CN104812481A - 用于使组合物脱硫的方法和组合物 - Google Patents
用于使组合物脱硫的方法和组合物 Download PDFInfo
- Publication number
- CN104812481A CN104812481A CN201380055101.2A CN201380055101A CN104812481A CN 104812481 A CN104812481 A CN 104812481A CN 201380055101 A CN201380055101 A CN 201380055101A CN 104812481 A CN104812481 A CN 104812481A
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- Prior art keywords
- sulphur
- composition
- oxidation catalyst
- oil
- oxidant
- Prior art date
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- Granted
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- 238000000034 method Methods 0.000 title claims abstract description 77
- 238000006477 desulfuration reaction Methods 0.000 title description 19
- 230000023556 desulfurization Effects 0.000 title description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 61
- 230000003647 oxidation Effects 0.000 claims abstract description 58
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 38
- 239000011593 sulfur Substances 0.000 claims abstract description 38
- 239000005864 Sulphur Substances 0.000 claims description 61
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 239000007800 oxidant agent Substances 0.000 claims description 28
- 230000001590 oxidative effect Effects 0.000 claims description 25
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- 229910052723 transition metal Inorganic materials 0.000 claims description 18
- 150000003624 transition metals Chemical class 0.000 claims description 13
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- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
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- 238000005470 impregnation Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- -1 t-butyl phosphate hydrogen salt Chemical class 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
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- 238000006277 sulfonation reaction Methods 0.000 description 7
