CN115845596B - Catalytic cracking flue gas renewable dry desulfurization process - Google Patents
Catalytic cracking flue gas renewable dry desulfurization process Download PDFInfo
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- flue gas
- desulfurizing agent
- catalytic cracking
- desulfurization
- cyclone separator
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000003546 flue gas Substances 0.000 title claims abstract description 156
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 79
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 74
- 230000023556 desulfurization Effects 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 71
- 230000008569 process Effects 0.000 title claims abstract description 61
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 160
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 155
- 230000008929 regeneration Effects 0.000 claims abstract description 35
- 238000011069 regeneration method Methods 0.000 claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 34
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 239000004005 microsphere Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 22
- 230000001603 reducing effect Effects 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 229910052596 spinel Inorganic materials 0.000 claims description 10
- 239000011029 spinel Substances 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
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- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- -1 organic acid salts Chemical class 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
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- 239000002253 acid Substances 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
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- 238000012216 screening Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 19
- 238000005457 optimization Methods 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 8
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- 239000003517 fume Substances 0.000 description 7
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- 235000011121 sodium hydroxide Nutrition 0.000 description 3
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- 239000002918 waste heat Substances 0.000 description 3
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 208000012886 Vertigo Diseases 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 229910052749 magnesium Inorganic materials 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
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- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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- 230000008014 freezing Effects 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- 238000005200 wet scrubbing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a renewable dry desulfurization process for catalytic cracking flue gas, which is characterized in that a solid microsphere desulfurizing agent is added into a flue gas pipeline of a catalytic cracking device, the desulfurizing agent flows along with the flue gas and completes desulfurization of the flue gas in the flowing process, the desulfurizing agent after adsorption is separated from desulfurization flue gas through a cyclone separator, the desulfurization flue gas from the cyclone separator enters a third cyclone separator of the catalytic cracking flue gas, the desulfurizing agent from the cyclone separator is conveyed into a fluidized bed desulfurizing agent regenerator, and the desulfurizing agent returns to the catalytic cracking flue gas pipeline for recycling after regeneration. The invention uses the flue gas pipeline as the down reactor, and compared with other technological methods, the invention omits a specially added desulfurization reactor, thereby obviously reducing the investment. In the down reactor, the down speed of the desulfurizing agent is faster than the flow speed of the flue gas along with time, which is equivalent to that one batch of desulfurizing agent particles pass through the flue gas, SO that the SO x content in the purified flue gas can realize clean emission of 0-35 mg/m 3 by adjusting the gas-to-gas ratio of the desulfurizing agent.
Description
Technical Field
The invention relates to the technical field of catalytic cracking flue gas treatment, in particular to a renewable dry desulfurization process for catalytic cracking flue gas.
Background
Catalytic cracking is an important heavy oil lightening and olefin production process for refineries, and the core equipment of the process is mainly a reactor and a regenerator. Under the action of the catalyst, the raw oil is cracked into light fraction and cracked gas in a catalytic cracking reactor, the catalyst is deactivated due to coking in the reaction process, and the deactivated catalyst is fluidized and conveyed to the regenerator for coke burning regeneration, and then is circulated and returned to the reactor for continuous catalytic reaction. During the catalytic cracking reaction, part of sulfide in the raw materials is deposited on the catalyst, and when the catalyst is burnt and regenerated in a regenerator, the sulfide on the catalyst is combusted to form sulfur oxide (SO x) which is discharged along with flue gas. The composition of the oxysulfide SO x in the flue gas approximately ranges from: 90-95% of SO 2 and 5-10% of SO 3, which not only severely pollute the environment, but also can react with water vapor in the flue gas to condense on the wall to generate acidic solution, thereby severely corroding equipment. Therefore, how to reduce and even completely remove SO x in catalytic cracking regenerated flue gas with lower investment, lower running cost and energy consumption, and simultaneously, not produce secondary pollution such as salt-containing wastewater and realize the recycling of SO x has become a problem to be solved.
The main method for reducing SO x emission in the catalytic cracking regenerator is as follows:
1. The catalytic cracking raw material is subjected to hydrogenation pretreatment such as ZL201510769249.3, ZL201410766839.6, ZL201210440586.4 and the like. The catalytic cracking raw material hydrogenation pretreatment can effectively reduce the emission of the catalytic cracking flue gas SO x, but still can not meet the emission requirement, and the catalytic cracking raw material hydrogenation pretreatment device has large investment cost and high operation cost, thereby limiting the application of the method.
2. Regenerated flue gas sulfur transfer agents such as ZL201510109947.0, ZL201210443822.8, ZL201210349980.7, ZL201110029268.4, and the like are used in the catalytic cracking process. The measure can effectively reduce the emission of SO x in catalytic cracking flue gas, and can reduce SO x in regenerated flue gas by 50-70%, but with the continuous improvement of the flue gas emission standard, the regenerated flue gas sulfur transfer agent is difficult to meet the flue gas emission requirement.
