CN114682245A - 一种Ma-Mb金属负载型催化剂的处理、活化和再生方法 - Google Patents
一种Ma-Mb金属负载型催化剂的处理、活化和再生方法 Download PDFInfo
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- CN114682245A CN114682245A CN202111600497.7A CN202111600497A CN114682245A CN 114682245 A CN114682245 A CN 114682245A CN 202111600497 A CN202111600497 A CN 202111600497A CN 114682245 A CN114682245 A CN 114682245A
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- Prior art keywords
- catalyst
- metal
- nitrogen
- carrier
- atom
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- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
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- ASFLJDMPHLYHLV-UHFFFAOYSA-N lanthanum zinc Chemical compound [Zn].[Zn].[Zn].[Zn].[Zn].[La] ASFLJDMPHLYHLV-UHFFFAOYSA-N 0.000 description 1
- CDOBVFVOKKCFEZ-UHFFFAOYSA-N lanthanum(3+) trinitrate heptahydrate Chemical compound O.O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CDOBVFVOKKCFEZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- CAMRHYBKQTWSCM-UHFFFAOYSA-N oxocyanamide Chemical compound O=NC#N CAMRHYBKQTWSCM-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003716 rejuvenation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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Abstract
本发明涉及一种Ma‑Mb金属负载型催化剂的处理、活化和再生方法,包括:在10℃‑700℃的条件下,用氨或含氮有机物处理Ma‑Mb金属负载型催化剂,其中Ma金属为活性金属,选自贵金属原子或过渡金属的一种或多种,所述载体为工业常用多孔催化剂,其中Ma金属以单原子位点状态分散在载体上。本发明方法处理后的Ma‑Mb金属负载型贵金属/锌催化剂,其催化低碳烷烃的直接脱氢转化率及选择性显著提升,本催化剂的制备方法工艺简单,再生后催化活性依旧保持,可大规模应用工业化生产。
Description
技术领域
本发明属于石油化工技术领域,具体涉及烷烃脱氢催化剂。
背景技术
低碳烯烃是石油化工的基础原料,广泛用于生产有机化工原料、树脂橡胶塑料、合成汽油等。过去,低碳烯烃以石油工业中催化裂解(FCC)装置的副产物为主要来源,近年来,全球范围内对低碳烯烃的需求与传统来源的产能差距日益增大。以中国为例,2015年国内消费的丙烯量为3040万吨,其中276万吨依赖进口。随着美国页岩气脱氢生产低碳烯烃技术的日益成熟,低碳烷烃脱氢生产成本显著降低,由于国内低碳烯烃缺口较大,价格上涨,使得低碳烷烃脱氢生产工艺得到广泛应用。
目前全球范围内应用最多的低碳烷烃脱氢工艺为UOP公司的Oleflex工艺和Lummus公司的Catofin工艺。Catofin工艺使用铬系催化剂,以氧化铝为载体,氧化铬为活性组分,催化脱氢使用固定床生产,其优点是催化剂成本低,转化率高,缺点是催化剂持续反应时间短,反应过程中催化剂表面快速积碳,需要频繁切换再生和催化两种工艺,并且铬的化合物毒性较大,容易造成环境污染。
Oleflex工艺使用铂系催化剂,以氧化铝为载体,贵金属铂为活性组分,锡和碱金属为助剂,催化脱氢使用移动床生产,其优点是催化剂使用再生周期长,环境污染小,缺点是催化剂成本较高。
近几年单原子催化剂受到广泛关注,该类催化剂上活性组分以单原子形式存在,具有最高的原子利用率,可以大幅降低活性组分用量,其中以CN修饰的贵金属单原子催化剂,由于CN材料中N对单原子金属的稳定及修饰作用展现出巨大的实际应用潜力(Adv.Mater.,2019,31,1901024;Nano Res.,2019,12,2584;Nat.Nanotech.,2020,15,390;CN109225306A)。但低碳烷烃脱氢反应往往伴随着严重的结焦问题,需要不断对结焦催化剂进行烧焦再生处理,而CN修饰贵金属单原子催化剂往往具有制备工艺复杂、催化剂结焦后难以实现工业烧焦再生等缺点,限制了其进一步工业推广。
