CN105682800A - 用于烯烃复分解反应的催化剂和方法 - Google Patents
用于烯烃复分解反应的催化剂和方法 Download PDFInfo
- Publication number
- CN105682800A CN105682800A CN201480056373.9A CN201480056373A CN105682800A CN 105682800 A CN105682800 A CN 105682800A CN 201480056373 A CN201480056373 A CN 201480056373A CN 105682800 A CN105682800 A CN 105682800A
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- Prior art keywords
- catalyst
- mgo
- preferable
- magnesian
- isomerization
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- 239000000395 magnesium oxide Substances 0.000 claims abstract description 118
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 102
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 99
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 47
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- 238000005649 metathesis reaction Methods 0.000 claims description 44
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- 239000012298 atmosphere Substances 0.000 claims description 17
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 17
- 239000001095 magnesium carbonate Substances 0.000 claims description 17
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 17
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 17
- 239000000347 magnesium hydroxide Substances 0.000 claims description 17
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 17
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- 239000002243 precursor Substances 0.000 claims description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 6
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- 230000000704 physical effect Effects 0.000 abstract description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- 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
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- 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
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
本发明涉及具有限定物理性质的氧化镁(MgO)作为催化剂用于烯烃异构化的用途、包含所述MgO的用于烯烃复分解的催化剂以及使用所述催化剂进行烯烃复分解的方法。
Description
