CN109453783A - A kind of regeneration fume from catalytic cracking desulphurization catalyst and preparation method thereof - Google Patents
A kind of regeneration fume from catalytic cracking desulphurization catalyst and preparation method thereof Download PDFInfo
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- CN109453783A CN109453783A CN201811425042.4A CN201811425042A CN109453783A CN 109453783 A CN109453783 A CN 109453783A CN 201811425042 A CN201811425042 A CN 201811425042A CN 109453783 A CN109453783 A CN 109453783A
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- magnesium
- manganese
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- desulphurization catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 230000008929 regeneration Effects 0.000 title claims abstract description 46
- 238000011069 regeneration method Methods 0.000 title claims abstract description 46
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 41
- 239000003517 fume Substances 0.000 title claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 78
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011777 magnesium Substances 0.000 claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011572 manganese Substances 0.000 claims abstract description 25
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 20
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 20
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 20
- 239000011029 spinel Substances 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 18
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 17
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- -1 magnesium aluminate Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 239000012798 spherical particle Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005096 rolling process Methods 0.000 claims abstract description 11
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010899 nucleation Methods 0.000 claims abstract description 6
- 230000006911 nucleation Effects 0.000 claims abstract description 6
- 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 abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims description 12
- 238000000967 suction filtration Methods 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
- 238000002156 mixing Methods 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 9
- 230000023556 desulfurization Effects 0.000 abstract description 8
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 17
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 239000003546 flue gas Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 230000001172 regenerating effect Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004868 gas analysis Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- IJJPOUUNTYKRHG-UHFFFAOYSA-N dialuminum hexanitrate Chemical compound [Al+3].[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O IJJPOUUNTYKRHG-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 235000001055 magnesium Nutrition 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The present invention provides a kind of regeneration fume from catalytic cracking desulphurization catalysts and preparation method thereof.This method comprises: being slowly added dropwise the mixed solution that magnesium salts and aluminium salt are prepared in sodium hydroxide and the mixed solution of sodium carbonate preparation, it is stirred to react nucleation crystallization after being added dropwise to complete, obtains magnesium aluminate spinel；The mixed solution that manganese salt, magnesium salts and aluminium salt are prepared is slowly added dropwise in sodium hydroxide and the mixed solution of sodium carbonate preparation, nucleation crystallization is stirred to react after being added dropwise to complete, obtains manganese magnesia-alumina hydrotalcite；Magnesium aluminate spinel, manganese magnesia-alumina hydrotalcite, cerous nitrate, copper nitrate and boehmite are uniformly mixed and obtain mixture, mixture is continuously sprayed into hydrochloric acid solution during continuous rolling, sieving obtains small spherical particles；It is roasted to obtain the regeneration fume from catalytic cracking desulphurization catalyst after drying.Its SOx removal efficiency with higher and preferable regenerability, desulfurization degree in regeneration fume from catalytic cracking are up to 99.5%, and regenerability is up to 100%.
Description
Technical field
The invention belongs to environmental protection catalyst technical fields, and in particular to a kind of regeneration fume from catalytic cracking desulphurization catalyst and
Preparation method.
Background technique
Catalytic cracking is important one of the secondary processing process of oil plant.Catalytic cracking unit is mainly by reactor and again
Raw device composition.Under the effect of the catalyst, raw material is processed into required product in catalyst cracker, is catalyzed in reaction process
Agent is inactivated because of coking, and the catalyst fluidization of inactivation carries out coke burning regeneration to regenerator, and then Returning reactor continues to urge
Change reaction.During catalytic cracking reaction, the partial vulcanization object in raw material is deposited on a catalyst, when catalyst regeneration,
Sulphides burn on catalyst forms sulfur oxide (SOx) with flue gas emission.Oxysulfide SOx not only seriously pollutes ring
Border can also be acted on the vapor in flue gas, and condensation generates acid solution on wall, cause heavy corrosion to equipment.Therefore,
How the discharge amount of in regeneration fume from catalytic cracking SOx is reduced, it has also become urgent problem to be solved.
