CN107999100A - 一种轻质烷烃芳构化的催化剂及其制备方法和应用 - Google Patents
一种轻质烷烃芳构化的催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种轻质烷烃芳构化的催化剂及其制备方法和应用。所述催化剂以活性炭为载体,负载磷或金属盐化合物,或者同时负载磷和金属盐化合物;以催化剂总质量计,所述催化剂中磷的质量百分比为0.01~20%,所述催化剂中金属盐化合物的质量百分比为0.01~20%。所述催化剂在催化轻质烷烃芳构化反应前需要活化,活化条件为:400~800℃惰性气氛下活化0.1~24h。本发明采用活性炭作为催化剂载体,孔隙发达,比表面积大;性质稳定,且廉价易得。通过对活性炭负载磷或金属盐活性组分,获得了性能优良的用于轻质烷烃芳构化反应的炭载体催化剂。
Description
技术领域
本发明涉及烷烃芳构化催化剂技术领域,具体涉及一种应用于轻质烷烃芳构化的炭载体催化剂及其制备方法和应用。
背景技术
苯、甲苯和二甲苯(BTX)是重要的有机化工基础原料,广泛应用于合成纤维、树脂、橡胶以及各种精细化学品,同时也是高辛烷值汽油的重要组成部分,需求量较大。目前芳烃主要由石脑油催化重整和蒸汽裂解制乙烯工艺提供。
近年来,煤基烯烃工艺(MTO、MTP)、FT工艺得到快速发展,并已实现工业化,烃类产物中含有较多的轻质正构烷烃(C3-C8烷烃),可以作为芳构化的优质原料,有针对性地利用轻质正构烷烃(C3-C8烷烃)开发芳构化技术,不但可以实现芳烃原料的多元化,而且可实现煤化工工艺过程中副产物的高附加值利用,对提高现代煤化工装置的经济效益有重要的意义。
轻质烷烃芳构化过程是将轻质烷烃(C3-C8烷烃)在催化剂作用下通过烷烃的芳构化、异构化、脱氢环化、氢解等反应使烷烃转化为芳烃。目前芳构化工艺中主要有Mobil公司开发的M2-Forming工艺、BP/UOP开发的Cyclar工艺、Asahi/Sanyo开发的Z-Forming工艺、IFP Axens开发的ParamaX工艺以及国内大连理工大学开发的Nano-Forming工艺等。所采用的催化剂均为分子筛型催化剂,如ZSM-5、MFI、L沸石等分子筛,但分子筛载体存在孔道易堵塞、热稳定性等问题,影响催化剂的活性和稳定性,为了寻求一种更好的工业化催化剂,又发展了一系列提高活性和稳定性的改进方法,主要集中在对此类分子筛载体的改进,如调整硅铝比、活性金属元素修饰、改变孔道结构、制备方法和预处理方式等。但是这些改进仍然难以满足市场对低成本、高活性的轻质烷烃芳构化催化剂的需求,因此迫切需要开发新型的烷烃芳构化催化剂。
发明内容
本发明的目的在于,提供一种轻质烷烃芳构化的催化剂及其制备方法和应用,以提高催化剂芳构化反应活性及目标产物BTX的选择性。
本发明为实现上述目的所采用的技术方案如下:
一种轻质烷烃芳构化的催化剂,所述催化剂以活性炭为载体,负载磷或金属盐化合物,或者同时负载磷和金属盐化合物;以催化剂总质量计,所述催化剂中磷的质量百分比为0.01~20%,所述催化剂中金属盐化合物的质量百分比为0.01~20%。
优选地,所述金属盐化合物选自Zn盐、Mo盐、Pt盐、Pd盐、Ga盐、La盐中的一种或多种;所述金属盐化合物为硝酸盐、卤化盐、硫酸盐或醋酸盐。
优选地,所述活性炭载体选自椰壳炭、煤基炭、竹炭、木质炭或生物质炭。进一步优选椰壳炭或煤基炭。
