US20050205465A1 - NOx reduction compositions for use in FCC processes - Google Patents
NOx reduction compositions for use in FCC processes Download PDFInfo
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- US20050205465A1 US20050205465A1 US11/015,912 US1591204A US2005205465A1 US 20050205465 A1 US20050205465 A1 US 20050205465A1 US 1591204 A US1591204 A US 1591204A US 2005205465 A1 US2005205465 A1 US 2005205465A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 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 27
- 238000003860 storage Methods 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 claims abstract description 20
- 238000005336 cracking Methods 0.000 claims abstract description 18
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 17
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 41
- 239000003513 alkali Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 40
- 239000000654 additive Substances 0.000 description 15
- 230000000996 additive effect Effects 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 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 4
- 239000011959 amorphous silica alumina Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
- 229940094989 trimethylsilane Drugs 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- -1 magnesium aluminate Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Classifications
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/83—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 rare earths or actinides
-
- B01J35/19—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/187—Controlling or regulating
-
- 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
Definitions
- FCC fluid catalytic cracking
- catalyst particles inventory
- catalyst regeneration zone In regeneration, coke deposits (from the cracking reaction) on the catalyst particles are removed at elevated temperatures by oxidation. The removal of coke deposits restores the activity of the catalyst particles to the point where they can be reused in the cracking reaction.
- gases such as SO x , CO, and NO x .
- additives have been used either as an integral part of the FCC catalyst particles themselves or as separate admixture particles in the FCC catalyst inventory in attempts to deal with these problematic gases.
- magnesium aluminate spinel additives are often used to prevent or mini m emission of SO x from the regenerator.
- Various noble metal catalysts have been used to minimize the emission of CO from the regenerator.
- compositions suitable for use in FCC processes which are capable of providing superior NO x control performance.
- the invention provides compositions for reducing NO x emissions in FCC processes, the compositions comprising a component containing (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) a transition metal selected from Groups lb and/or IIb of the Periodic Table.
- the acidic oxide support preferably contains silica alumina.
- Ceria is the preferred oxygen-storage oxide.
- Cu and Ag are preferred Group I/IIb transition metals.
- the invention encompasses FCC processes using the NO x reduction compositions of the invention either as an integral part of the FCC catalyst particles themselves or as separate admixture particles in the FCC catalyst inventory.
- the invention encompasses the discovery that certain classes of compositions are very effective for the reduction of NO x gas emissions in FCC processes.
- the NO x reduction compositions of the invention are characterized in that they comprise a component containing (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) a transition metal selected from Groups Ib and/or IIb of the Periodic Table.
- the acidic oxide support should be of sufficient acidity for the composition to act as an effective NO x reduction additive.
- the support preferably contains acidic silanol or bridged hydroxyl groups. These acid groups are preferably characterized by NMR shifts in the region of ⁇ 90 to ⁇ 100 ppm compared to a TMS (trimethyl silane) standard.
- the support may be crystalline or amorphous.
- the acidic oxide support contains at least some alumina. More preferably, the oxide support contains at least 50 wt. % alumina.
- the oxide support is preferably an oxide selected from the group consisting of alumina, silica alumina, and lanthana alumina. Amorphous silica aluminas are most preferred. Where an amorphous silica alumina support is used, the support preferably has an alumina to silica molar ratio of about 3-50:1.
- the acidic oxide support further preferably has sufficient surface area to promote the NO x reduction process.
- the oxide support has a surface area of at least 50 m 2 /g, more preferably about 70-200 m 2 /g.
- the alkali and/or alkaline earth metal may be any alkali metal, alkaline earth metal or combinations thereof.
- the NO x reduction component preferably contains an alkali metal selected from sodium, potassium and mixtures thereof.
- the amount of alkali/alkaline earth metal present in the NO x reduction component of the invention is preferably about 1-10 parts by weight (measured as alkali/alkaline earth metal oxide) per 100 parts by weight of the oxide support material. While the alkali/alkaline earth metal content is expressed as the amount of corresponding oxide, preferably the alkali/alkaline metal is present in cationic form rather than as discrete oxide.