3. Currently, the most widely used wet scrubbing flue gas desulfurization technology is ZL201410092858.5, ZL201410590103.8, ZL201610031292.4, ZL201120070516.5 and the like; the method has the functions of desulfurization and dust removal, but can cause secondary pollution such as wet smoke emission (white smoke), blue smoke plume (blue smoke), rain drop of a washing tower, icing, salt-containing wastewater and the like. Meanwhile, as the wet flue gas desulfurization is positioned at the tail end of the device, SO x limits the further reduction of the flue gas temperature at the outlet of the waste heat boiler, SO that the wet desulfurization has the result of higher energy consumption.
4. In recent years, sodium bicarbonate powder and slaked lime process technology for purifying flue gas of a coal-fired boiler are used for desulfurizing the catalytic cracking flue gas, and the product sulfite has low purity after desulfurization and denitrification, so that the high-value utilization is difficult.
The renewable dry flue gas desulfurization processes such as ZL200610171550.5 and ZL201811425856.8 which are being researched and developed adopt catalytic cracking catalysts per se or aluminum magnesium spinel as desulfurization adsorbents or catalysts, adopt fluidized bed adsorption-fluidized bed regeneration processes or adopt moving bed desulfurization-moving bed regeneration processes, and have the problems of high investment and/or high energy consumption and the like.
Disclosure of Invention
The invention aims to solve the problems of high investment and high energy consumption in the existing renewable dry flue gas desulfurization process and provides a catalytic cracking flue gas renewable dry desulfurization process.
The invention solves the technical problems, and adopts the following technical scheme: a process for desulfurizing the catalytically cracked fume by regenerated dry method features that the solid microballoon desulfurizing agent is added to the fume pipeline of catalytic cracker, the desulfurizing agent flows along with the fume and desulfurizing the fume is completed in the flowing course, the desulfurizing agent after adsorption is separated from the desulfurizing fume by cyclone separator, the desulfurizing fume from cyclone separator is delivered to the third cyclone separator of catalytically cracked fume, and after subsequent treatment, it is discharged to chimney.
As a further optimization of the catalytic cracking flue gas renewable dry desulfurization process, the invention: continuously and uniformly adding the regenerated solid microsphere desulfurizing agent into a flue gas pipeline of a catalytic cracking device, enabling the desulfurizing agent to flow along with flue gas, generating metal sulfate by SO 2 oxidation reaction and chemical adsorption of SO 3 at high temperature, and adsorbing the metal sulfate on the desulfurizing agent, wherein the solid microsphere desulfurizing agent is separated from desulfurized flue gas through a cyclone separator;
The desulfurization flue gas from the cyclone separator enters a third cyclone separator of catalytic cracking flue gas, and is discharged into a chimney after energy recovery, denitration and dust removal treatment;
The microsphere solid desulfurizing agent containing metal sulfate from the cyclone separator is conveyed to a fluidized bed desulfurizing agent regenerator, reducing gas after hydrogen sulfide is removed is introduced into the desulfurizing agent regenerator, the metal sulfate on the desulfurizing agent is reduced into metal oxide at high temperature, the metal oxide is returned to a catalytic cracking flue gas pipeline for recycling, and the desulfurizing agent regenerated gas rich in hydrogen sulfide is conveyed to an acid gas desulfurizing device for treatment and then conveyed to a sulfur device, so that recycling of sulfur is realized.
As a further optimization of the catalytic cracking flue gas renewable dry desulfurization process, the invention: the catalytic cracking flue gas pipeline is a flue gas conveying pipeline between the catalytic cracking regenerator and the third-stage cyclone separator of the flue gas, and the desulfurizing agent is continuously and uniformly added into the horizontal section, the vertical section, the inclined section and the turning section of the flue gas pipeline.
As a further optimization of the catalytic cracking flue gas renewable dry desulfurization process, the invention: the desulfurizing agent is continuously and uniformly added into the vertical downward section and the turning section of the flue gas pipeline, which vertically downward from the horizontal direction.
As a further optimization of the catalytic cracking flue gas renewable dry desulfurization process, the invention: the particle size range of the solid microsphere desulfurizing agent is 40-200 mu m, and the average particle size of the desulfurizing agent is 60-100 mu m.
As a further optimization of the catalytic cracking flue gas renewable dry desulfurization process, the invention: the ratio of the desulfurizing agent to the flue gas added into the catalytic cracking flue gas pipeline is 0.005-2.0 kg/Nm3, and the reaction adsorption time and the temperature of the catalytic cracking flue gas and the desulfurizing agent are respectively 0.01-60 s and 500-750 ℃.
As a further optimization of the catalytic cracking flue gas renewable dry desulfurization process, the invention: the ratio of the desulfurizing agent to the flue gas added into the catalytic cracking flue gas pipeline is 0.01-0.5 kg/Nm3, and the reaction adsorption time and the temperature of the catalytic cracking flue gas and the desulfurizing agent are respectively 0.1-5 s and 550-720 ℃.