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- 239000002283 diesel fuel Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
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- 229910052727 yttrium Inorganic materials 0.000 description 5
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
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- 239000010936 titanium Substances 0.000 description 4
- 229940035658 visco-gel Drugs 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- 229910052771 Terbium Inorganic materials 0.000 description 3
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- 125000003118 aryl group Chemical group 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
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- 239000010937 tungsten Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
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- XEFGHVQACKIFMS-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nitric acid Chemical compound O[N+]([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O XEFGHVQACKIFMS-UHFFFAOYSA-N 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本文公开了用于减少在包含硫的组合物中硫的量的方法和组合物。所述方法和组合物包括使用氧化剂和氧化催化剂。所述氧化催化剂可具有式M1 1-xM3 xM2O3。
Description
发明领域
本文所公开的方法和组合物涉及使包含硫的组合物(诸如,例如石油)脱硫。
发明背景
严格的环境法规日益针对降低石油中和在燃烧石油产品(例如燃料)之后排放的废气中的硫的允许水平。尽管全世界对于石油中可容许的硫量并未达成单一共识,但所有国家都有政府规定的法规。例如,在欧洲,大约从2005年开始,Euro V燃料标准允许道路用石油中的硫小于或等于百万分之10。自从2007年9月起美国所用的超低硫柴油(ULSD)的可容许的硫含量小于或等于百万分之15,这比早先美国的低硫柴油道路用标准(LSD-小于或等于百万分之500)低得多。在印度,所用的柴油中的硫含量先前小于或等于百万分之350,且从2010年4月1日起,印度法规规定可使用硫小于或等于百万分之15的ULSD。
以石油中的低硫含量为目标的主要原因是为了控制环境污染。可选地,通过处理排放物使污染减到最少的方法导致成本提高。此外,硫会毒化和缩短用于净化废气排放的汽车催化转化器中所用的催化剂的寿命。尽管ULSD是当今优选的燃料,但ULSD通常因去除大量硫所需要的繁重工艺而具有较低的能含量,从而导致较低的燃料经济性和更高的燃料成本。
炭黑原料油(CBFO)是制造炭黑的主要原材料。CBFO可从练油厂或从煤焦油蒸馏器或乙烯裂化装置获得。大多数CBFO所面临的主要问题之一是高硫含量。此硫因炭黑制造期间的SO2排放而导致严重的环境问题。另外,它导致制造和排放设备的腐蚀。另一个主要缺点是来自CBFO的相当数量的硫可作为污染物残留在最终的炭黑粉末中。因此需要开发一种适于从CBFO中去除‘S’的商业上可行的方法。
