CN115845596A - Catalytic cracking flue gas regenerative dry desulfurization process - Google Patents
Catalytic cracking flue gas regenerative dry desulfurization process Download PDFInfo
- Publication number
- CN115845596A CN115845596A CN202211428688.4A CN202211428688A CN115845596A CN 115845596 A CN115845596 A CN 115845596A CN 202211428688 A CN202211428688 A CN 202211428688A CN 115845596 A CN115845596 A CN 115845596A
- Authority
- CN
- China
- Prior art keywords
- flue gas
- desulfurizer
- catalytic cracking
- regenerator
- desulfurization process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003546 flue gas Substances 0.000 title claims abstract description 156
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 81
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 78
- 230000023556 desulfurization Effects 0.000 title claims abstract description 78
- 230000008569 process Effects 0.000 title claims abstract description 69
- 230000001172 regenerating effect Effects 0.000 title description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 44
- 230000008929 regeneration Effects 0.000 claims abstract description 44
- 238000011069 regeneration method Methods 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 38
- 239000004005 microsphere Substances 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000001179 sorption measurement Methods 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052596 spinel Inorganic materials 0.000 claims description 10
- 239000011029 spinel Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 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
- -1 magnesium aluminate Chemical class 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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 6
- 239000000428 dust Substances 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 150000002696 manganese Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- 230000006911 nucleation Effects 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
- 229910052815 sulfur oxide Inorganic materials 0.000 description 40
- 239000003054 catalyst Substances 0.000 description 20
- 230000009467 reduction Effects 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000779 smoke Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000003517 fume Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 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
- 239000003921 oil Substances 0.000 description 2
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class 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
- 206010019332 Heat exhaustion Diseases 0.000 description 1
- 206010019345 Heat stroke Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 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
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a renewable dry desulfurization process for catalytic cracking flue gas, which is characterized in that a solid microsphere desulfurizer is added into a flue gas pipeline of a catalytic cracking device, the desulfurizer flows along with the flue gas and completes the desulfurization of the flue gas in the flowing process, the adsorbed desulfurizer is separated from the desulfurized flue gas through a cyclone separator, the desulfurized flue gas discharged from the cyclone separator enters a third-stage cyclone separator for catalytic cracking flue gas, and the desulfurizer discharged from the cyclone separator is conveyed to a fluidized bed desulfurizer regenerator and is returned to the catalytic cracking flue gas pipeline for recycling after regeneration. The invention uses the flue gas pipeline as a descending reactor, and compared with other process methods, the invention cancels a special additional desulfurization reactor, thereby obviously reducing the investment. In the downflow reactor, the downward speed of the desulfurizer is faster and faster than the flow speed of flue gas along with time, and the desulfurizing agent is in phase with the flue gasWhen one batch of desulfurizer particles pass through the flue gas, SO in the flue gas is purified x The content can be realized by adjusting the gas ratio of the regulator to be 0-35 mg/m 3 And (4) clean discharge.
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 in oil refineries, and the core equipment of the process is mainly a reactor and a regenerator. Under the action of catalyst, the raw oil is cracked into light fraction and cracked gas in the catalytic cracking reactor, the catalyst is deactivated by coking in the reaction process, the deactivated catalyst is fluidized and conveyed to the regenerator for coke burning regeneration, and then the catalyst is circulated and returned to the reactor for continuous catalytic reaction. During the catalytic cracking reaction, partial sulfide in the material is deposited on the catalyst, and when the catalyst is burnt in the regenerator for regeneration, the sulfur in the catalyst is depositedCombustion of the compounds to form Sulfur Oxides (SO) x ) And is discharged along with the flue gas. Sulfur oxides SO in flue gases x The approximate range of the composition is as follows: 90 to 95 percent of SO 2 And 5% -10% of SO 3 It not only pollutes environment seriously, but also can act with the water vapor in the flue gas to condense on the wall of the device to generate acid solution, which causes serious corrosion to the device. Therefore, how to reduce or even completely remove SO in catalytic cracking regeneration flue gas under the conditions of lower investment, lower operation cost and energy consumption x Simultaneously, secondary pollution such as salt-containing wastewater is not generated and SO is realized x The resource utilization of the coal is a problem to be solved urgently.
Current reduction of SO in catalytic cracking regenerators x The main methods of discharge are as follows:
1. the catalytic cracking raw material is subjected to hydrogenation pretreatment, such as ZL201510769249.3, ZL201410766839.6, ZL201210440586.4 and the like. Although the hydrogenation pretreatment of the catalytic cracking raw material can effectively reduce the SO of the catalytic cracking flue gas x The emission of the method can not meet the emission requirement, and the catalytic cracking raw material hydrogenation pretreatment device has high investment cost and high running cost, so the application of the method is limited.
2. Regenerated flue gas sulfur transfer agents such as ZL201510109947.0, ZL201210443822.8, ZL201210349980.7, and ZL201110029268.4, and the like, are used in catalytic cracking processes. The measure can effectively reduce the SO of the catalytic cracking flue gas x Discharging SO in the regenerated flue gas x The reduction is 50-70%, but the regenerated flue gas sulfur transfer agent is difficult to meet the requirement of flue gas emission along with the continuous improvement of the flue gas emission standard.
