CN101665720A - 利用具有规定组成的硫化催化剂的选择加氢方法 - Google Patents
利用具有规定组成的硫化催化剂的选择加氢方法 Download PDFInfo
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- CN101665720A CN101665720A CN200910170584A CN200910170584A CN101665720A CN 101665720 A CN101665720 A CN 101665720A CN 200910170584 A CN200910170584 A CN 200910170584A CN 200910170584 A CN200910170584 A CN 200910170584A CN 101665720 A CN101665720 A CN 101665720A
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
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- 238000007600 charging Methods 0.000 claims description 16
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- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 239000010953 base metal Substances 0.000 claims description 8
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Classifications
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Abstract
本发明涉及进行结合多不饱和化合物选择加氢成汽油中包含的单不饱和化合物以及通过与不饱和化合物反应使含硫轻化合物增重的方法,所述方法利用负载型催化剂,所述负载型催化剂包含以在载体上沉积的硫化形式使用的至少一种第VIb族金属和至少一种第VIII族非贵金属。催化剂具有规定组成,第VIb族金属与第VIII族金属的优化比率,和优化的每单位催化剂表面积第VIb族元素密度。
Description
技术领域
生产满足新环境标准的汽油需要它们的硫含量实质降低到一般不超过50ppm,优选小于10ppm的值。
也已知可代表汽油池30%至50%的转化汽油,更具体来自催化裂化的那些汽油,具有高单烯烃和硫含量。
因此,汽油中存在的硫多于90%可归于来自催化裂化过程的汽油,以后称为FCC汽油(流化催化裂化)。因此,FCC汽油组成本发明方法所用的优选进料。
更一般本发明的方法适用于任何含一定比例二烯烃并且也可包含数种来自C3和C4馏分的较轻化合物的汽油馏分。
来自裂化装置的汽油一般富含单烯烃和硫,但对于来自催化裂化的汽油也富含一定含量二烯烃,二烯烃含量可以为1%重量至5%重量。二烯烃为不稳定化合物,这种化合物容易聚合,并且一般必须在此类汽油的任何处理之前除去,例如,可进行加氢脱硫处理,以满足与汽油中硫含量相关的技术要求。然而,为了限制单烯烃的加氢,限制氢的消耗以及汽油的辛烷损失,此加氢必须选择性应用到二烯烃。另外,如专利申请EP-01077247 A1所述,有利通过增重使饱和的含硫轻化合物转化;在脱硫步骤之前,由于这意味主要由含5个碳原子的单烯烃组成的经脱硫的汽油馏分可通过简单蒸馏在没有辛烷损失下制备,这些为具有低于噻吩沸点的含硫化合物,如甲硫醇、乙硫醇、甲硫醚。
