CN1222902A - 1,4-丁炔二醇催化氢化制备1,4-丁二醇的方法 - Google Patents
1,4-丁炔二醇催化氢化制备1,4-丁二醇的方法 Download PDFInfo
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- CN1222902A CN1222902A CN97195779A CN97195779A CN1222902A CN 1222902 A CN1222902 A CN 1222902A CN 97195779 A CN97195779 A CN 97195779A CN 97195779 A CN97195779 A CN 97195779A CN 1222902 A CN1222902 A CN 1222902A
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- butanediol
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Abstract
一种将1,4-丁炔二醇连续催化氢化制备1,4-丁二醇的方法,该方法包括在20至300℃,在1至200巴的压力,以及0.1秒-1至1秒-1的以体积表示的液体侧传质系数kLa值下,将1,4-丁炔二醇与氢气在氢化催化剂的存在下于液态连续相中进行反应,a)采用悬浮于反应介质中的催化剂,如果采用填充的泡罩塔,则其操作方式为向上流动,离开反应器的气体与加料进入反应器的气体的比例为0.99∶1至0.4∶1,或b)使液体和气体平行向上流经气体循环模式操作下的固定床反应器,同时使加料进入反应器的气体与离开反应器的气体的比例维持在0.99∶1至0.4∶1。
Description
本发明涉及1,4-丁二醇的制备方法,它是在固体氢化催化剂的存在下,在1至200巴压力和以体积表示的液体侧传质系数(volumetricliquid-side mass transfer coefficient)kLa值为0.1秒-1至1秒-1,通过1,4-丁炔二醇与氢气的催化氢化而实现的,其中液体构成连续相,氢气构成分散相。
由下式简要地表示出各个组成步骤的1,4-丁炔二醇氢化制备1,4-丁二醇的方法几十年来已为人们所熟知,并多次在文献中被报道: 但是,已知方法的缺点是时空产率(STY,space-time yield)低,即单位反应器容积和单位时间所消耗的起始原料的数量低,当在200巴以下的压力下进行氢化反应时,催化剂的使用寿命短且选择性低,因而是不经济的。此外,当采用固定床催化剂时,氢化反应需要在大于200巴的高压下进行,这进一步需要更多的资本投资。
此外,将1,4-丁炔二醇、1,4-丁烯二醇和它们的衍生物,例如丁二醇的缩醛和丁烯二醇的异构化所生成的羟基丁醛,通过蒸馏与1,4-丁二醇实现完全分离是很困难的。但在1,4-丁二醇的进一步应用中,大多数情况下没有未彻底氢化产物的存在是十分重要的。
在化学反应中,选择性一般随转化率的提高而降低。因此为了尽量获得较高的选择性,人们总是一方面设法将反应在尽可能低的温度下进行,另一方面使反应维持在部分转化的水平。在丁炔二醇的氢化反应中,为了在后处理中确保产物质量,反应物的完全转化是必需的,而且氢化反应往往分布在处于不同条件下的多个反应器中进行。
US-A5068468公开了在固体负载型镍/铜催化剂催化下的1,4-丁炔二醇的氢化反应,在250巴的压力下,丁二醇的时空产率为0.3千克/升·小时。
BE-B745225公开了在259巴的压力下采用兰尼镍固定床催化剂的制备方法,通过两步反应,丁二醇的时空产率为0.286千克/升·小时。
US-A4153578公开了在21巴的压力下采用悬浮的兰尼镍/钼催化剂催化的1,4-丁炔二醇氢化的两步法。该方法所达到的丁二醇的时空产率为0.06千克/升·小时。
DD-A272644叙述了在镍/SiO2催化剂催化下的丁炔二醇水溶液的悬浮型氢化反应。假定丁炔二醇采用通常的39%至50%重量的浓度并且假定其完全转化,在15巴的压力下丁二醇的理论时空产率为0.15至0.25千克/升·小时。仅仅经过50小时后,催化剂的活性损失达37%。
对于US-A2967893的实施例1,在兰尼镍/铜催化下的1,4-丁炔二醇的氢化反应,其理论丁二醇的时空产率约为0.01千克/升·小时。
