CN116635150A - 使用含磷zsm-5轻质烯烃添加剂进行的甘油酯油的催化裂化 - Google Patents
使用含磷zsm-5轻质烯烃添加剂进行的甘油酯油的催化裂化 Download PDFInfo
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- CN116635150A CN116635150A CN202180085976.1A CN202180085976A CN116635150A CN 116635150 A CN116635150 A CN 116635150A CN 202180085976 A CN202180085976 A CN 202180085976A CN 116635150 A CN116635150 A CN 116635150A
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- Prior art keywords
- oil
- catalytic cracking
- glyceride
- catalyst
- cracking
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 31
- 125000005456 glyceride group Chemical group 0.000 title claims abstract description 27
- 239000000654 additive Substances 0.000 title claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000003921 oil Substances 0.000 title claims description 44
- 238000004523 catalytic cracking Methods 0.000 title claims description 21
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000005336 cracking Methods 0.000 claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 239000011574 phosphorus Substances 0.000 claims abstract description 8
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- 150000002430 hydrocarbons Chemical class 0.000 claims description 32
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- 239000010457 zeolite Substances 0.000 claims description 13
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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 description 12
- 239000002808 molecular sieve Substances 0.000 claims description 10
- 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 10
- 239000011148 porous material Substances 0.000 claims description 9
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- 239000004927 clay Substances 0.000 claims description 5
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- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 claims description 2
- 239000010495 camellia oil Substances 0.000 claims description 2
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
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- 239000000203 mixture Substances 0.000 abstract description 12
