JP2019520969A - 炭化水素クラッキングのための熱生成触媒 - Google Patents
炭化水素クラッキングのための熱生成触媒 Download PDFInfo
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- JP2019520969A JP2019520969A JP2018559366A JP2018559366A JP2019520969A JP 2019520969 A JP2019520969 A JP 2019520969A JP 2018559366 A JP2018559366 A JP 2018559366A JP 2018559366 A JP2018559366 A JP 2018559366A JP 2019520969 A JP2019520969 A JP 2019520969A
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- Prior art keywords
- catalyst
- metal oxide
- cracking
- mfi zeolite
- bed reactor
- Prior art date
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Links
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- 238000005336 cracking Methods 0.000 title claims abstract description 113
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 61
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
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- 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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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- 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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- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
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- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
Description
Claims (20)
- 炭化水素クラッキングのための熱生成触媒を製造する方法であって、前記方法は、
Si/Alモル比が15以上の少なくとも1つのモルデナイト骨格が反転した(MFI)ゼオライト触媒を提供することと;
少なくとも1つの金属酸化物前駆体を提供することと;
前記MFIゼオライト触媒の微細構造の中に前記少なくとも1つの金属酸化物前駆体を分散させることと;
前記MFIゼオライト触媒の前記微細構造の中に分散した前記少なくとも1つの金属酸化物前駆体を用い、前記熱生成触媒を焼成し、系中で少なくとも1つの金属酸化物を作成することとを含み、
前記MFIゼオライト触媒と前記金属酸化物との比率が、重量基準で50:50〜95:5の範囲である、方法。 - 湿式含浸、沈殿、電解堆積、堆積−沈殿、化学蒸着および火炎式噴霧熱分解のうち少なくとも1つによって前記MFIゼオライト触媒の前記微細構造の中に前記少なくとも1つの金属酸化物前駆体が分散している、請求項1に記載の方法。
- 前記少なくとも1つの金属酸化物が、鉄、銅、亜鉛、クロム、モリブデン、バナジウム、セリウム、マンガン、ビスマス、銀、コバルト、バナジウム、ジルコニウム、タングステン、マグネシウム、およびこれらの組み合わせの酸化物のうち少なくとも1つである、請求項1に記載の方法。
- 前記少なくとも1つの金属酸化物が、酸化銅を含む、請求項3に記載の方法。
- 前記金属酸化物前駆体が、硝酸金属塩の水和物である、請求項1に記載の方法。
- 前記金属酸化物前駆体が、硝酸銅三水和物(Cu(NO3)2・3H2O)、硝酸コバルト(II)六水和物(Co(NO3)2・6H2O)または硝酸クロム(III)九水和物(Cr(NO3)3・9H2O)である、請求項5に記載の方法。
- 前記MFIゼオライト触媒の前記微細構造の中に前記金属酸化物前駆体を分散させることが、前記金属酸化物前駆体を水に溶解することと、前記MFIゼオライトに滴下することとを含む、請求項5に記載の方法。
- 前記少なくとも1つの金属酸化物が、前記MFIゼオライト触媒の前記微細構造に化学結合している、請求項1に記載の方法。
- 前記MFIゼオライト触媒が、平均粒径が5〜850ナノメートルである粉砕したZSM−5触媒である、請求項7に記載の方法。
- 前記ZSM−5触媒が、H−ZSM−5触媒である、請求項9に記載の方法。
- 前記金属酸化物前駆体を系中で金属酸化物に変換するのに十分な時間、空気中、400℃〜800℃で前記熱生成触媒の焼成を行う、請求項1に記載の方法。
- 前記熱生成触媒が、さらに促進剤を含む、請求項1に記載の方法。
- 前記促進剤が、アルカリ金属、アルカリ土類金属、希土類金属、遷移金属、リン、およびこれらの組み合わせのうち少なくとも1つである、請求項12に記載の方法。
- 炭化水素クラッキングプロセスにおいて熱生成触媒を使用する方法であって、前記方法は、
触媒床反応器を提供することを含み、前記触媒床反応器が、前記触媒床反応器に配置された前記熱生成触媒の触媒床を含み、
前記熱生成触媒は、
Si/Alモル比が15以上の少なくとも1つのモルデナイト骨格が反転した(MFI)ゼオライト触媒と;
前記MFIゼオライト触媒の微細構造の中に分散した少なくとも1つの金属酸化物とを含み、
前記触媒床反応器に炭化水素原料を導入することと;
前記炭化水素原料をクラッキングし、クラッキング生成物を生成することとを含む、方法。 - 前記触媒床反応器が、流動床反応器または固定床反応器を含む、請求項14に記載の方法。
- 前記触媒床反応器が、固定床反応器であり、前記熱生成触媒の前記触媒床が、MFIゼオライト触媒の層の前に配置された前記熱生成触媒の層、MFIゼオライト触媒の層の後に配置された熱生成触媒の層、またはMFIゼオライト触媒の少なくとも2つの層の間に配置された熱生成触媒の少なくとも1つの層を含む、請求項15に記載の方法。
- 前記少なくとも1つの金属酸化物が、前記MFIゼオライト触媒の前記微細構造に化学結合している、請求項14に記載の方法。
- 前記熱生成触媒が、さらに促進剤を含む、請求項14に記載の方法。
- 前記促進剤が、アルカリ金属、アルカリ土類金属、希土類金属、遷移金属、リン、およびこれらの組み合わせのうち少なくとも1つである、請求項18に記載の方法。
- 前記MFIゼオライト触媒が、ZSM−5触媒である、請求項14に記載の方法。
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