CN107429172A - 将烯烃型汽油中的硫醚类型的化合物脱硫的方法 - Google Patents
将烯烃型汽油中的硫醚类型的化合物脱硫的方法 Download PDFInfo
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- CN107429172A CN107429172A CN201680021718.6A CN201680021718A CN107429172A CN 107429172 A CN107429172 A CN 107429172A CN 201680021718 A CN201680021718 A CN 201680021718A CN 107429172 A CN107429172 A CN 107429172A
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- catalyst
- gasoline
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Classifications
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- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/613—10-100 m2/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
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Abstract
本发明涉及降低含有二烯烃、单烯烃和硫的汽油中的具有式R1‑S‑R2的硫醚类型的化合物的含量的方法,其中R1和R2选自甲基(CH3)和乙基(C2H5)基团,其中:A)在反应器中使所述汽油以与从步骤C)再循环的轻质汽油馏分的一部分的混合物的形式与氢气和催化剂A接触,催化剂A包含沉积于载体上的至少一种第VIb族的金属和至少一种第VIII族的非贵金属,从而产生具有低于起始汽油的二烯烃含量和具有式R1‑S‑R2的硫醚类型的化合物含量的流出物,其中R1和R2选自甲基(CH3)和乙基(C2H5)基团;B)将源自步骤A)的所述流出物送入分馏塔,以在所述塔的顶部分离出含有每分子具有少于6个碳原子的烃的轻质汽油馏分,并在所述塔的底部分离出含有每分子具有6个和多于6个碳原子的烃的重质汽油馏分;C)采用0.1‑0.7的再循环比将源自步骤B)的所述轻质汽油馏分的一部分再循环至步骤A)的所述反应器中。
Description
本发明涉及降低汽油中含有的具有式R1-S-R2的硫醚类型的化合物的含量的方法,其中R1和R2选自甲基和乙基。特别地,所述方法涉及称为烯烃型的汽油。
根据本发明的方法可以作为预处理步骤并入将汽油加氢脱硫的方法中,以限制硫醚类型的轻质硫化合物的含量。
现有技术
符合新的环境标准的汽油的生产要求其硫含量显著降低至通常不超过50重量ppm、优选小于10重量ppm的值。
还已知转化汽油、更具体而言是可占汽油池(gasoline pool)的30%-50%的源自催化裂化的那些转化汽油具有高的烯烃和硫含量。
因此,汽油中存在的几乎90%的硫可以归因于源自催化裂化方法的汽油,其将在下文被称为FCC(流化催化裂化)汽油(在流化床中催化裂化)。FCC汽油因此构成本发明的方法的优选进料。
在已经被广泛保留的生产具有低硫含量的燃料的可能途径之一包括在氢气和催化剂的存在下通过加氢脱硫方法来特别处理富含硫的汽油原料(stocks)。传统的方法通过氢化大部分的单烯烃来以非选择性的方式将汽油脱硫,这导致辛烷值的显著下降和高氢气消耗。最新的方法,例如Prime G+方法(商标),可将富含烯烃的裂化汽油脱硫,同时限制单烯烃的氢化,结果是限制辛烷值的损失和继而产生的高氢气消耗。这样的方法例如描述在专利申请EP 1077247和EP 1174485中。
如在专利申请EP 1077247和EP 1 800 748中所述,在加氢处理步骤之前实施将待处理的进料选择性氢化的步骤是有利的。该第一氢化步骤主要包括选择性氢化二烯烃,同时将饱和的轻质含硫化合物转化为较重质的化合物(通过增加其分子量),所述轻质含硫化合物是沸点低于噻吩的沸点的含硫化合物,例如甲硫醇、乙硫醇、丙硫醇、二甲基硫醚和乙基-甲基硫醚。通过将源自选择性氢化步骤的汽油分馏,产生其大部分由含有5或6个碳原子的单烯烃组成的轻质脱硫汽油馏分(或轻质裂化石脑油(LCN))而不损失辛烷值,该馏分可以被改质成用于配制车用燃料的汽油池。
