CN104245113A - 适用于氢化反应(i)的装置 - Google Patents

适用于氢化反应(i)的装置 Download PDF

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CN104245113A
CN104245113A CN201380020934.5A CN201380020934A CN104245113A CN 104245113 A CN104245113 A CN 104245113A CN 201380020934 A CN201380020934 A CN 201380020934A CN 104245113 A CN104245113 A CN 104245113A
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metal
metal oxide
metal alloy
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CN104245113B (zh
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沃纳尔·邦拉蒂
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DSM IP Assets BV
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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  • Powder Metallurgy (AREA)

Abstract

本发明涉及一种装置,其用于处理被传输通过所述装置的材料,所述装置包括至少一个由特定固体金属结构组成的多孔元件,所述金属结构允许所述材料错流通过所述多孔元件,并且其中所述多孔元件被由钯(Pd)浸渍的非酸性金属氧化物涂布。

Description

适用于氢化反应(I)的装置
本发明涉及一种装置,其用于处理被传输通过所述装置的材料,所述装置包括至少一个由特定固体金属结构组成的多孔元件,所述金属结构允许所述材料错流通过所述多孔元件,并且其中所述多孔元件被由钯(Pd)浸渍的非酸性金属氧化物涂布。
根据本发明的装置适用于在均相和非均相条件下进行化学反应。
所述装置适用于实验室规模以及工业规模的化学反应(尤其是氢化,如选择性加氢)。
WO2010/142806和WO2010/142809正在公开类似的装置,其适用作传输穿过这种装置的流体或流态化材料的混合器或换热器。这种装置也适用于在均相和非均相条件下进行化学反应。
本发明的目标在于提供性质改善(尤其就选择性加氢来说)而且制造容易的装置。
根据本发明的装置还很稳定(就反应条件(如pH值)、底物和溶剂(尤其是水)来说)。所述装置可极易于再次使用。
具体来说,根据本发明的装置包含管,该管具有壁,优选地具有圆柱形壁,以及至少一个入口端和至少一个出口端,其中在该管中布置至少一个由固体泡沫结构组成的多孔元件,其中多孔元件包含多个彼此相连并且形成互连网络的中空空间,并且其中至少一个元件由特定金属合金组成,该合金然后由非酸性金属氧化物涂布,所述非酸性金属氧化物然后还由Pd浸渍,并且其中至少一个元件和壁被制成整块。
可以通过选择性激光烧结(SLS),即例如US 5′639′070、US 5′732′323和US 6′676′892中所述的方法,或通过电子束熔融(EBM)将装置和至少一个多孔元件制成整块。
EBM方法具有如下一些优点:
●无热处理
●可得表面较之通过SLS所得表面更平滑