RU-A202913叙述了在镍/铬催化下的丁炔二醇的氢化反应,其丁二醇的时空产率约为0.1千克/升·小时。
EP-B0319207、DE-A1941633和DE-A2040501特别公开了适用于1,4-丁炔二醇的通用氢化方法,其中没有采用反应器的气体循环操作模式,而是采用了气体和液体并行向上通过固定床催化剂的模式。这里,气体和液体以转移物流的形式流经催化剂,液相构成连续相。
然而,这些方法共有的缺点是,当氢化反应的进料中丁炔二醇的量较多时,在反应区的末端出口处反应混合物中的氢气则被完全消耗,结果导致1,4-丁炔二醇不能完全转化,而要使因此产生的中间产物与丁二醇实现完全分离则非常困难。当丁炔二醇的量较少时,只有在显著地降低时空产率或提高操作压力下才能获得丁炔二醇的完全转化和理想的产物质量。
本发明的目标是提供1,4-丁炔二醇的催化氢化制备1,4-丁二醇的方法,在低于200巴的压力下和甚至当采用工业级的1,4-丁炔二醇时,该方法可以实现高的时空产率和高选择性,以及催化剂的长催化寿命。
我们发现通过1,4-丁炔二醇连续催化氢化而制备1,4-丁二醇的方法可以实现该目标,该方法包括在20至300℃、优选60至220℃、特别是120至180℃下,在1至200巴、优选3至150巴、特别是5至100巴的压力下,以及0.1秒-1至1秒-1、优选0.2秒-1至1秒-1的以体积表示的液体侧传质系数kLa值下,将1,4-丁炔二醇与氢气在氢化催化剂的存在下于液态连续相中进行反应,
a)采用悬浮于反应介质中的催化剂,如果采用填充的泡罩塔,则其操作方式为向上流动,离开反应器的气体与加料进入反应器的气体的比例为0.99∶1至0.4∶1,或
b)使液体和气体平行向上流经气体循环模式操作下的固定床反应器,同时使加料进入反应器的气体与离开反应器的气体的比例维持在0.99∶1至0.4∶1。
本发明的方法在低于200巴的压力下通过一步或多步氢化反应以较高的时空产率和较高的选择性实现了1,4-丁二醇的制备。此外,本发明中催化剂的使用寿命也比较长。
气相和液相之间的以体积表示的液体侧传质系数kLa定义为:
kLa=kGL×FGL其中kGL为气-液传质的传质系数和FGL为气-液相界面的面积。kLa值例如在Ullmanns技术化学百科全书(第4版)第3卷第495至499页(Ullmanns Encyclopdie der technischen Chemie,VerlagChemie,4th edition(1973),Volume 3,pages 495-499)中介绍,它也被定义为比吸附速率。
实验上是在给定操作温度下测量在50%重量丁二醇和50%重量水的混合物中所吸附的氢气量来确定kLa的数值。实验测定kLa值的方法在多种文献中已有过介绍,例如P.Wilkinson等发表的“在加压泡罩塔中的传质和气泡大小分布”,化工科学(Chemical EngineeringScience),第49卷(1994),1417-1427页;Ullmanns化学技术百科全书(Verlag Chemie,Weinheim/Bergstr.),第4版,1973,第3卷,495-499页;H.Hoffmann发表的“填充的上行泡罩塔(GepackteAufstrom-Blasensaulen)”,化学-工程师-技术(Chem.-Ing.-Tech.)54,(1982),第10期,865-876页;以及A.Marquez等发表的“测定气-液反应器中的体积传质系数KLa的近期化学方法的综述”,化学工程与加工(Chemical Engineering and Processing),33(1994)247-260页。
根据在实施本发明的方法时所采用的高kLa值,优选氢气吸附量的测量在连续操作的状态下进行。在预期的温度下以尽可能大的流量将液体混合物进料,其中不含氢气和根据需要与悬浮的催化剂一起进料。液体混合物的流速应高至足以使反应器中的液体物质在至少2分钟内、优选在1分钟或更短的时间内实现被新的液体物质所置换。与此同时,吸满氢气的液体混合物被放出,压力降至1大气压,测量此时释放的溶解氢气的体积。对气相中氢气的分压也进行测量。