在特定的操作条件下,该氢化选择性地将待处理的进料中存在的二烯烃氢化成具有更好的辛烷值的单烯烃化合物。选择性氢化的另一个作用是防止由于在催化剂的表面上或反应器中形成聚合胶状物而导致的选择性加氢脱硫催化剂的逐渐失活,和/或避免反应器的逐渐堵塞。事实上,多不饱和化合物是不稳定的并且具有通过聚合形成胶状物的倾向。
专利申请EP 2161076公开了多不饱和化合物、更具体而言是二烯烃的选择性氢化方法,其可以同时将饱和的轻质含硫化合物转化为较重质的化合物。该方法采用包含沉积在多孔载体上的至少一种第VIb族的金属和至少一种第VIII族的非贵金属的催化剂。
已经注意到,当轻质含硫化合物(即具有式R1-S-R2,其中R1和R2选自甲基和乙基)的含量显著时,选择性氢化步骤不足以有效地转化这些化合物,从而使得在分馏之后获得含有可观的量的轻质含硫化合物的轻质汽油馏分LCN。为了解决这个问题,很有可能设想使选择性氢化步骤的温度条件变得更严苛,但是以催化剂的过早失活和反应器内件的快速堵塞为代价,这些现象与通过待处理的汽油中所含的二烯烃聚合而形成焦炭有关。另一种解决方案将包括降低反应器中的待处理的汽油的液体时空速,但需要使用更多的催化剂并增加反应器的高度;然而,从经济和/或技术的角度来看,这种解决方案并不一定是合意的。
因此,本发明的目的是提出在降低汽油(或汽油的混合物)中的轻质硫醚类型的化合物的含量的效率方面得到改善、并且可以在更换催化剂和/或清洁实施该方法的设备之前运行较长的时间周期的方法。
发明概述
本发明涉及降低含有二烯烃、单烯烃和硫的汽油中的具有式R1-S-R2的硫醚类型的化合物的含量的方法,其中R1和R2选自甲基(CH3)和乙基(C2H5)基团,其中:
A)在反应器中使所述汽油以与从步骤C)再循环的轻质汽油馏分的混合物的形式与氢气和催化剂A接触,催化剂A包含沉积于载体上的至少一种第VIb族的金属和至少一种第VIII族的非贵金属,步骤A)在所述反应器中在60℃-150℃的温度下进行,其中液体时空速(LHSV)为1h-1-10h-1,压力为0.5-5MPa,并且其中体积比(加入的H2/汽油的混合物)为1-40标准升的氢气/升汽油混合物(体积/体积),从而产生具有低于起始汽油的二烯烃含量和具有式R1-S-R2的硫醚类型的化合物含量的流出物,其中R1和R2选自甲基(CH3)和乙基(C2H5)基团;
B)将源自步骤A)的所述流出物送入分馏塔,以在所述塔的顶部分离出含有每分子具有少于6个碳原子的烃的轻质汽油馏分,并在所述塔的底部分离出含有每分子具有6个和多于6个碳原子的烃的重质汽油馏分;
C)采用0.1-0.7的再循环比将源自步骤B)的所述轻质汽油馏分的一部分再循环至步骤A)的所述反应器中。所述再循环比被定义为再循环的轻质汽油馏分的量与在分馏塔的顶部取出的轻质汽油的总量的比。
本申请人已经注意到,将轻质汽油馏分再循环至步骤A)的反应器中不仅可以通过尽可能地保留汽油的辛烷值来促进轻质硫醚类型的化合物的转化,同时限制通过分别在催化剂上和反应器的内件上形成焦炭沉积物产生的催化剂的失活和反应器的堵塞。
在本发明的上下文中,表述“降低轻质硫醚类型的化合物的含量”表示在步骤A)之后存在于获得的反应流出物中的轻质硫醚类型的化合物的含量低于处理的汽油的轻质硫醚类型的化合物的含量的事实。
所述方法的优点与可以改善轻质硫醚类型的化合物的转化的收率而不必使所述步骤A)的温度条件更严苛,导致催化剂的过早失活和反应器内件的快速堵塞,或增加反应器的尺寸的事实有关。
优选地,在加氢脱硫单元中在氢气的存在下处理在分馏塔的底部回收的重质汽油馏分。
催化剂A优选以其硫化形式使用。优选地,构成所述催化剂的金属的硫化程度至少等于60%。
优选地,催化剂A包含:
•相对于所述催化剂的总重量,4-20重量%的第VIb族的金属的氧化物的含量,
•相对于所述催化剂的总重量,4-15重量%的第VIII族的金属的氧化物的含量,
•作为所述催化剂的组分的金属的硫化程度至少等于60%,
•所述第VIII族的非贵金属与所述第VIb族的金属之间的摩尔比为0.6-8mol/mol,
•所述催化剂的比表面积为30-300m²/g。
优选地,催化剂A具有小于或等于10-3克的第VIb族的金属的氧化物/m2的催化剂的每单位面积的催化剂的第VIb族的金属的密度。
优选地,催化剂A的第VIb族的金属选自钼和钨,优选钼。
优选地,催化剂A的第VIII族的金属选自镍、钴和铁,优选镍。
在一个优选实施方案中,第VIII族的金属是镍,并且第VIb族的金属是钼。
根据本发明的方法特别适用于处理源自催化裂化或热裂化、焦化方法、减粘裂化方法或热解方法的汽油。
