CN114632523A - 一种用于烷烃化学链脱氢制烯烃催化剂及其制备方法 - Google Patents

一种用于烷烃化学链脱氢制烯烃催化剂及其制备方法 Download PDF

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CN114632523A
CN114632523A CN202210437915.3A CN202210437915A CN114632523A CN 114632523 A CN114632523 A CN 114632523A CN 202210437915 A CN202210437915 A CN 202210437915A CN 114632523 A CN114632523 A CN 114632523A
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alkane
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olefin
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CN114632523B (zh
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梁衡
潘相米
韩伟
李扬
艾珍
吴砚会
张军
张琳
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Southwest Research and Desigin Institute of Chemical Industry
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Abstract

本发明属于烷烃脱氢催化剂制备技术领域，具体为一种用于烷烃化学链脱氢制烯烃催化剂及其制备方法。本发明方法制备的催化剂包含具有储放氧能力及脱氢性能的复合氧化物A3‑2xBxO3和掺杂改性组分，其中A是Zn、Ni、Co中的一种，B是Ti、Mn、Sn中的一种，掺杂改性组分是Fe、Zr、Bi、Ca、Mg、Ba的一种或多种，不含有Cr、贵金属，环保廉价，该催化剂经过不同的成型工艺，可以应用于固定床、移动床、流化床装置。

