WO2014207133A1 - An olefin cracking catalyst - Google Patents
An olefin cracking catalyst Download PDFInfo
- Publication number
- WO2014207133A1 WO2014207133A1 PCT/EP2014/063579 EP2014063579W WO2014207133A1 WO 2014207133 A1 WO2014207133 A1 WO 2014207133A1 EP 2014063579 W EP2014063579 W EP 2014063579W WO 2014207133 A1 WO2014207133 A1 WO 2014207133A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- olefins
- oxygenate
- reactor
- infrared
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 146
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 126
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000005336 cracking Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005977 Ethylene Substances 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 33
- 239000010457 zeolite Substances 0.000 claims description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- 238000002329 infrared spectrum Methods 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 21
- 238000001354 calcination Methods 0.000 description 17
- 239000000571 coke Substances 0.000 description 15
- 239000003085 diluting agent Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 230000008929 regeneration Effects 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 13
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
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- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
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- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 239000012018 catalyst precursor Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- -1 aliphatic alcohols Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
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- 230000015572 biosynthetic process Effects 0.000 description 5
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- 239000008096 xylene Substances 0.000 description 5
- 150000003738 xylenes Chemical class 0.000 description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
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- 239000000395 magnesium oxide Substances 0.000 description 2
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- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 1
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- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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- 238000005453 pelletization Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- B01J37/28—Phosphorising
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
- C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
- C07C2527/173—Phosphoric acid or other acids with the formula Hn+2PnO3n+1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Definitions
- the invention relates to the preparation of an olefin cracking catalyst and its use to convert C4+ hydrocarbons to ethylene and propylene.
- Oxygenate-to -olefin (“OTO") processes are well described in the art. Typically, oxygenate-to -olefin processes are used to produce predominantly ethylene and propylene. An example of such an oxygenate-to-olefm process is described in US Patent Application Publication No. 2011/112344, which is herein incorporated by reference.
- the publication describes a process for the preparation of an olefin product comprising ethylene and/or propylene, comprising a step of converting an oxygenate feedstock in an oxygenate-to -olefins conversion system, comprising a reaction zone in which an oxygenate feedstock is contacted with an oxygenate conversion catalyst under oxygenate conversion conditions, to obtain a conversion effluent comprising ethylene and/or propylene.
- Additional compounds especially higher molecular weight hydrocarbons are typically produced with the ethylene and propylene in an oxygenate-to -olefins process.
- a method of improving the yield of lower molecular weight olefins is desired as these olefins, mainly ethylene and propylene, serve as feeds for the production of numerous chemicals.
- the higher molecular weight hydrocarbons (C4+) can be cracked in an olefin cracking step to produce additional ethylene and propylene.
- the catalyst and the activity of the catalyst are important to the performance of the cracking step.
- the invention provides an olefin cracking catalyst having infrared peaks at 1455 and 1445 wherein the ratio of the area of the infrared peak at 1455 to the area of the infrared peak at 1445 is from 2.5: 1 to 7:1.
- the invention further provides a process for converting an oxygenate comprising feedstock to olefins comprising: a) feeding an oxygenate comprising feedstock into a reactor containing an oxygenate to olefins conversion catalyst; b) contacting the feedstock with the catalyst at oxygenate conversion conditions to produce C4+ hydrocarbons, ethylene and propylene; and c) removing the C4+ hydrocarbons from the reactor and contacting at least a portion of the C4+ hydrocarbons with an olefin cracking catalyst under olefin cracking conditions wherein the olefin cracking catalyst has infrared peaks at 1455 and 1445 wherein the ratio of the area of the infrared peak at 1455 to the area of the infrared peak at 1445 is from 2.5: l to 7:1.
- Figure 1 depicts the deconvoluted IR spectra for Catalyst A.
- Figure 2 depicts the deconvoluted IR spectra for Catalyst B.
- the catalyst and method of making the catalyst described herein provides an improved catalyst for the conversion of oxygenates to olefins.
- This catalyst is effective in any known oxygenate to olefin process, including processes known as methanol to olefins (MTO) and methanol to propylene (MTP).
- MTO methanol to olefins
- MTP methanol to propylene
- the oxygenate to olefins process can, in certain embodiments, be as described in any of the following references: US 2005/0038304, WO 2006/020083, WO 2007/135052, WO 2009/065848, WO 2009/065877, WO 2009/065875, WO 2009/065870, WO 2009/065855.
- the oxygenate to olefins process receives as a feedstock a stream comprising one or more oxygenates.
- An oxygenate is an organic compound that contains at least one oxygen atom.
- the oxygenate is preferably one or more alcohols, preferably aliphatic alcohols where the aliphatic moiety has from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 5 carbon atoms and most preferably from 1 to 4 carbon atoms.
- the alcohols that can be used as a feed to this process include lower straight and branched chain aliphatic alcohols.
- ethers and other oxygen containing organic molecules can be used. Suitable examples of oxygenates include methanol, ethanol, n-propanol, isopropanol, methyl ethyl ether, dimethyl ether, diethyl ether, di-isopropyl ether,
- the feedstock comprises one or more of methanol, ethanol, dimethyl ether, diethyl ether or a combination thereof, more preferably methanol or dimethyl ether and most preferably methanol.
- the oxygenate is obtained as a reaction product of synthesis gas.
- Synthesis gas can, for example, be generated from fossil fuels, such as from natural gas or oil, or from the gasification of coal.
- the oxygenate is obtained from biomaterials, such as through fermentation.
- the oxygenate feedstock can be obtained from a pre-reactor, which converts methanol at least partially into dimethylether and water. Water may be removed, by e.g., distillation. In this way, less water is present in the process of converting oxygenates to olefins, which has advantages for the process design and lowers the severity of hydrothermal conditions to which the catalyst is exposed.
- the oxygenate to olefins process may, in certain embodiments, also receive an olefin co-feed.
- This co-feed may comprise olefins having carbon numbers of from 1 to 8, preferably from 3 to 6 and more preferably 4 or 5.
- suitable olefin co-feeds include butene, pentene and hexene.
- the oxygenate feed comprises one or more oxygenates and olefins, more preferably oxygenates and olefins in an oxygenate:olefm molar ratio in the range of from 1000: 1 to 1 : 1, preferably 100: 1 to 1 :1.
- a oxygenate:olefm molar ratio in the range of from 20: 1 to 1 : 1, more preferably in the range of l8: l to 1 : 1, still more preferably in the range of l5: l to 1 : 1, even still more preferably in the range of 14 : 1 to 1 : 1. It is preferred to convert a C4 olefin, recycled from the oxygenate to olefins conversion reaction together with an oxygenate, to obtain a high yield of ethylene and propylene, therefore preferably at least one mole of oxygenate is provided for every mole of C4 olefin.
- the olefin co-feed may also comprise paraffins. These paraffins may serve as diluents or in some cases they may participate in one or more of the reactions taking place in the presence of the catalyst.
- the paraffins may include alkanes having carbon numbers from 1 to 10, preferably from 3 to 6 and more preferably 4 or 5.
- the paraffins may be recycled from separation steps occurring downstream of the oxygenate to olefins conversion step.
- the oxygenate to olefins process may, in certain embodiments, also receive a diluent co-feed to reduce the concentration of the oxygenates in the feed and suppress side reactions that lead primarily to high molecular weight products.
- the diluent should generally be non- reactive to the oxygenate feedstock or to the catalyst. Possible diluents include helium, argon, nitrogen, carbon monoxide, carbon dioxide, methane, water and mixtures thereof. The more preferred diluents are water and nitrogen with the most preferred being water.
- the diluent may be used in either liquid or vapor form.
- the diluent may be added to the feedstock before or at the time of entering the reactor or added separately to the reactor or added with the catalyst.
- the diluents is added in an amount in the range of from 1 to 90 mole percent, more preferably from 1 to 80 mole percent, more preferably from 5 to 50 mole percent, most preferably from 5 to 40 mole percent.
- steam is produced as a by-product, which serves as an in-situ produced diluent.
- additional steam is added as diluent.
- the amount of additional diluent that needs to be added depends on the in-situ water make, which in turn depends on the composition of the oxygenate feed. Where the diluent provided to the reactor is water or steam, the molar ratio of oxygenate to diluent is between 10: 1 and 1 :20.
- the oxygenate feed is contacted with the catalyst at a temperature in the range of from 200 to 1000 °C, preferably of from 300 to 800 °C, more preferably of from 350 to 700 °C, even more preferably of from 450 to 650°C.
- the feed may be contacted with the catalyst at a temperature in the range of from 530 to 620 °C, or preferably of from 580 to 610 °C.