3. The wet scrubbing flue gas desulfurization technology which is the most widely used in industry at present, such as 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 flue gas emission (white smoke), blue smoke plume (blue smoke), washing tower 'raining' and icing, salt-containing wastewater and the like. Meanwhile, because the wet flue gas desulfurization is positioned at the tail end of the device, SO x The further reduction of the temperature of the flue gas at the outlet of the waste heat boiler is limited, so that the wet desulphurization has the result of higher energy consumption。
4. In recent years, the sodium bicarbonate powder for purifying the flue gas of a coal-fired boiler and the lime hydrate process technology are used for reference, and the purity of sulfite which is a product of desulfurization and denitrification of catalytic cracking flue gas is not high, so that the high-value utilization is difficult.
However, the regenerative dry flue gas desulfurization processes under research and development, such as ZL200610171550.5, ZL201811425856.8 and the like, which adopt a catalytic cracking catalyst, or adopt magnesia alumina spinel as a desulfurization adsorbent or catalyst, adopt a fluidized bed adsorption-fluidized bed regeneration process, or use a moving bed desulfurization-moving bed regeneration process, have the problems of high investment and/or high energy consumption.
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 renewable dry flue gas desulfurization process for catalytic cracking.
In order to solve the technical problems, the invention adopts the technical scheme that: a process for regenerating dry desulfurizing the fume generated by catalytic cracking includes such steps as adding the solid microball as desulfurizing agent to the fume pipeline of catalytic cracking unit, flowing the desulfurizing agent along with fume while desulfurizing, separating the adsorbed desulfurizing agent from fume by cyclone separator, introducing the fume from cyclone separator to the third cyclone separator, post-treating, discharging it to chimney, delivering the desulfurizing agent from cyclone separator to the regenerator of fluidized bed desulfurizing agent, regenerating, and returning it back to the fume pipeline for cyclic use.
The catalytic cracking flue gas regenerable dry desulfurization process is further optimized as follows: continuously and uniformly adding the regenerated solid microsphere desulfurizer into a flue gas pipeline of a catalytic cracking unit, wherein the desulfurizer flows along with the flue gas and simultaneously generates SO at high temperature 2 Oxidation reaction and SO 3 The metal sulfate is generated by the chemical adsorption of the solid microsphere desulfurizer, and the solid microsphere desulfurizer is adsorbed on the desulfurizer, and is separated from the desulfurized flue gas by a cyclone separator;
enabling the desulfurized flue gas from the cyclone separator to enter a third-stage cyclone separator of catalytic cracking flue gas, and discharging the desulfurized flue gas into a chimney after energy recovery, denitration and dust removal treatment;
conveying the microsphere solid desulfurizer containing the metal sulfate from the cyclone separator to a fluidized bed desulfurizer regenerator, introducing the reducing gas subjected to hydrogen sulfide removal into the desulfurizer regenerator, reducing the metal sulfate on the desulfurizer into metal oxide at high temperature, returning the metal sulfate to a catalytic cracking flue gas pipeline for recycling, introducing the desulfurizer regeneration gas rich in hydrogen sulfide to an acid gas desulfurization device for treatment, and then conveying the desulfurizer regeneration gas to a sulfur device to realize resource recycling of sulfur.
The catalytic cracking flue gas renewable dry desulfurization process is further optimized as follows: the catalytic cracking flue gas pipeline is a flue gas conveying pipeline between a catalytic cracking regenerator and a third-stage flue gas cyclone separator, and a desulfurizing agent is continuously and uniformly added into a horizontal section, a vertical section, an inclined section and a turning section of the flue gas pipeline.
The catalytic cracking flue gas regenerable dry desulfurization process is further optimized as follows: the desulfurizing agent is continuously and uniformly added into a vertical descending section and a turning section which descends from the horizontal direction to the vertical direction of the flue gas pipeline.
The catalytic cracking flue gas regenerable dry desulfurization process is further optimized as follows: the particle size range of the solid microsphere desulfurizer is 40-200 mu m, and the average particle size of the desulfurizer is 60-100 mu m.
The catalytic cracking flue gas renewable dry desulfurization process is further optimized as follows: the ratio of the desulfurizer added into the catalytic cracking flue gas pipeline to the flue gas is 0.005-2.0 kg/Nm < 3>, and the reaction adsorption time and temperature of the catalytic cracking flue gas and the desulfurizer are 0.01-60 s and 500-750 ℃ respectively.
The catalytic cracking flue gas renewable dry desulfurization process is further optimized as follows: the ratio of the desulfurizer added into the catalytic cracking flue gas pipeline to the flue gas is 0.01-0.5 kg/Nm < 3>, and the reaction adsorption time and temperature of the catalytic cracking flue gas and the desulfurizer are 0.1-5 s and 550-720 ℃ respectively.
The catalytic cracking flue gas renewable dry desulfurization process is further optimized as follows: the reducing gas is one or any mixture of hydrogen, methane, ethane and ethylene, and the working parameters of the fluidized bed desulfurizer regenerator are as follows: the regeneration temperature is 500-750 ℃, the average residence time of the desulfurizer in the regenerator is 30 s-60 min, and the weight hourly space velocity of the desulfurizer regenerator is as follows: 0.05 to 50h < -1 >.
The catalytic cracking flue gas regenerable dry desulfurization process is further optimized as follows: the reducing gas is refinery dry gas, and the working parameters of the fluidized bed desulfurizer regenerator are as follows: the regeneration temperature is 600-700 ℃, the average residence time of the desulfurizer in the regenerator is 1-30 min, and the weight hourly space velocity of the desulfurizer regenerator is as follows: 0.1 to 20h < -1 >.