- the transition metal oxide having oxygen storage capability may be any transition metal oxide having oxygen storage capability similar to that of ceria.
- at least a portion of the oxygen storage oxide is ceria. More preferably, the oxygen storage oxide consists essentially of ceria. Other non-stoichiometric metal oxides having known oxygen storage capability may also be used.
- the oxygen storage oxide is preferably present as a microdispersed phase as opposed to large bulk oxide particles or ions located at exchange sites in the oxide support.
- the amount of the oxygen storage oxide present in the NO x reduction component may be varied considerably relative to the amount of acidic oxide support.
- the NO x reduction component contains at least about 1 part by weight of oxygen storage oxide per 100 parts by weight of the oxide support material, more preferably at least about 2-50 parts by weight per 100 parts of the oxide support material.
- the Group Ib and/or IIb transition metal may be any metal or combination of metals selected from those groups of the Periodic Table.
- the transition metal is selected from the group consisting of Cu, Ag and mixtures thereof.
- the amount of transition metal present is preferably at least about 100 parts by weight (measured as metal oxide) per million parts of the oxide support material, more preferably about 0.1-5 parts by weight per 100 parts of the oxide support material.
- the NO x reduction component may contain minor amounts of other materials which preferably do not adversely affect the NO x reduction function in a significant way. More preferably, however, the NO x reduction component consists essentially of items (i)-(iv) mentioned above.
- the NO x reduction component may be combined with fillers (e.g. clay, silica, alumina or silica alumina particles) and/or binders (e.g. silica sol, alumina sol, silica alumina sol, etc.) to form particles suitable for use in an FCC process.
- any added binders or fillers used do not significantly adversely affect the performance of the NO x reduction component.
- the amount of NO x reduction component in the additive particles is preferably at least 50 wt. %, more preferably at least 75 wt. %. Most preferably, the additive particles consist entirely of the NO x reduction component.
- the additive particles are preferably of a size suitable for circulation with the catalyst inventory in an FCC process.
- the additive particles preferably have an average particle size of about 20-200 ⁇ m.
- the additive particles preferably have a Davison attrition index (DI) value of about 0-45, more preferably about 0-15.
- DI Davison attrition index
- the NO x reduction composition of the invention may be integrated into the FCC catalyst particles themselves. In such case, any conventional FCC catalyst particle components may be used in combination with the NO x reduction composition of the invention. If integrated into the FCC catalyst particles, the NO x reduction composition of the invention is preferably represents at least about 0.02 wt % of the FCC catalyst particle, more preferably about 0.1-10 wt. %.
- the NO x reduction component of the invention is preferably made by the following procedure:
- the sources of alkali/alkaline earth metal oxide and oxygen storage oxide are preferably slurries, sols and/or solutions of the metal oxides themselves or salts of the respective metals which decompose to oxides on calcination or combinations of oxides and salts.
- the individual constituents may be separately added to the support particles with a calcination step in between each addition.
- the impregnated particles are spray dried before the calcination of step (d).
- the calcination steps are preferably performed at about 450-750° C.
- the NO x reduction component may be used as a separate additive particle or as an integral part of an FCC catalyst particle. If used as an additive, the NO x reduction component may itself be formed into particles suitable for use in an FCC process. Alternatively, the NO x reduction component may be combined with binders, fillers, etc. by any conventional technique. See for example, the process described in U.S. Pat. No. 5,194,413, the disclosure of which is incorporated herein by reference.
- the component of the invention is integrated into an FCC catalyst particle, preferably the component is first formed and then combined with the other constituents which make up the FCC catalyst particle.
