CN111151248A - 利用负载型金属氧化物催化杂环含卤有机物加氢脱卤方法 - Google Patents

利用负载型金属氧化物催化杂环含卤有机物加氢脱卤方法 Download PDF

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CN111151248A
CN111151248A CN201910531574.4A CN201910531574A CN111151248A CN 111151248 A CN111151248 A CN 111151248A CN 201910531574 A CN201910531574 A CN 201910531574A CN 111151248 A CN111151248 A CN 111151248A
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mixture
chloro
cyanopyridine
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王亮
肖丰收
王海
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Zhejiang University ZJU
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Abstract

本发明涉及加氢脱卤的催化剂，旨在提供一种利用负载型金属氧化物催化杂环含卤有机物加氢脱卤方法。包括：将溶剂、杂环含卤有机物、中和剂和催化剂材料，混合均匀；向反应容器中充入氢气，直至压力为0.1～3.0MPa；控制反应温度为25至180℃，反应时间0.1～24h；在反应过程中通过催化脱卤，最终得到脱卤后的杂环化合物。本发明可有效调控杂环含卤有机物脱卤过程中产物的选择性，通过调控金属组分的化学配位环境有效调控吡啶，噻吩等有机分子在催化材料表面的吸附，从而高效制备化工以及农业过程中的重要化合物。在脱卤过程中催化材料稳定，可循环使用，整个反应过程中无有毒有害的副产物产生，绿色环保，具有高的工业应用前景。

Description

利用负载型金属氧化物催化杂环含卤有机物加氢脱卤方法
技术领域
本发明涉及催化杂环含卤有机物加氢脱卤的催化剂，具体来说涉及到一种利用负载型金属氧化物材料催化杂环含卤有机物加氢脱卤的方法。
背景技术
近年来，随着化学和化工产业的迅速发展，有机杂原子化合物在农药、医药、有机合成、以及化工领域中都有着重要而广泛的应用。同时，工业生产过程中含卤素原子的杂原子有机物的大量排放也受到各国政府和广大研究人员的重视，主要是因为大多数的含氯有机物由于结构中含有卤素原子而表现出环境持久性、生物蓄积性以及高毒性等特点，不易被分解或生物降解，使得这些物质在自然界中不断累积，对环境的破坏日益严重，对人类身体健康的危害也日益凸显。如有机含氯农药等造成的水质、土质的严重污染等。因此，如果能够有效的将含卤素原子的杂原子有机物中的卤素脱去，既可以减少该类化合物对环境以及生物的危害，同时也可以得到具有高附加值的有机杂原子化合物。对杂环含卤有机物进行脱卤目前最直接，最具有前景的方法是加氢脱卤，这种方法可以在催化剂的作用下在相对温和的条件下将含有卤素的杂环有机物选择性的转化为脱卤后的高附加值有机杂原子化合物再应用到化工生产过程中，而且使用的多相催化剂可以再回收利用，可以有效降低催化剂成本，因此是对杂环含卤有机物进行脱卤最经济、绿色，也是最有前景的方法。
在杂环含卤有机物加氢脱卤过程中最关键的是选择具有高活性、高选择性以及高稳定性的加氢脱卤催化材料。从上世纪80年代以来，人们对于加氢脱卤催化剂的研究开始日益广泛，但真正具有工业化应用前景的催化材料很少，主要是大多数加氢脱卤催化剂普遍存在反应活性差、目标产物选择性差，催化材料结构不够稳定等原因。例如，对于某些含有两种或者两种以上可被加氢基团的含卤有机物进行加氢脱卤的时候，往往容易加氢卤素以外的官能团，造成产物选择性低等问题；除此之外，尤其是对于含氮、含硫化合物的加氢脱卤反应体系，这些类别的底物容易使催化材料活性组分流失、烧结，造成催化剂在使用后再生和回收困难，难以进行工业化放大生产。因此，研究开发出可以高效，高选择性，高稳定性的催化材料用于催化杂环含卤有机物加氢脱卤具有重要意义。
发明内容
本发明要解决的技术问题是，克服现有技术中的不足，提供一种利用负载型金属氧化物催化杂环含卤有机物加氢脱卤方法。
为解决技术问题，本发明的解决方案是：
提供一种利用负载型金属氧化物催化杂环含卤有机物加氢脱卤方法，包括以下步骤：
(1)在可密封的反应容器中加入溶剂、杂环含卤有机物、中和剂和催化剂材料，混合均匀；在混合物中，催化剂材料的质量百分比为0.01～10％，杂环含卤有机物的质量百分比为0.01～76.4％，中和剂的质量百分比为0.01～19.6％，余量为溶剂；
(2)向反应容器中充入氢气，直至压力为0.1～3.0MPa；控制反应温度为25℃至180℃，反应时间0.1～24小时；在反应过程中通过催化脱卤，最终得到脱卤后的杂环化合物；
所述催化剂材料中，载体是氧化铈(CeO2)、氧化钛(TiO2)、氧化铁(Fe2O3或Fe3O4)、氧化锰(MnO2、Mn3O4、Mn2O3或MnO)、氧化钴(Co3O4)、氧化铝(Al2O3)、氧化硅(SiO2)、氧化镁(MgO)、活性炭中的一种或多种；载体负载的金属组分，是Au、Pd、Pt、Rh、Ir、Ni、Sn中的一种或多种，且金属组分占整个催化剂材料的质量百分比为0.1～30％。
本发明中，所述溶剂是下述的任意一种或多种：水、甲醇、乙醇、叔丁醇、叔戊醇、甲苯、二氯甲烷、三氯甲烷、二甲亚砜或丙酮。
本发明中，所述杂环含卤有机物是下述的任意一种或多种：2-氯吡啶、2-溴吡啶、2-碘吡啶、2-氯噻吩、2-氯呋喃、2,3-二氯吡啶、2,3-二溴吡啶、2,5-二氯噻吩、2-氯-6-甲氧基吡啶、2-氯-6-三氟甲基吡啶、2-氯-6-氰基吡啶、5-氯-3-噻吩甲腈、2-甲基-6-氯吡啶、2-氯-6-乙烯基吡啶、6-氯-2-吡啶羧酸甲酯、2,6-二氯-4-(三氟甲基)吡啶、2,6-二氯-4-甲氧基吡啶、2,6-二氯-4-氰基吡啶、3-氰基-2,6-二氯-4-(三氟甲基)吡啶、3-甲氧基-2,6-二氯-4-(三氟甲基)吡啶、3-羧酸甲酯-2,6-二氯-4-(三氟甲基)吡啶、3-氰基-2,6-二氯-4-(甲氧基)吡啶。
本发明中，所述中和剂是下述的任意一种：吡啶、三乙胺、二乙胺、碳酸氢钠或碳酸钠(能与酸中和的试剂)。
发明原理描述：
本发明以Au、Pd、Pt、Rh、Ir、Ni、Sn等金属作为催化材料中负载的金属活性组分，能够利用这些金属优异的活化以及解离氢气的能力，以氧化铈(CeO2)、氧化钛(TiO2)、氧化铁(Fe2O3或Fe3O4)、氧化锰(MnO2、Mn3O4、Mn2O3或MnO)、氧化钴(Co3O4)、氧化铝(Al2O3)、氧化硅(SiO2)、氧化镁(MgO)、活性炭等作为催化材料载体，能够将负载的金属活性组分分散均匀，同时利用金属-载体相互作用修饰金属组分，调控对反应物分子的吸附进而调控反应选择性，同时稳定金属组分，使其具有高的稳定性，从而高效地催化芳香族含卤有机物脱卤。整个反应过程中无有毒有害的副产物产生，绿色环保。
