the action of a first catalyst to generate H 2 And CO, and mixing the solid CO 2 The calcined product of the carbonatation reaction product of the absorbent is returned to the CO in the step S1 2 The absorption device participates in the carbonation reaction.
2. The method for decarbonizing and co-converting refinery gases according to claim 1, comprising a step S3 of hydrogen enrichment, wherein H obtained in the step S2 2 Feeding the mixed gas product of the CO and the CO into a hydrogen enrichment device, introducing water vapor and part of the solid CO in the step S2 2 The calcined product of the absorbent is subjected to water gas reaction under the action of a second catalyst to prepare and obtain hydrogen, and the solid CO is used 2 The calcined product of the absorbent is sent back to the reforming device in the step S2 for calcination reaction after carbonation reaction occurs in the hydrogen enrichment device.
3. The method for decarbonizing and CO-converting refinery gases according to claim 1 or 2, wherein the solid CO is CO 2 The absorbent is CaO orCaO/Ca(OH) 2 /CaCO 3 Or Li 4 SiO 4 。
4. The method for decarbonizing and co-converting refinery flue gases according to claim 1 or 2, characterized in that the first catalyst is a nickel-based, copper-based, manganese-based, iron-based, cobalt-based, ruthenium-based or platinum-based catalyst.
5. The method for decarbonizing and co-converting refinery gases according to claim 2, wherein the second catalyst is a nickel-based, copper-based, manganese-based, iron-based, cobalt-based, ruthenium-based, or platinum-based catalyst.
6. The method for decarbonizing and CO-converting refinery gases according to claim 1 or 2, wherein the CO is introduced into the refinery gases 2 The reaction temperature in the absorption device is 500-750 ℃, the reaction pressure is 0.1-10 MPa, the reaction temperature in the reforming device is 500-900 ℃, and the reaction pressure is normal pressure.
7. The method for the cooperative conversion of refinery gases through the decarbonization of the refinery flue gases according to claim 2, wherein the reaction temperature in the hydrogen-rich device is 400-700 ℃, the reaction pressure is normal pressure, and the volume ratio of the introduced water vapor to the CO is 1-10.
8. A system for the decarbonization and cooperative conversion of refinery flue gas is characterized by comprising CO 2 Absorption plant and reformer, and CO 2 The absorption device is provided with a flue gas inlet, a tail gas outlet, an absorbent inlet and an absorbent outlet, the flue gas inlet is used for introducing carbon-containing flue gas of an oil refinery, the tail gas outlet is used for discharging tail gas subjected to decarburization, the reforming device is provided with a refinery gas inlet, a mixed gas outlet, an absorbent inlet and an absorbent outlet, the refinery gas inlet is used for introducing refinery gas, and the mixed gas outlet is used for discharging H 2 And CO, said CO 2 The absorbent outlet of the absorption unit is connected to the carbonated product/catalystA reagent storage tank, an outlet of the carbonated product/catalyst storage tank being connected to an absorbent inlet of the reformer, an absorbent outlet of the reformer being connected to a calcined product/catalyst storage tank, an outlet of the calcined product/catalyst storage tank being connected to the CO 2 An absorbent inlet of the absorption unit, the calcine/catalyst storage tank being used for storing solid CO 2 A calcined absorbent product after carbonation and a first catalyst, the carbonated product/catalyst storage tank for storing solid CO 2 An absorbent carbonation reaction product and a first catalyst for a reforming reaction within the reformer.
9. The system for decarbonizing and CO-converting refinery gases according to claim 8, comprising a hydrogen-enriching device having a mixture inlet, a steam inlet, an absorbent outlet, and a hydrogen-enriching gas outlet, wherein the absorbent outlet of the hydrogen-enriching device is connected to the carbonating product/catalyst storage tank, the mixture outlet of the reforming device is connected to the mixture inlet of the hydrogen-enriching device, and the outlets of the calcinating product/catalyst storage tanks are respectively connected to the CO inlets 2 An absorbent inlet of an absorption device and an absorbent inlet of the hydrogen enrichment device, the calcined product/catalyst storage tank being used for storing solid CO 2 A calcined product after absorbent carbonation, a first catalyst and a second catalyst, the carbonated product/catalyst storage tank is used for storing solid CO 2 An absorbent carbonation reaction product, a first catalyst, and a second catalyst for a water gas reaction within the hydrogen enrichment device.
10. The system for decarbonizing and CO-converting refinery gases according to claim 8 or 9, wherein the CO is introduced into the refinery gases 2 Heat exchangers are arranged between the absorbent outlet of the absorber and the carbonated product/catalyst storage tank, between the absorbent outlet of the reformer and the calcined product/catalyst storage tank, and at the mixed gas outlet of the reformer.
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