发明详述
本发明的其他特征和优点在阅读通过举例说明并且非限制性地给出的下文的描述并且参照作为根据本发明的方法的流程图的图1时将变得明显。
能够通过根据本发明的方法处理的烃原料是含有二烯烃、单烯烃和含硫化合物(特别是硫醇和轻质硫醚的形式)的烯烃型的汽油。在本发明的范围内,术语“轻质硫醚类型的化合物”是指具有式R1-S-R2的化合物,其中R1和R2选自甲基(CH3)和乙基(C2H5)基团。因此,存在于烯烃型汽油中的最轻质的硫醚是二甲基硫醚。
本发明可用于处理源自转化方法的汽油、特别是源自催化裂化或热裂化、焦化方法、减粘裂化方法或热解方法的汽油(单独或以混合物形式)。
本发明涉及的烃原料具有通常为0℃-280℃、优选15℃-250℃的沸点。
通过根据本发明的方法处理的汽油通常含有0.5重量%-5重量%的二烯烃、20重量%-55重量%的单烯烃、10重量ppm-1重量%的硫,并且具有按硫的重量计通常为1-150ppm的具有式R1-S-R2的轻质硫醚化合物的含量,其中R1和R2选自甲基(CH3)和乙基(C2H5)基团。
优选地,能够被处理的汽油源自流化催化裂化单元。还可以处理源自流化催化裂化单元的汽油与一种或多种源自其它转化方法的汽油的混合物。
参照图1,在第一催化步骤中,将汽油类型的烃原料以与再循环的轻质汽油馏分的混合物的形式进行处理。因此,将通过管线1供应的汽油原料和源自管线9的再循环流通过管线1'送入反应器2中,其中使混合物与氢气(通过管线3供应)和催化剂A接触,所述催化剂A特别可以将二烯烃选择性氢化成烯烃。反应器2可以是具有固定催化床或移动催化床,优选固定催化床的反应器。反应器可以包括一个或多个催化床。
注入的氢气的量使得体积比(加入的H2/汽油的混合物)为1-40标准升的氢气/升汽油混合物(体积/体积),优选为1-5标准升的氢气/升汽油混合物(体积/体积)。过量太多的氢气可导致单烯烃的强烈氢化,结果导致汽油的辛烷值的降低。通常将所有的原料注入反应器的入口中。然而,在某些情况下,将原料的一部分或全部注入放置在反应器中的两个连续的催化床之间是有利的。如果反应器的入口或第一催化床被存在于原料中的聚合物、颗粒或胶状物的沉积物堵塞,则该实施方案特别地可以继续运行反应器。
在60℃-150℃、优选80-130℃的温度下使汽油的混合物和氢气与催化剂A接触,其中液体时空速(LHSV)为1h-1-10h-1,液体时空速单位以升汽油混合物/小时/升催化剂(L/h/L,即h-1)表示。调节压力,从而使得反应混合物在反应器中大部分为液体形式。所述压力通常为0.5MPa-5MPa,优选1-4MPa。
如图1所示,将反应流出物通过管线4从反应器2中取出。该流出物具有低于待处理的汽油的二烯烃含量,因为该流出物经历了选择性氢化反应。源自氢化反应器2的流出物具有接近反应器2的平均温度的温度,并且通常高于(通常高1-3℃)反应器2的入口处的原料的温度,因为二烯烃的选择性氢化反应是放热的。
已经观察到在步骤A)之后获得的流出物还具有较低含量的轻质硫醚型化合物。然而,这些化合物尚未经历加氢脱硫(HDS)反应,因为在步骤A)之后获得的流出物不含有H2S。不受任何理论的约束,步骤A)中使用的催化剂可以使上述轻质硫醚化合物与原料的烯烃反应,以形成能够通过蒸馏从流出物中分离的具有较高分子量的硫醚化合物。应当注意,该催化步骤不同于其中通过与具有氢解特性的催化剂接触将含硫化合物转化为H2S以及转化为烃的加氢脱硫(或HDS)催化步骤。所述加氢脱硫通常在200-400℃的温度下、采用100-600标准升的氢气/升汽油(体积/体积)的加入的H2/汽油原料的体积比、在1MPa-3MPa的总压力下并采用1h-1-10h-1的液体时空速(LHSV)操作。
在根据本发明的方法中使用的催化剂A包含沉积于载体上的至少一种第VIb族(根据元素周期表的新命名的第6族:Handbook of Chemistry and Physics,第76版,1995-1996)的金属和至少一种第VIII族(根据元素周期表的新命名的第8族、第9族和第10族:Handbook of Chemistry and Physics,第76版,1995-1996)的非贵金属。
优选地,催化剂A以硫化形式使用。优选地,催化剂A的硫化程度为至少60%。
催化剂的硫化可以在硫还原介质中进行,即在H2S和氢气的存在下进行,以将金属氧化物转化成硫化物,例如MoS2和Ni3S2。例如,通过将含有H2S和氢气的流、或能够在催化剂和氢气的存在下分解成H2S的含硫化合物流注于催化剂上来进行硫化。多硫化物,例如二甲基二硫化物是通常用于硫化催化剂的H2S的前体。调节温度,从而使得H2S与金属氧化物反应以形成金属硫化物。这种硫化可以在200-600℃、更优选300-500℃的温度下在步骤A)的反应器的原位或非原位(内部或外部)进行。