已对用于使包含硫的组合物(诸如,例如石油)脱硫的各种方法和组合物进行了探究并且随着政府对石油和排放废气中硫的可容许量所规定的严格性的增强,对此仍在探究中。因此,需要一种用于使石油脱硫的改进且成本有效的方法。
本文提供用于使包含硫的组合物(诸如,例如石油)脱硫的方法和组合物。
发明概述
根据本发明的一个或多个目的,如本文中所实施和广泛描述的,本发明一方面涉及通过使组合物与氧化剂和氧化催化剂接触来减少硫在所述组合物中的量的方法。
本文公开了一种包含氧化剂和氧化催化剂的组合物,其中所述氧化催化剂具有式M1 1-xM3 xM2O3,其中M1是稀土元素,其中M2是过渡金属,其中M3是Ca或Sr,并且其中x是0.01至0.80。在一个实施方案中,氧化催化剂被酸诸如硫酸浸渍。
本文还公开了一种用于减少包含硫的组合物中硫的量的方法,所述方法包括以下步骤:(a)提供包含硫的组合物;和(b)使包含硫的组合物与氧化剂和氧化催化剂接触,其中所述氧化催化剂具有式M1 1-xSrxM2O3,其中M1是稀土元素,其中M2是过渡金属元素,并且其中x是0.01至0.80,从而减少所述包含硫的组合物中硫的量。在一个实施方案中,所述氧化催化剂被酸诸如硫酸浸渍。
虽然本发明的方面可以具体法定类别诸如系统法定类别进行描述和要求保护,但这仅进为了方便起见并且本领域技术人员将了解,本发明的各方面可以任何法定类别进行描述和要求保护。除非另外清楚地说明,否则本文所述的任何方法或方面绝不意图视为要求其步骤以特定顺序进行。因此,当要求保护的方法未在权利要求书或说明书中具体指出步骤将限于特定顺序时,绝不意图在任何方面推断一种顺序。这对于任何可能的未明确的基础均成立,所述解释基础包括:关于步骤或操作流程的安排的逻辑问题;得自语法组织或标点的明确含义;或在说明书中描述的方面的数量或类型。
详述
详述参考本发明的以下详述和本文所包括的实施例可更容易地理解本发明。
应理解,本文所用的术语仅仅是用于描述具体的方面,而不意图作为限制。虽然类似于或等价于本文所述的那些方法和材料的任何方法和材料可用于本发明的实践或测试,但现在描述示例性方法和材料。
本文所提及的全部出版物以引用方式并入本文,从而公开和描述了与出版物所引用的内容相关的方法和/或材料。本文所讨论的出版物只提供在本申请的申请日之前的公开内容。本文中的任何内容都不能被解释为承认本发明无权使借助于在先发明的这种出版日期提前。此外,本文所提供的出版日期可能不同于实际的出版日期,实际的出版日期可能需要单独确认。
1.定义
如本文所用,化合物(包括有机化合物)的命名可使用常用名称,关于命名的IUPAC、IUBMB或CAS推荐原则给出。
除非文中另外清楚指出,否则如说明书和所附权利要求书中所用,单数形式“一个/种(a,an)”和“所述”包括复数指示物。因此,例如,引用“氧化剂”包括两种或更多种这类氧化剂的混合物。
范围可在本文中表达为从“约”一个具体值和/或至“约”另一个具体值。当表达这样的范围时,另一方面包括从所述一个具体值和/或至另一个具体值。类似地,当通过使用先行词“约”将数值表示为近似值时,应了解所述具体值形成另一方面。还应理解,每个范围的端点相对于另一个端点以及独立于另一个端点都是有意义的。还应理解的是,本文公开了多个数值,并且每一个数值除其本身外也在本文中公开为“约”该具体值。举例来说,如果公开了数值“10”,那么也公开了“约10”。还应理解,还公开了两个具体单位之间的每个单位。举例来说,如果公开了10和15,那么还公开了11、12、13及14。
在说明书及结尾的权利要求书提及按组合物中特定部分或组分的重量份时,是表示组合物或制品中某部分或组分与任何其它部分或组分之间的重量关系,用重量份表示。因此,在含有2重量份的组分X和5重量份的组分Y的化合物中,X和Y以2:5的重量比存在,并且无论化合物中所包含的其它组分如何,X和Y总是以该比率存在。
如本文所用,术语“任选的”或“任选地”意指随后描述的事件或情况可能发生或可能不发生,并且描述内容包括所述事件或情况发生的场合以及事件或情况没有发生的场合。
