JP7216086B2 - 流動接触分解(fcc)で使用する金属トラップ - Google Patents
流動接触分解(fcc)で使用する金属トラップ Download PDFInfo
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- JP7216086B2 JP7216086B2 JP2020526027A JP2020526027A JP7216086B2 JP 7216086 B2 JP7216086 B2 JP 7216086B2 JP 2020526027 A JP2020526027 A JP 2020526027A JP 2020526027 A JP2020526027 A JP 2020526027A JP 7216086 B2 JP7216086 B2 JP 7216086B2
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- rare earth
- earth element
- organic acid
- microspheres
- fcc
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- 238000004231 fluid catalytic cracking Methods 0.000 title claims description 69
- 229910052751 metal Inorganic materials 0.000 title claims description 47
- 239000002184 metal Substances 0.000 title claims description 47
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- 239000000203 mixture Substances 0.000 claims description 72
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- 238000000034 method Methods 0.000 claims description 50
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- 229910052720 vanadium Inorganic materials 0.000 claims description 27
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 26
- 229930195733 hydrocarbon Natural products 0.000 claims description 22
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- 229910052746 lanthanum Inorganic materials 0.000 claims description 22
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- 239000005995 Aluminium silicate Substances 0.000 claims description 19
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
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- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 6
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 6
- PLOSEKHZRPLNLO-UHFFFAOYSA-K lanthanum(3+);triformate Chemical group [La+3].[O-]C=O.[O-]C=O.[O-]C=O PLOSEKHZRPLNLO-UHFFFAOYSA-K 0.000 claims description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
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- 239000004927 clay Substances 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002243 precursor Substances 0.000 claims description 4
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- 239000011029 spinel Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
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- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 8
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 4
- 229960001633 lanthanum carbonate Drugs 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 230000014509 gene expression Effects 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
