CN113274996A - 一种α-苯乙醇气相脱水制苯乙烯用催化剂 - Google Patents
一种α-苯乙醇气相脱水制苯乙烯用催化剂 Download PDFInfo
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- CN113274996A CN113274996A CN202110522469.1A CN202110522469A CN113274996A CN 113274996 A CN113274996 A CN 113274996A CN 202110522469 A CN202110522469 A CN 202110522469A CN 113274996 A CN113274996 A CN 113274996A
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- catalyst
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- styrene
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Classifications
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- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明属于工业催化技术领域，涉及一种α‑苯乙醇气相脱水制苯乙烯用催化剂，具体涉及环氧丙烷/苯乙烯联合生产过程中α‑苯乙醇气相脱水制苯乙烯用催化剂。该催化剂由氧化铝前驱体负载IA族、IIA族及IVB族元素改性而成，按照质量百分数计，由94.0～99.5％的Al2O3、0.01～3.0％的IVB族金属氧化物、0.01～1.0％的IA族金属氧化物和0.01～2.0％的IIA族金属氧化物组成。该催化剂孔径分布集中，对α‑苯乙醇脱水制苯乙烯产生了高效的择形控制效果，在保持高转化率的同时，有效提高了苯乙烯选择性。
Description
技术领域
本发明属于工业催化技术领域，涉及一种α-苯乙醇气相脱水制苯乙烯用催化剂，具体涉及环氧丙烷/苯乙烯联合生产过程中α-苯乙醇气相脱水制苯乙烯用催化剂。
背景技术
苯乙烯是一种重要的基本有机化工原料，主要用于生产聚苯乙烯树脂、丙烯腈-丁二烯-苯乙烯三元共聚物、苯乙烯-丙烯腈共聚物等。此外，还可用于制药、农药、染料等行业，用途十分广泛。苯乙烯工业化生产有乙苯脱氢和α-苯乙醇脱水两种技术路线。
α-苯乙醇液相脱水法一般采用均相酸类催化剂，常见的有硫酸、磷酸、对甲苯磺酸等。α-苯乙醇液相脱水过程中，均相酸类催化剂会参与并促进副反应发生，生成重组分副产物，降低原料利用率。US3639928采用硝基苯酚或硝基取代的磺酸作为抑制剂，CN1023618383A采用对甲苯磺酸与邻甲苯磺酸复配以降低催化剂用量等改进方式，但均无法从根本上避免上述副反应的发生。而且，苯乙烯中有均相催化剂残留，必须进行碱洗脱除，产生大量废碱液，回收难度大。
α-苯乙醇气相脱水法还通常采用固体催化剂，如氧化铝或氧化钛，US3442963和US3658928中均有报导。苯乙醇脱水反应温度一般在250～320℃、苯乙醇转化率98％以上，苯乙烯的选择性最高可达92～98％，催化剂对反应转化率和苯乙烯选择性呈相反趋势。国际壳牌研究有限公司的专利CN200880120037采用具有多峰型孔径分布的氧化铝催化剂，在1.0Bar压力、300℃的条件下，苯乙醇转化率为99.8％，苯乙烯的选择性为94.9～95.4％，活性下降速率为0.48％/100h。常州瑞华化工工程技术股份有限公司公开了一种适合α-苯乙醇脱水催化剂(CN201711349721)，为采用碱金属、碱土金属及磷元素改性的氧化铝催化剂，苯乙醇的转化率约90～95％，苯乙烯及苯乙酮的选择性约98～99％。