●比SLS快2-3倍。
本发明涉及一种装置,该装置处理传输通过该装置的材料,所述装置包括至少一个由特定固体金属结构组成的多孔元件,所述金属结构允许所述材料错流通过多孔元件,并且其中所述多孔元件由包含如下的金属合金制成:
(i)以金属合金的总重量计,60重量%-80重量%的Fe,以及
(ii)以金属合金的总重量计,1重量%-30重量%的Cr,以及
(iii)以金属合金的总重量计,0.5重量%-10重量%的Ni,以及
其中所述多孔元件由非酸性金属氧化物涂布并且所述非酸性金属氧化物由钯(Pd)浸渍。
显然所有百分比总是相加等于100。
用于形成装置的金属合金优选是不锈钢以及工具钢。
不锈钢的三种主要类型是已知的。这些由它们的结晶结构分类:奥氏体、铁素体和马氏体。
最重要的类型(不锈钢产量中超过70%)是奥氏体钢。奥氏体钢具有奥氏体作为其基础相。这些合金通常包含基于合金的总重18-20wt%的铬和基于合金的总量8-10wt%的镍。
铁素体钢具有铁素体作为其主相。这些钢中包含铁和基于合金的总重约17wt%的铬。
马氏体钢具有特有的斜方马氏体微结构。马氏体钢是低碳钢。
不锈钢可包含其它金属,即如Cu、Mn、Si、Mo、Ti、Al和Nb。
此外,不锈钢也可包含碳。
因此,本发明涉及一种装置,其中至少一个多孔元件由不锈钢制成,其中不锈钢包含:
(i)以不锈钢的总重量计,60重量%-80重量%的Fe,以及
(ii)以不锈钢的总重量计,12重量%-25重量%的Cr,以及
(iii)以不锈钢的总重量计,1重量%-8重量%的Ni,以及
(iv)以不锈钢的总重量计,1重量%-8重量%的Cu。
不锈钢可商购子许多生产商和贸易商。它可以购自诸如SverdrupHanssen、Nichelcrom Acciai Inox S.p.A或EOS GmbH的公司。
适当的产品即为来自EOS GmbH(德国)的EOS不锈钢
金属合金也可以是工具钢。
因此,本发明的进一步实施方式涉及一种装置,其中至少一个多孔元件由金属合金制成,所述金属合金是工具钢,包含:
(i)以工具钢的总重量计,60重量%-80重量%的Fe,以及
(ii)以工具钢的总重量计,1重量%-15重量%的Cr,以及
(iii)以工具钢的总重量计,1重量%-19重量%的Ni,以及
(iv)以工具钢的总重量计,0.5重量%-10重量%的Co,以及
(v)以工具钢的总重量计,0重量%-5重量%的W。
工具钢是明确定义的一类钢。即通过DIN(Duetsche Industrie Norm)标准进行分类,诸如DIN 1.2343、DIN 1.2344、DIN 1.2367、DIN 1.2365、DIN 1.2885、DIN 1.2323、DIN 1.2758和DIN 1.2706。
工具钢可商购自许多生产商和贸易商
本发明的实施方案的必要特征在于至少一个多孔元件由非酸性金属氧化物层涂布。
涂布至少一个多孔元件的非酸性金属氧化物层是碱性的或两性的。合适的非酸性金属氧化物层包含Zn、Cr、Mn、Cu或Al。优选地,氧化物层包含ZnO和任选地至少一种其它金属氧化物,其中所述金属选自由Cr、Mn、Mg、Cu和Al组成的组。
至少一个元件优选地用ZnO和任选地至少一种其它金属(Cr、Mn、Mg、Cu和Al)氧化物的薄层涂布。通过通常已知的方法,即如浸渍涂布来涂布金属合金。
通常,以催化剂的总重量计,本发明的装置包含在0.001重量%和2重量%之间,优选地在0.01重量%和1重量%之间的ZnO。
在本发明的一个优选实施方案中,非酸性金属氧化物层包含ZnO和至少一种其它金属氧化物,其中金属选自由Cr、Mn、Mg、Cu和Al组成的组。
在本发明的一个更优选实施方案中,非酸性金属氧化物层包含ZnO和Al2O3