- Incorporation of the NO x reduction component directly into FCC catalyst particles may be accomplished by an known technique. Example of suitable techniques for this purpose are disclosed in U.S. Pat. Nos. 3,957,689; 4,499,197; 4,542,188 and 4,458,623, the disclosures of which are incorporated herein by reference.
- compositions of the invention may be used in any conventional FCC process. Typical FCC processes are conducted reaction temperatures of 450 to 650° C. with catalyst regeneration temperatures of 600 to 850° C.
- the compositions of the invention may be used in FCC processing of any typical hydrocarbon feedstock.
- the compositions of the invention are used in FCC processes involving the cracking of hydrocarbon feedstocks which contain above average amounts of nitrogen, especially residual feedstocks or feedstocks having a nitrogen content of at least 0.1 wt. %.
- the amount of the NO x reduction component of the invention used may vary depending on the specific FCC process.
- the amount of NO x reduction component used (in the circulating inventory) is about 0.1-15 wt. % based on the weight of the FCC catalyst in the circulating catalyst inventory.
- An amorphous silica alumina particulate support containing 6 wt. % silica was impregnated with a sodium carbonate solution, dried and calcined to achieve a 3.6 wt. % Na content measured as Na 2 O based on the weight of the silica alumina
- the Na-containing silica alumina particles were then impregnated with a solution of cerium nitrate and then dried to achieve a ceria content of about 1 wt. % based on the weight of the silica alumina particles.
- the Ce-containing composition was then impregnated with a silver nitrate solution to achieve a silver content of about 5 wt. % (oxide basis) based on the weight of the silica alumina particles.
- the impregnated particles were then dried and calcined at about 704° C. to form a particulate composition in accordance with the invention.
- An amorphous silica alumina particulate support containing 6 wt. % silica was impregnated with a sodium carbonate solution, dried and calcined to achieve a 6 wt. % Na content measured as Na 2 O based on the weight of the silica alumina.
- the Na-containing silica alumina particles were then impregnated with a solution of cerium nitrate and then dried to achieve a ceria content of about 22 wt. % based on the weight of the silica alumina particles.
- the Ce-containing composition was then impregnated with a copper nitrate solution to achieve a copper content of about 2 wt. % (oxide basis) based on the weight of the silica alumina particles.
- the impregnated particles were then dried and calcined at about 704° C. to form a particulate composition in accordance with the invention.
- the 152 g of the composition of example 1 was admixed with 2908 grams of a commercial FCC catalyst (Grace Davison Orion® 842 equilibrium catalyst (ECAT)) and 10 g of a combustion promoter (Grace Davison CP-5). The admixture was then used to crack a hydrocarbon feedstock containing 0.3 wt. % nitrogen in a DCR pilot plant FCC unit. The cracking was performed at a 75% conversion rate and 1000 g/hr catalyst feed rate. As a control example, the same catalyst admixture was run without the composition of example 1. The NO x emission measured from the FCC unit regenerator was 65% less when the composition of example 1 was used compared to the control example.
- ECAT equilibrium catalyst
- the 10 g of the composition of example 2 was admixed with 2000 grams of a commercial FCC catalyst (Grace Davison Orion® 922G ECAT) and 5 g of a combustion promoter (Grace Davison CP-5). The admixture was then used to crack a Countrymark hydrocarbon feedstock (0.13 wt. % N) in an FCC pilot plant (DCR) unit. The cracking was performed at a 75% conversion rate and 1000 g/hr catalyst feed rate. As a control example, the same catalyst admixture was run without the composition of example 2. The NO x emission measured from the FCC unit regenerator was 46% less when the composition of example 2 was used compared to the control example.
Abstract
Compositions comprising a component containing (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) a transition metal selected from Groups Ib and/or IIb of the Periodic Table provide NOx control performance in FCC processes. The acidic oxide support preferably contains silica alumina. Ceria is the preferred oxygen storage oxide. Cu and Ag are preferred Group I/IIb transition metals. The compositions are especially useful in the cracking of hydrocarbon feedstocks having above average nitrogen content.