发明内容
本发明保护一种处理Ma-Mb金属负载型催化剂的方法,包括:在10℃-700℃的条件下,用氨或含氮有机物处理Ma-Mb金属负载型催化剂。
其中Ma金属为活性金属,选自贵金属原子或过渡金属的一种或多种,其中贵金属原子选自Pt、Au、Ru、Rh、Pd、Ir或Ag的一种或多种混合,所述过渡金属选自La、Fe、Co、Mn、Cr、Ni或Cu。优选该活性金属是Pt、Ru、Pd、Ir、Cr、Ni、PtPd、IrPt、IrPd、或者IrPtPd。Mb金属选自Zn、Co或Al中的一种或多种组合,优选为Zn、Co或Zn-Co混合金属。
所述载体为工业常用催化剂载体,包括的氧化铝、二氧化硅-氧化铝、氧化锆、氧化铈、氧化钛、或分子筛或其任意两种或更多种的混合物;所述催化剂载体起担载的作用。载体的形态选自非成型的粉末状,或具有成型的结构。成型结构包括球形、条状、圆柱状、多空通道、蜂窝体等。本发明实施了γ-氧化铝载体、氧化钛、氧化硅、NaY分子筛载体。
所述Ma金属以单原子位点状态,或单原子位点和团簇的状态和/或纳米颗粒状态,负载在载体上。具体包括,以单原子位点状态负载,或以单原子位点与团簇状态负载,或包括单原子位点、团簇和纳米颗粒三种状态负载在载体上。所述Ma金属的含量基于催化剂重量为0.01-5wt%,优选0.05-2wt%;Mb的含量基于催化剂重量为0.1-20wt%;优选含量为0.1-10wt%,特别优选0.5-4wt%。
所述Ma-Mb金属负载型催化剂的获取,可根据设计的负载量,将Ma金属前驱体和Mb前驱体负载到载体上,形成催化剂前体;所述负载方法包括浸渍、旋蒸、吸附、离子交换、初湿含浸法、沉淀、喷雾干燥等本领域常用方法,本发明实施例使用浸渍法、旋蒸法进行负载。
Ma金属和Mb金属的负载可同时进行或依次进行;所述Ma金属前驱体为在溶剂中可溶性的Ma金属的无机盐、有机盐或金属配合物,优选为金属的硝酸盐、氯化盐、硫酸盐、乙酸盐、乙酰丙酮盐、配合物。Mb金属前驱体为在溶剂中可溶性Mb的有机盐或无机盐,优选为Mb金属的硝酸盐、氯化盐、硫酸盐、乙酸盐、草酸盐、乙酰丙酮盐等,如硝酸锌,硝酸钴,氯化锌、氯化钴、醋酸锌、醋酸钴等。所述溶剂是指水或醇,其中醇为甲醇或乙醇。
氨包括氨气或能释放氨的物质;其中释放氨的物质包括尿素、硝酸铵、六次甲基四胺或硝酸铵,可将所述物质与催化剂处于相同空间,通过加热或加入碱能释放NH3,让NH3与催化剂作用。
所述含氮有机物包括C1-6烷烃胺,C2-6烯烃胺,C6-20芳族胺,C4-20的环烷烃胺,C4-20的含氮杂环,C4-20含氮杂芳环,(RCO)xNR3-x,其中,R为H或C1-6烷基,X为1或2,所述胺为一元胺或多元胺,所述烷烃基、烯烃基、芳基、含氮杂环、含氮杂芳环可以进一步被氧、羰基、羧基、酯基、胺基取代,所述芳族为单环芳香族或多环稠合芳香族;含氮杂环为含有环氮原子的单环或稠和的非芳香环,环碳原子可被氧原子取代;含氮杂芳环为含有环氮原子的单环或稠和的杂芳香环,环碳原子可被氧原子取代。所述含氮有机物优选C1-6烷基胺,C1-6烷基二胺,C6-20芳族胺,二甲基甲酰胺;本发明具体实施的含氮有机物为乙二胺,三乙胺,丁胺,苯胺和二甲基甲酰胺;优选乙二胺。
本发明所述氨或含氮有机物处理是指使用氨气或气态含氮有机物处理催化剂,可用惰性气体稀释处理气体实现低于100%的体积浓度占比;即所述气态化合物为1-100%的体积浓度占比。使用惰性气体稀释便于更精确的控制处理过程中碳和/或氮的加入量。本发明所述惰性气体包括但不限于氮气、氦气、氩气、氢气等对催化剂或烷烃脱氢反应惰性的气体。本发明具体实施了NH3气、氮气稀释的NH3、氮气稀释的含氮有机化合物气体,处理的温度在10℃至700℃范围之内,优选300-600℃,通气处理时间为1-400min,优选为5-150min。
对于大多数烷烃脱氢催化剂,都在力图避免催化剂表面积碳,以免导致催化剂失活。本发明意外发现,通过含氮有机物处理催化剂,使得催化剂表面覆盖CN层,出人意料的提升催化剂的转化率和选择性。此外,发明人发现仅使用NH3也能提升催化剂的转化率和选择性。
进一步,本发明保护一种Ma-Mb金属负载型催化剂的活化方法,包括:在10℃-700℃的条件下,用氨或含氮有机物处理处理催化剂,所述贵金属、载体、含氮有机物的定义与前述定义相同。
进一步,本发明保护一种Ma-Mb金属负载型催化剂的再生方法,包括:
步骤A、去除导致Ma-Mb金属负载型催化剂中毒或失活的物质,再生催化剂;
步骤B、在10℃-700℃的条件下,用氨或含氮有机物处理催化剂,得到活化的催化剂。
其中,步骤A中,可以通过常规的方法,去除失活物质,所述失活物质包括碳、硫等物质,去除方法包括,使用O2、空气氧化去除,或使用H2、CO2、水汽与失活物质反应去除该物质,本发明实施了空气氧化去除。
