CN115350703A - For reducing CO and NO in FCC regeneration flue gas x Composition for discharging and preparation method thereof - Google Patents
For reducing CO and NO in FCC regeneration flue gas x Composition for discharging and preparation method thereof Download PDFInfo
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- CN115350703A CN115350703A CN202210820631.2A CN202210820631A CN115350703A CN 115350703 A CN115350703 A CN 115350703A CN 202210820631 A CN202210820631 A CN 202210820631A CN 115350703 A CN115350703 A CN 115350703A
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- 239000000203 mixture Substances 0.000 title claims abstract description 163
- 238000011069 regeneration method Methods 0.000 title claims abstract description 61
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003546 flue gas Substances 0.000 title claims abstract description 59
- 230000008929 regeneration Effects 0.000 title claims abstract description 53
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000007599 discharging Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 65
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 63
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 36
- 238000004231 fluid catalytic cracking Methods 0.000 claims abstract description 33
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 24
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 20
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 13
- 238000004523 catalytic cracking Methods 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 24
- 230000000996 additive effect Effects 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- 238000001694 spray drying Methods 0.000 claims description 16
- 150000003863 ammonium salts Chemical class 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000004537 pulping Methods 0.000 claims description 11
- 238000005336 cracking Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- -1 rare earth compound Chemical class 0.000 claims description 7
- 239000002671 adjuvant Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 239000010451 perlite Substances 0.000 claims description 4
- 235000019362 perlite Nutrition 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000001935 peptisation Methods 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000010009 beating Methods 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims 1
- 239000005909 Kieselgur Substances 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 abstract description 16
- 238000009826 distribution Methods 0.000 abstract description 10
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 230000002411 adverse Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000012065 filter cake Substances 0.000 description 14
- 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 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 239000000571 coke Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 101150003085 Pdcl gene Proteins 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 6
- 238000002386 leaching Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003637 basic solution Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910018516 Al—O Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910021076 Pd—Pd Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 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 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002601 lanthanoid compounds Chemical class 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Catalysts (AREA)
Abstract
The application relates to a method for reducing CO and NO in FCC (fluid catalytic cracking) regeneration flue gas x A composition for emissions and a method for the preparation thereof, said composition comprising, in terms of oxides: (1) 0.5 to 30% by weight of a rare earth element, (2) 0.01 to 0.15% by weight of a noble metal element, and (3) the balance of an inorganic oxide support substantially free of alkali metals and alkaline earth metals; in the preparation method, the composition introduced with the noble metal is treated by an alkaline solution before being dried and/or roasted. The composition is used for fluid catalytic cracking, and can effectively avoid the problem of overhigh CO concentration of regenerated flue gasThe post combustion can effectively control CO and NO in the regenerated flue gas x The emission concentration of the flue gas NO is obviously reduced x Emissions, substantially without adversely affecting FCC product distribution.
Description
The application is a divisional application of an invention patent application, the application date of the parent application is 2014, 8 and 29, the application number is 201410437782.5, and the invention name is' used for reducing CO and NO in FCC regenerated flue gas x Discharged composition and method of making the same ".
Technical Field
The invention relates to a method for reducing CO and NO in catalytic cracking regeneration flue gas x An exhausted noble metal-containing composition and a method for preparing the same.
Background
In the process of Fluid Catalytic Cracking (FCC), raw oil is in quick contact with regenerated catalyst in riserAnd (3) carrying out catalytic cracking reaction, depositing coke generated by the reaction on the catalyst to deactivate the catalyst, and feeding the coke-formed deactivated catalyst into a regenerator for coke burning regeneration after steam stripping. During the regeneration process, the coke and nitrogen-containing compounds in the coke can generate CO and NO under the action of regeneration air x Etc. contaminants, with environmental regulations on CO and NO x The control indexes of the pollutants are increasingly strict, and the pollution of CO and NO to FCC (fluid catalytic cracking) regenerated flue gas is reduced x Emissions are of increasing general concern.
The main technical measures for reducing the emission of the pollutants in the regenerated flue gas of the FCC unit comprise: raw oil hydrogenation pretreatment, regenerator transformation, auxiliary agent and flue gas aftertreatment and the like, wherein the auxiliary agent technology is generally concerned and applied due to the advantages of flexible and simple operation, no need of device transformation, no secondary pollution and the like.
Noble metal promoters (noble metal CO combustion promoters) have been widely used to reduce CO emissions from the regenerated flue gas, however, the use of existing CO noble metal combustion promoters often results in NO in the flue gas x The emissions are greatly increased.
CN1151878C discloses a non-noble metal carbon monoxide combustion catalyst containing a copper-aluminum-cerium-aluminum composite oxide and an alumina carrier and a preparation method thereof, wherein the catalyst contains a cerium-aluminum composite oxide and a copper-aluminum composite oxide which are sequentially loaded on alumina, and the loading weight ratio of the cerium-aluminum composite oxide to the copper-aluminum composite oxide is Ce-Al-O/Al 2 O 3 0.02-0.10, and Cu-Al-O/Al 2 O 3 0.05-0.15, wherein the copper-aluminum composite oxide is uniformly dispersed on the alumina carrier covered with the highly dispersed cerium-aluminum composite oxide nano microcrystal on the surface of the copper-aluminum composite oxide in a cluster state.
CN1688508A discloses a method for reducing NO in fluidized catalytic cracking flue gas x And CO emissions, and uses thereof, the composition comprising copper and/or cobalt and a support selected from the group consisting of hydrotalcite like compounds, spinels, alumina, zinc titanate, zinc aluminate, zinc titanate/zinc aluminate.
