CN101495435A - 氧化催化剂 - Google Patents
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Abstract
在作为第一氧化剂的氧气的存在下,将烷烃氧化为经氧化的烃的催化剂,包括可以以氧化形式和还原形式存在的氧化还原活性金属中心、酸、用于对氧化还原活性金属中心的还原形式进行氧化的第二氧化剂和一氧化氮源。
Description
本发明涉及催化领域,更具体而言,涉及在氧气的存在下,用于将甲烷直接氧化为经氧化的烃(oxygenated hydrocarbons)的催化剂。
将天然气转换为经氧化的烃在工业上一般以两个阶段来完成。首先,将甲烷通过例如部份氧化、蒸汽转化或自热转化的工艺转换为合成气(一氧化碳和氢气的混合物)。第二阶段是将合成气转换为经氧化的烃,例如,使用Cu/ZnO/Al2O3催化剂生产甲醇,或使用铑催化剂来生产乙醇和/或更高级的烃。
为了最小化工艺的复杂度,使用单一阶段将甲烷直接转换为经氧化的烃将具有极大的优势。
WO 92/14738描述了在金属催化剂和氧化剂的存在下使甲烷与强酸反应的方法。产物是该酸的甲基盐或酯。WO 92/14738的实施例所包括的催化体系包含作为活性金属的钯、作为酸的三氟甲磺酸或硫酸和作为氧化剂的氧气。
虽然氧气是期望使用的氧化剂(由于其低廉的成本和高充裕度),但是,当其使用时所达到的甲烷转化率倾向偏低。其他氧化剂,例如SO3、过硫酸盐或者过酸能够提高转化率,但它们相对昂贵且不断需要被更新以维持催化反应。WO92/14738描述了汞催化剂,在硫酸的存在下,在氧气的存在下,并且任选地在SO3的存在下,与其他金属(例如钯、铊、金和铂)相比,如何能够更有效地氧化甲烷。然而,因为汞是有毒的和破坏环境的金属,所以仍然需要具有高氧化产率的氧化烃的催化剂和方法,但是其避免需要使用这类潜在破坏性组分。
根据本发明,提供了在作为第一氧化剂的氧气的存在下,用于将烃氧化为经氧化的烃的催化剂,该催化剂包括氧化还原活性金属中心(redox active metalcentre)、酸和第二氧化剂,其特征在于该催化剂还包括一氧化氮源。
本发明的催化剂能够在氧气的存在下将烃转化为经氧化的烃。当使用时,与不存在一氧化氮源的催化剂相比,从一氧化氮源产生的一氧化氮提供了更优异的催化活性并且提高了经氧化的烃的产率。
所述催化剂可以是均相催化剂,其中组分在液相中混合或溶解,例如溶解在液体酸中。可选择地,所述催化剂可以是非均相的,其中一种或多种组分为固相,例如其中组分负载于耐高温氧化物或固体酸(例如铝硅酸盐沸石)上。均相催化剂是优选的,这是因为在更温和的条件下,它们一般比非均相的对应物(counterparts)更具活性,并且使得能够实现催化剂的构成组分之间改进的接触。
一氧化氮(NO)源包括一氧化氮本身,其他氮的氧化物例如NO2、N2O3、N2O4和N2O5,包含氮的阴离子氧化物例如NO2 -(亚硝酸根)的盐,和包含NO+(亚硝鎓离子)阳离子的盐。包含亚硝酸根离子的合适化合物包括碱金属盐、碱土金属盐和过渡金属盐。在一个实施方案中,亚硝酸盐的阳离子是本发明组合物的氧化还原活性金属中心。包含亚硝鎓离子的合适化合物包括:四氟硼酸的亚硝酰基盐([NO]BF4)和高氯酸的亚硝酰基盐([NO]ClO4),和亚硝酰基硫酸([NO]HSO4)。方便地,碱金属亚硝酸盐是所述一氧化氮源,例如亚硝酸钠或亚硝酸钾,其可在酸的存在下产生一氧化氮。
当使用所述催化剂时,一氧化氮源释放或产生一氧化氮。在使用所述催化剂时,在氧气的存在下,一氧化氮被可逆地氧化成NO2,而NO2又能再生电子转移剂(electron transfer agent)的氧化形式,其中该电子转移剂在还原的氧化还原活性金属中心的再氧化过程中已经被还原。在本发明的催化剂中使用一氧化氮源是有利的,这是由于在使用所述催化剂时普遍存在的酸性条件下一氧化氮/二氧化氮循环是稳定的,这不同于大环金属络合物例如钴-卟啉络合物。
所述催化剂包括能够以氧化形式和还原形式存在的氧化还原活性金属中心。在本文中,术语“金属”包括被描述为准金属的那些元素,例如锗,锑,碲等等。和许多主族金属一样,大多数过渡金属、镧系元素和锕系元素能够以超过一种形式存在。在本发明中,适合用作氧化还原活性金属的金属实例包括:Cu,Zn,Pd,Ag,In,Sn,Sb,Te,Pt,Au,Pb,Bi,Ga,Ge,As,Rh,Ir,Os和Ru。尽管例如Hg、Cd或者Tl的金属也能够被用在本发明中,但是它们优选是避免使用的,这是由于它们的高毒性和破坏环境的潜力。在一个优选实施方案中,氧化还原活性金属选自V,Fe,Co,Ni,Cu,Rh,Pd和Pt。
所述氧化还原活性金属中心能够以任何形式提供,从而在使用时,其能够在二种氧化态之间循环。因此,例如,其能够以金属(O氧化态)形式引入,或作为其中金属中心处于更高氧化态的化合物或络合物引入。例如,能够将所述氧化还原活性金属中心作为盐添加到催化剂中,例如硝酸盐、硫酸盐、草酸盐、卤化物、醋酸盐。在一个实施方案中,所述氧化还原活性金属中心可以配位到阴离子和/或任何其他配体,例如胺、膦类、肟类或者大环配体,例如冠醚、卟啉类、萨罗汾类(salophens)等等。在另一个实施方案中,它能够以氧化物的形式添加。在仍旧另一个实施方案中,其能够在具有多于一个氧化还原活性金属中心的化合物中进行提供,例如杂多酸,例如通式为H3+xPMo(12-X)Vx的钼钒磷酸(molybdovanadophosphoric acid)的形式,其中x通常在1和3之间。在该实施方案中,所述杂多酸也能够作为所述催化剂的酸组分。
在使用时,所述氧化还原活性金属中心能够以氧化形式和还原形式存在,从而金属中心能够在两种不同的氧化态之间进行循环,例如Pd(0)/Pd(II),Pt(0)/Pt(II)和/或Pt(II)/Pt(IV),Rh(I)/Rh(III),Ni(0)和Ni(II)和Co(II)/Co(III)。在烷烃的氧化中,例如甲烷的氧化中,氧化还原活性金属中心通过裂解(cleaving)碳-氢键来氧化或活化所述烃。这可以通过均裂机理,由自由基途径实现,或通过异裂(heterolytic)机理实现。单电子氧化还原循环倾向于导致C-H键的均裂,其产生能够攻击或分解一种或多种催化剂成分的高反应性自由基。因此,优选双电子氧化还原循环(two-electron redox cycles),其倾向于促进C-H键的异裂。这延长催化剂组分的寿命,并且改进对所需产物的选择性。具有双电子氧化还原循环的优选氧化还原活性金属中心是Ni、Rh、Pd或Pt。
所述氧化还原活性金属中心可以与促进剂(promoter)或助催化剂联用,其提高催化速率和/或改善催化剂寿命和/或改进产物选择性。在一个实施方案中,所述促进剂或助催化剂是第二氧化还原活性金属中心。在本发明又一实施方案中,所述第二氧化还原活性金属中心起第二氧化剂的作用,并且在第一金属中心和一氧化氮源之间传递电子。作为例子,Cu能够在包括Pd和Cu的催化剂中用作第二氧化剂,其中Cu(II)物种将Pd(0)物种氧化到Pd(II),结果Cu(II)被还原到Cu(I)。通过一氧化氮源由Cu(I)再生Cu(II),其接下来被转化成一氧化氮。
所述催化剂组合物包括酸。该酸,在均相系统中其能够作为其他催化剂组分的溶剂,能与被氧化的烃形成酯。例如,在甲烷氧化的情况下,该酸形成甲酯。本发明中适用的酸的实例通常是强布朗斯台德酸,并且包括无机酸(inorganicmineral acids),例如杂多酸(如磷钨酸、硅钨酸、磷钼酸或硅钼酸,或它们的经取代的类似物,例如钼钒磷酸),硫酸,发烟硫酸(oleum),甲磺酸(methyl sulphonicacid),三氟甲磺酸,和有机酸,例如三氟乙酸。
在使用中,在烃的氧化过程中,氧化还原活性金属中心被还原到更低的氧化态。为了维持催化,所述金属中心通过第二氧化剂被再氧化到更高的氧化态。虽然氧气(第一氧化剂)在某些情况下能够实现金属中心的再氧化,但该氧化一般非常缓慢。催化剂组合物中第二氧化剂的存在能够提高金属中心的再氧化速率。在本发明中适用的第二氧化剂的实例包括:过氧化物,例如过氧化氢、过氧化氢叔丁基(tert-butyl hydrogen peroxide)或者氢过氧化枯烯(cumene hydroperoxide),过酸,例如过乙酸,醌(quinone),醌衍生物,和第二氧化还原活性金属中心。能用作第二氧化剂的合适的第二氧化还原活性金属中心是Cu、Fe或Co,其在一个实施方案中能够以卟啉或萨罗汾络合物形式来提供。
当使用所述催化剂时,所述一氧化氮源产生一氧化氮。一氧化氮在氧气的存在下被氧化成二氧化氮。二氧化氮接下来又能够氧化被还原的第二氧化剂,并且再次产生一氧化氮。
本发明的一个优点是:与化学计量的量相反,仅需要催化量的催化剂组分,并且在方法中仅仅消耗氧气和烃。
在特别优选的一个实施方案中,第二氧化剂是醌或其衍生物。在使用所述催化剂时,与其他氧化剂,例如过渡金属大环络合物相比,醌类和它们的衍生物倾向于更耐失活。醌类的衍生物包括基本醌单元(即O=C6H4=O),其中一个或多个碳原子具有官能团,例如烷基、芳基、卤化物(halide)、氢氧化物(hydroxide)、酯或者醚。在使用时,所述醌或醌衍生物氧化氧化还原活性金属的还原形式而形成对苯二酚。这在酸的存在下完成,需要两个质子来平衡在醌单元的还原中获得的负电荷。当对苯二酚被氧化时,所述质子被重新释放。在使用之前,所述醌或其衍生物可以以氧化或还原形式,即作为醌或对苯二酚(或其衍生物)存在于催化剂中。
在本发明催化剂中,在与醌或醌衍生物联用时所述一氧化氮源是特别有益的。在使用所述催化剂时,能实现对苯二酚到醌(或其衍生物)的高度再氧化,这接下来又有益于催化速率和经氧化的烃的产率。
典型地,所述氧化还原活性金属中心与第二氧化剂的摩尔比是1∶100到100∶1,优选1∶0.5到1∶50。所述氧化还原活性金属中心与一氧化氮源的摩尔比合适地是1∶100到100∶1,优选1∶0.5到1∶50。
所述催化剂可以用于在氧气的存在下将烃氧化成经氧化的烃。经氧化的烃产物包括醇、醚、酯、羧酸、环氧化物、醛和酮。在一个实施方案中,所述催化剂可以用于将烷烃,例如C1到C4烷烃氧化成醇。对于将甲烷直接氧化成甲醇,所述催化剂显示出令人惊奇的高活性。通常用于甲烷氧化反应的温度是50到250℃,并且压力最高至100barg(10.1MPa),例如在20到70barg(2.1到7.1MPa)。
现在将通过以下非限制实施例和图1来说明本发明,图1显示了使用根据本发明催化剂的甲烷氧化机理的示意总结。
在图1中,说明了在氧气(第一氧化剂)的存在下,用于均相催化甲烷氧化反应的典型催化机理,其中氧化还原活性金属中心是钯,酸是三氟乙酸,第二氧化剂是对-醌,并且一氧化氮源是亚硝酸盐(亚硝酸钠的形式)。在该实施方案中,三氟乙酸在Pd(II)氧化还原活性中心的存在下,与甲烷反应产生三氟乙酸甲酯和两个质子,钯在该过程中被还原到Pd(0)。该Pd(0)在所述两个质子的存在下,被对-醌氧化回Pd(II),从而产生对苯二酚。接着,该对苯二酚通过二氧化氮的作用被再氧化成对-醌,二氧化氮被还原成一氧化氮,释放出水。一氧化氮被氧气氧化成二氧化氮。通过用水进行水解(由酸催化),从三氟乙酸甲酯释放甲醇。该方法的净结果可以由下式表示:
CH4+1/2O2→CH3OH
实验1
向50mL玻璃衬里的高压釜中加入ptfe涂覆的磁力搅拌器、期望量的醋酸钯和第二氧化剂,以及3mL三氟乙酸。该高压釜在30atm用甲烷净化三次,然后加入55atm甲烷。然后,在恒定搅拌下,将该高压釜在保持于80℃的油浴中加热10小时,然后在冰浴中淬灭并对该高压釜进行减压。
产物鉴定使用GC-MS和NMR谱来测定,并且由GC定量。
实验2
向50mL玻璃衬里的高压釜(安装了PTFE-涂覆的磁力搅拌棒)中加入3mL三氟乙酸和期望量的醋酸钯、第二氧化剂和任选的亚硝酸钠。该反应器在30atm用甲烷净化三次。然后向该高压釜中装入甲烷(54atm分压)和任选的氧气(1atm分压),然后,在恒定搅拌下,在保持于80℃的油浴中加热。在10小时以后,该反应通过在冰浴中冷却进行淬灭并释放压力。
产物鉴定使用GC-MS和NMR谱测定,并且由GC定量,并且在溶液中剩余的Pd(II)量在沉淀以后由重量分析测定。
比较实施例1-7.
根据在实验1中所列的过程,评价在三氟乙酸的存在下,使用钯催化剂将甲烷转化为三氟乙酸甲酯的转化。这些实施例不是根据本发明,因为没有一氧化氮源。
在不同第二氧化剂存在下甲烷氧化实验的结果在表1示出。结果显示,与其他氧化剂相比,使用对-醌作为第二氧化剂,达到令人惊讶的优越的三氟乙酸甲酯产率。
只可以实现化学计量的甲烷转化,这是由于在该反应中没有使用氧气或其他第一氧化剂来再氧化催化剂的第二氧化剂和因而再氧化钯。
比较实施例8-11
使用实验2的过程。没有添加亚硝酸钠。结果在表2中示出。这些不是根据本发明的实施例,因为没有一氧化氮源。
比较实施例12到15
按照实验2的过程,评价使用钯催化剂、对-醌作为第二氧化剂,在没有亚硝酸钠的存在下,甲烷转化为三氟乙酸甲酯的转化。这些实施例未根据本发明,因此没有一氧化氮源。结果在表3中示出。
实施例16到20
按照实验2的过程,使用对-醌作为第二氧化剂,使用亚硝酸钠作为一氧化氮源。这些实施例是根据本发明的。结果在表4中示出。
表1
实施例 | Pd(OAc)2(mmol) | 第二氧化剂 | 第二氧化剂的量(mmol) | CH3COOCH3产率(%)a |
1 | 0.10 | - | - | 70 |
2 | 0.05 | Cu(OAc)2 | 0.5 | 80 |
3 | 0.05 | FeCl3 | 0.5 | 60 |
4 | 0.05 | K2S2O8 | 0.5 | 120 |
5 | 0.05 | 对-醌 | 0.5 | 240 |
6 | 0.05 | LiNO3 | 0.5 | 140 |
7 | 0.05 | H2O2 | 0.88 | 180 |
a基于Pd(OAc)2
表2
实施例 | Pd(OAc)2(μmol) | 第二氧化剂 | 第二氧化剂的量(μmol) | CH3COOCH3产率(%) |
8 | 10 | NHPIb | 20 | 27 |
9 | 10 | CoCl2 | 20 | 29 |
10 | 10 | VOSO4 | 20 | 17 |
11 | 10 | 5%Ru/Cc | 5mg | 12 |
bN-羟基邻苯二甲酰亚胺
c在碳上负载5wt%钌的非均相催化剂。
表3
实施例 | Pd(OAc)2(μmol) | 对-醌(μmol) | NaNO2(μmol) | O2(atm) | CF3COOCH3产率(μmol) | Pd2+剩余(%)d |
12 | 10 | 0 | 0 | 0 | 9.5 | b.d.e |
13 | 10 | 20 | 0 | 0 | 30 | b.d.e |
14 | 10 | 50 | 0 | 0 | 55 | b.d.e |
15 | 10 | 20 | 0 | 1 | 34 | 15 |
16 | 10 | 50 | 0 | 1 | 67 | 27 |
17 | 10 | 20 | 20 | 1 | 69 | 98 |
18 | 10 | 50 | 100 | 1 | 70 | 95 |
19 | 5 | 20 | 20 | 1 | 32 | 95 |
20 | 20 | 20 | 20 | 1 | 106 | 54 |
d在反应结束时,溶液中剩余钯的百分比
e检测不到。
这些实施例显示:一氧化氮源的存在能够显著增加氧化还原活性金属中心氧化形式的浓度,这可导致延长的催化剂寿命。所述结果也显示出:使用作为氧化剂的对醌和一氧化氮源的组合可实现经氧化的烃产物显著改进的产率。
Claims (10)
1.在作为第一氧化剂的氧气的存在下将烃氧化为经氧化的烃的催化剂,该催化剂包括氧化还原活性金属中心、酸和第二氧化剂,其特征在于该催化剂还包括一氧化氮源。
2.如权利要求1所述的催化剂,其中所述氧化还原活性金属中心选自Cu,Zn,Pd,Ag,In,Sn,Sb,Te,Pt,Au,Pb,Bi,Ga,Ge,As,Rh,Ir,Os和Ru。
3.如权利要求2所述的催化剂,其中所述氧化还原活性金属中心在使用时经历两电子氧化还原循环。
4.如权利要求2或权利要求3所述的催化剂,其中所述氧化还原活性金属中心是Ni、Rh、Pd或Pt。
5.如权利要求1到4任何一项所述的催化剂,其中所述第二氧化剂选自第二氧化还原活性金属中心、过氧化物、过酸、醌和醌衍生物。
6.如权利要求5所述的催化剂,其中所述第二氧化剂是对醌或其衍生物。
7.如权利要求1到6任何一项所述的催化剂,其中所述酸选自三氟乙酸、发烟硫酸、硫酸、甲磺酸、三氟甲磺酸和杂多酸。
8.如权利要求6所述的催化剂,其中所述酸是三氟乙酸。
9.如权利要求1到8任何一项所述的催化剂,其中所述一氧化氮源是亚硝酸盐。
10.在氧气的存在下,将烃氧化为经氧化的烃的方法,该方法包括使烃和氧气与根据权利要求1到9中任何一项的催化剂接触。
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- 2007-06-28 US US12/309,020 patent/US20090203944A1/en not_active Abandoned
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CN102086152A (zh) * | 2009-12-08 | 2011-06-08 | 北京化工大学 | 一种甲烷催化氧化生产三氟乙酸甲酯的方法 |
CN102086152B (zh) * | 2009-12-08 | 2013-06-19 | 北京化工大学 | 一种甲烷催化氧化生产三氟乙酸甲酯的方法 |
CN102285864A (zh) * | 2010-06-17 | 2011-12-21 | 北京化工大学 | 一种甲烷催化氧化生产甲醇的方法 |
CN102285864B (zh) * | 2010-06-17 | 2014-02-05 | 北京化工大学 | 一种甲烷催化氧化生产甲醇的方法 |
CN103113175A (zh) * | 2013-02-04 | 2013-05-22 | 浙江工业大学 | 一种钯催化氧化烯烃生成甲基酮的新方法 |
CN103113175B (zh) * | 2013-02-04 | 2015-01-28 | 浙江工业大学 | 一种钯催化氧化烯烃生成甲基酮的新方法 |
CN105722959A (zh) * | 2013-08-06 | 2016-06-29 | 斯克里普思研究院 | 烷烃转化成有机硒和有机碲 |
CN105722959B (zh) * | 2013-08-06 | 2017-12-26 | 斯克里普思研究院 | 烷烃转化成有机硒和有机碲 |
CN106795088A (zh) * | 2014-08-26 | 2017-05-31 | 斯克利普斯研究所 | 功能化化合物的反应产物的回收方法 |
CN114345400A (zh) * | 2021-11-24 | 2022-04-15 | 中国科学院大连化学物理研究所 | 一种过渡金属-分子筛催化剂及改性方法和应用 |
CN114345400B (zh) * | 2021-11-24 | 2023-03-14 | 中国科学院大连化学物理研究所 | 一种过渡金属-分子筛催化剂及改性方法和应用 |
Also Published As
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WO2008006244A1 (en) | 2008-01-17 |
CA2656931A1 (en) | 2008-01-10 |
WO2008003934A2 (en) | 2008-01-10 |
US20090203944A1 (en) | 2009-08-13 |
EA200900074A1 (ru) | 2009-06-30 |
CN101495435B (zh) | 2013-09-18 |
EP2038242A2 (en) | 2009-03-25 |
ZA200900085B (en) | 2010-06-30 |
AU2007271002A1 (en) | 2008-01-10 |
WO2008003934A3 (en) | 2008-03-13 |
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