当使用ZnO和Al2O3的混合物时,则优选的是,ZnO∶Al2O3的比率是2∶1至1∶2。
然后,通过Pd纳米颗粒浸渍因此涂布的元件。通过通常已知的方法,即通过使用PdCl2作为前体,然后通过氢将其还原,来合成纳米颗粒。
通常,在非酸性金属氧化物层上的Pd纳米颗粒具有在0.5nm和20nm之间,优选地在2nm和15nm之间,更优选地在5nm和12nm之间,并且最优选地在7nm至10nm之间的平均粒度。(通过光散射法测量尺寸)。
以催化剂的总重量计,根据本发明的装置包含在0.0001重量%和1重量%之间,优选地在0.001重量%和0.1重量%之间的Pd纳米颗粒。
根据所述装置的另一实施方案,至少一个多孔元件的中空空间是大致球形的并且具有0.5mm至20mm,优选为1mm至10mm,更优选为1.5mm至5mm的平均当量直径。
界定球形中空空间的表面区域的壳进一步包含多个互连洞,其允许材料错流。所述洞的平均当量直径在0.01mm至5mm的范围内,优选地在0.1mm至5mm的范围内,更优选地在0.1mm至2mm的范围内。
在本发明的一个具体实施方案中,将壳制造成使其包含光滑的或粗糙的或部分光滑、部分粗糙的表面。在一个优选实施方案中,将该装置设计成用作混合器或换热器或用于单相和多相化学反应,例如快速的放热性、混合敏感性或热敏性反应的连续操作。装置提供反应物的快速混合和极其增强的传热。多孔结构与反应器壁的固定连接对于保证良好的传热和极高的机械稳定性是至关重要的。这使方法可达到高温和压力。多孔元件的结构还分别对反应器中的轴向分散、停留时间分布(标定化工厂的重要参数)具有重大影响。
对于化工厂中常用的常规分批反应器而言,可以通过搅拌器的旋转速度来控制能量耗散。对于连续系统,仅可改变流动速率,而流动速率直接与停留时间和其分布相关。与分批反应器相比,这种相关性是缺点,但是可通过借助于计算流体动力学(CFD)设计,然后例如通过上述SLS方法制造的多孔元件的清楚界定的几何形状来处理。
有机分子中官能团的氢化是快速多相放热反应的实例。这些反应是可用于有机合成的环境上可接受的反应途径的一部分。例如,前体即维生素A和维生素E的中间体是通过三个主要类型的反应制造的。其中之一是催化选择性加氢、多相即三相反应,其中反应混合物包含液相、不溶解的固体催化相和气相。
进行这些氢化反应的最常见的反应器类型是分批操作的浆料反应器。主要地,搅拌槽和环流反应器处于使用中。由于强烈的放热反应,外部和内热交换器的组合对于有效的温度控制是必要的。另外,反应中使用的催化剂的浓度相对较低(<10%),其限制了反应速率。最终,常规反应器的传热性能为约0.2kW m-3K-1至5kW m-3K-1。因此,大的反应器体积是有必要的以得到可接受的生产率。
加氢过程的性能和产物分布受到催化剂活性/选择性和化学动力学与反应器中传输现象的相互作用的重大影响。在三相反应中,要克服的主要问题之一是避免内部和外部传质限制。因此,需要小直径的催化剂颗粒。在技术应用中,然而,由于催化剂处理,如固体装料、过滤和排放,经常造成安全和环境问题,并且可引起重大的催化剂损失和在经济上不宜的方法,因此最小尺寸受限。
此外,因为氢化是高度放热的,所以除去反应热变成反应器性能的主要限制。因此,在浆料反应器中,每个体积的催化剂质量受到热交换能力的限制。
另一方面涉及工艺安全性和在控制压力下的可持续制造。如上所述的多步化工方法中的产物中间体经常不稳定并且会分解放出大量的热。后果是热失控和爆炸。
为了提高化学反应的安全性,需要严格的热管理。另外,反应器中反应物的量应尽可能地小以降低危险可能性。