As a further optimization of the catalytic cracking flue gas renewable dry desulfurization process, the invention: the reducing gas is one or any mixture of hydrogen, methane, ethane and ethylene, and the working parameters of the fluidized bed desulfurizer are as follows: the regeneration temperature is 500-750 ℃, the average residence time of the desulfurizing agent in the regenerator is 30 s-60 min, and the weight hourly space velocity of the desulfurizing agent regenerator is: 0.05-50 h < -1 >.
As a further optimization of the catalytic cracking flue gas renewable dry desulfurization process, the invention: the reducing gas is refinery dry gas, and the working parameters of the fluidized bed desulfurizer are as follows: the regeneration temperature is 600-700 ℃, the average residence time of the desulfurizing agent in the regenerator is 1-30 min, and the weight hourly space velocity of the desulfurizing agent regenerator is: 0.1-20 h < -1 >.
As a further optimization of the catalytic cracking flue gas renewable dry desulfurization process, the invention: the desulfurizing agent comprises 10-30% of V2O5, 1-8% of CeO2, 20-40% of MgO, 20-55% of Al2O3 and 0.5-2% of MnO2 by the weight content of metal oxide being 100%.
As a further optimization of the catalytic cracking flue gas renewable dry desulfurization process, the invention: the preparation method of the desulfurizing agent comprises the following steps:
1) Slowly dripping a mixed solution prepared from magnesium salt and aluminum salt into a mixed solution prepared from sodium hydroxide and sodium carbonate, and stirring to react for nucleation and crystallization after the dripping is completed to obtain magnesia-alumina spinel;
2) Sequentially adding ammonium metavanadate, cerium nitrate, dan Mei aluminum spinel and manganese salt into deionized water at 50-90 ℃, stirring until the ammonium metavanadate, the cerium nitrate, the Dan Mei aluminum spinel and the manganese salt are completely dissolved, adding pseudo-boehmite, stirring, adding a binder, and continuously stirring to obtain slurry;
3) Spray drying the slurry under the operation conditions that the hearth temperature is 300-400 ℃, the furnace outlet temperature is 180-250 ℃ and the pressure is 3.0-5.0 MPa to obtain solid microsphere particles, screening and selecting to obtain microsphere particles with target particle size, and roasting for 3-10 hours at the temperature of 650-760 ℃ to obtain the desulfurizing agent.
As a further optimization of the catalytic cracking flue gas renewable dry desulfurization process, the invention: manganese salt, magnesium salt and aluminum salt are chloride, nitrate, sulfate or organic acid salt thereof, and the binder is aluminum sol, silica sol or silica-alumina mixed sol.
The invention has the following beneficial effects: the invention uses the flue gas pipeline as the down reactor, and compared with other technological methods, the invention omits a specially added desulfurization reactor, thereby obviously reducing the investment. In the down reactor, the down speed of the desulfurizing agent is faster than the flow speed of the flue gas along with time, which is equivalent to that one batch of desulfurizing agent particles pass through the flue gas, SO that the SO x content in the purified flue gas can realize clean emission of 0-35 mg/m 3 by adjusting the gas-to-gas ratio of the desulfurizing agent.
Drawings
FIG. 1 is a schematic diagram of the process flow of the catalytic cracking flue gas renewable dry desulfurization process of the invention.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate, but are not to be construed as limiting the invention.
Example 1]
A solid microsphere desulfurizing agent is prepared by the following steps:
1) Adding 1.25 tons of deionized water into a 2.5 cubic meter enamel reaction kettle, gradually adding 22.25 kilograms of sodium carbonate (Na 2CO3) and 57 kilograms of caustic soda (NaOH) under the condition that the rotation speed of a stirrer is 120rpm, heating while stirring, adding 750 kilograms of aqueous solution containing 55.25 kilograms of magnesium nitrate hexahydrate (Mg (NO 3)2·6H2 O) and 46.75 kilograms of aluminum nitrate nonahydrate (Al (NO 3)3·9H2 O)) at the temperature of 70 ℃ at the speed of 20 liters per minute, continuing to uniformly stir after the filling is finished, keeping the constant temperature when the temperature of the reaction kettle is reduced to 65 ℃, stirring at the rotation speed of 25rpm for nucleation and crystallization for 18 hours, cooling, discharging and filtering, washing to be neutral by using deionized water, and drying to obtain magnesium aluminate spinel (MgAl 2O4).
2) 1.25 Tons of deionized water is added into a 2.5 cubic meter enamel reaction kettle, the stirring speed of 20rpm is maintained, 21.78 kilograms of ammonium metavanadate (NH 4VO3), 18.6 kilograms of magnesium aluminate spinel, 2.38 kilograms of manganese nitrate tetrahydrate (Mn (NO 3)2·4H2 O), 22.1 kilograms of active magnesium oxide (90% in dry basis) and 17.5 kilograms of cerium nitrate hexahydrate (Ce (NO 3)2·6H2 O) are added, the stirring is carried out for 100 minutes at 85 ℃, 40.1 kilograms of pseudo-boehmite is added after complete dissolution, and the stirring is continued for 9 hours, so as to obtain slurry.