Description

一种用于烷烃化学链脱氢制烯烃催化剂及其制备方法
技术领域
本发明属于烷烃化学链脱氢催化剂制备技术领域，具体为一种用于烷烃化学链脱氢制烯烃催化剂及其制备方法，以及该催化剂的制备方法。
背景技术
低碳烷烃催化脱氢制烯烃技术备受关注，成功发展低碳烷烃脱氢制烯烃技术不仅可以提高油气资源的利用率，更能生产出高附加值的低碳烯烃产品，这项技术的发展与推广兼具社会效益与经济效益。现有的工业化烷烃脱氢技术均为使用铂系(CN 105582919 A，CN 104588009 A)和铬系(CN 105749986 A，CN 103796078 A)催化剂的脱氢工艺，但铂系催化剂成本高、易烧结失活且对硫、烯烃等毒物比较敏感，因此对原料要求比较苛刻，需要对原料预处理；铬系催化剂对人体和环境毒害过大且运行稳定性差，在Cr基催化剂制备、使用及后续回收环节均可能造成严重的环境污染。从工艺操作来说，工业化脱氢工艺受热力学平衡限制，需要在高温、低压的环境中才能达到较好的烷烃转化率和丙烯产率，操作能耗高，且在高温下烷烃和烯烃极易发生深度裂解和缩聚反应，造成烯烃选择性降低和催化剂积炭失活，需对催化剂进行频繁再生操作。因此，有必要开发低成本、新型烷烃脱氢催化剂。烷烃化学链脱氢催化剂环境友好、价格低廉且易于制备，可以促进烷烃脱氢反应的正向进行，降低能量消耗和副反应。
发明内容
本发明针对现有技术的不足，开发一种复合金属氧化物型烷烃化学链脱氢催化剂，该催化剂环境友好、价格低廉且易于制备，可用于流化床、固定床、移动床装置中。
本申请公开了以上所述催化剂的制备方法，该制备方法工艺简单，操作性强，适于工业化运用。
为实现以上发明目的，本发明的具体技术方案为：
一种复合金属氧化物型烷烃化学链脱氢催化剂，所述的催化剂包含具有储放氧能力及脱氢性能的复合氧化物A3-2xBxO3和掺杂改性组分，其中A是Zn、Ni、Co中的一种，B是Ti、Mn、Sn中的一种，掺杂改性组分C是Fe、Zr、Bi、Ca、Mg、Ba的一种或多种，总质量百分含量之和为100％。
作为本申请中一种较好的实施方式，所述具有储放氧能力及脱氢性能的复合氧化物A3-2xBxO3中的A选自Zn、Ni、Co中的任意一种。
作为本申请中一种较好的实施方式，所述具有储放氧能力及脱氢性能的复合氧化物A3-2xBxO3中的B选自Ti、Mn、Sn中的任意一种。
作为本申请中一种较好的实施方式，所述具有储放氧能力及脱氢性能的复合氧化物A3-2xBxO3中x取值为0.1～1.45，优选0.7～1.3。
作为本申请中一种较好的实施方式，所述的掺杂改性组分C为Fe、Zr、Bi、Ca、Mg、Ba的一种或多种。
作为本申请中一种较好的实施方式，以上所述催化剂用于烷烃脱氢，所述的烷烃包括2～6个碳原子的烷烃，更优选的，所述的烷烃包括乙烷、丙烷、正丁烷或异丁烷，优选乙烷、丙烷、异丁烷，尤其优选丙烷。
作为本申请中一种较好的实施方式，所述烷烃脱氢催化剂的制备方法为将一定量的A、B、C前驱体溶于水中，搅拌均匀，采用溶胶凝胶法、共沉淀法或水热合成法，得到掺杂C组分的复合氧化物A3-2xBxO3；经过不同的成型工艺得到适用于固定床、移动床、流化床的烷烃脱氢催化剂。
制备所发明的脱氢催化剂的原料，从催化剂的反应性能方面没有特殊的要求，可以是盐、可以是碱，也可以直接使用氧化物。但从催化剂物性方面考虑，则有一定的要求，比如，催化剂用于固定床脱氢反应器，选用的原料必须满足催化剂挤条成形的要求；若催化剂用于流化床反应器，则选用的原料必须能够形成具有一定流动性的浆液，以便于进行喷雾造粒。
采用挤条法制备的催化剂用于固定床反应器，采用油氨柱滴球法制备的催化剂用于移动床反应器，采用喷雾造粒的用于流化床反应器。粒度分布主要通过调变喷雾造粒过程中的一些操作参数，比如温度、固含量或泵的转速等。当然喷雾造粒成型的催化剂未必能确保耐磨损强度，有时需要加入一些助剂等。
与现有技术相比，本发明的积极效果体现在：
(一)、催化剂中不含Pt等贵金属，价格相对低廉，对原料中的氧、硫等元素也不敏感；催化剂中不含Cr等有毒的组分，不污染环境；催化剂活性高，烷烃脱氢生成相应的烯烃的选择性高；催化剂稳定性好，机械强度高。
(二)、复合金属氧化物A3-2xBxO3中的晶格氧，可以与产物氢气反应，促进脱氢反应的进一步向右进行，提高烷烃转化率。
(三)、可以通过调变掺杂组分C的种类及含量优化A3-2xBxO3结构，调节晶格氧数量、表面氧空位、结构缺陷及储放氧性能，优化催化剂的反应性能，提高烯烃选择性。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
测试条件：制备10g催化剂，在固定床装置上进行性能评价，以丙烷为原料，反应温度600℃，质量空速2h-1，反应3min后取样分析。
实施例1：
取20.63g六水硝酸镍、5.56g硝酸锰和12.82g六水硝酸镁溶于水中，搅拌均匀，加入适量氨水，调节pH约为6.5～7.5，静置4h，120℃烘干4h，640℃焙烧4h，得到掺杂Mg的Ni1.6Mn0.7O3；
催化剂评价结果表明：丙烷转化率为30.32％，选择性为95.44％。
实施例2：
取19.90g六水硝酸锌、7.25g四氯化钛和7.58g九水硝酸铁溶于水中，搅拌均匀，加入适量碳酸钠，使金属离子完全沉淀，过滤，水洗4次，100℃烘干5h，650℃焙烧3h，得到掺杂Fe的Zn1.4Ti0.8O3；
催化剂评价结果表明：丙烷转化率为28.58％，选择性为96.25％。
实施例3
取4.64g六水硝酸钴、13.49g四氯化锡和1.35g三氯化铋溶于水中，搅拌均匀，加入适量氨水，调节pH5～6，于110℃水热晶化24h，130℃烘干3h，600℃焙烧3h，得到掺杂Bi的Co0.4Sn1.3O3；
催化剂评价结果表明：丙烷转化率为28.47％，选择性为95.32％。
实施例4
取17.29g六水硝酸钴、11.27g四氯化钛和2.09g八水氧氯化锆溶于水中，搅拌均匀，加入适量氨水，调节pH5～6，于100℃水热晶化48h，120℃烘干3h，580℃焙烧3h，得到掺杂Zr的CoTiO3；
催化剂评价结果表明：丙烷转化率为27.86％，选择性为93.33％。
实施例5
取6.18g六水硝酸镍、13.85g四氯化锡、1.28g六水硝酸镁和1.01g九水硝酸铁溶于水中，搅拌均匀，加入适量碳酸钠，使金属离子完全沉淀，过滤，水洗4次，90℃烘干8h，680℃焙烧4h，得到掺杂Fe、Mg的Ni0.5Sn1.25O3；
催化剂评价结果表明：丙烷转化率为31.26％，选择性为91.85％。
实施例6
取13.92g六水硝酸锌、11.51g硝酸锰和3.80g硝酸钙溶于水中，搅拌均匀，加入适量氨水，调节pH5～6，于150℃水热晶化12h，于100℃对条件下烘干3h，再于650℃对条件下焙烧4h，得到Ca掺杂的Zn0.8Mn1.1O3；
催化剂评价结果表明：丙烷转化率为28.12％，选择性为90.25％。
实施例7
取23.70g六水硝酸钴、6.37g硝酸锰、5.13g硝酸钡溶于水中，搅拌均匀，加入适量氨水，调节pH约为6.5～7.5，静置12h，100℃烘干8h，700℃焙烧4h，得到Ba掺杂的Co1.6Mn0.7O3；
催化剂评价结果表明：丙烷转化率为27.83％，选择性为96.47％。
实施例8
取22.23g六水硝酸镍、8.28g四氯化钛、1.09g八水氧氯化锆和1.08g三氯化铋溶于水中，搅拌均匀，加入适量氨水，调节pH5～6，于85℃水热晶化24h，140℃烘干2h，660℃焙烧4h，得到掺杂Bi、Zr的Ni1.4Ti0.8O3；
催化剂评价结果表明：丙烷转化率为29.34％，选择性为93.76％。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (9)

