CN107913731B - 一种甲醇制对二甲苯催化剂的制备方法 - Google Patents
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Abstract
本发明公开了一种甲醇制对二甲苯催化剂方法，二氧六环、均三甲苯、冰醋酸、COF‑1纳米材料,FeSO4·7H2O、KBH4为主要原料，采用了独特的工艺及技术参数,热膨胀一氨基改性一纳米铁反应生成负载，经过热膨胀处理,COF‑1表面附着性能提升,为后面的氨基改性提供基础，经过氨基改性,表面性质得到改善,有利于反应生成的纳米铁充分且均匀地负载在多孔载体上，本发明通过甲醇烷基化反应，得到对二甲苯，省去传统工艺中异构化等步骤,工艺路线缩短,对二甲苯单程收率大幅提高。
Description
技术领域
本发明涉及一种甲醇制对二甲苯催化剂及其制备方法,属于催化剂技术领域。
背景技术
对二甲苯是极为重要的大宗化工原料,主要用于生产对苯二甲酸和对苯二甲酸二甲醋。由于我国聚酯行业发展迅猛,带动了和消费量的增长,从而导致对二甲苯的消费量也快速增长。工业上一般是通过石油裂解产物进行芳烃分离、甲苯歧化或重芳烃烷基转移的方法生产对二甲苯,由于这些方法副产大量的苯,而苯的经济价值低,在一定程度上影响对二甲苯制备工艺的经济性。传统方法多采用固定床技术,床层温度不均匀,催化剂稳定性差、容易失活且不易再生为了提高催化剂稳定性,在反应过程中多需通入氢气作为载气,而氢气本身具有较高的价值,因此成本较高上；催化剂的制备和改性步骤繁琐,成本昂贵上述技术中苯的转化率多在30%一40%之间,原料利用率不够高。
发明内容
本发明的目的在于提供一种甲醇制对二甲苯催化剂的制备方法，对二甲苯在二甲苯异构体中的选择性大幅度提高,省去了传统工艺中异构化等步骤,工艺路线缩短,对二甲苯单程收率大幅提高。
一种甲醇制对二甲苯催化剂的制备方法，包括以下步骤：
步骤1、将100g COF-1纳米材料冷冻干燥后粉碎,置于管式炉内,通氮气10min,流量为0.5L/min,并快速升温,达到350℃后保持恒温5h,得到热膨胀多孔材料；
步骤2、将上述COF-1纳米材料置于1mol/L稀盐酸中,恒温搅拌,过滤得到固体；取固体100g,加入体积比为50ml浓硫酸和50ml浓硝酸混合溶液,然后机械搅拌反应4小时,抽滤、
清洗并烘干；
步骤3、将上述烘干后产物加入25ml氨水中,机械搅拌15min后,加入25g连二亚硫酸钠,恒速搅拌24小时,抽滤、清洗、烘干后,得氨基改性COF-1纳米材料；
步骤4、取50g氨基改性COF-1纳米材料,加入160ml含15gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。
所述的COF-1纳米材料制备方法如下：
步骤1、将2.36mmol二氧六环、5.74mmol均三甲苯和0.6mmol冰醋酸分散在5.56mmol蒸馏水中,形成混合溶液；将0.08mmol的2,4,6一三(4一氨基苯基)一1,3,5三嗪和0.12mmol的2,5一二甲氧基一对苯二甲醛分散在所述混合溶液中；
步骤2、在氮气氛下,所得混合液静止于120℃下反应72小时,过滤,用干燥的四氢呋喃和丙酮分别洗涤3次,得到固体粉末；
步骤3、将所述的固体粉末80℃真空干燥12小时,得到具有高结晶性、高比表面积和孔容的亚胺连接共价有机骨架材料COF-1。
有益效果：本发明催化剂采用了独特的工艺及技术参数,热膨胀一氨基改性一纳米铁反应生成负载，经过热膨胀处理,COF-1表面附着性能提升,为后面的氨基改性提供基础，经过氨基改性,表面性质得到改善,有利于反应生成的纳米铁充分且均匀地负载在多孔载体上,提升负载量采用液相还原法制备纳米铁,即时反应、即时负载,保持了纳米铁的活性,避免了团聚效应；改善催化剂表面特性和稳定性,吸附容量显著增加另一方面可同时发挥多孔的吸附作用及纳米铁的还原作用,提高甲醇烷基化反应效果；使得对二甲苯在二甲苯异构体中的选择性大幅度提高,最高达到95%以上对二甲苯单程收率最高达到20%以上,省去了传统工艺中异构化等步骤,工艺路线缩短,对二甲苯单程收率大幅提高。
具体实施方式
实施例1
一种甲醇制对二甲苯催化剂的制备方法，包括以下步骤：
步骤1、将100g COF-1纳米材料冷冻干燥后粉碎,置于管式炉内,通氮气10min,流量为0.5L/min,并快速升温,达到350℃后保持恒温5h,得到热膨胀多孔材料；
步骤2、将上述COF-1纳米材料置于1mol/L稀盐酸中,恒温搅拌,过滤得到固体；取固体100g,加入体积比为50ml浓硫酸和50ml浓硝酸混合溶液,然后机械搅拌反应4小时,抽滤、