本发明的方法优选采用工业级的1,4-丁炔二醇,它是一种含水溶液,其中还可含有不溶解的或溶解的源于丁炔二醇合成中的组分,如铜、铋、铝或硅化合物。当然也可以采用经纯化的例如蒸馏过的丁炔二醇。工业上丁炔二醇是由乙炔和甲醛水溶液为原料而制备的,通常以30至60%重量浓度的水溶液形式来进行氢化。但氢化反应也可以在其它溶剂中进行,例如醇类溶剂如甲醇、乙醇、丙醇、丁醇或1,4-丁二醇。氢化反应所需要的氢气优选采用纯氢气,但它也可以含有其它组分例如甲烷和一氧化碳。
根据本发明,催化剂选用那些能够将C-C叁键和双键氢化为单键的催化剂。这种催化剂通常含有一种或多种元素周期表中第Ⅰ、Ⅵ、Ⅶ和Ⅷ过渡族中的元素,优选铜、铬、钼、锰、铼、铁、钌、钴、镍、铂和钯。特别优选那些含有选自铜、铬、钼、铁、镍、铂和钯的至少一种元素的催化剂。
这些催化剂中金属元素的含量一般为0.1至100%重量,优选为0.2至95%重量,特别是0.5至95%重量。
催化剂优选还含有选自元素周期表第Ⅱ、Ⅲ、Ⅳ和Ⅵ主族,第Ⅱ、Ⅲ、Ⅳ和Ⅴ过渡族和镧系中的至少一种元素作为促进剂以提高催化剂的活性。
催化剂中促进剂的含量一般至多为5%重量,优选为0.001至5%重量,特别是0.01至3%重量。
催化剂可以采用沉淀型、负载型或兰尼型催化剂,它们的制备在例如Ullmanns技术化学百科全书(第4版,1977年)第13卷第558至665页中有介绍。
催化剂可采用的载体材料有氧化铝、氧化钛、二氧化锆、二氧化硅、粘土如蒙脱土、硅酸盐如硅酸镁或硅酸铝、沸石和活性炭。优选载体材料为氧化铝、二氧化钛、二氧化硅、二氧化锆和活性炭。当然,各种载体材料的混合物也可以作为本发明方法的催化剂的载体。
这些催化剂可制成一定形状如球形、柱形、环形或螺旋形的催化剂来使用,或以粉末的形式使用。
使用的兰尼型催化剂例如有兰尼镍、兰尼铜、兰尼钴、兰尼镍/钼、兰尼镍/铜、兰尼镍/铬、兰尼镍/铬/铁或铼海绵状物。兰尼镍/钼催化剂例如可采用US-A4153578所述的方法来制备。但这些催化剂也可以购买得到,例如可向Degussa,63403 Hanau,Germany购买。例如,Degussa公司的一种兰尼镍/铬/铁催化剂的商品名为Katalysator Typ11112W_。
当采用沉淀型或负载型催化剂时,这些催化剂在反应的初始时在150至500℃下在氢气或氢气/惰性气体中被还原。这种还原处理可以直接在合成反应器中进行。如果这种还原在一个独立的反应器中进行,在催化剂从该独立的反应器中取出之前可以在30℃下用含有氧气的气体混合物将催化剂的表面进行钝化。在这种情况下,被钝化的催化剂可以在使用之前在180℃下于合成反应器中用氮气/氢气流进行活化,也可以不经过活化直接使用。
催化剂可以固定床或以悬浮体的形式使用。如果催化剂采用固定床形式,则根据本发明,反应器不采用通常的向下流动的模式,而是采用液体与气体平行向上流动的方式进行操作,并且作为流动相的是液体而不是气体。
所用的悬浮催化剂一般其粒径为0.1至500微米,优选为0.5至200微米,特别是1至100微米。
如果采用悬浮催化剂,那么当采用填充泡罩塔时,反应同样也是采用液体与气体平行向上流动的方式而实施的,作为流动相的是液体而不是气体。当采用固定床反应器和当采用填充的泡罩塔而且催化剂悬浮于反应介质中时,离开反应器的气体与加料进入反应器的气体的比例为0.99∶1至0.4∶1。
在本发明采用固定床反应器的情况下和采用在填充的泡罩塔内悬浮于反应介质中的催化剂的情况下,通过计量加入新的氢气,或如工业中优选的那样将气体进行再循环、同时补偿由于化学反应造成的氢气损失和用新的氢气来替换废气,可以容易地将离开反应器的气体与加料进入反应器的气体的比例维持在应达到的水平。
在反应器中氢气与丁炔二醇的摩尔比至少为3∶1,优选为4∶1至100∶1。
本发明的方法采用固定床催化剂,在气体循环的方式下进行,即离开反应器的气体,如需要在补偿新的氢气之后,通过一气体压缩机的压缩而返回反应器中。可以用喷射压缩机来传输所有的循环气体或其中的部分气体。在该优选的实施方案中,循环气体压缩机被一较便宜的喷嘴所代替。压缩动力通过同样进行循环的液体来传输。操作喷射压缩机所需的液体压力的增加为约3至5巴。
实施采用固定床催化剂的本发明方法所适用的反应器有例如图1所示的固定床反应器或图2所示的管束反应器。