本发明涉及根据权利要求1的氧化镁作为用于烯烃异构化的催化剂的用途,根据权利要求9的用于烯烃转化的催化剂以及根据权利要求15的用于获得烯烃的方法。
说明
丁烯是C4H8单烯烃异构体如1-丁烯、顺-2-丁烯、反-2-丁烯和异丁烯(2-甲基丙烯)。如果没有特别提及,则在本发明的框架内,顺-2-丁烯、反-2-丁烯也称作2-丁烯。顺-2-丁烯、反-2-丁烯和1-丁烯的总和表示为正丁烯。丁烯在商业上几乎总是作为石油精炼厂中通过裂解工艺或通过催化乙烯二聚反应的副产品产生。丁烯可以用于多种目的,如用于制造聚合物和其他化学品如杀虫剂、抗氧化剂、粘合剂、密封剂或弹性体。
在过去的几十年中,使用2-丁烯来生产丙烯已具有工业重要性。使用2-丁烯作为起始材料合成丙烯是基于复分解反应。由此,根据以下总反应方案,在乙烯的存在下2-丁烯转化为丙烯:
该反应通常在包含元素周期表(PSE)第6族或第7族金属氧化物的催化剂存在下发生。用于烯烃复分解的催化剂的典型活性组分为负载在二氧化硅上的氧化钨(US3,365,513)、负载在氧化铝或二氧化硅-氧化铝上的氧化铼或氧化钼(US4,547,617;US6,281,402)。
已描述了复分解催化剂的各种修改和改进。已证明复分解催化剂与用于使1-丁烯中双键转移为2-丁烯的异构化催化剂的物理混合提高了总丙烯生产率(US3,865,751;US3,915,897;US4,575,575)。
典型的双键异构化催化剂包括可以与复分解催化剂共混的碱性金属氧化物,例如氧化镁或氧化钙。使用氧化镁(MgO)作为助催化剂使反应温度能够从约400℃(对于纯的二氧化硅负载的氧化钨(WO3/SiO2))降低至250℃至300℃。氧化镁与WO3/SiO2的重量比在0.1至20的范围内。氧化镁的功能是使1-丁烯异构化为2-丁烯和/或使2-丁烯异构化为1-丁烯(该异构化是平衡反应)。
氧化镁除了其充当异构化催化剂的能力之外,还已知其从烯烃进料中去除或消除对复分解催化剂有害的痕量污染物的能力,特别是在用作“防护床”时(J.Mol.Cat.,1985,28:117-131)。氧化镁可以例如布置在包含复分解催化剂和异构化催化剂的组合物顶部(US2010/0056839A1,US2010/167911A1)。此处,最佳的催化剂性能与防护预床去除毒物的功能和1-丁烯至2-丁烯和/或2-丁烯至1-丁烯的异构化相结合。当应用该方法时,工业复分解反应器通常填充有作为催化剂主床的MgO与WO3/SiO2的混合物以及在主床上游的作为预床的MgO。
必须使MgO活化以实现期望性质。已描述了不同的活化过程。根据US4,071,471,氧化镁通过在含氧气体的流动流中在300℃至约550℃下加热约1小时至30小时来活化。另一种活化方法包括在约250℃至650℃下用一氧化碳或氢处理氧化镁约0.1小时至4小时(US3,546,313)。还可以在惰性气流中在最高至600℃的温度范围内加热根据以上所述方法之一预活化的预活化催化剂(ChemicalReviews,95(3),(1995)537-558)。
氧化镁可以由多种原料产生,例如,通过煅烧碳酸镁或氢氧化镁或者通过用石灰处理氯化镁随后加热。已知的是由可以以天然存在的水镁石矿物的形式得到的Mg(OH)2(氢氧化镁)制备MgO。可在升高的温度下在空气或真空中煅烧Mg(OH)2,其中只有通过在真空中煅烧Mg(OH)2获得的MgO显示出对1-丁烯的任何异构化活性(ProceedingsoftheInternationalCongressonCatalysis1973,1,233-242)。还应指出,特别是由于其高度扰动的晶格结构,Mg(OH)2可包含不确定量的碳酸盐。
根据BulletinoftheChemicalSocietyofJapan(49(4),(1976)969-72),通过在真空中在不同温度下加热Mg(OH)2或(MgCO3)4·Mg(OH)2·5H2O(碱式碳酸镁)来获得MgO,以研究前体材料和处理参数对MgO的表面积以及其结构性质和在用甲醇使苯酚烷基化和丁烯异构化中的催化性质的影响。证明前体不影响MgO在1-丁烯异构化中的活性和选择性(顺-2-丁烯与反-2-丁烯的比例)。然而,顺-2-丁烯异构化的活性和选择性,就反-2-丁烯与1-丁烯比例而言,在由Mg(OH)2制备MgO的情况中是在由(MgCO3)4·Mg(OH)2·5H2O制备MgO的情况中的约4倍。由(MgCO3)4·Mg(OH)2·5H2O制备的MgO的低活性被认为是由所述MgO的较低的稳定性(由于不规则排列的结构)引起的。还认为所述MgO的不规则结构导致了所述氧化镁的表面积随着上升的真空温度而减小。为了将通过在真空中加热而由(MgCO3)4·Mg(OH)2·5H2O获得的MgO用作适合的异构化催化剂,需要进行稳定化;例如通过添加如US2011/0021858A1中所述的适合的稳定剂。此处,将特定的稳定剂如二氧化硅或硅酸钠添加到MgO中以增加MgO的表面积稳定性。