其中,Ma金属为活性金属,选自贵金属原子或过渡金属的一种或多种组合,其中贵金属原子选自Pt、Au、Ru、Rh、Pd、Ir或Ag的一种或多种混合,所述过渡金属选自La、Fe、Co、Mn、Cr、Ni或Cu。优选该活性金属是Pt、Ru、Pd、Ir、Cr、Ni、PtPd、IrPt、IrPd、或者IrPtPd。Mb金属选自Zn、Co或Al中的一种或多种组合,优选为Zn、Co或Zn-Co混合金属。
所述载体为本领域常用催化剂载体,起到担载作用的催化剂载体都能使用。进一步,载体选自氧化铝、二氧化硅-氧化铝、氧化锆、氧化铈、氧化钛、或分子筛或其任意两种或更多种的混合物。本发明实施了γ-氧化铝载体、氧化钛、二氧化硅、NaY分子筛。
所述Ma金属以单原子位点状态,或单原子位点和团簇的状态和/或纳米颗粒状态,负载在载体上。具体包括,以单原子位点状态负载,或以单原子位点状态与团簇状态混合负载,或包括单原子、团簇和纳米颗粒三种状态混合负载在载体上。所述Ma金属的含量基于催化剂重量为0.01-5wt%,优选0.05-2wt%;Mb的含量基于催化剂重量为0.1-20wt%;优选含量为0.1-10wt%,特别优选0.5-4wt%。
步骤B中,所述氨包括氨气或能释放氨的物质;其中释放氨的物质包括尿素、硝酸铵、六次甲基四胺或硝酸铵,可将所述物质与催化剂处于相同空间,通过加热或加入碱能释放NH3,让NH3与催化剂作用。
所述含氮有机物包括C1-6烷烃胺,C2-6烯烃胺,C6-20芳族胺,C4-20的环烷烃胺,C4-20的含氮杂环,C4-20含氮杂芳环,(RCO)xNR3-x,其中,R为H或C1-6烷基,X为1或2,所述胺为一元胺或多元胺,所述烷烃基、烯烃基、芳基、含氮杂环、含氮杂芳环可以进一步被氧、羰基、羧基、酯基、胺基取代,所述芳族为单环芳香族或多环稠合芳香族;含氮杂环为含有环氮原子的单环或稠和的非芳香环,环碳原子可被氧原子取代;含氮杂芳环为含有环氮原子的单环或稠和的杂芳香环,环碳原子可被氧原子取代。所述含氮有机物优选C1-6烷基胺,C1-6烷基二胺,C6-20芳族胺,二甲基甲酰胺;本发明具体实施的含氮有机物为乙二胺,三乙胺,丁胺,苯胺和二甲基甲酰胺;优选乙二胺。
步骤B中,所述氨或含氮有机物处理是指使用氨气或气态含氮有机物处理催化剂,可用惰性气体稀释处理气体实现低于100%的体积浓度占比;即所述气态化合物为1-100%的体积浓度占比。使用惰性气体稀释便于更精确的控制处理过程中碳和/或氮的加入量。本发明所述惰性气体包括但不限于氮气、氦气、氩气、氢气等对催化剂或烷烃脱氢反应惰性的气体。本发明具体实施了NH3气、氮气稀释的NH3、氮气稀释的含氮有机化合物气体,处理的温度在10℃至700℃范围之内,优选300-600℃,通气处理时间为1-400min,优选为5-150min。
本发明的另外一个方面是,保护一种低级烷烃脱氢制低级烯烃的方法,包括,使用加碳氮处理后的催化剂,催化低级烷烃脱氢得到低级烯烃。所述低级烷烃是指C2-6的烷烃,包括乙烷、丙烷、丁烷、异丁烷,或两种或多种低级烷烃的混合物,本发明实施了丙烷脱氢制丙烯反应。
定义与解释
本发明中所述以单原子位点状态分散、单原子状态、单原子分布、单原子形态或单原子级别的分散状态,是指活性金属元素的呈现金属原子(离子)间彼此独立分离的孤立状态,活性金属原子之间彼此不形成直接连接的金属–金属键,以原子级分散或以单原子位点分散的状态。以单原子位点状态分散的金属可能以原子状态存在,也可能以离子状态存在,更多可能是处于原子和离子状态之间。金属纳米颗粒中,同一纳米颗粒中的金属原子之间是彼此键连的,不属于本发明定义的单原子状态或单原子分散状态;对于金属与其他元素(如O、S乃至其他金属)形成的化合物或混合物纳米颗粒,尽管金属之间都被其他元素分隔,而且特别是这些化合物或混合物纳米颗粒往往很容易转化为金属态纳米颗粒(如氧化物纳米颗粒经过还原即发生转变),同样不属于本发明定义的单原子位点状态或单原子分离状态。本发明保护的单原子位点状态的金属理论上是彼此之间完全独立。但不同批次制备操作条件控制的随机偏差,所得产品中不排除存在少量团聚状态金属物种,例如包含少量原子或离子形成的团簇;也不排除部分金属呈现纳米颗粒的状态。换句话说,本发明的催化剂中可能活性金属以单原子位点分散态存在,同时,部分存在含有金属原子聚集的团簇态,和/或部分金属呈现纳米颗粒状态。本申请保护的单原子状态要求催化剂中贵金属单原子、贵金属团簇及贵金属纳米颗粒等不同存在形式中单原子贵金属有一定的占比,例如高于10%,优选高于20%,特别优选高于50%。但限于当前的技术手段,仅能通过相对粗略的统计手段,可通过高分辨球差电镜对催化剂测试样品中随机大量选取不同局部区域进行分析表征并随机选取各种形式的贵金属存在状态进行统计分析,或通过能够表征样品整体信息的X射线吸收精细结构谱(EXAFS)分析催化剂样品,获得金属和其它原子键合信号与金属-金属键合信号比例,确定大致的单原子状态的比例。需要指出的是,实质上只要产品中使用了本发明的技术获取了哪怕仅具备部分的单原子状态的催化剂产品,该产品也显示出性能的提升。因此,只要产品依据本发明的方法,制备得到了具备烷烃脱氢活性的催化剂,理应属于本申请保护的范围之内。