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-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
- 241000195493 Cryptophyta Species 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011027 product recovery Methods 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
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- 241000251468 Actinopterygii Species 0.000 description 1
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- 241000196324 Embryophyta Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
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- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-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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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
- C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
- C10G3/57—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds according to the fluidised bed technique
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- 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
-
- 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
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- 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
-
- 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
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
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Abstract
提供了一种使用催化剂组合物来催化裂化甘油酯油原料的方法,所述催化剂组合物含有含磷ZSM‑5轻质烯烃添加剂。
Description
技术领域
本公开涉及甘油酯油的催化裂化,并且更具体而言涉及使用含磷ZSM-5轻质烯烃添加剂作为催化剂进行的甘油三酯材料的催化裂化。
背景技术
催化裂化,特别是流化催化裂化(FCC),常规地用于将重烃原料转化成轻质产物,诸如汽油和馏出物范围级分。另外,越来越需要提高来自催化裂化方法的产物构成中的石油化学结构单元(诸如丙烯、乙烯和芳烃(苯、甲苯、二甲苯等))的收率。
FCC催化剂通常为催化活性的大孔沸石组分(例如,FAU框架型沸石)和含有其他沸石的添加剂的共混物。这些催化剂通常具有约10至约50重量%的结晶沸石含量,其余为基质或稀释剂。大孔组分催化催化裂化反应的初级产物分解为清洁产物(诸如石脑油和用于燃料的馏出物以及用于化学原料的烯烃)。常规添加剂通常含有磷活化的ZSM-5,它是一种中孔沸石,将初级裂化产物(例如,汽油烯烃)选择性地转化为C3和C4烯烃,并且提高汽油辛烷值。已知使用磷改善活性或选择性可增加ZSM-5的有效性。FCC方法的添加剂通常不超过催化剂总量的10%。
为了减少对化石燃料的依赖,从可再生资源(诸如天然油)产生燃料和其他有用的材料是所期望的。天然油主要含有甘油酯,尤其是甘油三酯。虽然天然油适合催化裂化,但是当使用常规催化剂(诸如商业化FCC催化剂)时,收率和产物分布低于预期。