图1图示出本发明方法可采用的固定床反应器的装置示意图。反应器1含有平均粒径约为1至20毫米,优选为2至5毫米的催化剂颗粒2的床。为防止催化剂颗粒从反应器中被带出,在催化剂床的上端有一线网3。通过管线4传输的含有丁炔二醇和水的液体进料流与通过管线5的循环液体(作为驱动喷射流)一道进入混合喷嘴6,这里同时混入的还有通过管线7传输的新的氢气和通过管线8传输的循环气体。气液两相混合物9从反应器的上端离开反应器,在气液分离器10中进行相分离。气体流11的分支流12被排放到外界以避免惰性组分的过多富集。循环气体流8经压缩机13的压缩循环进入喷嘴6中。如果通过泵21传输的循环液体5能够提供足够高的压力并且混合喷嘴6被设计成一喷射压缩机的话,压缩机13可以被省略。循环液体的分支流14作为产物流进行放料。反应所放出的热量通过热交换器16而被交换。
本发明的方法不仅能够在图1所示的绝热控制的固定床反应器中进行,而且也可以在图2所示的等温控制的管束反应器中进行。
图2图示出管束反应器的装置示意图,其中平均粒径约为1至20毫米,优选为2至5毫米的催化剂颗粒2分布在管15中。
在图1所示的固定床反应器和图2所示的管束反应器中,循环液体5与产物14的比例为100∶1至500∶1,优选为200∶1。反应器直径大小的选择应使液体的空管速度达到100至1000米/小时。每种催化剂适合的空管速度在实验室设备上测定。空管速度最好选择催化剂未发生磨损所允许的最大速度。在空管速度超过约1000米/小时下,发现对于小催化剂颗粒,存在因压力降的增加而带来的附加的限制。
决定空管速度的主要影响参数是催化剂的尺寸、形状、粒径分布和磨损行为。根据经验,大小为约0.02至0.15巴/米的压力降可作为指导性的数值。反应器出口处的气体量优选使所产生的空管速度大约与液体的空管速度相当。但可至多比其低90%。
在催化剂悬浮于反应介质中的条件下实施本发明的方法时,适用的反应器为喷射喷嘴反应器、带搅拌的容器和填充表面积至少为500米2/米3、优选为1000至2000米2/米3的填充的泡罩塔。根据经验,通过向其中施加超过2千瓦/米3的足够的高能量,只要能够保证本发明所必需的从气相向含有悬浮的催化剂颗粒的液相实现高的传质,任何类型的喷射喷嘴反应器都可以使用。配有脉冲交换管的喷射喷嘴反应器特别适用。工业上广泛采用的一种喷射喷嘴反应器例如是EP-A0419419所介绍的反应器。在大小为3至5千瓦/米3的输入能量下,这种反应器还能够在简单的分离器中实现气相的分离,不需要采用其它的设备,如泡沫离心机或旋风分离器。
图3图示了一个喷射喷嘴反应器,其中液体通过位于含有热交换器16的外循环回路上的管线5传输,在驱动喷射压缩机6中将氢气吸入。为增加传质的量,通过脉冲交换管17来传输两相混合物。在反应器1的下端可以用一挡板18使流动转向并使气体的分离更容易。气体在外环形空间19中向上升至反应器顶部并再次被吸入驱动喷射压缩机6中。在反应器的下端将气体已从中基本上分离的液体放出,通过流经热交换器16除去反应热量,并再次进入驱动喷嘴压缩机6中。
只有当输入能量为2至10千瓦/米3的情况下,本发明的方法才能够在带搅拌的反应器中进行。为了将搅拌能量转化以获得本发明所需的高kLa值,带搅拌的反应器应该含有能确保气体和液体充分混合的内部装置,如挡板。
另外,图4所示的带有填充物20的泡罩塔也适用于本发明的方法。填充物的表面积应至少为500米2/米3,优选为1000至2000米2/米3。填充物20可以是有序填充或无序填充,有序填充如已知那样是指几何上的有序,在蒸馏分离技术中已知其具有最低压力降。如在蒸馏技术中以相同的形式所使用的那样,含有丝网的填充物具有特别突出的性能。网状填充物的例子有瑞士Sulzer Chemtechn.公司(8404 Winterthur,Switzerland)的商品Sulzer DX_和Sulzer EX_。
上述填充物也可以直接涂布催化活性成分。这种填充物在EP-A068862、EP-A201614和EP-A448884中有介绍。采用含有这种填充物的这些填充的泡罩塔中的一种得到的固定床反应器,在相同高的液体和气体的空管速度下,即空管速度为100至1000米/小时、优选200至1000米/小时,它们具有的kLa值与悬浮过程中的kLa值一样高。
通过对不同类型的反应器采用不同的技术手段,本发明方法中的kLa值被保持在0.1秒-1至1秒-1之间,这对于同时获得高选择性和高时空产率是至关重要的。与其它途径相比较,本发明方法中所有类型的反应器都有较高的能量输入。采用特定的结构设计和操作条件,输入的能量能够很高效地发生转化来提高传质的量。