烷烃胺表示该烷烃带有1个或多个胺基官能团,上述烷烃可被一个或多个C1-6烷烃基、C4-20的环烷烃或C6-20芳香族基团替代,或上述烷烃中C–C键可以被不饱和的烯烃或炔烃替代,形成不饱和碳链;前述C6-20芳香环胺表示具有6-20个碳原子的芳香族环胺基化合物,C4-20含氮杂芳环表示具有芳香的2n+4的特征,同时部分环碳原子被杂原子替换,所述杂原子为O或N原子。C4-20含氮杂环表示含有4-20个环碳原子的含氮杂环;C4-20的环烷烃胺表示含有4-20个环碳原子的环烷烃,该环烷烃含有一个或多个胺基官能团。上述的环烷烃、含氮杂环、芳香环为一元环或稠合多元环,所述环可继续被C1-6烷烃取代。
所述金属包括贵金属、过渡金属的含量是以金属元素计量,即仅计算金属的质量百分比。
所述能释放氨气的物质是指能释放NH3的无机物或有机物,比如尿素、氨水、六次甲基四胺,硝酸铵。
所述室温是指不需要额外加热,但由于室温根据地域、季节或室内环境的差别发生变化,因此,所述室温通常指10℃以上的温度。
所述活化,也被称为催化剂预处理,通常是催化剂装入反应设备后进行。经过活化后的催化剂表现出更高的转化率和/或选择性。
所述再生,也被称为重生,通常是指将失活后的催化剂重新恢复催化活性的过程。
配合物也被称为络合物,包括贵金属或过渡金属与配位体形成的络合物,常见的配位体包括卤素(氟、氯、溴、碘)、硝基、亚硝基、氰根、氨、水分子或有机基团,常见为络合物为氯络合物,氨络合物,氰络合物等,包括氯铂酸、氯铂酸盐、氯铂酸水合物。可参见《贵金属化合物及配合物合成手册(精)》(余建民,2009年,化学工业出版社)。
有益效果:
1、通过本发明方法处理后的Ma-Mb金属负载型催化剂,其催化低碳烷烃的直接脱氢转化率及选择性显著提升,实现催化剂的预活化。
2、本催化剂制备方法工艺简单,能高效制备,可大规模工业化生产。
3、本制备方法得到的催化剂稳定,经过多次再生,活性依然保持。为催化剂的工业化生产和应用提供坚实的基础。
附图说明
图1为新制备催化剂的球差电镜照片,其中a图显示单原子位点状态金属(部分用点虚线圈出);b图显示催化剂中也存在金属的团簇或纳米颗粒。
图2为反复再生50次的催化剂的球差电镜照片,其中a图视野中出现单原子位点状态的金属(部分用点虚线圈出);b图显示催化剂中也存在金属的团簇和纳米颗粒。
具体实施方式
实施例中使用的术语与解释:
金属前驱体的浓度:是以金属元素的质量计算,如0.02g/g浓度的Pd的水溶液中,表示每克溶液中,Pd元素的含量为0.02克
微反装置:固定床微型反应器或微型反应装置
微反尾气:在微型反应器或微型反应装置中反应后产生的尾气
min:分钟
wt%:质量百分比
TEM:透射电子显微镜(Transmission Electron Microscope)
HR-TEM:高分辨率的透射电镜(High Resolution Transmission ElectronMicroscope)
AC-STEM:球差校正透射电镜(Spherical Aberration-Corrected ScanningTransmission Electron Microscopy)
下面通过丙烷脱氢的实施对本发明的技术给予进一步说明。
制备实施例1:活性金属/锌负载型催化剂的制备
1.1 Ir(0.1wt%)Zn(3wt%)/Al2O3
称取IrCl3·3H2O、NaCl各0.5g,加入19g水,在80℃下完全溶解。取7.4g以上溶液,加入16.4g Zn(NO3)2·6H2O,溶解后定容至小球饱和浸渍体积。将以上浸渍液等体积浸渍于96.9g氧化铝小球上,120℃干燥过夜。获得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),标记为Ir(0.1wt%)Zn(3wt%)/Al2O3。
Ir(0.3wt%)Zn(3wt%)/Al2O3
50g氧化铝小球,8.25g Zn(NO3)2·6H2O溶于水定容至小球饱和浸渍体积,等体积浸渍,室温陈化6h后120℃干燥一夜,600℃煅烧4h,取10g样品。称取IrCl3·3H2O、NaCl各0.5g,加入19g水,在80℃下完全溶解。2.2g前述IrCl3溶液定容至饱和浸渍体积,等体积浸渍,120℃干燥一夜。400℃煅烧1h。获得铱锌催化剂(Ir 0.3wt%;Zn 3wt%),标记为Ir(0.3wt%)Zn(3wt%)/Al2O3。
1.2Pt(0.3wt%)Zn(1wt%)/Al2O3
称取5g Al2O3小球,称取含0.015g Pt的氯铂酸和含0.05gZn的硝酸锌溶解于水中,定容至小球饱和浸渍体积2.21ml,加入上述Al2O3小球中浸渍,80℃干燥8h后,600℃煅烧4h。获得铂锌催化剂(Pt 0.3wt%;Zn 1wt%),标记为Pt(0.3wt%)Zn(1wt%)/Al2O3。
1.3Cr-Zn/Al2O3(200713a)
制备负载量分别为0.5%和1.5%的铬和锌负载Al2O3催化剂100g,取用3.85g九水合硝酸铬和6.82g六水合硝酸锌并用乙醇溶解、稀释至83.3g,随后加入98g Al2O3,在40℃下进行旋蒸处理,待乙醇完全蒸发、铬和锌物种充分负载在Al2O3表面,即可制得铬锌负载Al2O3催化剂,标记为Cr(0.5wt%)Zn(1.5wt%)/Al2O3。