如本文所用,术语“石油”是指石油和石油产品。在各种实施方案中,石油可包括但不限于选自由以下组成的组的产物:原油、柏油、焦油、精炼石油、石油的蒸馏产物像柴油、汽油、煤油、炭黑原料、炭黑原料油等、以及使用石油的馏出物形成的合成混合物。如本文所用,术语“硫(sulphur)”(如英式英语中所拼写的)可另外拼写为“硫(sulfur)”(如美式英语中所拼写的)。在一个实施方案中,石油可以是炭黑原料。炭黑原料为本领域技术人员所知并且通常被视为萘、甲基茚、蒽、芴及其它聚芳族组分中富含的C12和更高级组分。在另一个实施方案中,炭黑原料可包含各种碳化油和/或石化油,例如,具有高含量的芳香烃和/或含有多个稠环的油。在一个实施方案中,炭黑原料来源于石油馏分的高温裂化。在另一个实施方案中,石油可以是残油。如本文所用的“残油”是指由催化裂化过程产生的石化油,例如,催化裂化装置倾析油;或由使用石脑油或气油作为原材料在蒸汽裂化器中生产烯烃所产生的石化油。
术语“脱硫”意在指示减少和/或消除组合物中的硫和/或含硫种类。
术语“稀土元素”为本领域技术人员所理解并且包括但不限于镧(La)、铈(Ce)、镨(Pr)、钐(Sm)、钆(Gd)、钇(Y)、钕(Nd)、铕(Eu)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、钪(Sc)、钷(Pm)以及镥(Lu)。
术语“过渡金属”和“过渡元素”在本文中可互换使用并且为本领域技术人员所理解且包括但不限于铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、锌(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、锝(Tc)、钌(Ru)、铑(Rh)、钯(Pd)、银(Ag)、镉(Cd)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、汞(Hg)、及金(Au)。
2.方法和组合物
本文所公开的方法和组合物用于减少包含硫的组合物中硫的量。
本文所公开的方法的实施方案提供一种用于使包含硫的组合物诸如石油脱硫的改进的方法。已知原油是基于在合适的氧化催化剂存在下通过合适的氧化剂氧化硫种类来脱硫的。如上所提及,随着在各个国家中按照政府规定的硫的可容许量的严格性提高,正在不断探究用于从石油中去除硫、特别是去除有机硫的改进的、高效的和成本有效的方法。因此,在一个实施方案中,提供一种用于使包含硫的组合物诸如石油脱硫的方法。
有利的是,已发现在本文中用于脱硫过程的催化剂能够在相对较低温度下,即在约20℃至150℃范围内的温度下发挥作用。此外,在一个实施方案中,本文中所用的催化剂能够实现在例如柴油、汽油等的石油产品中大于等于约97%硫量的减少以及在蒸馏各种石油产品之后残留的原油馏分中大于等于约50%硫量的减少。
所公开的方法涉及使用一种催化剂系统,所述系统能够提高氧化剂诸如过氧化氢在从各种组合物中去除硫的效率。由于催化剂系统的高效率,所公开的方法和组合物具有针对从液体诸如石油中去除硫的高效率。
在一个实施方案中,所公开的方法是一种用于使石油脱硫的方法。
本文公开了一种包含氧化剂和氧化催化剂的组合物,其中所述氧化催化剂具有式M1 1-xM3 xM2O3,其中M1是稀土元素,其中M2是过渡金属,其中M3是Ca或Sr,并且其中x是0.01至0.80。在一个实施方案中,所述氧化催化剂被酸如硫酸浸渍。
本文还公开了一种减少包含硫的组合物中硫的量的方法,所述方法包括以下步骤:(a)提供包含硫的组合物;及(b)使包含硫的组合物与氧化剂和氧化催化剂接触,其中所述氧化催化剂具有式M1 1-xM3 xM2O3,其中M1是稀土元素,其中M2是过渡金属,其中M3是Ca或Sr,并且其中x是0.01至0.80,从而减少所述包含硫的组合物中硫的量。在一个实施方案中,所述氧化催化剂被酸诸如硫酸浸渍。
本文还公开了一种使石油脱硫的方法,所述方法包括使石油的原料流与氧化催化剂在氧化剂存在下接触,其中所述氧化催化剂具有式M1 1-xM3 xM2O3,其中M1是稀土元素,其中M2是过渡金属,其中M3是Ca或Sr,并且其中x是0.01至0.80。在一个实施方案中,所述氧化催化剂被酸诸如硫酸浸渍。
在一个实施方案中,提供包含硫的组合物的步骤包括提供包含硫的组合物的原料流。
在一个实施方案中,包含硫的组合物包括石油,例如,包含硫的组合物可以是石油。在一个实施方案中,石油可以是石油的蒸馏产物或使用石油的馏出物形成的合成混合物。石油的蒸馏产物的非限制性实例包括柴油、汽油和煤油。在一个实例中,石油可以是柴油或汽油。在另一个实施方案中,石油可以是原油、柏油、焦油或精炼石油。
