CN114585435A - 通过催化氧化正丁烷制备马来酸酐的新催化剂体系 - Google Patents
通过催化氧化正丁烷制备马来酸酐的新催化剂体系 Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
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- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
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- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及通过催化氧化正丁烷制备马来酸酐的催化剂体系,其包括至少一个反应管,所述反应管具有两个由不同的催化剂颗粒组成的催化剂层,其特征在于,在气体流过方向上的第一催化剂层中,每个催化剂颗粒的几何表面积比第二催化剂层中更大。本发明另外涉及通过催化氧化正丁烷制备马来酸酐的方法,其中引导包含氧气和正丁烷的反应物气体通过根据本发明的催化剂体系和使至少一个反应管处于升高的温度。
Description
本发明涉及通过催化氧化正丁烷制备马来酸酐的催化剂体系,其包括至少一个反应管,所述反应管具有两个由不同的催化剂颗粒组成的催化剂层,其特征在于,在气体流过方向上,第一催化剂层中的每个催化剂颗粒的几何表面积比在第二催化剂层中的每个催化剂颗粒的几何表面积更大。
本发明另外涉及通过催化氧化正丁烷制备马来酸酐的方法,其中引导氧气和正丁烷的混合物通过根据本发明的双层催化剂体系和使至少一个反应管处于升高的温度。
马来酸酐是一种具有重大经济意义的化学中间产品。例如将其单独或与其它酸组合用于制备醇酸树脂和聚酯树脂。此外,它也是一种用于化学合成的多用途中间产品,例如用于合成γ-丁内酯、四氢呋喃和1,4-丁二醇,而它们又可以作为溶剂使用或被加工成聚合物,例如聚四氢呋喃或聚乙烯基吡咯烷酮。
由正丁烷制备马来酸酐(MA)的工业制造在经冷却的管束反应器中通过选择性气相氧化进行,其中催化剂颗粒作为VPO催化剂填充到反应管中并且在那里形成催化剂床。由于在反应过程中释放大量热量(正丁烷到MA:-1260kJ/mol,正丁烷到CO2:2877kJ/mol),所以反应通常在管内径常规为21mm的管束反应器中进行,以便能够将这些热量通过管壁散发至由熔盐组成的冷却介质中。
EP 2643086 A1公开了用于在固定床反应器中将正丁烷催化转化成马来酸酐的催化剂成型体,其中将催化剂成型体成形为具有底面、柱面、柱体轴和至少一个贯穿的平行于柱体轴延伸的开口的柱体,并且柱体的底面具有至少四个凸角,其中,包围催化剂成形体的几何基体是棱柱体,所述棱柱体具有棱柱体底面,棱柱体底面具有长度和宽度,其中长度大于宽度。
US 6,005,121公开了一种通过催化氧化在直链中具有至少四个碳原子的非芳族烃制备马来酸酐的改进方法,其中使含氧气和烃的气体通过管式反应器中的催化剂固定床。将催化剂床的活性如此分级,使得反应器在超过1.5体积%的初始(反应物气体)烃浓度,气体与冷却液之间的整体平均温差为至少约15℃的情况下能够在床的气体温度超过冷却流体温度的部分上运行,以及每小时至少约5.0磅马来酸酐的生产率,而在反应过程中在催化剂床中的任意位置处的气体与冷却液之间的温差不超过80℃。优选地,催化剂活性和床的气体渗透性在气流方向上变化,使得催化剂活性以及每单位距离的压降在临界区域中是较低的,否则在所述临界区域中温度与烃浓度的组合可能导致,与低的温度和低的烃浓度的区域中相比,反应以过快的速率进行。
因此,任务在于提供用于将正丁烷催化氧化成马来酸酐的反应器系统,尤其是管束反应器,采用它来使得热稳定的运行和高MA产率成为可能。
该任务通过一种催化剂体系得以解决,在所述催化剂体系中将两种类型的不同形状的催化剂颗粒串联填充至反应管中,所述催化剂体系包括具有两个各自由不同催化剂颗粒组成的催化剂层的反应管,其特征在于,在气体流过方向上,第一催化剂层中的每个催化剂颗粒的几何表面积比第二催化剂层中每个催化剂颗粒的几何表面积更大。