- the feed may be contacted with the catalyst at a pressure in the range of from 0.1 kPa (1 mbar) to 5 MPa (50 bar), preferably of from 100 kPa (1 bar) to 1.5 MPa (15 bar), more preferably of from 100 kPa (1 bar) to 300 kPa (3 bar).
- Reference herein to pressures is to absolute pressures.
- WHSV is defined as the mass of the feed (excluding diluents) per hour per mass of catalyst.
- the WHSV should preferably be in the range of from 1 hr -1 to 5000 hr 1 .
- the process takes place in a reactor and the catalyst may be present in the form of a fixed bed, a moving bed, a fluidized bed, a dense fluidized bed, a fast or turbulent f uidized bed, a circulating fluidized bed.
- riser reactors, hybrid reactors or other reactor types known to those skilled in the art may be used.
- more than one of these reactor types may be used in series.
- the reactor is a riser reactor.
- the advantage of a riser reactor is that it allows for very accurate control of the contact time of the feed with the catalyst, as riser reactors exhibit a flow of catalyst and reactants through the reactor that approaches plug flow.
- the feedstocks described above are converted primarily into olefins.
- the olefins produced from the feedstock typically have from 2 to 30 carbon atoms, preferably from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms, most preferably ethylene and/or propylene.
- diolefms having from 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins may be produced in the reaction.
- the feedstock preferably one or more oxygenates
- the oxygenate is methanol
- the olefins are ethylene and/or propylene.
- the products from the reactor are typically separated and/or purified to prepare separate product streams in a recovery system.
- Such systems typically comprise one or more separation, fractionation or distillation towers, columns, and splitters and other associated equipment, for example, various condensers, heat exchangers, refrigeration systems or chill trains, compressors, knock-out drums or pots, pumps and the like.
- the recovery system may include a demethanizer, a deethanizer, a depropanizer, a wash tower often referred to as a caustic wash tower and/or quench tower, absorbers, adsorbers, membranes, an ethylene-ethane splitter, a propylene-propane splitter, a butene- butane splitter and the like.
- the preferred products, ethylene and propylene are preferably separated and purified for use in derivative processes such as polymerization processes.
- the products may comprise C4+ olefins, paraffins and aromatics that may be further reacted, recycled or otherwise further treated to increase the yield of the desired products and/or other valuable products.
- C4+ olefins may be recycled to the oxygenate to olefins conversion reaction or fed to a separate reactor for cracking.
- the paraffins may also be cracked in a separate reactor, and/or removed from the system to be used elsewhere or possibly as fuel.
- the product will typically comprise some aromatic compounds such as benzene, toluene and xylenes. Although it is not the primary aim of the process, xylenes can be seen as a valuable product. Xylenes may be formed in the OTO process by the alkylation of benzene and, in particular, toluene with oxygenates such as methanol.
- a separate fraction comprising aromatics, in particular benzene, toluene and xylenes is separated from the gaseous product and at least in part recycled to the oxygenate to olefins conversion reactor as part of the oxygenate feed.
- part or all of the xylenes in the fraction comprising aromatics are withdrawn from the process as a product prior to recycling the fraction comprising aromatics to the oxygenate to olefins conversion reactor.
- the C4+ olefins and paraffins formed in the oxygenate to olefins conversion reactor may be further reacted in an additional reactor containing the same or a different molecular sieve catalyst.
- the C4+ feed is converted over the molecular sieve catalyst at a temperature in the range of from 500 to 700 °C.
- the additional reactor is also referred to as an OCP reactor and the process that takes place in this reactor is referred to as an olefin cracking process.
- a product which includes at least ethylene and/or propylene and preferably both.
- the gaseous product may comprise higher olefins, i.e. C4+ olefins, and paraffins.
- the gaseous product is retrieved from the second reactor as part of a second reactor effluent stream.
- the olefin feed is contacted with the catalyst at a temperature in the range of from 500 to 700 °C, preferably of from 550 to 650°C, more preferably of from 550 to 620°C, even more preferably of from 580 to 610°C; and a pressure in the range of from 0.1 kPa (1 mbara) to 5 MPa (50 bara), preferably of from 100 kPa (1 bara) to 1.5 MPa (15 bara), more preferably of from 100 kPa ( 1 bara) to 300 kPa (3 bara).
- Reference herein to pressures is to absolute pressures.
- the C4+ olefins are separated into at least two fractions: a C4 olefin fraction and a C5+ olefin fraction.
- the C4 olefins are recycled to the oxygenate to olefins conversion reactor and the C5+ olefins are fed to the OCP reactor.
- the cracking behavior of C4 olefins and C5 olefins is believed to be different when contacted with a molecular sieve catalyst, in particular above 500 °C.
- the cracking of C4 olefins is an indirect process which involves a primary oligomerisation process to a C8, C12 or higher olefin followed by cracking of the oligomers to lower molecular weight hydrocarbons including ethylene and propylene, but also, amongst other things, to C5 to C7 olefins, and by-products such as C2 to C6 paraffins, cyclic hydrocarbons and aromatics.
- the cracking of C4 olefins is prone to coke formation, which places a restriction on the obtainable conversion of the C4 olefins.
- paraffins, cyclics and aromatics are not formed by cracking. They are formed by hydrogen transfer reactions and cyclisation reactions. This is more likely in larger molecules.
- the C4 olefin cracking process which as mentioned above includes intermediate oligomerisation, is more prone to by-product formation than direct cracking of C5 olefins.
- the conversion of the C4 olefins is typically a function of the temperature and space time (often expressed as the weight hourly space velocity). With increasing temperature and decreasing weight hourly space velocity (WHSV) conversion of the C4 olefins in the feed to the OCP increases.
- WHSV weight hourly space velocity
- C5 olefin cracking is ideally a relatively straight forward- process whereby the C5 olefin cracks into a C2 and a C3 olefin, in particular above 500°C.
- This cracking reaction can be run at high conversions, up to 100%, while maintaining, at least compared to C4 olefins, high ethylene and propylene yields with a significantly lower byproduct and coke make.
- C5+ olefins can also oligomerise, this process competes with the more beneficial cracking to ethylene and propylene.
- the C4 olefins are recycled to the oxygenate to olefins conversion reactor.
- the C4 olefins are alkylated with, for instance, methanol to C5 and/or C6 olefins.
- These C5 and/or C6 olefins may subsequently be converted into at least ethylene and/or propylene.
- the main by-products from this oxygenate to olefins conversion reaction are again C4 and C5 olefins, which can be recycled to the oxygenate to olefins conversion reactor and olefin cracking reactor, respectively.
- the gaseous products further include C4 olefins
- at least part of the C4 olefins are provided to (i) the oxygenate to olefins conversion reactor together with or as part of the oxygenate feed, and/or (ii) the olefin cracking reactor as part of the olefin feed, more preferably at least part of the C4 olefins is provided to the oxygenate to olefins conversion reactor together with or as part of the oxygenate feed.
- the gaseous products further include C5 olefins
- at least part of the C5 olefins are provided to the olefin cracking reactor as part of the olefin feed.
- the olefin feed to the olefin cracking reactor comprises C4+ olefins, preferably C5+ olefins, more preferably C5 olefins.
- the oxygenate to olefins conversion reactor and the optional OCP reactor are operated as riser reactors where the catalyst and feedstock are fed at the base of the riser and an effluent stream with entrained catalyst exits the top of the riser.
- gas/solid separators are necessary to separate the entrained catalyst from the reactor effluent.
- the gas/solid separator may be any separator suitable for separating gases from solids.
- the gas/solid separator comprises one or more centrifugal separation units, preferably cyclone units, optionally combined with a stripper section.
- the reactor effluent is preferably cooled in the gas/solid separator to terminate the conversion process and prevent the formation of by-products outside the reactors.
- the cooling may be achieved by use of a water quench.
- the catalyst may be returned to the reaction zone from which it came, to another reaction zone or to a regeneration zone.
- the catalyst that has been separated in the gas/solid separator may be combined with catalyst from other gas/solid separators before it is sent to a reaction zone or to the regeneration zone.
- a portion of the coked molecular sieve catalyst is withdrawn from the reactor and introduced into a regeneration system.
- the regeneration system comprises a regenerator where the coked catalyst is contacted with a regeneration medium, preferably an oxygen-containing gas, under regeneration temperature, pressure and residence time conditions.
- Suitable regeneration media include oxygen, 0 3 , SO 3 , N 2 0, NO, N0 2 , N 2 0 5 , air, air enriched with oxygen, air diluted with nitrogen or carbon dioxide, oxygen and water, carbon monoxide and/or hydrogen.