选择性反应的这些问题可以通过使用在下文中还称为塞流反应器的装置,即如由本发明定义的设计来解决。这种反应器可以用连续模式操作。这种操作模式避免了如在分批方法的情况下存储大量的不稳定产物中间体并且提高了化学反应的安全性。
这种方法集成对于将热不稳定性中间体加工成稳定中间体尤其重要。
下文所述的连续塞流反应器的结构化几何形状就传热和传质来说得到优化。反应器中的活塞流如速度场保证了等温且均质的操作模式。其可在几何学上适于化学反应所用的流体的传热系数、粘度、密度和混合行为以优化操作费用(压降、热能等)和产物质量(选择性、转化率等)的比率。另一方面,至少一个多孔元件的结构不仅满足静态混合元件的要求,其还充当危急反应的阻火器,并且其通过方便的模制和正确的材料选择来允许连续系统的机械和化学稳定性。
为了满足所有那些要求,至少一个多孔元件的几何形状不能在元件长度上都一致并且可针对不同条件进行调整。此外并且根据管中进行的反应,可以在管的全长上拉伸多孔元件或者所述多孔元件可以具有反应器管总长的10%至90%,优选地50%至80%的长度。
根据本发明的塞流反应器具有毫米范围内的特征尺寸。优选地,所用反应器的通道直径在0.5mm和300mm之间。
在本发明的一个优选实施方案中,反应器管的直径在1mm至300mm的范围内,优选地在2mm至100mm的范围内,更优选地在5mm至50mm的范围内。
关于所述装置作为进行化学反应的反应器的用途,在本发明的范围内的一个基本目的在于提出催化剂的使用。在塞流反应器中,催化剂颗粒可如在传统的悬浮液反应器中以运动或固定形式使用。如果催化剂颗粒以固定形式使用,那么优选地,多孔元件的烧结金属结构可充当催化剂的载体。
反应器的另一主要特征是与传统的化学反应器相比面容比(surface tovolume ratio)较高。通过至少一个多孔元件确立的反应器的比表面处于500m2m-3至50,000m2m-3的范围内,而典型实验室和制造容器中的比表面为约10m2m-3并且极少有超过100m2m-3
在塞流反应器的一个优选实施方案中,管包含界定环形室的双壁圆柱形外罩,其中所述环形室包括至少一个流体入口和至少一个流体出口,它们被连接到换热器以便连续传输热交换流体通过所述室以便冷却或加热反应混合物。
替代或补充双壁圆柱形外罩,所述管可以包含在圆柱形壁的纵向布置的中央内管,其中所述内管包括至少一个用于将反应过程的化合物添加到传输通过所述管的材料中的出口,或其布置有没有用于传输热交换流体通过反应器的出口的内管。
通常,如下制造根据本发明的装置:
(i)由金属合金(尤其是不锈钢或工具钢)制造装置(包括至少一个多孔元件),以及
(ii)由非酸性金属氧化物层涂布所述装置(其内部部分),以及
(iii)用Pd纳米颗粒浸渍非酸性金属氧化物层。
将根据本发明的装置用于有机起始物,尤其是包含碳-碳三键的有机起始物,更加尤其是炔醇化合物的选择性催化氢化中。因此,本发明还涉及根据本发明的装置在有机起始物、尤其是包含碳-碳三键的有机起始物、更加尤其是炔醇化合物的选择性催化氢化中的用途。
优选地,本发明涉及使式(I)化合物与氢气反应的方法,
其中
R1是直链或支链C1-C35烷基或直链或支链C5-C35烯基片段,其中C链可被取代,并且
R2是直链或支链C1-C4烷基,其中C链可被取代,
R3是H或-C(CO)C1-C4烷基,
而反应溶液被泵送(或以其它方式传送)通过根据本发明的装置。
氢气通常以H2气体形式使用。
如下是优选的式(I)化合物:
它们被氢化成式(Ia′)、(Ib′)、(Ic′)和(Id′)的相应化合物:
反应通常在压力下进行。通常介于2巴与10巴之间。
反应通常在高温下进行。通常介于30℃与80℃之间。
反应通常在没有任何溶剂的情况下进行。但是也可使用对氢化具有惰性的溶剂。
图1:示出了加氢工艺的合适布置。