另外,在要处理的进料中存在的二烯化合物不稳定,并且倾向于聚合成胶。这种成胶导致选择加氢催化剂逐渐去活化,或者逐渐阻塞反应器。因此,对于工业应用,重要的是使用限制聚合物生成的催化剂,即,具有低酸性或具有最佳化孔隙率的催化剂,以便为了保证最大催化剂循环时间,促进进料中的烃连续浸提聚合物或胶前体。
本发明涉及在一种方法中使用一种新催化剂,所述方法允许结合多不饱和化合物(更具体为二烯烃)加氢和含硫轻化合物(更具体为硫醇)增重。
本发明的一个优点是通过使硫醇增重促进除硫,以便能够将它们更容易地分离,并因此在后续加氢脱硫步骤将它们除去。
本发明的另一个优点是制备具有高辛烷值的汽油。
本发明的第三个优点在于调节催化剂配方设计,以提供高去二烯活性、对聚合物生成的较佳催化剂稳定性、对二烯烃加氢的优良选择性以及对硫醇和其他含硫轻化合物转化的优良活性。
背景技术
在文献中描述了一些催化设计或方法,这些设计或方法能够允许在一个或两个步骤中将二烯烃选择加氢成单烯烃,或通过增重使硫醇转化,或者进行这两种类型反应。
使用含至少一种贵金属的催化剂已知。因此,一些专利提出含钯的选择加氢催化剂。钯以加氢活性而为人所知,并广泛用于选择加氢方法。然而,钯对毒物敏感,特别是对硫的存在敏感。本发明与此类催化剂的不同之处在于,本发明的催化剂不含钯,更一般不含贵金属。
欧洲专利申请EP-06 85552 B1提出基于含0.1%重量至1%重量钯的催化剂使二烯烃加氢和使催化裂化汽油中的硫醇含量减少的方法。
US-6 469 223涉及一种在基于氧化铝的载体上包含镍和钼的催化剂上使二烯烃选择加氢的方法。所述方法的特征在于以氧化物形式使用金属镍和钼。本发明与此现有技术的不同之处在于,以金属硫化物而非氧化物的形式使用金属。
以下专利和专利申请提出通过硫醚化反应使硫醇增重并任选使二烯烃选择加氢的解决方法。
专利US-5 807 477提出一种方法,此方法在第一步骤通过含第VIII族金属(优选镍的氧化物形式)的催化剂加成到二烯烃使硫醇转化成硫化物,然后在第二步骤在氢存在下在反应蒸馏柱中使二烯烃选择加氢。本发明与此专利的不同之处在于,选择加氢步骤和使含硫化合物增重的步骤结合在以硫化形式使用的相同催化剂上进行。
专利US-5 851 383描述一种C3-C5馏分选择加氢和硫醚化的方法,其特征在于蒸馏装置包含可单独回收轻化合物和硫醚的两个分馏区域。所述催化剂为基于第VIII族金属的催化剂或含金属的树脂。含15%至35%镍的催化剂是优选的。本发明催化剂与此专利的不同之处在于,加氢金属为第VIb族金属,并且镍含量小于15%重量。
专利申请US-2007/7173674提出一种使用催化剂的选择加氢方法,所述催化剂包含在氧化铝上负载的至少一种第VIb族金属和第VIII族金属。第VIII族金属和第VIb族金属的摩尔比为0.2至0.5摩尔/摩尔。本发明催化剂与此现有技术催化剂的不同之处在于第VIII族金属和第VIb族金属摩尔比为0.6至3摩尔/摩尔,和每单位催化剂表面积的第VIb族元素密度。
鉴于文献所述方法,本发明提出一种利用具有规定组成的催化剂的方法,所述催化剂可用于进行结合多不饱和化合物(更具体为二烯烃)加氢和含硫轻化合物(更具体为硫醇)增重。
发明内容
本发明描述一种使多不饱和化合物(更具体为二烯烃)选择加氢的方法,所述选择加氢可结合进行饱和含硫轻化合物(更具体为硫醇)的增重,所述方法利用包含在多孔载体上沉积的至少一种第VIb族金属和至少一种第VIII族非贵金属的催化剂,其中:
第VIb族元素氧化物以重量计的量为4%重量至20%重量;
第VIII族元素氧化物以重量计的量小于15%重量;
所述催化剂的组成金属的硫化度为至少60%;
第VIII族非贵金属和第VIb族金属的摩尔比为0.6至3摩尔/摩尔;
每单位催化剂表面积的第VIb族元素密度严格小于10-3克第VIb族元素氧化物/m2催化剂。
所述方法由使待处理汽油和氢组成的混合物通过催化剂组成。