当本发明的方法采用悬浮的催化剂在带搅拌的反应器中进行时,应选用具有优良导入气体性能的搅拌器,例如已知的发酵技术中采用的盘式搅拌器或节齿叶片搅拌器,这样kLa值能够保持在0.1秒-1至1秒-1之间。体积能量输入为2至10千瓦/米3,该低限的能量值对于较小的设备能够获得优良的氢化效果。在反应器大小超过约0.5米3的情况下,能量输入应为5至10千瓦/米3。在带搅拌的反应器中,能量是通过搅拌器的驱动能量而导入反应器中的。这些能量输入值比通常的在搅拌容器中进行的有气体导入的反应要高,例如发酵或氢化反应,它们的能量输入值为约0.2至1.0千瓦/米3。
采用悬浮催化剂的喷射喷嘴反应器需要的体积能量输入值大于2千瓦/米3,优选为3至5千瓦/米3。能量的导入是通过在循环泵21中提高液体的压力以及在驱动喷射压缩机6中进行压力补偿的手段来完成的。循环量的变动和在循环泵中的增压保证所需能量的输入。泵中压力的增加范围通常为2至5巴。
如果本发明的方法采用在填充的泡罩塔中悬浮于反应介质中的催化剂,则单位体积填充物的表面积应至少为500米2/米3,但优选为1000至2000米2/米3。为了获得本发明所要求的在0.1秒-1至1秒-1之间的kLa值,需要同时使液体和气体都达到100至1000米/小时的较高的速度。除了使填充物具有指定的几何构型外,将气体和液体的速度保持在所需的水平则能够确保所需的能量输入。该能量值由于结构类型的影响,它要比带搅拌的反应器或喷射喷嘴反应器情况下的能量值低一些。由流动液体和气体的压力降所形成的能量输入,其适宜值的获得可通过测量压力降来监测,该压力降一般为0.02至0.15巴/米填充物。为了设定所需的压力降,如果需要的话,可以相应地改变液体的速度。
上面针对填充泡罩塔中的悬浮方法给出的单位体积表面积的、填充物的压力降和液体与气体的循环速度也适用于其中填充物本身涂布有催化活性物质的泡罩塔。
当本发明的方法采用固定床反应器时,为使kLa值保持在0.1秒-1至1秒-1之间,催化剂颗粒的平均大小应为1至20毫米,优选为2至5毫米,液体和气体的流动速度应为100至1000米/小时。固定床应建立的压力降约为0.02至0.15巴/米。
1,4-丁二醇在工业上的用量很大,例如在四氢呋喃的制备中或作为聚酯的二醇组分。
本发明的方法通过下面的实施例得到进一步的说明。除非特别指出,丁炔二醇采用工业级,它是浓度为54%重量的水溶液,其中含有不同量的丙炔醇。实施例中给出与反应产物中丙醇的量大约相对应的丙炔醇的量。除非特别指出,实施例中反应产物中的百分数均为由气相色谱测定无水形式产物并计算得到的重量百分数。实施例实施例1
在一装有两个挡板、盘式搅拌器和内部物料面控制装置(一种防止催化剂被带出的的烧结的金属网料),液体容积大小为130毫升的的处于搅拌状态下的高压釜中加入溶于50毫升水中的10克兰尼镍/钼(2%重量钼,以钼计,兰尼镍浸于钼酸铵溶液中制备),然后用氢气使压力升至35巴。用外部油浴手段将反应器内部温度升到140℃,调节使氢气的流速为80标准升/小时。搅拌速度为每分钟700转,此条件确保kLa值为0.2秒-1。然后通过泵以100克/小时的速度将浓度为54%重量的丁炔二醇水溶液加入。反应器内部温度升至149℃。反应产物生成的速率为103克/小时,含有94.2%重量1,4-丁二醇、1.3%重量正丁醇、3.3%重量正丙醇和一些其它产物,其中每种产物的量不超过0.08%重量。丁二醇的时空产率为0.4千克/升·小时。实施例2
采用与实施例1类似的方法,在10克兰尼镍/钼(2.5%重量钼,以钼计)的催化下将170克/小时丁炔二醇溶液进行氢化。起始温度为150℃,在反应过程中反应器升温至173℃。反应产物生成的速率为176克/小时,含有92.4%重量1,4-丁二醇、0.4%重量2-甲基丁二醇、2%重量正丁醇和4.7%重量正丙醇以及一些其它产物,其它产物的量不超过0.08%重量。丁二醇的时空产率为0.7千克/升·小时。实施例3
采用与实施例1类似的方法,在10克兰尼镍/铁/铬(Degussa公司,11112W型)的催化下将60克/小时丁炔二醇溶液进行氢化。反应器中液体的体积为85毫升,kLa值为0.2秒-1。起始温度为140℃,然后升温至144℃。反应产物生成的速率为64克/小时,含有95.7%重量1,4-丁二醇、0.6%重量正丁醇和1.8%重量正丙醇以及一些其它产物,其它产物的量不超过0.08%重量。丁二醇的时空产率为0.25千克/升·小时。实施例4