在下文中,将更详细地描述本发明。除非另有提及,否则所有的份数都与重量有关并且温度以℃给出。
实施例1
制造装置(塞式反应器)
就在金属泡沫结构中的化学反应来说,必须解决市售泡沫的一些困难。一方面,市售材料,如铝或铜,尤其就腐蚀来说对于化学反应器是重要的。另一方面,从泡沫连接到壁是传热中的限制性步骤。测试了不同的方法,如焊接,但是都没有实现持久连接。因此并且根据本发明,提出一种新的制造方法,其为所谓的激光烧结技术(SLS),如引言中所述。用这种技术,可在计算机辅助设计(CAD)软件中设计几乎每一形状的三维结构,然后制造成一个单一部分。这如下进行:沉积金属粉末(EOS不锈钢)层,在对应于CAD模型的所选位置引导能量以将其烧结,随后沉积新一层,并且再次开始所述程序,例如US 5′639′070、US 5′732′323和US 6′676′892中所述。因为所述制造方法就高达约50μm的长度尺度的几何形状来说几乎没有限制,所以制造商能满足每一方法特定的设计准则。这些优选通过调适下文所列的最有影响力的参数来允许极精确地标定化学处理。替代性方法将为所谓的电子束熔融(EBM)方法,其也描述于引言中。
装置长度为200mm,外径为10mm,内径为6mm,并且管的排空容积为4.4ml。
之后,用金属氧化物层涂布装置,然后将Pd纳米颗粒沉积到这个层上。
之后在450℃下对装置进行热预处理持续3小时。
沉积ZnO+Al 2 O 3 (涂布多孔元件)
制备Al2O3+ZnO前体溶液:向100mL烧瓶中添加Al(NO3)3·9H2O(20.0g,53.3mMol)和水(70mL)。搅拌混合物直到Al(NO3)3·9H2O完全溶解为止。将溶液加热到95℃。然后将氧化锌粉(4.34g,53.3mmol)缓慢添加到溶液中。维持加热和搅拌直到ZnO完全溶解为止。然后将溶液冷却到室温并且通过膜过滤器过滤。
通过用前体溶液冲洗被氧化的装置的内部来沉积ZnO+Al2O3。然后在60℃下在125毫巴下干燥装置2小时,接着在450℃下煅烧1小时。重复这个过程2次。
用Pd浸渍
制备pd°悬浮液:在加热(约95℃)和搅拌下,在30mL去离子水中添加二水合钼酸钠(79.5mg,0.329mmol)和无水氯化钯(II)(53.0mg,0.299mmol)。继续加热和搅拌直到水完全蒸发(形成固体残留物)为止。之后,在搅拌下将30mL去离子水添加到残留物中。将蒸发-溶解循环重复两次以完全溶解PdCl2。最终,将50mL热水添加到固体残留物中。将深棕色溶液冷却到室温并且通过纸滤器过滤到100mL量筒中。用水洗涤过滤器。前体溶液的最终体积应为60mL。通过在玻璃量筒中在室温下将氢气鼓泡通过前体溶液持续1小时来形成pd°悬浮液。
装置的一端用橡皮塞封闭并且用所得Pd°悬浮液填充反应器,并且以垂直位置在90℃下在减压下缓慢蒸发液体。重复这个过程3次。
所得装置包含0.58wt%的ZnO、0.3wt%的Al2O3和0.06wt%的Pd,所有都基于装置的总重。
在氢化之前,通过H2活化催化剂。
将如上制造和处理的装置在300℃下在H2-Ar流(1∶9;总流速-450ml/min)下进行温度处理4小时(温度梯度-10°/min)。然后,将其在相同的H2-Ar流下冷却到室温。
实施例2:MBY(式(Ia)的化合物)到MBE(式(Ia’)的化合物)的选择性氢化
将MBY(233.1g,2.73Mol)倒入500ml容器中。以图1中可以见到的布置使用实施例1的装置。
关闭反应器(高压釜),然后用4巴N2冲洗体系三次。此后,在搅拌下,将反应混合物加热直到65℃。
然后,停止搅拌,并用4巴H2冲洗反应器四次,接着对高压釜施压(4巴H2)。
以一定间隔,从反应混合物中进行抽样,并对其进行分析。