The catalytic cracking flue gas renewable dry desulfurization process is further optimized as follows: the desulfurizer comprises 10-30% of V2O5, 1-8% of CeO2, 20-40% of MgO, 20-55% of Al2O3 and 0.5-2% of MnO2 by mass of metal oxide of 100%.
The catalytic cracking flue gas renewable dry desulfurization process is further optimized as follows: 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 dripping is finished to obtain magnesium aluminate 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 operating 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 to obtain microsphere particles with target particle sizes, and roasting at 650-760 ℃ for 3-10 hours to obtain the desulfurizer.
The catalytic cracking flue gas regenerable dry desulfurization process is further optimized as follows: manganese salt, magnesium salt and aluminum salt are chlorides, nitrates, sulfates or organic acid salts thereof, and the binder is aluminum sol, silica sol or silicon-aluminum mixed sol.
The invention has the following beneficial effects: the invention uses the flue gas pipeline as a descending reactor, and compared with other process methods, the invention cancels a special additional desulfurization reactor, thereby obviously reducing the investment. In the downward reactor, the descending speed of the desulfurizer is faster and faster than the flow speed of the flue gas along with time, which means that one batch of desulfurizer and one batch of desulfurizer particles pass through the flue gas, SO that SO in the flue gas is purified x The content can be realized by adjusting the gas ratio of the regulator to be 0-35 mg/m 3 And (4) clean discharge.
Drawings
FIG. 1 is a schematic view of the process flow of the catalytic cracking flue gas regenerable dry desulfurization process of the present invention.
Detailed Description
For a better understanding of the present invention, the following examples are included to further illustrate the present invention, but the present invention is not limited to the following examples.
< example 1>
A solid microsphere desulfurizer is prepared by the following steps:
1) 1.25 tons of deionized water are added into a 2.5 cubic meter enamel reactor, and 22.25 kilograms of sodium carbonate (Na) are gradually added under the condition that the rotating speed of a stirrer is 120rpm 2 CO 3 ) And 57 kg of caustic soda (NaOH), heating with stirring, and adding magnesium nitrate hexahydrate (Mg (NO) containing 55.25 kg of magnesium nitrate at a temperature of 70 ℃ and a rate of 20 liters per minute 3 ) 2 ·6H 2 O) and 46.75 kg of aluminum nitrate nonahydrate (Al (NO) 3 ) 3 ·9H 2 O) 750 kg of aqueous solution. After the filling is finished, the mixture is continuously and evenly stirred, the constant temperature is kept when the temperature of the reaction kettle is reduced to 65 ℃, and the rotating speed is reduced to 25rpm to stir, nucleate and crystallize for 18 hours. Then cooling, discharging and filtering, washing with deionized water to be neutral, and drying to obtain the magnesium aluminate spinel (MgAl) 2 O 4 )。
2) 1.25 tons of deionized water were added to a 2.5 cubic meter enamel reactor and held at 20rpmStirring speed, 21.78 kg of ammonium metavanadate (NH) 4 VO 3 ) 18.6 kg of magnesium aluminate spinel, 2.38 kg of manganese nitrate tetrahydrate (Mn (NO) 3 ) 2 ·4H 2 O), 22.1 kg of activated magnesium oxide (90% on a dry basis) and 17.5 kg of cerium nitrate hexahydrate (Ce (NO) 3 ) 2 ·6H 2 O, keeping the temperature of 85 ℃, stirring for 100 minutes, adding 40.1 kg of pseudo-boehmite after complete dissolution, and continuing stirring for 9 hours to obtain slurry.
3) Spray-drying the slurry in a 50 kg/h spray dryer under the operating conditions of 360 ℃ of hearth temperature, 190 ℃ of furnace outlet temperature and 3.9MPa of pressure to obtain solid microsphere granules, screening the microsphere granules with the particle diameter range of 40-200 mu m and the average particle diameter of 87 mu m, and roasting at 750 ℃ for 8 hours to obtain the fresh desulfurizer (F-Sorb). The F-Sorb desulfurizer comprises 12.7 percent of V by mass content of metal oxide of 100 percent 2 O 5 30.0% of MgO and 50.6% of Al 2 O 3 6.1% of CeO 2 And 0.6% MnO 2 。
The desulfurizer is a formula catalyst, and particularly, catalysts with various functions can achieve specific effects only by matching various specific active components with carriers. The desulfurizer of the invention has a plurality of outstanding functional characteristics:
1) The desulfurizer can be used as an oxygen carrier with a catalytic function to remove SO in flue gas in an oxidizing atmosphere 2 Rapid catalytic oxidation to SO 3 Wherein V plays a major role 2 O 5 And Ce 2 O 3 Two active components. The idea of selecting vanadium comes from the traditional V 2 O 5 Catalytic oxidation of SO 2 Process for the preparation of sulfuric acid V 2 O 5 Will not react with SO 2 Or SO 3 A reaction takes place, thus V 2 O 5 And cannot be directly used as a desulfurizing agent.
2) The magnesia-alumina spinel used as a carrier not only provides a skeleton structure and micro channels, provides high strength and high stability for the desulfurizer, but also provides strong oxidation products for the desulfurizer due to rich alkaline sitesSO 3 The capture capability of (a).