采用与实施例1类似的方法,在每分钟600转的转速,对应的kLa值为0.1秒-1和反应器温度为105℃下将60克/小时丁炔二醇溶液进行氢化。反应器排出物含有90%重量丁二醇、1.8%重量丁烯二醇、5%重量4-羟基丁醛与丁二醇的缩醛、2%重量4-羟基丁醛和4%重量丁醇。当反应温度升温至136℃后,转化率提高,排出物中含有以下产物:92%重量丁二醇、2.7%重量4-羟基丁醛与丁二醇的缩醛、0.7%重量4-羟基丁醛和3%重量丁醇。实施例4表明本发明的方法能在较高的转化率下获得较高的选择性。实施例5
在一用油浴加热的容积为400毫升,直径2.7厘米的管式反应器中填充400毫升直径为5毫米的腊希圈(Raschig rings,由材料号为1.4541的金属网丝圈制成,该材料登录于Verein DeutshcerEisenhuttenleute,第8版,Verlag Stahleisen mbH,Dusseldorf 1990,(UNS-No.S32100)一书的钢系列中)。该管式反应器安置于其中反应液体通过气/液分离器用齿轮泵驱动而进行循环的反应体系中。分离器含有过滤装置,液体和气体能够通过此过滤装置连续进行分离排出,但催化剂予以保留。与实施例1相同,丁炔二醇的进料速度为200克/小时,100标准升/小时新的氢气在反应器之前进料。反应器以向上流动方式操作。液体的时空速度为170米3/米2·小时,kLa值为0.25秒-1。
反应前,采用与实施例1类似的方式将溶于300毫升水中的20克兰尼镍/钼加入到反应体系中。在30巴压力和反应温度为145至151℃下,反应产物生成的速率为213克/小时,含有93.3%重量丁二醇、0.3%重量2-甲基丁二醇、1.5%重量正丁醇、4.2%重量正丙醇和一些其它产物,其它产物的量不超过0.08%重量。丁二醇的时空产率为约0.25千克/升·小时。实施例6
重复实施例5的步骤,采用5克兰尼镍/钼为催化剂。在反应器温度为122℃、压力20巴和300升/小时的氢气进料速率下将进料速率为100克/小时的丁炔二醇溶液进行氢化。在液体的时空速度为225米3/米2·小时,kLa值为0.3秒-1和丁炔二醇的完全转化下,产物中正丁醇的含量为2.2至2.7%重量,1,4-丁二醇的含量为77%重量,剩余的为中间产物。将液体的时空速度提高到263米3/米2·小时,对应的kLa值为0.4秒-1后,正丁醇的含量降低至1.3%重量,丁二醇的含量升至88%重量。实施例7
采用与实施例1类似的方法,在反应器温度为127℃,对应的kLa值为0.2秒-1下将60克/小时浓度为57%重量丁炔二醇水溶液(水含量:42%(重量))进行氢化。反应125小时后,产物含有95.4%重量丁二醇、0.1%重量2-甲基丁二醇、1.5%重量4-羟基丁醛与丁二醇的缩醛、2.6%重量丁醇和0.3%重量丙醇。然后将反应器温度升至141℃。中间产物向最终产物的转化完全,选择性也增加。反应进行173小时后,排出物中含有以下产物:98.8%重量丁二醇、0.1%重量2-甲基丁二醇、0.7%重量丁醇和0.3%重量丙醇。比较实施例1
采用与实施例1类似的方法,将浓度为50%重量的蒸馏丁炔二醇水溶液进行氢化。用氢氧化钠将加料溶液的pH值调节至6.6。油浴温度为140℃,加料速率为100克/小时时反应器内部的温度为150℃。经过24小时后,反应器排出物含有3%重量正丁醇、0.5%重量正丙醇和96%重量1,4-丁二醇。当搅拌速度降至350转/分钟,对应的kLa值为0.05秒-1,反应温度降至141℃后,反应器排出物中含有10%重量丁炔二醇、31%重量丁烯二醇、41%重量丁二醇、3%重量4-羟基丁醛、0.5%重量丙醇、4%重量丁醇和7%重量丁烯醇。余下的主要为缩醛。比较实施例2
采用与实施例1类似的方法,在油浴温度为140℃,采用10克兰尼镍/钼(1.8%重量钼,以钼计)为催化剂将加料速度为100克/小时的工业级丁炔二醇溶液进行氢化反应。反应器内部的温度为149℃。反应产物具有如下组成:94.1%重量丁二醇、0.2%重量2-甲基丁二醇、1.5%重量丁醇和4.2%重量丙醇。当搅拌速度降至350转/分钟,对应的kLa值为0.05秒-1后,得到的氢化产物中含有40.3%重量丁二醇、37%重量丁烯二醇、2.1%重量丁炔二醇、3%重量丁醇、2.6%重量丁烯醇和3.1%重量4-羟基丁醛。余下的主要为丙醇、丙烯醇和4-羟基丁醛与二醇的缩醛。
Claims (8)