WO2005040311A1 discloses reduction of FCC regeneration process NO x A discharged composition, the composition comprising: anionic clay or solid solution containing Mg and Al, rare earth metal oxideAlumina and/or silica-alumina and Y-type zeolite, and the composition may further contain a transition metal Cu.
CN102371165A discloses a method for reducing CO and NO in FCC (fluid catalytic cracking) regeneration flue gas x A discharged low-bulk-ratio composition comprising rare earth elements and one or more non-noble metal elements, preferably a non-noble metal supported on Y-zeolite.
In the prior art, non-noble metals are used, but noble metal element active components are not adopted, so that the CO oxidation activity is low, the content of the used non-noble metal element components is high, and the addition amount of the auxiliary agent composition in the main catalyst is usually high.
US6165933 discloses a method for reducing NO in catalytic cracking process x CO emitted comburant composition (adjuvant). The composition comprises: (
) An acidic metal oxide substantially free of zeolite; (
) Alkali metals, alkaline earth metals or mixtures thereof; (
) An oxygen storage component and
) Palladium (II). The acidic oxide support is preferably silica-alumina, and the oxygen storage transition metal oxide is preferably ceria.
US7045056B2 discloses a method for reducing CO and NO simultaneously in flue gas of catalytic cracking process x A discharged composition, said composition comprising: (
) An acidic oxide support; (
) Cerium (Ce)An oxide of (a); (
) A lanthanide oxide other than cerium, wherein (A), (B)
) And (a)
) At least 1.66 by weight; (
) Optionally one kind
B and
a group B transition metal oxide, and: (
) At least one noble metal element.
In the above prior assistants using noble metals, the assistant composition containing alkali metals, alkaline earth metals and unstable transition metal elements has adverse effects on the cracking activity and selectivity of the cracking catalyst during use; in addition, the CO-combustion performance and NO reduction of the adjuvant composition x The emission properties still need to be improved and the hydrothermal stability of the auxiliaries needs to be further improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a noble metal-containing regenerated flue gas for reducing CO and NO in catalytic cracking x Composition for emission with better reduction of CO and NO in catalytic cracking regeneration flue gas x The effect of discharging; another technical problem to be solved by the present invention is to provide a method for preparing and applying the above composition.
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x A discharged composition comprising, in terms of oxides, based on the weight of the composition: (1) 0.5 to 30% by weight of a rare earth element, (2) 0.01 to 0.15% by weight of a noble metal element, and (3) the balance of an inorganic oxide support substantially free of alkali metals and alkaline earth metals, in which composition the noble metal element is incorporated into the composition and, after introduction, treated with an alkaline solution before drying and/or calcining. The noble metal elements are preferably loaded on the oxide carrier by adopting an impregnation method, and the composition loaded with the noble metal is treated by an alkaline solution before drying and/or roasting.
The compositions provided herein may also contain up to 5% by weight, calculated as the oxide, of a compound selected from
B～
A metal additive component of one or more of the non-rare earth elements of group B.
The invention also provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x A process for the preparation of discharged compositions comprising the steps of preparing a slurry containing a rare earth element component and an inorganic oxide support component and spray drying, calcining, impregnating with a noble metal element, treating with an alkaline solution and drying and/or calcining.
The invention further provides a fluidized catalytic cracking method, which comprises the steps of contact reaction and regeneration of hydrocarbon oil and a catalyst, wherein the catalyst contains 0.05-5 wt% of the regenerated flue gas CO and NO for catalytic cracking, which are provided by the invention, based on the total weight of the catalyst x The composition of the discharge.
The invention provides a method for reducing CO and NO in catalytic cracking (FCC) regeneration flue gas x The composition is discharged by adopting an oxide carrier modified by rare earth elements and treating by adopting an alkaline solution after loading a noble metal component, and the composition is used as a catalytic cracking auxiliary agent, can keep higher hydrothermal stability in a regenerator hydrothermal environment, and has higher effect of reducing NO of regenerated flue gas x Emission activity and higher CO combustion-supporting activity; also, the present invention provides compositions for reducing CO and NO as a fluid catalytic cracking catalyst x The yield of emissions aids, coke and dry gas is low. The invention provides a fluidized catalytic cracking method for reducing CO and NO x The chemical composition of the discharge auxiliary agent is modulated and stabilized, so that the auxiliary agent has higher activity and stability, and the existing method for reducing CO and NO is used x Compared with the FCC method for discharging the auxiliary agent, the method not only has lower dosage of the auxiliary agent, but also reduces CO and NO x The emission activity is higher. For example, ceO provided by the present invention 2 10% by mass of Cr 2 O 3 The assistant composition which has the content of 0.5 percent by mass and the PdO content of 0.06 percent by mass and is treated by ammonia solution after being dipped in the noble metal Pd is mixed with the FCC main catalyst (the trade mark GOR-
) After being mixed evenly, the mixture is aged for 12 hours at 800 ℃ in the atmosphere of 100 percent of water vapor, and then catalytic cracking reaction-regeneration evaluation is carried out, compared with the CeO prepared by the prior art by adopting an active component saturated dipping method 2 Compared with the results of reaction-regeneration evaluation of a comparative composition which has the content of 12 percent and the PdO content of 0.06 percent and is not treated by ammonia water after being impregnated with noble metal, when the comparative composition accounts for 0.9 percent of the total catalyst inventory and other operating conditions are the same, the result of the reaction-regeneration evaluation of NO in the regenerated flue gas of the auxiliary composition provided by the invention is compared with the result of the reaction-regeneration evaluation of the comparative composition which has the content of 12 percent and the PdO content of 0.06 percent and is not treated by ammonia water x Has an emission concentration of 102ppm, and the comparative composition regenerates flue gas NO x Is 128ppm, the flue gas CO emission concentration is also further reduced from 0.51% by volume to 0.42% by volume of the comparative composition.