当存在于催化剂上的硫(S)和元素之间的摩尔比优选至少等于对应于所考虑的元素的全部硫化的理论摩尔比的60%时,所述元素被认为是基本硫化的:
(S/元素)催化剂≥0.6×(S/元素)理论值
其中:
(S/元素)催化剂=存在于催化剂上的硫(S)与元素之间的摩尔比
(S/元素)理论值=对应于元素全部硫化成硫化物的硫与元素之间的摩尔比。
该理论摩尔比根据所考虑的元素而变化:
- (S/Fe)理论值= 1
- (S/Co)理论值= 8/9
- (S/Ni)理论值= 2/3
- (S/Mo)理论值= 2/1
- (S/W)理论值= 2/1
当催化剂包含若干种金属时,存在于催化剂上的S与所有元素之间的摩尔比优选至少等于对应于每种元素全部硫化成硫化物的理论摩尔比的60%,计算以与每种元素的相对摩尔分数成比例的方式进行。
例如,对于含有相对摩尔分数为0.7和0.3的钼和镍的催化剂而言,最小摩尔比(S/Mo + Ni)由以下关系式给出:
(S/Mo + Ni)催化剂= 0.6×{(0.7×2)+(0.3×(2/3)}
非常优选地,金属的硫化程度将大于80%。
优选地,在氧化物形式的金属上实施硫化,而不进行将金属还原的先前步骤。事实上,已知的是被还原的金属的硫化比氧化物形式的金属的硫化更加困难。
根据本发明的催化剂A可以具有以下特征:
•相对于所述催化剂的总重量,4-20重量%的第VIb族的金属的氧化物的含量,
•相对于所述催化剂的总重量,4-15重量%的第VIII族的金属的氧化物的含量,
•构成所述催化剂的金属的硫化程度至少等于60%
•所述第VIII族的非贵金属与所述第VIb族的金属之间的摩尔比为0.6-8mol/mol,
•所述催化剂的比表面积为30-300m²/g。
优选地,相对于所述催化剂的重量,催化剂A具有6重量%-18重量%、优选8-12重量%、还更优选10-12重量%的氧化物形式的第VIb族的元素的重量含量。第VIb族的金属优选选自钼和钨。更优选地,第VIb族的金属是钼。
催化剂A还含有优选选自镍、钴和铁的第VIII族的金属。更优选地,第VIII族的金属是镍。相对于所述催化剂的重量,以氧化物形式表示的第VIII族的金属的含量为4-12重量%,优选6-10重量%,还更优选6-8重量%。
第VIII族的非贵金属与第VIb族的金属之间的摩尔比为0.6-8mol/mol,优选为1-3mol/mol。第VIb族的金属的密度,表示为第VIb族的金属的氧化物的所述重量含量与催化剂的比表面积之间的比,小于或等于10-3g/m2,优选10-4-10-3g/m2。优选地,第VIb族的金属的密度为4-6.10-4g/m2。因此,例如在其中催化剂包含相对于催化剂的重量为11重量%的氧化钼且具有219m2/g的比表面积的特定情况下,而钼的密度,表示为氧化钼(MoO3)的重量含量与催化剂的比表面积之间的比,等于(0.11/219),即5.10-4g/m2。
催化剂A的比表面积优选为100-300m2/g,更优选为150-250m2/g。比表面积根据标准ASTM D3663测定。
优选地,催化剂A具有通过水银测孔法测量的大于0.3cm3/g、优选0.4-1.4cm3/g、优选0.5-1.3cm3/g的总孔体积。水银测孔法根据标准ASTM D4284-92,采用140°的润湿角,采用型号为Autopore III商标为Micromeritics的装置测量。
催化剂A的载体优选选自氧化铝、铝酸镍、二氧化硅、碳化硅或其混合物。优选地,使用氧化铝。
根据一个变体,催化剂A的载体由立方γ氧化铝或δ氧化铝构成。
根据一个特别优选的变体,催化剂A是氧化铝上的NiMo催化剂。
根据本发明的催化剂A可以使用本领域技术人员已知的任何技术制备,特别是通过将第VIII族和第VIb族的元素浸渍在所选择的载体上。这种浸渍可以例如根据本领域技术人员以术语干浸渍已知的方法进行,其中将确切量的所需的元素以可溶于所选择的溶剂(例如去矿物质水)中的盐的形式引入,从而尽可能精确地填充载体的孔隙。
在引入第VIII族和第VIb族的元素,以及任选地形成催化剂之后,将催化剂进行活化处理。这种处理通常具有将元素的分子前体转化为氧化物相的目的。在这种情况下,它是氧化处理,但也可以进行催化剂的简单干燥。在氧化处理(也称为煅烧)的情况下,其通常在空气或稀释氧气下进行,处理温度通常为200℃-550℃,优选300℃-500℃。