The main method for reducing SOx discharge in catalytic cracking regenerator at present is as follows: first is that carrying out to catalytically cracked material
Weighted BMO spaces, as ZL201510769249.3, ZL201410766839.6, ZL201210440586.4,
ZL201110156347.1 etc..Although catalytically cracked material weighted BMO spaces can be effectively reduced the row of catalytic cracking flue gas SOx
It puts, but still cannot reach emission request, and cat feed hydrotreating unit investment is very high, limits this
The application of method.Second is that using catalytic cracking regeneration flue gas sulphur transfer agent in catalytic cracking process, such as
ZL201510109947.0、ZL201210443822.8、ZL201210349980.7、ZL201110029268.4、
ZL201110328746.1 etc..The SOx content in flue gas can be effectively reduced in this method, and SOx removal efficiency is 50-70%, still
Higher and higher with discharge standard, regeneration flue gas sulphur transfer agent has been difficult to meet discharge standard requirement.Third is that catalytic cracking
Regenerated flue gas carries out wet desulphurization, and the method being most widely used at present, as ZL201410092858.5,
ZL201410590103.8, ZL201610031292.4, ZL201120070516.5 etc..But wet process of FGD was being applied
Find that it easily causes " blue smoke (SO in journey3) ", " white cigarette (vapor) " and brine waste discharge, formed secondary pollution.
Compared with fixed bed reactors, moving bed can realize particle circular regeneration and continuous circulate operation；And compared to stream
Change bed, moving bed particle solid holdup is high, two-phase contacting efficiency is higher.But operated using moving bed, not only to guarantee desulfurizing agent
Desulfurization effect, while higher requirement also proposed to its mechanical performance.Moving bed is thus used for the correlation of flue gas desulfurization
Technology is extremely limited, as used active Jiaozhuo in the technique using the proposition of ZL201410111683.8, ZL 200610017066.7
For adsorbent, ZL201220236757.7 is in light filler ball surface layer " carrying " desulfurizing agent, and the then base of ZL 200720066552.8
In the optimization of the moving bed import and export mix, these are not related to the preparation of desulfurizing agent.Therefore, a kind of suitable for movable bed dress is developed
The regeneration fume from catalytic cracking desulphurization catalyst set has great importance.
Summary of the invention
Based on problem of the existing technology, the purpose of the present invention is to provide a kind of high-temperature catalytics suitable for moving bed
Cracking regeneration flue gas desulfurization catalyst and preparation method thereof.The regeneration fume from catalytic cracking desulphurization catalyst under the high temperature conditions can
Regeneration fume from catalytic cracking SOx is enough removed, there is very high removal efficiency, and " blue smoke ", " white cigarette " can be eliminated and contained
The discharge of salt waste water avoids the generation of secondary pollution.
On the one hand, the present invention provides a kind of preparation method of regeneration fume from catalytic cracking desulphurization catalyst, and this method includes
Following steps:
The mixed solution that magnesium salts and aluminium salt are prepared is slowly added dropwise in the mixing of sodium hydroxide and sodium carbonate preparation step 1
In solution, it is stirred to react nucleation crystallization after being added dropwise to complete, obtains magnesium aluminate spinel；
The mixed solution that manganese salt, magnesium salts and aluminium salt are prepared is slowly added dropwise in sodium hydroxide and sodium carbonate preparation step 2
Mixed solution in, nucleation crystallization is stirred to react after being added dropwise to complete, obtains manganese magnesia-alumina hydrotalcite；
Magnesium aluminate spinel, manganese magnesia-alumina hydrotalcite, cerous nitrate, copper nitrate and boehmite are uniformly mixed by step 3
Mixture is obtained, mixture is continuously sprayed into hydrochloric acid solution during continuous rolling, sieving obtains small spherical particles；
Step 4 will be roasted to obtain the regeneration fume from catalytic cracking desulphurization catalyst after small spherical particles drying.
In above-mentioned preparation method, it is preferable that in step 1, in the mixed solution of magnesium salts and aluminium salt preparation, with metal
The molar ratio of oxide meter, the magnesium salts and the aluminium salt is (1-5): 1.
In above-mentioned preparation method, it is preferable that the magnesium salts includes one of magnesium nitrate, magnesium chloride and magnesium sulfate or more
Kind；One of the aluminium salt aluminum nitrate, aluminium chloride and aluminum sulfate are a variety of.