催化剂性能的优化是多个技术工艺中普遍关注的。特别地,进料组分转化率、产物选择性和产率的增加对工艺经济性具有强烈影响。
催化剂性能很大程度上取决于制备过程。异构化催化剂(例如,MgO)的活化过程的一般参数是公知的(参见现有技术),但是在用于通过乙烯和2-丁烯的交叉复分解生产丙烯的催化剂制备的情况中,关于活化参数、晶体结构和催化性质之间的关系还一无所知。
因此,本发明的目的是提供用于烯烃复分解的异构化催化剂,其与目前已知的化合物相比表现出改善的活性和选择性。
本发明的此目的和其他目的通过具有权利要求特征的用于烯烃转化的氧化镁和催化剂来实现。
因此,使用氧化镁(MgO)作为用于烯烃异构化,特别是1-丁烯和/或2-丁烯异构化的催化剂,其中所述氧化镁的特征在于特定的物理性质。目前使用的MgO的比表面积BET为80m2/g至300m2/g;晶粒尺寸为5nm至25nm;总孔体积为0.1cm3/g至0.5cm3/g;并且最大孔径分布为5nm至15nm。此外,目前用作异构化催化剂的氧化镁不含任何结构稳定剂。
这样的MgO优选地通过在含氧气体的存在下,特别是在空气的存在下(如在空气流中)对化学式为(MgCO3)4·Mg(OH)2·5H2O的碱式碳酸镁进行煅烧获得。因此,本发明的MgO由具有确定量碳酸盐的前体化合物获得。
如以下实施例中所示,与由Mg(OH)2常规制备的MgO相比,当在烯烃转化中(特别是在乙烯与2-丁烯的交叉复分解中)与复分解催化剂组合时,本发明的氧化镁出人意料地显示出增加的活性,特别是异构化活性和运转时间活性。因此,由于优化的MgO性质,提供了改善的复分解催化剂,其具有更好的运转时间活性(更低的失活率)和改善的运转时间异构化性质。
由于到目前为止通过在空气中煅烧而由(MgCO3)4·Mg(OH)2·5H2O制备的MgO对1-丁烯没有显示出任何异构化活性(Proc.Int.Congr.Catal,(1972),233-243);只有通过在真空中煅烧(MgCO3)4·Mg(OH)2·5H2O而获得的MgO显示出任何异构化活性,所以活性和稳定性的增加是没有预料到的。认为在空气中由(MgCO3)4·Mg(OH)2·5H2O获得的MgO无活性是由在空气中煅烧时少量水和二氧化碳覆盖MgO的活性位点引起的。
在一个实施方案中,本发明的MgO的比表面积BET为80m2/g至150m2/g,优选地100m2/g至120m2/g。典型的BET为约105m2/g至115m2/g。
在另一个实施方案中,本发明的MgO的晶粒尺寸为10nm至20nm,优选地10nm至15nm,其中典型的晶粒尺寸为13nm至14nm。
在另一个实施方案中,本发明的MgO的总孔体积为0.2cm3/g至0.4cm3/g,优选地0.3cm3/g至0.4cm3/g,其中典型的值为0.35cm3/g至0.36cm3/g。
此外优选的是,本发明的MgO的孔径分布最大值为7nm至10nm,优选地8nm至9nm。
如果本发明的MgO通过在含氧气体中在300℃至700℃,优选地400℃至600℃,最优选地450℃至550℃的温度下煅烧(MgCO3)4·Mg(OH)2·5H2O获得,则是有利的。
如上所述,本发明所用的氧化镁不含任何结构稳定剂,即,在碱式碳酸镁(MgCO3)4·Mg(OH)2·5H2O煅烧成氧化镁之前没有向碱式碳酸镁(MgCO3)4·Mg(OH)2·5H2O中或者在煅烧之后没有向氧化镁中添加另外的外部试剂。结构稳定剂可包含以下元素中的至少一种:Al、Si、Ti、Cr、Mn、Fe、Y、Zr及其组合。典型的结构稳定剂可以呈二氧化硅、氧化铝、MgAlO4或天然粘土中至少一种的粘合剂的形式。这样的结构稳定剂通常可以异构化催化剂的0.04重量%至40重量%的量添加。这样的结构稳定剂的实例为例如US2011/0021858A1中所述的。添加结构稳定剂还可以影响晶体结构,晶体结构进而可以影响氧化镁的性质。
通过省去任何结构稳定剂例如二氧化硅(例如呈水性二氧化硅粘合剂的形式),使用了使出人意料的高稳定性(通过保持大的BET表面)与由此的高反应性结合的氧化镁。鉴于US2011/0021858A1的教导,这是出人意料的,因为此处高度稳定的BET表面仅能通过添加结构稳定剂获得。
如上所述,使用本发明的MgO作为用于烯烃,特别是1-丁烯和/或2-丁烯(顺-2-丁烯或反-2-丁烯)异构化的催化剂。当与适合的复分解催化剂组合时,本发明的MgO的异构化活性及其防护性质是特别普遍的。
因此提供了催化剂(主催化剂床),其特别适合于烯烃转化技术(包括复分解),所述催化剂包含a)含有复分解催化剂的至少一种第一催化剂组分,和b)含有用于双键异构化的催化剂的至少一种第二催化剂组分,其中所述用于双键异构化的催化剂是通过在含氧气体的存在下煅烧式(MgCO3)4·Mg(OH)2·5H2O的碱性碳酸镁而获得的本发明的MgO。第一催化剂和第二催化剂彼此物理混合。