在煅烧之后,沉积在载体上的金属是氧化物的形式。在镍和钼的情况下,发现所述金属主要为MoO3和NiO的形式。优选地,催化剂A以硫化形式使用,即在氧化处理之后其已经经历了硫化活化步骤。
根据本发明,将源自反应器2的流出物从所述反应器中取出,并通过管线4送入专用的分馏塔5,以提供在塔5的顶部取出的至少一种轻质汽油馏分6(或轻质裂化石脑油(LCN))以及在塔5底部回收的重质汽油馏分7(重质裂化石脑油(HCN))。应当注意,不同于其中催化反应和分离同时进行的催化蒸馏塔中的操作,该分馏步骤在催化步骤A)之后在仅专门用于分离的塔中进行。
选择蒸馏塔的分馏点,从而使得轻质汽油馏分含有具有少于六个碳原子的烃(基本上是烯烃)以及低含量的轻质硫醚类型的化合物,并且使得重质汽油馏分具有显著量的含硫化合物(例如硫醇、噻吩族的化合物和硫醚)和具有六个或多于六个碳原子的烃(基本上是烯烃)(“C6+”)。典型地,调节分馏点,从而使得所述轻质汽油馏分具有-5℃至70℃、优选-5℃至65℃的沸腾温度。关于所述重质汽油馏分,其可具有60℃-280℃、优选65℃-280℃的沸腾温度。本领域技术人员已知烃的分离是不完全的,因此在分馏点附近可能出现轻质馏分和重质馏分的沸点的某些重叠。典型地,所述轻质汽油馏分具有小于15重量ppm、优选小于10重量ppm的总硫含量和按硫的重量计小于10 ppm的轻质硫醚的含量。
根据本发明,在任选地除去氢气和稳定化之后,将由此通过分馏产生的富含烯烃(因此具有高辛烷值)和缺乏含硫化合物(包括轻质硫醚)的轻质汽油馏分6分成两个流8和9。如图1所示,将流8送至用于配制汽油型燃料的汽油池。这种缺乏硫的轻质汽油馏分通常不需要额外的加氢脱硫处理。
关于补充流9,根据本发明,将其再循环到反应器2中。被定义为流9与流6之比的缺乏硫的轻质汽油馏分的再循环比为0.1-0.7,优选0.3-0.6。
将含有大部分的有机硫化合物(包括硫醚)的重质汽油馏分7有利地在包括装备有具有氢解特性的催化剂床的反应器10的加氢脱硫(HDS)单元中进行处理。HDS催化剂可以包含沉积于载体上的至少一种第VIb族的金属(例如钼)以及至少一种第VIII族的金属(例如钴)。可以具体参考本申请人的描述HDS催化剂的文献EP 1 369 466和EP 1 892 039。
在氢气的存在下的重质汽油馏分的加氢脱硫的操作条件是:
•约200℃-约400℃、优选250-350℃的温度;
•1MPa-3MPa、优选1MPa-约2.5MPa的总压力;
•100-600标准升的氢气/升汽油(体积/体积)的加入的H2/汽油原料的体积比;和
•1h-1-10h-1、优选2h-1-8h-1的液体时空速(LHSV)。
在除去由催化加氢脱硫反应形成的H2S和稳定化之后,经脱硫的重质汽油馏分然后可以根据炼厂的需求被送至汽油池和/或柴油池。
根据本发明的方法因此可以在自身的加氢脱硫步骤之前作为汽油的预处理步骤并入加氢脱硫单元中。
实施例
实施例1(对比例)
表1显示了已经根据本发明处理的汽油的总体特性。MAV是马来酸酐值,并给出了汽油中的共轭二烯烃(胶状物的前体化合物)含量的指征。
汽油的组成 | 单位 | 值 |
在15℃下的密度 | g/cm3 | 0.718 |
MAV | g/100g | 15 |
元素硫的含量 | %m/m | 0.192 |
轻质硫醚的含量 | ||
二甲基硫醚 | ppm S | 1.8 |
甲基-乙基硫醚 | ppm S | 4.5 |
烯烃的含量 | % m/m | 49.0 |
模拟蒸馏 | ||
T 5% | ℃ | 23 |
T 95% | ℃ | 179 |
汽油的RON | - | 87.2 |
汽油的MON | - | 76.6 |
表1:汽油的特性。
在选择性氢化反应器中在催化剂A的存在下处理所述汽油。
催化剂A是γ-氧化铝上的NiMo型催化剂。相对于催化剂的总重量,金属的含量分别为7重量%的NiO和11重量%的MoO3,即Ni/Mo摩尔比为1.2。催化剂的比表面积为230m²/g。在使用之前,在大气压力下、在硫化台上、在包含15体积%的H2S的H2S/H2混合物对1L/g.h的催化剂下、在400℃下将催化剂A硫化两小时。该方案可以获得大于80%的硫化程度。
表2示出了在选择性氢化步骤期间实施的操作条件以及轻质硫醚的转化结果。
表2。
将选择性氢化步骤的流出物送入分馏塔,以在塔的顶部分离出含有每分子具有少于6个碳原子的烃的轻质汽油馏分,并且在塔的底部分离出含有每分子具有6个和多于6个碳原子的烃的重质汽油馏分。
轻质汽油馏分中的二甲基硫醚和甲基-乙基硫醚的含量分别为4.5重量ppm和6.3重量ppm,即硫醚的总含量为10.8重量ppm。
实施例2(根据本发明)
