CN1300272A - 苯乙烯的制法 - Google Patents
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Abstract
苯乙烯的制法,该方法包括在脱水催化剂存在下将1-苯基—乙醇高温气相脱水,其中该脱水催化剂由异形氧化铝催化剂颗粒组成,该催化剂颗粒表面积(BET)的范围为80—140m2/g且孔体积(Hg)的范围为0.35—0.65ml/g,其中直径至少1000nm的孔为0.03—0.15ml/g。
Description
本发明涉及在特定基于氧化铝的脱水催化剂存在下,由含1-苯基-乙醇(也称α-苯基-乙醇或甲基-苯基-甲醇)或取代1-苯基-乙醇的原料制备苯乙烯或取代苯乙烯的方法。
生产苯乙烯的公知方法是起始于乙苯的环氧丙烷和苯乙烯的联合生产法。通常,该方法涉及步骤:(ⅰ)使乙苯与氧或空气反应形成乙苯的氢过氧化物,(ⅱ)在环氧化催化剂存在下将这样获得的乙苯氢过氧化物与丙烯反应得到环氧丙烷和1-苯基-乙醇,和(ⅲ)通过采用合适脱水催化剂的脱水作用将1-苯基-乙醇转化为苯乙烯。本发明特别涉及最后这一步骤,即,1-苯基-乙醇脱水产生苯乙烯的步骤。
本申请进一步的上下文中,术语“苯乙烯”还包括取代苯乙烯,这是指含一个或多个键合于芳香环或乙烯基上的取代基的苯乙烯。这类取代基一般包括:烷基例如甲基或乙基。类似地,术语“1-苯基-乙醇”也包括取代的1-苯基-乙醇,其具有与相应取代苯乙烯相同的取代基。
1-苯基-乙醇脱水制造苯乙烯的方法为本领域所熟知。它不但可在气相中而且可在液相中完成。气相和液相脱水都适用的非均相脱水催化剂包括:例如酸性物质象氧化铝,碱氧化铝、硅酸铝和H-型合成沸石。液相脱水法中适用的均相催化剂的实例是:对甲苯磺酸。脱水条件也是熟知的,且通常包括对于液相脱水100-300℃,而对于气相脱水210-330℃的反应温度。通常的压力范围是0.1-10巴。
本发明重点是1-苯基-乙醇气相脱水制造苯乙烯时使用的特定的、异形的氧化铝催化剂的应用。如上述,氧化铝催化剂在1-苯基-乙醇脱水中的应用为本领域所熟知。
例如,US-3526674公开了氧化铝催化剂在液相脱水法将1-苯基-乙醇制成苯乙烯中的应用,其中所述氧化铝催化剂适宜地具有40-250m2/g的BET表面积,并以细分的形式,即以颗粒尺寸约0.15 mm(100目)或更小的颗粒形式使用。
US-3658928公开了在受控量的添加蒸汽存在下并且在一种催化剂的存在下,将1-苯基-乙醇制成苯乙烯的气相脱水法,该适宜的催化剂为市售的氧化铝催化剂,象Harshaw A1-0104。表Ⅳ列出了所采用的新鲜氧化铝催化剂的比表面积是109 m2/g。
通常,气相脱水法通过将进料气体穿过催化剂颗粒固定床来进行。催化剂床的充填很重要。即,一方面采用小颗粒催化剂意味着接触表面大且因此转化水平高,但另一方面小颗粒意味着密集填装且因此压力降高。因此找到转化水平和压力降之间的恰当平衡非常重要。
本发明的目的是提供1-苯基-乙醇气相脱水制造苯乙烯的方法,其中以改进的选择性和高收率获得苯乙烯。而且,所用的脱水催化剂应当有足够的机械稳定性并且应当把经过反应器的压力降减到最小。因此致力于转化水平和压力降之间的最佳平衡。
通过采用有特定特征的异形氧化铝催化剂达到这些目的,这些特征包括一定量的大孔隙率(macroporosity)。
因此,本发明涉及苯乙烯的制法,其包括在脱水催化剂存在下高温将1-苯基-乙醇气相脱水,其中脱水催化剂由异形氧化铝催化剂颗粒组成,该催化剂颗粒的表面积(BET)在80-140 m2/g范围,且孔体积(Hg)在0.35-0.65 ml/g范围,其中直径至少1000 nm的孔为0.03-0.15 ml/g。
本发明所用术语“氧化铝”是指构成至少90重量%(wt%),优选至少95重量%且最优选至少99重量%的无机氧化物是Al2O3。按100重量%计的其余成分可由最少量的其它无机氧化物例如SiO2和碱金属氧化物组成。合适的氧化铝包括γ-氧化铝、δ-氧化铝、η-氧化铝和θ-氧化铝,其中优选γ-氧化铝。