3) The desulfurizer can also play a role in catalyzing the reduction of metal sulfate in a reducing atmosphere, wherein Ce plays a main role 2 O 3 An active component.
< example 2>
Solid microsphere desulfurizing agent, preparation method and application thereof<Example 1>Basically the same, except that the addition proportions of the raw materials are different, and the finally prepared F-Sorb desulfurizer comprises 22.6 percent of V by taking the mass content of the metal oxide as 100 percent 2 O 5 25.6% of MgO and 45.4% of Al 2 O 3 4.6% of CeO 2 And 1.8% MnO 2 。
< example 3>
Solid microsphere desulfurizing agent, preparation method and application thereof<Example 1>Basically the same, except that the adding proportion of each raw material is different, and the finally prepared F-Sorb desulfurizer comprises 29.2 percent of V based on 100 percent of the mass content of the metal oxide 2 O 5 41.2% of MgO and 20.6% of Al 2 O 3 7.8% of CeO 2 And 1.2% MnO 2 。
< example 4>
A catalytic cracking flue gas renewable dry desulfurization process is shown in a schematic flow diagram in figure 1, and the process method specifically comprises the following steps:
step one, the fresh solid microsphere desulfurizer F-Sorb prepared in example 1 is added with 0.5kg desulfurizer/Nm 3 The concentration of the flue gas is continuously and uniformly added into a flue gas pipeline of the catalytic cracking unit shown in figure 1 (for example, the flue gas can be continuously added through an agent adding device at agent adding ports distributed at multiple points on the cross section of a flue), and the SO of the flue gas 2 Content 1556mg/Nm3, SO 3 Content 47mg/Nm 3 The dry basis volume composition is: (13.65% CO) 2 +5.21％O 2 +81.14％N 2 ) The desulfurizing agent flows to the lower side along with the smoke gas at 703 ℃ and reacts. SO is generated under the condition of the average temperature of the reactor of about 706 ℃ and the catalytic action of a desulfurizer 2 Oxidation reaction and SO 3 To produce metal sulfates by chemisorption.
The generated metal sulfate is adsorbed on the desulfurizer F-Sorb microsphere particles, and after the reaction lasts for 1.9 seconds, the mixture of the desulfurizer and the flue gas is subjected to cyclone separation to realize the separation of the desulfurizer to be generated and the desulfurized flue gas; the desulfurized flue gas from the cyclone separator enters a third-stage cyclone separator of catalytic cracking flue gas, the desulfurized flue gas is discharged into a chimney after passing through an energy recovery system and a denitration and dust removal facility, and SO at the inlet/outlet of the chimney 2 Content 9mg/Nm3, SO 3 The content is 0mg/Nm 3 。
Step two, conveying the microsphere solid desulfurizer (to-be-generated desulfurizer) containing the metal sulfate from the cyclone separator into a fluidized bed desulfurizer regenerator at a Weight Hourly Space Velocity (WHSV) of 12.2h -1 The flow rate of (2) was determined by introducing a volume composition (40.4% by weight) into the desulfurizing agent regenerator 2 +8.01％N 2 +19.25％CH 4 +16.12％C 2 H 4 +8.98％C 2 H 6 +7.24％C 3 + ) The dry gas of the catalytic cracking device after removing the hydrogen sulfide keeps the average residence time of the desulfurizer to be generated in a fluidized bed desulfurizer regenerator for 21 minutes under the condition that the bed temperature is about 710 ℃, and the metal sulfate on the desulfurizer can be reduced into metal oxide (regenerated desulfurizer).
The regenerated desulfurizer is returned to the catalytic cracking flue gas pipeline for recycling; and introducing the desulfurizer regeneration gas rich in hydrogen sulfide to an acid gas desulfurization device for treatment, and then delivering the desulfurizer regeneration gas to a sulfur device to realize resource recycling of sulfur.
The catalytic cracking regenerator adopts a fast bed coking process, the coked microspherical catalyst is subjected to gas-solid separation in a first cyclone and a second cyclone at the upper part of the regenerator, most of the microspherical 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, and generally, the content of particulate matters in the flue gas at the second cyclone outlet of the regenerator is 300-400 mg/m 3 The grain size is distributed between 0 and 40 mu m; the content of particulate matters in the smoke at the triple-rotation outlet is not more than 200mg/m 3 And the proportion of the particles with the particle size larger than 10 μm is not more than 3w%. When the desulfurization is reversedWhen the reaction zone is provided in the flue between the second and third cyclones, a large amount of catalyst fines needs to be faced. If the moving bed process is adopted to treat the flue gas at the secondary cyclone outlet, the problem of bed layer blockage caused by dust is firstly solved, the moving bed process proposed by ZL201811425856.8 treats the flue gas at the tertiary cyclone outlet, the dust in the flue gas has serious influence on the process, and an elutriator is specially arranged to separate the intercepted catalyst fine powder. It is therefore impossible for the skilled person to treat flue gases between the secondary and tertiary cyclones in a moving bed desulfurization process.