在根据本发明的方法中采用0.5的再循环比处理实施例1的汽油。
考虑到再循环,在选择性氢化反应器中在催化剂A的存在下处理的原料具有分别为2.1重量ppm和4.4重量ppm的二甲基硫醚和甲基-乙基硫醚的含量。
催化剂A是γ-氧化铝上的NiMo型催化剂。相对于催化剂的总重量,金属的含量分别为7重量%的NiO和11重量%的MoO3,即Ni/Mo摩尔比为1.2。催化剂的比表面积为230m²/g。在使用之前,在大气压力下、在硫化台上、在包含15体积%的H2S的H2S/H2混合物对1L/g.h的催化剂下、在400℃下将催化剂A硫化两小时。该方案可以获得大于80%的硫化程度。
表3。
将选择性氢化步骤的流出物送入分馏塔,以在塔的顶部分离出含有每分子具有少于6个碳原子的烃的轻质汽油馏分,并且在塔的底部分离出含有每分子具有6个和多于6个碳原子的烃的重质汽油馏分。
产生的轻质汽油馏分中的二甲基硫醚和甲基-乙基硫醚的含量分别为3.3重量ppm和3.8重量ppm,即硫醚的总含量为7.1重量ppm。
实施例3(根据本发明)
在根据本发明的方法中采用0.33的再循环比处理实施例1的汽油。
考虑到再循环,在选择性氢化反应器中在催化剂A的存在下处理的原料具有分别为2.0重量ppm和4.5重量ppm的二甲基硫醚和甲基-乙基硫醚的含量。
催化剂A是γ-氧化铝上的NiMo型催化剂。相对于催化剂的总重量,金属的含量分别为7重量%的NiO和11重量%的MoO3,即Ni/Mo摩尔比为1.2。催化剂的比表面积为230m²/g。在使用之前,在大气压力下、在硫化台上、在包含15体积%的H2 S的H2S/H2混合物对1L/g.h的催化剂下、在400℃下将催化剂A硫化两小时。该方案可以获得大于80%的硫化程度。
表4。
将选择性氢化步骤的流出物送入分馏塔,以在塔的顶部分离出含有每分子具有少于6个碳原子的烃的轻质汽油馏分,并且在塔的底部分离出含有每分子具有6个和多于6个碳原子的烃的重质汽油馏分。
产生的轻质汽油馏分中的二甲基硫醚和甲基-乙基硫醚的含量分别为3.7重量ppm和4.6重量ppm,即硫醚的总含量为8.3重量ppm。
Claims (7)
1.降低含有二烯烃、单烯烃和硫的汽油中的具有式R1-S-R2的硫醚类型的化合物的含量的方法,其中R1和R2选自甲基(CH3)和乙基(C2H5)基团,其中:
A)在反应器中使所述汽油以与从步骤C)再循环的轻质汽油馏分的混合物的形式与氢气和催化剂A接触,催化剂A包含沉积于载体上的至少一种第VIb族的金属和至少一种第VIII族的非贵金属,步骤A)在所述反应器中在60℃-150℃的温度下进行,其中液体时空速(LHSV)为1h-1-10h-1,压力为0.5-5MPa,并且其中体积比(加入的H2/汽油的混合物)为1-40标准升的氢气/升汽油混合物(体积/体积),从而产生具有低于起始汽油的二烯烃含量和具有式R1-S-R2的硫醚类型的化合物含量的流出物,其中R1和R2选自甲基(CH3)和乙基(C2H5)基团;
B)将源自步骤A)的所述流出物送入分馏塔,以在所述塔的顶部分离出含有每分子具有少于6个碳原子的烃的轻质汽油馏分,并在所述塔的底部分离出含有每分子具有6个和多于6个碳原子的烃的重质汽油馏分;
C)采用0.1-0.7的再循环比将源自步骤B)的所述轻质汽油馏分的一部分再循环至步骤A)的所述反应器中,
其中催化剂A包含:
•相对于所述催化剂的总重量,4-20重量%的第VIb族的金属的氧化物的含量,
•相对于所述催化剂的总重量,4-15重量%的第VIII族的金属的氧化物的含量,
•构成所述催化剂的金属的硫化程度至少等于60%,
•所述第VIII族的非贵金属与所述第VIb族的金属之间的摩尔比为0.6-8mol/mol,
•所述催化剂的比表面积为30-300m²/g。
2.根据权利要求1的方法,其中在加氢脱硫单元中在氢气的存在下处理源自步骤B)的所述重质汽油馏分。
3.根据前述权利要求之一的方法,其中每单位面积的催化剂的第VIb族的金属的密度小于或等于10-3克的第VIb族的金属的氧化物/m2的催化剂。
4.根据前述权利要求之一的方法,其中催化剂A的第VIb族的金属选自钼和钨,优选钼。
5.根据前述权利要求之一的方法,其中催化剂A的第VIII族的金属选自镍、钴和铁,优选镍。
6.根据前述权利要求之一的方法,其中催化剂A的第VIII族的金属是镍,并且催化剂A的第VIb族的金属是钼。
7.根据前述权利要求之一的方法,其中所述汽油源自催化裂化或热裂化、焦化方法、减粘裂化方法或热解方法。