因此，开发一种具有高活性和高选择性的α-苯乙醇气相脱水制苯乙烯催化剂，可以有效提高装置生产效率。
发明内容
本发明的目的是提供一种α-苯乙醇气相脱水制苯乙烯用催化剂，该催化剂由氧化铝前驱体负载IA族、IIA族及IVB族元素改性而成，孔径分布集中，对α-苯乙醇脱水制苯乙烯产生了高效的择形控制效果，在保持高转化率的同时，有效提高了苯乙烯选择性。
本发明所述的一种α-苯乙醇气相脱水制苯乙烯用催化剂，其特征在于，该催化剂由氧化铝前驱体负载IA族、IIA族及IVB族元素改性而成，按照质量百分数计，由94.0～99.5％的Al2O3、0.01～3.0％的IVB族金属氧化物、0.01～1.0％的IA族金属氧化物和0.01～2.0％的IIA族金属氧化物组成。
更进一步的，所述的氧化铝前驱体为拟薄水铝石、薄水铝石、三水铝石、一水铝石、γ-氧化铝或氢氧化铝中的一种或几种。α-苯乙醇脱水反应为L酸催化反应，选用适宜的氧化铝前驱体，并进行活化，可有效地形成L酸中心供体，提高催化转化效率。
更进一步的，所述的IA族元素为Na或K中的一种或几种，以氧化物形式存在。所述的IIA族元素为Mg、Ca、Sr或Ba中的一种或几种，以氧化物形式存在。氧化铝催化剂以L酸中心为主，由于表面不均匀性，存在少数强酸中心位，采用碱金属及碱土金属修饰后，可屏蔽强酸位，从而防止苯乙烯在催化剂表面聚合，减少积炭，延长催化剂使用周期。
更进一步的，所述的IVB族元素为Ti或Zr中的一种或几种，以氧化物形式存在。由键参数理论可知，Ti及Zr的电负性较小，可以形成弱酸点，在反应温度较低时活化α-苯乙醇，而对产物苯乙烯基本无活化作用，从而提高催化剂反应活性。
更进一步的，所述的IA族、IIA族和IVB族元素由共沉淀法、混捏法或浸渍法中的一种或几种方式引入到氧化铝前驱体中。
更进一步的，该催化剂为实心或中空的五齿球形催化剂，其粒径为2～6mm，孔径为10～30nm的孔占比达到90％以上(N2吸附-脱附法测定结果)。α-苯乙醇脱水反应为一级反应，反应物及产物分子在催化剂孔道内扩散是反应控制步骤，集中的介孔结构可以提供高效的扩散通道，提高α-苯乙醇脱水转化率；同时由于择形作用，限制了苯乙烯在催化剂孔道内聚合反应，减少重组分生成，提高苯乙烯选择性。
更进一步的，该催化剂的五齿球形结构采用挤出成型加整形的方式制得，整形后的颗粒进一步在80～150℃条件下干燥2～6h，再用高温炉在600～1100℃条件下活化2～8h，最终获得催化剂。在挤出成型过程中添加缩孔助剂，所述的缩孔助剂为硝酸、草酸、甲酸或乙酸中的一种或几种。
另外，在制备过程中，根据实际需要，可以有选择性的加入粘合剂、助挤剂等助剂，其中，粘合剂可以选用硝酸水溶液、柠檬酸水溶液、草酸水溶液、乙酸水溶液等等，助挤剂可以选用田菁粉、淀粉、甲基纤维素、羧丙基甲基纤维素等等。本发明并不对上述助剂做出具体限制，值得注意的是，添加有上述助剂的原料配方，均应在本发明的创新思想下，属于本发明的保护范围内。
与现有技术相比，本发明的有益效果如下：
(1)该催化剂催化活性及选择性高，在反应温度240～320℃、反应压力5～200kPa的条件下，对α-苯乙醇的转化率高于98.0％，苯乙烯产品选择性达到98.8％以上。