The invention selects the flue between the second cyclone and the third cyclone as a desulfurization reactor, adopts a microsphere desulfurizing agent and a downer process, the desulfurizing agent and the flue gas move in the same direction, the desulfurizing agent is microsphere, the agent-gas ratio is very small, the flue gas immediately enters a special cyclone separator for gas-solid separation after being discharged, and the problem of blockage can not occur. In addition, the preparation of the desulfurizer is specially designed (for example, the density of the desulfurizer is far greater than that of an FCC catalyst, and the particle size distribution of the desulfurizer is concentrated at 60-100 microns), the characteristics of the desulfurizer and a specially designed cyclone separator can ensure the separation of the volume of the desulfurizer and flue gas, and meanwhile, 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 a triple rotation process. The technical route of the invention also fully utilizes the triple cyclone of the catalytic cracking device to separate the fine powder generated by the abrasion of the desulfurizer from the triple cyclone, thereby avoiding the influence of the fine powder of the desulfurizer on a subsequent smoke machine.
< simplified simulation experiment >
A laboratory example of two key steps in a regenerable 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 down-flow desulfurization reactor, a metallurgical powder filter is used to simulate a cyclone separator, and a fixed fluidized bed reactor with the desulfurizing agent reserve of 200 g is used to simulate a desulfurizing agent fluidized bed regenerator; simulated smoke (the composition of which is 2650 mg/Nm) 3 SO 2 、4.0v％O 2 、96.0v％N 2 The prepared mixed gas) to simulate catalytic cracking flue gas; using simulated regeneration gas (composition 40v% 2 +60v％CH 4 ) Coming dieThe catalytic cracking desulfurization dry gas of the refinery is prepared by the following specific operations:
200 g of the F-Sorb desulfurizer prepared in example 1 is weighed and loaded into a fixed fluidized bed reactor, a small amount of nitrogen is introduced, the desulfurizer is heated to a certain temperature at the gas linear speed of a bubbling bed, and is kept stable at a stable temperature and pressure, and the stage is a desulfurizer preparation stage. Opening a connecting pipe valve at the lower part of the fixed fluidized bed, enabling the thermal desulfurization agent to enter the vertical quartz tube reactor by virtue of a pressure head, mixing with preheated simulated flue gas, descending along the vertical quartz tube reactor, carrying out chemical reaction and chemical adsorption, collecting the desulfurization flue gas at the outlet of the quartz tube reactor, and analyzing SO x (SO 2 +SO 3 ) Concentration, the process is a reaction adsorption stage. The desulfurization chemical reaction and chemisorption equations that occur at this stage are:
2SO 2 +O 2 ＝2SO 3 (1)
Me 2 O 3 +3SO 3 ＝Me 2 (SO 4 ) 3 (2)
MeO+SO 3 ＝MeSO 4 (3)
in the reaction formulas (1) to (3), meO and Me 2 O 3 Oxides representing different metal elements, correspondingly, meSO 4 And Me 2 (SO 4 ) 3 Denotes sulfates of different metal elements. And after the reaction adsorption stage is finished, feeding the desulfurizing agent to be generated into the fixed fluidized bed reactor, introducing a small amount of nitrogen, heating the desulfurizing agent to be generated to a preset temperature at the gas linear speed of the bubbling bed, and switching the nitrogen into simulated regeneration gas, wherein the stage is a regeneration stage. The chemical reaction and the chemical desorption reaction formula which occur at the stage are as follows:
MeSO 4 +4H 2 ＝MeO+H 2 S+3 H 2 O (4)
Me 2 (SO 4 ) 3 +12H 2 ＝Me 2 O 3 +3H 2 S+9H 2 O (5)
collecting the to-be-regenerated desulfurizer and the regenerated desulfurizer samples for sulfur determination analysis. And after the regeneration stage is finished, the simulated regeneration gas is switched to nitrogen again, the regenerated desulfurizer is heated to the preset temperature at the gas linear speed of the bubbling bed, and the reaction adsorption process is carried out again. Thus, a cycle experiment of the desulfurizer to be regenerated by a plurality of cycles of absorption simulation flue gas and regeneration reduction simulation gas is carried out.
The desulfurization effect in the reaction adsorption stage is realized by simulating SO before and after reaction adsorption of the flue gas x The rate of change of the concentration. The recovery condition of the desulfurization effect of the to-be-generated desulfurizer after reduction and regeneration is represented by the change rate of the sulfur content on the desulfurizer, namely the difference value of the sulfur content of the to-be-generated desulfurizer and the sulfur content of the regenerated desulfurizer sample.
Effect of the reactive adsorption stage:
in the formula: desox is SO of desulfurizer x Removal rate (%); c 0 Simulating the content of SOx (mg/Nm) in the flue gas before reaction adsorption 3 )，C 1 The SOx content (mg/Nm 3) in the desulfurization gas after the reaction adsorption was obtained.
The spent desulfurizer has the reduction regeneration effect:
in the formula: the Rect is the regeneration rate (%) of the desulfurizing agent to be regenerated; s 0 The sulfur content (mg/g) of the desulfurizing agent to be generated; s 1 The sulfur content (mg/g) of the regenerated desulfurization agent.
The simulated flue gas and the simulated regeneration gas are adopted to carry out 10 rounds of experiments of adsorbing the simulated flue gas by the desulfurizer and reducing and regenerating the to-be-regenerated desulfurizer by the regenerated dry catalytic cracking flue gas desulfurization process, and the process conditions and the desulfurization effect of the reaction adsorption experiment are listed in table 1; table 2 shows the reduction regeneration process conditions and the regeneration effect of the desulfurizing agent to be regenerated.