根据本公开,现已发现,基于含磷ZSM-5的轻质烯烃添加剂可以用作可再生原料的催化裂化的基础催化剂,出乎意料地表现出轻质烯烃和富含芳烃的石脑油的高收率,并且相对于常规大孔FCC催化剂而言,提高了汽油馏分的辛烷值。
发明内容
在一个方面,提供了一种用于甘油酯油的催化裂化的方法,所述方法包括:(a)在催化裂化条件下使所述甘油酯油与裂化催化剂接触以获得包含烃的产物流,所述裂化催化剂包含至少80重量%的含磷ZSM-5轻质烯烃添加剂;以及(b)从所述产物流中分离至少一种烃馏分。
附图说明
图1是根据说明性实施方案的实例部分中的实验设置的示意图。
具体实施方式
定义
如本文所用,术语“甘油酯油”是指包含甘油三酯作为其主要组分的油或脂肪。例如,甘油三酯组分可以是甘油酯油的至少50重量%。甘油酯油还可以包括甘油单酯和/或甘油二酯。甘油酯油包括植物油、海洋油和动物油/脂肪,它们通常还包括粗制形式的磷脂组分。
术语“甘油三酯”是指具有三个脂肪酸单元的甘油的三酯。甘油三酯中存在的脂肪酸单元可以是彼此相同的,或者它们可以是不同的。
术语“脂肪酸”用于指具有四至28个碳的链(通常是非支链的并且具有偶数个碳)的脂族一元羧酸,所述链可以是饱和的或不饱和的(顺式或反式,单不饱和或多不饱和)。
术语“烃”是指含有与碳键合的氢的化合物类别,并且涵盖(i)饱和烃化合物,(ii)不饱和烃化合物,以及(iii)烃化合物(饱和和/或不饱和)的混合物,包括具有不同的碳原子数的烃化合物的混合物。
术语“Cn”意指每分子具有n个碳原子的烃,其中n是正整数。如本文所用,术语“Cn+”是指由具有“n”个或更多个碳原子的烃定义的烃组合物,其中“n”是大于0的整数。这包括链烷烃、烯烃、环烃和芳烃以及它们的异构体。类似地,术语“Cn-”是指由具有“n”个或更少个碳原子的烃定义的烃组合物,其中“n”是大于0的整数。这包括链烷烃、烯烃、环烃、芳烃以及它们的异构体。
术语“轻质烯烃”在本文中用于表示具有2至4个碳原子的烯烃(例如,乙烯、丙烯和丁烯)。
术语“大孔”意指具有至少12个四面体原子的最大环大小的分子筛框架,“中孔”意指具有至少10个四面体原子的最大环大小的分子筛框架,并且术语“小孔”意指具有至少8个四面体原子的最大环大小的分子筛框架。
术语“重量%”是指基于包含组分的材料总重量的组分的重量百分比。在一个非限制性实例中,100克材料中的10克组分是10重量%的组分。
甘油酯油
甘油酯油来源于可再生或生物来源,并且在本文中意指包括除了从原油(矿物油)或页岩油或煤获得的原料之外的原料。
甘油酯油可来源于植物、动物、藻类、鱼和微生物过程。
甘油酯油包含至少50重量%(至少60重量%、至少70重量%、至少80重量%、至少90重量%或至少95重量%)的甘油三酯。甘油酯油还可以甘油酯油还可以包括甘油单酯和/或甘油二酯,游离脂肪酸和其他物质通常以低水平存在于来源于天然来源的脂肪和油中。甘油酯油可以含有单一类型的甘油三酯,但是更通常地含有两种或更多种不同的甘油三酯的混合物。
代表性甘油酯油包括菜籽油、芥花籽油、芥花油、妥尔油、葵花油、大豆油、大麻籽油、棉籽油、玉米油、橄榄油、亚麻籽油、芥子油、棕榈油、花生油、蓖麻油、椰子油、山茶油、麻风树油、来源于微生物来源的油,它们可能经过基因修饰,并且包括至少藻类、细菌、霉菌和丝状真菌;动物脂肪、鱼油、猪油、牛油、鲸油、从食品行业回收的脂肪以及所述油的任何混合物。
可以对甘油酯油进行预处理以除去与裂化催化剂接触的杂质。预处理可以包括使甘油酯油通过吸附剂以除去金属、对甘油酯油进行过滤以除去沉积物或者其他过程。
裂化催化剂
本公开的裂化催化剂包含至少80重量%(例如,至少85重量%、至少90重量%、至少95重量%或至少99重量%)的含磷ZSM-5轻质烯烃添加剂。
通常用于轻质烯烃产生的FCC方法中的任何常规含磷ZSM-5轻质烯烃添加剂均可以用于本公开。
含磷ZSM-5轻质烯烃添加剂可以包含(a)25至50重量%(例如,40至50重量%)的ZSM-5沸石;(b)以P2O5计,3至15重量%(例如,5至10重量%)的磷;(c)5至40重量%(例如,10至20重量%)的粘土;以及(d)5至20重量%(例如,10至20重量%)的粘结剂。
粘土可以选自由以下各项组成的组:高岭土、埃洛石、膨润土以及它们的任何组合。在一些方面,粘土是高岭土。
粘结剂可以选自由以下各项组成的组:二氧化硅溶胶、氧化铝溶胶、拟薄水铝石氧化铝、三羟铝石氧化铝、γ-氧化铝以及它们的任何组合。
合适的P/ZSM-5轻质烯烃添加剂的实例包括可从Grace(例如,OHZ、/>MZ和XZ)、Johnson Matthey(例如,INTERCATTM、PEN TACATTMHP、PROPYL MAXTM、SUPER ZTM、SUPER Z EXCEL、SUPER Z EXCEED、ISOCATTM和OCTAMAXTM)和BASF(例如,ZIPOlefins Additive)商购获得的那些。