氢一般以略微过量引入,相对于使二烯烃加氢所需的化学计量(1摩尔氢/摩尔二烯烃)每摩尔最多5摩尔。
由汽油和氢组成的混合物在0.5至5MPa压力和80℃至220℃温度与催化剂接触,液体时空速(LHSV)为1h-1至10h-1,液体时空速以升进料/升催化剂小时(l/l.h)表示。
具体实施方式
本发明涉及一种处理汽油的方法,所述汽油包含任何类型的化学族,特别为二烯烃、单烯烃及硫醇和轻硫化物形式的含硫化合物。本发明特别用于转化汽油的转变,特别为来自催化裂化、流化催化裂化(FCC)、焦化(cokefaction)法、减粘裂化法或热解法的汽油。本发明适用的进料具有0℃至280℃,更精确30℃至250℃的沸点。进料也可包含含3或4个碳原子的烃。
例如,由催化裂化装置(FCC)得到的汽油包含平均0.5%重量至5%重量二烯烃、20%重量至50%重量单烯烃、10ppm至0.5%重量硫,一般有至少300ppm硫醇。硫醇一般富集于汽油的轻馏分中,更准确富集于沸点小于120℃的馏分中。
本发明方法所述的汽油处理主要由以下步骤组成:
使二烯烃选择加氢成单烯烃;
使饱和含硫轻化合物(主要为硫醇)通过与单烯烃反应转化成硫化物或较重的硫醇。
以下通过1,3-戊二烯的转化说明二烯烃加氢成单烯烃的反应,1,3-戊二烯为一种不稳定化合物,可容易地加氢成戊-2-烯。然而,次级单烯烃加氢反应应受到限制,因为如以下实例所见,它们导致正戊烷的生成:
要转化的含硫化合物主要为硫醇和硫化物。主要硫醇转化反应由单烯烃通过硫醇的硫醚化反应组成。以下通过丙-2-硫醇在戊-2-烯上加成为丙基·戊基硫醚说明此反应:
在氢存在下,含硫化合物转化也可通过生成H2S中间体,然后中间体加到进料中存在的不饱和化合物来进行。然而,此途径在优选的反应条件下为次要途径。
除了硫醇外,可转化和增重的化合物为硫化物,主要为甲硫醚、甲基·乙基硫醚和乙硫醚、CS2、COS、四氢噻吩和甲基四氢噻吩。
在某些情况下,可观察到含氮轻化合物增重反应,主要为腈、吡咯及其衍生物。
本发明所述方法由要作为与氢流的混合物处理的进料与催化剂接触组成,所述催化剂包含在多孔载体上沉积的至少一种第VIb族金属(元素周期表新符号表示法中的第6族:Handbook of Chemistry andPhysics(化学和物理手册),第76版,1995-1996)和所述分类的至少一种第VIII族金属(第8、9和10族)。
具体地讲,已发现在催化剂具有以下特征时催化剂性能改善:
氧化物形式的第VIb族元素氧化物以重量计的量为4%重量至20%重量,优选5%重量至15%重量。第VIb族金属优选选自钼和钨。更优选第VIb族金属为钼。
催化剂也包含优选选自镍、钴和铁的第VIII族非贵金属。更优选第VIII族非贵金属由镍组成。以氧化物形式表示的第VIII族非贵金属的量小于15%重量,优选1%重量至10%重量。
第VIII族非贵金属和第VIb族金属的摩尔比为0.6至3摩尔/摩尔,优选1至2.5摩尔/摩尔。
Ni/Mo摩尔比超过3并且钼含量大于4%重量,溶解物质制备浸渍溶液很难。
每单位催化剂表面积的钼密度严格小于10-3克MoO3/m2催化剂,优选严格小于7x10-4克MoO3/m2催化剂。
优选使用由汞孔隙率法测定大于0.3cm3/g,优选大于0.4cm3/g并且小于1.4cm3/g总孔体积的催化剂。汞孔隙率根据美国标准ASTMD4284-92用购自Micrometrics的Autopore III型以140°湿润角测定。催化剂的比表面积优选小于300m2/g。优选本发明的催化剂不含碱金属,也不含碱土金属。
催化剂载体优选为选自氧化铝、铝酸镍、二氧化硅、碳化硅和这些氧化物的混合物的多孔金属氧化物。优选使用氧化铝,更优选使用纯氧化铝。优选所用载体具有由汞孔隙率法测定0.4至1.4cm3/g,优选0.5至1.3cm3/g的总孔体积。载体的比表面积优选小于350m2/g。