Detailed Description
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x The discharged composition adopts an oxide carrier modified by rare earth, and is treated by alkaline solution after a noble metal component is loaded. Based on the weight of the composition, the composition comprises the following components in terms of oxides: (1) 0.5 to 30% by weight of a rare earth element, (2) 0.01 to 0.15% by weight of a noble metal element, and (3) the balance substantially free ofAn inorganic oxide support comprising an alkali metal and an alkaline earth metal. The composition preferably contains: (1) 2 to 29.99 wt%, e.g., 2 to 20 wt%, calculated as oxide, of a rare earth element, (2) 0.01 to 0.1 wt%, calculated as the simple substance, of a noble metal element, and (3) 70 to 97.99 wt%, e.g., 70 to 95 wt%, calculated as oxide, of an inorganic oxide support substantially free of alkali metals and alkaline earth metals; more preferably contains: (1) 5 to 15 wt% of a rare earth element, (2) 0.03 to 0.08 wt% of a noble metal element, and (3) 84.2 to 94.97 wt%, for example 80 to 90 wt%, of an inorganic oxide support substantially free of alkali metals and alkaline earth metals. By substantially free of alkali and alkaline earth metals is meant that the total content of alkali and alkaline earth metals, calculated as oxides, in the inorganic oxide support does not exceed 1% by weight, preferably does not exceed 0.5% by weight.
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x In the discharged composition, the rare earth element is selected from one or more of lanthanides, preferably one or more of Ce, la and Pr or a misch metal containing at least one of Ce, la and Pr, more preferably Ce.
The group provided by the invention is used for reducing CO and NO in catalytic cracking regeneration flue gas x In the discharged compound, the noble metal element is one or more of Pd, ir and Rh, preferably Pd.
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x In the discharged composition, the inorganic oxide carrier is selected from one or more of alumina, zeolite, spinel, kaolin, diatomite and perlite, and is preferably alumina. The alumina is selected from one or more of pseudo-boehmite, macroporous activated alumina and alumina sol, and is preferably pseudo-boehmite.
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x The composition of the discharge may also contain up to 5% by weight, e.g. from 0.1 to 5% by weight, calculated as oxide, of a compound selected from the group consisting of
B～
The metal additive component of one or more of the non-rare earth elements in group B is usually the metal additive component with a content of not more than 2 wt%, and the metal is preferably one or more of Ti, zr, V, cr, mo, W and Mn, more preferably the metal additive component is a compound of Cr with a content of not more than 2 wt%, for example 0.2 to 2 wt%, calculated as oxide, based on the weight of the composition. One embodiment of the method is used for reducing CO and NO in catalytic cracking regeneration flue gas x The composition of the emissions, calculated as oxides: (1) 0.5 to 30% by weight of a rare earth element, (2) 0.01 to 0.15% by weight of a noble metal element, (3) 0 to 5% by weight of the metal additive component and (4) the balance of an inorganic oxide support substantially free of alkali metals and alkaline earth metals, and further the composition consists of (1) 2 to 29.99% by weight, e.g., 2 to 20% by weight, in terms of oxide, of a rare earth element, (2) 0.01 to 0.1% by weight, in terms of an element, of a noble metal element, (3) 70 to 97.99% by weight, e.g., 70 to 95% by weight, in terms of oxide, of the inorganic oxide support substantially free of alkali metals and alkaline earth metals and 0 to 2% by weight of the metal additive component; more preferably consists of: 5 to 15% by weight of a rare earth element, (2) 0.03 to 0.08% by weight of a noble metal element, and (3) 84.2 to 94.97% by weight, for example 80 to 90% by weight, of the essentially alkali and alkaline earth metal-free inorganic oxide support and 0 to 2% by weight of the metal additive component.
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x In the preparation method of the discharged composition, the rare earth element component is one or more of lanthanide compounds, preferably one or more of compounds of Ce, la and Pr, or mixed rare earth of compounds including one or more of Ce, la and Pr, more preferably a compound of Ce. The rare earth element is preferably supported on the support by a method of mixing the rare earth element component with an oxide support component to form a gel prior to spray drying. The rare earth element component can be mixed with the oxide carrier component to form a gel in a solid or solution mode of a compound containing the rare earth element, and the compound is preferably dissolvedLiquid mode.
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x A method for preparing a discharged composition, said inorganic oxide support component being said inorganic oxide or inorganic oxide precursor. The inorganic oxide is one or more of alumina, spinel, kaolin, diatomite, perlite and other common clay materials, preferably one or more of alumina, kaolin, diatomite and perlite, and more preferably alumina. The inorganic oxide precursor is one or more of alumina precursors, the alumina precursors preferably comprise one or more of pseudo-boehmite and macroporous activated alumina, or further comprise alumina sol, and more preferably, the alumina precursors are pseudo-boehmite. The pseudo-boehmite is preferably subjected to acidification peptization before being mixed with the rare earth element component, and the acidification peptization is a conventional method, for example, the pseudo-boehmite and water are beaten to form slurry with the alumina content of 5 to 45 wt%, and then inorganic acid aqueous solution with the concentration of 15 to 40 wt% is added, wherein the inorganic acid is one or more of hydrochloric acid, nitric acid and sulfuric acid, and the acid-to-aluminum ratio (molar ratio) is 0.05 to 0.5, preferably 0.08 to 0.2.