In above-mentioned preparation method, it is preferable that in step 1, in the mixed solution that sodium hydroxide and sodium carbonate are prepared,
The concentration of the sodium hydroxide is 3-5mol/L, and the concentration of the sodium carbonate is 0.15-0.25mol/L, and the sodium hydroxide
Solution with the sodium carbonate is isometric mixing.
In above-mentioned preparation method, it is preferable that in step 2, in the mixed solution that manganese salt, magnesium salts and aluminium salt are prepared, with
Metal oxide meter, the molar ratio of the manganese salt, the magnesium salts and the aluminium salt are (0.01-0.2): (1-4.5): 1.
In above-mentioned preparation method, it is preferable that the manganese salt includes manganese nitrate and/or manganese sulfate；The magnesium salts includes nitre
One of sour magnesium, magnesium chloride, magnesium sulfate and magnesium acetate are a variety of；The aluminium salt includes in aluminum nitrate, aluminium chloride and aluminum sulfate
It is one or more.
In above-mentioned preparation method, it is preferable that in step 2, in the mixed solution that sodium hydroxide and sodium carbonate are prepared,
The concentration of the sodium hydroxide is 3-5mol/L, and the concentration of the sodium carbonate is 0.1-0.2mol/L, and the sodium hydroxide and
The solution of the sodium carbonate is isometric mixing.
In above-mentioned preparation method, it is preferable that in step 3, mixture is continuously sprayed salt during continuous rolling
Acid solution, sieving obtain small spherical particles method particularly includes:
Mixture is even added in turntable bowling machine, hydrochloric acid solution is sprayed into turntable bowling machine using sprayer,
By the continuous penetrating of the continuous rolling and hydrochloric acid solution of turntable bowling machine, so that the material of mixture is gradually grown up balling-up, pass through
Screening obtains the small spherical particles of 0.2-2.5mm partial size.
In above-mentioned preparation method, it is preferable that the magnesium aluminate spinel, the manganese magnesia-alumina hydrotalcite, the cerous nitrate,
The copper nitrate and the dosage for intending thin water aluminium meet in the desulphurization catalyst being prepared, with metal oxide mass content
For 100% meter, the Al of MgO, 30%-55% including 25%-50%2O3, 7.5%-15% CeO2, 0.5%-2% MnO2
With the CuO of 1%-5%.
In above-mentioned preparation method, it is preferable that the concentration of the hydrochloric acid solution is 18%.
In above-mentioned preparation method, it is preferable that in step 1, dropping temperature is 50-70 DEG C, time for adding 0.2-
0.5h。
In above-mentioned preparation method, it is preferable that control solution ph is 8-10 during being added dropwise.
In above-mentioned preparation method, it is preferable that the time being stirred to react after being added dropwise to complete is 4-18h.
In above-mentioned preparation method, it is preferable that further include cooling, suction filtration, washing to neutral and baking after being stirred to react
Dry step；It is further preferred that drying temperature is 150 DEG C.
In above-mentioned preparation method, it is preferable that in step 2, dropping temperature is 60-80 DEG C, time for adding 0.4-
1h。
In above-mentioned preparation method, it is preferable that control solution ph is 8-10 during being added dropwise.
In above-mentioned preparation method, it is preferable that the time being stirred to react after being added dropwise to complete is 4-20h.
In above-mentioned preparation method, it is preferable that further include cooling, suction filtration, washing to neutral and baking after being stirred to react
Dry step；Preferably, drying temperature is 150 DEG C.
In above-mentioned preparation method, it is preferable that in step 4, the temperature that the small spherical particles are dried is 120-
150 DEG C, drying time 5-12h.
In above-mentioned preparation method, it is preferable that the temperature roasted is 700-850 DEG C, calcining time 3-12h.
On the other hand, the present invention also provides a kind of regeneration fume from catalytic cracking desulphurization catalyst, the desulphurization catalyst is
It is prepared by the preparation method.
In above-mentioned desulphurization catalyst, it is preferable that in the desulphurization catalyst, be with metal oxide mass content
100% meter, the desulphurization catalyst includes the Al of MgO, 30%-55% of 25%-50%2O3, 7.5%-15% CeO2、
The MnO of 0.5%-2%2With the CuO of 1%-5%.