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FR2888583A1 (fr) * | 2005-07-18 | 2007-01-19 | Inst Francais Du Petrole | Nouveau procede de desulfuration d'essences olefiniques permettant de limiter la teneur en mercaptans |
US20120043260A1 (en) * | 2008-01-25 | 2012-02-23 | Catalytic Distillation Technologies | Process to hydrodesulfurize fcc gasoline resulting in a low-mercaptan product |
FR2993571A1 (fr) * | 2012-07-17 | 2014-01-24 | IFP Energies Nouvelles | Procede de desulfuration d'une essence |
CN104232156A (zh) * | 2013-06-19 | 2014-12-24 | Ifp新能源公司 | 制造具有低硫和硫醇含量的汽油的方法 |
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FR2797639B1 (fr) | 1999-08-19 | 2001-09-21 | Inst Francais Du Petrole | Procede de production d'essences a faible teneur en soufre |
FR2811328B1 (fr) | 2000-07-06 | 2002-08-23 | Inst Francais Du Petrole | Procede comprenant deux etapes d'hydrodesulfuration d'essence et une elimination intermediaire de l'h2s forme au cours de la premiere etape |
FR2840315B1 (fr) | 2002-06-03 | 2004-08-20 | Inst Francais Du Petrole | Procede d'hydrodesulfuration de coupes contenant des composes soufres et des olefines en presence d'un catalyseur supporte comprenant des metaux des groupes viii et vib |
FR2895416B1 (fr) | 2005-12-22 | 2011-08-26 | Inst Francais Du Petrole | Procede d'hydrogenation selective mettant en oeuvre un catalyseur sulfure |
FR2904242B1 (fr) | 2006-07-28 | 2012-09-28 | Inst Francais Du Petrole | Procede d'hydrodesulfuration de coupes contenant des composes soufres et des olefines en presence d'un catalyseur supporte comprenant des elements des groupes viii et vib |
FR2935389B1 (fr) | 2008-09-04 | 2012-05-11 | Inst Francais Du Petrole | Procede d'hydrogenation selective mettant en oeuvre un catalyseur sulfure de composition specifique |
FR2988732B1 (fr) * | 2012-03-29 | 2015-02-06 | IFP Energies Nouvelles | Procede d'hydrogenation selective d'une essence |
-
2015
- 2015-04-15 FR FR1553340A patent/FR3035117B1/fr not_active Expired - Fee Related