3) The slurry is spray dried in a spray dryer with a scale of 50 kg/h under the operation condition that the hearth temperature is 360 ℃, the outlet temperature is 190 ℃ and the pressure is 3.9MPa, so as to obtain solid microsphere particles, and microsphere particles with the particle diameter range of 40-200 mu m and the average particle diameter of 87 mu m are selected by screening and then are roasted for 8 hours at the temperature of 750 ℃ so as to obtain the fresh desulfurizing agent (F-Sorb). The F-Sorb desulfurizing agent comprises 12.7% of V 2O5, 30.0% of MgO, 50.6% of Al 2O3, 6.1% of CeO 2 and 0.6% of MnO 2, based on 100% of the metal oxide mass content.
The desulfurizing agent is a catalyst with a formula, and particularly, the catalyst with multiple functions needs multiple specific active components and carriers to be matched with each other to obtain specific effects. The desulfurizing agent of the invention has a plurality of outstanding functional characteristics:
1) The desulfurizing agent can be used as a carrier oxygen with a catalytic function to rapidly catalyze and oxidize SO 2 in flue gas into SO 3 in an oxidizing atmosphere, wherein two active components of V 2O5 and Ce 2O3 play a main role. The idea of selecting vanadium is derived from the traditional process of preparing sulfuric acid by catalyzing and oxidizing SO 2 by V 2O5, V 2O5 does not react with SO 2 or SO 3, and therefore V 2O5 cannot be directly used as a desulfurizing agent.
2) The magnesia-alumina spinel is used as a carrier, not only provides a framework structure and a micro-pore canal, but also provides high strength and high stability for the desulfurizing agent, and the rich alkaline position provides strong capturing capability of the desulfurizing agent for an oxidation product SO 3.
3) The desulfurizing agent can also play a role in catalyzing the reduction of metal sulfate in a reducing atmosphere, wherein the active component Ce 2O3 plays a main role.
Example 2]
A solid microsphere desulfurizing agent is prepared by the same method as in the < example 1> except that the addition ratio of the raw materials is different, and the final F-Sorb desulfurizing agent comprises 22.6% of V 2O5, 25.6% of MgO, 45.4% of Al 2O3, 4.6% of CeO 2 and 1.8% of MnO 2 based on 100% of metal oxide mass content.
Example 3 ]
A solid microsphere desulfurizing agent is prepared by the same method as in the < example 1> except that the addition ratio of the raw materials is different, and the final F-Sorb desulfurizing agent comprises 29.2% of V 2O5, 41.2% of MgO, 20.6% of Al 2O3, 7.8% of CeO 2 and 1.2% of MnO 2 based on 100% of metal oxide mass content.
Example 4 ]
A flow diagram of the catalytic cracking flue gas renewable dry desulfurization process is shown in figure 1, and the process method specifically comprises the following steps:
Step one, continuously and uniformly adding the fresh solid microsphere desulfurizer F-Sorb prepared in the embodiment 1 into a flue gas pipeline of a catalytic cracking device shown in the attached figure 1 at the concentration of 0.5kg of desulfurizer/Nm 3 flue gas (for example, the fresh solid microsphere desulfurizer F-Sorb can be continuously added through an adding port which is distributed in a multipoint manner on the section of a flue gas through an adding device), wherein the SO 2 content 1556mg/Nm3 and the SO 3 content 47mg/Nm 3 of the flue gas are formed by the following dry basis volume components: (13.65% CO 2+5.21％O2+81.14％N2) and the desulfurizing agent reacts with the flue gas at 703 ℃ downwards. Under the condition of the average temperature of the reactor of about 706 ℃, under the catalysis of a desulfurizing agent, SO 2 oxidation reaction and the chemical adsorption of SO 3 are carried out to generate metal sulfate.
The generated metal sulfate is adsorbed on F-Sorb microsphere particles of the desulfurizing agent, and after the reaction is carried out for 1.9 seconds, the mixture of the desulfurizing agent and the flue gas is subjected to cyclone separation to realize the separation of the spent desulfurizing agent and the desulfurized flue gas; the desulfurized flue gas from the cyclone separator enters a third cyclone separator of the catalytic cracking flue gas, and after that, the desulfurized flue gas is discharged into a chimney after passing through an energy recovery system, a denitration and dust removal facility, and the SO 2 content of the inlet/outlet of the chimney is 9mg/Nm3, and the SO 3 content of the chimney is 0mg/Nm 3.