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x A method of making an emitted composition, said metal additive component being selected from the group consisting of
B～
One or more metal elements in B group non-rare earth elements, wherein the content of the metal additive component is not more than 5 wt% in terms of oxide based on the weight of the composition. The metal additive component is preferably one or more of Ti, zr, V, cr, mo, W and Mn, more preferably the metal additive component is Cr, the content of Cr not exceeding 2 wt% calculated as oxide, based on the weight of the composition. When the composition contains a metal additive component, the metal additive componentThe additive can be loaded on the spray-formed carrier particles by adopting an impregnation method, and can also be loaded by adopting a method of mixing the additive with the carrier components to form glue before spray drying. Preferably onto the support prior to the noble metal of the metal additive component; more preferably, the metal additive component is mixed with the carrier component to form a slurry or colloid prior to spray drying and then spray dried; more preferably, the metal additive component is added to mix with the carrier component after the rare earth element component is added to form a gel, for example, by mixing the rare earth element component with the carrier component to form a gel, then adding the metal additive component and then spray drying.
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x In the preparation method of the discharged composition, the noble metal element is one or more of Pd, ir and Rh, preferably Pd. The noble metal element is preferably supported on the oxide support by a soluble salt solution containing the noble metal component. The soluble salt solution containing the precious metal component can be added into the oxide carrier component before spray drying, or can be loaded by adopting an impregnation method after the oxide carrier is subjected to spray drying molding and roasting. Preferably, the soluble salt solution containing the noble metal component is loaded on the oxide carrier after spray drying forming and roasting by adopting an impregnation method. The impregnation method may be saturation impregnation or excess impregnation, and excess impregnation is preferable. Preferably, the volume of the noble metal solution at the time of impregnation is 1.5 to 15 times the pore volume of the support, for example 5 to 10 times the pore volume of the support.
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x In the preparation method of the discharged composition, the oxide carrier is loaded with noble metal elements and then is treated by alkaline solution. The alkaline solution is preferably an alkaline solution of a nonmetallic element. The non-metallic element alkaline solution is preferably a solution of ammonia and an alkaline ammonium salt such as ammonium carbonate, ammonium bicarbonate, diammonium hydrogen phosphate. The basic solution of the non-noble metal element is more preferably ammonia water. The alkaline solution treatment method can be used for beating and contacting the composition loaded with noble metal elements in an alkaline solution,or leaching the composition loaded with the noble metal element by adopting an alkaline solution. And filtering, drying and/or roasting the composition treated by the alkaline solution. The volume of the alkaline solution is 1 to 10 times, preferably 1.5 to 5 times, the pore volume of the composition. The concentration of the basic solution (the concentration of the non-noble metal element compound in the basic solution, for example, ammonia in the case of ammonia water, and the concentration of the basic ammonium salt in the case of a basic ammonium salt solution) is 0.01 to 10mol/L, preferably 0.05 to 5mol/L, and more preferably 0.5 to 2mol/L. The treatment is to contact the composition loaded with the noble metal with an alkaline solution for less than or equal to 60min, such as 2 to 59 min, preferably 5 to 20min, the temperature is not particularly required, and the treatment can be carried out at room temperature (15 to 40 ℃) for example, 0 to 100 ℃.
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x The spray drying process may be carried out by any conventional method, wherein the spray drying process produces particles having a particle size distribution which is not particularly critical in comparison to conventional catalytic cracking catalysts. Typically, the average particle size is from 60 to 75 microns, with a particle size distribution of predominantly 20 to 149 microns, with particle sizes of 40 to 80 microns typically accounting for over 50%.
The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x A method of preparing the discharged composition, a preferred embodiment, comprises the steps of:
(1) Pulping pseudo-boehmite with water, acidifying by adding acid, adding a rare earth compound solution, and optionally adding a metal additive component; wherein the molar ratio of the acidified aluminum acid to the acidified aluminum acid is 0.05 to 0.5, preferably 0.08 to 0.2;
(2) Spray drying the slurry obtained in the step (1); obtaining carrier particles;
(3) Impregnating the carrier particles obtained in the step (2) with a noble metal compound; the dipping time is preferably 5-20min;
(4) And (4) contacting the particles impregnated with the noble metal compound obtained in the step (3) with ammonia water for treatment, drying and roasting.
The fluidized catalytic cracking method provided by the invention comprises the steps of mixing hydrocarbon oil and a catalystThe method comprises the steps of contact reaction and regeneration, wherein the total weight of the catalyst is taken as a reference, the CO and NO in the regenerated flue gas generated by catalytic cracking are reduced x The content of the discharging composition is 0.05 to 5% by weight, preferably 0.1 to 1.5% by weight. The invention provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x The exhaust composition may be a separate particle or be an integral part of the cracking catalyst particle, preferably a separate particle. Namely, the catalyst of the invention contains CO and NO which are provided by the invention and used for reducing the catalytic cracking regeneration flue gas x The invention provides an emission composition and a cracking active component, and provides a method for reducing CO and NO in catalytic cracking regeneration flue gas x The emission composition and the cracking active component may be in the same particle or in different particles. Preferably, the invention provides the method for reducing CO and NO in catalytic cracking regeneration flue gas x The emission composition and the cracking active component are in different particles, namely the catalyst comprises the CO and NO for reducing the catalytic cracking regeneration flue gas x The exhaust composition particles and the catalytic cracking catalyst particles, wherein the catalytic cracking catalyst is one or more of the existing catalytic cracking catalysts, and can be purchased or prepared according to the existing method.
In the fluid catalytic cracking process of the present invention, the method of catalyst regeneration has no special requirements compared to the existing regeneration methods, including partial regeneration, incomplete regeneration and complete regeneration modes of operation. The regeneration method can be seen in pages 1234-1343 of catalytic cracking process and engineering published by Chenjun Wu Shu, chinese petrochemical Press 2005. The preferred regeneration temperature is 650 deg.C-730 deg.C. The hydrocarbon oil is a hydrocarbon oil commonly used for fluid catalytic cracking, such as vacuum gas oil, atmospheric residue, vacuum residue, deasphalted oil, coker gas oil or hydrotreated oil.