1、一种将1,4-丁炔二醇连续催化氢化制备1,4-丁二醇的方法,该方法包括在20至300℃,在1至200巴的压力,以及0.1秒-1至1秒-1的以体积表示的液体侧传质系数kLa值下,将1,4-丁炔二醇与氢气在氢化催化剂的存在下于液态连续相中进行反应,
a)采用悬浮于反应介质中的催化剂,如果采用填充的泡罩塔,则其操作方式为向上流动,离开反应器的气体与加料进入反应器的气体的比例为0.99∶1至0.4∶1,或
b)使液体和气体平行向上流经气体循环模式操作下的固定床反应器,同时使加料进入反应器的气体与离开反应器的气体的比例维持在0.99∶1至0.4∶1。
2、权利要求1所要求的方法,它在3至150巴的压力下进行。
3、权利要求1所要求的方法,它在5至100巴的压力下进行。
4、权利要求1至3任一项中所要求的方法,其中以体积表示的液体侧传质系数为0.2秒-1至1秒-1。
5、权利要求1至4任一项中所要求的方法,其中所用的催化剂含有至少一种选自元素周期表中第Ⅰ、Ⅵ、Ⅶ和Ⅷ过渡族的元素。
6、权利要求5所要求的方法,其中催化剂含有选自铜、铬、钼、锰、铼、铁、钌、钴、镍、铂和钯的至少一种元素。
7、权利要求5或6所要求的方法,其中催化剂含有至多为5%重量的选自元素周期表第Ⅱ、Ⅲ、Ⅳ和Ⅵ主族,第Ⅱ、Ⅲ、Ⅳ和Ⅴ过渡族和镧系中的至少一种元素。
8、权利要求5至7任一项中所要求的方法,其中催化剂含有选自氧化铝、氧化钛、二氧化锆、二氧化硅、粘土、硅酸盐、沸石和活性炭的载体材料。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19641707A DE19641707A1 (de) | 1996-10-10 | 1996-10-10 | Verfahren zur Herstellung von 1,4-Butandiol durch katalytische Hydrierung von 1,4-Butindiol |
DE19641707.4 | 1996-10-10 |
Publications (2)
Publication Number | Publication Date |
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CN1222902A true CN1222902A (zh) | 1999-07-14 |
CN1097574C CN1097574C (zh) | 2003-01-01 |
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CN97195779A Expired - Fee Related CN1097574C (zh) | 1996-10-10 | 1997-09-23 | 1,4-丁炔二醇催化氢化制备1,4-丁二醇的方法 |
Country Status (10)
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US (1) | US6262317B1 (zh) |
EP (1) | EP0934239B1 (zh) |
JP (1) | JP3995719B2 (zh) |
KR (1) | KR100510233B1 (zh) |
CN (1) | CN1097574C (zh) |
CA (1) | CA2260810C (zh) |
DE (2) | DE19641707A1 (zh) |
ES (1) | ES2170416T3 (zh) |
MY (1) | MY119458A (zh) |
WO (1) | WO1998015513A1 (zh) |
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EP0177912B1 (de) | 1984-10-12 | 1988-03-16 | BASF Aktiengesellschaft | Verfahren zur Herstellung von Alkandiolen |
US4864066A (en) | 1987-05-23 | 1989-09-05 | Basf Aktiengesellschaft | Preparation of alkanediols from alkynols |