TABLE 1 reaction adsorption experiment process conditions and desulfurization effect
| Experiment number | Run 1 | Run 2 | Run 3 | Run 4 | Run 5 |
| The used desulfurizing agent | F-Sorb | F-Sorb | F-Sorb | F-Sorb | F-Sorb |
| Simulating SO2 content of flue gas, mg/Nm3 | 2650 | 2650 | 2650 | 2650 | 2650 |
| Simulated flue gas O 2 Content, v% | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 |
| Simulated smoke N 2 Content, v% | 96.0 | 96.0 | 96.0 | 96.0 | 96.0 |
| Average reaction adsorption temperature,. Degree.C | 710 | 700 | 680 | 650 | 600 |
| Average reaction adsorption pressure, MPa | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 |
| Simulating flue gas flow, m/s | 1130 | 1118 | 1107 | 1095 | 1089 |
| Gas to dose 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 desulfurization 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 |
| Simulated regeneration gas H 2 Content, v% | 40 | 40 | 40 | 40 | 40 |
| Simulated regeneration gas CH 4 Content, v% | 60 | 60 | 60 | 60 | 60 |
| Average temperature of regeneration of desulfurizing agent, DEG C | 675 | 680 | 690 | 700 | 710 |
| Regeneration average pressure of desulfurizing agent, MPa | 0.13 | 0.13 | 0.13 | 0.13 | 0.13 |
| Heavy hourly space velocity of desulfurizer regenerator h-1 | 3.69 | 3.39 | 2.95 | 2.68 | 2.51 |
| Regeneration time of desulfurizing agent 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 data in tables 1 and 2, it can be seen that: the desulfurization performance and the desulfurizer regeneration performance of the desulfurization process of the renewable dry catalytic cracking flue gas are good. The desulfurization rate reaches over 99.27 percent under the experimental condition, and the current most severe emission standard can be completely reached. Under experimental conditions, the desulfurization activity can be completely recovered as long as the regeneration time of the desulfurizing agent is longer than 20 minutes.
Compared with the wet flue gas desulfurization technology which is widely applied at present, the renewable dry catalytic cracking flue gas desulfurization process has the advantages of high flue gas purification efficiency, realization of sulfur resource utilization of SOx and the like, and can also avoid the problems of 'blue smoke', 'white smoke', washing tower 'rain', icing, 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 The method can meet the most harsh environmental protection emission standard, and simultaneously, the temperature of the flue gas at the outlet of the waste heat boiler is reduced to be 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 renewable catalytic cracking flue gas desulfurization process can realize high-temperature desulfurization-high-temperature reduction regeneration through oxidation reaction absorption, the oxidation adsorption temperature and the reduction regeneration temperature of the desulfurizer are relatively close, and the increase of energy consumption and the increase of operating cost caused by heat collapse of the desulfurizer due to repeated heating-cooling circulation of the desulfurizer are avoided.
Compared with the dry desulfurization process of moving bed high-temperature adsorption-moving bed high-temperature regeneration, the dry regenerative dry catalytic cracking flue gas desulfurization process can effectively avoid the problem of local hot spots in the desulfurization catalyst bed layer in the moving bed reactor or the regenerator in the adsorption desulfurization and reduction regeneration processes (because the two processes are both exothermic reactions), thereby realizing the safe and stable long-period operation of the desulfurization reactor and the regenerator equipment.
The method has the greatest benefit of utilizing the flue gas pipeline as a descending reactor. Compared with other process methods, the method eliminates a special additional desulfurization reactor, thereby remarkably reducing the investment. In the downward reactor, the descending speed of the desulfurizer is faster and faster than the flow speed of the flue gas along with the time, which is equivalent to that one batch of desulfurizer and one batch of desulfurizer pass through the flue gas, so that the SOx content in the purified flue gas can be realized to be 0-35 mg/m through the gas ratio of the regulator 3 And (4) clean discharge.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (12)
1. A renewable dry desulfurization process for catalytic cracking flue gas is characterized in that a solid microsphere desulfurizer is added into a flue gas pipeline of a catalytic cracking device, the desulfurizer flows along with flue gas and completes desulfurization of the flue gas in the flowing process, the adsorbed desulfurizer is separated from the desulfurization flue gas through a cyclone separator, the desulfurization flue gas discharged from the cyclone separator enters a third-stage cyclone separator for the catalytic cracking flue gas, is discharged to a chimney after subsequent treatment, is conveyed into a fluidized bed desulfurizer regenerator, and is recycled after regeneration.
2. The regenerable dry desulfurization process for catalytic cracking flue gas according to claim 1, wherein the regenerated solid microsphere desulfurizer is continuously and uniformly added into the flue gas duct of the catalytic cracking unit, flows with the flue gas, and simultaneously generates SO at high temperature 2 Oxidation reaction and SO 3 The metal sulfate is generated by the chemical adsorption of the solid microsphere desulfurizer, and the solid microsphere desulfurizer is adsorbed on the desulfurizer, and is separated by cycloneThe device realizes the separation from the desulfurized flue gas;
the desulfurized flue gas from the cyclone separator enters a third-stage cyclone separator of catalytic cracking flue gas, and is discharged into a chimney after energy recovery, denitration and dust removal treatment;
conveying the microsphere solid desulfurizer containing the metal sulfate from the cyclone separator to a fluidized bed desulfurizer regenerator, introducing the reducing gas subjected to hydrogen sulfide removal into the desulfurizer regenerator, reducing the metal sulfate on the desulfurizer into metal oxide at high temperature, returning the metal sulfate to a catalytic cracking flue gas pipeline for recycling, introducing the desulfurizer regeneration gas rich in hydrogen sulfide to an acid gas desulfurization device for treatment, and then conveying the desulfurizer regeneration gas to a sulfur device to realize resource recycling of sulfur.