The following examples further illustrate the invention but are not intended to limit the invention thereto. Raw materials used in examples and comparative examples: cerium nitrate [ Ce (NO) 3 ) 3 ·6H 2 O ] is analytically pure, produced by chemical reagents of national drug group, inc.; palladium chloride (PdCL) 2 ) For analytical purification, the Pd content is more than or equal to 59.5% (the content units are not specified, and are all weight percentage contents), and the Pd-Pd alloy is produced by Cai-Yi-Au new material GmbH; chromium nitrate [ Cr (NO) 3 ) 3 ·9H 2 O ] is analytically pure, produced by Beijing Yili fine chemicals, inc.; sodium carbonate is analytically pure, produced by Beijing Yili Fine chemicals, inc.;γ-Al 2 O 3 the particle size range of the microspheres is 20-120 microns, the pore volume is 0.36 ml/g (0.50 ml/g after drying at 120 ℃), the alumina content excluding water is 99.5% (solid content is 95.5%), and the microspheres are produced by Shandong aluminum industry company; pseudo-boehmite is an industrial grade product, the content of alumina is 61 weight percent, and the pore volume is 0.31 ml/g, which is produced by Shandong aluminum company; hydrochloric acid with the concentration of 36.5 weight percent, analytically pure, produced by Beijing chemical plants; ammonia water with concentration of 25-28%, analytically pure, produced in Beijing chemical plant, and diluted for use; catalytic cracking catalyst industrial product (commercial brand GOR-II, herein denoted as Cat-A), na 2 O content 0.24%, RE 2 O 3 3.2% of Al 2 O 3 48.0 percent of the total weight, and 67 microns of the average grain diameter, which are produced by China petrochemical catalyst company Limited.
Example 1
This example illustrates the reduction of CO and NO in FCC regeneration flue gas according to the invention x Preparation of the discharge composition S1.
Weighing 4kg of pseudo-boehmite, adding into 16kg of deionized water, pulping and dispersing, adding 250mL of hydrochloric acid, acidifying for 20min, adding CeO 2 1136mL of cerous nitrate solution with the mass content of 240g/L is beaten and dispersed, and then Cr is added 2 O 3 And (3) continuously pulping 239mL of chromium nitrate solution with the mass content of 57g/L, spray-drying, and roasting at 600 ℃ for 1h to obtain the composition carrier M1. Weighing 100g (by dry weight basis) of the carrier M1, adding the carrier M1 into 400mL of water, and adding PdCl with the mass content of 12.5g/L in terms of PdO 2 4.8mL of the solution is stirred for 20min, a composition filter cake after precious metal impregnation is obtained by filtration, 80mL of ammonia water solution with the concentration of 2mol/L is used for leaching the filter cake, and the mixture is dried to obtain the composition, which is marked as S1 (wherein CeO 2 Content 10% by mass, cr 2 O 3 Content 0.5% by mass, pdO content 0.06% by mass).
Example 2
This example illustrates the reduction of CO and NO in FCC regeneration flue gas according to the invention x Preparation of the discharge composition S2.
Weighing 4kg of pseudoboehmite, adding into 16kg of deionized water, pulping and dispersing, adding 250mL of hydrochloric acid, acidifying for 20min, and adding CeO 2 Calculated) of 240g/L cerous nitrate solution 1386mL, slurried, dispersed, spray-dried, and calcined at 600 ℃ for 1h to obtain a composition carrier M2. 100g (calculated by dry weight) of carrier M2 is weighed and added into 500mL of water, and PdCl with the mass content (calculated as PdO) of 12.5g/L is added 2 4.8mL of the solution is stirred for 20min, the mixture is filtered to obtain a filter cake of the composition after being impregnated with the noble metal, 100mL of ammonia water solution with the concentration of 2mol/L is used for leaching the filter cake, and the filter cake is roasted for 2h at 400 ℃ to obtain the composition S2 (wherein CeO is 2 Content 12 mass%, pdO content 0.06 mass%).
Example 3
This example illustrates the reduction of CO and NO in FCC regeneration flue gas according to the invention x Preparation of the discharge composition S3.
Weighing 4kg of pseudo-boehmite, adding into 16kg of deionized water for pulping and dispersing, adding 250mL of hydrochloric acid for acidification for 20min, and adding CeO 2 And (3) pulping and dispersing 1815mL of a cerium nitrate solution with the mass content of 240g/L, spray drying, and roasting at 600 ℃ for 1h to obtain the composition carrier M3. 100g (based on dry weight) of carrier M3 is weighed and added into 350mL of water, pdCl with the PdO mass content of 12.5g/L is added 2 4mL of the solution is stirred for 20min, the mixture is filtered to obtain a composition filter cake after being soaked with noble metal, 100mL of ammonia water solution with the concentration of 2mol/L is used for leaching the filter cake, and the filter cake is roasted for 2h at 400 ℃ to obtain the composition S3 (wherein CeO is 2 Content 15 mass%, pdO content 0.05 mass%).
Example 4
This example illustrates the reduction of CO and NO in FCC regeneration flue gas according to the invention x Preparation of discharge composition S4.