- the regeneration conditions are those capable of burning at least a portion of the coke from the coked catalyst, preferably to a coke level of less than 75% of the coke level on the catalyst entering the regenerator. More preferably the coke level is reduced to less than 50% of the coke level on the catalyst entering the regenerator and most preferably the coke level is reduced to less than 30% of the coke level on the catalyst entering the regenerator. Complete removal of the coke is not necessary as this may result in degradation of the catalyst.
- the regeneration temperature is in the range of from 200 °C to 1500 °C, preferably from 300 °C to 1000 °C, more preferably from 450 °C to 700 °C and most preferably from 500 °C to 700 °C.
- the catalyst is regenerated at a temperature in the range of from 550 to 650 °C.
- the preferred residence time of the coked molecular sieve catalyst in the regenerator is in the range of from 1 minute to several hours, most preferably 1 minute to 100 minutes.
- the preferred volume of oxygen in the regeneration medium is from 0.01 mole percent to 10 mole percent based on the total volume of the regeneration medium.
- regeneration promoters typically metal containing compounds such as platinum and palladium are added to the regenerator directly or indirectly, for example with the coked catalyst composition.
- a fresh molecular sieve catalyst is added to the regenerator.
- a portion of the regenerated molecular sieve catalyst from the regenerator is returned to the reactor, directly to the reaction zone or indirectly by pre- contacting with the feedstock.
- the burning of coke is an exothermic reaction and in certain embodiments, the temperature in the regeneration system is controlled to prevent it from rising too high.
- Various known techniques for cooling the system and/or the regenerated catalyst may be employed including feeding a cooled gas to the regenerator, or passing the regenerated catalyst through a catalyst cooler. A portion of the cooled regenerated catalyst may be returned to the regenerator while another portion is returned to the reactor.
- a liquid or gaseous fuel may be fed to the regenerator where it will combust and provide additional heat to the catalyst.
- Catalysts suitable for use in the conversion of oxygenates to olefins may be made from practically any small or medium pore molecular sieve.
- a suitable type of molecular sieve is a zeolite.
- Suitable zeolites include, but are not limited to AEI, AEL, AFT, AFO, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI, DAC, DDR, EDI, ERI, EUO, FER, GOO, HEU, KFI, LEV, LOV, LTA, MFI, MEL, MON, MTT, MTW, PAU, PHI, RHO, ROG, THO, TON and substituted forms of these types.
- Suitable catalysts include those containing a zeolite of the ZSM group, in particular of the MFI type, such as ZSM-5, the MTT type, such as ZSM-23, the TON type, such as ZSM-22, the MEL type, such as ZSM-11, and the FER type.
- Other suitable zeolites are for example zeolites of the STF-type, such as SSZ-35, the SFF type, such as SSZ-44 and the EU-2 type, such as ZSM-48.
- Preferred zeolites for this process include ZSM-5, ZSM-22 and ZSM-23.
- a suitable molecular sieve catalyst may have a silica-to-alumina ratio (SAR) of less than 280, preferably less than 200 and more preferably less than 100.
- the SAR may be in the range of from 10 to 280, preferably from 15 to 200 and more preferably from 20 to 100.
- a preferred MFI-type zeolite for the oxygenate to olefins conversion catalyst has a silica-to-alumina ratio, SAR, of at least 60, preferably at least 80. More preferred MFI-type zeolite has a silica-to-alumina ratio, SAR, in the range of 60 to 150, preferably in the range of 80 to 100.
- the zeolite-comprising catalyst may comprise more than one zeolite.
- the catalyst comprises at least a more-dimensional zeolite, in particular of the MFI type, more in particular ZSM-5, or of the MEL type, such as zeolite ZSM-11, and a one- dimensional zeolite having 10-membered ring channels, such as of the MTT and/or TON type.
- zeolites in the hydrogen form are used in the zeolite-comprising catalyst, e.g., HZSM-5, HZSM-11, and HZSM-22, HZSM-23.
- the zeolite-comprising catalyst e.g., HZSM-5, HZSM-11, and HZSM-22, HZSM-23.
- at least 50wt%, more preferably at least 90wt%, still more preferably at least 95wt% and most preferably 100wt% of the total amount of zeolite used is in the hydrogen form. It is well known in the art how to produce such zeolites in the hydrogen form.
- SAPOs siliocoaluminophosphates
- SAPOs have a three dimensional microporous crystal framework of P02+, A102-, and Si02 tetrahedral units.
- Suitable SAPOs include SAPO-17, -18, 34, -35, -44, but also SAPO-5, -8, -11, -20, -31, -36, 37, -40, -41, -42, -47 and -56; aluminophosphates (A1PO) and metal substituted (silico)aluminophosphates (MeAlPO), wherein the Me in MeAlPO refers to a substituted metal atom, including metal selected from one of Group IA, IIA, IB, IIIB, IVB, VB, VIB, VIIB, VIIIB and lanthanides of the Periodic Table of Elements.
- Preferred SAPOs for this process include SAPO-34, SAPO-17 and SAPO-18.
- Preferred substituent metals for the MeAlPO include Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr.
- the molecular sieves described above are formulated into molecular sieve catalyst compositions for use in the oxygenates to olefins conversion reaction and the olefin cracking step.
- the molecular sieves are formulated into catalysts by combining the molecular sieve with a binder and/or matrix material and/or filler and forming the composition into particles by techniques such as spray-drying, pelletizing, or extrusion.
- the molecular sieve may be further processed before being combined with the binder and/or matrix. For example, the molecular sieve may be milled and/or calcined.
- Suitable binders for use in these molecular sieve catalyst compositions include various types of aluminas, aluminophosphates, silicas and/or other inorganic oxide sol.
- the binder acts like glue binding the molecular sieves and other materials together, particularly after thermal treatment.
- Various compounds may be added to stabilize the binder to allow processing.
- Matrix materials are usually effective at among other benefits, increasing the density of the catalyst composition and increasing catalyst strength (crush strength and/or attrition resistance).
- Suitable matrix materials include one or more of the following: rare earth metals, metal oxides including titania, zirconia, magnesia, thoria, beryllia, quartz, silica or sols, and mixtures thereof, for example, silica-magnesia, silica-zirconia, silica-titania, and silica- alumina.
- matrix materials are natural clays, for example, kaolin.
- a preferred matrix material is kaolin.
- the molecular sieve, binder and matrix material are combined in the presence of a liquid to form a molecular sieve catalyst slurry.
- the amount of binder is in the range of from 2 to 40 wt%, preferably in the range of from 10 to 35 wt%, more preferably in the range of from 15 to 30 wt%, based on the total weight of the molecular sieve, binder and matrix material, excluding liquid (after calcination).
- the slurry may be mixed, preferably with rigorous mixing to form a substantially homogeneous mixture.
- suitable liquids include one or more of water, alcohols, ketones, aldehydes and/or esters. Water is the preferred liquid.
- the mixture is colloid-milled for a period of time sufficient to produce the desired texture, particle size or particle size distribution.
- the molecular sieve, matrix and optional binder can be in the same or different liquids and are combined in any order together, simultaneously, sequentially or a combination thereof. In a preferred embodiment, water is the only liquid used.
- the slurry is mixed or milled to achieve a uniform slurry of sub-particles that is then fed to a forming unit.
- a slurry of the zeolite may be prepared and then milled before combining with the binder and/or matrix.
- the forming unit is a spray dryer. The forming unit is typically operated at a temperature high enough to remove most of the liquid from the slurry and from the resulting molecular sieve catalyst composition.
- the particles are then exposed to ion- exchange using an ammonium nitrate or other appropriate solution.
- the ion exchange is carried out before the phosphorous impregnation.
- the ammonium nitrate is used to ion exchange the zeolite to remove alkali ions.
- the zeolite can be impregnated with phosphorous using phosphoric acid followed by a thermal treatment to H+ form.
- the ion exchange is carried out after the phosphorous impregnation.
- alkali phosphates or phosphoric acid may be used to impregnate the zeolite with phosphorous, and then the ammonium nitrate and heat treatment are used to ion exchange and convert the zeolite to the H+ form.
- the zeolite is prepared and made into a slurry.
- the zeolite is then spray dried to form particles.
- the particles are dried and then impregnated with a phosphorous containing compound.
- the catalyst precursor is then dried and calcined.
- the catalyst may be formed into spheres, tablets, rings, extrudates or any other shape known to one of ordinary skill in the art.
- the catalyst may be extruded into various shapes, including cylinders and trilobes.
- the average particle size is in the range of from 1-200 ⁇ , preferably from 50-100 ⁇ . If extrudates are formed, then the average size is in the range of from 1 mm to 10 mm, preferably from 2 mm to 7 mm.
- the catalyst may further comprise phosphorus as such or in a compound, i.e.
- a MEL or MFI-type zeolite comprising catalyst additionally comprises phosphorus.