Beneficial effects of the present invention:
Regeneration fume from catalytic cracking desulphurization catalyst provided by the invention has higher content of MgO, can effectively improve
The desulfuration efficiency of catalyst；In the preparation method of the desulphurization catalyst, boehmite is acidified, improves desulfurization catalyst
The intensity of agent small spherical particles；And contain boehmite and manganese magnesia-alumina hydrotalcite in small spherical particles, enrich the micro- of catalyst
Type structure improves the specific surface area of catalyst；The desulphurization catalyst is applied in regeneration fume from catalytic cracking, is had higher
SOx removal efficiency and preferable regenerability, desulfurization degree be up to 99.5%, regenerability is up to 100%.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
The present embodiment provides a kind of preparation methods of regeneration fume from catalytic cracking desulphurization catalyst comprising following steps:
Step 1, aluminum-spinel (MgAl2O4) preparation:
The H of 2500g is added in 5 liters of three-necked flask2The Na of the NaOH and 44.5g of O, 114.0g2CO3, stirred in 65 DEG C
Uniformly, the H containing 1500g is added thereto2Mg (the NO of O, 108.5g3)2·6H2Al (the NO of O, 93.5g3)3·9H2O's is molten
Liquid, time for adding 0.6h continue to stir into core crystallization 15h after dripping, and then, cooling, suction filtration is washed to neutrality and dried
It is dry, obtain magnesium aluminate spinel A1.
Step 2, the preparation of manganese magnesia-alumina hydrotalcite (MnMgAl-LDH):
The H of 2500g is added in 5 liters of three-necked flask2The Na of the NaOH and 53.0g of O, 126.0g2CO3, stirred in 75 DEG C
Uniformly, the H containing 1500g is added thereto2Mn (the NO of O, 7.5g3)2·4H2Mg (the NO of O, 285.0g3)2·6H2O,
Al (the NO of 123.5g3)3·9H2The solution of O, time for adding 0.7h continue to stir into core crystallization 18h after dripping, then,
Cooling, suction filtration is washed to neutrality simultaneously, obtains manganese magnesia-alumina hydrotalcite B1.
Step 3, the acquisition of regeneration fume from catalytic cracking desulphurization catalyst:
By the Ce (NO of 42.5g magnesium aluminate spinel A1,27.3g manganese magnesia-alumina hydrotalcite B1,70.0g3)·6H2O, 22.0g's
Cu(NO3)2·6H2O and boehmite 97.0g is added to after mixing to be added in turntable bowling machine, using sprayer to turn
Disk bowling machine sprays into 18% dilute hydrochloric acid solution.By the continuous penetrating of the continuous rolling and dilute hydrochloric acid of bowling machine, material in pot
It gradually grows up balling-up, it is 8 hours dry at 120 DEG C by screening selection 1.0-1.5mm partial size bead, it is small that 5 are roasted at 750 DEG C
When, purpose product regeneration fume from catalytic cracking desulphurization catalyst is obtained, which is named as S1.With metal oxide matter
Measuring content is 100% meter, and desulphurization catalyst S1 includes 35.0% MgO, 51.6% Al2O3, 10.8% CeO2, 0.6%
MnO2With 2.0% CuO.
Embodiment 2
The present embodiment provides a kind of preparation methods of regeneration fume from catalytic cracking desulphurization catalyst comprising following steps:
Step 1, aluminum-spinel (MgAl2O4) preparation:
The H of 2500g is added in 5 liters of three-necked flask2The Na of the NaOH and 44.5g of O, 114.0g2CO3, stirred in 65 DEG C
Uniformly, the H containing 1500g is added thereto2Mg (the NO of O, 108.5g3)2·6H2Al (the NO of O, 93.5g3)3·9H2O's is molten
Liquid, time for adding 0.6h continue to stir into core crystallization 18h after dripping, and then, cooling, suction filtration is washed to neutrality and dried
It is dry, obtain magnesium aluminate spinel A2.