Weighing 4kg of pseudoboehmite, adding into 16kg of deionized water for pulping and dispersing, adding 250mL of hydrochloric acid for acidifying 20After min, ceO is added 2 894mL of cerous nitrate solution with the mass content of 240g/L is beaten and dispersed, and then Cr is added 2 O 3 470mL of chromium nitrate solution with the mass content of 57g/L is continuously pulped, spray-dried and roasted at 600 ℃ for 1h to obtain the composition carrier M4. 100g (based on dry weight) of the carrier M4 is weighed and added into 400mL of water, pdCl with the PdO mass content of 12.5g/L is added 2 5.2mL of the solution, stirring for 20min, filtering to obtain a noble metal-impregnated composition filter cake, leaching the filter cake with 120mL of 2mol/L ammonia water solution, and drying to obtain the composition S4 (wherein CeO is 2 Content 8% by mass, cr 2 O 3 Content 1 mass%, pdO content 0.065 mass%).
Comparative example 1
This example illustrates the preparation of comparative composition CS1 according to the invention.
A comparative composition was prepared by reference to the procedure of example 2 except that no ammonia treatment was used after precious metal impregnation. Weighing 4kg of pseudoboehmite, adding into 16kg of deionized water, pulping and dispersing, adding 250mL of hydrochloric acid, acidifying for 20min, and adding CeO 2 Calculated) 240g/L cerous nitrate solution 1386mL, slurried, dispersed, spray-dried, and calcined at 600 ℃ for 1h to obtain the composition carrier CM1. Weighing 100g (calculated by dry weight) of carrier CM1, adding into 500mL of water, and adding PdCl with mass content (calculated as PdO) of 12.5g/L 2 4.8mL of the solution is stirred for 20min, a filter cake of the composition is obtained after the precious metal is soaked by filtration, and the filter cake is roasted for 2h at 400 ℃ to obtain the composition CS1 (wherein CeO) of the invention 2 Content 12 mass%, pdO content 0.06 mass%).
Comparative example 2
This example illustrates the preparation of comparative composition CS2 according to the invention.
Impregnating with active ingredientsγ-Al 2 O 3 The comparative composition is prepared by the microsphere method (rare earth elements are loaded on a microsphere carrier by a dipping method), the metal additive component Cr is not added in the composition, and ammonia water treatment is not adopted after precious metals are dipped. Weighingγ-Al 2 O 3 Drying a microsphere sample of 92.2g, and measuring CeO 2 In mass content of50mL of 240g/L cerium nitrate solution is added to the driedγ-Al 2 O 3 And (3) uniformly stirring the microsphere sample, drying, and roasting at 600 ℃ for 1h to obtain a comparative composition carrier CM2. Taking PdCl with the mass content of PdO of 12.5g/L 2 Diluting the solution with 4.8mL of water to 48mL of total volume, adding the diluted solution into a carrier CM2, uniformly stirring, and drying to obtain a comparative composition CS2 (wherein CeO is 2 Content 12%, pdO content 0.06%).
Comparative example 3
Comparative composition CS3 was prepared according to the prior art, with the same active ingredient ratios as in comparative example 1, except for the alkali metal Na also introduced during the preparation of the composition.
Weighing 4kg of pseudoboehmite, adding into 16kg of deionized water, pulping and dispersing, adding 250mL of hydrochloric acid, acidifying for 20min, and adding CeO 2 Calculated) is 240g/L, 1410mL of cerous nitrate solution is pulped and dispersed, then 72.3g of sodium carbonate is added for pulping and dispersion, spray drying is carried out, and roasting is carried out for 1h at 600 ℃ to obtain the composition carrier CM3. Weighing 100g (calculated by dry weight) of carrier CM3, adding into 500mL of water, and adding PdCl with mass content (calculated as PdO) of 12.5g/L 2 4.8mL of the solution is stirred for 20min, a filter cake of the composition is obtained after the precious metal is soaked by filtration, and the filter cake is roasted for 2h at 400 ℃ to obtain the composition CS3 (wherein CeO) of the invention 2 Content 12% by mass, na 2 O content 1.5%, pdO content 0.06% by mass).
The following examples and comparative examples illustrate the compositions provided by the present invention and the adjuvants of the comparative compositions for the regeneration of flue gas NO x CO emissions and FCC product distribution.
The auxiliary agent composition (or the comparison composition) provided by the invention is added into a main catalyst (Cat-A) according to a certain proportion (accounting for 0.6-0.9 wt% of the total catalyst inventory), and after being uniformly mixed, the mixture is aged for 12 hours at 800 ℃ in a 100% steam atmosphere, and then catalytic cracking reaction-regeneration evaluation is carried out.
In examples 5 to 8 and comparative examples 4 to 6, the reaction-regeneration evaluation was carried out using a small-sized fixed fluidized bed apparatus, the total catalyst loading was 9g, the reaction temperature was 500 ℃, the agent/oil ratio was 5, and the raw oilThe properties are shown in Table 1. The gas product is analyzed by on-line chromatography to obtain cracked gas composition; performing off-line chromatographic analysis on the liquid product to obtain the yields of gasoline, diesel oil and heavy oil; on-line coke burning regeneration by air according to CO 2 And integrating and calculating the coke yield by an infrared analyzer, and obtaining the FCC product distribution after the yields of all products are normalized. After the reaction, the reaction is carried out by N 2 Stripping for 10min, and carrying out in-situ coke-burning regeneration, wherein the flow rate of regeneration air is 200mL/min, the regeneration time is 15min, the initial regeneration temperature is the same as the reaction temperature, and the highest temperature is 685 ℃. Collecting the flue gas in the regeneration process, and measuring the concentration of NOx and CO in the flue gas by using a Testo350Pro flue gas analyzer after the regeneration is finished.
Examples 5 to 8
The compositions S1 to S4 provided by the invention are added into the group of examples to regenerate the flue gas NO x CO emissions and FCC product distribution.