- the molecular sieve catalyst is prepared by first forming a molecular sieve catalyst precursor as described above, optionally impregnating the catalyst with a phosphorous containing compound and then calcining the catalyst precursor to form the catalyst.
- the phosphorous impregnation may be carried out by any method known to one of skill in the art.
- the phosphorus-containing compound preferably comprises a phosphorus species such as P0 4 3 ⁇ , P-(OCH 3 ) 3 , or P2O5, especially P0 4 3 ⁇ .
- the phosphorus-containing compound comprises a compound selected from the group consisting of ammonium phosphate, ammonium dihydrogen phosphate, dimethylphosphate, metaphosphoric acid and trimethyl phosphite and phosphoric acid, especially phosphoric acid.
- the phosphorus containing compound is preferably not a Group II metal phosphate.
- Group II metal species include magnesium, calcium, strontium and barium; especially calcium.
- phosphorus can be deposited on the catalyst by impregnation using acidic solutions containing phosphoric acid (H 3 P0 4 ). The concentration of the solution can be adjusted to impregnate the desired amount of phosphorus on the precursor. The catalyst precursor may then be dried.
- the catalyst precursor containing phosphorous (either in the framework or impregnated) is calcined to form the catalyst.
- the calcination of the catalyst is important to determining the performance of the catalyst in the oxygenate to olefins process.
- the calcination may be carried out in any type of calciner known to one of ordinary skill in the art.
- the calcination may be carried out in a tray calciner, a rotary calciner, or a batch oven optionally in the presence of an inert gas and/or oxygen and/or steam
- the calcination may be carried out at a temperature in the range of from 400 °C to 1000 °C, preferably in a range of from 450 °C to 800 °C, more preferably in a range of from 500 °C to 700 ° C.
- Calcination time is typically dependent on the degree of hardening of the molecular sieve catalyst composition and the temperature and ranges from about 15 minutes to about 2 hours.
- the calcination temperatures described above are temperatures that are reached for at least a portion of the calcination time.
- a rotary calciner there may be separate temperature zones that the catalyst passes through.
- the first zone may be at a temperature in the range of from 100 to 300 °C. At least one of the zones is at the temperatures specified above.
- the temperature is increased from ambient to the calcination temperatures above and so the temperature is not at the calcination temperature for the entire time.
- the calcination is carried out in air at a temperature of from 500 °C to 600 °C.
- the calcination is carried out for a period of time from 30 minutes to 15 hours, preferably from 1 hour to 10 hours, more preferably from 1 hour to 5 hours.
- the calcination is carried out on a bed of catalyst.
- a bed of catalyst For example, if the calcination is carried out in a tray calciner, then the catalyst precursor added to the tray forms a bed which is typically kept stationary during the calcination. If the calcination is carried out in a rotary calciner, then the catalyst added to the rotary drum forms a bed that although not stationary does maintain some form and shape as it passes through the calciner.
- the performance of the olefin cracking catalysts is important to the performance of the overall system. Further, catalyst development can require considerable effort and expense, so it is beneficial to develop methods for determining which catalysts perform well without having to do extensive performance tests of each different catalyst.
- This new method of testing olefin cracking catalysts to determine their activity relative to the IR spectra obtained will allow for faster screening of new catalysts and allow for speeding up the catalyst development process.
- Example 1 two catalyst samples (A and B) were prepared as follows. ZSM-5 with a SAR (silica-to-alumina) ratio of 80 was used. The ZSM-5 powder was first calcined at 550 °C. Then, the powder was added to an aqueous solution to form a slurry that was then milled. Next, kaolin clay and a silica sol were added and the resulting mixture was spray dried to form particles that had a weight-based average particle size of 70-90 ⁇ . The spray dried catalyst precursors were exposed to ion-exchange using an ammonium nitrate solution. Then phosphorous was deposited on the catalyst precursor by means of impregnation using an acidic solution of phosphoric acid (H 3 PO 4 ).
- SAR silicon-to-alumina
- the concentration of the solution was adjusted to impregnate the catalyst with 2.0 wt % of phosphorous on the catalyst. After impregnation the catalysts were dried at 120 °C. The phosphorous loading on the final catalysts is given based on the weight percentage of the elemental phosphorous in any phosphor species, based on the total weight of the formulated catalyst.
- the catalyst sample was calcined in a stationary oven at a temperature of 550 °C. Catalyst A was calcined in a bed of catalyst 3 cm high, while Catalyst B was calcined in a bed of catalyst 1 cm high.
- Example 2 each of the catalyst samples prepared in Example 1 were tested to determine their infrared peaks after pyridine adsorption.
- the samples were prepared as follows. A sample of 25 mg of each catalyst, finely ground, was pressed in an 18 mm diameter dye to form a self-supporting wafer. The applied pressure and time for Catalyst A was 5 tons for 25 seconds and for Catalyst B 4.5 tons for 15 seconds. The samples were dried in-situ at 450 °C in vacuum, at a pressure of less than lxlO "4 mbar after being heated at a ramp rate of 10°C per minute. The samples were dried for 30 minutes and then allowed to cool down to 150 °C at a cooling rate of 20 °C per minute.
- the resulting IR spectra for Catalyst A and B were deconvoluted according to the following method. First the baseline was removed by taking the difference of the spectra before the pyridine adsorption from the spectra after the pyridine adsorption. The focus was on values between 1473 and 1430 cm "1 so 2-points linear baseline correction was applied. Then curve-fitting was applied using Voigt fit with GRAMS version 9 based on the
- Example 3 each of the catalyst samples prepared in Example 1 were tested to determine their performance in conversion of C5 hydrocarbons to ethylene and propylene.
- the experiments were carried out as follows. A sieve fraction of 40-80 mesh of catalyst was used, which was treated ex-situ in air at 550°C for 2 hours. The catalyst was placed in a quartz reactor tube of 1.8 mm internal diameter. The catalyst was then heated under a flow of nitrogen to the reaction temperature of 525 °C and subsequently the feed composition, comprising about 3 vol. % C5 olefins was passed over the catalyst at atmospheric pressure (1 bar atmosphere).
- the catalysts that had infrared peaks at 1455 cm “1 and 1445 cm “1 wherein the ratio of the area of the infrared peak at 1455 cm “1 to the area of the infrared peak at 1445 cm “1 is from 2.5: 1 to 7: 1 demonstrated improved C2+C3 (desired products) make and improved C5 conversion in the olefin cracking process.
- Catalyst B which did not have such a ratio of areas of the specific IR peaks, demonstrated a reduced C2+C3 make in the performance tests to convert C5 olefins to C2 and C3 hydrocarbons.
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Abstract
An olefin cracking catalyst having infrared peaks at 1455 cm-1 and 1445 cm-1 wherein the ratio of the area of the infrared peak at 1455 cm"1 to the area of the infrared peak at 1445 cm-1 is from 2.5:1 to 7:1. A process for converting an oxygenate comprising feedstock to olefins comprising: a) feeding an oxygenate comprising feedstock into a reactor containing an oxygenate to olefins conversion catalyst; b) contacting the feedstock with the catalyst at oxygenate conversion conditions to produce C4+ hydrocarbons, ethylene and propylene; and c) removing the C4+ hydrocarbons from the reactor and contacting the C4+ hydrocarbons with an olefin cracking catalyst under olefin cracking conditions wherein the olefin cracking catalyst has infrared peaks at 1455 cm-1 and 1445 cm-1 wherein the ratio of the area of the infrared peak at 1455 cm-1 to the area of the infrared peak at 1445 cm-1 is from 2.5:1 to 7:1.
Description
An Olefin Cracking Catalyst
Field of the Invention
The invention relates to the preparation of an olefin cracking catalyst and its use to convert C4+ hydrocarbons to ethylene and propylene.
Background
Oxygenate-to -olefin ("OTO") processes are well described in the art. Typically, oxygenate-to -olefin processes are used to produce predominantly ethylene and propylene. An example of such an oxygenate-to-olefm process is described in US Patent Application Publication No. 2011/112344, which is herein incorporated by reference. The publication describes a process for the preparation of an olefin product comprising ethylene and/or propylene, comprising a step of converting an oxygenate feedstock in an oxygenate-to -olefins conversion system, comprising a reaction zone in which an oxygenate feedstock is contacted with an oxygenate conversion catalyst under oxygenate conversion conditions, to obtain a conversion effluent comprising ethylene and/or propylene.
Additional compounds, especially higher molecular weight hydrocarbons are typically produced with the ethylene and propylene in an oxygenate-to -olefins process. A method of improving the yield of lower molecular weight olefins is desired as these olefins, mainly ethylene and propylene, serve as feeds for the production of numerous chemicals. The higher molecular weight hydrocarbons (C4+) can be cracked in an olefin cracking step to produce additional ethylene and propylene. The catalyst and the activity of the catalyst are important to the performance of the cracking step.