在一种变化中,载体由立方γ氧化铝或由δ氧化铝组成。
在本发明的一个优选的实施方案中,所用催化剂包含1%重量至15%重量含量NiO形式的氧化镍,大于5%重量含量MoO3形式的氧化钼,镍/钼摩尔比为1至2.5,金属沉积于纯氧化铝载体上,组成催化剂的金属的硫化度大于80%。
本发明的催化剂可用本领域技术人员已知的任何技术制备,具体通过使第VIII族和第VIb族元素浸渍于选择的载体上。例如,用本领域的技术人员已知的方式,作为干浸渍进行浸渍,其中以能够尽可能精确填充载体孔隙的可溶于所选择溶剂(例如软化水)的盐的形式精确引入一定量所需元素。优选将已用溶液填充的载体干燥。优选的载体为氧化铝,氧化铝可用本领域技术人员已知的任何类型前体和形成工具制备。
在引入第VIII族和第VIb族元素并任选形成催化剂后,经过活化处理。此处理一般旨在使元素的分子前体转化成氧化物相。在此情况下,这是一种氧化处理,但也可进行催化剂的简单干燥。在氧化处理(也称为煅烧)的情况下,这一般在空气或稀释的氧中进行,处理温度一般为200℃至550℃,优选300℃至500℃。用于催化剂制备方法的第VIb族和第VIII族金属的盐的实例为硝酸钴、硝酸镍、七钼酸铵和偏钨酸铵。也可使用本领域技术人员已知的具有足够溶解性并且可在活化处理期间分解的任何其他盐。
煅烧后,在载体上沉积的金属为氧化物形式。在镍和钼的情况下,金属主要为MoO3和NiO的形式。在与要处理的进料接触前,催化剂经过硫化步骤。硫化优选在硫还原介质中进行,即在H2S和氢存在下,以使金属氧化物转化成硫化物,如MoS2或Ni3S2。通过将含H2S和氢的流或在催化剂和氢存在下能够分解成H2S的含硫化合物注入到催化剂上,可进行硫化。多硫化物,如二甲基二硫醚,为常规用于使催化剂硫化的H2S前体。调节温度,以使H2S与金属氧化物反应,生成金属硫化物。此硫化可在200℃至600℃温度,更优选300℃至500℃加氢脱硫反应器原位或异位(反应器内或外)进行。
为了为活性,金属必须实质上硫化。在研究的催化剂中存在的硫(S)和一种元素的摩尔比为相当于元素全部硫化的理论摩尔比的至少60%时,认为所述元素被实质上硫化:
(S/元素)催化剂≥0.6x(S/元素)理论
其中:
(S/元素)催化剂为催化剂中存在的硫(S)和元素的摩尔比;
(S/元素)理论为相当于元素全部硫化成硫化物的硫和元素的摩尔比。
此理论摩尔比作为研究的元素的函数变化:
(S/Fe)理论=1
(S/CO)理论=8/9
(S/Ni)理论=2/3
(S/Mo)理论=2/1
(S/W)理论=2/1
对于包含多种金属的催化剂,催化剂上存在的S和元素组的摩尔比也必须至少等于相当于每种元素全部硫化成硫化物的理论摩尔比的60%,用每种元素的相对摩尔分数按比例进行计算。
例如,对于包含0.7和0.3相应摩尔分数钼和镍的催化剂,最小摩尔比(S/Mo+Ni)由以下关系给出:
(S/Mo+Ni)催化剂=0.6x{(0.7x2)+(0.3x(2/3)}
金属的硫化度大于80%非常优选。
硫化对氧化物形式的金属进行,不用进行预先金属还原步骤。实际上已知硫化已还原的金属比硫化氧化物形式的金属更难。
在本发明的选择加氢方法中,在与催化剂接触前使要处理的进料与氢混合。注入的氢的量应使得氢和要氢化的二烯烃的摩尔比大于1(化学计量)且小于10,优选为1至5mol/mol。氢过量太大可导致单烯烃高度加氢,并因此导致汽油的辛烷值降低。一般将全部进料注入反应器入口。然而,在某些情况下,在反应器中放置的两个连续催化剂床之间注入一部分或所有的进料可能有利。如果反应器入口被进料中存在的聚合物、颗粒或胶的沉积物堵塞,此实施可特别允许继续操作反应器。
由汽油和氢组成的混合物在80℃至220℃,优选90℃至200℃温度与催化剂接触,液体时空速(LHSV)为1h-1至10h-1,液体时空速的单位为升进料/升催化剂小时(l/l.h)。调节压力,以使反应混合物在反应器中主要为液体形式。压力为0.5MPa至5MPa,优选1至4MPa。