Wherein the proportion ratio of the compositions S1 to S4 in the total catalyst inventory is 0.6 wt%, 0.8 wt% and 0.6 wt%.
The results of the emission test of pollutants in the regenerated flue gas and the distribution of FCC products are shown in Table 2.
Comparative examples 4 to 6
This comparative example illustrates the addition of comparative compositions CS1, CS2 and CS3 to the regeneration flue gas NO x CO emissions and FCC product distribution.
Wherein the comparative compositions CS1, CS2 and CS3 are each present in an amount of 0.9% by weight based on the total catalyst inventory
The results of the emission measurements of pollutants in the flue gas and the FCC product distribution are also shown in Table 2.
TABLE 1
TABLE 2
| Example numbering | Example 5 | Example 6 | Example 7 | Example 8 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Adjuvant composition | S1 | S2 | S3 | S4 | CS1 | CS2 | CS3 |
| The addition amount of the composition is percent by weight | 0.6 | 0.8 | 0.8 | 0.6 | 0.9 | 0.9 | 0.9 |
| NO x Concentration, ppm | 102 | 106 | 97 | 92 | 125 | 128 | 117 |
| CO concentration,% by volume | 0.42 | 0.36 | 0.44 | 0.39 | 0.59 | 0.51 | 0.68 |
| Product distribution,% by weight | |||||||
| Dry gas | 1.69 | 1.68 | 1.71 | 1.70 | 1.70 | 1.72 | 1.75 |
| Liquefied gas | 19.27 | 19.39 | 19.56 | 19.48 | 19.39 | 19.2 | 19.43 |
| Coke | 7.15 | 7.2 | 7.22 | 7.19 | 7.19 | 7.27 | 7.34 |
| Gasoline (R) and its preparation method | 49.65 | 49.61 | 49.53 | 49.35 | 49.06 | 49.50 | 48.73 |
| Diesel oil | 15.14 | 15.09 | 14.86 | 15.24 | 15.43 | 15.26 | 15.54 |
| Heavy oil | 7.10 | 7.03 | 7.12 | 7.04 | 7.23 | 7.05 | 7.21 |
| Conversion rate% | 77.76 | 77.88 | 78.02 | 77.72 | 77.34 | 77.69 | 77.25 |
As can be seen from Table 2, the auxiliary composition for reducing CO and NOx emissions provided by the invention is used in the catalytic cracking process, and can achieve higher CO combustion-supporting activity under the condition of lower dosage compared with the auxiliary (comparative composition) prepared by the prior art, and meanwhile, the catalytic conversion activity of NOx in the regenerated flue gas is obviously improved.
Claims (24)
1. Reduction of CO and NO in FCC (fluid catalytic cracking) regenerated flue gas x An emitted adjuvant composition comprising, in terms of oxides based on the weight of the composition: (1) 0.5 to 30% by weight of a rare earth element, (2) 0.01 to 0.15% by weight of a noble metal element, and (3) the balance of an inorganic oxide support substantially free of alkali metals and alkaline earth metals, wherein the composition, after introduction of the noble metal element, is treated with aqueous ammonia or a basic ammonium salt solution before drying and/or calcination, and when the noble metal element is supported on the inorganic oxide support by impregnation, the composition after supporting the noble metal element is treated with the aqueous ammonia or the basic ammonium salt solution after filtration.
2. The composition of claim 1, wherein the ammonia water or the alkaline ammonium salt solution is treated by beating the noble metal element-loaded composition in the ammonia water or the alkaline ammonium salt solution, or rinsing the noble metal element-loaded composition with the ammonia water or the alkaline ammonium salt solution.
3. The composition according to claim 1, wherein the composition comprises, in terms of oxides: (1) 2 to 29.99% by weight of a rare earth element, (2) 0.01 to 0.1% by weight of a noble metal element, and (3) 70 to 97.99% by weight of an inorganic oxide support substantially free of alkali metals and alkaline earth metals.
4. A composition according to claim 3, characterized in that it comprises, in oxide terms: (1) 5 to 15% by weight of a rare earth element, (2) 0.03 to 0.08% by weight of a noble metal element, and (3) 84.92 to 94.97% by weight of an inorganic oxide support substantially free of alkali metals and alkaline earth metals.
5. The composition of claim 1, wherein the rare earth element is one or more of Ce, la and Pr or comprises at least one of the foregoing elements.
6. The composition of claim 1, wherein the noble metal element is one or more of Pd, ir, rh.
7. The composition of claim 1, wherein the inorganic oxide support is selected from one or more of alumina, zeolite, spinel, kaolin, diatomaceous earth, and perlite.
8. A composition according to any of claims 1 to 7, wherein the composition further comprises up to 5% by weight, calculated as oxide, of a metal additive component selected from one or more of the group IB-VIIB non-rare earth elements.
9. The composition of claim 8 wherein said metal additive component is Cr; the content of Cr is not more than 2% by weight, calculated as oxide, based on the weight of the composition.
10. The composition of claim 2, wherein the composition is prepared by a process comprising the steps of slurrying the substantially alkali and alkaline earth metal free inorganic oxide support component and rare earth element component, spray drying, calcining, impregnating with the noble metal element, filtering, treating with aqueous ammonia or a basic ammonium salt solution, and drying and/or calcining.
11. The composition of claim 1 or 2, wherein the inorganic oxide support component substantially free of alkali and alkaline earth metals is an alumina component that has been subjected to an acidifying peptization treatment prior to mixing with the rare earth element component.
12. The composition of claim 11 wherein the inorganic oxide support component is pseudoboehmite.
13. The composition of claim 2 wherein said noble metal element is supported on the support by excess impregnation, the volume of said noble metal solution being from 1.5 to 15 times the pore volume of the support during impregnation.