Description
- Public policy and cost/benefit pressures have created an increasing desire to reduce the amount of polluting gases released by industrial processes. As a result, there has been a drive to find ways of decreasing pollution by modifying industrial processes.
- In the petroleum refining industry, fluid catalytic cracking (FCC) of hydrocarbons is a commonly used petroleum refining method. In an FCC process, catalyst particles (inventory) are repeatedly circulated between a catalytic cracking zone and a catalyst regeneration zone. In regeneration, coke deposits (from the cracking reaction) on the catalyst particles are removed at elevated temperatures by oxidation. The removal of coke deposits restores the activity of the catalyst particles to the point where they can be reused in the cracking reaction.
- While FCC processes are efficient from the point of catalyst use, the regeneration step typically results in the evolution of undesirable gases such as SOx, CO, and NOx. Various attempts have been made to limit the amounts of these gases created during the FCC regeneration step or otherwise to deal with the gases after their formation. Most typically, additives have been used either as an integral part of the FCC catalyst particles themselves or as separate admixture particles in the FCC catalyst inventory in attempts to deal with these problematic gases. For example, magnesium aluminate spinel additives are often used to prevent or mini m emission of SOx from the regenerator. Various noble metal catalysts have been used to minimize the emission of CO from the regenerator.
- Unfortunately, the additives used to control CO emissions typically cause a dramatic increase (e.g., 300%) in NOx evolution from the regenerator. Some of the spinel-based (SOx reduction) additives act to lessen the amount of NOx emission, but with limited success. Thus, there remains a need for more effective NOx control additives suitable for use in FCC processes.
- The invention provides compositions suitable for use in FCC processes which are capable of providing superior NOx control performance.
- In one aspect, the invention provides compositions for reducing NOx emissions in FCC processes, the compositions comprising a component containing (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) a transition metal selected from Groups lb and/or IIb of the Periodic Table. The acidic oxide support preferably contains silica alumina. Ceria is the preferred oxygen-storage oxide. Cu and Ag are preferred Group I/IIb transition metals.
- In another aspect, the invention encompasses FCC processes using the NOx reduction compositions of the invention either as an integral part of the FCC catalyst particles themselves or as separate admixture particles in the FCC catalyst inventory.
- These and other aspects of the invention are described in further detail below.
- The invention encompasses the discovery that certain classes of compositions are very effective for the reduction of NOx gas emissions in FCC processes. The NOx reduction compositions of the invention are characterized in that they comprise a component containing (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) a transition metal selected from Groups Ib and/or IIb of the Periodic Table.
- The acidic oxide support should be of sufficient acidity for the composition to act as an effective NOx reduction additive. The support preferably contains acidic silanol or bridged hydroxyl groups. These acid groups are preferably characterized by NMR shifts in the region of −90 to −100 ppm compared to a TMS (trimethyl silane) standard. The support may be crystalline or amorphous. Preferably, the acidic oxide support contains at least some alumina. More preferably, the oxide support contains at least 50 wt. % alumina. The oxide support is preferably an oxide selected from the group consisting of alumina, silica alumina, and lanthana alumina. Amorphous silica aluminas are most preferred. Where an amorphous silica alumina support is used, the support preferably has an alumina to silica molar ratio of about 3-50:1.
- The acidic oxide support further preferably has sufficient surface area to promote the NOx reduction process. Preferably, the oxide support has a surface area of at least 50 m2/g, more preferably about 70-200 m2/g.
- The alkali and/or alkaline earth metal may be any alkali metal, alkaline earth metal or combinations thereof. The NOx reduction component preferably contains an alkali metal selected from sodium, potassium and mixtures thereof. The amount of alkali/alkaline earth metal present in the NOx reduction component of the invention is preferably about 1-10 parts by weight (measured as alkali/alkaline earth metal oxide) per 100 parts by weight of the oxide support material. While the alkali/alkaline earth metal content is expressed as the amount of corresponding oxide, preferably the alkali/alkaline metal is present in cationic form rather than as discrete oxide.