本发明还提供一种轻质烷烃芳构化的催化剂的制备方法,该方法包括如下步骤:
步骤1,活性炭预处理:将活性炭经过酸洗干燥或者双氧水浸泡干燥处理后作为载体备用;
步骤2,磷改性炭基催化剂:取预处理好的活性炭载体,加入等体积的质量浓度为1~68%的磷酸溶液中,采用水热法或浸渍法处理,然后洗净干燥得到磷改性炭基催化剂;
步骤3,金属盐化合物改性炭基催化剂:取预处理后的活性炭载体或者已负载磷的活性炭,放入Zn、Mo、Pt、Pd、Ga、La中的一种或者几种金属盐水溶液(金属盐浓度为0.001-1mol/L)中,浸渍1~24小时后于80~150℃烘干2~20h。
优选地,所述活性炭为椰壳炭时预处理方法为:将椰壳活性炭原料和10~30%wt浓度的双氧水按照1:1~3的体积比在30~80℃的温度下浸泡2h以上后,抽虑洗净于100~150℃下干燥1~15h,得到椰壳炭载体。
所述活性炭为煤基炭时预处理方法为:将煤基活性炭原料和1~3M的HCL水溶液按照1:1~3的体积比在40~60℃的温度下浸泡2h以上后,抽虑洗净于100~150℃下干燥1~15h,得到煤基炭载体。
优选地,所述步骤2中磷改性炭基催化剂为水热法或浸渍法制备,水热法处理条件为:80~200℃水热处理0.2~24h,浸渍法处理条件为:25~80℃下浸渍2~24h;抽滤洗净后的干燥条件为:于100~150℃干燥2~24h。
优选地,所述的浸渍法采用等体积浸渍、真空浸渍、微波浸渍、超声波浸渍或干法浸渍。
优选地,所述步骤3中金属盐水溶液为硝酸盐、卤化盐、硫酸盐或醋酸盐。
本发明还提供了一种轻质烷烃芳构化的催化剂用于催化轻质烷烃的芳构化反应。所述催化剂在催化轻质烷烃芳构化反应前需要活化,活化条件为:400~800℃惰性气氛下活化0.1~24h。
本发明采用正己烷为探针分子,在固定床反应器内进行评价催化剂的催化活性,石英反应管(长1m,外径15mm,内径11mm),催化剂装填量为10ml,在常压、500-600℃及液时空速0.1h~2条件下进行反应,反应器出口气体经过加热保温200℃保持气化,产物经过六通阀进入气相色谱进行在线分析。
与现有技术相比,本发明的有益效果如下:
1,本发明采用活性炭作为催化剂载体,孔隙发达,比表面积大;性质稳定,且廉价易得。通过对活性炭负载磷或金属盐活性组分,获得了性能优良的用于轻质烷烃芳构化反应的炭载体催化剂。
2,本发明采用P和金属活性组份改性,将活性组分均匀的分散在载体表面,提高了催化剂的比表面积,同时通过调节催化剂酸性位,提高了催化剂的活性和芳烃选择性。
具体实施方式
以下通过具体实施例来说明本发明的技术方案。本发明中所用的原料和试剂均市售可得。
本发明实施例中采用的活性炭为椰壳炭和煤基炭。两种活性炭的预处理方法如下:
椰壳炭预处理:将200g椰壳炭加入到500mL浓度为30%双氧水中并在80℃下浸泡5h,冷却后抽虑并用水洗三次,将得到的椰壳炭放置于120℃烘箱中12h。得到预处理椰壳活性炭。
煤基炭预处理:将200g煤基活性炭加入到400mL 2M的HCL水溶液中,40~60℃的温度下浸泡20h后,洗净至中性,置烘箱中在120℃下干燥10h,得到预处理煤基活性炭。
利用上述预处理后的椰壳炭或煤基炭制备磷(P)负载和/或金属(Zn、Mo、Pt、Pd、Ga、La)盐化合物负载的炭基催化剂。
实施例1(P/椰壳C催化剂)