(2)该催化剂活性稳定性好，连续运转480h，对α-苯乙醇转化率下降0.4个百分点/100h，苯乙烯产品选择性无明显降低。
(3)制备方法简单易行。
具体实施方式
下面结合实施例对本发明做进一步说明，但本发明不只限于以下实施例。
实施例1：
一种α-苯乙醇气相脱水制苯乙烯催化剂，按照以下制备方法进行制备：
取拟薄水铝石500g，加入10g锐钛矿型钛白粉、2g无水碳酸钠、10g硝酸钙、12g田菁粉，混合均匀，加入浓度为2％的稀硝酸溶液300g，捏合均匀，至适宜挤出成型；选用外径5.0mm的中空五齿轮孔板，挤出五齿轮条，随即采用整形机进行整形，使颗粒保持中空五齿球形外观。
整形后湿颗粒在120℃条件下干燥4h，再用高温炉在950℃下活化4h，获得催化剂，编号CAT-1。
实施例2：
一种α-苯乙醇气相脱水制苯乙烯催化剂，按照以下制备方法进行制备：
取薄水铝石300g，加入6.5g二氧化锆粉、7g田菁粉、混合均匀，加入浓度3％的草酸水溶液175g，捏合均匀；选用外径3.2mm的五齿轮孔板，挤出五齿轮条，随即采用整形机进行整形，使颗粒保持五齿球形外观。
整形后湿颗粒在120℃条件下干燥4h，再用高温炉在900℃下活化3h，获得载体，测得载体吸水率52％。
取硝酸钾4g、硝酸镁20g，溶于90g去离子水中，配制共浸液；取200g载体，将配制的共浸液喷洒于载体上，至吸附饱和；室温养生1h，120℃干燥2h，再用马弗炉在450℃下活化4h，获得催化剂，编号CAT-2。
实施例3：
一种α-苯乙醇气相脱水制苯乙烯催化剂，按照以下制备方法进行制备：
取九水硝酸铝800g，溶解于400g去离子水中，搅拌溶解；取125g碳酸钠，溶解于300g去离子水中，作为沉淀剂。控制温度60～65℃、搅拌速率500rpm，向硝酸铝溶液中，加入碳酸钠溶液进行共沉淀反应；反应过程中，通过调节碳酸钠溶液滴加速率，使体系pH值保持在8～9之间。碳酸钠溶液滴加结束后，体系温度保持60～65℃下老化1h，过滤母液，并用去离子水冲洗滤饼，至滤液pH＝7～7.5。将滤饼于150℃烘干，研磨至200目以上。
取上述改性拟薄水铝石350g、偏钛酸1g、氢氧化钙7g、田菁粉7.5g，混合均匀；加入2％浓度乙酸水溶液195g，捏合均匀；选用外径5.0mm的五齿轮孔板，挤出五齿轮条，随即采用整形机进行整形，使颗粒保持五齿球形外观。
整形后湿颗粒在120℃条件下干燥4h，再用高温炉在1000℃下活化2h，获得催化剂，编号CAT-3。
实施例4：
一种α-苯乙醇气相脱水制苯乙烯催化剂，按照以下制备方法进行制备：
取十八水硫酸铝1332g、硫酸氧钛2g，溶解于500g去离子水中，搅拌溶解；取164g偏铝酸钠，溶解于500g去离子水中，作为沉淀剂。控制温度60～65℃、搅拌速率500rpm，向铝、钛混合溶液中，加入偏铝酸钠溶液进行共沉淀反应；反应过程中，通过调节偏铝酸钠溶液滴加速率，使体系pH值保持在8～9之间。偏铝酸钠溶液滴加结束后，体系温度保持60～65℃下老化1h，过滤母液，并用去离子水冲洗滤饼，至滤液pH＝7。将滤饼于150℃烘干，研磨至200目以上。
取上述改性拟薄水铝石450g、碳酸钙5g、田菁粉5g，混合均匀；加入1％浓度硝酸水溶液260g，捏合均匀；选用外径3.5mm的五齿轮孔板，挤出五齿轮条，随即采用整形机进行整形，使颗粒保持五齿球形外观。
整形后湿颗粒在120℃条件下干燥4h，再用高温炉在980℃下活化2h，获得催化剂，编号CAT-4。
实施例5：
一种α-苯乙醇气相脱水制苯乙烯催化剂，按照以下制备方法进行制备：