该任务还通过催化氧化正丁烷制备马来酸酐的方法得以解决,其中引导氧气和正丁烷的混合物通过根据本发明的催化剂体系和使所述反应管处于升高的温度。
反应管的用催化剂颗粒填充的部分典型地具有3至8m,优选4至6m的长度。但根据本发明的催化剂体系特别适合于短的反应管,其具有长度为介于4和5m之间的经填充的部分,或例如4.5m。在反应管的所述用催化剂颗粒填充的区段中,发生正丁烷到马来酸酐的催化氧化,因此必须控制该区域中的温度,即必须调温。必须含有正丁烷和氧气的反应物气体包含例如介于0.2至10体积%的正丁烷和5至50体积%的氧气的混合物。典型地,反应物气体由0.5至3体积%的正丁烷、10至30体积%的氧气和余量惰性气体如氮气和1至4体积%的水的混合物组成。特别优选的是,反应物气体含有空气并且添加适量的正丁烷和任选的水。优选地,基于气体体积计,少量0.5至5ppm或1至3ppm的有机磷酸酯如磷酸三甲酯或磷酸三乙酯可以存在于反应物气体中,以平衡催化剂的磷酸酯/盐损失。将反应物气体引导至反应管中(典型地从下方)并且在反应管的用催化剂颗粒填充的部分中在升高的温度与催化剂颗粒接触,在此将正丁烷氧化成马来酸酐。
优选的是,存在多个可以单独或一起调温的反应管。由于将正丁烷选择性氧化成马来酸酐是放热反应,所以必须散发多余的热量,同时必须确保反应管具有必需的反应温度。优选地,通过盐浴(例如约1:1比例的硝酸钾和亚硝酸钠的低共熔体)进行调温,在所述盐浴中嵌入大量反应管。在反应期间,盐浴典型地具有介于380℃和430℃之间的温度。在反应期间,在反应管内沿轴向形成温度分布,其中在反应管的前三分之一中产生具有最高温度的区域(“热点”)。典型地,反应管中的最高温度为430℃至460℃,根据本发明优选的是介于440℃与450℃之间的最高温度。
催化剂颗粒优选含有焦磷酸钒相(VPO相),并且可以被负载或完全由VPO相组成。VPO相可以具有常规的掺杂物,在此尤其是钼和/或碱金属,例如如在DE 10 2014 004786A1中所描述。
根据本发明,反应管包括两个催化剂层或由两个催化剂层组成,所述催化剂层具有几何形状不同的催化剂颗粒。这两种催化剂颗粒床层在反应管内被反应物气体穿过,其中管的一个开口用作气体入口,而相对的开口用作气体出口。根据本发明,靠近气体入口的催化剂层是沿气体流过方向的第一催化剂层,而沿气体流过方向的后续催化剂层是第二催化剂层。优选的是,当两个催化剂层直接相继,即彼此接触。催化剂层的长度是被分别的催化剂颗粒占据的反应管的轴向截面。第一催化剂层在气体流过方向上的长度等于或大于第二催化剂层在气体流过方向上的长度。优选的是,第一催化剂层与第二催化剂层的长度的比例在1:1至5:1,特别优选2:1至4:1范围内。
根据本发明,在气体流过方向上,第一催化剂层中的每个催化剂颗粒的几何表面积大于在第二催化剂层中的每个催化剂颗粒的几何表面积。优选地,第一催化剂层的催化剂颗粒具有大于1.9cm2,优选大于2.2cm2的表面积。第二催化剂层的催化剂颗粒具有小于1.8cm2,优选小于1.5cm2的表面积。优选的是,反应管的内径大于等于20mm至23mm,优选大于或等于21mm。反应器管典型地具有1至2mm的壁厚,因此反应管的外径相应大于内径。
对于根据本发明的实施方式优选的是,反应管中的第一催化剂层的催化剂颗粒的堆积密度小于0.8g/cm3,特别是小于0.7g/cm3。相比之下,反应管中的第二催化剂层的催化剂颗粒的堆积密度优选大于0.7g/cm3,尤其大于0.8g/cm3。
用于根据本发明的催化剂体系的优选的催化剂颗粒是在EP 2643086A1中描述的那些。这些优选的催化剂颗粒的特征尤其在于,每个单独的催化剂颗粒各自被成形为具有外底面[1]、柱面[2]、柱体轴和至少一个贯穿的平行于柱体轴延伸的开口的[3]的柱体以及柱体的外底面[1]具有至少四个凸角[4a、4b、4c、4d],其中包围催化剂颗粒的几何基体是棱柱体,该棱柱体具有棱柱体底面,棱柱体底面具有长度和宽度,其中长度大于宽度,其中棱柱体底面的棱柱体角围绕凸角[4a、4b、4c、4d]。