对于现有技术，本发明的有益效果在于：
1、本发明涉及通过调控催化材料负载的金属组分以及催化材料载体可以有效地调控杂环含卤有机物脱卤过程中产物的选择性，即使在含卤有机物中含有两种或两种以上可被还原的官能团时，仍能高选择性地脱卤，并且可以通过调控金属组分的化学配位环境有效调控吡啶，噻吩等有机分子在催化材料表面的吸附，从而高效制备化工以及农业过程中的重要化合物。
2、本发明提供了一种更催化杂环含卤有机物脱卤的方法，且在脱卤过程中催化材料稳定，可循环使用，整个反应过程中无有毒有害的副产物产生，绿色环保，具有高的工业应用前景。
具体实施方式
下面结合具体实施方式对本发明作进一步详细描述。下述实施例的反应均在可封闭的反应容器中完成。实施例可以使本专业的专业技术人员更全面地理解本发明，但不以任何方式限制本发明。
实施例1
在6g乙醇中加入100mg Au/CeO2(Au负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率74.9％，对应的2-氰基吡啶的选择性为85.1％。
实施例2
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为>99.0％。
实施例3
在6g乙醇中加入100mg Pt/CeO2(Pt负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率98.4％，对应的2-氰基吡啶的选择性为>99.0％。
实施例4
在6g乙醇中加入100mg Rh/CeO2(Rh负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率69.0％，对应的2-氰基吡啶的选择性为90.1％。
实施例5
在6g乙醇中加入100mg Ir/CeO2(Ir负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率58.8％，对应的2-氰基吡啶的选择性为73.5％。
实施例6
在6g乙醇中加入100mg Ni/CeO2(Ni负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率70.4％，对应的2-氰基吡啶的选择性为97.9％。
实施例7
在6g乙醇中加入100mg Sn/CeO2(Sn负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率32.6％，对应的2-氰基吡啶的选择性为50.5％。
实施例8
在6g乙醇中加入100mg Pd-Sn/CeO2(Pd负载质量百分比:2.5％，Sn负载质量百分比:2.5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率96.0％，对应的2-氰基吡啶的选择性为>99.0％。
实施例9
在6g乙醇中加入100mg Pd-Ni/CeO2(Pd负载质量百分比:2.5％，Ni负载质量百分比:2.5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率98.2％，对应的2-氰基吡啶的选择性为>99.0％。
基于在各个考察的金属组分中，金属钯(Pd)表现出了最优的催化性能，故选择金属钯(Pd)为负载的金属组分，继续考察其他载体负载金属钯(Pd)对杂环含卤有机物加氢脱卤的影响。
实施例10
在6g乙醇中加入100mg Pd/TiO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为94.9％。
实施例11
在6g乙醇中加入100mg Pd/Fe2O3(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为93.7％。
实施例12
在6g乙醇中加入100mg Pd/Fe3O4(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为85.0％。
实施例13
在6g乙醇中加入100mg Pd/MnO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为49.2％。
实施例14
在6g乙醇中加入100mg Pd/Mn3O4(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为56.4％。
实施例15
在6g乙醇中加入100mg Pd/Mn2O3(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为20.3％
实施例16
在6g乙醇中加入100mg Pd/MnO(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为49.9％
实施例17
在6g乙醇中加入100mg Pd/Co3O4(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为36.3％
实施例18
在6g乙醇中加入100mg Pd/Al2O3(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为77.8％
实施例19
在6g乙醇中加入100mg Pd/SiO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为68.5％
实施例20
在6g乙醇中加入100mg Pd/MgO(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为49.2％
实施例21
在6g乙醇中加入100mg Pd/C(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为11.3％
基于在各个考察的金属组分中，氧化铈负载的金属钯(Pd)表现出了最优的催化性能，以下将着重针对这个催化材料继续考察其他参数或者条件的改变对其催化杂环含卤有机物加氢脱卤的影响。
实施例22
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:0.1％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率63.2％，对应的2-氰基吡啶的选择性为>99.0％。
实施例23
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:15.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为43.6％
实施例24