Summary of the Invention
The invention provides an olefin cracking catalyst having infrared peaks at 1455 and 1445 wherein the ratio of the area of the infrared peak at 1455 to the area of the infrared peak at 1445 is from 2.5: 1 to 7:1.
The invention further provides a process for converting an oxygenate comprising feedstock to olefins comprising: a) feeding an oxygenate comprising feedstock into a reactor containing an oxygenate to olefins conversion catalyst; b) contacting the feedstock with the catalyst at oxygenate conversion conditions to produce C4+ hydrocarbons, ethylene and propylene; and c) removing the C4+ hydrocarbons from the reactor and contacting at least a portion of the C4+ hydrocarbons with an olefin cracking catalyst under olefin cracking conditions wherein the olefin cracking catalyst has infrared peaks at 1455 and 1445 wherein the ratio of the area of the infrared peak at 1455 to the area of the infrared peak at 1445 is from 2.5: l to 7:1.
Brief Description of the Drawings
Figure 1 depicts the deconvoluted IR spectra for Catalyst A.
Figure 2 depicts the deconvoluted IR spectra for Catalyst B.
Detailed Description
The catalyst and method of making the catalyst described herein provides an improved catalyst for the conversion of oxygenates to olefins. This catalyst is effective in any known oxygenate to olefin process, including processes known as methanol to olefins (MTO) and methanol to propylene (MTP). The oxygenate to olefins process can, in certain embodiments, be as described in any of the following references: US 2005/0038304, WO 2006/020083, WO 2007/135052, WO 2009/065848, WO 2009/065877, WO 2009/065875, WO 2009/065870, WO 2009/065855.
The oxygenate to olefins process receives as a feedstock a stream comprising one or more oxygenates. An oxygenate is an organic compound that contains at least one oxygen
atom. The oxygenate is preferably one or more alcohols, preferably aliphatic alcohols where the aliphatic moiety has from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 5 carbon atoms and most preferably from 1 to 4 carbon atoms. The alcohols that can be used as a feed to this process include lower straight and branched chain aliphatic alcohols. In addition, ethers and other oxygen containing organic molecules can be used. Suitable examples of oxygenates include methanol, ethanol, n-propanol, isopropanol, methyl ethyl ether, dimethyl ether, diethyl ether, di-isopropyl ether,
formaldehyde, dimethyl carbonate, dimethyl ketone, acetic acid and mixtures thereof. In a preferred embodiment, the feedstock comprises one or more of methanol, ethanol, dimethyl ether, diethyl ether or a combination thereof, more preferably methanol or dimethyl ether and most preferably methanol.
In one embodiment, the oxygenate is obtained as a reaction product of synthesis gas. Synthesis gas can, for example, be generated from fossil fuels, such as from natural gas or oil, or from the gasification of coal. In another embodiment, the oxygenate is obtained from biomaterials, such as through fermentation.
The oxygenate feedstock can be obtained from a pre-reactor, which converts methanol at least partially into dimethylether and water. Water may be removed, by e.g., distillation. In this way, less water is present in the process of converting oxygenates to olefins, which has advantages for the process design and lowers the severity of hydrothermal conditions to which the catalyst is exposed.
The oxygenate to olefins process may, in certain embodiments, also receive an olefin co-feed. This co-feed may comprise olefins having carbon numbers of from 1 to 8, preferably from 3 to 6 and more preferably 4 or 5. Examples of suitable olefin co-feeds include butene, pentene and hexene.
Preferably, the oxygenate feed comprises one or more oxygenates and olefins, more preferably oxygenates and olefins in an oxygenate:olefm molar ratio in the range of from 1000: 1 to 1 : 1, preferably 100: 1 to 1 :1. More preferably, in a oxygenate:olefm molar ratio in the range of from 20: 1 to 1 : 1, more preferably in the range of l8: l to 1 : 1, still more preferably in the range of l5: l to 1 : 1, even still more preferably in the range of 14 : 1 to 1 : 1. It is preferred to convert a C4 olefin, recycled from the oxygenate to olefins conversion reaction together with an oxygenate, to obtain a high yield of ethylene and propylene, therefore preferably at least one mole of oxygenate is provided for every mole of C4 olefin.
The olefin co-feed may also comprise paraffins. These paraffins may serve as diluents or in some cases they may participate in one or more of the reactions taking place in the presence of the catalyst. The paraffins may include alkanes having carbon numbers from 1 to 10, preferably from 3 to 6 and more preferably 4 or 5. The paraffins may be recycled from separation steps occurring downstream of the oxygenate to olefins conversion step.
The oxygenate to olefins process may, in certain embodiments, also receive a diluent co-feed to reduce the concentration of the oxygenates in the feed and suppress side reactions that lead primarily to high molecular weight products. The diluent should generally be non- reactive to the oxygenate feedstock or to the catalyst. Possible diluents include helium, argon, nitrogen, carbon monoxide, carbon dioxide, methane, water and mixtures thereof. The more preferred diluents are water and nitrogen with the most preferred being water.
The diluent may be used in either liquid or vapor form. The diluent may be added to the feedstock before or at the time of entering the reactor or added separately to the reactor or added with the catalyst. In one embodiment, the diluents is added in an amount in the range of from 1 to 90 mole percent, more preferably from 1 to 80 mole percent, more preferably from 5 to 50 mole percent, most preferably from 5 to 40 mole percent.
During the conversion of the oxygenates in the oxygenate to olefins conversion reactor, steam is produced as a by-product, which serves as an in-situ produced diluent.
Typically, additional steam is added as diluent. The amount of additional diluent that needs to be added depends on the in-situ water make, which in turn depends on the composition of the oxygenate feed. Where the diluent provided to the reactor is water or steam, the molar ratio of oxygenate to diluent is between 10: 1 and 1 :20.
The oxygenate feed is contacted with the catalyst at a temperature in the range of from 200 to 1000 °C, preferably of from 300 to 800 °C, more preferably of from 350 to 700 °C, even more preferably of from 450 to 650°C. The feed may be contacted with the catalyst at a temperature in the range of from 530 to 620 °C, or preferably of from 580 to 610 °C. The feed may be contacted with the catalyst at a pressure in the range of from 0.1 kPa (1 mbar) to 5 MPa (50 bar), preferably of from 100 kPa (1 bar) to 1.5 MPa (15 bar), more preferably of from 100 kPa (1 bar) to 300 kPa (3 bar). Reference herein to pressures is to absolute pressures.
A wide range of WHS V for the feedstock may be used. WHSV is defined as the mass of the feed (excluding diluents) per hour per mass of catalyst. The WHSV should preferably be in the range of from 1 hr-1 to 5000 hr 1.
The process takes place in a reactor and the catalyst may be present in the form of a fixed bed, a moving bed, a fluidized bed, a dense fluidized bed, a fast or turbulent f uidized bed, a circulating fluidized bed. In addition, riser reactors, hybrid reactors or other reactor types known to those skilled in the art may be used. In another embodiment, more than one of these reactor types may be used in series. In one embodiment, the reactor is a riser reactor. The advantage of a riser reactor is that it allows for very accurate control of the contact time of the feed with the catalyst, as riser reactors exhibit a flow of catalyst and reactants through the reactor that approaches plug flow.
The feedstocks described above are converted primarily into olefins. The olefins produced from the feedstock typically have from 2 to 30 carbon atoms, preferably from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms, most preferably ethylene and/or propylene. In addition to these olefins, diolefms having from 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins may be produced in the reaction.
In a preferred embodiment, the feedstock, preferably one or more oxygenates, is converted in the presence of a molecular sieve catalyst into olefins having from 2 to 6 carbon atoms. Preferably the oxygenate is methanol, and the olefins are ethylene and/or propylene.
The products from the reactor are typically separated and/or purified to prepare separate product streams in a recovery system. Such systems typically comprise one or more separation, fractionation or distillation towers, columns, and splitters and other associated equipment, for example, various condensers, heat exchangers, refrigeration systems or chill trains, compressors, knock-out drums or pots, pumps and the like.
The recovery system may include a demethanizer, a deethanizer, a depropanizer, a wash tower often referred to as a caustic wash tower and/or quench tower, absorbers, adsorbers, membranes, an ethylene-ethane splitter, a propylene-propane splitter, a butene- butane splitter and the like.
Typically in the recovery system, additional products, by-products and/or
contaminants may be formed along with the preferred olefin products. The preferred products, ethylene and propylene are preferably separated and purified for use in derivative processes such as polymerization processes.