根据本发明,催化剂颗粒的表面积OP不是指催化剂材料的BET比表面积,而是指催化剂颗粒的几何外表面积,即在催化剂颗粒是实心无孔物体的情况下产生的表面积。催化剂颗粒的几何外表面仅由其几何尺寸产生。相比之下,BET比表面积是每克多孔粉末的内表面面积。
将反应管的轴向截面理解为通过两条垂直于反应管的纵向延伸的假想的线界定的截面,因此在这种情况下设想假想的截面是圆形的。轴向截面具有长度L,从而在反应器的内径为D的情况下得出以下值:反应器内壁的表面积(OR)OR=π*D*L,该反应器截面的体积(VR)VR=π/4*D2*L,反应管内侧横截面积(QR)QR=D2*π/4。
根据本发明必须适用:
OP1>OP2
优选的是,OP1-OP2>1cm2,特别优选>0.8cm2,最优选>0.5cm2。
优选地,OP1大于1.9cm2,特别优选大于2.0cm2,最优选大于2.2cm2,和OP2小于1.8cm2,特别优选小于1.7cm2,最优选小于1.5cm2。
在一个实施方案中,OP1为介于2.1cm2与2.8cm2之间,优选介于2.3cm2与2.5cm2之间,和OP2为介于0.9cm2与1.8cm2,优选介于1.1cm2与1.3cm2之间。
图1:与常规催化剂体系相比,根据本发明的催化剂体系的催化测试结果(双α形状/中空柱体1和中空柱体2,GHSV=1,900h-1,1.8体积%正丁烷)。
图2:与常规催化剂体系相比,在使用本发明的催化剂体系的情况下的最高床温度(双α形状/中空柱体1和中空柱体2,GHSV=1,900h-1,1.8体积%正丁烷)。
图3:与常规催化剂体系相比,根据本发明的催化剂体系的催化测试结果(双α形状/中空柱体1、中空柱体2,GHSV=2,100h-1,1.9体积%正丁烷)。
图4:与常规催化剂体系相比,在使用本发明的催化剂体系的情况下的最高床温度(双α形状/中空柱体1、中空柱体2,GHSV=2,100h-1,1.9体积%正丁烷)。
图5:在四个角度上的在气体流过方向上的第一催化剂层的优选催化剂颗粒,“双α形式”。
图6:根据本发明的催化剂体系与常规催化剂体系相比的示意图。
实施例
反应混合物的制备和还原:首先添加1069.5g异丁醇和156.0g苯甲醇。在搅拌下添加150g V2O5。在V2O5添加之后,添加2.52g二钼酸铵。然后将232.50g磷酸(100%或者无水)添加至悬浮液并且在N2下回流加热10h。
过滤:在中间产物悬浮液冷却之后,将其从四颈烧瓶中转移至吸滤器中,并吸出液体。将潮湿的滤饼在压机中在14至18巴过夜压干。
干燥:将经压制的滤饼装入旋转蒸发器的蒸发瓶中。在水喷射真空下将滤饼在110℃过夜干燥。将如此干燥的粉末置于烘箱中的合适的煅烧坩埚中,并在N2气氛中在200至300℃的温度下煅烧9小时。获得经干燥的中间产物(VMo0.0088OHPO4 x 0.5H2O)。
压片:在压实/压片之前,向经煅烧的粉末状中间产物添加5重量%石墨,并且借助于笼式混合器均一地混匀。将该粉末用挤压力为190巴、间隙宽度为0.60mm和辊速率为7转/min的辊压机压实成片料,并通过1mm筛造粒。
将粒料用回转式压片机压制成期望的的片剂形状和侧压强度:
压制出高度为5.6mm、长度为6.7mm、宽度为5.8mm、孔内径为2.1mm的双α形状。这些催化剂颗粒具有2.37cm2的几何表面积、0.154cm3的体积和0.24g的质量。在填充至21mm反应器中时,产生0.60至0.62g/cm3的填充密度。
作为对比,按照具有4.7mm的高度,4.7mm的外径和直径为1.3mm的中心轴开口的中空柱形状1,将催化剂颗粒压制成常规的柱形状1。该成型体具有1.2cm2的几何表面积,0.075cm3的体积和0.12g的质量。在填充至21mm反应器中时,产生0.85至0.89g/cm3的填充密度。
按照具有5.6mm的高度,5.5mm的外径和直径为2.3mm的中心轴开口的中空柱形状2。该成型体具有1.77cm2的几何表面积,0.111cm3的体积和0.18g的质量。在填充至21mm反应器中时,产生0.72至0.76g/cm3的填充密度。
活化成焦磷酸盐:在产生焦磷酸钒时的活化在内置于可编程炉中的蒸馏罐中在受控的条件下进行。将经煅烧的片料均匀填充至蒸馏罐中并且将其密封。然后将催化剂在潮湿的空气-氮气混合物(50%绝对空气湿度)中首先在超过300℃活化5h,然后在超过400℃活化9h。