取20g预处理过的椰壳活性炭,加入50mL浓度为20%wt的磷酸水溶液后置于高压釜中180℃水热处理4h;抽虑并水洗三次,放置于120℃烘箱中烘干15h。得到P/椰壳C催化剂。
实施例2(Zn/椰壳C催化剂)
将10g预处理后的椰壳活性炭加入到15ml浓度0.2mol/L的硝酸锌水溶液中,浸渍12小时后于120℃干燥15h,即得到Zn/椰壳C催化剂。
实施例3(P/Zn/椰壳C催化剂)
磷锌改性催化剂采用分步负载的方法。首先如实施例1方法制备得到P/椰壳C催化剂。然后,取10g干燥的P/椰壳C催化剂加入到15ml浓度0.05mol/L的硝酸锌水溶液中,浸渍12小时后放置于120℃烘箱中烘干15h,得到P/Zn/椰壳C催化剂。
实施例4(P/Mo/椰壳C催化剂)
磷钼改性催化剂采用分步负载的方法。首先如实施例1方法制备得到P/椰壳C催化剂。然后,取10g干燥的P/椰壳C催化剂加入到15ml浓度0.03mol/L的钼酸铵水溶液中,浸渍12小时后放置于120℃烘箱中烘干15h,得到P/Mo/椰壳C催化剂。
实施例5(P/煤基C催化剂)
将10g预处理后的煤基活性炭加入50mL浓度为20%的磷酸水溶液后置于高压釜中180℃水热处理4h;抽虑并水洗三次,放置于120℃烘箱中烘干15h。得到P/煤基C催化剂。
实施例6(Mo/煤基C催化剂)
取10g预处理后的煤基活性炭催化剂加入到15ml浓度0.05mol/L的钼酸铵水溶液中浸渍12小时后放置于120℃烘箱中烘干15h,得到Mo/煤基C催化剂。
实施例7(P/Mo/Zn/椰壳C催化剂)
磷钼锌改性催化剂采用分步负载的方法。首先如实施例1方法制备得到P/椰壳C催化剂。首先,取20g干燥的P/椰壳C催化剂加入到30ml浓度0.03mol/L的钼酸铵水溶液中,浸渍12小时后放置于120℃烘箱中烘干15h,得到P/Mo/椰壳C催化剂。然后再取10g干燥的P/Mo/椰壳C催化剂加入到15ml浓度0.05mol/L的硝酸锌水溶液中,浸渍12小时后放置于120℃烘箱中烘干15h,得到P/Mo/Zn/椰壳C催化剂。
对比例1(椰壳C催化剂)
将200g椰壳炭加入到500mL浓度为30%双氧水中并在80℃下浸泡5h,冷却后抽虑并用水洗三次,将得到的椰壳炭放置于120℃烘箱中12h。得到预处理椰壳活性炭,作为椰壳C催化剂。
对比例2(煤基C催化剂)
将200g煤基活性炭加入到400mL 2M的HCL水溶液中,60℃的温度下浸泡20h后,洗净至中性,置烘箱中在120℃下干燥10h,得到预处理煤基活性炭,作为煤基C催化剂。
将上述实施例1-7、对比例1-2得到的催化剂均在相同的催化反应条件下进行催化性能评价。
首先,催化剂在催化反应前均需要进行活化,活化条件为:600℃惰性气氛下活化5h。
活化后的催化剂再进行催化反应,催化反应过程具体如下:
首先,将10ml催化剂填充于内径为10mm的石英反应管反应区域内,氮气(流速40ml/min)气氛下升温至反应温度。然后用精密液体进样泵将正己烷泵入催化剂床层。在常压、500-600℃及液时空速0.5h-1条件下进行反应,反应器出口气体经过加热保温200℃保持气化,产物经过六通阀进入气相色谱进行在线分析,反应稳定30min后取样分析,催化剂反应性能参见表1。
表1催化剂反应性能