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:30.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为8.9％。
实施例25
在6g乙醇中加入1mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：0.01％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：0.98％)，60mg二乙胺(在混合物中的质量百分比：0.98％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率6.3％，对应的2-氰基吡啶的选择性为38.2％。
实施例26
在6g乙醇中加入300mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：4.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：0.93％)，60mg二乙胺(在混合物中的质量百分比：0.93％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为74.9％。
实施例27
在6g乙醇中加入700mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：10.0％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：0.87％)，60mg二乙胺(在混合物中的质量百分比：0.87％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为35.5％。
基于金属Pd的负载量太低或者催化剂投料太少导致催化材料活性不足，负载量太高或者催化剂投料太多导致产物选择性不高，故继续采用Pd负载量为5％的Pd/CeO2催化材料，催化剂投料量100mg进行研究。
实施例28
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应0.1小时，2-氯-6-氰基吡啶转化率4.9％，对应的2-氰基吡啶的选择性为66.8％。
实施例29
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应0.5小时，2-氯-6-氰基吡啶转化率20.4％，对应的2-氰基吡啶的选择性为>99.0％。
实施例30
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应24小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为<0.1％。
实施例31
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；25℃反应5小时，2-氯-6-氰基吡啶转化率13.6％，对应的2-氰基吡啶的选择性为>99.0％。
实施例32
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；130℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为64.0％。
实施例33
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；180℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为28.1％。
实施例34
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入3.0MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为6.6％。
实施例35
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.1MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率20.3％，对应的2-氰基吡啶的选择性为>99.0％。
实施例36
在6g水中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率6.2％，对应的2-氰基吡啶的选择性为48.1％。
实施例37
在6g甲醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为46.8％。
实施例38
在6g叔丁醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率60.6％，对应的2-氰基吡啶的选择性为95.3％。
实施例39
在6g叔戊醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率73.8％，对应的2-氰基吡啶的选择性为98.1％。
实施例40
在6g甲苯中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为>99.0％。
实施例41
在6g二氯甲烷中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为94.1％。
实施例42
在6g三氯甲烷中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为96.9％。
实施例43
在6g二甲亚砜中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率84.5％，对应的2-氰基吡啶的选择性为82.9％。
实施例44
在6g丙酮中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为90.9％。
基于在对溶剂的筛选中，催化材料在乙醇，叔丁醇，叔戊醇，甲苯，三氯甲烷中均表现出了较好的催化性能，故继续采用乙醇作为溶剂进行研究。
实施例45
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.6％)，1mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：0.01％)，60mg二乙胺(在混合物中的质量百分比：0.97％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为<0.1％。
实施例46
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：0.98％)，4g 2-氯-6-氰基吡啶(在混合物中的质量百分比：40.0％)，60mg二乙胺(在混合物中的质量百分比：0.59％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率25.5％，对应的2-氰基吡啶的选择性为95.2％。