在一个实施方案中,氧化剂可包括H2O2、NO2、N2O3、N2O4、乙酸、叔丁基过氧化氢(TBHP)、甲酸、硫酸、硝酸、O2、空气、或臭氧、或其组合。例如,氧化剂可包括H2O2、NO2、N2O3、N2O4、乙酸、叔丁基过氧化氢(TBHP)、甲酸、硫酸、或硝酸、或其组合。在另一个实例中,氧化剂可包括H2O2、NO2、N2O3、N2O4、乙酸、或叔丁基过氧化氢、或其组合。在又一个实施例中,氧化剂可包括H2O2。
在一个实施方案中,所述氧化催化剂具有式M1 1-xSrxM2O3,其中M1是稀土元素,其中M2是过渡金属,并且其中x是0.01至0.80。
在一个实施方案中,M1是选自由以下组成的组的稀土元素:镧(La)、铈(Ce)、镨(Pr)、钐(Sm)、钆(Gd)、钇(Y)、钕(Nd)、铕(Eu)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、钪(Sc)及镥(Lu)。在另一个实例中,M1是选自由以下组成的组的稀土元素:La、Y、Yb、Nd、Ce及Tb。在又一个实例中,M1是选自由以下组成的组的稀土元素:La、Pr、Gd、Sm、Nd及Ce。在又一个实例中,M1是稀土元素La。
在一个实施方案中,M2是选自由以下组成的组的过渡金属:铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、锌(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、锝(Tc)、钌(Ru)、铑(Rh)、钯(Pd)、银(Ag)、镉(Cd)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、汞(Hg)及金(Au)。例如,M2可以是选自由以下组成的组的过渡金属:Fe、Ru、Ir、Co、Rh、Pt、Pd及Mo。在另一个实例中,M2是选自由以下组成的组的过渡金属:Fe、Mn、Ni、Co、Mo及Cu。在另一个实例中,M2是过渡金属Fe。
在一个实施方案中,M3是Ca。在另一个实施方案中,M3是Sr。
在一个实施方案中,M1 1-xM3 xM2O3是M1 1-xSrxM2O3。
在一个实施方案中,M1是选自由以下组成的组的稀土元素:La、Pr、Gd、Sm、Nd及Ce;M2是选自由以下组成的组的过渡金属:Fe、Mn、Ni、Co、Mo及Cu;并且M3是Sr或Ca。在一个实例中,M1是选自由以下组成的组的稀土元素:La、Pr、Gd、Sm、Nd及Ce;M2是选自由以下组成的组的过渡金属:Fe、Mn、Ni、Co、Mo及Cu;并且M3是Sr。在另一个实例中,M1是稀土元素La;M2是过渡金属Fe;并且M3是Sr。
在一个实施方案中,在式M1 1-xM3 xM2O3中,x可以是0.01至0.80。例如,x可以是0.10至0.50。在另一个实例中,x可以是0.10至0.30。在又一个实例中,x可以是0.15至0.25。如果x是0.20,那么M1 1-xM3 xM2O3具有式M1 0.80M3 0.20M2O3。因此,在一个实例中,式M1 1-xM3 xM2O3可以是La0.80Sr0.20FeO3
一方面,氧化催化剂被硫酸溶液浸渍。
在一个实施方案中,氧化催化剂呈纳米结晶形式。因此,式M1 1-xM3 xM2O3可呈纳米结晶形式。在另一个实施方案中,氧化催化剂可呈盐形式。在又一个实施方案中,氧化催化剂的纳米结晶形式可以是氧化催化剂的盐形式。例如,氧化催化剂可被包含硫酸的溶液浸渍,这形成了M1 1-xM3 xM2O3的纳米结晶硫酸盐。因此,在一个实例中,氧化催化剂可被包含酸诸如硫酸的溶液浸渍。在一个实施方案中,氧化催化剂的纳米结晶形式的平均尺寸为约5nm至约100nm,诸如例如约5nm至约80nm;约5nm至约50nm;约25nm至约100nm;或约50nm至约100nm。
在一个实施方案中,氧化催化剂存在于有机溶剂中。有机溶剂的非限制性实例包括烷烃,例如戊烷、己烷、庚烷及辛烷。在另一个实例中,溶剂可以是芳基、环烷烃、环烯烃、链烯烃等,例如甲苯和二甲苯。
在一个实施方案中,使包含硫的组合物与氧化剂和氧化催化剂接触可在20℃至150℃,诸如60℃至150℃的温度下进行。
在一个实施方案中,使包含硫的组合物与氧化剂和氧化催化剂接触可以发生至少15分钟、30分钟、60分钟、90分钟、120分钟、180分钟、240分钟、或300分钟。
在其它实施方案中,接触的顺序可以变化并且包括用于所期望产物的任何合适的顺序。在一个实施方案中,含硫组合物可首先与氧化催化剂接触,然后与氧化剂接触。在另一个实施方案中,含硫组合物可首先与氧化剂接触,然后与氧化催化剂接触。在另一个实施方案中,含硫组合物可同时地或基本上同时地与氧化催化剂和氧化剂两者接触。