在以上限定条件下处理的汽油具有减小的二烯烃和硫醇含量。通常,制备的汽油包含小于1%重量二烯烃,优选小于0.5%重量二烯烃。一般使沸点小于噻吩(84℃)沸点的含硫轻化合物大于50%转化。因此,可通过蒸馏从汽油分离轻馏分,并将此馏分直接送到汽油池,而不用辅助处理。汽油的轻馏分一般具有小于120℃,优选小于100℃,更优选小于80℃的终馏点。
这种新催化剂特别适用于专利申请EP-01077247 A1所述的工艺环境。
实施例1:制备催化剂A和B(非本发明)和C、D及E(本发明)
通过干燥浸渍制备催化剂A、B、C、D和E。合成方案由进行七钼酸铵和硝酸镍溶液的干燥浸渍组成,含金属前体的水溶液的体积等于相应于要被浸渍的载体的质量的水吸收体积(可渗入孔隙的水的总体积)。调节溶液中前体的浓度,以使所需重量的金属氧化物沉积到载体上。
使固体在环境温度熟化12小时,然后在120℃干燥12小时。最后将固体在500℃空气流(1 l/g.h)中煅烧两小时。
所用载体为具有0.7ml/g孔体积的氧化铝。制备的催化剂的特性在以下表1中提供。制备的催化剂有不同的活性相含量。
表1:氧化物形式的催化剂A、B、C、D、E、F的特性
催化剂 | A | B | C | D | E |
%重量,MoO3 | 11 | 12 | 9 | 5 | 7 |
%重量,NiO | 0.6 | 1.9 | 4.7 | 5.2 | 5.5 |
Ni/Mo摩尔比 | 0.1 | 0.3 | 1 | 2 | 1.5 |
dMoO3(10-4g/m2催化剂) | 4.5 | 5.0 | 3.8 | 1.9 | 2.9 |
载体的比表面积,m2/g | 280 | 280 | 280 | 280 | 280 |
催化剂C、D和E为本发明的催化剂;相比之下,催化剂A和B具有太小的Ni/Mo比率,因此不为本发明的催化剂。
Ni/Mo摩尔比超过3并且钼含量大于4%重量,溶解物质制备浸渍溶液很难。
催化剂评价
通过在500ml搅拌式高压釜反应器中对模型分子的混合物进行选择加氢试验,评价催化剂A、B、C、D和E的活性。在1 l/g.h催化剂由15%体积H2S组成的H2S/H2混合物下,在硫化工作台大气压力和400℃硫化2克和6克之间的催化剂2小时。对于本发明的所有催化剂,此方案产生大于80%硫化比。然后在没有空气存在下将硫化的催化剂转移到反应器中,并在1.5MPa总压力和160℃温度与250ml模型进料接触。在试验期间通过加入氢使压力保持恒定。
活性试验所用的进料具有以下组成:正庚烷中甲基-3-噻吩形式的1000ppm重量硫、丙-2-硫醇形式的100ppm重量硫、己烯-1形式的10%重量烯烃。
试验的时间t=0相当于使催化剂与进料接触。试验时间固定在45分钟,得到的液体流出物的气体色谱分析允许评价不同催化剂使异戊二烯加氢(生成甲基丁烯)、使己烯-1加氢(生成正己烷)和轻硫醇增重(转化丙-2-硫醇)的活性。
相对于对各反应得到的每克催化剂归一化速率常数限定各反应的催化剂活性。通过对各反应假定一级计算速率常数。
A(X)=k(X)/m
其中:
A(X):催化剂对反应X的活性,分钟-1/克催化剂;
k:研究的反应的速率常数,分钟-1,根据以下公式计算:
k(X)=(1/45)*ln(100/(100-conv(X)))
其中:
45:试验时间,分钟;
conv(X):化合物X的转化率;X=异戊二烯或丙-2-硫醇或己烷-1;
m:试验中使用的催化剂(氧化物形式)的质量;
X:研究的反应;
X=异戊二烯:异戊二烯的加氢;
X=己烯-1:己烯-1的加氢;
X=丙-2-硫醇:丙-2-硫醇的转化。
催化剂对异戊二烯加氢的选择性等于催化剂在异戊二烯和己烯-1加氢中活度的比率:
A(异戊二烯)/A(己烯-1).