所述BTX选择性是指催化反应产物中生成BTX(苯、甲苯、二甲苯的统称)的质量百分含量。从表1可以看出,以正己烷为原料进行催化芳构化反应,直接采用活化后的椰壳炭或煤基炭作为催化剂时,反应生成BTX的选择性只有19.8%和10.3%。当在椰壳炭或煤基炭上负载磷或者金属盐化合物后则大大提高了生成BTX的选择性。
上述仅为本发明的部分优选实施例,本发明并不仅限于实施例的内容。对于本领域中的技术人员来说,在本发明技术方案的构思范围内可以有各种变化和更改,所作的任何变化和更改,均在本发明保护范围之内。
Claims (10)
1.一种轻质烷烃芳构化的催化剂,其特征在于:所述催化剂以活性炭为载体,负载磷酸或金属盐化合物,或者同时负载磷酸和金属盐化合物;以催化剂总质量计,所述催化剂中磷的质量百分比为0.01~20%,所述催化剂中金属盐化合物的质量百分比为0.01~20%。
2.如权利要求1所述的一种轻质烷烃芳构化的催化剂,其特征在于:所述金属盐化合物选自Zn盐、Mo盐、Pt盐、Pd盐、Ga盐、La盐中的一种或多种;所述金属盐化合物为硝酸盐、卤化盐、硫酸盐、醋酸盐或磷酸盐。
3.如权利要求1所述的一种轻质烷烃芳构化的催化剂,其特征在于:所述活性炭载体选自椰壳炭、煤基炭、竹炭、木质炭或生物质炭。
4.权利要求1所述的一种轻质烷烃芳构化的催化剂的制备方法,其特征在于,该方法包括如下步骤:
步骤1,活性炭预处理:将活性炭经过酸洗干燥或者双氧水浸泡干燥处理后作为载体备用;
步骤2,磷改性炭基催化剂:取预处理好的活性炭载体,加入等体积的浓度为1~68%wt的磷酸溶液中,采用水热法或浸渍法处理,然后洗净干燥得到磷改性炭基催化剂;
步骤3,金属盐化合物改性炭基催化剂:取预处理后的活性炭载体或者已负载磷的活性炭,放入Zn、Mo、Pt、Pd、Ga、La中的一种或者几种金属盐水溶液中,浸渍1~24小时后于80~150℃烘干2~20h。
5.如权利要求4所述的一种轻质烷烃芳构化的催化剂的制备方法,其特征在于,所述活性炭为椰壳炭时预处理方法为:将椰壳活性炭原料和10~30%wt浓度的双氧水按照1:1~3的体积比在30~80℃的温度下浸泡2h以上后,抽虑洗净于100~150℃下干燥1~15h,得到椰壳炭载体;所述活性炭为煤基炭时预处理方法为:将煤基活性炭原料和1~3M的HCL水溶液按照1:1~3的体积比在40~60℃的温度下浸泡2h以上后,抽虑洗净于100~150℃下干燥1~15h,得到煤基炭载体。
6.如权利要求4所述的一种轻质烷烃芳构化的催化剂的制备方法,其特征在于:所述步骤2中磷改性炭基催化剂水热法处理条件为:80~200℃水热处理0.2~24h,浸渍法处理条件为:25~80℃下浸渍2~24h;抽滤洗净后的干燥条件为:100~150℃干燥2~24h。
7.如权利要求4所述的一种轻质烷烃芳构化的催化剂的制备方法,其特征在于:所述的浸渍法采用等体积浸渍、真空浸渍、微波浸渍、超声波浸渍或干法浸渍。
8.如权利要求4所述的一种轻质烷烃芳构化的催化剂的制备方法,其特征在于:所述步骤3中金属盐水溶液为硝酸盐、卤化盐、硫酸盐或醋酸盐。
9.权利要求1-3任一项所述的一种轻质烷烃芳构化的催化剂用于催化轻质烷烃的芳构化反应。
10.如权利要求9所述的一种轻质烷烃芳构化的催化剂用于催化轻质烷烃的芳构化反应,其特征在于:所述催化剂在催化轻质烷烃芳构化反应前需要活化,活化条件为:400~800℃惰性气氛下活化0.1~24h。
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