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CN1187180A - 制备烃的催化剂和方法 - Google Patents

制备烃的催化剂和方法 Download PDF

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CN1187180A
CN1187180A CN96194640A CN96194640A CN1187180A CN 1187180 A CN1187180 A CN 1187180A CN 96194640 A CN96194640 A CN 96194640A CN 96194640 A CN96194640 A CN 96194640A CN 1187180 A CN1187180 A CN 1187180A
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manganese
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J·J·C·格尔林斯
M·F·高斯
H·M·惠斯曼
J-P·兰格
H·奥斯特比克
P·J·M·里克
D·沙德霍斯特
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Abstract

本发明涉及一种用于制备烃方法中的、含有钴和锰和/或钒的、负载于载体上的催化剂,其中钴:(锰+钒)的原子比至少为12∶1。优选钴:(锰+钒)的原子比至少为1500∶1。本发明进一步涉及一种制备烃的方法,它包括将高温高压的氢气和一氧化碳的混合物与上述所说的催化剂接触。一般是至少部分钴以金属状态存在。

Description

制备烃的催化剂和方法
本发明涉及一种用于由合成气，即一氧化碳和氢气的混合物制备烃的催化剂和方法。
用合成气制备烃的方法在现有技术中是已知的，并且一般是指费-托法合成。
适用于费-托合成法的催化剂一般含有元素周期表中的VIII族的催化活性金属(化学和物理手册(Handbook of Chemistry and Physics)，第68期，CRC出版社，1987-1988)。尤其是铁、镍、钴和钌是用于这种催化剂的公知的催化活性金属。钴被发现最适合于催化其中合成气被转变成含有5个或更多个碳原子的初级链烷烃的方法。换句话说，这种催化剂的C5 +选择性高。
已经作了大量研究目的是找到具有相同或更高活性的、比已知催化剂的C5 +选择性更高的催化剂。
因此，欧洲专利说明书398420记载了通过将催化剂与具有小的氢气和一氧化碳比例，一般是1.1到1.2的合成气接触可以提高催化剂的C5 +选择性，这种催化剂含有在多孔载体上的钴和锆、钛或铬并具有小的外表面积。
欧洲专利说明书178008公开了负载于多孔载体上的钴催化剂，其中大多数钴集中在这种催化剂颗粒的表面。
欧洲专利说明书167215公开了一种用于固定催化剂床的负载于二氧化硅的钴/氧化锆催化剂，该催化剂满足外表面积和内表面积的关系式。
欧洲专利说明书168894公开了一种理想的活化步骤来提高钴基费-托催化剂的C5 +选择性。
欧洲专利说明书363537记载了通过将最多为15％重量的二氧化硅加入到二氧化钛载体中提高负载于二氧化钛载体上的钴催化剂的活性的方法。
欧洲专利说明书498976记载了含有负载在二氧化钛载体上的钴和铼的催化剂。它要求保护这些具有高的体积产率(活性)的催化剂。
尽管在该领域进行了研究，但有地方仍需要改进。因此如果能够发现一种具有比现有催化剂更高的C5 +选择性，同时或者优选地具有较高活性的催化剂是所希望的。
现在出乎意料地发现了一种催化剂，它含有催化活性化合物钴和少量的锰和/或钒，一般是钴∶(锰+钒)的原子比至少为12∶1，当其用于制备烃的方法中时，具有与其中其他的均相同但只含有钴或者含有比较大量的锰和/或钒的催化剂相比具有较高的C5 +选择性和较高的活性。
欧洲专利申请说明书71770记载了从合成气制备直链α-烯烃的方法。其中该方法要求用钴/锰和钴/钒催化剂。以1∶6的比例含有钴和锰的催化剂的C5 +选择性只有50％。
Van der Riet et al.(1986)J.Chem.Soc．Chem.Commun.，第798-799记载了采用钴-锰氧化物催化剂，从一氧化碳和氢选择性合成C3烃。钴/锰的比例一般是1∶1。
国际PCT申请WO93/05000记载了含有钴和钪的费-托催化剂。该催化剂可选择性地含有其他助催化剂，如氧化钍和/或其他原料，如氧化镁和锰。
H.H.Storch，N.Golumbic，和R.B.Anderson(John Wiley和Sons，NewYork，1951)的“The Fischer-Tropsch and Related Synthesis”，即国际PCT申请WO93/05000，它提出了对费-托催化剂早期工作的回顾，包括含有钴和锰和/或钒的催化剂。在120页引证了在其中发现钴-钒氧化物和钴-锰氧化物催化剂作为费-托催化剂没有活性的试验。但是在198页引证了其中发现以原子比为6.2∶1含有钴和锰的催化剂具有与含有钴和氧化钍的催化剂相比更高的C5 +选择性，但是它的合成气转化率极低的实验。
澳大利亚专利申请46119/85记载了含有钴、二氧化硅和碱或碱性原料，一般是碱金属或碱土金属的催化剂。其它助催化剂可以选择性地选自铝、镁、锌、铜、锰、铬、钒、锗、硼、钼、镧、稀土金属等或者它们的混合物和砷或锑等元素的盐。它要求保护这些对低沸点的1-烯烃具有较高选择性的催化剂。
本发明的催化剂一般不含碱金属或碱土金属，不考虑在本发明催化剂的制备过程中由原料可能引入的杂质的情况。碱金属或碱土金属与钴金属的原子比一般小于0.01，优选地小于0.005。
美国专利说明书4588708公开了用于烯烃的异构反应和加氢反应和氢解反应的含有钴和锰的催化剂。钴/锰的原子比可以在宽范围内变化。在一个实施例中公开了一种以原子比为39∶1含有负载在二氧化硅载体上的钴和锰的催化剂。
因此，根据本发明提供一种含有负载于载体上的钴和锰和/或钒的催化剂，其中钴∶(锰+钒)原子比至少为12∶1，其特征在于该催化剂不以39∶1的原子比在二氧化硅载体上含有钴和锰。
另一方面，该催化剂含有负载于载体上的钴和锰和/或钒，其中钴∶(锰+钒)的原子比至少为12∶1，并且其中这种载体包括二氧化钛、氧化锆或它们的混合物。
这种催化剂优选含有钴和锰，其中钴∶锰的原子比至少为12∶1。
钴∶(锰+钒)的原子比优选地最多为1500∶1；更优选最多为500∶1；最优选最多为100∶1；最最优选38∶1。
钴∶(锰+钒)的原子比优选地至少为15∶1；更优选地为至少16∶1；最优选地为至少18∶1。
在优选实施方案中，载体是难熔氧化物载体。合适的难熔氧化物载体的实例包括氧化铝、二氧化硅、二氧化钛、氧化锆或它们的混合物，如二氧化硅-氧化铝或诸如二氧化硅和二氧化钛的物理混合物。载体优选地包括二氧化钛、氧化锆或它们的混合物。
根据优选实施方案，包括二氧化钛、氧化锆或它们的混合物的载体可以进一步含有至多50％重量的其它难熔氧化物，一般是二氧化硅或氧化铝。如果存在这种其它难熔氧化物更优选地含有至多20％重量的，甚至更优选地至多10％重量的载体。
该载体最优选包括二氧化钛，特别是在没有含硫化合物存在情况下制备的二氧化钛。这种制备方法的一个实施例包括四氯化钛的燃烧水解反应(flame hydrolysis)。可以预料到从这种制备方法得到的二氧化钛粉末不具有所需的粒度和形状。因此通常需要成形步骤来制备这种载体。成形技术是本领域技术人员已知的，它包括造粒、挤压、喷射干燥和热油滴入方法。
在该催化剂中存在的钴的含量可以在宽范围内变化。该催化剂每100份重量的载体一般含有1-100份重量，优选3-60份重量，更优选5-40份重量的钴。
除了锰和/或钒之外，该催化剂可含有一种或者多种其它本领域已知的助催化剂。任何其它助催化剂优选地选自元素周期表中IIIB族、IVB族的、周期表的VIII族的贵金属或者铼、铌或钽的，更优选地选自元素周期表的IVB族、周期表的VIII族贵金属的铼、铌或钽。特别优选的其它助催化剂包括锆、钛、钌、铂、钯和/或铼。如果存在其它助催化剂，其量一般为每100份重量载体为0.1-150份重量，例如为1-150份重量。
本发明的催化剂可以适当地通过本领域已知的方法制备，如通过在载体上沉淀催化活性化合物或者前体；在载体上喷射涂覆、捏合或者浸渍催化活性化合物或前体；和/或将一种或多种催化活性化合物或前体连同载体原料一起制备催化剂挤压物。
本领域技术人员可以预计最优选的制备方法可以根据催化剂颗粒所需的粒径来选择。选择满足给定条件和要求的最适合的方法是本领域技术人员所熟知的。
制备本发明催化剂的优选方法是通过在载体上浸渍催化活性化合物或者前体。因此，一般是将载体用钴盐溶液或者锰和/或钒盐溶液浸渍。优选的是将载体用相应金属盐同时浸渍。因此，根据优选的实施方案，制备本发明催化剂的方法包括用钴盐和锰和/或钒盐的溶液共渗载体。在制备含有钴和锰的催化剂的情况下，更优选的是采用高度浓缩的溶液。得到这样浓缩溶液的合适方法是采用熔融硝酸钴和硝酸锰盐的混合物。
一般浸渍处理之后进行干燥和选择性的焙烧。干燥一般是在50-300℃的温度下进行至多24小时，优选地是1-4小时。
焙烧一般是在200-900℃，优选地在250-600℃的温度下进行。焙烧处理的时间一般是0.5-24小时，优选地为1-4小时。焙烧处理适于在含氧气体，优选地是空气中进行。可以预计在焙烧处理过程中的平均温度一般高于在干燥处理过程中的平均温度。
本发明的催化剂一般用于催化用合成气制备烃的方法。当用于该方法时，一般至少部分钴盐以金属状态存在。
因此，通常在使用之前通过在有高温氢存在情况下进行还原处理来活化催化剂是有利的。还原处理一般包括在100-450℃温度的高压下，通常是1-200巴处理催化剂1-48小时。在该还原处理中可以采用纯氢气，但是通常优选采用氢和惰性气体，如氮气的混合物。氢在混合物中存在的相对量为0-100％体积。
根据优选实施方案，将催化剂置于氮气的所需温度和压力下。接着将催化剂与只含有少量氢气、其余为氮气的混和气体接触。在还原处理过程中，氢气在混和气体中的相对量通常可升高到至多50％或者甚至100％体积。
如果可能，优选在反应器内就地活化催化剂。欧洲专利申请95203040.1记载了就地催化剂活化的方法，它包括烃液体存在情况下于氢分压至少15巴，优选20巴，更优选至少30巴时将催化剂与含氢气体接触。在该方法中氢的分压一般是至多为200巴。
本发明另一方面涉及一种制备烃的方法，包括将一氧化碳和氢气的混合物在高温和高压与上述催化剂接触，该催化剂一般含有钴和锰和/或钒，其中钴∶(锰+钒)的原子比至少为11∶1。
该方法一般是在125-350℃，优选在175-275℃的温度下进行。压力一般为5-150巴，优选5-80巴，特别是5-50巴。
氢气和一氧化碳(合成气)一般是以1-2.5的原子比用于该方法的。已知氢气与一氧化碳的原子比低会加大费-托催化剂的C5 +选择性。现出乎意料的发现，本发明催化剂的C5 +选择性明显增大，甚至当采用氢气与一氧化碳原子比高的合成气时也如此。在本发明的烃合成方法的优选实施方案中，氢气与一氧化碳的原子比为1.5-2.5。
该气体的时空间速度可在宽范围内变化，一般是在400-10000N1/1/h，例如为400-4000N1/1/h。
制备烃的方法可以采用各种类型反应器和反应方案，例如固定床方案、膏糊相方案或者沸腾床方案。显然，催化剂颗粒的粒度根据它们采用的反应方案而变化。对给定反应方案选择最合适的催化剂颗粒粒度，这属于本领域技术人员的常识。
另外，应当了解，本领域技术人员能够选择具体反应器配置和反应方案的最佳条件。例如，优选的气体时空间速度可以根据所采用的反应方案确定。因此，如果需要采用固定床方式进行烃合成方法，优选的气体时空间速度为500-2500N1/1/h。如果需要通过采用膏糊相方式进行烃合成方法，优选的气体时空间速度为1500-7500N1/1/h。
本发明通过下面实施例进行进一步说明。实施例1(对比)
将金红石类的市售二氧化钛颗粒(30-80目)用浓缩的硝酸钴溶液浸渍。
该溶液的制备是通过将硝酸钴固体(Co(NO3)2.6H2O)加热到60℃，使硝酸钴溶解在其结晶水中。将浸渍的二氧化钛颗粒在120℃干燥2小时，接着在空气中在400℃焙烧4小时。这样生成的催化剂(I)用金属钴表示，含有10％重量的钴化合物。实施例II
重复实施例I的步骤，不同的是浸渍溶液还含有硝酸锰。以与实施例I同样的方式制备溶液，但是部分硝酸钴固体用硝酸锰代替(Mn(NO3)2.4H2O)。
催化剂(II)用金属表示，含有10％重量的金属化合物。钴∶锰的原子比为20∶1。实施例III(对比)
重复实施例II的步骤，但是，浸渍溶液含有更多的硝酸锰。
催化剂(III)用金属表示，含有10％重量的金属化合物。钴∶锰的原子比为10∶1。实施例IV
将催化剂I、II和III在制备烃的方法中进行试验。将分别装有10克催化剂I、II和III的微流反应器A、B和C加热到260℃，用连续的氮气流加压到2巴的压力。用氮气和氢气的混合物将催化剂就地还原24小时。在还原反应过程中，氢气在混合物中的相对量一般从0％升高到100％。在排出气体中的水浓度保持低于3000ppmv。
之后还原，反应压力升高到26巴。进行还原反应时氢气和一氧化碳的混合物的原子比H2/CO为2∶1的，并在200℃进行。GHSV量为800N1/1/h。
用每升催化剂每小时烃产物的克数来表示的时空产率(STY)和用烃产物的总的重量百分数表示的C5 +选择性，对每个反应器在进行100小时之后测定。
结果列于表I。
                        表I反应器：      A              B                C催化剂        I(无Mn)        II(Co/Mn＝20)    III(Co/Mn＝10)STY(g/l/h)    70             100              65C5+选择性(％)89             91               87
显然，本发明催化剂II的活性和选择性优于不属于本发明的催化剂I和II。
因此，本发明进一步涉及锰和/或钒在用于制备烃的方法中提高了含钴催化剂的活性和/或C5 +选择性。

Claims (10)

1.一种含有负载于载体上的钴和锰和/或钒的催化剂，其中钴∶(锰+钒)的原子比至少为12∶1，其条件是：催化剂在二氧化硅载体上不以39∶1的原子比含有钴和锰。
2.一种含有负载于载体上的钴和锰和/或钒的催化剂，其中钴∶(锰+钒)的原子比至少为12∶1，并且其中载体包括二氧化钛、氧化锆或其混合物。
3.根据权利要求1或2所说的催化剂，其中钴∶(锰+钒)的原子比至少为15∶1。
4.根据权利要求1到3中任意一个所说的催化剂，其中钴∶(锰+钒)的原子比至多为1500∶1。
5.根据前面任意一个权利要求所说的催化剂，至少部分钴是金属状态。
6.一种制备权利要求1到4中任意一个所说的催化剂的方法，它包括用钴盐的溶液和锰盐和/或钒盐的溶液浸渍，接着干燥，并选择性的焙烧。
7.根据权利要求6所说的制备方法，它包括用钴盐和锰盐和/钒盐的溶液共同浸渍载体。
8.根据权利要求5所说的制备方法，它包括将在权利要求1到4中任意一个所说的催化剂在氢存在情况下进行还原反应。
9.一种烃的制备方法，它包括将高温高压的一氧化碳和氢气的混合物与权利要求5所说的催化剂接触。
10.权利要求1到5中任意一个所说的催化剂用于制备烃的用途。
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TW349882B (en) 1999-01-11
DZ2051A1 (fr) 2002-10-23
CN1087193C (zh) 2002-07-10
NO975881L (no) 1997-12-15
CA2224690C (en) 2007-06-05
ZA965078B (en) 1997-01-23
PE12497A1 (es) 1997-05-09
EA000319B1 (ru) 1999-04-29
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US5981608A (en) 1999-11-09
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BR9608451A (pt) 1999-01-05
DE69632189T2 (de) 2005-04-21
EP0833807B1 (en) 2004-04-14
AU6303396A (en) 1997-01-15
AU698391B2 (en) 1998-10-29
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JP4319701B2 (ja) 2009-08-26
JPH11507866A (ja) 1999-07-13
EA199800068A1 (ru) 1998-08-27
WO1997000231A1 (en) 1997-01-03
MY117350A (en) 2004-06-30
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