除含磷ZSM-5轻质烯烃添加剂外,裂化催化剂还可以包含大孔分子筛组分。大孔分子筛组分可以包括例如*BEA框架型沸石(例如,β沸石)和/或FAU框架型沸石(例如,Y沸石)。当使用时,大孔分子筛组分通常以基于裂化催化剂的重量计不超过20重量%(例如,0.1至20重量%,或1至15重量%)的量存在。任选地,另一种分子筛组分还可以包含基质、粘结剂和/或粘土。
裂化催化剂可以是成形微粒(诸如微球)的形式。如上所述,“微粒”是指尺寸为0.1微米至100微米的颗粒。微粒的尺寸是指沿微粒的最长距离测量的从一侧至另一侧的颗粒的最大长度。
裂化催化剂可以在用于转化原料的反应器之前通过与蒸汽接触而失活。蒸汽处理的目的是使在可运行的FCC再生器中发生的水热老化加速以获得平衡催化剂。蒸汽处理可以使铝从框架中除去,导致在水热和热条件下可以发生框架水解的位置数量减少。这种铝的除去导致脱铝沸石的热和水热稳定性增加。催化剂可以在至少300℃(例如,300℃至800℃)的温度下在5%至100%蒸汽的气氛中进行汽蒸至少1小时(例如,1小时至200小时)。
催化裂化
催化方法可以是固定床、移动床或流化床,并且原料流可以与催化剂流并流或逆流。本方法特别适用于流化催化裂化(FCC)方法。
本公开的方法特别适用于流化催化裂化(FCC),其中裂化催化剂通常是细粉。该细粉通常悬浮于进料中并且在反应区中向上推进。将原料与裂化催化剂掺和以提供流化悬浮液,并且在高温下在细长反应器或提升器中裂化以提供轻质烃产物的混合物。气态反应产物和废催化剂从提升器排放到定位于封闭汽提容器或汽提塔上部内的分离器(例如,旋风分离器单元),反应产物被输送到产物回收区,废催化剂进入汽提塔下部内的致密催化剂床。为了从废催化剂中除去夹带的烃然后将废催化剂输送到催化剂再生器单元,使惰性汽提气体(例如,蒸汽)通过催化剂床,在催化剂床中解吸这些烃,将它们输送到产物回收区。可流化催化剂在提升器和再生器之间连续循环,并用于将热量从后者传递到前者,从而满足吸热裂化反应的热需求。
通常,FCC转化条件包括:提升器顶部温度为450℃至650℃(例如,450℃至600℃,或500℃至575℃);压力为100kPa至1100kPa(例如,200kPa至400kPa);催化剂与油的质量比为3至12(例如,4至11,或5至10);催化剂停留时间为0.1至15秒(例如,0.2至10秒)。合适的再生温度包括在100kPa至1100kPa的压力范围内600℃至800℃的温度范围。
矿物油组分(诸如通常来源于原油或页岩油的那些,所述原油页岩油已经任选地经历一个或多个分离和/或其他精炼过程)可以与甘油酯油原料组合。然而,鉴于甘油酯油和矿物油原料的不同裂化特征,在专用于生物进料裂化的单元中进行裂化,即使用完全由生物组分组成的原料通常是优选的。
从裂化步骤获得的包含裂化的可再生烃的产物流可以使用例如分馏器分离成一种或多种烃馏分。产物流可以包括干燥气体(例如,氢、甲烷和乙烷中的一种或多种)、液化石油气(例如,丙烷和丁烷中的一种或多种)、轻质烯烃(例如,乙烯、丙烯和丁烯中的一种或多种)、汽油(沸程为C5至221℃)、轻循环油(沸程为221℃+至343℃)和重质循环油(沸程为343℃+至最终沸点)。一些重质烃可以回收到反应器中。
在一些方面,产物流可以包含30重量%至60重量%(例如,40重量%至50重量%)的汽油沸程烃,如通过ASTM D2887所测定。在一些方面,汽油沸程烃可以包含至少80重量%(例如,至少85重量%,或85重量%至95重量%)的C6至C8芳族化合物。所得的汽油馏分可以用作高质量可再生汽油燃料和/或石脑油燃料,或者用作这些燃料的共混组分。
在一些方面,产物流可以包含二甲苯,其中二甲苯馏分内的对二甲苯选择性为50%至99.9%(例如,60%至80%)。在二甲苯异构体中,对二甲苯具有特定值,因为它可用于制造对苯二甲酸,对苯二甲酸是制造合成纤维和树脂的中间体。
在一些方面,产物流可以包含至少25重量%(25重量%至40重量%,或30重量%至40重量%)的轻质烯烃,如通过ASTM D2887所测定。可再生C3和C4产物烯烃可以被输送到石油化学单元或烷基化单元,以通过异链烷烃(例如,异丁烷)与轻质烯烃中的一种或多种(通常是丙烯和丁烯)的反应产生高辛烷值汽油。可再生乙烯产物可以被输送到石油化学单元进行进一步加工。
烃馏分在商业使用之前可以经历进一步加工。这种加工的实例可以包括加氢处理和添加添加剂。
实施例
以下说明性实施例旨在为非限制性的。
实施例
进行一系列实验室测试,以研究使用以下三种不同的催化剂进行的大豆油或减压瓦斯油(VGO)在FCC条件下的裂解:商业化基于含磷ZSM-5的FCC添加剂,废FCC平衡催化剂(FCC ECAT)以及ZSM-5添加剂和FCC ECAT的50/50混合物(以重量计)。废FCC ECAT从处理加氢进料的FCC单元获得,总金属(Ni+V)含量低于500ppm,总表面积为185m2/g,晶胞大小为在使用前,使ZSM-5添加剂在800℃下经历50%蒸汽处理24小时。