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- 241000473391 Archosargus rhomboidalis Species 0.000 description 1
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- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- 229910052788 barium Inorganic materials 0.000 description 1
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- B01J21/16—Clays or other mineral silicates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/70—Catalyst aspects
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Description
2017年11月10日に出願されたアメリカ合衆国優先出願番号62/584244号は、明細書、図面、特許請求の範囲および要約を含み、その全体が参照により本明細書に組み込まれる。
一態様では、希土類元素の有機酸塩を含浸させた、事前に形成されたミクロスフェアを含む金属トラップが本明細書に開示される。
一態様では、希土類元素の有機酸塩を含浸させた、事前に形成されたミクロスフェアを含む金属トラップが提供される。金属トラップは、酸化物基準で、少なくとも約1重量%の希土類元素を含むことができる。これは、酸化物基準で、少なくとも約2重量%、少なくとも約5重量%、少なくとも約10重量%、少なくとも約15重量%、または少なくとも約20重量%の希土類元素を含み得る。これはまた、酸化物基準で、約1重量%~約50重量%、約2重量%~約25重量%、または約10重量%~約20重量%の希土類元素を含み得る。
組成物を製造する方法に関して、活性ゼオライト成分は、2つの一般的な技術のうちの1つによって触媒のミクロスフェアに組み込むことができる。1つ目の技術では、ゼオライト成分は結晶化され、次いで別の工程でミクロスフェアに組み込まれる。2つ目の技術では、in-situ技術であり、ミクロスフェアが最初に形成され、次いでゼオライト成分をミクロスフェア自体で結晶化させて、ゼオライト成分および非ゼオライト成分の両方を含むミクロスフェアが提供される。
上記のFCC触媒および/または金属トラップはいずれも、金属を含有する炭化水素仕込み原料の接触分解に使用することができる。典型的な供給原料は、重質ガス油、または金属汚染物質が濃縮されている原油のより重質な留分である。
Claims (45)
- 希土類元素の有機酸塩が含浸された、事前に形成されたミクロスフェアを含む金属トラップ。
- 前記事前に形成されたミクロスフェアが、カオリナイト、モンモリロナイト、ベントナイト、アタパルジャイト、カオリン、アモルファスカオリン、メタカオリン、ムライト、スピネル、含水カオリン、か焼含水カオリン、粘土、またはそれらの任意の2つ以上の混合物を含む、請求項1に記載の金属トラップ。
- 前記事前に形成されたミクロスフェアが、か焼含水カオリンを含む、請求項2に記載の金属トラップ。
- 酸化物基準で、少なくとも1重量%の前記希土類元素を含む、請求項1~3のいずれか一項に記載の金属トラップ。
- 前記希土類元素が、ランタン、セリウム、イッテルビウム、ガドリニウム、イットリウム、ネオジム、またはそれらの任意の2つ以上の混合物である、請求項1~4のいずれか一項に記載の金属トラップ。
- 前記希土類元素が、ランタン、セリウム、またはそれらの混合物である、請求項1~5のいずれか一項に記載の金属トラップ。
- 前記有機酸塩が、ギ酸塩、酢酸塩、プロピオン酸塩、またはそれらの混合物である、請求項1~6のいずれか一項に記載の金属トラップ。
- 前記有機酸塩が、ギ酸塩である、請求項7に記載の金属トラップ。
- 前記希土類元素の前記有機酸塩が、ギ酸ランタン、酢酸ランタン、ギ酸セリウム、酢酸セリウム、またはそれらの任意の2つ以上の混合物である、請求項7に記載の金属トラップ。
- 前記事前に形成されたミクロスフェアを、前記希土類元素のアルカリ塩と有機酸との反応生成物と接触させることにより形成される、請求項1~9のいずれか一項に記載の金属トラップ。
- 前記事前に形成されたミクロスフェアが、約40~150ミクロンの粒子サイズを有する、請求項1~10のいずれか一項に記載の金属トラップ。
- 前記事前に形成されたミクロスフェアが、約60~100ミクロンの粒子サイズを有する、請求項1~10のいずれか一項に記載の金属トラップ。
- 前記事前に形成されたミクロスフェアが、少なくとも約0.10cm3/グラムの細孔容積を有する、請求項1~12のいずれか一項に記載の金属トラップ。
- 流動接触分解(FCC)触媒組成物であって、
第1のミクロスフェアを含むゼオライト成分と、
前記第1のミクロスフェアとは別に、希土類元素の有機酸塩が含浸された、事前に形成された第2のミクロスフェアを含む非ゼオライト成分と、を含む、FCC触媒組成物。 - 前記事前に形成された第2のミクロスフェアが、カオリナイト、モンモリロナイト、ベントナイト、アタパルジャイト、カオリン、アモルファスカオリン、メタカオリン、ムライト、スピネル、含水カオリン、か焼含水カオリン、粘土、またはそれらの任意の2つ以上の混合物を含む、請求項14に記載のFCC触媒組成物。