取一水铝石400g，加入3g钙钛矿粉、2g田菁粉，混合均匀，加入浓度为2％的稀硝酸溶液240g，捏合均匀，至适宜挤出成型；选用外径4.0mm的五齿轮孔板，挤出五齿轮条，随即采用整形机进行整形，使颗粒保持中空五齿球形外观。
整形后湿颗粒在120℃条件下干燥4h，再用高温炉在920℃下活化4h，获得催化剂，编号CAT-5。
对比例：
采用市售拟薄水铝石500g，加入3g田菁粉，混和均匀；加入浓度为2％的稀硝酸溶液300g，捏合均匀，至适宜挤出成型；选用选用外径3.5mm的五齿轮孔板，挤出五齿轮条，随即采用整形机进行整形，使颗粒保持五齿球形外观。
整形后湿颗粒在120℃条件下干燥4h，再用高温炉在950℃下活化4h，获得对比催化剂，编号对比剂。
测试例：
采用20mL固定床反应器，α-苯乙醇质量空速2.0h-1，水蒸汽做稀释气，α-苯乙醇：水＝5:1(体积比)。
产物分析条件：气相色谱配FID检测器，DB-WAX固定相色谱柱，采用高纯氦气作载气，流速1mL/min，入口温度80℃。
分别采用实施例1～5中制备的催化剂进行物性检测以及苯乙醇脱水试验，结果见表1。
表1：催化剂物性及对苯乙醇脱水的催化性能
在测试例的基础上，实施例1～5中制备的催化剂连续运行1000h后，α-苯乙醇转化率保持98.5％以上，苯乙烯选择性高于97.5％，催化剂未粉化，长周期运行效果良好。
以上显示和描述了本发明的基本原理、主要特征及优点。但以上所述仅为本发明的具体实施例，本发明的技术特征并不局限于此，任何本领域的技术人员在不脱离本发明的技术方案下得出的其他实施方式均应涵盖在本发明的专利范围之内。
Claims (9)
1.一种α-苯乙醇气相脱水制苯乙烯用催化剂，其特征在于，该催化剂由氧化铝前驱体负载IA族、IIA族及IVB族元素改性而成，按照质量百分数计，由94.0～99.5％的Al2O3、0.01～3.0％的IVB族金属氧化物、0.01～1.0％的IA族金属氧化物和0.01～2.0％的IIA族金属氧化物组成。
2.根据权利要求1所述的一种α-苯乙醇气相脱水制苯乙烯用催化剂，其特征在于，所述的IA族、IIA族和IVB族元素由共沉淀法、混捏法或浸渍法中的一种或几种方式引入到氧化铝前驱体中。
3.根据权利要求1或2所述的一种α-苯乙醇气相脱水制苯乙烯用催化剂，其特征在于，所述的氧化铝前驱体为拟薄水铝石、薄水铝石、三水铝石、一水铝石、γ-氧化铝或氢氧化铝中的一种或几种。
4.根据权利要求1或2所述的一种α-苯乙醇气相脱水制苯乙烯用催化剂，其特征在于，所述的IA族元素为Na或K中的一种或几种，以氧化物形式存在。
5.根据权利要求1或2所述的一种α-苯乙醇气相脱水制苯乙烯用催化剂，其特征在于，所述的IIA族元素为Mg、Ca、Sr或Ba中的一种或几种，以氧化物形式存在。
6.根据权利要求1或2所述的一种α-苯乙醇气相脱水制苯乙烯用催化剂，其特征在于，所述的IVB族元素为Ti或Zr中的一种或几种，以氧化物形式存在。
7.根据权利要求1所述的一种α-苯乙醇气相脱水制苯乙烯用催化剂，其特征在于，该催化剂为实心或中空的五齿球形催化剂，其粒径为2～6mm，孔径为10～30nm的孔占比达到90％以上。
8.根据权利要求7所述的一种α-苯乙醇气相脱水制苯乙烯用催化剂，其特征在于，该催化剂的五齿球形结构采用挤出成型加整形的方式制得，在挤出成型过程中添加缩孔助剂。
9.根据权利要求8所述的一种α-苯乙醇气相脱水制苯乙烯用催化剂，其特征在于，所述的缩孔助剂为硝酸、草酸、甲酸或乙酸中的一种或几种。
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