表述“异形氧化铝催化剂”是指氧化铝颗粒组成的催化剂,该颗粒具有一定的立体形状。这类催化剂颗粒可合适地通过包括挤出和煅烧的方法获得。其中用具有口模板(dieplate)的挤出机取得颗粒的立体形状,该口模板带有所需形状的模孔。
将用于本发明方法中的异形氧化铝催化剂的表面积在80-140 m2/g的范围。该表面积是按照熟知的Brunauer-Emmett-Teller(BET)方法测定的。所用催化剂的表面积优选在85-115 m2/g的范围。
异形氧化铝催化剂的孔体积数值范围为0.35-0.65 ml/g,其中直径至少1000 nm的孔为0.03-0.15 ml/g,并且孔体积是按照熟知的水银孔隙度测定法测定的。该孔体积(Hg)优选在0.40-0.60 ml/g范围,其中直径至少1000 nm的孔为0.05-0.12 ml/g。直径1000 nm或更大的孔也称为大孔。已经发现,本发明方法使用的异形氧化铝催化剂中存在一定水平的大孔孔隙率非常有益。
对本发明而言,催化剂颗粒的直径并非关键。可采用这类催化剂常用的直径。与此联系使用的术语“直径”是指催化剂颗粒横截面的周边上相对两点间的最大距离。在具有异形横截面的棒状颗粒情形,该异形横截面是相关横截面。已经发现,使用直径1.5-8mm,优选2.5-4.5mm的催化剂颗粒特别有利于实现本发明的目的。
催化剂颗粒可为任意形状,包括球形、柱形、三叶形、四叶形、星形、环形、十字形等等。但是,已发现特别优选使用星形催化剂,即具有星形横截面的棒状催化剂颗粒。星形可有所需的任何角数目,但优选四-、五-或六-角的星形。已发现应优选使用催化剂颗粒(平均)长度/直径比值为0.5-3,优选1.0-2.0范围的星形催化剂颗粒。与此相关的“长度”是指棒的长度。
将被使用的催化剂颗粒适宜有一种堆积密度,该密度使固定床操作中反应器有效充填,但又不引起太高的压力降。在这方面,已经发现使用堆积密度至少为0.5 g/ml,优选在0.6-1.5 g/ml范围的催化剂颗粒是有益的。
催化剂颗粒应当还有足够的机械强度。本发明的优点之一是待使用的具体催化剂颗粒机械强度甚佳,以侧抗碎强度(SCS)和体积抗碎强度(BCS)来说都是如此,而同时又具有大孔孔隙率。因此,所用的催化剂颗粒SCS至少为20 N,优选至少40 N,并且BCS至少0.8 MPa,合适的是1.0-2.5 MPa。
按照本发明,将1-苯基-乙醇脱水变为苯乙烯是在气相中完成。将采用的脱水条件是常规采用的那些条件,包括210-330℃,适宜地280-320℃的反应温度,和0.1-10巴范围的压力。
在本发明方法中,此前描述的催化剂对苯乙烯的反应选择性为至少95%并且活性至少为95%,而99%或更高的选择性以及97%和更高的活性也已经达到。与此联系的反应选择性定义为:每摩尔被转化的1-苯基-乙醇形成苯乙烯的摩尔数。活性定义为:在测试条件下测定的1-苯基-乙醇的总转化水平,即相对进料中存在的1-苯基-乙醇总摩尔数转化的1-苯基-乙醇的摩尔百分数。
现在用以下实施例举例说明本发明,本发明的范围不限于这些具体的实施方案。在这些实施例中,按BET方法测定表面积,用水银孔隙度测定法测定孔体积。
实施例1
在13 mm直径的活塞流反应器、1-苯基-乙醇进料设备及产物蒸汽冷凝设备组成的微流单元中测试物理性能如表Ⅰ(Ex-1)所示的星形催化剂的脱水性能。当使用1-苯基-乙醇原料时,此加工物流的样品用于商品化的环氧丙烷/苯乙烯单体成套设备的苯乙烯反应器系统中。该原料含79.8%的1-苯基-乙醇,11.1%的甲基苯基酮和1.8%的水。按100%计的其余成分由杂质和前面环氧化阶段的(副)产物组成。经冷凝使微流单元的流出物液化,并且用气相色谱分析手段分析所获得的两相液态体系。
在1.0巴(bara)压力和300℃温度的标准测试条件下进行脱水实验。1-苯基-乙醇的进料速度保持在30克/小时,且反应管用20立方厘米的催化剂装填,其相当于长/径比约1.1的星形催化剂颗粒13.8克。连续进行反应约90小时,然后停止反应。