中试,反应条件
催化测试反应在21mm内径的管式反应器中在4.5m的催化剂床长度在相当的条件下进行。在两种条件:低负载场景和高负载场景测试催化剂。在第一场景中使用1,900h-1的时空速度(GHSV,以h-1表达)并且反应物流由1.8体积%的在空气中稀释的正丁烷、2.3至2.7体积%水和约2ppm磷酸三甲酯组成。对于高负载场景,在1.9体积%的在空气中稀释的正丁烷、3体积%水和约3ppm磷酸三甲酯的反应物气体组成的情况下使用2,100h-1的时空速度。基于所使用的正丁烷的重量给出以重量百分比(重量%)计的马来酸酐的产率。
图1至4示出了在使用根据本发明的催化剂体系时的催化测试反应的结果和温度分布,该催化剂体系在第一催化剂层中使用双α形催化剂颗粒并且在第二催化剂层中使用按照中空柱形状1的催化剂颗粒,相比之下,在常规催化剂体系中在反应管中仅存在按照中空柱形状2的催化剂颗粒。图1和图2示出了低负载场景,而图3和图4示出了高负载场景。
显然,通过使用根据本发明的催化剂体系,马来酸酐的产率在相同转化率时在低负荷条件下高出约2重量%。换言之,根据本发明的催化剂体系在相同转化率时对期望的反应产物马来酸酐显示出更高的选择性。在高负载条件下确定了类似的效果,通过根据本发明的催化剂体系随后导致MA产率增加超过4重量%。
如在图2和4中显而易见的,通过根据本发明的反应器系统经由曲线的扩宽和部分地形成第二热点来降低反应器出口侧的热点温度。这导致提高的MA选择性。
Claims (13)
1.通过催化氧化正丁烷制备马来酸酐的催化剂体系,其包括至少一个反应管,所述反应管具有两个由不同的催化剂颗粒组成的催化剂层,其特征在于,在气体流过方向上,第一催化剂层中的每个催化剂颗粒的几何表面积比第二催化剂层中每个催化剂颗粒的几何表面积更大。
2.根据权利要求1所述的催化剂体系,其特征在于,第一催化剂层中的每个催化剂颗粒的几何表面积比第二催化剂层中的每个催化剂颗粒的几何表面积大至少0.5cm2,优选1cm2。
3.根据权利要求1或2所述的催化剂体系,其特征在于,第一催化剂层中的每个催化剂颗粒的几何表面积大于1.9cm2,优选大于2.2cm2,而第二催化剂层中的每个催化剂颗粒的几何表面积小于1.8cm2,优选小于1.5cm2。
4.根据前述权利要求任一项所述的催化剂体系,其特征在于,在气体流过方向上,第一催化剂层中的催化剂颗粒的堆积密度小于0.8g/cm3,优选小于0.7g/cm3。
5.根据前述权利要求任一项所述的催化剂体系,其特征在于,在气体流过方向上,第一催化剂层中的催化剂颗粒被成形为具有外底面[1]、柱面[2]、柱体轴和至少一个贯穿的平行于柱体轴延伸的开口[3]的柱体,并且柱体的外底面[1]具有至少四个凸角[4a、4b、4c、4d],其中包围催化剂颗粒的几何基体是棱柱体,所述棱柱体具有棱柱体底面,所述棱柱体底面具有长度和宽度,其中长度大于宽度,其中棱柱体底面的棱柱体角围绕凸角[4a、4b、4c、4d]。
6.根据前述权利要求任一项所述的催化剂体系,其特征在于,至少一个反应管能够在盐浴中进行调温。
7.根据前述权利要求任一项所述的催化剂体系,其特征在于,其为管束反应器,所述管束反应器具有多个能够通过盐浴进行调温的反应管。
8.根据前述权利要求任一项所述的催化剂体系,其特征在于,反应管的经填充部分为4m至5m长。
9.通过催化氧化正丁烷制备马来酸酐的方法,其中引导包含氧气和正丁烷的反应物气体通过根据权利要求1至8任一项所述的催化剂体系和使至少一个反应管处于升高的温度。
10.根据权利要求9所述的方法,其特征在于,所述至少一个反应管处于介于300℃与420℃之间的温度。
11.根据权利要求9或10任一项所述的方法,其特征在于,所述反应物气体含有介于0.2至10体积%之间的正丁烷和介于5与50体积%之间的氧气,和以1,500h-1至2,700h-1,优选1,700h-1至2,500h-1之间的时空速度引导通过反应管。
12.根据权利要求1至8任一项所述的催化剂体系用于通过选择性催化氧化正丁烷制备马来酸酐的用途。