Step 2, the preparation of manganese magnesia-alumina hydrotalcite (MnMgAl-LDH):
The H of 2500g is added in 5 liters of three-necked flask2The Na of the NaOH and 53.0g of O, 126.0g2CO3, stirred in 75 DEG C
Uniformly, the H containing 1500g is added thereto2Mn (the NO of O, 9.5g3)2·4H2Mg (the NO of O, 262.4g3)2·6H2O,
Al (the NO of 123.5g3)3·9H2The solution of O, time for adding 0.7h continue to stir into core crystallization 18h after dripping, then,
Cooling, suction filtration is washed to neutrality simultaneously, obtains manganese magnesia-alumina hydrotalcite B2.
Step 3, the acquisition of regeneration fume from catalytic cracking desulphurization catalyst:
By the Ce (NO of manganese the magnesia-alumina hydrotalcite B2,68.0g of the magnesium aluminate spinel A2,39.4g of 56.2g3)·6H2O,
Cu (the NO of 24.0g3)2·6H2The boehmite of O and 107.0g is added to after mixing to be added in turntable bowling machine, is used
Sprayer sprays into 18% dilute hydrochloric acid solution to turntable bowling machine.Pass through the continuous spray of the continuous rolling and dilute hydrochloric acid of bowling machine
Entering, material is gradually grown up balling-up in pot, and it is 12 hours dry at 130 DEG C by screening selection 1.5-2.0mm partial size bead,
It is roasted 7 hours at 800 DEG C, obtains purpose product regeneration fume from catalytic cracking desulphurization catalyst, which is named as S2.
It is in terms of 100% by metal oxide mass content, desulphurization catalyst S2 includes 42% MgO, 45% Al2O3, 8.0%
CeO2, 1.0% MnO2With 4.0% CuO.
Embodiment 3
The present embodiment provides a kind of preparation methods of regeneration fume from catalytic cracking desulphurization catalyst comprising following steps:
Step 1, aluminum-spinel (MgAl2O4) preparation:
The H of 2500g is added in 5 liters of three-necked flask2The Na of the NaOH and 44.5g of O, 114.0g2CO3, stirred in 70 DEG C
Uniformly, the H containing 1500g is added thereto2Mg (the NO of O, 108.5g3)2·6H2Al (the NO of O, 93.5g3)3·9H2O's is molten
Liquid, time for adding 0.6h continue to stir into core crystallization 18h after dripping, and then, cooling, suction filtration is washed to neutrality and dried
It is dry, obtain magnesium aluminate spinel A3.
Step 2, the preparation of manganese magnesia-alumina hydrotalcite (MnMgAl-LDH):
The H of 2500g is added in 5 liters of three-necked flask2The Na of the NaOH and 53.0g of O, 126.0g2CO3, stirred in 75 DEG C
Uniformly, the H containing 1500g is added thereto2Mn (the NO of O, 9.5g3)2·4H2Mg (the NO of O, 346.2g3)2·6H2O,
Al (the NO of 123.5g3)3·9H2The solution of O, time for adding 1.0h continue to stir into core crystallization 20h after dripping, then,
Cooling, suction filtration is washed to neutrality simultaneously, obtains manganese magnesia-alumina hydrotalcite B3.
Step 3, the acquisition of regeneration fume from catalytic cracking desulphurization catalyst:
By the Ce (NO of manganese the magnesia-alumina hydrotalcite B3,55.0g of the magnesium aluminate spinel A3,64.2g of 36.8g3)·6H2O,
Cu (the NO of 32.0g3)2·6H2The boehmite of O and 85.0g is added to after mixing to be added in turntable bowling machine, is used
Sprayer sprays into 18% dilute hydrochloric acid solution to turntable bowling machine.Pass through the continuous spray of the continuous rolling and dilute hydrochloric acid of bowling machine
Entering, material is gradually grown up balling-up in pot, and it is 10 hours dry at 150 DEG C by screening selection 1.0-1.5mm partial size bead,
It is roasted 6 hours at 850 DEG C, obtains purpose product regeneration fume from catalytic cracking desulphurization catalyst, which is named as S3.
It is in terms of 100% by metal oxide mass content, desulphurization catalyst S3 includes 54.5% MgO, 30% Al2O3, 12.5%
CeO2, 2.0% MnO2With 1.0% CuO.