由运行小时数17和运行小时数30之间收集的反应产物样品进行气相色谱分析测定星形催化剂的活性和反应选择性。
结果如表Ⅰ所示。
对比例1
重复实施例1,不同的是,微流反应管用20克(20立方厘米)商品氧化铝的0.32厘米(1/8英寸)片(Al-0104,产自Engelhard DeMeern B.V.)装填,它可适用于1-苯基-乙醇的脱水反应。表Ⅰ中(Cex-1)列出了这些催化片剂的物理性能。
用气相色谱对运行19小时和运行27小时之间收集的反应产物样品进行分析,由此测定这些催化剂片的活性和反应选择性。
结果示于表Ⅰ。
对比例2
重复实施例1,不同的是,微流反应管用13.6克(20立方厘米)星形氧化铝催化剂颗粒装填,这些颗粒基本上无任何大孔(直径1000纳米以上的孔),表Ⅰ中(Cex-2)列出了这些催化剂颗粒的物理性能。
用气相色谱对运行14小时和运行27小时之间收集的反应产物样品进行分析,由此测定这些催化剂的活性和反应选择性。
结果示于表Ⅰ。
由表Ⅰ可以看出,本发明方法中使用的催化剂把优异活性和选择性与非常优良的机械性能相结合。
表Ⅰ 催化剂的性质和性能
实施例1(Ex-1) | 对比例1(CEx-1) | 对比例2(CEx-2) | |
形状 | 星形 | 片形 | 星形 |
表面积(m2/g) | 99 | 102 | 111 |
孔体积(ml/g) | 0.57 | 0.35 | 0.45 |
孔体积>1000 nm(ml/g) | 0.07 | 0.02 | 无 |
侧抗碎强度(N) | 61 | 44.2 | 50 |
体积抗碎强度(MPa) | 1.1 | >1.6 | 1.1 |
堆积密度(ml/g) | 0.71 | 1.0 | 0.69 |
颗粒直径(mm) | 3.6 | 3.2 | 3.5 |
活性(%) | 97.82 | 95.97 | 97.36 |
反应选择性(%) | 98.35 | 96.16 | 97.04 |
Claims (7)
1.苯乙烯的制法,该方法包括在脱水催化剂存在下将1-苯基-乙醇高温气相脱水,其中该脱水催化剂由异形氧化铝催化剂颗粒组成,该催化剂颗粒的表面积(BET)在80-140 m2/g范围,且孔体积(Hg)在0.35-0.65 ml/g范围,其中直径至少1000 nm的孔为0.03-0.15ml/g。
2.根据权利要求1的方法,其中该表面积在85-115 m2/g的范围。
3.根据权利要求1或2的方法,其中该孔体积(Hg)在0.40-0.60ml/g范围,其中直径至少1000 nm的孔为0.05-0.12 ml/g。
4.根据前述权利要求中任何一项的方法,其中该催化剂颗粒的直径为1.5-8mm。
5.根据前述权利要求中任何一项的方法,其中该催化剂颗粒为星形。
6.根据权利要求5的方法,其中该催化剂颗粒的长径比在0.5-3.0的范围。
7.根据前述权利要求中任何一项的方法,其中该催化剂颗粒的堆积密度为至少0.5 g/ml,优选在0.6-1.5 g/ml的范围。
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BR9910328A (pt) | 2001-01-30 |
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BR9910328B1 (pt) | 2012-02-22 |
WO1999058480A1 (en) | 1999-11-18 |
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CA2331580A1 (en) | 1999-11-18 |
DE69911765T2 (de) | 2004-08-05 |
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ES2207212T3 (es) | 2004-05-16 |
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