GB8728156D0 (en) | 1987-12-02 | 1988-01-06 | Davy Mckee Ltd | Process |
US5068468A (en) | 1990-10-19 | 1991-11-26 | Basf Aktiengesellschaft | Hydrogenation of acetylenic alcohols |
-
1996
- 1996-10-10 DE DE19641707A patent/DE19641707A1/de not_active Withdrawn
-
1997
- 1997-09-23 KR KR10-1999-7003051A patent/KR100510233B1/ko not_active IP Right Cessation
- 1997-09-23 DE DE59706114T patent/DE59706114D1/de not_active Expired - Lifetime
- 1997-09-23 ES ES97943884T patent/ES2170416T3/es not_active Expired - Lifetime
- 1997-09-23 EP EP97943884A patent/EP0934239B1/de not_active Expired - Lifetime
- 1997-09-23 CN CN97195779A patent/CN1097574C/zh not_active Expired - Fee Related
- 1997-09-23 CA CA002260810A patent/CA2260810C/en not_active Expired - Fee Related
- 1997-09-23 WO PCT/EP1997/005205 patent/WO1998015513A1/de active IP Right Grant
- 1997-09-23 JP JP51712598A patent/JP3995719B2/ja not_active Expired - Fee Related
- 1997-09-23 US US09/284,209 patent/US6262317B1/en not_active Expired - Lifetime
- 1997-10-10 MY MYPI97004749A patent/MY119458A/en unknown
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CN112004589A (zh) * | 2018-04-20 | 2020-11-27 | 西门子股份公司 | 用于运行反应器设施的方法 |
TWI829737B (zh) * | 2018-08-08 | 2024-01-21 | 美商W R 康格雷氏公司 | 催化劑、其製備方法、及選擇性氫化製程 |
Also Published As
Publication number | Publication date |
---|---|
EP0934239B1 (de) | 2002-01-02 |
US6262317B1 (en) | 2001-07-17 |
WO1998015513A1 (de) | 1998-04-16 |
MY119458A (en) | 2005-05-31 |
JP3995719B2 (ja) | 2007-10-24 |
CA2260810C (en) | 2005-05-10 |
KR100510233B1 (ko) | 2005-08-26 |
KR20000048993A (ko) | 2000-07-25 |
DE59706114D1 (de) | 2002-02-28 |
ES2170416T3 (es) | 2002-08-01 |
CN1097574C (zh) | 2003-01-01 |
JP2001501631A (ja) | 2001-02-06 |
EP0934239A1 (de) | 1999-08-11 |
CA2260810A1 (en) | 1998-04-16 |
DE19641707A1 (de) | 1998-04-16 |
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