14. The composition of claim 13, wherein the volume of the noble metal solution is 5 to 10 times the pore volume of the carrier.
15. The composition of claim 1, wherein the basic ammonium salt solution is a solution of ammonium carbonate, ammonium bicarbonate or diammonium phosphate.
16. The composition according to claim 1, wherein the composition is used for reducing CO and NO in catalytic cracking regeneration flue gas x The discharged adjuvant composition is prepared by a process comprising the steps of:
(1) Pulping pseudo-boehmite with water, acidifying by adding acid, adding a rare earth compound solution, and optionally adding a metal additive component; wherein the molar ratio of the acidified aluminum acid is 0.05-0.5;
(2) Spray drying the slurry obtained in the step (1); obtaining carrier particles;
(3) Impregnating the carrier particles obtained in the step (2) with a noble metal compound and filtering;
(4) And (4) contacting the particles impregnated with the noble metal compound obtained in the step (3) with ammonia water for treatment, drying and roasting.
17. The composition of claim 1 wherein the volume of said composition after noble metal introduction is from 1 to 10 times the pore volume of the composition when said composition is treated with aqueous ammonia or a basic ammonium salt solution.
18. The composition of claim 17 wherein the volume of said aqueous ammonia or basic ammonium salt solution is 1.5 to 5 times the pore volume of the composition.
19. The composition according to claim 1, 2, 16, 17 or 18, wherein the concentration of the aqueous ammonia or the basic ammonium salt solution is 0.01 to 10mol/L.
20. The composition according to claim 19, wherein the concentration of the aqueous ammonia or the basic ammonium salt solution is 0.05 to 5mol/L.
21. The composition of claim 20, wherein the concentration of the aqueous ammonia or the basic ammonium salt solution is 0.5 to 2mol/L.
22. A fluid catalytic cracking process comprising the steps of contacting a hydrocarbon oil with a catalyst for reaction and regeneration, wherein the catalyst comprises the composition of any one of claims 1 to 21, and the composition of any one of claims 1 to 21 is contained in an amount of 0.05 to 5 wt%.
23. A process according to claim 22, wherein the composition of any one of claims 1 to 21 is present in the catalyst in an amount of from 0.1 to 1.5% by weight.
24. A process according to claim 22 or 23, wherein the catalyst comprises a composition according to any one of claims 1 to 21 and a cracking active component, the composition according to any one of claims 1 to 21 being in a different particle to the cracking active component or comprising the composition according to any one of claims 1 to 21 and the cracking active component in the same catalyst particle.
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| CN202210820631.2A CN115350703A (en) | 2014-08-29 | 2014-08-29 | For reducing CO and NO in FCC regeneration flue gas x Composition for discharging and preparation method thereof |
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| CN202210820631.2A CN115350703A (en) | 2014-08-29 | 2014-08-29 | For reducing CO and NO in FCC regeneration flue gas x Composition for discharging and preparation method thereof |
| CN201410437782.5A CN105363444A (en) | 2014-08-29 | 2014-08-29 | Composition for reducing emission of CO and NOx of FCC regeneration flue gas and preparation method of composition |
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| CN201410437782.5A Division CN105363444A (en) | 2014-08-29 | 2014-08-29 | Composition for reducing emission of CO and NOx of FCC regeneration flue gas and preparation method of composition |
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| CN202210820631.2A Pending CN115350703A (en) | 2014-08-29 | 2014-08-29 | For reducing CO and NO in FCC regeneration flue gas x Composition for discharging and preparation method thereof |
| CN202210751715.5A Pending CN115025777A (en) | 2014-08-29 | 2014-08-29 | For reducing CO and NO in FCC (fluid catalytic cracking) regeneration flue gas x Composition for discharging and preparation method thereof |
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| EP3693085A4 (en) | 2017-07-05 | 2021-04-14 | Research Institute Of Petroleum Processing, Sinopec | Composition capable of reducing co and nox emissions, preparation method therefor and use thereof, and fluid catalytic cracking method |
| CN109201080B (en) * | 2017-07-05 | 2020-12-04 | 中国石油化工股份有限公司 | Composition capable of reducing CO and NOx emission, preparation method and application thereof, and fluidized catalytic cracking method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6165933A (en) * | 1995-05-05 | 2000-12-26 | W. R. Grace & Co.-Conn. | Reduced NOx combustion promoter for use in FCC processes |
| CN1684766A (en) * | 2002-10-10 | 2005-10-19 | 恩格哈德公司 | Cooxidation promoters for use in FCC processes |
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| US20050100494A1 (en) * | 2003-11-06 | 2005-05-12 | George Yaluris | Ferrierite compositions for reducing NOx emissions during fluid catalytic cracking |
| CN102371150B (en) * | 2010-08-26 | 2013-06-05 | 中国石油化工股份有限公司 | Composition for reducing discharge of NOx in regeneration flue gas of fluid catalytic cracking (FCC) |
| AU2012202584B2 (en) * | 2011-05-11 | 2013-10-17 | Bharat Petroleum Corporation Limited | A multifunctional catalyst additive composition and process of preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6165933A (en) * | 1995-05-05 | 2000-12-26 | W. R. Grace & Co.-Conn. | Reduced NOx combustion promoter for use in FCC processes |
| CN1684766A (en) * | 2002-10-10 | 2005-10-19 | 恩格哈德公司 | Cooxidation promoters for use in FCC processes |
Non-Patent Citations (1)
| Title |
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| 吴忠标等: "《环境催化原理及应用》", 北京工业出版社环境·能源出版中心, pages: 117 - 118 * |
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| CN105363444A (en) | 2016-03-02 |
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