Embodiment 4
The present embodiment provides a kind of preparation methods of regeneration fume from catalytic cracking desulphurization catalyst comprising following steps:
Step 1, aluminum-spinel (MgAl2O4) preparation:
The H of 2500g is added in 5 liters of three-necked flask2The Na of the NaOH and 44.5g of O, 114.0g2CO3, stirred in 70 DEG C
Uniformly, the H containing 1500g is added thereto2Mg (the NO of O, 126.5g3)2·6H2Al (the NO of O, 93.5g3)3·9H2O's is molten
Liquid, time for adding 0.5h continue to stir into core crystallization 18h after dripping, and then, cooling, suction filtration is washed to neutrality and dried
It is dry, obtain magnesium aluminate spinel A4.
Step 2, the preparation of manganese magnesia-alumina hydrotalcite (MnMgAl-LDH):
The H of 2500g is added in 5 liters of three-necked flask2The Na of the NaOH and 53.0g of O, 126.0g2CO3, stirred in 75 DEG C
Uniformly, the H containing 1500g is added thereto2Mn (the NO of O, 5.0g3)2·4H2Mg (the NO of O, 301.8g3)2·6H2O,
Al (the NO of 123.5g3)3·9H2The solution of O, time for adding 1.0h continue to stir into core crystallization 20h after dripping, then,
Cooling, suction filtration is washed to neutrality simultaneously, obtains manganese magnesia-alumina hydrotalcite B4.
Step 3, the acquisition of regeneration fume from catalytic cracking desulphurization catalyst:
By the Ce (NO of manganese the magnesia-alumina hydrotalcite B3,35.0g of the magnesium aluminate spinel A4,32.0g of 64.2g3)·6H2O,
Cu (the NO of 16.0g3)2·6H2The boehmite of O and 115.0g is added to after mixing to be added in turntable bowling machine, is used
Sprayer sprays into dilute hydrochloric acid solution to turntable bowling machine.Pass through the continuous spray of the continuous rolling of bowling machine and 18% dilute hydrochloric acid
Entering, material is gradually grown up balling-up in pot, and it is 10 hours dry at 150 DEG C by screening selection 1.5-2.5mm partial size bead,
It is roasted 12 hours at 750 DEG C, obtains purpose product regeneration fume from catalytic cracking desulphurization catalyst, which is named as
S4.It is in terms of 100% by metal oxide mass content, desulphurization catalyst S4 includes 25.5% MgO, 53.5% Al2O3、
14.5% CeO2, 5.0% MnO2With 1.5% CuO.
The physical property of 5 desulphurization catalyst of embodiment is tested
The test that physical property is carried out to the regeneration fume from catalytic cracking desulphurization catalyst of above-described embodiment 1-4 preparation, is surveyed
Test result is as shown in table 1.
Table 1
Desulphurization catalyst granularity prepared by the present invention is 1-2.5mm, intensity 30.4- it can be seen from 1 experimental data of table
40.5N/, specific surface area 65.9-82.4m2/kg。
The SO of 6 desulphurization catalyst of embodimentXRemoval performance and reducing/regenerating henchnmrk test
SO is carried out to the regeneration fume from catalytic cracking desulphurization catalyst of above-described embodiment 1-4 preparationXRemoval performance and reduction
Regenerability evaluation experimental.Catalyst desulfurizing reaction is carried out using miniature quartz reactor, is 650 DEG C, simulates in reaction temperature
Flue gas volume air speed is 1000h-1, catalyst regeneration temperature is 650 DEG C, regeneration gas hydrogen volume air speed 1000h-1Under the conditions of comment
The SOx removal performance and reducing/regenerating performance of valence desulphurization catalyst.
Flue gas is by SO2、N2And O2The mixed gas being made by a certain percentage.Wherein SO2For 2000mg/m3, O2It is 3.5
(v) %, remaining is N2。SO2The H generated with micro-coulometric determination, regenerative process2S is analyzed with chromatography.
The desulphurization catalyst for weighing 1.0g is packed into the quartz tube reactor of 8 × 1mm of Φ, is heated under stream of nitrogen gas
650 DEG C, then stop nitrogen, be passed through sulfur dioxide mixture gas 60 minutes, gas flow 17mL/min collects gas, this mistake
Journey is the stage of reaction.The gas analysis SO being collected into2Concentration.After reaction, stop sulfur dioxide mixture gas, lead to nitrogen purging
10 minutes, pure hydrogen is passed through 60 minutes at a temperature of 650 DEG C, and hydrogen flowing quantity 17mL/min collects gas, this stage is regeneration
Stage.The gas analysis H being collected into2S concentration.