对不同催化剂得到的结果显示于以下表2中。
表2:模型分子试验中催化剂的性能
催化剂 | A | B | C | D | E |
A(异戊二烯)*103 | 6.1 | 8.3 | 25.2 | 28.3 | 23 |
A(己烯-1)*103 | 0.23 | 0.26 | 0.25 | 0.26 | 0.23 |
A(异戊二烯)/A(己烯-1) | 27 | 32 | 102 | 109 | 98 |
与非本发明的催化剂A和B相比,对异戊二烯加氢而不使己-1-烯显著加氢而言,本发明的催化剂C、D和E具有高活性。
实施例2:Mo表面密度的影响
在本实施例中,用实施例1所述的操作方案制备催化剂G和H。
表3:氧化物形式的催化剂G和H的特性
催化剂 | G | H |
%重量,MoO3 | 12 | 8 |
%重量,NiO | 8 | 8 |
Ni/Mo摩尔比 | 1.3 | 1.9 |
dMoO3(10-4g/m2催化剂) | 11.5 | 7.2 |
载体的比表面积,m2/g | 130 | 130 |
催化剂G和H在实施例1所述的模型分子试验中评价。
表4:模型分子试验中催化剂G和H的性能
催化剂 | G | H |
A(异戊二烯)*103 | 6.9 | 13.6 |
A(己烯-1)*103 | 0.14 | 0.13 |
A(异戊二烯)/A(己烯-1) | 48 | 104 |
与本发明的催化剂H相比,非本发明的催化剂G(dMoO3>10-3g/m2催化剂)显示不足的异戊二烯加氢活性。
Claims (17)
1.一种使多不饱和化合物选择加氢成单不饱和化合物的方法,所述选择加氢可与饱和含硫轻化合物的增重结合进行,所述饱和含硫轻化合物的增重通过饱和含硫轻化合物与汽油中所含的所述不饱和化合物反应进行,所述方法利用包含在载体上沉积的至少一种第VIb族金属和至少一种第VIII族非贵金属的催化剂,其中:
第VIb族元素氧化物以重量计的量为4%重量至20%重量;
第VIII族元素氧化物以重量计的量小于15%重量;
所述催化剂的组成金属的硫化度为至少60%;
第VIII族非贵金属和第VIb族金属的摩尔比为0.6至3摩尔/摩尔;
每单位催化剂表面积的第VIb族元素密度严格小于10-3克第VIb族元素氧化物/m2催化剂。
2.权利要求1的方法,其中催化剂包含选自钼和钨的第VIb族金属。
3.权利要求2的方法,其中第VIb族金属为钼。
4.权利要求1的方法,其中催化剂包含选自镍、钴和铁的第VIII族非贵金属。
5.权利要求4的方法,其中第VIII族非贵金属为镍。
6.前述权利要求中任一项的方法,其中催化剂包含1%重量至10%重量含量的第VIII族元素的氧化物。
7.权利要求1的方法,其中所述催化剂的组成金属的硫化度大于80%。
8.权利要求1的方法,其中第VIII族非贵金属和第VIb族金属的摩尔比为1至2摩尔/摩尔。
9.前述权利要求中任一项的方法,其中催化剂具有大于0.3cm3/g的总孔体积。
10.权利要求9的方法,其中催化剂具有0.4cm3/g至1.4cm3/g的总孔体积。
11.前述权利要求中任一项的方法,其中催化剂的比表面积小于300m2/g。
12.权利要求1的方法,其中催化剂载体为选自氧化铝、二氧化硅、碳化硅和所述氧化物的混合物的多孔金属氧化物。
13.权利要求12的方法,其中催化剂载体由纯氧化铝组成。
14.权利要求12或13的方法,其中载体由立方γ氧化铝或δ氧化铝组成。
15.权利要求12至14中任一项的方法,其中催化剂载体具有0.4至1.4cm3/g的孔体积。
16.权利要求15的方法,其中催化剂载体具有0.5至1.3cm3/g的孔体积。
17.前述权利要求中任一项的选择加氢方法,其中进料以1h-1至10h-1液体时空速在80℃至220℃温度和0.5至5MPa压力与催化剂接触。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103146420A (zh) * | 2011-12-06 | 2013-06-12 | 中国石油天然气股份有限公司 | 一种汽油加氢处理的方法 |
CN103361110A (zh) * | 2012-03-29 | 2013-10-23 | Ifp新能源公司 | 汽油的选择性氢化方法 |
WO2014047753A1 (zh) * | 2012-09-28 | 2014-04-03 | 中国石油天然气股份有限公司 | 一种使不饱和化合物选择加氢的方法 |
CN104755595A (zh) * | 2012-10-29 | 2015-07-01 | Ifp新能源公司 | 制备具有低硫含量的汽油的方法 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2986799B1 (fr) | 2012-02-15 | 2015-02-06 | IFP Energies Nouvelles | Procede de conversion d'une charge lourde, mettant en oeuvre une unite de craquage catalytique et une etape d'hydrogenation selective de l'essence issue du craquage catalytique |
FR2993569B1 (fr) * | 2012-07-17 | 2015-12-04 | IFP Energies Nouvelles | Procede de desulfuration d'une essence |
FR3014896B1 (fr) | 2013-12-18 | 2018-07-27 | IFP Energies Nouvelles | Procede d'hydrodesulfuration de coupes d'hydrocarbures |
FR3030563B1 (fr) * | 2014-12-18 | 2018-06-29 | IFP Energies Nouvelles | Procede d'adoucissement en composes du type sulfure d'une essence olefinique |