3. The catalytic cracking flue gas regenerable dry desulfurization process of claim 1 or 2, wherein the catalytic cracking flue gas pipeline is a flue gas conveying pipeline from the catalytic cracking regenerator to the flue gas third-stage cyclone separator, and the desulfurizing agent is continuously and uniformly added to the horizontal section, the vertical section, the inclined section and the turning section of the flue gas pipeline.
4. A regenerable dry desulfurization process for cracked flue gas as claimed in claim 3, wherein the desulfurizing agent is continuously and uniformly added to the vertical descending portion and the turning portion of the flue gas duct descending vertically from horizontal.
5. The catalytic cracking flue gas regenerable dry desulfurization process of claim 1 or 2, wherein the particle size of the solid microsphere desulfurizing agent is 40-200 μm, and the average particle size of the desulfurizing agent is 60-100 μm.
6. The catalytic cracking flue gas regenerable dry desulfurization process of claim 1 or 2, wherein the ratio of the desulfurizing agent added to the catalytic cracking flue gas pipeline to the flue gas is 0.005-2.0 kg/Nm 3 The reaction adsorption time and temperature of the catalytic cracking flue gas and the desulfurizer are respectively 0.01-60 s and 500-750 ℃.
7. The catalytic cracking flue gas regenerable dry desulfurization process of claim 6, wherein the ratio of the desulfurizing agent added to the catalytic cracking flue gas pipeline to the flue gas is 0.01-0.5 kg/Nm 3 The reaction adsorption time and temperature of the catalytic cracking flue gas and the desulfurizer are respectively 0.1-5 s and 550-720 ℃.
8. The catalytic cracking flue gas regenerable dry desulfurization process of 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 desulfurizer regenerator are as follows: the regeneration temperature is 500-750 ℃, the average residence time of the desulfurizer in the regenerator is 30 s-60 min, and the weight hourly space velocity of the desulfurizer regenerator is as follows: 0.05 to 50 hours -1 。
9. The catalytic cracking flue gas regenerable dry desulfurization process of claim 2, wherein the reducing gas is refinery dry gas, and the working parameters of the fluidized bed desulfurizer regenerator are as follows: the regeneration temperature is 600-700 ℃, the average residence time of the desulfurizer in the regenerator is 1-30 min, and the weight hourly space velocity of the desulfurizer regenerator is as follows: 0.1 to 20 hours -1 。
10. The catalytic cracking flue gas regenerable dry desulfurization process of claim 1 or 2, wherein the desulfurizing agent comprises 10-30% of V based on 100% of metal oxide mass content 2 O 5 1 to 8 percent of CeO 2 20 to 40 percent of MgO and 20 to 55 percent of Al 2 O 3 And 0.5 to 2% of MnO 2 。
11. The catalytic cracking flue gas regenerable dry desulfurization process of claim 10, wherein the desulfurizing agent is prepared by the following method:
1) Slowly dropwise adding 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 dropwise adding is finished to obtain magnesium aluminate 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 operating 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 to obtain microsphere particles with target particle sizes, and roasting at 650-760 ℃ for 3-10 hours to obtain the desulfurizer.
12. The catalytic cracking flue gas regenerable dry desulfurization process of claim 11, wherein the manganese salt, the magnesium salt and the aluminum salt are chlorides, nitrates, sulfates or organic acid salts thereof, and the binder is an aluminum sol, a silica sol or a silica-alumina hybrid sol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211428688.4A CN115845596B (en) | 2022-11-15 | 2022-11-15 | Catalytic cracking flue gas renewable dry desulfurization process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211428688.4A CN115845596B (en) | 2022-11-15 | 2022-11-15 | Catalytic cracking flue gas renewable dry desulfurization process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115845596A true CN115845596A (en) | 2023-03-28 |
| CN115845596B CN115845596B (en) | 2024-05-17 |
Family
ID=85663556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211428688.4A Active CN115845596B (en) | 2022-11-15 | 2022-11-15 | Catalytic cracking flue gas renewable dry desulfurization process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115845596B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1014955A (en) * | 1962-05-26 | 1965-12-31 | Siemens Ag | Improvements in or relating to the desulphurisation of gases |
| EP0063537A2 (en) * | 1981-04-20 | 1982-10-27 | Ashland Oil, Inc. | Method for the disposal of sulfur oxides from a catalytic cracking operation |
| MX9602302A (en) * | 1996-06-12 | 1997-12-31 | Mexicano Inst Petrol | Improved process to obtain a sox emission-reducing additive for fcc units. |
| CN1348830A (en) * | 2001-09-30 | 2002-05-15 | 孙学信 | Desulfurizing technology and system with regenerable metal oxide as desulfurizing agent |
| US20060100096A1 (en) * | 2004-11-10 | 2006-05-11 | Beijing Sj Environmental Protection And New Material Co., Ltd. | Trifunctional catalyst for sulphur transfer, denitrogenation and combustion promoting and a method for preparing the same |