And secondly, conveying the microsphere solid desulfurizing agent (spent desulfurizing agent) containing the metal sulfate from the cyclone separator into a fluidized bed desulfurizing agent regenerator, introducing dry gas of a catalytic cracking device with the volume composition of (40.4％H2+8.01％N2+19.25％CH4+16.12％C2H4+8.98％C2H6+7.24％C3 +) for removing hydrogen sulfide into the desulfurizing agent regenerator at the Weight Hourly Space Velocity (WHSV) of 12.2h -1, and keeping the average residence time of the spent desulfurizing agent in the fluidized bed desulfurizing agent regenerator for 21 minutes under the condition that the bed temperature is about 710 ℃, so as to reduce the metal sulfate on the desulfurizing agent into metal oxide (regenerated desulfurizing agent).
The regenerated desulfurizing agent is returned to the catalytic cracking flue gas pipeline for recycling; the desulfurizing agent regeneration gas rich in hydrogen sulfide is led to an acid gas desulfurizing device for treatment, and then is sent to a sulfur device, so that the recycling of sulfur is realized.
The catalytic cracking regenerator adopts a rapid bed coking process, the burnt microsphere catalyst is subjected to gas-solid separation in a first rotating way and a second rotating way at the upper part of the regenerator, most of the microsphere catalyst is subjected to sedimentation separation, a small amount of worn catalyst fine powder is discharged out of the regenerator along with regenerated flue gas, generally, the content of particles in the flue gas at the second rotating outlet of the regenerator is 300-400 mg/m 3, and the particle size is distributed at 0-40 mu m; the content of particles in the flue gas of the triple-rotation outlet is not more than 200mg/m 3, and the proportion of particles with the particle size of more than mu m10 is not more than 3w percent. When the desulfurization reaction zone is disposed in the flue between the two-and three-rotors, a large amount of catalyst fines is required. If the moving bed process is adopted to treat the flue gas of the secondary spinning outlet, the problem of bed layer plug caused by dust is the first problem, the moving bed process proposed by ZL201811425856.8 is used to treat the flue gas of the tertiary spinning outlet, the dust in the flue gas has serious influence on the process, and a special elutriator is required to separate the intercepted catalyst fine powder. It is therefore not possible for the skilled person to treat flue gas between two and three revolutions for a moving bed desulfurization process.
The invention selects the flue between the two-spiral flue and the three-spiral flue as a desulfurization reactor, adopts microsphere desulfurizing agent and a down bed process, the desulfurizing agent moves in the same direction with the flue gas, the desulfurizing agent is microspheres, the agent-gas ratio is small, and the flue gas immediately enters a special cyclone separator for gas-solid separation after exiting the flue, so that the problem of blockage can not occur. In addition, the special design is provided in the aspect of desulfurizing agent preparation (for example, the desulfurizing agent density is far greater than that of FCC catalyst, the particle size distribution of the desulfurizing agent is concentrated at 60-100 microns), the desulfurizing agent and the special cyclone separator can ensure the separation of the desulfurizing agent from the flue gas, and meanwhile, the catalyst fine powder in the flue gas can not be intercepted, and the FCC catalyst fine powder in the flue gas is still removed in three revolutions. The technical route of the invention also fully utilizes the triple rotation of the catalytic cracking device to separate the fine powder generated by abrasion of the desulfurizing agent in the triple rotation, thereby avoiding the influence of the desulfurizing agent fine powder on the subsequent smoke machine.
< Simplified simulation experiment >
A laboratory example of two key steps in a renewable dry catalytic cracking flue gas desulfurization process. A vertical quartz tube reactor (with the inner diameter phi of 12 mm) is adopted to simulate a downlink desulfurization reactor, a metallurgical powder filter is adopted to simulate a cyclone separator, and a fixed fluidized bed reactor with the desulfurizing agent reserve of 200 g is adopted to simulate a desulfurizing agent fluidized bed regenerator; adopting simulated flue gas (the composition of the simulated flue gas is mixed gas prepared from 2650mg/Nm 3 SO2、4.0v％O2、96.0v％N2) to simulate catalytic cracking flue gas; the simulated regeneration gas (40 v% H 2+60v％CH4) is used for simulating refinery catalytic cracking desulfurization dry gas, and the specific operation is as follows:
200 g of the F-Sorb desulfurizing agent prepared in example 1 was weighed and charged into a fixed fluidized bed reactor, and a small amount of nitrogen was introduced, and the desulfurizing agent was heated to a certain temperature at the gas line speed of the bubbling bed, and kept stable at a stable temperature and pressure, which was the desulfurizing agent preparation stage. And opening a connecting pipe valve at the lower part of the fixed fluidized bed, enabling the thermal desulfurizing agent to enter the vertical quartz tube reactor by virtue of a pressure head, mixing the thermal desulfurizing agent with preheated simulated flue gas, enabling the mixture to go down along the vertical quartz tube reactor, carrying out chemical reaction and chemical adsorption, collecting the desulfurized flue gas at the outlet of the quartz tube reactor, and analyzing SO x(SO2+SO3), wherein the process is a reaction adsorption stage. The desulfurization chemistry and chemisorption equations that occur at this stage are:
2SO2+O2＝2SO3 (1)
Me2O3+3SO3＝Me2(SO4)3 (2)
MeO+SO3＝MeSO4 (3)
In the reaction formulae (1) to (3), meO and Me 2O3 represent oxides of different metal elements, and correspondingly, meSO 4 and Me 2(SO4)3 represent sulfates of different metal elements. After the reaction adsorption stage is completed, the spent desulfurizing agent is sent into a fixed fluidized bed reactor, a small amount of nitrogen is then introduced, the spent desulfurizing agent is heated to a preset temperature at the gas linear velocity of a bubbling bed, and the nitrogen is switched into simulated regeneration gas, wherein the stage is a regeneration stage. The chemical reaction and chemical desorption reaction formulas occurring at this stage are:
MeSO4+4H2＝MeO+H2S+3 H2O (4)
Me2(SO4)3+12H2＝Me2O3+3H2S+9H2O (5)
And collecting samples of the spent desulfurizing agent and the regenerated desulfurizing agent for sulfur determination analysis. After the regeneration stage is completed, the simulated regeneration gas is switched into nitrogen again, the regenerated desulfurizing agent is heated to a preset temperature at the gas linear velocity of the bubbling bed, and the reaction adsorption process is carried out again. And thus, carrying out a cycle experiment of simulating flue gas by absorbing the desulfurizing agent in a plurality of rounds and simulating reduction and regeneration of the regenerating desulfurizing agent by the regenerated gas.