- 前記希土類元素が、ランタン、セリウム、イッテルビウム、ガドリニウム、イットリウム、ネオジム、またはそれらの任意の2つ以上の混合物である、請求項14または15に記載のFCC触媒組成物。
- 前記希土類元素が、ランタン、セリウム、またはそれらの混合物である、請求項14~16のいずれか一項に記載のFCC触媒組成物。
- 前記有機酸塩が、ギ酸塩、酢酸塩、またはプロピオン酸塩、またはそれらの任意の2つ以上の混合物である、請求項14~17のいずれか一項に記載のFCC組成物。
- 前記有機酸塩が、ギ酸塩である、請求項18に記載のFCC組成物。
- 前記希土類元素の前記有機酸塩が、ギ酸ランタン、酢酸ランタン、ギ酸セリウム、酢酸セリウム、またはそれらの任意の2つ以上の混合物である、請求項18に記載のFCC組成物。
- 前記希土類元素が、酸化物基準で、0.1重量%~約20.0重量%の範囲で存在する、請求項14~20のいずれか一項に記載のFCC触媒組成物。
- 金属トラップを調製する方法であって、事前に形成された第2のミクロスフェアを、希土類元素の有機酸塩と接触させることを含む、方法。
- 事前に形成された第2のミクロスフェアを希土類元素の前記有機酸塩との前記接触が、コーティング、噴霧乾燥、および含浸からなる群から選択される、請求項22に記載の方法。
- 前記希土類元素の前記有機酸塩が、前記有機酸を含む水性媒体中に含まれている、請求項22に記載の方法。
- 前記希土類元素のアルカリ塩を前記有機酸と反応させることにより、前記希土類元素の前記有機塩を調製することをさらに含む、請求項22~24のいずれか一項に記載の方法。
- 前記希土類元素の前記アルカリ塩が、炭酸塩である、請求項25に記載の方法。
- 前記希土類元素が、ランタン、セリウム、イッテルビウム、ガドリニウム、イットリウム、ネオジム、またはそれらの任意の2つ以上の混合物である、請求項22~26のいずれか一項に記載の方法。
- 前記希土類元素が、ランタン、セリウム、またはそれらの混合物である、請求項27に記載の方法。
- 前記有機酸が、ギ酸、酢酸、プロピオン酸、またはそれらの任意の2つ以上の混合物である、請求項25に記載の方法。
- 前記有機酸が、ギ酸である、請求項29に記載の方法。
- 前記希土類元素の前記有機酸塩が、ギ酸ランタン、酢酸ランタン、ギ酸セリウム、酢酸セリウム、またはそれらの任意の2つ以上の混合物である、請求項29に記載の方法。
- 請求項14に記載のFCC触媒組成物を調製する方法であって、前記ゼオライト成分および前記非ゼオライト成分を配合することを含む、方法。
- 前記ゼオライト成分が、
非ゼオライト材料およびアルミナを含む、前駆体の第1のミクロスフェアを事前に形成することと、
前記事前に形成された第1のミクロスフェア上でゼオライトをその場で結晶化して前記ゼオライト成分を提供することと、を含む方法によって調製される、請求項32に記載の方法。 - 流動接触分解条件下で炭化水素供給物を分解する方法であって、前記炭化水素供給物を請求項14に記載のFCC触媒組成物と接触させることを含む、方法。
- FCCユニット床中の炭化水素油供給物由来の少なくとも1つの金属汚染物質を、不動態化および/または捕捉する方法であって、前記炭化水素油供給物を請求項14に記載のFCC触媒組成物と接触させることを含む、方法。
- 前記少なくとも1つの金属汚染物質が、バナジウムである、請求項34に記載の方法。
- 流動接触分解(FCC)触媒組成物であって、
第1のミクロスフェアを含む非分解成分と、
前記第1のミクロスフェアとは別に、希土類元素の有機酸塩が含浸された、事前に形成された第2のミクロスフェアを含む非ゼオライト成分と、を含む、FCC触媒組成物。 - 前記事前に形成された第2のミクロスフェアが、カオリナイト、モンモリロナイト、ベントナイト、アタパルジャイト、カオリン、アモルファスカオリン、メタカオリン、ムライト、スピネル、含水カオリン、か焼含水カオリン、粘土、またはそれらの任意の2つ以上の混合物を含む、請求項37に記載のFCC触媒組成物。
- 前記希土類元素が、ランタン、セリウム、イッテルビウム、ガドリニウム、イットリウム、ネオジム、またはそれらの任意の2つ以上の混合物である、請求項37または38に記載のFCC触媒組成物。
- 前記希土類元素が、ランタン、セリウム、またはそれらの混合物である、請求項37~39のいずれか一項に記載のFCC触媒組成物。
- 前記有機酸塩が、ギ酸塩、酢酸塩、またはプロピオン酸塩、またはそれらの任意の2つ以上の混合物である、請求項37~40のいずれか一項に記載のFCC組成物。
- 前記有機酸塩が、ギ酸塩である、請求項41に記載のFCC組成物。
- 前記希土類元素の前記有機酸塩が、ギ酸ランタン、酢酸ランタン、ギ酸セリウム、酢酸セリウム、またはそれらの任意の2つ以上の混合物である、請求項41に記載のFCC組成物。
- 前記希土類元素が、酸化物基準で、0.1重量%~約20.0重量%の範囲で存在する、請求項37~43のいずれか一項に記載のFCC触媒組成物。
- 請求項37に記載のFCC触媒組成物を調製する方法であって、前記非分解成分および前記非ゼオライト成分を配合することを含む、方法。
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PCT/US2018/059845 WO2019094603A1 (en) | 2017-11-10 | 2018-11-08 | A metal trap for use in fluid catalytic cracking (fcc) |
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