催化裂化实验使用由Kayser Technology制造的高级裂化评估(ACE)模型C单元来进行。ACE模型C单元的示意图如图1所示。ACE单元中采用的反应器是1.6cm ID的固定流化反应器。氮气被用作流化气体,从底部和顶部引入。顶部流化气体被用于携带通过三通阀从校准注射器进料泵注入的进料。进料的催化裂化在大气压和975℉下进行。对于每个实验,以1.2g/min的速率注入恒定量的进料75秒。对于每种测试的催化剂,催化剂与油的质量比维持在7。在进料注入75秒后,用氮气来汽提催化剂525秒。
在催化裂化和汽提过程期间,液态产物被收集在附接至玻璃接收器的样品小瓶中,玻璃接收器定位于反应器出口的末端并且维持在-15℃下。气态产物被收集在预填充有1atm N2的封闭不锈钢容器(12.6L)中。在进料注入完成后,立即通过以60rpm旋转的电动搅拌器来混合气态产物。在汽提后,将气态产物进一步混合10分钟以确保均匀性。然后使用炼厂气分析仪(RGA)来分析最终气态产物。
在汽提过程完成后,在存在1300℉的空气的情况下进行原位催化剂再生。使再生烟气通过填充有CuO丸粒的催化转化器(LECO Inc.)以将CO氧化为CO2。然后通过定位于催化转化器下游的联机红外(IR)分析仪来分析再生烟气。在裂化过程中沉积的焦炭由通过红外分析仪测量的CO2浓度计算。
如上所述,在RGA中解析气态产物(主要是C1至C7烃)。RGA是定制的Agilent 7890B气相色谱仪(GC),配备有三个检测器,即一个用于检测烃的火焰电离检测器和两个用于检测氮和氢的热导检测器。RGA上还安装有甲烷化器以定量气态产物中的痕量CO和CO2。气态产物分为干燥气体(C2烃和H2)和液化石油气(C3和C4烃)。CO和CO2被排除在干燥气体之外。使用ASTM D2887在模拟蒸馏GC(Agilent 6890)中对液态产物进行称重和分析。液态产物被分解成汽油(C5至430℉)、轻循环油(430℉+至650℉)和重循环油(650℉+)。将气态产物中的汽油(C5+烃)与液态产物中的汽油合并为总汽油。液态产物中的轻质馏分(C5-)也被从液态产物中减去,并且使用一些经验分布添加回C3和C4物质中。大多数实验的物料平衡在98%和101%之间。
还使用Agilent 6890A(Separation Systems Inc.)对PONA(链烷烃、烯烃、环烷烃和芳烃)和辛烷(RON和MON)的液态产物的汽油部分进行详细烃分析(DHA)。未对气态产物中的汽油部分进行DHA分析。因此,未对总汽油性质进行调整。然而,DHA结果仍然为评估催化裂化产物性质提供了有价值的信息。
表1大豆油和VGO的催化裂化
结果表明,对于大豆油的催化裂化,随着裂化催化剂制剂中的P/ZSM-5添加剂的量的增加,轻质烯烃和汽油芳烃的转化率和收率也增加。当使用P/ZSM-5添加剂来裂化VGO原料时,观察到轻质烯烃和汽油的转化率和收率较低。不受理论的束缚,据信ZSM-5的孔尺寸限制了活性位点对VGO进料分子的可及性。
Claims (11)
1.一种用于甘油酯油的催化裂化的方法,所述方法包括:
(a)在催化裂化条件下使所述甘油酯油与裂化催化剂接触以获得包含烃的产物流,所述裂化催化剂包含至少80重量%的含磷ZSM-5轻质烯烃添加剂;以及
(b)从所述产物流中分离至少一种烃馏分。
2.如权利要求1所述的方法,其中所述含磷ZSM-5轻质烯烃添加剂包含:
(a)25至50重量%的ZSM-5;
(b)以P2O5计,3至15重量%的磷;
(c)5至45重量%的粘土;以及
(d)5至20重量%的粘结剂。
3.如权利要求1所述的方法,其中所述裂化催化剂还包含大孔分子筛组分。
4.如权利要求3所述的方法,其中所述大孔分子筛组分选自*BEA框架型沸石和FAU框架型沸石。
5.如权利要求3所述的方法,其中所述裂化催化剂包含0.1至20重量%的所述大孔分子筛组分。
6.如权利要求1所述的方法,其中所述甘油酯油包含至少80重量%的甘油三酯。
7.如权利要求1所述的方法,其中所述甘油酯油选自菜籽油、芥花籽油、芥花油、妥尔油、葵花油、大豆油、大麻籽油、棉籽油、玉米油、橄榄油、亚麻籽油、芥子油、棕榈油、花生油、蓖麻油、椰子油、山茶油、麻风树油、微生物油、动物脂肪、鱼油、猪油、牛油、鲸油、从食品行业回收的脂肪以及它们的任何组合。
8.如权利要求1所述的方法,其中所述方法是流化催化裂化方法。
9.如权利要求1所述的方法,其中所述催化裂化条件包括温度为450℃至650℃;压力为100kPa至1100kPa;催化剂与油的质量比为3至12。
10.如权利要求1所述的方法,其还包括将所述产物流分馏成一种或多种烃馏分。
11.如权利要求1所述的方法,其中一种或多种烃流选自轻质烯烃和汽油。
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