The desulfurization effect in the reaction adsorption stage is expressed by simulating the concentration change rate of SO x of the flue gas before and after the reaction adsorption. The resumption of the desulfurization effect of the spent desulfurizing agent after the reduction regeneration is represented by the change rate of the sulfur content on the desulfurizing agent, namely the difference value of the sulfur content of the spent desulfurizing agent and the regenerated desulfurizing agent sample.
Effect of the reaction adsorption stage:
Wherein: SOx is SO x removal (%) of the desulfurizing agent; c 0 is the SOx content in the simulated flue gas before the reaction adsorption (mg/Nm 3),C1 is the SOx content in the desulfurized gas after the reaction adsorption (mg/Nm 3).
Reducing and regenerating effects of spent desulfurizing agent:
Wherein: reAct is the regeneration rate (%) of the spent desulfurizing agent; s 0 is the sulfur content (mg/g) of the spent desulfurizing agent; s 1 is the sulfur content (mg/g) of the regenerated desulfurizing agent.
10 Rounds of experiments of desulfurizing agent adsorption simulation flue gas-simulated regeneration gas reduction regeneration spent desulfurizing agent are carried out on the renewable dry catalytic cracking flue gas desulfurization process by adopting the simulated flue gas and the simulated regeneration gas, and the reaction adsorption experimental process conditions and desulfurization effects are listed in table 1; table 2 shows the conditions and regeneration effects of the spent desulfurizing agent.
TABLE 1 reaction adsorption experimental conditions and desulfurization effect
| Experiment number | Run 1 | Run 2 | Run 3 | Run 4 | Run 5 |
| Desulfurizing agent used | F-Sorb | F-Sorb | F-Sorb | F-Sorb | F-Sorb |
| Simulating SO2 content of flue gas, mg/Nm3 | 2650 | 2650 | 2650 | 2650 | 2650 |
| Simulating the O 2 content of the flue gas, v% | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 |
| Simulating the content of N 2 in the flue gas, v% | 96.0 | 96.0 | 96.0 | 96.0 | 96.0 |
| Average reaction adsorption temperature, DEG C | 710 | 700 | 680 | 650 | 600 |
| Average reaction adsorption pressure, MPa | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 |
| Simulating smoke flow, m/s | 1130 | 1118 | 1107 | 1095 | 1089 |
| Gas-to-agent ratio, nm 3 flue gas/kg desulfurizing agent | 2.1 | 4.0 | 5.8 | 8.2 | 10.1 |
| Reaction adsorption time, s | 0.60 | 0.61 | 0.98 | 1.53 | 1.54 |
| SOx content of desulfurized flue gas, mg/Nm 3 | 19.3 | 15.7 | 11.1 | 9.5 | 2.6 |
| SOx removal rate% | 99.27 | 99.41 | 99.58 | 99.69 | 99.90 |
TABLE 2 reduction regeneration process conditions and regeneration Effect of spent desulfurizing agent
| Experiment number | Run 6 | Run 7 | Run 8 | Run 9 | Run 10 |
| Spent desulfurizing agent | F-Sorb | F-Sorb | F-Sorb | F-Sorb | F-Sorb |
| Sulfur content of spent desulfurizing agent, mg/g | 82.5 | 60.8 | 39.6 | 21.2 | 8.7 |
| Simulating the content of regenerated gas H 2, v% | 40 | 40 | 40 | 40 | 40 |
| Simulating the content of regenerated gas CH 4, v% | 60 | 60 | 60 | 60 | 60 |
| Desulfurizing agent regeneration average temperature, DEG C | 675 | 680 | 690 | 700 | 710 |
| Desulfurizing agent regeneration average pressure, MPa | 0.13 | 0.13 | 0.13 | 0.13 | 0.13 |
| Desulfurizing agent regenerator hourly space velocity, h-1 | 3.69 | 3.39 | 2.95 | 2.68 | 2.51 |
| Desulfurizing agent regeneration time, min | 30 | 20 | 15 | 8 | 5 |
| Sulfur content of spent desulfurizing agent, mg/g | 0.0 | 0.0 | 0.10 | 0.19 | 0.23 |
| Regeneration rate of desulfurizing agent,% | 100 | 100 | 99.74 | 99.09 | 97.33 |
From the simulation experiment data of tables 1 and 2, it can be seen that: the regenerable dry catalytic cracking flue gas desulfurization process has good desulfurization performance and good desulfurizing agent regeneration performance. The desulfurization rate reaches more than 99.27% under experimental conditions, and can completely reach the current most severe emission standard. Under experimental conditions, the desulfurization activity can be completely recovered as long as the regeneration time of the desulfurizing agent is more than 20 minutes.