实施例47
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：0.38％)，20g 2-氯-6-氰基吡啶(在混合物中的质量百分比：76.4％)，60mg二乙胺(在混合物中的质量百分比：0.22％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率10.7％，对应的2-氰基吡啶的选择性为74.5％。
实施例48
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯吡啶转化率>99.0％，对应的吡啶的选择性为>99.0％。
实施例49
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-溴吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-溴吡啶转化率>99.0％，对应的吡啶的选择性为>99.0％。
实施例50
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-碘吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-碘吡啶转化率82.9％，对应的吡啶的选择性为>99.0％。
实施例51
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯噻吩(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯噻吩转化率>99.0％，对应的噻吩的选择性为>99.0％。
实施例52
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯呋喃(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯呋喃转化率>99.0％，对应的呋喃的选择性为>99.0％。
实施例53
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2,3-二氯吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2,3-二氯吡啶转化率>99.0％，对应的吡啶的选择性为>99.0％。
实施例54
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2,3-二溴吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2,3-二溴吡啶转化率>99.0％，对应的吡啶的选择性为>99.0％。
实施例55
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2,5-二氯噻吩(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2,5-二氯噻吩转化率>99.0％，对应的噻吩的选择性为>99.0％。
实施例56
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-甲氧基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-甲氧基吡啶转化率>99.0％，对应的2-甲氧基吡啶的选择性为>99.0％。
实施例57
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-三氟甲基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-三氟甲基吡啶转化率>99.0％，对应的2-三氟甲基吡啶的选择性为>99.0％。
实施例58
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为>99.0％。
实施例59
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 5-氯-3-噻吩甲腈(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，5-氯-3-噻吩甲腈转化率>99.0％，对应的3-氰基噻吩的选择性为>99.0％。
实施例60
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-甲基-6-氯吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-甲基-6-氯吡啶转化率>99.0％，对应的2-甲基吡啶的选择性为>99.0％。
实施例61
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-乙烯基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-乙烯基吡啶转化率>99.0％，对应的2-乙烯基吡啶的选择性为83.9％。
实施例62
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 6-氯-2-吡啶羧酸甲酯(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，6-氯-2-吡啶羧酸甲酯转化率>99.0％，对应的2-吡啶甲酸甲酯的选择性为>99.0％。
实施例63
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2,6-二氯-4-(三氟甲基)吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2,6-二氯-4-(三氟甲基)吡啶转化率>99.0％，对应的4-三氟甲基吡啶的选择性为>99.0％。
实施例64
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2,6-二氯-4-甲氧基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2,6-二氯-4-甲氧基吡啶转化率>99.0％，对应的4-甲氧基吡啶的选择性为>99.0％。
实施例65
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2,6-二氯-4-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2,6-二氯-4-氰基吡啶转化率>99.0％，对应的4-氰基吡啶的选择性为>99.0％。
实施例66