- The transition metal oxide having oxygen storage capability may be any transition metal oxide having oxygen storage capability similar to that of ceria. Preferably, at least a portion of the oxygen storage oxide is ceria. More preferably, the oxygen storage oxide consists essentially of ceria. Other non-stoichiometric metal oxides having known oxygen storage capability may also be used. The oxygen storage oxide is preferably present as a microdispersed phase as opposed to large bulk oxide particles or ions located at exchange sites in the oxide support. The amount of the oxygen storage oxide present in the NOx reduction component may be varied considerably relative to the amount of acidic oxide support. Preferably, the NOx reduction component contains at least about 1 part by weight of oxygen storage oxide per 100 parts by weight of the oxide support material, more preferably at least about 2-50 parts by weight per 100 parts of the oxide support material.
- The Group Ib and/or IIb transition metal may be any metal or combination of metals selected from those groups of the Periodic Table. Preferably, the transition metal is selected from the group consisting of Cu, Ag and mixtures thereof. The amount of transition metal present is preferably at least about 100 parts by weight (measured as metal oxide) per million parts of the oxide support material, more preferably about 0.1-5 parts by weight per 100 parts of the oxide support material.
- The NOx reduction component may contain minor amounts of other materials which preferably do not adversely affect the NOx reduction function in a significant way. More preferably, however, the NOx reduction component consists essentially of items (i)-(iv) mentioned above. Where the composition of the invention is used as an additive particle for an FCC process, the NOx reduction component may be combined with fillers (e.g. clay, silica, alumina or silica alumina particles) and/or binders (e.g. silica sol, alumina sol, silica alumina sol, etc.) to form particles suitable for use in an FCC process. Preferably, any added binders or fillers used do not significantly adversely affect the performance of the NOx reduction component.
- Where the NOx reduction composition is used as an additive particulate (as opposed to being integrated into the FCC catalyst particles themselves), the amount of NOx reduction component in the additive particles is preferably at least 50 wt. %, more preferably at least 75 wt. %. Most preferably, the additive particles consist entirely of the NOx reduction component. The additive particles are preferably of a size suitable for circulation with the catalyst inventory in an FCC process. The additive particles preferably have an average particle size of about 20-200 μm. The additive particles preferably have a Davison attrition index (DI) value of about 0-45, more preferably about 0-15.
- If desired, the NOx reduction composition of the invention may be integrated into the FCC catalyst particles themselves. In such case, any conventional FCC catalyst particle components may be used in combination with the NOx reduction composition of the invention. If integrated into the FCC catalyst particles, the NOx reduction composition of the invention is preferably represents at least about 0.02 wt % of the FCC catalyst particle, more preferably about 0.1-10 wt. %.
- While the invention is not limited to any particular method of manufacture, the NOx reduction component of the invention is preferably made by the following procedure:
-
- (a) impregnate the acidic oxide porous support particles with an alkali/alkaline earth metal oxide source and an oxygen storage oxide source to achieve the desired alkali/alkaline earth metal and oxygen storage oxide content,
- (b) calcine the impregnated support of step (a),
- (c) impregnate the calcined support from step (b) with a source of Group Ib and/or IIb metal, and
- (d) calcine the impregnated support from step (c).
- The sources of alkali/alkaline earth metal oxide and oxygen storage oxide are preferably slurries, sols and/or solutions of the metal oxides themselves or salts of the respective metals which decompose to oxides on calcination or combinations of oxides and salts. If desired, the individual constituents may be separately added to the support particles with a calcination step in between each addition. If desired, the impregnated particles are spray dried before the calcination of step (d). The calcination steps are preferably performed at about 450-750° C.