Compared with the wet flue gas desulfurization technology widely applied at present, the renewable dry catalytic cracking flue gas desulfurization technology has the advantages of high flue gas purification efficiency, capability of realizing the recycling of sulfur of SOx and the like, and can also avoid the problems of blue smoke, white smoke, rain falling of a washing tower, freezing, salt-containing wastewater discharge and the like caused by wet flue gas desulfurization. In addition, the SOx content in the purified flue gas can be reduced to 0-35 mg/m 3, so that the most severe environment-friendly emission standard can be met, the temperature of the flue gas at the outlet of the waste heat boiler is reduced to below 120 ℃, and the heat recovery rate of the waste heat boiler is obviously improved.
Compared with the dry desulfurization process of fluidized bed low-temperature adsorption-fluidized bed high-temperature regeneration, the dry regenerable dry catalytic cracking flue gas desulfurization process of the invention can realize high-temperature desulfurization-high-temperature reduction regeneration through oxidation reaction absorption, the oxidation adsorption and reduction regeneration temperature of the desulfurizing agent are relatively close, and the energy consumption increase and the operation cost increase caused by the thermal collapse of the desulfurizing agent due to repeated heating-cooling circulation of the desulfurizing agent are avoided.
Compared with the dry desulfurization process of high-temperature adsorption of a moving bed and high-temperature regeneration of a moving bed, the dry regenerable dry catalytic cracking flue gas desulfurization process can effectively avoid the problem of local hot spots in a desulfurization catalyst bed in a moving bed reactor or a regenerator in adsorption desulfurization and reduction regeneration processes (because the two processes are exothermic reactions), thereby realizing safe and stable long-period operation of a desulfurization reactor and a regenerator device.
The method has the greatest benefit of utilizing the flue gas pipeline as a downlink reactor. Compared with other technological processes, the special desulfurization reactor is omitted, so that the investment is obviously reduced. In the down reactor, the down speed of the desulfurizing agent is faster than the flow speed of the flue gas along with time, which is equivalent to that one batch of desulfurizing agent particles pass through the flue gas, so that the SOx content in the purified flue gas can be realized by adjusting the gas-gas ratio of 0-35 mg/m 3.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (10)
1. A renewable dry desulfurization process of catalytic cracking flue gas is characterized in that a solid microsphere desulfurizing agent is added into a flue gas pipeline of a catalytic cracking device, the desulfurizing agent flows along with the flue gas and completes desulfurization of the flue gas in the flowing process, the desulfurizing agent after adsorption is separated from desulfurization flue gas through a cyclone separator, the desulfurization flue gas from the cyclone separator enters a third cyclone separator of the catalytic cracking flue gas, is discharged to a chimney after subsequent treatment, and the desulfurizing agent from the cyclone separator is conveyed to a fluidized bed desulfurizing agent regenerator and is returned to the catalytic cracking flue gas pipeline for recycling after regeneration;
The catalytic cracking flue gas pipeline is a flue gas conveying pipeline from the catalytic cracking regenerator to the third-stage cyclone separator of the flue gas, and the desulfurizing agent is continuously and uniformly added into the horizontal section, the vertical section, the inclined section and the turning section of the flue gas pipeline;
The particle size range of the solid microsphere desulfurizing agent is 40-200 mu m, and the average particle size of the desulfurizing agent is 60-100 mu m.