在一个实施方案中,氧化剂的量可以是每体积包含硫的组合物约5体积%至约300体积%。例如,氧化剂的量可以是每体积包含硫的组合物约5体积%至约100体积%。在另一个实例中,氧化剂的量可以是每体积包含硫的组合物约20体积%至约80体积%。在一个实施方案中,基于将过氧化氢(H2O2)用作氧化剂而采用的氧化催化剂的量在每体积油或石油约1体积%至约50体积%的范围内。
在一个实施方案中,氧化催化剂可以在约1%容重至约60%容重范围内的溶剂的量存在。在一个实施方案中,当氧化催化剂是式M1 1-xM3 xM2O3的纳米结晶化合物时,氧化反应可以在按体积计约1体积%至约60体积%范围内的溶剂的量进行。在一个实施方案中,当式M1 1-xM3 xM2O3的氧化催化剂被硫酸溶液浸渍时,氧化反应可以在约1%容重至约60%容重范围内的溶剂的量进行。
在一个实施方案中,本文所公开的方法可使组合物中存在的硫的量减少至少40%、50%、60%、70%、80%、85%、90%、95%、97%、98%、99%、或99.5%。在一个实施方案中,本文所公开的方法可使组合物中的硫的量减少至少97%、98%、99%或99.5%,其中所述包含硫的组合物包含正辛烷和噻吩。在一个实例中,本文所公开的方法可使组合物中的硫的量减少至少85%、90%、95%、97%、98%、99%或99.5%,其中所述包含硫的组合物包含蒸馏的石油产品。在另一个实例中,本文所公开的方法可使组合物中的硫的量减少至少50%、60%、70%或80%,其中所述包含硫的组合物包含原油。例如,当组合物包含正辛烷和噻吩时,所公开的方法可将组合物中的初始硫含量从约20,000ppm减少到约70ppm。
在一个实施方案中,本文所公开的组合物还可包含溶剂。有机溶剂的非限制性实例包括烷烃,例如戊烷、己烷、庚烷及辛烷。在另一个实例中,溶剂可以是芳基、环烷烃、环烯烃、链烯烃等,例如甲苯和二甲苯。
通过采用本文所公开的方法,用于石油脱硫的改进的、高效的和成本有效的方法在降低的反应温度下并且从具有相对较高硫浓度的原料是可能的。
在一个实施方案中,氧化催化剂可以是式M1 1-xM3 xM2O3的化合物的硫酸盐的纳米结晶形式。在一个实施方案中,当氧化催化剂可能是式M1 1-xM3 xM2O3的化合物的硫酸盐时,氧化催化剂的晶体尺寸可在5nm至约100nm范围内。在一个实施方案中,基于将过氧化氢(H2O2)用作氧化剂而采用的呈纳米结晶形式的氧化催化剂的量是在每体积油或石油约1体积%至约50体积%的范围内。
合成本文中所用的催化剂的合适的方法包括但不限于选自由以下组成的组的方法:凝胶燃烧、柠檬酸盐-硝酸盐、溶胶-凝胶法、热液法、声化学法等。在一个实施方案中,使用本文所提及的方法合成的氧化催化剂可以是纳米结晶化合物。在一个实施方案中,所述氧化催化剂进一步通过用硫酸处理来磺化。在一个实施方案中,用硫酸处理纳米结晶形式产生磺化的纳米结晶氧化催化剂。
在一个实施方案中,所述方法包括含有在正辛烷中的噻吩的原料流,其中脱硫具有至少97%的效率。例如,对含有大于或等于百万分之15,000的高初始硫浓度的原料流进行的脱硫方法可以产生含有小于或等于百万分之500的硫的脱硫产物。
在一个实施方案中,本文所公开的方法可以显著地减少在蒸馏上部馏分之后留下的石油诸如汽油、柴油、煤油等中的硫的量。这些残余物或残油通常已知具有大于或等于约百万分之20,000的硫含量。体积比为50:50(相当于约百万分之20,000的初始硫含量)的残油于正辛烷中的溶液可以通过使用本文所公开的方法展现至少50%的硫减少。
实施例
给出以下实施例以便为本领域技术人员提供本文所要求保护的方法和组合物是如何制备、进行和评价的完整公开和描述,并且旨在仅仅是示例性的方法和组合物且不意图限制本发明的范围。已努力确保关于数字(例如数量、温度等)的精确性,但应说明存在一些错误和偏差。除非另外指出,否则份均指重量份,温度以℃计或在环境温度下,并且压力为大气压或接近大气压。
本公开进一步借助于以下实施例来说明,这些实施例不应被视为以任何方式限制本公开。
A.实施例1
使用凝胶燃烧合成方法合成催化剂La0.80Sr0.20FeO3(LSF)。因此,氧化镧[La2O3(99.99%)]、硝酸锶[Sr(NO3)2(99%)]及硝酸铁[Fe(NO3)3·9H2O(98%)]被用作原料。首先将化学计量的氧化镧溶于稀释的HNO3(50%)中。向此溶液中添加化学计量的硝酸锶和硝酸铁。最终,将适量柠檬酸溶于蒸馏水中且添加至此硝酸盐溶液中。然后在约80℃下小心地为全部溶液脱水以去除过量的水。溶液的热脱水之后,形成粘性凝胶。一旦形成粘性凝胶,热板的温度就增加到约250℃。自燃之后获得的粉末在600℃下锻烧1小时以获得化学纯的和结晶粉末。