1.4Mn-Zn/Al2O3(d200829a)
制备负载量分别为0.5%和1.5%的锰和锌负载Al2O3催化剂100g,取用1.80g四水合硝酸锰和6.82g六水合硝酸锌并用乙醇溶解、稀释至91.9g,随后加入98g Al2O3,在40℃下进行旋蒸处理,待乙醇完全蒸发、锰和锌物种充分负载在Al2O3表面,即可制得锰锌负载Al2O3催化剂,标记为Mn(0.5wt%)Zn(1.5wt%)/Al2O3。
1.5Fe-Zn/Al2O3(200713b)
制备负载量分别为0.5%和1.5%的铁和锌负载Al2O3催化剂100g,取用3.62g九水合硝酸铁和6.82g六水合硝酸锌并用乙醇溶解、稀释至83.3g,随后加入98g Al2O3,在40℃下进行旋蒸处理,待乙醇完全蒸发、铁和锌物种充分负载在Al2O3表面,即可制得铁锌负载Al2O3催化剂,标记为Fe(0.5wt%)Zn(1.5wt%)/Al2O3。
1.6Co-Zn/Al2O3(200918a)
制备负载量分别为0.5%和1.5%的钴和锌负载Al2O3催化剂100g,取用2.47g六水合硝酸钴和6.82g六水合硝酸锌并用乙醇溶解、稀释至83.3g,随后加入98g Al2O3,在40℃下进行旋蒸处理,待乙醇完全蒸发、钴和锌物种充分负载在Al2O3表面,即可制得钴锌负载Al2O3催化剂,标记为Co(0.5wt%)Zn(1.5wt%)/Al2O3。
1.7Ni-Zn/Al2O3(200918b)
制备负载量分别为0.5%和1.5%的镍和锌负载Al2O3催化剂100g,取用2.48g六水合硝酸镍和6.82g六水合硝酸锌并用乙醇溶解、稀释至83.3g,随后加入98g Al2O3,在40℃下进行旋蒸处理,待乙醇完全蒸发、镍和锌物种充分负载在Al2O3表面,即可制得镍锌负载Al2O3催化剂,标记为Ni(0.5wt%)Zn(1.5wt%)/Al2O3。
1.8Cu-Zn/Al2O3(d200730)
制备负载量分别为0.5%和1.5%的铜和锌负载Al2O3催化剂100g,取用1.90g三水硝酸铜和6.82g六水合硝酸锌并用乙醇溶解、稀释至92.0g,随后加入98g Al2O3,在40℃下进行旋蒸处理,待乙醇完全蒸发、铜和锌物种充分负载在Al2O3表面,即可制得铜锌负载Al2O3催化剂,标记为Cu(0.5wt%)Zn(1.5wt%)/Al2O3。
1.9La-Zn/Al2O3(d200829b)
制备负载量分别为0.5%和1.5%的镧和锌负载Al2O3催化剂100g,取用1.34g七水硝酸镧和6.82g六水合硝酸锌并用乙醇溶解、稀释至91.4g,随后加入98g Al2O3,在40℃下进行旋蒸处理,待乙醇完全蒸发、镧和锌物种充分负载在Al2O3表面,即可制得镧锌负载Al2O3催化剂,标记为La(0.5wt%)Zn(1.5wt%)/Al2O3。
1.10Ir(0.1wt%)Co(0.5wt%)Zn(1wt%)/Al2O3(200608b)
预先用0.37g三水合氯化铱、0.36g氯化钠用水加热溶解并稀释至40.0g,配置铱浓度为0.005g/g的水溶液,取用1.0g,再加入0.11g六水合硝酸钴和0.23g六水硝酸锌,用超纯水溶解并稀释至2.2g,随后加入4.9g小球状Al2O3进行等体积浸渍,随后120℃下干燥过夜。即可制得铱钴锌负载Al2O3催化剂,标记为Ir(0.1wt%)Co(0.5wt%)Zn(1wt%)/Al2O3。
1.11Ir(0.1wt%)Co(0.75wt%)Zn(0.75wt%)/Al2O3(200608c)
预先用0.37g三水合氯化铱、0.36g氯化钠用水加热溶解并稀释至40.0g,配置铱浓度为0.005g/g的水溶液,取用1.0g,再加入0.17g六水合硝酸钴和0.17g六水硝酸锌,用超纯水溶解并稀释至2.2g,随后加入4.9g小球状Al2O3进行等体积浸渍,随后120℃下干燥过夜。即可制得铱钴锌负载Al2O3催化剂,标记为Ir(0.1wt%)Co(0.75wt%)Zn(0.75wt%)/Al2O3。
1.12Ir(0.1wt%)Co(1.5wt%)/Al2O3(200611d)
预先用0.37g三水合氯化铱、0.36g氯化钠用水加热溶解并稀释至40.0g,配置铱浓度为0.005g/g的水溶液,取用1.0g,再加入0.33g六水合硝酸钴,用超纯水溶解并稀释至2.2g,随后加入4.9g小球状Al2O3进行等体积浸渍,随后120℃下干燥过夜。即可制得铱钴锌负载Al2O3催化剂,标记为Ir(0.1wt%)Co(1.5wt%)/Al2O3。
1.13制备得到催化剂,标记为Ir(0.1wt%)Zn(1.5wt%)Al(1.24wt%)/Al2O3
1.14制备得到催化剂,标记为Ir(0.15wt%)Zn(1.5wt%)Al(1.24wt%)/Al2O3
1.15Ir(0.1wt%)Zn(1wt%)/NaY分子筛
称取5g NaY分子筛小球,于含IrCl3、Zn(NO3)2分别为0.26%和7.8%的水溶液中过体积浸渍30min,固液分离后120℃干燥过夜。获得铱锌催化剂(Ir 0.15wt%;Zn 1.5wt%)。
1.16Ir(0.3wt%)Zn(3wt%)/SiO2