在另一个实施方案中,复分解催化剂包含来自PSE第6族和第7族金属的金属氧化物,特别是氧化钨、氧化钼和/或其前体,其为活性组分并且沉积在至少一种无机载体上。最优选的金属氧化物是氧化钨。
优选地,至少一种无机载体选自包含二氧化硅、氧化铝、二氧化硅-氧化铝或磷酸铝的组。无机载体可以包含至少约0.1重量%且最多至40重量%的活性组分。优选为1重量%至30重量%的量,其中最优选为2重量%至15重量%的量。
复分解催化剂还可包含PSE第I族金属的至少一种氧化物或其前体,例如包含钠或钾的氧化物、氢氧化物、碳酸盐、碳酸氢盐、硝酸盐、乙酸盐或其混合物。尤其优选的是钠和钾的氢氧化物。相对于复分解催化剂,这些改性化合物的量可以为0.01重量%至10重量%,优选地0.1重量%至10重量%。
还可用PSE第1族成员的至少一种氧化物或其前体使复分解催化剂经历预处理。例如,优选地,如果将二氧化硅负载的氧化钨用作复分解催化剂,则用氢氧化钾使其经历预处理。
复分解催化剂的BET表面积为至少>10m2/g,优选地至少>50m2/g,并且最优选地至少≥100m2/g。
复分解催化剂的粒径取决于反应器尺寸。当作为粉末应用在例如实验室规模的反应器中时,复分解催化剂的典型粒径为0.3mm至0.7mm。当用在更大的反应器如工业反应器中时,粒径在1mm至10mm,优选地1mm至8mm,最优选地1mm至5mm的范围中。
然后,本发明的催化剂可以通过使作为双键异构化催化剂的本发明MgO与复分解催化剂混合来制备。催化剂优选地以粉末、粒料或挤出物的形式混合。
异构化催化剂的量优选地超过复分解催化剂的量。然而,用作异构化催化剂的本发明MgO也可以以更少的量使用。在一个实施方案中,催化剂组合物或混合物包含至少一种异构化催化剂组分和至少一种复分解催化剂组分,至少一种异构化催化剂组分和至少一种复分解催化剂组分的重量比为5:1至1:1,优选地重量比为4:1至2:1,最优选地重量比为3:1。重要的是注意异构化催化剂与复分解催化剂的重量比对催化剂性能或活性和产率没有显示出任何影响。
还可以将本发明的MgO另外布置为在复分解催化剂和异构化催化剂的催化剂混合物上游的预床(催化剂预床)。在这种催化剂床配置的情况下,作为预床的本发明MgO可位于紧邻复分解催化剂和异构化催化剂的混合物的主催化剂床的上游和/或直接作为顶层位于所述主催化剂床的顶面上。
通常,也可使用未改性的市售MgO作为预床。因此,可以想到这样的催化剂床配置,其包括:复分解催化剂和本发明的改性MgO作为主催化剂床;以及包含未改性MgO的催化剂预床。
如果预床MgO与主催化剂床(复分解催化剂和异构化催化剂的混合物)的质量比为1:10至3:1,优选地1:6至2:1,最优选地1:4至1:2,则是有利的。
由本发明的MgO制备的预床可用于纯化烯烃流。该纯化是基于通过吸附去除痕量的水分、二氧化碳和其他极性化合物。这些化合物在进入反应器时充当催化剂毒物。所述化合物被吸附在复分解催化剂组分(特别是MgO)上并形成酸性中心,所述酸性中心形成焦炭形成的源。随后,焦炭覆盖活性位点导致催化剂失活。该过程的结果由于产率/转化曲线随反应时间(tos)下降而可见。因此,当使用本发明的MgO预床时烯烃流在进入主催化剂混合物之前被纯化。
在烯烃的实际复分解反应之前使本发明的催化剂(主催化剂床)活化,所述本发明的催化剂为复分解催化剂与作为异构化催化剂的本发明MgO的混合物。这样的活化过程包括以下步骤:
a)在惰性气体气氛中将催化剂加热至300℃至500℃,优选400℃的温度;
b)在含氧气氛(例如,空气)中在400℃至600℃,优选400℃至550℃的温度下氧化催化剂;
c)在含氢气氛中在300℃至500℃,优选400℃的温度下还原催化剂;
d)在惰性气体气氛中在400℃至600℃,优选400℃至550℃的温度下再次加热催化剂;以及
e)随后在惰性气体气氛中冷却催化剂。
在上述催化剂(主催化剂床)的活化过程中,首先使MgO活化,然后使复分解催化剂活化,其中形成水。所述水进而可使MgO部分失活,其活性最终恢复。
在活化过程的一个典型实施方案中,将催化剂从室温开始以5℃/分钟的加热速率加热直至达到最终温度(例如,约400℃),并在该温度下保持约2小时。
在下一步中使催化剂在空气中氧化,其中起始温度可为400℃并且最终温度可为525℃。氧化期间的加热速率为约5℃/分钟,并且在最终温度下的保持时间可为约2小时。
随后,在惰性气体气氛(如氮气气氛)中使经氧化的催化剂从例如525℃的氧化温度冷却至400℃并在后面的温度下保持约0.5小时。催化剂的还原在比例为约80:20,优选70:30的氮和氢的气体混合物中,在例如约400℃下进行约0.5小时至1小时,优选约0.5小时。还原之后在400℃下用氮气吹扫催化剂约0.5小时至1小时,优选约0.5小时。