合成La0.80Sr0.20FeO3(LSF)催化剂系统之后,测试系统的脱硫效率。使用含硫种类即噻吩(99%,spectrochem)和有机溶剂正辛烷(99%,Merck)制备模拟的硫原料溶液。通过溶解噻吩以获得20,950ppm的硫含量来制备模拟的储备溶液。将约20ml的此模拟储备溶液与约1.0g纳米结晶LSF催化剂混合。然后将此混合物置于配备有磁力搅拌器和回流冷凝器的100ml三颈圆底烧瓶中。在水浴中在连续的搅拌下加热系统至约70℃的温度。在混合物达到所述温度之后,使用加料漏斗在15分钟的期间内滴加60ml的过氧化氢(30%,FisherScientific)。使反应继续进行2.5小时。反应完成之后,使整个系统冷却并且使其再静置15分钟,以便形成反应混合物的两个单独的层。在氧化之后,两个层是油层(顶部)和水层(底部)。然后过滤上部原料油层并且发现含有低至110ppm的硫含量,即约99%脱硫。
B.实施例2
使用凝胶燃烧合成方法合成催化剂La0.80Sr0.20FeO3(LSF)。因此,氧化镧[La2O3(99.99%)]、硝酸锶[Sr(NO3)2(99%)]及硝酸铁[Fe(NO3)3·9H2O(98%)]被用作原料。首先将化学计量的氧化镧溶于稀释的HNO3(50%)中。向此溶液中添加化学计量的硝酸锶和硝酸铁。最终,将适量柠檬酸溶于蒸馏水中且添加至此硝酸盐溶液中。然后在约80℃下小心地使全部溶液脱水以去除过量的水。在对溶液热脱水之后,形成粘性凝胶。一旦形成粘性凝胶,热板的温度就增加到约250℃。自燃之后获得的粉末在600℃下锻烧1小时以获得化学纯的和结晶粉末。
在此实例中,合成的催化剂被硫酸溶液(30%)浸渍24小时的时间段。倾析出过量的酸,且然后在100℃下在烘箱中干燥催化剂。赐此外,在600℃下锻烧干燥的催化剂2小时,从而产生磺化的LSF催化剂。然后测试磺化的LSF催化剂的脱硫效率。使用含硫物质即噻吩(99%,spectrochem)和有机溶剂如正辛烷(99%,Merck)制备模拟的硫原料溶液。模拟物料通过溶解噻吩以获得20,950ppm的硫含量来制备。将约20ml的此模拟物料与约1.0g纳米结晶LSF催化剂混合。然后将此混合物置于配备有磁力搅拌器和回流冷凝器的100ml三颈圆底烧瓶中。在水浴中在连续的搅拌下加热系统至约70℃的温度。在混合物达到所述温度之后,使用加料漏斗在15分钟期间内滴加约60ml的过氧化氢(30%,Fisher Scientific)。使反应继续进行2.5小时。反应完成之后,使整个系统冷却并且使其再静置15分钟,以便形成反应混合物的两个单独的层。在氧化之后,两个层是油层(顶部)和水层(底部)。然后过滤上部原料油层并且发现含有低至70ppm的硫含量,即约99.5%脱硫。
C.实施例3
为了确定催化剂对脱硫的作用,在无任何催化剂下进行对照实验。模拟物料通过溶解噻吩以获得12,000ppm的硫含量来制备。然后将约20ml的此模拟物料置于配备有磁力搅拌器和回流冷凝器的100ml三颈圆底烧瓶中。在水浴中在连续的搅拌下加热系统至约80℃的温度。在混合物达到所述温度之后,使用加料漏斗在15分钟期间内滴加100ml的过氧化氢(30%,Fisher Scientific)。使反应继续进行5小时。反应完成之后,使整个系统冷却并且使其再沉降15分钟,以便形成反应混合物的两个单独的层。因此,在氧化之后,两个层是油层(顶部)和水层(底部)。然后过滤上部原料油层并且发现含有高达11,900ppm的硫含量,即<1.0%脱硫。
D.实施例4
进行此实验来使炭黑原料油(CBFO)脱硫。出于此目的,制备初始硫含量为2.11%的(CBFO-异辛烷)的50%混合物。将约30ml的此溶液与约0.5g纳米结晶LSF催化剂混合。然后将全部混合物置于配备有磁力搅拌器和回流冷凝器的100ml三颈圆底烧瓶中。在水浴中在连续的搅拌下加热系统至约75℃的温度。在混合物达到所述温度之后,使用加料漏斗在15分钟期间内滴加10ml的过氧化氢(30%,Fisher Scientific)。使反应继续进行1小时。反应完成之后,使整个系统冷却并且使其再静置15分钟,以便形成反应混合物的两个单独的层。因此,在氧化之后,两个层是油层(顶部)和水层(底部)。然后过滤上部原料油层并且发现含有高达11,900ppm的硫含量,初始硫含量为21,100ppm,即约44%脱硫。