1.一种用于烷烃化学链脱氢制烯烃催化剂，其特征在于,所述的催化剂包括复合氧化物A3-2xBxO3和掺杂改性组分C，其中A是Zn、Ni、Co中的任意一种，B是Ti、Mn、Sn中的任意一种；掺杂改性组分C是Fe、Zr、Bi、Ca、Mg、Ba的任意一种或多种；以氧化物含量计，A3-2xBxO3占催化剂总重量的80～98％，余量为掺杂改性组分，总质量百分含量之和为100％。
2.如权利要求1所述的烷烃化学链脱氢制烯烃催化剂，其特征在于：所述的复合氧化物A3-2xBxO3具有储放氧能力及脱氢性能。
3.如权利要求1所述的烷烃化学链脱氢制烯烃催化剂，其特征在于：所述复合氧化物A3-2xBxO3中x取值为0.1～1.45。
4.如权利要求1所述的烷烃化学链脱氢制烯烃催化剂，其特征在于：所述复合氧化物A3-2xBxO3中x取值为0.7～1.3。
5.如权利要求1-4中任一所述的烷烃化学链脱氢制烯烃催化剂的制备方法，其特征在于包括以下步骤：
将按比例称取的A、B、C前驱体溶于水中，搅拌均匀，采用溶胶凝胶法、共沉淀法或水热合成法，得到掺杂C组分的复合氧化物A3-2xBxO3；经成型工艺得到适用于固定床、移动床、流化床的烷烃脱氢催化剂。
6.如权利要求5所述的烷烃化学链脱氢制烯烃催化剂的制备方法，其特征在于:在催化剂的制备过程中，还可以加入常规助剂，使其达到催化剂的使用条件。
7.如权利要求1-5中任一项所述的烷烃化学链脱氢制烯烃催化剂的应用，其特征在于：该催化剂用于烷烃化学链脱氢，所述的烷烃包括2～4个碳原子的烷烃。
8.如权利要求7所述烷烃化学链脱氢制烯烃催化剂的应用，其特征在于：所述的烷烃为乙烷、丙烷、正丁烷或异丁烷。
9.如权利要求8所述烷烃化学链脱氢制烯烃催化剂的应用，其特征在于：所述的烷烃为丙烷。
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