FR3035117B1 (fr) | 2015-04-15 | 2019-04-19 | IFP Energies Nouvelles | Procede d'adoucissement en composes du type sulfure d'une essence olefinique |
US9828093B2 (en) * | 2015-05-27 | 2017-11-28 | First Principles, Inc. | System for recharging remotely controlled aerial vehicle, charging station and rechargeable remotely controlled aerial vehicle, and method of use thereof |
US9714012B1 (en) | 2016-01-22 | 2017-07-25 | International Business Machines Corporation | Power source element replacement during vehicle operation |
FR3049955B1 (fr) | 2016-04-08 | 2018-04-06 | IFP Energies Nouvelles | Procede de traitement d'une essence |
FR3057578B1 (fr) | 2016-10-19 | 2018-11-16 | IFP Energies Nouvelles | Procede d'hydrodesulfuration d'une essence olefinique. |
FR3109897B1 (fr) | 2020-05-07 | 2023-11-24 | Ifp Energies Now | Catalyseur d’hydrogénation sélective comprenant un support spécifique en partie sous forme aluminate |
FR3109899B1 (fr) | 2020-05-07 | 2023-11-24 | Ifp Energies Now | Catalyseur d’hydrogénation comprenant un support et un ratio NiMo spécifique |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1314288A (en) * | 1970-12-16 | 1973-04-18 | Inst Francais Du Petrole | Catalyst its preparation and its use in the hydrogenation of unsaturated hydrocarbons |
CN1342102A (zh) * | 1999-01-15 | 2002-03-27 | 阿克佐诺贝尔公司 | 新型混合金属催化剂、利用共沉淀的其制备及其用途 |
CN101024779A (zh) * | 2005-12-22 | 2007-08-29 | 法国石油公司 | 使用硫化催化剂的选择性氢化方法 |
CN101214455A (zh) * | 2007-12-27 | 2008-07-09 | 长沙矿冶研究院 | 一种负载型纳米加氢催化剂的制备方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2556235A1 (fr) * | 1983-12-09 | 1985-06-14 | Pro Catalyse | Procede de fabrication d'un catalyseur a base d'alumine |
FR2720754B1 (fr) | 1994-06-01 | 1996-07-26 | Inst Francais Du Petrole | Procédé et installation pour le traitement par hydrogénation sélective d'une essence de craquage catalytique. |
ZA956008B (en) * | 1994-07-21 | 1996-02-22 | Shell Int Research | Catalyst use thereof and process for preparation thereof |
US5807477A (en) | 1996-09-23 | 1998-09-15 | Catalytic Distillation Technologies | Process for the treatment of light naphtha hydrocarbon streams |
US5851383A (en) * | 1997-01-09 | 1998-12-22 | Uop Llc | Process for thioetherification and selective hydrogenation of light olefins |
FR2797639B1 (fr) | 1999-08-19 | 2001-09-21 | Inst Francais Du Petrole | Procede de production d'essences a faible teneur en soufre |
US6469223B2 (en) | 2000-01-04 | 2002-10-22 | Fina Technology, Inc. | Selective hydrogenation of dienes |