E.实施例5
进行此实验来使炭黑原料油(CBFO)脱硫。出于此目的,制备初始硫含量为2.14%的(CBFO-异辛烷)的50%混合物。将约30ml的此溶液与约0.5g磺化纳米结晶LSF催化剂混合。催化剂的磺化通过浸渍在硫酸溶液(30%)中24小时的时期来进行。倾析出过量的酸,并且在100℃下在烘箱中干燥催化剂。此外,在600℃下锻烧经干燥的催化剂2小时,从而产生磺化的LSF催化剂。然后将全部混合物置于配备有磁力搅拌器和回流冷凝器的100ml三颈圆底烧瓶中。在水浴中在连续的搅拌下加热系统至约65℃的温度。在混合物达到所述温度之后,使用加料漏斗在15分钟期间内滴加10ml的过氧化氢(30%,FisherScientific)。使反应继续进行1小时。反应完成之后,使整个系统冷却并且使其再静置15分钟,以便形成反应混合物的两个单独的层。因此,在氧化之后,两个层是油层(顶部)和水层(底部)。然后过滤上部原料油层并且在这种情况下还发现含有高达10,900ppm的硫含量,初始硫含量为21,490ppm,即约50%脱硫。
所有这些结果都列入以下表1和2中:
表1
表2
上述实施方案满足如上所概述的本公开的总体目标。然而,本领域技术人员清楚地认识到以上描述仅依据最优选的具体实施方案做出。因此,可在不背离本公开的范围的情况下清楚和容易地做出许多其它变化和修改,这些变化和修改还是有用的改进并且明确地在现有技术之外而不背离本发明的范围,实际上其保持在其很宽的整体范围内,并且其公开的内容将由所附权利要求书相对于现有技术进行限定。
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Claims (21)
1.一种减少在包含硫的组合物中硫的量的方法,所述方法包括以下步骤:
a.提供包含硫的组合物;以及
b.使所述包含硫的组合物与氧化剂和氧化催化剂接触,其中所述氧化催化剂具有式M1 1-xM3 xM2O3,其中M1是稀土元素,其中M2是过渡金属,其中M3是Ca或Sr,并且其中x是0.01至0.80,
从而减少所述包含硫的组合物中硫的量。
2.如权利要求1所述的方法,其中所述包含硫的组合物包括石油。
3.如权利要求1或2所述的方法,其中所述包含硫的组合物是石油。
4.如权利要求1-3中任一项所述的方法,其中所述氧化剂包括H2O2、NO2、N2O3、N2O4、乙酸、叔丁基磷酸氢盐(TBHP)、甲酸、硫酸、硝酸、O2、空气、或臭氧、或其组合。
5.如权利要求1-4中任一项所述的方法,其中所述氧化剂包括H2O2。
6.如权利要求1-5中任一项所述的方法,其中所述稀土元素是La、Pr、Gd、Sm、Nd及Ce。
7.如权利要求1-6中任一项所述的方法,其中所述稀土元素是La。
8.如权利要求1-7中任一项所述的方法,其中所述过渡金属是Fe、Mn、Ni、Co、Mo及Cu。
9.如权利要求1-8中任一项所述的方法,其中所述过渡金属是Fe。
10.如权利要求1-9中任一项所述的方法,其中是Sr。
11.如权利要求1-10中任一项所述的方法,其中x是0.10至0.50。
12.如权利要求1-10中任一项所述的方法,其中x是0.10至0.30。
13.如权利要求1-12中任一项所述的方法,其中所述方法使所述组合物中硫的量减少了至少40%、50%、60%、70%、80%、85%、90%、95%、97%、98%、99%、或99.5%。
14.如权利要求1-13中任一项所述的方法,其中所述氧化催化剂呈纳米结晶形式。
15.如权利要求14所述的方法,其中所述纳米结晶形式的尺寸为5nm至100nm。
16.如权利要求1-15中任一项所述的方法,其中所述接触发生在20℃至150℃的温度下。
17.如权利要求1-16中任一项所述的方法,其中氧化剂的量是每体积所述包含硫的组合物5体积%至300体积%。
18.如权利要求1-17中任一项所述的方法,其中所述氧化催化剂被包含硫酸的溶液浸渍。
19.如权利要求18所述的方法,其中所述氧化催化剂是硫酸盐的M1 1-xSrxM2O3的纳米结晶形式。
20.如权利要求1-19中任一项所述的方法,其中所述氧化催化剂存在于有机溶剂中。
21.一种包含氧化剂和氧化催化剂的组合物,其中所述氧化催化剂具有式M1 1-xSrxM2O3,其中M1是稀土元素,其中M2是过渡金属元素,并且其中x是0.01至0.80。
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