清洗并烘干；
步骤3、将上述烘干后产物加入25ml氨水中,机械搅拌15min后,加入25g连二亚硫酸钠,恒速搅拌24小时,抽滤、清洗、烘干后,得氨基改性COF-1纳米材料；
步骤4、取50g氨基改性COF-1纳米材料,加入160ml含15gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。
所述的COF-1纳米材料制备方法如下：
步骤1、将2.36mmol二氧六环、5.74mmol均三甲苯和0.6mmol冰醋酸分散在5.56mmol蒸馏水中,形成混合溶液；将0.08mmol的2,4,6一三(4一氨基苯基)一1,3,5三嗪和0.12mmol的2,5一二甲氧基一对苯二甲醛分散在所述混合溶液中；
步骤2、在氮气氛下,所得混合液静止于120℃下反应72小时,过滤,用干燥的四氢呋喃和丙酮分别洗涤3次,得到固体粉末；
步骤3、将所述的固体粉末80℃真空干燥12小时,得到具有高结晶性、高比表面积和孔容的亚胺连接共价有机骨架材料COF-1。
实施例2
步骤4、取20g氨基改性COF-1纳米材料,加入160ml含15gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。其余步骤同实施例1。
实施例3
步骤4、取10g氨基改性COF-1纳米材料,加入160ml含15gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。其余步骤同实施例1。
实施例4
步骤4、取50g氨基改性COF-1纳米材料,加入160ml含5gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。其余步骤同实施例1。
实施例5
步骤4、取60g氨基改性COF-1纳米材料,加入160ml含15gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。其余步骤同实施例1。
实施例6
步骤4、取30g氨基改性COF-1纳米材料,加入160ml含15gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。其余步骤同实施例1。
实施例7
步骤4、取50g氨基改性COF-1纳米材料,加入160ml含10gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。其余步骤同实施例1。
实施例8
步骤4、取50g氨基改性COF-1纳米材料,加入160ml含20gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。其余步骤同实施例1。
实施例9
步骤4、取50g氨基改性COF-1纳米材料,加入160ml含25gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。其余步骤同实施例1。
实施例10
步骤4、取50g氨基改性COF-1纳米材料,加入160ml含1gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。其余步骤同实施例1。
实施例11
步骤4、取50g氨基改性COF-1纳米材料和15g有机酸化纳米硅混合,加入160ml含15gFeSO4•7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂。其余步骤同实施例1。
所述的有机酸化纳米硅的制备方法如下：
将200g粒径为30nm的纳米氧化硅投入到水溶液中,在20℃下以3000rpm的搅拌速度机械搅拌15min后,得到纳米氧化硅的水分散液；向得到的纳米氧化硅的水分散液中加入15g改性剂L一硫代水杨酸,在80℃温度下,3000rpm的转速下搅拌,得到改性纳米氧化硅悬浮液；将所得的悬浮液进行喷雾干燥,喷雾干燥的转速为16000rpm,喷雾干燥的温度为100℃,得到有机酸化纳米硅。
对照例1
与实施例1不同点在于：催化剂制备的步骤1中，通氮气10min,流量为0.1L/min，其余步骤与实施例1完全相同。
对照例2
与实施例1不同点在于：催化剂制备的步骤1中，通氮气10min,流量为1L/min，其余步骤与实施例1完全相同。
对照例3
与实施例1不同点在于：催化剂制备的步骤2中，取固体100g,加入体积比为25ml浓硫酸和25ml浓硝酸混合溶液，其余步骤与实施例1完全相同。
对照例4