13.根据权利要求12的用途,其特征在于,第一催化剂层的催化剂颗粒被成形为具有外底面[1]、柱面[2]、柱体轴和至少一个贯穿的平行于柱体轴延伸的开口[3]的柱体,并且柱体的外底面[1]具有至少四个凸角[4a、4b、4c、4d],其中包围催化剂颗粒的几何基体是棱柱体,所述棱柱体具有棱柱体底面,所述棱柱体底面具有长度和宽度,其中长度大于宽度,其中棱柱体底面的棱柱体角围绕凸角[4a、4b、4c、4d]。
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PCT/EP2020/078408 WO2021074029A1 (de) | 2019-10-15 | 2020-10-09 | Neues katalysatorsystem für die herstellung von maleinsäureanhydrid durch katalytische oxidation von n-butan |
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US4342699A (en) * | 1981-02-23 | 1982-08-03 | Standard Oil Company (Indiana) | Process for production of maleic anhydride |
WO2006099092A1 (en) * | 2005-03-11 | 2006-09-21 | Saint-Gobain Ceramics & Plastics, Inc. | Bed support media |
CN101568378A (zh) * | 2006-12-21 | 2009-10-28 | 巴斯夫欧洲公司 | 用于使用上游层进行气相氧化的催化剂体系和方法 |
CN103269798A (zh) * | 2010-11-22 | 2013-08-28 | 南方化学知识产权有限公司 | 用于流通固定床反应器的成形催化剂体 |
CN105163844A (zh) * | 2013-02-27 | 2015-12-16 | 托普索公司 | 用于自动中毒过程的反应器 |
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CA2110579C (en) * | 1991-07-08 | 2005-06-21 | Jerry Rudolph Ebner | High productivity process for the production of maleic anhydride |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4342699A (en) * | 1981-02-23 | 1982-08-03 | Standard Oil Company (Indiana) | Process for production of maleic anhydride |
WO2006099092A1 (en) * | 2005-03-11 | 2006-09-21 | Saint-Gobain Ceramics & Plastics, Inc. | Bed support media |
CN101568378A (zh) * | 2006-12-21 | 2009-10-28 | 巴斯夫欧洲公司 | 用于使用上游层进行气相氧化的催化剂体系和方法 |
CN103269798A (zh) * | 2010-11-22 | 2013-08-28 | 南方化学知识产权有限公司 | 用于流通固定床反应器的成形催化剂体 |
CN105163844A (zh) * | 2013-02-27 | 2015-12-16 | 托普索公司 | 用于自动中毒过程的反应器 |
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HUP2200125A1 (hu) | 2022-07-28 |
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