称取IrCl3·3H2O、NaCl各0.5g,加入19g水,在80℃下完全溶解。取1.1g以上溶液,加入0.8g Zn(NO3)2·6H2O,溶解后定容至小球饱和浸渍体积。将以上浸渍液等体积浸渍于5g二氧化硅小球上,120℃干燥过夜。获得铱锌催化剂(Ir 0.3wt%;Zn 3wt%)。
制备实施例2:催化剂再生预处理方法
通过本实验将催化剂进行再生,将待处理催化剂在400-450℃下,49.8mL/min的空气烧积炭3小时,形成再生催化剂。
应用测试实施例3:烷烃脱氢实验方法
以丙烷脱氢制备丙烯为例
采用固定床连续流动反应装置评价催化剂的催化性能,将1.0g催化剂装载于10mm内径直型石英反应管内。
处理或活化催化剂。
以管式电阻炉控制反应温度600℃,以质量流量计控制反应气流速,反应前后使用氮气或其它惰性气体进行吹扫。
使用岛津的气相色谱仪装配HP-PLOT Al2O3 S毛细管色谱柱对反应产物进行分析。
实施例1
称取1g制备例1.1所得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),在100%氨气气氛下500℃处理30min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例2-11
参照实施例1的实验操作,使用N2作为稀释气体,调节氨气的浓度,处理温度,处理时长,其余操作与实施例1相同。具体为:
实施例2中,氨气含量为80%(N2 2.6mL/min,NH3 10.5mL/min),处理温度500℃,处理时长30min。
实施例3中,氨气含量为50%(N2 6.55mL/min,NH3 6.55mL/min),处理温度500℃,处理时长30min。
实施例4中,氨气含量为20%(N2 10.5mL/min,NH3 2.6mL/min),处理温度500℃,处理时长30min。
实施例5中,氨气含量为3%(N2 12.7mL/min,NH3 0.4mL/min),处理温度500℃,处理时长30min。
实施例6中,氨气含量为3%(N2 12.7mL/min,NH3 0.4mL/min),处理温度500℃,处理时长15min。
实施例7中,氨气含量为3%(N2 12.7mL/min,NH3 0.4mL/min),处理温度500℃,处理时长30min。
实施例8中,氨气含量为3%(N2 12.7mL/min,NH3 0.4mL/min),处理温度500℃,处理时长45min。
实施例9中,氨气含量为3%(N2 12.7mL/min,NH3 0.4mL/min),处理温度500℃,处理时长75min。
实施例10中,氨气含量为3%(N2 12.7mL/min,NH3 0.4mL/min),处理温度500℃,处理时长120min。
实施例11中,氨气含量为3%(N2 12.7mL/min,NH3 0.4mL/min),处理温度500℃,处理时长150min。
实施例12
称取1g制备例1.1所得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),在2%乙二胺/氮气气氛下500℃处理15min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例13
称取1g制备例1.1所得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),在2%乙二胺/氮气气氛下500℃处理60min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例14
称取1g制备例1.1所得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),在4%乙二胺/氮气气氛下室温(10℃)处理30min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例15
称取1g制备例1.1所得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),在4%乙二胺/氮气气氛下700℃处理30min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例16
称取1g制备例1.1所得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),在1%乙二胺/氮气气氛下500℃处理30min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例17
称取1g制备例1.1所得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),在4%正丁胺/氮气气氛下500℃处理30min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例18
称取1g制备例1.1所得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),在4%三乙胺/氮气气氛下500℃处理30min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例19