与实施例1不同点在于：催化剂制备的步骤2中，取固体100g,加入体积比为10ml浓硫酸和10ml浓硝酸混合溶液，其余步骤与实施例1完全相同。
对照例5
与实施例1不同点在于：催化剂制备的步骤3中，加入5g连二亚硫酸钠，其余步骤与实施例1完全相同。
对照例6
与实施例1不同点在于：催化剂制备的步骤3中，加入55g连二亚硫酸钠，其余步骤与实施例1完全相同。
对照例7
与实施例1不同点在于：COF-1纳米材料制备步骤1 中，将0.36mmol二氧六环、2.74mmol均三甲苯和0.3mmol冰醋酸分散在5.56mmol蒸馏水中,形成混合溶液，其余步骤与实施例1完全相同。
对照例8
与实施例1不同点在于：COF-1纳米多孔材料制备步骤1 中，将4.36mmol二氧六环、10.74mmol均三甲苯和0.9mmol冰醋酸分散在5.56mmol蒸馏水中,形成混合溶液，其余步骤与实施例1完全相同。
对照例9
与实施例1不同点在于：COF-1纳米多孔材料制备步骤3中，将0.8mmol的2,4,6一三(4一氨基苯基)一1,3,5三嗪和0.2mmol的2,5一二甲氧基一对苯二甲醛分散在所述混合溶液中，其余步骤与实施例1完全相同。
对照例10
与实施例1不同点在于：COF-1纳米多孔材料制备步骤3中，将18mmol的2,4,6一三(4一氨基苯基)一1,3,5三嗪和1.2mmol的2,5一二甲氧基一对苯二甲醛分散在所述混合溶液中，其余步骤与实施例1完全相同。
苯和甲醇烷基化反应在流化床反应装置上进行。反应条件为：催化剂装填100g，反应温度为500℃，原料苯和甲醇摩尔比为1：2，原料重时空速为2.8h-1，反应压力为0.1MPa，反应产物用在线气相色谱进行分析，结果如表所示。
实验结果表明催化剂对甲醇烷基化具有良好的催化效果，在反应条件一定时，对二甲苯选择性越高，催化性能越好，反之越差；在COF-1和 FeSO4•7H2O质量比为10：3时，其他配料固定，催化效果最好，与实施例1不同点在于，实施例2至实施例10分别改变催化剂COF-1和 FeSO4•7H2O的用量和配比，对催化剂的催化性能有不同的影响，值得注意的是实施例11加入了有机酸化纳米硅，对二甲苯选择性明显提高，说明有机酸化纳米硅对催化材料的结构活性有更好的优化作用；对照例1至对照例 2改变了氮气的流量，其他步骤完全相同，导致催化剂的活性发生变化，对二甲苯选择性明显降低；对照例3至对照例4，浓硫酸和浓硝酸的混合比，效果依然不好，说明酸的配比很重要；对照例5至对照例6改变强还原剂连二亚硫酸钠用量，对二甲苯选择性也不高，说明强还原剂的多少对改性效果影响很大；对照例7和对照例10，改变COF-1原料的摩尔配比，导致多孔材料的结构性质发生变化，效果明显变差；因此使用本发明制备的催化剂对甲醇烷基化反应具有优异的催化效果。
Claims (1)
1.一种甲醇制对二甲苯催化剂的制备方法，包括以下步骤：
步骤1、将100g COF-1纳米材料冷冻干燥后粉碎,置于管式炉内,通氮气10min,流量为0.5L/min,并快速升温,达到350℃后保持恒温5h,得到热膨胀多孔材料；
步骤2、将上述COF-1纳米材料置于1mol/L稀盐酸中,恒温搅拌,过滤得到固体；取固体100g,加入体积比为50ml浓硫酸和50ml浓硝酸混合溶液,然后机械搅拌反应4小时,抽滤、清洗并烘干；
步骤3、将上述烘干后产物加入25ml氨水中,机械搅拌15min后,加入25g连二亚硫酸钠,恒速搅拌24小时,抽滤、清洗、烘干后,得氨基改性COF-1纳米材料；
步骤4、取50g氨基改性COF-1纳米材料,加入160ml含15gFeSO4·7H2O和5g PEG-4000醇-水混合体系中,其中水和无水乙醇体积比1:2，通入高纯氮气,恒速搅拌,同时逐滴加入30ml浓度为0.5mol/L的KBH4溶液，然后持续搅拌20min,真空冷冻干燥,得纳米铁负载氨基改性COF-1催化剂；
所述的COF-1纳米材料制备方法如下：
步骤1、将2.36mmol二氧六环、5.74mmol均三甲苯和0.6mmol冰醋酸分散在5.56mmol蒸馏水中,形成混合溶液；将0.08mmol的2,4,6一三(4一氨基苯基)一1,3,5三嗪和0.12mmol的2,5一二甲氧基一对苯二甲醛分散在所述混合溶液中；
步骤2、在氮气氛下,所得混合液静止于120℃下反应72小时,过滤,用干燥的四氢呋喃和丙酮分别洗涤3次,得到固体粉末；
步骤3、将所述的固体粉末80℃真空干燥12小时,得到具有高结晶性、高比表面积和孔容的亚胺连接共价有机骨架材料COF-1。
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