In addition to the propylene and ethylene, the products may comprise C4+ olefins, paraffins and aromatics that may be further reacted, recycled or otherwise further treated to increase the yield of the desired products and/or other valuable products. C4+ olefins may be
recycled to the oxygenate to olefins conversion reaction or fed to a separate reactor for cracking. The paraffins may also be cracked in a separate reactor, and/or removed from the system to be used elsewhere or possibly as fuel.
Although less desired, the product will typically comprise some aromatic compounds such as benzene, toluene and xylenes. Although it is not the primary aim of the process, xylenes can be seen as a valuable product. Xylenes may be formed in the OTO process by the alkylation of benzene and, in particular, toluene with oxygenates such as methanol.
Therefore, in a preferred embodiment, a separate fraction comprising aromatics, in particular benzene, toluene and xylenes is separated from the gaseous product and at least in part recycled to the oxygenate to olefins conversion reactor as part of the oxygenate feed.
Preferably, part or all of the xylenes in the fraction comprising aromatics are withdrawn from the process as a product prior to recycling the fraction comprising aromatics to the oxygenate to olefins conversion reactor.
The C4+ olefins and paraffins formed in the oxygenate to olefins conversion reactor may be further reacted in an additional reactor containing the same or a different molecular sieve catalyst. In this additional reactor, the C4+ feed is converted over the molecular sieve catalyst at a temperature in the range of from 500 to 700 °C. The additional reactor is also referred to as an OCP reactor and the process that takes place in this reactor is referred to as an olefin cracking process. In contact with the molecular sieve catalyst, at least part of the olefins in the C4+ feed is converted to a product, which includes at least ethylene and/or propylene and preferably both. In addition to ethylene and/or propylene, the gaseous product may comprise higher olefins, i.e. C4+ olefins, and paraffins. The gaseous product is retrieved from the second reactor as part of a second reactor effluent stream.
The olefin feed is contacted with the catalyst at a temperature in the range of from 500 to 700 °C, preferably of from 550 to 650°C, more preferably of from 550 to 620°C, even
more preferably of from 580 to 610°C; and a pressure in the range of from 0.1 kPa (1 mbara) to 5 MPa (50 bara), preferably of from 100 kPa (1 bara) to 1.5 MPa (15 bara), more preferably of from 100 kPa ( 1 bara) to 300 kPa (3 bara). Reference herein to pressures is to absolute pressures.
In one embodiment, the C4+ olefins are separated into at least two fractions: a C4 olefin fraction and a C5+ olefin fraction. In this embodiment, the C4 olefins are recycled to the oxygenate to olefins conversion reactor and the C5+ olefins are fed to the OCP reactor. The cracking behavior of C4 olefins and C5 olefins is believed to be different when contacted with a molecular sieve catalyst, in particular above 500 °C.
The cracking of C4 olefins is an indirect process which involves a primary oligomerisation process to a C8, C12 or higher olefin followed by cracking of the oligomers to lower molecular weight hydrocarbons including ethylene and propylene, but also, amongst other things, to C5 to C7 olefins, and by-products such as C2 to C6 paraffins, cyclic hydrocarbons and aromatics. In addition, the cracking of C4 olefins is prone to coke formation, which places a restriction on the obtainable conversion of the C4 olefins.
Generally, paraffins, cyclics and aromatics are not formed by cracking. They are formed by hydrogen transfer reactions and cyclisation reactions. This is more likely in larger molecules. Hence the C4 olefin cracking process, which as mentioned above includes intermediate oligomerisation, is more prone to by-product formation than direct cracking of C5 olefins. The conversion of the C4 olefins is typically a function of the temperature and space time (often expressed as the weight hourly space velocity). With increasing temperature and decreasing weight hourly space velocity (WHSV) conversion of the C4 olefins in the feed to the OCP increases. Initially, the ethylene and propylene yields increase, but, at higher conversions, yield decreases at the cost of a higher by-product make and, in particular, a higher coke make, limiting significantly the maximum yield obtainable.
Contrary to C4 olefins, C5 olefin cracking is ideally a relatively straight forward- process whereby the C5 olefin cracks into a C2 and a C3 olefin, in particular above 500°C. This cracking reaction can be run at high conversions, up to 100%, while maintaining, at least compared to C4 olefins, high ethylene and propylene yields with a significantly lower byproduct and coke make. Although, C5+ olefins can also oligomerise, this process competes with the more beneficial cracking to ethylene and propylene.
In a preferred embodiment of the process according to the present invention, instead of cracking the C4 olefins in the OCP reactor, the C4 olefins are recycled to the oxygenate to olefins conversion reactor. Again without wishing to be bound by any particular theory, it is believed that in the oxygenate to olefins conversion reactor the C4 olefins are alkylated with, for instance, methanol to C5 and/or C6 olefins. These C5 and/or C6 olefins may subsequently be converted into at least ethylene and/or propylene. The main by-products from this oxygenate to olefins conversion reaction are again C4 and C5 olefins, which can be recycled to the oxygenate to olefins conversion reactor and olefin cracking reactor, respectively.
Therefore, preferably, where the gaseous products further include C4 olefins, at least part of the C4 olefins are provided to (i) the oxygenate to olefins conversion reactor together with or as part of the oxygenate feed, and/or (ii) the olefin cracking reactor as part of the olefin feed, more preferably at least part of the C4 olefins is provided to the oxygenate to olefins conversion reactor together with or as part of the oxygenate feed.
Preferably, where the gaseous products further include C5 olefins, at least part of the C5 olefins are provided to the olefin cracking reactor as part of the olefin feed. Preferably, the olefin feed to the olefin cracking reactor comprises C4+ olefins, preferably C5+ olefins, more preferably C5 olefins.
In a preferred embodiment, the oxygenate to olefins conversion reactor and the optional OCP reactor are operated as riser reactors where the catalyst and feedstock are fed at
the base of the riser and an effluent stream with entrained catalyst exits the top of the riser. In this embodiment, gas/solid separators are necessary to separate the entrained catalyst from the reactor effluent. The gas/solid separator may be any separator suitable for separating gases from solids. Preferably, the gas/solid separator comprises one or more centrifugal separation units, preferably cyclone units, optionally combined with a stripper section.
The reactor effluent is preferably cooled in the gas/solid separator to terminate the conversion process and prevent the formation of by-products outside the reactors. The cooling may be achieved by use of a water quench.
Once the catalyst is separated from the effluent, the catalyst may be returned to the reaction zone from which it came, to another reaction zone or to a regeneration zone.
Further, the catalyst that has been separated in the gas/solid separator may be combined with catalyst from other gas/solid separators before it is sent to a reaction zone or to the regeneration zone.
During conversion of the oxygenates to olefins, carbonaceous deposits known as "coke" are formed on the surface of and/or within the molecular sieve catalysts. To avoid a significant reduction in activity of the catalyst, the catalyst must be regenerated by burning off the coke deposits.
In one embodiment, a portion of the coked molecular sieve catalyst is withdrawn from the reactor and introduced into a regeneration system. The regeneration system comprises a regenerator where the coked catalyst is contacted with a regeneration medium, preferably an oxygen-containing gas, under regeneration temperature, pressure and residence time conditions.
Examples of suitable regeneration media include oxygen, 03, SO3, N20, NO, N02, N205, air, air enriched with oxygen, air diluted with nitrogen or carbon dioxide, oxygen and water, carbon monoxide and/or hydrogen. The regeneration conditions are those capable of
burning at least a portion of the coke from the coked catalyst, preferably to a coke level of less than 75% of the coke level on the catalyst entering the regenerator. More preferably the coke level is reduced to less than 50% of the coke level on the catalyst entering the regenerator and most preferably the coke level is reduced to less than 30% of the coke level on the catalyst entering the regenerator. Complete removal of the coke is not necessary as this may result in degradation of the catalyst.
The regeneration temperature is in the range of from 200 °C to 1500 °C, preferably from 300 °C to 1000 °C, more preferably from 450 °C to 700 °C and most preferably from 500 °C to 700 °C. In a preferred embodiment, the catalyst is regenerated at a temperature in the range of from 550 to 650 °C.
The preferred residence time of the coked molecular sieve catalyst in the regenerator is in the range of from 1 minute to several hours, most preferably 1 minute to 100 minutes. The preferred volume of oxygen in the regeneration medium is from 0.01 mole percent to 10 mole percent based on the total volume of the regeneration medium.
In one embodiment, regeneration promoters, typically metal containing compounds such as platinum and palladium are added to the regenerator directly or indirectly, for example with the coked catalyst composition. In another embodiment, a fresh molecular sieve catalyst is added to the regenerator.
In an embodiment, a portion of the regenerated molecular sieve catalyst from the regenerator is returned to the reactor, directly to the reaction zone or indirectly by pre- contacting with the feedstock.