Desulphurization catalyst SOx removal performance SO in reaction mixture gas body2React the change rate of concentration of front and back to indicate, also
Former regenerability is indicated with the ratio of the adsorbed sulphur of desulphurization catalyst in the sulphur and reaction adsorption process for generating hydrogen sulfide.
Desulphurization catalyst SOx removal performance takes following formula to calculate:
In formula: DeSOx is the SOx removal efficiency (%) of desulphurization catalyst；C1For SO in gas after reaction2Content (mg/
m3)；C2To react SO in preceding gaseous mixture2Content (mg/m3)。
Desulphurization catalyst reducing/regenerating performance takes following formula to calculate:
In formula: K is the regeneration efficiency % of desulphurization catalyst)；N is H in regeneration gas2S sulfur content (mg)；W1To react
Reaction gas total sulfur content (mg) in journey；W2For the total sulfur content (mg) in gas after reaction.
Table 2 is the SOx removal performance and reducing/regenerating Evaluation results of inventive desulfurization catalyst.
Table 2
| Desulphurization catalyst | Catalyst SOx removal efficiency, % | Catalyst regeneration efficiency, % |
| S1 | 99.2 | 100 |
| S2 | 99.5 | 100 |
| S3 | 99.5 | 100 |
| S4 | 99.3 | 100 |
The regeneration fume from catalytic cracking desulphurization catalyst SO provided by the invention it can be seen from 2 experimental data of tableXDetachability
Can be excellent with reducing/regenerating, desulfurization degree is up to 99.5%, and regeneration efficiency reaches 100%.
Embodiment described above is merely to illustrate technical idea and feature of the invention, in the art its object is to make
Technical staff it will be appreciated that the contents of the present invention and implement accordingly, patent of the invention only cannot be limited with the present embodiment
It encloses, i.e., same changes or modifications made by all disclosed spirit are still fallen in the scope of the patents of the invention.
Claims (10)
1. a kind of preparation method of regeneration fume from catalytic cracking desulphurization catalyst, which is characterized in that method includes the following steps:
The mixed solution that magnesium salts and aluminium salt are prepared is slowly added dropwise in the mixed solution of sodium hydroxide and sodium carbonate preparation step 1
In, it is stirred to react nucleation crystallization after being added dropwise to complete, obtains magnesium aluminate spinel；
The mixed solution that manganese salt, magnesium salts and aluminium salt are prepared is slowly added dropwise and mixes in what sodium hydroxide and sodium carbonate were prepared by step 2
It closes in solution, nucleation crystallization is stirred to react after being added dropwise to complete, obtains manganese magnesia-alumina hydrotalcite；
Magnesium aluminate spinel, manganese magnesia-alumina hydrotalcite, cerous nitrate, copper nitrate and boehmite are uniformly mixed and obtain by step 3
Mixture is continuously sprayed hydrochloric acid solution by mixture during continuous rolling, and sieving obtains small spherical particles；
Step 4 will be roasted to obtain the regeneration fume from catalytic cracking desulphurization catalyst after small spherical particles drying.
2. preparation method according to claim 1, it is characterised in that: in step 1, the mixing of magnesium salts and aluminium salt preparation
In solution, in terms of metal oxide, the molar ratio of the magnesium salts and the aluminium salt is (1-5): 1；
Preferably, the magnesium salts includes one of magnesium nitrate, magnesium chloride and magnesium sulfate or a variety of；The aluminium salt includes nitric acid
One of aluminium, aluminium chloride and aluminum sulfate are a variety of；
Preferably, in step 1, in the mixed solution that sodium hydroxide and sodium carbonate are prepared, the concentration of the sodium hydroxide is 3-
5mol/L, the concentration of the sodium carbonate are 0.15-0.25mol/L, and the solution of the sodium hydroxide and the sodium carbonate is etc.
Volume mixture.