- The NOx reduction component may be used as a separate additive particle or as an integral part of an FCC catalyst particle. If used as an additive, the NOx reduction component may itself be formed into particles suitable for use in an FCC process. Alternatively, the NOx reduction component may be combined with binders, fillers, etc. by any conventional technique. See for example, the process described in U.S. Pat. No. 5,194,413, the disclosure of which is incorporated herein by reference.
- Where the NOx reduction component of the invention is integrated into an FCC catalyst particle, preferably the component is first formed and then combined with the other constituents which make up the FCC catalyst particle. Incorporation of the NOx reduction component directly into FCC catalyst particles may be accomplished by an known technique. Example of suitable techniques for this purpose are disclosed in U.S. Pat. Nos. 3,957,689; 4,499,197; 4,542,188 and 4,458,623, the disclosures of which are incorporated herein by reference.
- The compositions of the invention may be used in any conventional FCC process. Typical FCC processes are conducted reaction temperatures of 450 to 650° C. with catalyst regeneration temperatures of 600 to 850° C. The compositions of the invention may be used in FCC processing of any typical hydrocarbon feedstock. Preferably, the compositions of the invention are used in FCC processes involving the cracking of hydrocarbon feedstocks which contain above average amounts of nitrogen, especially residual feedstocks or feedstocks having a nitrogen content of at least 0.1 wt. %. The amount of the NOx reduction component of the invention used may vary depending on the specific FCC process. Preferably, the amount of NOx reduction component used (in the circulating inventory) is about 0.1-15 wt. % based on the weight of the FCC catalyst in the circulating catalyst inventory. The presence of the compositions of the invention during the FCC process catalyst regeneration step dramatically reduces the level of NOx emitted during regeneration.
- An amorphous silica alumina particulate support containing 6 wt. % silica was impregnated with a sodium carbonate solution, dried and calcined to achieve a 3.6 wt. % Na content measured as Na2O based on the weight of the silica alumina The Na-containing silica alumina particles were then impregnated with a solution of cerium nitrate and then dried to achieve a ceria content of about 1 wt. % based on the weight of the silica alumina particles. The Ce-containing composition was then impregnated with a silver nitrate solution to achieve a silver content of about 5 wt. % (oxide basis) based on the weight of the silica alumina particles. The impregnated particles were then dried and calcined at about 704° C. to form a particulate composition in accordance with the invention.
- An amorphous silica alumina particulate support containing 6 wt. % silica was impregnated with a sodium carbonate solution, dried and calcined to achieve a 6 wt. % Na content measured as Na2O based on the weight of the silica alumina. The Na-containing silica alumina particles were then impregnated with a solution of cerium nitrate and then dried to achieve a ceria content of about 22 wt. % based on the weight of the silica alumina particles. The Ce-containing composition was then impregnated with a copper nitrate solution to achieve a copper content of about 2 wt. % (oxide basis) based on the weight of the silica alumina particles. The impregnated particles were then dried and calcined at about 704° C. to form a particulate composition in accordance with the invention.
- The 152 g of the composition of example 1 was admixed with 2908 grams of a commercial FCC catalyst (Grace Davison Orion® 842 equilibrium catalyst (ECAT)) and 10 g of a combustion promoter (Grace Davison CP-5). The admixture was then used to crack a hydrocarbon feedstock containing 0.3 wt. % nitrogen in a DCR pilot plant FCC unit. The cracking was performed at a 75% conversion rate and 1000 g/hr catalyst feed rate. As a control example, the same catalyst admixture was run without the composition of example 1. The NOx emission measured from the FCC unit regenerator was 65% less when the composition of example 1 was used compared to the control example.
- The 10 g of the composition of example 2 was admixed with 2000 grams of a commercial FCC catalyst (Grace Davison Orion® 922G ECAT) and 5 g of a combustion promoter (Grace Davison CP-5). The admixture was then used to crack a Countrymark hydrocarbon feedstock (0.13 wt. % N) in an FCC pilot plant (DCR) unit. The cracking was performed at a 75% conversion rate and 1000 g/hr catalyst feed rate. As a control example, the same catalyst admixture was run without the composition of example 2. The NOx emission measured from the FCC unit regenerator was 46% less when the composition of example 2 was used compared to the control example.