称取1g制备例1.1所得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),在4%苯胺/氮气气氛下500℃处理30min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例20
称取1g制备例1.1所得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),在4%DMF/氮气气氛下500℃处理30min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例21
称取1g制备例1.2所得铂锌催化剂(Pt 0.3wt%;Zn 1wt%),在4%乙二胺/氮气气氛下500℃处理30min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例22-35
使用实施例1类似方法,分别称取制备例一制备的1.3-1.16金属负载催化剂,在4%乙二胺/氮气气氛下500℃处理30min。在600℃下,通入丙烷纯气体(体积空速:1000h-1)反应,测试丙烷直接催化脱氢反应的转化率和选择性。
实施例36再生实施例
称取1g制备例1.1所得铱锌催化剂(Ir 0.1wt%;Zn 3wt%),在4%乙二胺/氮气气氛下500℃处理30min。在600℃下,0.25氢烃比(氢气与丙烷的比)条件下丙烷直接催化脱氢反应(丙烷体积空速:1000h-1),测得丙烷转化率为40%,丙烯选择性为92%。连续测试6h后,丙烷转化率降至33%,丙烯选择性为93%。
将此催化剂于400℃空气气氛下焙烧3h,进行烧积碳操作,得到再生样品在4%乙二胺/氮气气氛下500℃处理30min。
在600℃0.25氢烃比条件下测试丙烷直接催化脱氢反应(丙烷体积空速:1000h-1),测得丙烷转化率为39%,丙烯选择性为93%。
对比例1
称取1g铱锌催化剂(Ir 0.1wt%;Zn 3wt%,Al2O3为载体),不做任何处理后,在600℃下,通入丙烷纯气进行反应,测试丙烷直接催化脱氢反应的转化率和选择性(体积空速:1000h-1)。
应用测试及结果:
1、实施例1-20以及对比例1的处理条件和性能比较
表1实施例1-20与对比例1的测试结果
*EX1表示实施例1,以此类推。
从实施例1-20与对比例1的测试结果看,经过本发明的催化剂处理方式,无论是用NH3还是使用含氮有机物处理,处理后的催化剂转化率和选择性明显提升,充分显示用NH3和含氮有机物处理的效果。
2、对于实施例21-35,活性测试条件及测试结果如表2:
表2实验21-35的实验参数及测试结果
从表2测试结果看,使用Zn、Co或Al作为活化金属,得到的催化剂具有较好的催化烷烃脱氢的活性,无论活性金属为贵金属还是过渡金属。贵金属的催化活性高于过渡金属。
3、催化剂再生
实施例36证明本发明的催化剂的再生方法简单高效,经过再生后的催化剂,催化性能并未出现明显下降。将新制备催化剂与再生后的催化剂,在使用相同的测试条件下(0.25氢烃比),测试得到的催化剂转化率和选择性相当。
事实上,发明人将催化剂进行了50次的再生,形成的催化剂依然保持较高的转化率和选择性。
需要指出,实施例36使用的测试条件与其它实施例略有不同,在丙烷气体中掺入一定比例的氢气,以模拟工业生产的实际工况。
4、产品结构表征:
发明人对新制备的未经过碳氮处理后的催化剂进行结构表征,其中催化剂的组成为Ir(0.3%)Zn(2wt%)/Al2O3。表征结果参见图1。其中,图1为新制备催化剂的球差电镜照片,其中a图显示单原子位点状态金属(部分用点虚线圈出);b图催化剂中也存在金属的团簇或纳米颗粒。从图可以看到催化剂中存在大量以单原子位点分散的金属,也存在以团簇甚至纳米颗粒存在的金属。但本发明的提升催化剂的转化率和选择性的方法都有效。
图2为反复再生50次的催化剂经烧积碳处理后的球差电镜照片,催化剂组分同图1,其中a图视野中出现单原子位点状态的金属(部分用点虚线圈出);b图催化剂中也存在金属的团簇和纳米颗粒。也同样表明反复再生后的催化剂,活性金属同样以单原子位点、团簇和纳米颗粒三种状态存在,本发明的方法也同样有效。
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (10)
1.一种Ma-Mb金属负载型催化剂的处理方法,包括:在10℃-700℃的条件下,用氨或含氮有机物处理Ma-Mb金属负载型催化剂。其中Ma金属为活性金属,选自贵金属原子或过渡金属的一种或多种,其中贵金属原子选自Pt、Au、Ru、Rh、Pd、Ir或Ag的一种或多种混合,所述过渡金属选自La、Fe、Co、Mn、Cr、Ni或Cu;优选该活性金属是Pt、Ru、Pd、Ir、Cr、Ni、PtPd、IrPt、IrPd、或者IrPtPd;Mb金属选自Zn、Co或Al中的一种或多种组合,优选为Zn、Co或Zn-Co混合金属;