催化剂还原之后是在惰性气体(例如,氮气)流中的进一步加热步骤。此处,发生被吸附的杂质从催化剂表面的脱附。脱附步骤可持续10小时至20小时,优选地14小时至16小时。在此期间可将温度以约5℃/分钟的加热速率从约400℃升高至约550℃。最终,在惰性气体气氛(例如,氮气)中冷却催化剂。
应理解,如上所述的用于活化主催化剂床的工艺条件仅是示例性的,并且取决于催化剂床的尺寸和反应器尺寸。工艺条件应当由此进行调整。然而,这是本领域技术人员(如工艺工程师)日常工作的一部分。
本发明的催化剂混合物优选地用于通过复分解转化至少两种烯烃的反应器和过程。如果本发明的催化剂混合物用于通过复分解使乙烯和至少一种丁烯(例如,2-丁烯)转化为丙烯,则是特别优选的。
催化剂混合物优选地为固定床反应器的一部分。催化固定床反应器的基本类型是绝热固定床反应器和等温固定床反应器。绝热固定床反应器优选用于工业过程。催化剂通常以粉末、粒料或挤出物(例如催化粒料)的无规填料的形式提供到固定床反应器中。
通常,反应器是广泛用于气固反应的填充固定床反应器。
在一个实施方案中,反应器的长径比(l/d比)为1至15,优选1至10,最优选1至5,甚至更优选1.5至3.5。
所述催化剂混合物和所述反应器用于通过复分解获得烯烃(特别是丙烯)的方法,所述方法包括以下步骤:
-将至少两种烯烃作为起始材料供给至反应器,特别是固定床反应器中,所述反应器包括复分解催化剂和本发明MgO的至少一种催化剂混合物;以及
-在1巴至50巴,特别是10巴至30巴的压力下,在100℃至600℃,特别是250℃至500℃的温度下,通过复分解使所述至少两种烯烃转化为至少一种新的烯烃。
复分解反应优选地在1小时-1至100小时-1,优选地1小时-1至50小时-1,更优选地1小时-1至10小时-1的重时空速(WHSV)下进行(WHSV值涉及主催化剂床和所供给的2-丁烯)。
在一个实施方案中,用作起始材料的至少两种烯烃中的一种包含至少两个碳原子,如乙烯,并且用作起始材料的所述至少两种烯烃中的第二种包含至少四个碳原子,如2-丁烯。包含至少两个碳原子的所述烯烃与包含至少四个碳原子的所述烯烃之间的摩尔比可为20:1,优选10:1,最优选5:1,并且特别优选2.5:1。
所述至少两种烯烃可作为混合流或以独立流的形式供给至反应器中。当使用2-丁烯作为起始材料时,丁烯组分可作为顺-2-丁烯或反-2-丁烯或其混合物供给。工业2-丁烯流可包含另外的少量正丁烷、异丁烷、异丁烯、1-丁烯。在一些实施方案中,对混合C4流进行预处理以增加用于复分解反应的进料中2-丁烯的含量。如果使用来自例如石脑油裂化装置的粗制C4馏分,则必须通过选择性氢化步骤去除化合物如1,3-丁二烯、丙二烯或乙炔。
然后使烯烃混合物与催化剂床接触,其中烯烃首先与催化剂预床接触,然后与主催化剂床接触。在催化剂预床中,发生进料的异构化和纯化。当进入包含复分解催化剂和异构化催化剂的主催化剂床时,发生异构化,特别是1-丁烯至2-丁烯的异构化,以及由乙烯和2-丁烯合成丙烯。除了丙烯,还可以形成其他反应产物,例如C5至C6烯烃。
该方法可通过使烯烃与催化剂在液相或气相中接触来进行,这取决于用作起始材料的烯烃的结构和分子量、所使用的催化剂和/或所施加的反应条件如压力、温度等。稀释剂如饱和脂肪烃如甲烷、乙烷、丙烷、丁烷,和/或惰性气体如氮气或氩气可能是适合的。在任何情况下,应避免灭活物质如水或氧的存在。
复分解催化剂对进料流中的杂质非常敏感。这样的进料毒物为,例如,强极性或质子化合物如N-、O-、S-和含卤素化合物,或碳氧化物衍生物(含氧化合物)。典型实例为水、醇、醚、酮、醛、酸、二氧化碳、一氧化碳、氧硫化碳等。后果是降低的催化剂活性以及缩短的周期时间。因此,进料流在供给至反应器之前必须使其通过适当的吸附剂来进行纯化。
也可在氢的存在下进行反应(EP1854776A1)。
可以将来自复分解反应器的流出物传送至分离系统以使一种或更多种产物与未反应的进料组分分离。例如,分离系统的产物可包括乙烯、丙烯、C4化合物及C5化合物。从反应流中分离的丙烯的特征是高纯度。乙烯和C4烯烃可再循环回到复分解反应器或预处理阶段。
参考附图通过以下实施例进一步更详细地解释了本发明。所述附图示出:
图1示出对于根据本发明的催化剂的一个实施方案,在乙烯与2-丁烯的复分解中运转时间-a)正丁烯转化率和b)丙烯产率的图;
图2示出在使用包含由Mg(OH)2制备的MgO的催化剂进行的乙烯与2-丁烯的复分解中运转时间-a)正丁烯转化率和b)丙烯产率的图;
图3示出在使用包含商业MgO的催化剂进行的乙烯与2-丁烯的复分解中,运转时间-a)正丁烯转化率和b)丙烯产率的图;
图4示出使用根据本发明的MgO(标记为MgOL1)、由Mg(OH)2制备的MgO(标记为MgOL2)和商业MgO(标记为MgOC)在标准反应条件下获得的a)1-丁烯和b)顺-2-丁烯的运转时间-摩尔分数的图。
实施例1:发明实施例
MgOL1(根据本发明的MgO)通过在550℃下在空气流中将(MgCO3)4·Mg(OH)2·5H2O煅烧16小时制备。下表2中给出了通过BET和XRD的MgOL1表征结果。
(WOx/SiO2)L1通过用偏钨酸铵水合物(Aldrich99.99%,痕量金属基准)和氢氧化钾(Merck)的溶液对SiO2(3038,Evonik)进行湿浸渍来制备。如US4,575,575中所述,钨(计算为WO3)和钾(计算为K2O)的负载量分别设定为约7重量%和0.2重量%。将经干燥的催化剂前体在具有循环空气流的马弗炉中在538℃下煅烧8小时。
然后对经煅烧的(WOx/SiO2)L1和MgOL1粉末进行挤压、粉碎和筛分以获得315μm至710μm的颗粒。
然后根据表1中所概述的活化步骤使催化剂活化。
表1:催化剂的活化过程
在300℃下在乙烯的存在下测试了对于纯MgOL1的反-2-丁烯异构化。还研究了在300℃下但使用由MgOL1预床以及MgOL1与(WOx/SiO2)L1的混合物组成的催化剂床(即,MgO预床/(MgO:(WOx/SiO2)=3:1)=0.25)进行的乙烯和反-2-丁烯的交叉复分解。另外使用3A分子筛纯化乙烯和反-2-丁烯。使用另外的三重气体过滤器滤筒(氧、水分和烃捕集器,Restek)以从氮、氢和氢混合物中去除氧、水分和烃。标准反应进料由C2H4、反-2-C4H8和N2(10体积%)组成,C2H4/反-2-C4H8的比例为2.5。对于共同进料的反-2-丁烯,重时空速(涉及主催化剂床即MgO/WOx-SiO2-混合物质的WHSV)设定为1.9小时-1(标准反应条件)。
复分解和异构化测试的结果示于图1中。图1中的图示出在标准反应条件下在MgOL1/(MgOL1:WOx/SiO2)L1=0.25上的运转时间-(a)正丁烯转化率和(b)丙烯产率。由图1的图可推断,显然通过在空气中煅烧而由(MgCO3)4·Mg(OH)2·5H2O制备的MgOL1示出非常好的运转时间稳定性。
实施例2:比较例
MgOL2通过在550℃下在空气流中将Mg(OH)2煅烧16小时来制备。下表2中提供了通过BET和XRD的MgOL2表征结果。
类似于(WOx/SiO2)L1(参见实施例1)但使用SiO2(DavisilTM,Aldrich)代替SiO2(3038,Evonik)来制备(WOx/SiO2)L2。如实施例1所述测试两种催化材料。应注意,两种载体材料3038和DavisilTM具有相同的表面性质和结构。
图2中示出了使用该催化制备物的复分解和异构化测试的结果。图2的图示出,与用MgOL1进行的实验相比,MgOL2的总体稳定性显著降低。
实施例3:比较例
使用商业MgO和WOx/SiO2。将其分别表示为MgOC和(WOx/SiO2)C。下表2中提供了通过BET和XRD的MgOC表征结果。如实施例2所述测试两种催化材料。
图3中示出了复分解和异构化测试的结果。图3的图示出,市售MgOC的总体稳定性低于MgOL1。
图4示出了在根据本发明的MgOL1、由Mg(OH)2获得的MgOL2和商业MgOC上形成的1-丁烯和顺-2-丁烯的流出物摩尔分数的运转时间图。这种直接比较支持了图1至3中示出的结果。显然当使用更稳定的MgOL1时,随时间转化的丁烯量显著增加。
实施例4:不同来源的MgO的本体性质和表面性质
表2:包括本体性质和表面性质的MgO参考类型的列表
从以上图1至4所示的结果清楚的是,MgOL1是用于复分解催化剂WO3-SiO2的最佳促进剂或助催化剂。尤其是运转时间稳定性(通过例如150小时之后的转化率来表征)明显提高。该材料还具有更好的异构化活性。突出的促进剂性质是更高的比BET表面积、更高的最大孔径和低晶粒尺寸结合的结果。
用于测定催化剂性质的方法为标准方法。
S
BET
-比表面积
采用在BELSORP-miniII装置(BELJapan,Inc.)上在-196℃下的氮物理吸附以测定比表面积(SBET)。使用BJH法获得孔径分布和总孔体积。测量之前将样品暴露于真空(2Pa),然后在250℃下加热2小时。
X射线衍射(XRD)-晶粒尺寸
使用CuKα辐射(λ=0.154nm)在STOEStadiP装置上在5°至65°的布拉格角(2θ)范围内以0.01°s-1的速率记录新煅烧的MgO的X射线衍射图。基于ICDD数据库进行相鉴定。
Claims (15)
1.氧化镁(MgO)作为用于烯烃异构化,特别是1-丁烯和/或2-丁烯异构化的催化剂的用途,其中所述氧化镁(MgO)的特征在于:
-比表面积BET为80m2/g至300m2/g;
-晶粒尺寸为5nm至25nm;
-总孔体积为0.1cm3/g至0.5cm3/g;以及
-孔径分布最大值为5nm至15nm,以及
其中所述氧化镁(MgO)不含结构稳定剂。
2.根据权利要求1所述的氧化镁的用途,其特征在于氧化镁的比表面积BET为80m2/g至150m2/g,优选地100m2/g至120m2/g。
3.根据权利要求1或2所述的氧化镁的用途,其特征在于氧化镁的晶粒尺寸为10nm至20nm,优选地10nm至15nm。
4.根据前述权利要求中任一项所述的氧化镁的用途,其特征在于总孔体积为0.2cm3/g至0.4cm3/g,优选地0.3cm3/g至0.4cm3/g。
5.根据前述权利要求中任一项所述的氧化镁的用途,其特征在于氧化镁的孔径分布最大值为7nm至10nm,优选地8nm至9nm。
6.根据前述权利要求中任一项所述的氧化镁的用途,其特征在于所述氧化镁由式(MgCO3)4·Mg(OH)2·5H2O的碱式碳酸镁通过在含氧气体的存在下煅烧获得。
7.根据权利要求6所述的氧化镁的用途,其特征在于所述煅烧在300℃至700℃,优选地400℃至600℃,最优选地450℃至550℃的温度下进行。
8.根据前述权利要求中任一项所述的氧化镁的用途,其特征在于所述氧化镁不含外部添加的结构稳定剂,所述结构稳定剂包含以下元素中的至少一种:Al、Si、Ti、Cr、Mn、Fe、Y、Zr、Mo或其组合。
9.一种用于烯烃转化的催化剂,包含以下的混合物:
a)含有复分解催化剂的至少一种第一催化剂组分,和
b)至少一种第二催化剂组分,所述第二催化剂组分含有根据权利要求1至8中任一项所述的氧化镁作为用于双键异构化的催化剂。
10.根据权利要求9所述的催化剂,其特征在于所述催化剂包含作为异构化催化剂组分的MgO和至少一种复分解催化剂组分,所述作为异构化催化剂组分的MgO和所述至少一种复分解催化剂组分的重量比为5∶1至1∶1,优选地重量比为4∶1至2∶1,最优选地重量比为3∶1。
11.根据权利要求9或10中任一项所述的催化剂,其特征在于所述复分解催化剂包含沉积在至少一种无机载体上的PSE第6族和第7族金属的氧化物,特别是氧化钨、氧化钼和/或其前体。
12.根据权利要求9至11中任一项所述的催化剂,其特征在于将根据权利要求1至8中任一项所述的氧化镁另外布置为在复分解催化剂与异构化催化剂的催化剂混合物上游的预床。
13.根据权利要求12所述的催化剂,其特征在于所述预床与主催化剂床的质量比为1∶10至3∶1,优选地1∶6至2∶1,最优选地1∶4至1∶2,所述主催化剂床为复分解催化剂与异构化催化剂的混合物。
14.根据权利要求9至13中任一项所述的催化剂,其特征在于所述催化剂在包括以下步骤的方法中活化:
a)在惰性气体气氛中将所述催化剂加热至300℃至500℃,优选400℃的温度;
b)在含氧气氛中在400℃至600℃,优选400℃至550℃的温度下氧化所述催化剂;
c)在含氢气氛中在300℃至500℃,优选400℃的温度下还原所述催化剂,
d)在惰性气体气氛中在400℃至600℃,优选400℃至550℃的温度下加热所述催化剂;以及
e)随后在惰性气体气氛中冷却所述催化剂。
15.一种用于获得烯烃,特别是丙烯的方法,包括以下步骤:
-将作为起始材料的至少两种烯烃供给至反应器,特别是固定床反应器中,所述反应器包括至少一种根据权利要求9至14中任一项所述的催化剂;
-在1巴至50巴,特别地10巴至30巴的压力下,在100℃至600℃,特别地250℃至500℃的温度下,使所述至少两种烯烃气体转化为至少一种新烯烃。
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EP20130188709 EP2862629A1 (en) | 2013-10-15 | 2013-10-15 | Catalyst and process for olefin metathesis reaction |
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PCT/EP2014/071920 WO2015055594A1 (en) | 2013-10-15 | 2014-10-13 | Catalyst and process for olefin metathesis reaction |
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KR102387487B1 (ko) | 2015-07-02 | 2022-04-18 | 사우디 아라비안 오일 컴퍼니 | 프로필렌을 제조하기 위한 시스템 및 방법 |