| CN103920450A (en) * | 2013-01-14 | 2014-07-16 | 北京三聚环保新材料股份有限公司 | Preparation method of microsphere sulfur transfer agent with high wear resistance |
| CN104722311A (en) * | 2015-03-12 | 2015-06-24 | 张伟 | Sulfur-transferring additive for regenerative flue gas in catalytic cracking and preparation method thereof |
| CN104759202A (en) * | 2015-03-12 | 2015-07-08 | 张伟 | Additive of removing catalytic-cracking regenerated flue gas pollutant and preparation method of same |
| CN109351183A (en) * | 2018-11-27 | 2019-02-19 | 中国石油大学(北京) | A kind of regeneration fume from catalytic cracking dry desulfurization dedusting technique |
| 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 |
| CN109718663A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of method and device removing sulfureous in flue gas oxide and/or nitrogen oxides |
| 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 |
-
2022
- 2022-11-15 CN CN202211428688.4A patent/CN115845596B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1014955A (en) * | 1962-05-26 | 1965-12-31 | Siemens Ag | Improvements in or relating to the desulphurisation of gases |
| EP0063537A2 (en) * | 1981-04-20 | 1982-10-27 | Ashland Oil, Inc. | Method for the disposal of sulfur oxides from a catalytic cracking operation |
| MX9602302A (en) * | 1996-06-12 | 1997-12-31 | Mexicano Inst Petrol | Improved process to obtain a sox emission-reducing additive for fcc units. |
| CN1348830A (en) * | 2001-09-30 | 2002-05-15 | 孙学信 | Desulfurizing technology and system with regenerable metal oxide as desulfurizing agent |
| US20060100096A1 (en) * | 2004-11-10 | 2006-05-11 | Beijing Sj Environmental Protection And New Material Co., Ltd. | Trifunctional catalyst for sulphur transfer, denitrogenation and combustion promoting and a method for preparing the same |
| CN103920450A (en) * | 2013-01-14 | 2014-07-16 | 北京三聚环保新材料股份有限公司 | Preparation method of microsphere sulfur transfer agent with high wear resistance |
| CN104722311A (en) * | 2015-03-12 | 2015-06-24 | 张伟 | Sulfur-transferring additive for regenerative flue gas in catalytic cracking and preparation method thereof |
| CN104759202A (en) * | 2015-03-12 | 2015-07-08 | 张伟 | Additive of removing catalytic-cracking regenerated flue gas pollutant and preparation method of same |
| CN109718663A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of method and device removing sulfureous in flue gas oxide and/or nitrogen oxides |
| CN109351183A (en) * | 2018-11-27 | 2019-02-19 | 中国石油大学(北京) | A kind of regeneration fume from catalytic cracking dry desulfurization dedusting technique |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115845596B (en) | 2024-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4434147A (en) | Simultaneous sulfur oxide and nitrogen oxide control in FCC units using cracking catalyst fines with ammonia injection | |
| US4692318A (en) | Process for simultaneously removing nitrogen oxides, sulfur oxides, and particulates | |
| US4609537A (en) | Process for simultaneously removing nitrogen oxides, sulfur oxides, and particulates | |
| CN109351183B (en) | Dry desulfurization and dust removal process method for catalytic cracking regeneration flue gas | |
| CA1201706A (en) | Preparative process for alkaline earth metal, aluminum-containing spinels | |
| JPS6313730B2 (en) | ||
| US5728358A (en) | Sox sorbent regeneration | |
| CN111068456B (en) | Flue gas desulfurization and denitrification method | |
| JP3005690B2 (en) | Method for desulfurization of gas effluent in circulating fluidized bed with renewable absorbent | |
| CA1262247A (en) | Catalyst for reduction of so.sub.x emissions from fcc units | |
| AU737471B2 (en) | Process for treating hydrogen sulfide lean streams with partial combustion of feed stream | |
| US4917875A (en) | Gas/solid contact method for removing sulfur oxides from gases | |
| JPS6268527A (en) | Method of removing sulfur oxide from gas by using absorbing material capable of being regenerated by reaction with hydrogen sulfide | |
| CA1201699A (en) | Preparative process for alkaline earth metal, aluminum-containing spinels | |
| WO2013013506A1 (en) | Method for removing sulfur oxide and nitrogen oxide from flue gas | |
| CN101433821B (en) | Sorbent for reducing sulfur content in hydrocarbon oils | |
| CN109453783A (en) | A kind of regeneration fume from catalytic cracking desulphurization catalyst and preparation method thereof | |
| CN115845596B (en) | Catalytic cracking flue gas renewable dry desulfurization process | |
| CN206529433U (en) | A kind of two-stage regeneration adsorbs desulfurization reactor | |
| JPS631425A (en) | Improved gas/solid contact method for removing sulfur oxide from gas | |
| JP2003534897A (en) | Method and apparatus for regenerating spent absorbent generated in heat generator flue gas treatment | |
| CN111097271B (en) | Method and device for removing SOx and NOx in catalytic cracking flue gas | |
| CN114130154B (en) | Low-temperature flue gas denitration method and device and flue gas desulfurization and denitration method and device | |
| CN101433820B (en) | Sorbent for reducing sulfide in hydrocarbon oils | |
| EP1062025B1 (en) | IMPROVED PROCESS FOR TREATING H2S-LEAN STREAMS WITH RECYCLE OF SOx FROM BURNER |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |