CN103140459A - 改善的非氧化脱氢的方法 - Google Patents

改善的非氧化脱氢的方法 Download PDF

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CN103140459A
CN103140459A CN2011800474074A CN201180047407A CN103140459A CN 103140459 A CN103140459 A CN 103140459A CN 2011800474074 A CN2011800474074 A CN 2011800474074A CN 201180047407 A CN201180047407 A CN 201180047407A CN 103140459 A CN103140459 A CN 103140459A
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alkane
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L.罗
D.C.罗森菲尔德
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Abstract

本申请披露使用包含催化剂载体以及镍、镓和任选的在碱金属、碱土金属和镧系金属中的一种或多种的组合的负载型催化剂来实现无氧气流非氧化脱氢成产物流，所述无氧气流包含烷烃诸如乙烷、丙烷或丁烷，所述产物流包含相应的烯烃，诸如当所述烷烃是丙烷时丙烯。

Description

改善的非氧化脱氢的方法
本申请是非临时申请，其要求2010年9月30日提交的标题为“IMPROVED NON-OXIDATIVE DEHYDROGENATIVE PROCESS"的美国临时专利申请61/388,087的优先权，该美国临时专利申请的教导引入本文作为参考，如同其完全复制在下文中那样。
本发明总的涉及在循环流化床反应器(优选，基于提升管反应器的循环流化床反应器)中将烷烃非氧化型脱氢为其相应的烯烃(具体用于将乙烷脱氢为乙烯、将丙烷脱氢为丙烯、或者将丁烷脱氢为丁烯)的改善方法，更具体涉及用于所述改善方法中的活性稳定催化剂。
一般而言烷烃脱氢(ADH)以及具体而言丙烷脱氢(PDH)受到热力学的限制。通过升高反应温度增大了烷烃转化率，具体地丙烷转化率，然而导致比未升高反应温度时更快速的催化剂失活和更高比率的成焦。此外，升高反应温度的努力导致向用于实现烷烃(例如丙烷)脱氢的装置供应更多热量的难题。
常规的ADH或PDH催化剂通常要求高载量(例如10重量%(wt%)以上，基于总的催化剂重量)的氧化铬(作为Cr2O3，带来一些环境顾虑的物质)或者铂(Pt，非常昂贵的贵金属)。除了非常昂贵之外，至少部分地由于Pt损失、消耗、Pt金属烧结和被焦块阻断活性位点中的一种或多种原因，基于Pt的催化剂还会发生失活。
美国专利(US)4,056,576(Gregory et al.)披露了通过在负载的镓(Ga)催化剂的存在下使含有3-8个碳原子(C3-C8)的饱和烃脱氢制备不饱和烃的方法。合适的载体包括氧化铝诸如η-氧化铝，γ氧化铝和勃姆石，具有或者不具有可被选自Ga、铝(Al)、铁(Fe)和镍(Ni)的金属离子交换的表面羟基的氧化铝和二氧化硅，活性炭和耐火氧化镓。催化剂可包含其它金属诸如钯(Pd),Pt,铟(In)、铊(Tl)、锗(Ge)、铬(Cr)、锡(Sn)和锌(Zn)。
US4,125,565(Antos)教导使用在多孔载体上包含铂族组分(Pt、Pd、铱(Ir)、锇(Os)、钌(Ru)、铑(Rh)或它们的混合物)、镍(Ni)组分和铋(Bi)组分的催化复合物使烃脱氢。该复合物还可包含碱金属或碱土金属组分。
US4,914,075(Bricker,J.C.et al.)披露烃脱氢催化剂，其包括VIII族贵金属(Pt、Pd、Ir、Rh、Os、Ru或者它们的混合物)，选自锡(Sn)、锗(Ge)、铅(Pb)、铟(In)、Ga、铊(Tl)或者它们的混合物的第二组分，和选自碱金属、碱土金属或者它们的混合物的第三组分。这些组分负载在θ-氧化铝上。催化剂在固定床、移动床或流化床系统中接触可脱氢的烃。类似的催化剂组合物还可参见US6,756,340(Voskoboynikov et al.)。
US7,235,706(Iezzi et al.)提供在流化床型反应器和再生器中脱氢相应的石蜡制备轻烯烃的方法。该催化剂包括在氧化铝上的Ga(作为Ga2O3)、Pt、碱土金属或碱金属和二氧化硅。所述氧化铝呈δ+θ相、θ+α相、或者δ+θ+α混合相。
PCT申请(WO)2005/077867(Pretz et al.)讨论了循环流化床(CFB)方法用于使用包含在氧化铝或氧化铝-二氧化硅载体上的Ga的催化剂将石蜡烃化合物诸如烷烃(例如丙烷)脱氢至其相应的烯烃(丙烯，在丙烷作为烷烃的情形中)或者将烷基芳族化合物(例如乙基苯)脱氢至其相应的芳族化合物(苯乙烯，在乙基苯作为烷基芳族化合物的情形中)。催化剂也可包含至少一种碱金属或碱土金属以及Pt和锰(Mn)中的至少一种。CFB方法适宜地采用管型、圆柱状提升管反应器，其在上端连接产物气体出口管线并且在下端连接新鲜或再生的催化剂管线。该方法使用分离装置来从产物气体中分离消耗或者失活的催化剂并将该消耗或失活的催化剂送至再生器中。再生的催化剂经新鲜或再生催化剂管线流回反应器。燃烧空气和任选的补充燃料提供实现脱氢反应所需的反应热和显热。
US6,031,143(Buonomo et al.)教导了使用催化剂进行脱氢制备苯乙烯的方法，所述催化剂基于在氧化铝上的Ga和Pt，该氧化铝呈δ或θ相，或者呈δ和θ的混合相、呈θ和α的混合相、或者呈δ、θ和α相的混合相，其用二氧化硅改性并具有小于100m2/g的BET表面积。
包括US7,498,289(Liu)、US7,227,049(Liu)、US6,777,371(Liu)、US6,417,422(Liu)、US6,355,854(Liu)和US6,436,871(Liu)的案例家族提供关于催化剂和烷烃(例如丙烷)氧化脱氢的方法的教导。该催化剂包含(i)镍(Ni)或者含镍化合物，以及(ii)钛(Ti)、钽(Ta)、铌(Nb)、铪(Hf)、钨(W)、钇(Y)、锌(Zn)、锆(Zr)或铝(Al)中至少一种，或者包含一种或多种所述元素的化合物。优选的催化剂包括催化剂载体。该方法要求氧气与烷烃在250°C至350°C的温度共进料。US6,436,871指出催化金属是氧化物。还可参见相关的WO00/48971。
US5,639,929(Bharadwaj et al.)涉及通过使2-6个碳(C2-C6)的烷烃与含氧气体在负载在α-氧化铝或氧化锆上的铂(Pt)、铑(Rh)、Ni或铂-金(Pt-Au)的催化剂流化床中接触氧化脱氢烃。还可参见相关的PCT申请WO96/33149。
US5,254,779(Mazzocchia et al.)教导了镍-钼氧化物催化剂及其在丙烷于400°C至700°C的温度氧化脱氢的用途。还可参见相关的EP379433。
US4,751,342(Kimble)披露了在游离氧、蒸汽和包含Ni、磷(P)、锡(Sn)、氧(O)和任选的碱金属的催化剂的存在下将C2-C12石蜡脱氢至烯烃的方法。该方法要求氨气(NH3)以NH3:石蜡之比为至少1:100存在。
在一些方面中，本发明是将包含选自乙烷、丙烷和丁烷的烷烃的无氧气体进料流催化转化为包含与所述烷烃对应的烯烃(乙烯源自乙烷，丙烯源自丙烷，丁烯源自丁烷)的产物流的改善的非氧化脱氢方法，其通过使气体进料流与在反应温度下并顺流通过脱氢反应器的脱氢催化剂接触进行，气流与催化剂之间的平均接触时间小于或等于20秒，其中所述改善包括使用负载型催化剂，所述负载型催化剂基本上由在催化剂载体上的镍、镓和任选的选自VIII族贵金属、碱金属、碱土金属和镧系金属中一种或多种元素组成。
使用Ni允许在比使用Pt作为催化剂金属时低的成本下实现PDH。还允许避免使用Cr作为催化剂金属时的上述环境顾虑。
反应温度优选在570°C至750°C范围内。在反应器中的压力优选在50.7千帕(KPa)至2兆帕(MPa)的范围内，更优选101KPa至304KPa的范围内。
在提升管反应器中，将烷烃(例如乙烷、丙烷或丁烷)进料流注入提升管反应器中并将进料流与热催化剂混合形成合并的流料，其在提升管反应器中向上移动，与所述向上移动顺流的进料流发生脱氢。催化剂和气体产物离开提升管反应器，进入分离区或分离装置诸如旋风分离器。分离之后，用氮气(N2)汽提催化剂，然后将其送至再生器中。在再生器中，从催化剂中除去焦块，将其加热至目标温度(例如600°C至800°C)，任选地用惰性气体汽提，然后将已经加热的催化剂循环回到提升管反应器中。本文所述的提升管反应器、分离区和再生器的组合也称之为“循环流化床反应器”。
催化剂包含中过渡金属或后过渡金属，有时也称之为VIII族(也称为VIIIA族或第8、9和10族，取决于所用的元素周期表的命名或版本)金属。所述金属包括铁(Fe)、钌(Ru)、锇(Os)、钴(Co)、铑(Rh)、铱(Ir)、镍(Ni)和钯(Pd)。除了中过渡金属或后过渡金属(优选Ni)之外，催化剂必须包含镓(Ga)并且它任选地包含选自VIII族贵金属(不同于中过渡金属或后过渡金属、碱金属、碱土金属和镧系金属)的一种或多种元素。VIII族贵金属包括Rh、Ir、铂(Pt)、Pd、Ru和Os，其中当存在VIII族贵金属时优选Rh、Ir、Pt和Pd。当存在VIII族贵金属时，其为不同于所述中过渡金属或后过渡金属的元素。例如，当所述中过渡金属或后过渡金属(广义上也命名为VIII族)是Ni时，Pt是优选的VIII族贵金属。将所有的所述金属分散在催化剂载体优选氧化铝载体上。氧化铝载体任选地还包含0wt%(当不存在二氧化硅时)至2wt%的二氧化硅，其中1.5wt%二氧化硅得到非常满意的结果，并且各wt%均基于载体总重量。氧化铝载体可包含下面氧化铝相中的一种或多种：α、δ、γ和θ。催化剂优选包含以下物质或者基本上由以下物质组成或者由以下物质组成：镍、钌、钴或铁中的至少一种(更优选镍)以及镓和任选的选自铯、锂和钾的碱金属(优选钾)。
催化剂载体的Brunauer、Emmet和Teller(BET)表面积为50平方米/克(m2/g)至150m2/g，优选65m2/g至125m2/g，其中使用表面积70m2/g获得非常满意的结果。
中过渡金属或后过渡金属(优选Ni)的存在量为10重量份/百万重量份的负载型催化剂(ppm)至500ppm，优选25ppm至500ppm，更优选50ppm至200ppm。Ga的存在量为0.1wt%至5wt%，优选0.2wt%至2.0wt%，基于负载型催化剂的重量。碱金属、碱土金属或镧系金属，优选碱金属，更优选铯、锂或钾的存在量为0wt%至5wt%，优选0.05wt%至1wt%。当催化剂包括VIII族贵金属时，VIII族贵金属(例如，Pt)替换了部分但不是全部的中过渡金属或后过渡金属(例如Ni)。中过渡金属或后过渡金属与VIII族贵金属之比优选为100:0至小于0:100。为了避免困惑，0wt%载量是指催化剂不包含任选的碱金属、碱土金属或镧系金属中任一种。
催化剂制备可经任何常规技术诸如在下面的说明性实施例中采用的水性初始湿润(aqueous incipient wetness)进行。催化剂制备包括用一种或多种催化剂金属前体的溶液湿润经干燥的催化剂载体，干燥该湿润的催化剂载体，而后煅烧该湿润然后干燥的催化剂载体。煅烧优选在小于750°C的温度例如在约600°C的温度进行。
上文所述的循环流化床反应器允许烷烃进料流与经加热的催化剂之间的短暂接触时间。接触时间优选小于20秒，更优选2秒至5秒。短暂的接触时间最小化了次级反应诸如产物(烯烃)分解和成焦。催化剂在反应器中具有短暂的停留时间，通常大约0.5秒至40秒，这相对于长得多的停留时间诸如9至15分钟时提高了催化剂活性的保持。
在后续的段落中，带有阿拉伯数字的“Ex”表示说明本发明方面的实施例，而带有大写之母的“CEx”指示对比例。
Ex1
在操作在350°C的设置点温度的烘箱中，预干燥300克(g)的氧化铝/二氧化硅等分试样(1.5wt%二氧化硅，基于氧化铝和二氧化硅的总重量)(SIRALOXTM1.5/70，可商购自Sasol)两(2)小时(hr)。从烘箱中移出等分试样，使其冷却至环境温度(通常25°C)。将60g的预干燥等分试样置于600毫升(mL)烧杯中。向装备磁搅拌子的100mL烧杯中装入0.016g六水合硝酸镍(Ni(NO3)2(H2O)6)、0.388g硝酸钾(KNO3)、5.01g六水合硝酸镓(Ga(NO3)3(H2O)6)和13.2mL去离子水(DI)。搅拌该100mL烧杯中的内容物直至金属硝酸盐溶解形成视觉上均匀的溶液。搅拌下，向在该600mL烧杯内的预干燥的等分试样中加入少量等分试样(小于1mL的所述100mL烧杯中的内容物)以实现金属硝酸盐分散至预干燥的等分试样之中和之上。用约2mL去离子水淋洗100mL烧杯，然后将淋洗水加入该600mL烧杯中，继续搅拌以提供湿润的载体。停止搅拌并将该600mL烧杯置于通风橱中过夜。从通风橱中移出烧杯，将其内容物在120°C干燥4小时，然后将内容物在600°C煅烧4小时。经煅烧材料(催化剂)的镍含量为50重量份/百万重量份(ppm)的经煅烧材料，钾含量为0.25wt%，以及镓含量为1.6wt%，各wt%均基于经煅烧材料的重量。移出10g的经煅烧的烧杯内容物，使其在750°C经受第二次煅烧，煅烧历时4小时。
使用塞流反应器评价在600°C煅烧的催化剂的性能，该塞流反应器经改进以测试在反应物与催化剂之间的短暂接触时间下的催化剂，将与1g作为稀释剂的碳化硅(SiC)混合的0.5g催化剂暴露于包含56.4摩尔%(mol%)丙烷、40.7mol%氦气和2.9mol%氮气的进料流，各mol%均基于丙烷、氦气和氮气的总摩尔数，以30小时-1(hr-1)流速流动，反应压力为1个大气压(atm)(101.3千帕(KPa)，反应温度为580°C。催化剂通过以下方法再生：在150标准立方厘米/分钟的空气流下，使其暴露于700°C的温度900秒的时段。
气相色谱用于分析流出物组成。在20秒的催化剂反应运行时间(TOS或者催化剂在上述反应条件下暴露于进料流)之后以及再在10分钟的催化剂TOS之后进行取样用于GC分析。被分析的化合物包括甲烷、乙烷、乙烯、丙烷、丙烯、C4(丁烷和丁烯)、C5、C6、N2内标、CO和CO2。
如下计算烷烃转化率和对其相应的烯烃的选择性(例如乙烷至乙烯、丙烷至丙烯或者丁烷至丁烯)：
·烷烃转化率=每分钟在产物中烷烃当量的总摩尔数/(每分钟在流出物中的烷烃摩尔数+每分钟在产物中烯烃当量的总摩尔数)
·对烯烃的选择性=每分钟在烯烃中的烷烃当量的摩尔数/每分钟在产物中烷烃当量的总摩尔数
Ex2、Ex3和CEx A至CEx F
重复Ex1，其中煅烧仅在600°C进行，但是对于CEx A将镍含量改变为0ppm，对于CEx B改变为10ppm，对于CEx C改变为25ppm，对于Ex2改变为100ppm，对于Ex3改变为200ppm，对于CEx D改变为500ppm，对于CEx E改变为1000ppm，对于CEx F改变为5000ppm。对于20秒TOS，丙烷转化率、丙烯选择性和丙烯产率数据参见下表。
CEx G
重复Ex3，但是除去镓。结果总结于下表1中。
CEx H至CEx M
重复Ex1，但是将催化剂的镍含量如下表1所示进行改变，并且如上所详述，所使用的催化剂已经在750°C进行第二煅烧。结果总结于下表1中。
表1.催化剂性能数据
Figure BDA00002988701600071
将Ex1至Ex3与CEx A至CEx F进行比较，表明在这些实施例和对比例中所指出的催化剂制备和反应条件下，镍载量大于25ppm(CEx C)和小于500ppm(CEx D)提供比镍载量为0ppm(CEx A)或500ppm(CEx D)时更大的丙烷转化率，其中镍载量50ppm(Ex1)提供最佳的丙烷转化率。Ex3与CExH的比较表明催化剂必须包含3种金属(镓、镍和钾)，而不是两种金属(镍和钾)。CEx H至CEx M显示在750°C的第二煅烧负面地影响丙烷转化率，但是最高镍载量5000ppm除外。CEx H至CEx M因此建议催化剂在小于750°C的温度煅烧，其中Ex1至Ex3的600°C煅烧得到非常满意的结果。

Claims (10)

1.一种将包含选自乙烷、丙烷和丁烷的烷烃的无氧气流催化转化为包含与所述烷烃对应的烯烃的产物流的改善的非氧化脱氢方法，其通过使气体进料流与在反应温度下并顺流通过脱氢反应器的脱氢催化剂接触进行，气流与催化剂之间的平均接触时间小于或等于20秒，
其中所述改善包括使用负载型催化剂，所述负载型催化剂基本上由在催化剂载体上的镍、镓和任选的选自VIII族贵金属、碱金属、碱土金属和镧系金属中一种或多种元素组成。
2.权利要求1的改善的方法，其中所述负载型催化剂的镍载量在从大于25重量份至小于500重量份的范围内，在各情形中均基于百万重量份的负载型催化剂。
3.权利要求1或2的改善的方法，其中所述催化剂是在与气体进料流接触之前已经在小于750°C的温度经受煅烧的催化剂。
4.权利要求1～3中任一项的改善的方法，其中所述载体选自氧化铝和氧化铝-二氧化硅。
5.权利要求4的改善的方法，其中所述催化剂载体是BET表面积在50平方米/克至150平方米/克范围内的氧化铝。
6.权利要求1～5中任一项的改善的方法，其中所述反应温度在570°C至750°C的范围内，并且脱氢反应器内的压力在50.7千帕至2兆帕的范围内。
7.权利要求1～6中任一项的改善的方法，其中所述烷烃是丙烷，相应的烯烃是丙烯。
8.权利要求1～7中任一项的改善的方法，其中所述负载型催化剂的镓载量在0.1wt%至5wt%的范围内，在各情形中都基于负载型催化剂的重量。
9.权利要求1～8中任一项的改善的方法，其中所述负载型催化剂的碱金属、碱土金属或镧系金属载量在0wt%至5wt%的范围内，在各情形中都基于负载型催化剂的总重量。
10.权利要求9的改善的方法，其中所述碱金属、碱土金属或镧系金属是选自铯、锂和钾的碱金属。
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Application publication date: 20130605