Claims (20)
1. A NOx control composition suitable for use in a fluidized catalytic cracking process, said composition comprising a component which contains (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) a transition metal selected from Groups Ib and/or IIb of the Periodic Table.
2. The composition of claim 1 wherein said acidic oxide support contains alumina.
3. The composition of claim 2 wherein said acidic oxide support is selected from the group consisting of alumina, silica alumina, and lanthana alumina.
4. The composition of claim 3 wherein said oxide support is a silica alumina.
5. The composition of claim 4 wherein said silica alumina has an alumina:silica mole ratio of about 3-50:1.
6. The composition of claim 1 wherein said oxygen storage oxide contains ceria.
7. The composition of claim 1 wherein said component contains an alkali metal selected from the group consisting of sodium, potassium, and mixtures thereof.
8. The composition of claim 1 wherein said component contains Group lb transition metal selected from the group consisting of copper, silver, and mixtures thereof.
9. The composition of claim 1 wherein said component contains about 1-10 parts by weight (measured as alkali/alkaline earth metal oxide) of said alkali/alkaline earth metal per 100 parts by weight of said acidic oxide support material.
10. The composition of claim 1 wherein said component contains at least about 1 part by weight of said oxygen storage oxide per 100 parts by weight of said acidic oxide support material.
11. The composition of claim 10 wherein said component contains about 2 to 50 parts by weight of said oxygen storage oxide per 100 parts by weight of said acidic oxide support material.
12. The composition of claim 1 wherein said component contains about 0.01-5 parts by weight total of said Group Ib and/or IIb metal (measured as metal oxide) per 100 parts by weight of said acidic oxide support material.
13. The composition of claim 1 wherein said component consists essentially of constituents (i)-(iv).
14. The composition of claim 13 wherein said composition consists essentially of said component and said composition is in the form of particles.
15. A fluid cracking catalyst comprising (a) a cracking component suitable for use in cracking hydrocarbons, and (b) a component which contains (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) a transition metal selected from Groups Ib and/or IIb of the Periodic Table.
16. The cracking catalyst of claim 15 wherein said cracking catalyst comprises an admixture of component (a) in particulate form and component (b) in particulate form.
17. The cracking catalyst of claim 15 wherein said cracking catalyst is a particulate composition comprising integral particles which contain both components (a) and (b).
18. A method of cracking a hydrocarbon feedstock into lower molecular weight components, said method comprising contacting said hydrocarbons with a cracking catalyst comprising (a) a cracking component suitable for use in cracking hydrocarbons, and (b) a component which contains (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) a transition metal selected from Groups Ib and/or IIb of the Periodic Table, at elevated temperature whereby said lower molecular weight components are formed.
19. The method of claim 18 wherein said catalyst is fluidized during said contacting and said method further comprises recovering used cracking catalyst from said contacting step and treating said used catalyst under conditions suitable to regenerate said catalyst.
20. The method of claim 18 wherein said hydrocarbon feedstock contains at least 0.1 wt. % nitrogen.
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WO2016127054A3 (en) * | 2015-02-06 | 2016-11-03 | Wisconsin Alumni Research Foundation | Catalysts with enhanced dispersion of two-dimensional metal oxide surface species on silica using an alkali promoter |
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WO2016127054A3 (en) * | 2015-02-06 | 2016-11-03 | Wisconsin Alumni Research Foundation | Catalysts with enhanced dispersion of two-dimensional metal oxide surface species on silica using an alkali promoter |
US10130935B2 (en) | 2015-02-06 | 2018-11-20 | Wisconsin Alumni Research Foundation | Enhanced dispersion of two-dimensional metal oxide surface species on silica using an alkali promoter |
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