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 3-氰基-2,6-二氯-4-(三氟甲基)吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，3-氰基-2,6-二氯-4-(三氟甲基)吡啶转化率83.7％，对应的3-氰基-4-三氟甲基吡啶的选择性为92.5％。
实施例67
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 3-甲氧基-2,6-二氯-4-(三氟甲基)吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，3-甲氧基-2,6-二氯-4-(三氟甲基)吡啶转化率86.1％，对应的3-甲氧基-4-三氟甲基吡啶的选择性为96.9％。
实施例68
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 3-羧酸甲酯-2,6-二氯-4-(三氟甲基)吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，3-羧酸甲酯-2,6-二氯-4-(三氟甲基)吡啶转化率72.5％，对应的3-羧酸甲酯-4-三氟甲基吡啶的选择性为90.2％。
实施例69
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5.0％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 3-氰基-2,6-二氯-4-(甲氧基)吡啶(在混合物中的质量百分比：1.0％)，60mg二乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，3-氰基-2,6-二氯-4-(甲氧基)吡啶转化率87.8％，对应的3-氰基-4-甲氧基吡啶的选择性为97.3％。
实施例70
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg三乙胺(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为>99.0％。
实施例71
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg吡啶(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率75.2％，对应的2-氰基吡啶的选择性为>99.0％。
实施例72
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg碳酸钠(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率43.1％，对应的2-氰基吡啶的选择性为>99.0％。
实施例73
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.7％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：1.0％)，60mg碳酸氢钠(在混合物中的质量百分比：1.0％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率37.8％，对应的2-氰基吡啶的选择性为>99.0％。
实施例74
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.6％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：0.97％)，1mg二乙胺(在混合物中的质量百分比：0.01％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率69.3％，对应的2-氰基吡啶的选择性为>99.0％。
实施例75
在6g乙醇中加入100mg Pd/CeO2(Pd负载质量百分比:5％，整个催化材料在混合物中的质量百分比：1.3％)，60mg 2-氯-6-氰基吡啶(在混合物中的质量百分比：0.78％)，1.5g二乙胺(在混合物中的质量百分比：19.6％)，冲入0.5MPa氢气，混合均匀；80℃反应5小时，2-氯-6-氰基吡啶转化率>99.0％，对应的2-氰基吡啶的选择性为>99.0％。
最后，需要注意的是，以上列举的仅是本发明的具体实施例。显然，本发明不限于以上实施例，还可以有很多变形，如：本发明中Pd/CeO2以外的不同催化材料也可以应用于各个不同的杂环含卤有机物的加氢脱卤反应中，负载的金属组分类别，负载量可以多变，反应温度，反应时间亦可多变等等。本领域的普通技术人员能从本发明公开的内容中直接导出或联想到的所有变形，均应认为是本发明的保护范围。

Claims (4)

1.一种利用负载型金属氧化物催化杂环含卤有机物加氢脱卤方法，其特征在于，包括以下步骤：
(1)在可密封的反应容器中加入溶剂、杂环含卤有机物、中和剂和催化剂材料，混合均匀；在混合物中，催化剂材料的质量百分比为0.01～10％，杂环含卤有机物的质量百分比为0.01～76.4％，中和剂的质量百分比为0.01～19.6％，余量为溶剂；
(2)向反应容器中充入氢气，直至压力为0.1～3.0MPa；控制反应温度为25℃至180℃，反应时间0.1～24小时；在反应过程中通过催化脱卤，最终得到脱卤后的杂环化合物；
所述催化剂材料中，载体是氧化铈、氧化钛、氧化铁、氧化锰、氧化钴、氧化铝、氧化硅、氧化镁、活性炭中的一种或多种；载体负载的金属组分，是Au、Pd、Pt、Rh、Ir、Ni、Sn中的一种或多种，且金属组分占整个催化剂材料的质量百分比为0.1～30％。
2.根据权利要求1所述的方法，其特征在于，所述溶剂是下述的任意一种：水、甲醇、乙醇、叔丁醇、叔戊醇、甲苯、二氯甲烷、三氯甲烷、二甲亚砜或丙酮。
3.根据权利要求1所述的方法，其特征在于，所述杂环含卤有机物是下述的任意一种或多种：2-氯吡啶、2-溴吡啶、2-碘吡啶、2-氯噻吩、2-氯呋喃、2,3-二氯吡啶、2,3-二溴吡啶、2,5-二氯噻吩、2-氯-6-甲氧基吡啶、2-氯-6-三氟甲基吡啶、2-氯-6-氰基吡啶、5-氯-3-噻吩甲腈、2-甲基-6-氯吡啶、2-氯-6-乙烯基吡啶、6-氯-2-吡啶羧酸甲酯、2,6-二氯-4-(三氟甲基)吡啶、2,6-二氯-4-甲氧基吡啶、2,6-二氯-4-氰基吡啶、3-氰基-2,6-二氯-4-(三氟甲基)吡啶、3-甲氧基-2,6-二氯-4-(三氟甲基)吡啶、3-羧酸甲酯-2,6-二氯-4-(三氟甲基)吡啶、3-氰基-2,6-二氯-4-(甲氧基)吡啶。
4.根据权利要求1所述的方法，其特征在于，所述中和剂是下述的任意一种：吡啶、三乙胺、二乙胺、碳酸氢钠或碳酸钠。
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