US10059645B2 (en) | 2015-07-02 | 2018-08-28 | Saudi Arabian Oil Company | Systems and methods for producing propylene |
CN107921425B (zh) | 2015-07-02 | 2021-11-30 | 沙特阿拉伯石油公司 | 使用介孔二氧化硅泡沫复分解催化剂生产丙烯 |
US10550048B2 (en) | 2017-01-20 | 2020-02-04 | Saudi Arabian Oil Company | Multiple-stage catalyst system for self-metathesis with controlled isomerization and cracking |
US10934231B2 (en) | 2017-01-20 | 2021-03-02 | Saudi Arabian Oil Company | Multiple-stage catalyst systems and processes for propene production |
US10329225B2 (en) | 2017-01-20 | 2019-06-25 | Saudi Arabian Oil Company | Dual catalyst processes and systems for propylene production |
US10961171B2 (en) | 2018-10-10 | 2021-03-30 | Saudi Arabian Oil Company | Catalysts systems that include metal co-catalysts for the production of propylene |
US11242299B2 (en) | 2018-10-10 | 2022-02-08 | Saudi Arabian Oil Company | Catalyst systems that include metal oxide co-catalysts for the production of propylene |
US10975004B2 (en) | 2019-01-03 | 2021-04-13 | Saudi Arabian Oil Company | Integrated process for production of ethylene from propylene |
US11517892B2 (en) | 2019-12-03 | 2022-12-06 | Saudi Arabian Oil Company | Methods of producing isomerization catalysts |
US11311869B2 (en) * | 2019-12-03 | 2022-04-26 | Saudi Arabian Oil Company | Methods of producing isomerization catalysts |
US11339332B2 (en) | 2020-01-29 | 2022-05-24 | Saudi Arabian Oil Company | Systems and processes integrating fluidized catalytic cracking with metathesis for producing olefins |
US11572516B2 (en) | 2020-03-26 | 2023-02-07 | Saudi Arabian Oil Company | Systems and processes integrating steam cracking with dual catalyst metathesis for producing olefins |
US11679378B2 (en) | 2021-02-25 | 2023-06-20 | Saudi Arabian Oil Company | Methods of producing isomerization catalysts |
US11845705B2 (en) | 2021-08-17 | 2023-12-19 | Saudi Arabian Oil Company | Processes integrating hydrocarbon cracking with metathesis for producing propene |
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