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2016
- 2016-02-17 US US15/566,611 patent/US10822555B2/en active Active
- 2016-02-17 WO PCT/EP2016/053303 patent/WO2016165853A1/fr active Application Filing
- 2016-02-17 PL PL16704661T patent/PL3283601T3/pl unknown
- 2016-02-17 ES ES16704661T patent/ES2729669T3/es active Active
- 2016-02-17 CN CN201680021718.6A patent/CN107429172B/zh active Active
- 2016-02-17 EP EP16704661.4A patent/EP3283601B1/fr active Active
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FR918705A (fr) * | 1944-12-21 | 1947-02-17 | Shell Dev | Procédé de traitement catalytique des produits de distillation des hydrocarbures contenant du soufre |
FR2104631A1 (zh) * | 1967-04-28 | 1972-04-21 | Universal Oil Prod Co | |
US20030230516A1 (en) * | 2001-10-16 | 2003-12-18 | Johnson Kenneth H. | Process for ultra low sulfur gasoline |
US20040000506A1 (en) * | 2002-02-13 | 2004-01-01 | Catalytic Distillation Technologies | Process for the treatment of light naphtha hydrocarbon streams |
FR2888583A1 (fr) * | 2005-07-18 | 2007-01-19 | Inst Francais Du Petrole | Nouveau procede de desulfuration d'essences olefiniques permettant de limiter la teneur en mercaptans |
US20120043260A1 (en) * | 2008-01-25 | 2012-02-23 | Catalytic Distillation Technologies | Process to hydrodesulfurize fcc gasoline resulting in a low-mercaptan product |
FR2993571A1 (fr) * | 2012-07-17 | 2014-01-24 | IFP Energies Nouvelles | Procede de desulfuration d'une essence |
CN104232156A (zh) * | 2013-06-19 | 2014-12-24 | Ifp新能源公司 | 制造具有低硫和硫醇含量的汽油的方法 |
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US20180148658A1 (en) | 2018-05-31 |
PL3283601T3 (pl) | 2019-11-29 |
ES2729669T3 (es) | 2019-11-05 |
WO2016165853A1 (fr) | 2016-10-20 |
FR3035117A1 (fr) | 2016-10-21 |
FR3035117B1 (fr) | 2019-04-19 |
US10822555B2 (en) | 2020-11-03 |
CN107429172B (zh) | 2020-07-03 |
EP3283601A1 (fr) | 2018-02-21 |
EP3283601B1 (fr) | 2019-04-10 |
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