2. The dry desulfurization process for renewable flue gas of catalytic cracking according to claim 1, wherein the regenerated solid microsphere desulfurizing agent is continuously and uniformly added into a flue gas pipeline of a catalytic cracking device, the desulfurizing agent flows along with flue gas, and simultaneously, SO 2 oxidation reaction and chemical adsorption of SO 3 occur at high temperature to generate metal sulfate which is adsorbed on the desulfurizing agent, and the solid microsphere desulfurizing agent is separated from desulfurization flue gas by a cyclone separator;
The desulfurization flue gas from the cyclone separator enters a third cyclone separator of catalytic cracking flue gas, and is discharged into a chimney after energy recovery, denitration and dust removal treatment;
The microsphere solid desulfurizing agent containing metal sulfate from the cyclone separator is conveyed to a fluidized bed desulfurizing agent regenerator, reducing gas after hydrogen sulfide is removed is introduced into the desulfurizing agent regenerator, the metal sulfate on the desulfurizing agent is reduced into metal oxide at high temperature, the metal oxide is returned to a catalytic cracking flue gas pipeline for recycling, and the desulfurizing agent regenerated gas rich in hydrogen sulfide is conveyed to an acid gas desulfurizing device for treatment and then conveyed to a sulfur device, so that recycling of sulfur is realized.
3. The process for dry desulfurization of catalytically cracked flue gas according to claim 1, wherein the desulfurizing agent is continuously and uniformly added to the vertically downward section and the turning section of the flue gas duct which vertically downward from the horizontal.
4. The process for the renewable dry desulfurization of catalytic cracking flue gas according to claim 1 or 2, wherein the ratio of desulfurizing agent to flue gas added into a catalytic cracking flue gas pipeline is 0.005-2.0 kg/Nm 3, and the reaction adsorption time and temperature of the catalytic cracking flue gas and desulfurizing agent are 0.01-60 s and 500-750 ℃ respectively.
5. The process for the renewable dry desulfurization of catalytic cracking flue gas according to claim 4, wherein the ratio of desulfurizing agent to flue gas added into the catalytic cracking flue gas pipeline is 0.01-0.5 kg/Nm 3, and the reaction adsorption time and temperature of the catalytic cracking flue gas and desulfurizing agent are 0.1-5 s and 550-720 ℃ respectively.
6. The process for dry desulfurization of catalytic cracking flue gas according to claim 2, wherein the reducing gas is one or any mixture of hydrogen, methane, ethane and ethylene, and the operating parameters of the fluidized bed desulfurizing agent regenerator are as follows: the regeneration temperature is 500-750 ℃, the average residence time of the desulfurizing agent in the regenerator is 30 s-60 min, and the weight hourly space velocity of the desulfurizing agent regenerator is: 0.05-50 h -1.
7. The process for dry desulfurization of catalytic cracking flue gas according to claim 2, wherein the reducing gas is refinery dry gas and the operating parameters of the fluidized bed desulfurizer are as follows: the regeneration temperature is 600-700 ℃, the average residence time of the desulfurizing agent in the regenerator is 1-30 min, and the weight hourly space velocity of the desulfurizing agent regenerator is: 0.1-20 h -1.
8. The process for dry desulfurization of catalytic cracking flue gas according to claim 1 or 2, wherein the desulfurizing agent comprises, based on 100% of the metal oxide, 10 to 30% V 2O5, 1 to 8% CeO 2, 20 to 40% MgO, 20 to 55% Al 2O3 and 0.5 to 2% MnO 2.
9. The process for dry desulfurization of catalytic cracking flue gas according to claim 8, wherein the desulfurizing agent is prepared by the following steps:
1) Slowly dripping a mixed solution prepared from magnesium salt and aluminum salt into a mixed solution prepared from sodium hydroxide and sodium carbonate, and stirring to react for nucleation and crystallization after the dripping is completed to obtain magnesia-alumina spinel;
2) Sequentially adding ammonium metavanadate, cerium nitrate, dan Mei aluminum spinel and manganese salt into deionized water at 50-90 ℃, stirring until the ammonium metavanadate, the cerium nitrate, the Dan Mei aluminum spinel and the manganese salt are completely dissolved, adding pseudo-boehmite, stirring, adding a binder, and continuing stirring to obtain slurry;
3) And carrying out spray drying on the slurry under the operation conditions that the temperature of a hearth is 300-400 ℃, the temperature of a furnace outlet is 180-250 ℃ and the pressure is 3.0-5.0 MPa to obtain solid microsphere particles, screening and selecting to obtain microsphere particles with target particle size, and roasting for 3-10 hours at the temperature of 650-760 ℃ to obtain the desulfurizing agent.
10. The process for the dry desulfurization of flue gas in catalytic cracking according to claim 9, wherein manganese salt, magnesium salt and aluminum salt are chlorides, nitrates, sulfates or organic acid salts thereof, and the binder is an aluminum sol, silica sol or silica alumina mixed sol.
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| CN109453783A (en) * | 2018-11-27 | 2019-03-12 | 新淳(上海)环保科技有限公司 | A kind of regeneration fume from catalytic cracking desulphurization catalyst and preparation method thereof |
| CN113713800A (en) * | 2021-09-15 | 2021-11-30 | 中国石油化工股份有限公司 | High-temperature flue gas desulfurizer and preparation method thereof |
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