The burning of coke is an exothermic reaction and in certain embodiments, the temperature in the regeneration system is controlled to prevent it from rising too high.
Various known techniques for cooling the system and/or the regenerated catalyst may be employed including feeding a cooled gas to the regenerator, or passing the regenerated
catalyst through a catalyst cooler. A portion of the cooled regenerated catalyst may be returned to the regenerator while another portion is returned to the reactor.
In certain embodiments, there is not sufficient coke on the catalyst to raise the temperature of the catalyst to desired levels. In one embodiment, a liquid or gaseous fuel may be fed to the regenerator where it will combust and provide additional heat to the catalyst.
Catalysts suitable for use in the conversion of oxygenates to olefins may be made from practically any small or medium pore molecular sieve. One example of a suitable type of molecular sieve is a zeolite. Suitable zeolites include, but are not limited to AEI, AEL, AFT, AFO, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI, DAC, DDR, EDI, ERI, EUO, FER, GOO, HEU, KFI, LEV, LOV, LTA, MFI, MEL, MON, MTT, MTW, PAU, PHI, RHO, ROG, THO, TON and substituted forms of these types. Suitable catalysts include those containing a zeolite of the ZSM group, in particular of the MFI type, such as ZSM-5, the MTT type, such as ZSM-23, the TON type, such as ZSM-22, the MEL type, such as ZSM-11, and the FER type. Other suitable zeolites are for example zeolites of the STF-type, such as SSZ-35, the SFF type, such as SSZ-44 and the EU-2 type, such as ZSM-48. Preferred zeolites for this process include ZSM-5, ZSM-22 and ZSM-23.
A suitable molecular sieve catalyst may have a silica-to-alumina ratio (SAR) of less than 280, preferably less than 200 and more preferably less than 100. The SAR may be in the range of from 10 to 280, preferably from 15 to 200 and more preferably from 20 to 100.
A preferred MFI-type zeolite for the oxygenate to olefins conversion catalyst has a silica-to-alumina ratio, SAR, of at least 60, preferably at least 80. More preferred MFI-type zeolite has a silica-to-alumina ratio, SAR, in the range of 60 to 150, preferably in the range of 80 to 100.
The zeolite-comprising catalyst may comprise more than one zeolite. In that case it is preferred that the catalyst comprises at least a more-dimensional zeolite, in particular of the MFI type, more in particular ZSM-5, or of the MEL type, such as zeolite ZSM-11, and a one- dimensional zeolite having 10-membered ring channels, such as of the MTT and/or TON type.
It is preferred that zeolites in the hydrogen form are used in the zeolite-comprising catalyst, e.g., HZSM-5, HZSM-11, and HZSM-22, HZSM-23. Preferably at least 50wt%, more preferably at least 90wt%, still more preferably at least 95wt% and most preferably 100wt% of the total amount of zeolite used is in the hydrogen form. It is well known in the art how to produce such zeolites in the hydrogen form.
Another example of suitable molecular sieves is siliocoaluminophosphates (SAPOs). SAPOs have a three dimensional microporous crystal framework of P02+, A102-, and Si02 tetrahedral units. Suitable SAPOs include SAPO-17, -18, 34, -35, -44, but also SAPO-5, -8, -11, -20, -31, -36, 37, -40, -41, -42, -47 and -56; aluminophosphates (A1PO) and metal substituted (silico)aluminophosphates (MeAlPO), wherein the Me in MeAlPO refers to a substituted metal atom, including metal selected from one of Group IA, IIA, IB, IIIB, IVB, VB, VIB, VIIB, VIIIB and lanthanides of the Periodic Table of Elements. Preferred SAPOs for this process include SAPO-34, SAPO-17 and SAPO-18. Preferred substituent metals for the MeAlPO include Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr.
The molecular sieves described above are formulated into molecular sieve catalyst compositions for use in the oxygenates to olefins conversion reaction and the olefin cracking step. The molecular sieves are formulated into catalysts by combining the molecular sieve with a binder and/or matrix material and/or filler and forming the composition into particles by techniques such as spray-drying, pelletizing, or extrusion. The molecular sieve may be
further processed before being combined with the binder and/or matrix. For example, the molecular sieve may be milled and/or calcined.
Suitable binders for use in these molecular sieve catalyst compositions include various types of aluminas, aluminophosphates, silicas and/or other inorganic oxide sol. The binder acts like glue binding the molecular sieves and other materials together, particularly after thermal treatment. Various compounds may be added to stabilize the binder to allow processing.
Matrix materials are usually effective at among other benefits, increasing the density of the catalyst composition and increasing catalyst strength (crush strength and/or attrition resistance). Suitable matrix materials include one or more of the following: rare earth metals, metal oxides including titania, zirconia, magnesia, thoria, beryllia, quartz, silica or sols, and mixtures thereof, for example, silica-magnesia, silica-zirconia, silica-titania, and silica- alumina. In one embodiment, matrix materials are natural clays, for example, kaolin. A preferred matrix material is kaolin.
In one embodiment, the molecular sieve, binder and matrix material are combined in the presence of a liquid to form a molecular sieve catalyst slurry. The amount of binder is in the range of from 2 to 40 wt%, preferably in the range of from 10 to 35 wt%, more preferably in the range of from 15 to 30 wt%, based on the total weight of the molecular sieve, binder and matrix material, excluding liquid (after calcination).
After forming the slurry, the slurry may be mixed, preferably with rigorous mixing to form a substantially homogeneous mixture. Suitable liquids include one or more of water, alcohols, ketones, aldehydes and/or esters. Water is the preferred liquid. In one embodiment, the mixture is colloid-milled for a period of time sufficient to produce the desired texture, particle size or particle size distribution.
The molecular sieve, matrix and optional binder can be in the same or different liquids and are combined in any order together, simultaneously, sequentially or a combination thereof. In a preferred embodiment, water is the only liquid used.
In a preferred embodiment, the slurry is mixed or milled to achieve a uniform slurry of sub-particles that is then fed to a forming unit. A slurry of the zeolite may be prepared and then milled before combining with the binder and/or matrix. In a preferred embodiment, the forming unit is a spray dryer. The forming unit is typically operated at a temperature high enough to remove most of the liquid from the slurry and from the resulting molecular sieve catalyst composition. In a preferred embodiment, the particles are then exposed to ion- exchange using an ammonium nitrate or other appropriate solution.
In one embodiment, the ion exchange is carried out before the phosphorous impregnation. The ammonium nitrate is used to ion exchange the zeolite to remove alkali ions. The zeolite can be impregnated with phosphorous using phosphoric acid followed by a thermal treatment to H+ form. In another embodiment, the ion exchange is carried out after the phosphorous impregnation. In this embodiment, alkali phosphates or phosphoric acid may be used to impregnate the zeolite with phosphorous, and then the ammonium nitrate and heat treatment are used to ion exchange and convert the zeolite to the H+ form.
In a preferred embodiment, the zeolite is prepared and made into a slurry. The zeolite is then spray dried to form particles. The particles are dried and then impregnated with a phosphorous containing compound. The catalyst precursor is then dried and calcined.
Alternatively to spray drying the catalyst may be formed into spheres, tablets, rings, extrudates or any other shape known to one of ordinary skill in the art. The catalyst may be extruded into various shapes, including cylinders and trilobes.
The average particle size is in the range of from 1-200 μιη, preferably from 50-100 μιη. If extrudates are formed, then the average size is in the range of from 1 mm to 10 mm, preferably from 2 mm to 7 mm.
The catalyst may further comprise phosphorus as such or in a compound, i.e.
phosphorus other than any phosphorus included in the framework of the molecular sieve. It is preferred that a MEL or MFI-type zeolite comprising catalyst additionally comprises phosphorus.
The molecular sieve catalyst is prepared by first forming a molecular sieve catalyst precursor as described above, optionally impregnating the catalyst with a phosphorous containing compound and then calcining the catalyst precursor to form the catalyst. The phosphorous impregnation may be carried out by any method known to one of skill in the art.
The phosphorus-containing compound preferably comprises a phosphorus species such as P04 3~, P-(OCH3)3, or P2O5, especially P04 3~. Preferably the phosphorus-containing compound comprises a compound selected from the group consisting of ammonium phosphate, ammonium dihydrogen phosphate, dimethylphosphate, metaphosphoric acid and trimethyl phosphite and phosphoric acid, especially phosphoric acid. The phosphorus containing compound is preferably not a Group II metal phosphate. Group II metal species include magnesium, calcium, strontium and barium; especially calcium.
In one embodiment, phosphorus can be deposited on the catalyst by impregnation using acidic solutions containing phosphoric acid (H3P04). The concentration of the solution can be adjusted to impregnate the desired amount of phosphorus on the precursor. The catalyst precursor may then be dried.