反应之后,可以通过用甲醇洗涤来清洁装置。
下表中,列出了一定反应次数后的选择性、转化率和产率。
由此可见,根据本发明的装置的选择性优异。

Claims (16)

1.一种装置,其用于处理被传输通过所述装置的材料,所述装置包括至少一个由特定的固体金属结构组成的多孔元件,所述金属结构允许所述材料错流通过所述多孔元件,并且其中所述多孔元件由包含以下的金属合金制成:
(i)以所述金属合金的总重量计,60重量%-80重量%的Fe,以及
(ii)以所述金属合金的总重量计,1重量%-30重量%的Cr,以及
(iii)以所述金属合金的总重量计,0.5重量%-10重量%的Ni,
其中所述多孔元件被非酸性金属氧化物涂布并且所述非酸性金属氧化物被钯(Pd)浸渍。
2.根据权利要求1所述的装置,其中所述金属合金是不锈钢钢。
3.根据权利要求1所述的装置,其中所述金属合金是工具钢。
4.根据前述权利要求中任一项所述的装置,其中所述金属合金包含选自Cu、Cr、Mn、Si、Ti、Al和Nb的其它金属。
5.根据前述权利要求中任一项所述的装置,其中所述金属合金包含碳。
6.根据权利要求2所述的装置,其中所述不锈钢包含:
(i)以所述不锈钢的总重量计,60重量%-80重量%的Fe,以及
(ii)以所述不锈钢的总重量计,10重量%-30重量%的Cr,以及
(iii)以所述不锈钢的总重量计,0.5重量%-10重量%的Ni。
7.根据权利要求3所述的装置,其中所述工具钢包含:
(i)以所述工具钢的总重量计,60重量%-80重量%的Fe,以及
(ii)以所述工具钢的总重量计,1重量%-15重量%的Cr,以及
(iii)以所述工具钢的总重量计,1重量%-19重量%的Ni,以及
(iv)以所述工具钢的总重量计,0.5重量%-10重量%的Co,以及
(v)以所述工具钢的总重量计,0重量%-15重量%的W。
8.根据前述权利要求中任一项所述的装置,其中涂布所述至少一个多孔元件的所述非酸性金属氧化物层是碱性的或两性的。
9.根据前述权利要求中任一项所述的装置,其中所述非酸性金属氧化物层包含ZnO和任选地至少一种其它金属氧化物,其中所述金属选自由Cr、Mn、Mg、Cu和Al组成的组。
10.根据前述权利要求中任一项所述的装置,其中所述非酸性金属氧化物层包含ZnO和Al2O3
11.根据前述权利要求中任一项所述的装置,其中在所述非酸性金属氧化物层上的Pd纳米颗粒具有在0.5nm和20nm之间、优选地在2nm和15nm之间、更优选地在5nm和12nm之间、并且最优选地在7nm至10nm之间的平均粒度。
12.根据前述权利要求中任一项所述的装置,其中以所述催化剂的总重量计,所述装置包含0.001重量%和2重量%的ZnO。
13.根据前述权利要求中任一项所述的装置,其中以所述装置的总重量计,所述装置包含在0.0001重量%和1重量%之间的所述Pd纳米颗粒。
14.根据前述权利要求中任一项所述的装置,其中所述至少一个多孔元件的中空空间是大致球形的并且具有0.5mm至20mm、优选为1mm至10mm、更优选为1.5mm至5mm的平均当量直径。
15.根据前述权利要求1至14中任一项所述的装置在有机起始物,尤其是包含碳-碳三键的有机起始物,更尤其是炔醇化合物的选择性催化氢化中的用途,其中反应溶液被泵送通过所述装置。
16.根据权利要求15所述的用途,其中所述有机起始物是式(I)化合物:
其中
R1是直链或支链C1-C35烷基或直链或支链C5-C35烯基片段,其中C链可被取代,并且
R2是直链或支链C1-C4烷基,其中C链可被取代,
R3是H或-C(CO)C1-C4烷基。
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