FR2895415B1 (fr) * | 2005-12-22 | 2011-07-15 | Inst Francais Du Petrole | Procede d'hydrogenation selective mettant en oeuvre un catalyseur presentant un support specifique |
FR2895414B1 (fr) * | 2005-12-22 | 2011-07-29 | Inst Francais Du Petrole | Procede d'hydrogenation selective mettant en oeuvre un catalyseur presentant une porosite controlee |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1314288A (en) * | 1970-12-16 | 1973-04-18 | Inst Francais Du Petrole | Catalyst its preparation and its use in the hydrogenation of unsaturated hydrocarbons |
CN1342102A (zh) * | 1999-01-15 | 2002-03-27 | 阿克佐诺贝尔公司 | 新型混合金属催化剂、利用共沉淀的其制备及其用途 |
CN101024779A (zh) * | 2005-12-22 | 2007-08-29 | 法国石油公司 | 使用硫化催化剂的选择性氢化方法 |
CN101214455A (zh) * | 2007-12-27 | 2008-07-09 | 长沙矿冶研究院 | 一种负载型纳米加氢催化剂的制备方法 |
Cited By (13)
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CN103146420B (zh) * | 2011-12-06 | 2015-11-18 | 中国石油天然气股份有限公司 | 一种汽油加氢处理的方法 |
CN103145516A (zh) * | 2011-12-06 | 2013-06-12 | 中国石油天然气股份有限公司 | 一种使不饱和化合物选择加氢的方法 |
CN103146429A (zh) * | 2011-12-06 | 2013-06-12 | 中国石油天然气股份有限公司 | 一种液化气加氢处理的方法 |
CN103146420A (zh) * | 2011-12-06 | 2013-06-12 | 中国石油天然气股份有限公司 | 一种汽油加氢处理的方法 |
US9611435B2 (en) | 2011-12-06 | 2017-04-04 | Petrochina Company Limited | Method for selective hydrogenation of unsaturated compound |
CN103145516B (zh) * | 2011-12-06 | 2015-01-21 | 中国石油天然气股份有限公司 | 一种使不饱和化合物选择加氢的方法 |
US9422486B2 (en) | 2011-12-06 | 2016-08-23 | Petrochina Company Limited | Selective hydrogenation catalyst for unsaturated compound |
CN103146429B (zh) * | 2011-12-06 | 2015-08-19 | 中国石油天然气股份有限公司 | 一种液化气加氢处理的方法 |
CN103361110A (zh) * | 2012-03-29 | 2013-10-23 | Ifp新能源公司 | 汽油的选择性氢化方法 |
CN103361110B (zh) * | 2012-03-29 | 2017-05-17 | Ifp新能源公司 | 汽油的选择性氢化方法 |
WO2014047753A1 (zh) * | 2012-09-28 | 2014-04-03 | 中国石油天然气股份有限公司 | 一种使不饱和化合物选择加氢的方法 |
CN104755595A (zh) * | 2012-10-29 | 2015-07-01 | Ifp新能源公司 | 制备具有低硫含量的汽油的方法 |
CN104755595B (zh) * | 2012-10-29 | 2018-10-23 | Ifp 新能源公司 | 制备具有低硫含量的汽油的方法 |
Also Published As
Publication number | Publication date |
---|---|
DK2161076T3 (en) | 2018-08-06 |
TWI492788B (zh) | 2015-07-21 |
EP2161076B1 (fr) | 2018-04-25 |
JP2010090366A (ja) | 2010-04-22 |
JP5563259B2 (ja) | 2014-07-30 |
TW201016318A (en) | 2010-05-01 |
KR101668481B1 (ko) | 2016-10-21 |
EP2161076A1 (fr) | 2010-03-10 |
SG159489A1 (en) | 2010-03-30 |
FR2935389A1 (fr) | 2010-03-05 |
BRPI0902949A2 (pt) | 2010-06-01 |
KR20100028502A (ko) | 2010-03-12 |
CN106867575A (zh) | 2017-06-20 |
BRPI0902949B1 (pt) | 2022-09-20 |
FR2935389B1 (fr) | 2012-05-11 |
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