所述载体为工业常用载体,包括氧化铝、二氧化硅-氧化铝、氧化锆、氧化铈、氧化钛、或分子筛或其任意两种或更多种的混合物;优选使用γ-氧化铝载体、氧化钛、氧化硅、NaY分子筛等载体;载体的形态选自非成型的粉末状,或具有成型的结构;成型结构包括球形、条状、圆柱状、多空通道、蜂窝体等。
2.根据权利要求1所述的方法,所述Ma金属以单原子位点状态,或单原子位点和团簇的状态和/或纳米颗粒状态,负载在载体上;优选以单原子位点状态负载,或以单原子位点与团簇状态负载,或包括单原子位点、团簇和纳米颗粒三种状态负载在载体上;所述Ma金属的含量基于催化剂重量为0.01-5wt%,优选0.05-2wt%;Mb的含量基于催化剂重量为0.1-20wt%;优选含量为0.1-10wt%,特别优选0.5-4wt%。
3.根据权利要求1或2所述方法,其中,所述Ma-Mb金属负载型催化剂,通过将Ma金属前驱体和Mb前驱体负载到载体上制备得到;Ma金属和Mb金属的负载可同时进行或依次进行。
4.根据权利要求1-3任一的方法,其中,氨包括氨气或能释放氨的物质;所述含氮有机物为C1-6烷烃胺,C2-6烯烃胺,C6-20芳族胺,C4-20的环烷烃胺,C4-20的含氮杂环,C4-20含氮杂芳环,(RCO)xNR3-x,其中,R为H或C1-6烷基,X为1或2,所述胺为一元胺或多元胺,所述烷烃基、烯烃基、芳基、含氮杂环、含氮杂芳环可以进一步被氧、羰基、羧基、酯基、胺基取代,所述芳族为单环芳香族或多环稠合芳香族;含氮杂环为含有环氮原子的单环或稠和的非芳香环,环碳原子可被氧原子取代;含氮杂芳环为含有环氮原子的单环或稠和的杂芳香环,环碳原子可被氧原子取代;所述含氮有机物优选C1-6烷基胺,C1-6烷基二胺,C6-20芳族胺,二甲基甲酰胺;进一步优选乙二胺,三乙胺,丁胺,苯胺或二甲基甲酰胺;特别优选乙二胺。
5.根据权利要求1-4任一的方法,使用氨气或气态含氮有机物处理处理催化剂;优选使用NH3气、氮气稀释的NH3、氮气稀释的含氮有机化合物气体处理,处理的温度在10℃至700℃范围之内,优选300-600℃范围内,通气处理时间为1-400min,优选5-150min。
6.一种Ma-Mb金属负载型催化剂的活化方法,包括:在10℃-700℃的条件下,用氨或含氮有机物处理处理催化剂,所述贵金属、载体、含氮有机物的定义与权利要求1-5定义相同。
7.一种Ma-Mb金属负载型催化剂的再生方法,包括:
步骤A、去除导致Ma-Mb金属负载型催化剂中毒或失活的物质,再生催化剂;
步骤B、在10℃-700℃的条件下,用氨或含氮有机物处理催化剂,得到活化的催化剂;
其中,步骤A中,可以通过常规的方法,去除失活物质,所述失活物质包括碳、硫等物质,去除方法包括,使用O2、空气氧化去除,或使用H2还原去除;
其中,Ma金属为活性金属,选自贵金属原子或过渡金属的一种或多种组合,其中贵金属原子选自Pt、Au、Ru、Rh、Pd、Ir或Ag的一种或多种混合,所述过渡金属选自La、Fe、Co、Mn、Cr、Ni或Cu;优选该活性金属是Pt、Ru、Pd、Ir、Cr、Ni、PtPd、IrPt、IrPd、或者IrPtPd;Mb金属选自Zn、Co或Al中的一种或多种组合,优选为Zn、Co或Zn-Co混合金属;
所述载体为本领域常用催化剂载体,起到担载作用的催化剂载体都能使用;进一步,载体选自氧化铝、二氧化硅-氧化铝、氧化锆、氧化铈、氧化钛、或分子筛或其任意两种或更多种的混合物;优选为γ-氧化铝载体、氧化钛、二氧化硅、NaY分子筛;
所述Ma金属以单原子位点状态,或单原子位点和团簇的状态和/或纳米颗粒状态,负载在载体上,优选,Ma金属以单原子状态负载,或以单原子状态与团簇状态混合负载,或包括单原子、团簇和纳米颗粒三种状态混合负载在载体上;所述Ma金属的含量基于催化剂重量为0.01-5wt%,优选0.05-2wt%;Mb的含量为基于催化剂重量为0.1-20wt%;优选含量为0.1-10wt%,特别优选0.5-4wt%;
所述含氮有机物为C1-6烷烃胺,C2-6烯烃胺,C6-20芳族胺,C4-20的环烷烃胺,C4-20的含氮杂环,C4-20含氮杂芳环,(RCO)xNR3-x,其中,R为H或C1-6烷基,X为1或2,所述胺为一元胺或多元胺,所述烷烃基、烯烃基、芳基、含氮杂环、含氮杂芳环可以进一步被氧、羰基、羧基、酯基、胺基取代,所述芳族为单环芳香族或多环稠合芳香族;含氮杂环为含有环氮原子的单环或稠和的非芳香环,环碳原子可被氧原子取代;含氮杂芳环为含有环氮原子的单环或稠和的杂芳香环,环碳原子可被氧原子取代;所述含氮有机物优选C1-6烷基胺,C1-6烷基二胺,C6-20芳族胺,二甲基甲酰胺。
8.根据权利要求7所述的再生方法,其中,Ma金属为Pt、Ru、Ir或Au的一种或多种混合:Mb为Zn;载体优选氧化铝;含氮有机物为乙二胺,三乙胺,丁胺,苯胺或二甲基甲酰胺。
9.一种催化剂在C2-6烷烃脱氢制备C2-6烯烃中的应用,所述催化剂是依据权利要求1-4的方法处理、权利要求5所述方法活化,或依据权利要求7-8所述方法再生的催化剂。
10.一种低级烷烃脱氢制低级烯烃的方法,包括,使用根据权利要求1-8任一方法制备得到的催化剂,催化C2-6烷烃脱氢得到C2-6烯烃。
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