3. preparation method according to claim 1, it is characterised in that: in step 2, what manganese salt, magnesium salts and aluminium salt were prepared
In mixed solution, in terms of metal oxide, the molar ratio of the manganese salt, the magnesium salts and the aluminium salt is (0.01-0.2): (1-
4.5): 1；
Preferably, the manganese salt includes manganese nitrate and/or manganese sulfate；The magnesium salts includes magnesium nitrate, magnesium chloride, magnesium sulfate and vinegar
One of sour magnesium is a variety of；The aluminium salt includes one of aluminum nitrate, aluminium chloride and aluminum sulfate or a variety of；
Preferably, in step 2, in the mixed solution that sodium hydroxide and sodium carbonate are prepared, the concentration of the sodium hydroxide is 3-
5mol/L, the concentration of the sodium carbonate is 0.1-0.2mol/L, and the solution of the sodium hydroxide and the sodium carbonate is to wait bodies
Product mixing.
4. preparation method according to claim 1, which is characterized in that in step 3, by mixture in continuous rolling mistake
Hydrochloric acid solution is continuously sprayed in journey, sieving obtains small spherical particles method particularly includes:
Mixture is even added in turntable bowling machine, hydrochloric acid solution is sprayed into turntable bowling machine using sprayer, is passed through
The continuous penetrating of the continuous rolling and hydrochloric acid solution of turntable bowling machine makes the material of mixture gradually grow up balling-up, passes through screening
Obtain the small spherical particles of 0.2-2.5mm partial size.
5. preparation method according to claim 1 or 4, which is characterized in that the magnesium aluminate spinel, the manganese magnesia-alumina water
Talcum, the cerous nitrate, the copper nitrate and the dosage for intending thin water aluminium meet in the desulphurization catalyst being prepared, with gold
Belonging to oxide mass content is 100% meter, the Al of MgO, 30%-55% including 25%-50%2O3, 7.5%-15%
CeO2, 0.5%-2% MnO2With the CuO of 1%-5%；
Preferably, the concentration of the hydrochloric acid solution is 18%.
6. preparation method according to claim 1 or 2, it is characterised in that: in step 1, dropping temperature is 50-70 DEG C,
Time for adding is 0.2-0.5h；
Preferably, control solution ph is 8-10 during being added dropwise；
Preferably, the time being stirred to react after being added dropwise to complete is 4-18h；
Preferably, cooling, suction filtration is further included the steps that after being stirred to react, is washed to neutral and drying；Preferably, drying temperature
Degree is 150 DEG C.
7. preparation method according to claim 1 or 3, it is characterised in that: in step 2, dropping temperature is 60-80 DEG C,
Time for adding is 0.4-1h；
Preferably, control solution ph is 8-10 during being added dropwise；
Preferably, the time being stirred to react after being added dropwise to complete is 4-20h；
Preferably, cooling, suction filtration is further included the steps that after being stirred to react, is washed to neutral and drying；Preferably, drying temperature
Degree is 150 DEG C.
8. preparation method according to claim 1, it is characterised in that: in step 4, the small spherical particles are dried
Temperature be 120-150 DEG C, drying time 5-12h；
Preferably, the temperature roasted is 700-850 DEG C, calcining time 3-12h.
9. a kind of regeneration fume from catalytic cracking desulphurization catalyst, it is characterised in that: the desulphurization catalyst is by claim 1-7
Any one preparation method is prepared.
10. desulphurization catalyst according to claim 9, it is characterised in that: with metal oxide mass content for 100%
Meter, the desulphurization catalyst includes the Al of MgO, 30%-55% of 25%-50%2O3, 7.5%-15% CeO2, 0.5%-
2% MnO2With the CuO of 1%-5%.
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| CN113713800B (en) * | 2021-09-15 | 2024-06-04 | 中国石油化工股份有限公司 | High-temperature flue gas desulfurizing agent and preparation method thereof |
| CN115845596A (en) * | 2022-11-15 | 2023-03-28 | 中国石油化工股份有限公司 | Catalytic cracking flue gas regenerative dry desulfurization process |
| CN115845596B (en) * | 2022-11-15 | 2024-05-17 | 中国石油化工股份有限公司 | Catalytic cracking flue gas renewable dry desulfurization process |
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Application publication date: 20190312 |