The catalyst precursor, containing phosphorous (either in the framework or impregnated) is calcined to form the catalyst. The calcination of the catalyst is important to determining the performance of the catalyst in the oxygenate to olefins process.
The calcination may be carried out in any type of calciner known to one of ordinary skill in the art. The calcination may be carried out in a tray calciner, a rotary calciner, or a batch oven optionally in the presence of an inert gas and/or oxygen and/or steam
The calcination may be carried out at a temperature in the range of from 400 °C to 1000 °C, preferably in a range of from 450 °C to 800 °C, more preferably in a range of from 500 °C to 700 ° C. Calcination time is typically dependent on the degree of hardening of the molecular sieve catalyst composition and the temperature and ranges from about 15 minutes to about 2 hours.
The calcination temperatures described above are temperatures that are reached for at least a portion of the calcination time. For example, in a rotary calciner, there may be separate temperature zones that the catalyst passes through. For example, the first zone may be at a temperature in the range of from 100 to 300 °C. At least one of the zones is at the temperatures specified above. In a stationary calciner, the temperature is increased from ambient to the calcination temperatures above and so the temperature is not at the calcination temperature for the entire time.
In a preferred embodiment, the calcination is carried out in air at a temperature of from 500 °C to 600 °C. The calcination is carried out for a period of time from 30 minutes to 15 hours, preferably from 1 hour to 10 hours, more preferably from 1 hour to 5 hours.
The calcination is carried out on a bed of catalyst. For example, if the calcination is carried out in a tray calciner, then the catalyst precursor added to the tray forms a bed which is typically kept stationary during the calcination. If the calcination is carried out in a rotary calciner, then the catalyst added to the rotary drum forms a bed that although not stationary does maintain some form and shape as it passes through the calciner.
The performance of the olefin cracking catalysts is important to the performance of the overall system. Further, catalyst development can require considerable effort and
expense, so it is beneficial to develop methods for determining which catalysts perform well without having to do extensive performance tests of each different catalyst.
It has now been determined that catalysts that exhibit specific IR spectra after pyridine adsorption perform better in an olefin cracking system than those which do not exhibit such IR spectra. The IR spectra of the catalyst are measured by first adsorbing pyridine onto the catalyst and then recording the IR spectra using FTIR techniques.
This new method of testing olefin cracking catalysts to determine their activity relative to the IR spectra obtained will allow for faster screening of new catalysts and allow for speeding up the catalyst development process.
Examples
Example 1
In Example 1, two catalyst samples (A and B) were prepared as follows. ZSM-5 with a SAR (silica-to-alumina) ratio of 80 was used. The ZSM-5 powder was first calcined at 550 °C. Then, the powder was added to an aqueous solution to form a slurry that was then milled. Next, kaolin clay and a silica sol were added and the resulting mixture was spray dried to form particles that had a weight-based average particle size of 70-90 μιη. The spray dried catalyst precursors were exposed to ion-exchange using an ammonium nitrate solution. Then phosphorous was deposited on the catalyst precursor by means of impregnation using an acidic solution of phosphoric acid (H3PO4). The concentration of the solution was adjusted to impregnate the catalyst with 2.0 wt % of phosphorous on the catalyst. After impregnation the catalysts were dried at 120 °C. The phosphorous loading on the final catalysts is given based on the weight percentage of the elemental phosphorous in any phosphor species, based on the total weight of the formulated catalyst. The catalyst sample was calcined in a stationary oven at a temperature of 550 °C. Catalyst A was calcined in a bed of catalyst 3 cm high, while Catalyst B was calcined in a bed of catalyst 1 cm high.
Example 2
In Example 2, each of the catalyst samples prepared in Example 1 were tested to determine their infrared peaks after pyridine adsorption. The samples were prepared as follows. A sample of 25 mg of each catalyst, finely ground, was pressed in an 18 mm diameter dye to form a self-supporting wafer. The applied pressure and time for Catalyst A was 5 tons for 25 seconds and for Catalyst B 4.5 tons for 15 seconds. The samples were dried in-situ at 450 °C in vacuum, at a pressure of less than lxlO"4 mbar after being heated at a ramp rate of 10°C per minute. The samples were dried for 30 minutes and then allowed to cool down to 150 °C at a cooling rate of 20 °C per minute.
Then 8-9 torr pyridine vapor was admitted into the cell at 150 °C for 15 minutes after which the pyridine vapor was pumped for 30 minutes. The IR spectra were recorded after drying and after pyridine desorption on a Bruker Tensor 27 FTIR with a spectral resolution of 2 cm"1 and 256 scans co-added.
The resulting IR spectra for Catalyst A and B were deconvoluted according to the following method. First the baseline was removed by taking the difference of the spectra before the pyridine adsorption from the spectra after the pyridine adsorption. The focus was on values between 1473 and 1430 cm"1 so 2-points linear baseline correction was applied. Then curve-fitting was applied using Voigt fit with GRAMS version 9 based on the
Levenburg-Marquardt method. The IR spectra and the resulting deconvoluted IR spectra are shown in Figures 1 and 2 for Catalyst A and B respectively.
The area of each of the infrared peaks is reported in Table 1.
Table 1
Area of Infrared Peak
Catalyst Peak at 1455 cm"1 Peak at 1450 cm"1 Peak at 1445 cm"1
A 0.133 0.052 0.043
B 0.085 0.050 0.034
Example 3
In Example 3, each of the catalyst samples prepared in Example 1 were tested to determine their performance in conversion of C5 hydrocarbons to ethylene and propylene. The experiments were carried out as follows. A sieve fraction of 40-80 mesh of catalyst was used, which was treated ex-situ in air at 550°C for 2 hours. The catalyst was placed in a quartz reactor tube of 1.8 mm internal diameter. The catalyst was then heated under a flow of nitrogen to the reaction temperature of 525 °C and subsequently the feed composition, comprising about 3 vol. % C5 olefins was passed over the catalyst at atmospheric pressure (1 bar atmosphere). The gas hourly space velocity (GHSV), i.e. the total gas flow per gram of zeolite per hour, was 48,000 (ml-g zeolite"1 -h"1). The effluent from the reactor was analyzed by gas chromatography (GC) to determine which products were formed. The combined C2+C3 make is shown in Table 2. The amount of each component below includes paraffins and olefins.
Table 2
As can be seen from the examples and Table 2, the catalysts that had infrared peaks at 1455 cm"1 and 1445 cm"1 wherein the ratio of the area of the infrared peak at 1455 cm"1 to the area of the infrared peak at 1445 cm"1 is from 2.5: 1 to 7: 1 demonstrated improved C2+C3 (desired products) make and improved C5 conversion in the olefin cracking process. Catalyst B, which did not have such a ratio of areas of the specific IR peaks, demonstrated a reduced C2+C3 make in the performance tests to convert C5 olefins to C2 and C3 hydrocarbons.
Claims
1. An olefin cracking catalyst having infrared peaks at 1455 and 1445 cm"1 wherein the ratio of the area of the infrared peak at 1455 cm"1 to the area of the infrared peak at 1445 cm"1 is from 2.5: 1 to 7: 1.
2. The catalyst of claim 1 wherein the ratio of the area of the infrared peak at 1455 cm"1 to the area of the infrared peak at 1445 cm"1 is from2.75: l to 5: 1.
3. The catalyst of any of claims 1-2 wherein the infrared peaks are measured after pyridine adsorption.
4. The catalyst of any of claims 1-3 wherein the catalyst comprises a molecular sieve.
5. The catalyst of any of claims 1-4 wherein the catalyst comprises a zeolite.
6. The catalyst of any of claims 1-5 wherein the infrared peaks are those observed after deconvolution of initial IR spectra measurements.
7. A process for converting an oxygenate comprising feedstock to olefins comprising: a) feeding an oxygenate comprising feedstock into a reactor containing an
oxygenate to olefins conversion catalyst;
b) contacting the feedstock with the catalyst at oxygenate conversion conditions to produce C4+ hydrocarbons, ethylene and propylene; and
c) removing the C4+ hydrocarbons from the reactor and contacting at least a portion of the C4+ hydrocarbons with an olefin cracking catalyst under olefin cracking conditions
wherein the olefin cracking catalyst has infrared peaks at 1455 cm"1 and 1445 cm"1 wherein the ratio of the area of the infrared peak at 1455 cm"1 to the area of the infrared peak at 1445 cm"1 is from 2.5: 1 to 7: 1.
8. The process of claim 7 wherein the infrared peaks are measured after pyridine
adsorption.
9. The process of claim 7 wherein the catalyst comprises a molecular sieve.
10. The process of claim 7 wherein the catalyst comprises a zeolite.
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