CN115282968B - 一种金属掺杂自组装催化剂 - Google Patents
一种金属掺杂自组装催化剂 Download PDFInfo
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 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
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Abstract
本发明涉及一种过渡金属掺杂氧化钴催化剂及其制备方法，催化剂可促进长链α‑烯烃与合成气反应制高碳醇；通过引入尿素和过渡金属的调配，获得了具有合适活性中心浓度的催化剂体系，显著提高了高碳数烯烃氢甲酰化反应的选择性，提高了醇收率。本发明方案具有反应时间短、过程可控，活性金属不易流失等优势，便于规模应用和推广。
Description
技术领域
本发明属于催化剂制备领域，具体涉及催化长链α-烯烃与合成气发生氢甲酰化反应制高碳醇的催化剂及其制备方法，尤其涉及壬醇的制备。
背景技术
高碳醇是重要的精细化工原料，例如C6～C10醇被称为增塑剂醇，用于提高塑料制品的塑性、耐温性和耐候性。氢甲酰化反应过程是制备高碳醇的方法之一，即在一定的温度和压力条件，使用金属络合物催化剂，烯烃与合成气反应转化为碳链增长的羰基化合物的反应。如丁醇/辛醇的合成，以丙烯为原料，首先通过氢甲酰化反应得到丁醛，进一步通过加氢反应得到丁醇；丁醛经二聚、加氢得辛醇产物 (四川化工, 2009, 12(3): 20-24)。异壬醇生产主要通过传统工艺、ExxonMobil 工艺、Oxeno工艺和Johnson Matthey工艺 (石油化工技术与经济, 2018, 34(5): 59-62)。一般以C8支链烯烃、丁烯二聚物为原料，采用Co/Rh均相催化剂；其中ExxonMobil化学公司的Co催化技术处主导地位，反应分两步进行：(1) 高压条件下，在羰基化反应器中采用四羰基钴盐催化辛烯与合成气进行氢甲酰化反应生成C9-醛；(2) C9-醛与催化剂分离后转移至加氢反应器进一步加氢生成壬醇。
现有氢甲酰化制醇反应工艺过程，需经过两步反应，反应压力高；所用的均相催化剂存在含有毒的磷配体，活性金属容易流失、分离困难等问题。
氧化钴被报道能催化1-辛烯经氢甲酰化-加氢反应过程生成壬醇(Catal. Today,2018, 309: 147-152)，但是生成壬醇所需要的反应时间长，催化剂性能稳定性有待进一步验证。类似研究也显示氧化钴的催化性能存在反应时间长、醇产物选择性低的问题(Fuel,2020, 269: 117397)。即使使用贵金属、碱金属调变氧化钴，仍然需要长的反应时间才能获得目标产物 (Appl. Catal. A-Gen, 2020, 602: 117735)
基于现有催化剂性能不足的现状，本发明方案通过掺杂过渡金属调控氧化钴，较好的实现了长链α-烯烃与合成气经氢甲酰化反应制醇，具有反应时间短、醇产物选择性高、活性金属不易流失的优势。
发明内容
本发明提供一种简单、快速合成高碳醇的催化剂。本发明催化剂制备步骤简单，重复性好，易于工业应用。
本发明催化剂是一种具有特定晶面和电子效应、可催化C6～C12长链α-烯烃与合成气氢甲酰化反应一步制醇催化剂，为铁、铜、镍掺杂氧化钴催化剂。
本发明使用的铁、铜、镍掺杂氧化钴催化剂，应用于合成高碳醇时，催化剂在制醇反应过程中被还原为钴催化活性中心，无需预还原程序。铜促进了氧化钴的还原，提高了催化活性；铁促进提高了醇产物选择性。掺杂过渡金属协同提高催化活性。
本发明催化剂产品技术方案及有益效果：掺杂金属与氧化钴间存在电子转移效应，促进了氧化钴的还原，提高了催化一步制醇反应活性。铜、镍、铁和尿素浓度的调配以及钴盐的选择，结合微波和水热条件促使材料中钴氧化物晶面(111)和(220)的暴露。氧化钴暴露晶面(111)和(220)有利于氢甲酰化，其中(220)有利于醛加氢制醇。
催化剂为过渡金属TM掺杂氧化钴材料，表述为xTM1yTM2-Co3O4，TM为过渡金属铁、镍、铜的一种；氧化钴暴露晶面(111)和(220)；催化剂制备方法通过引入尿素和过渡金属盐，采用微波法或者水热法制备；其中微波法制备催化剂呈3D棒状结构；水热法制备催化剂呈层状纳米片堆叠结构。催化剂可以应用于高碳醇制备，原料为长链烯烃包括C6～C12直链α-烯烃，目标产物醇包括C7～C13醇，尤其壬醇的制备选择性＞40%。具体为催化剂应用于醇制备，原料底物为长链烯烃，含α-辛烯，溶剂为四氢呋喃，合成气体积比CO/H2=1，催化剂与α-辛烯质量比为5～20%，反应温度为140～160 °C；反应压力5～7 MPa，反应时间4～7 h，长链α-烯烃与合成气在本发明制备方法下所得催化剂催化作用下制备得到醇。微波法制备催化剂粒径为 190 nm～1.5um，长度不一，比表面积≥20 m2/g；水热法制备催化剂比表面积≥30 m2/g。
催化剂制备方法包括将硝酸钴、尿素溶解，尿素与硝酸钴摩尔比为1～5；掺杂金属TM1和TM2与钴的摩尔比分别为x和y，x和y的取值为1～8之间。加入过渡金属硝酸盐，搅拌混匀得均相混合溶液，混合液中，每43 mL溶剂中含有0.25～1.0 g 钴和0.25～0.5 g尿素。
混合液通过微波法MW或者水热法HT获得固液混合物，冷却至室温、过滤、干燥得催化剂前躯体，进一步将催化剂前躯体焙烧，获得目标催化剂。水热法晶化温度为140～200 °C，晶化时间为16～20 h。微波法反应温度为100～180 °C，反应时间为0.25～1 h。
其中，均相溶液经微波条件处理获得催化剂记为TM1TM2-Co3O4-MW；经水热条件处理获得催化剂记为TM1TM2-Co3O4-HT。
催化剂亦可应用于制高碳醛，原料底物为长链烯烃，合成气体积比CO/H2=1，催化剂与α-辛烯质量比为1～5%，反应温度为130～150 °C；反应压力5～7 MPa，反应时间1～2h。
附图说明
图1所示为实施例2制备催化剂样品的高倍率TEM图。
图2所示为实施例4制备催化剂样品的高倍率TEM图。
图3为实施例2制备催化剂样品的SEM图（左）和TEM图（右）。
图4为实施例4制备催化剂样品的SEM图（左）和TEM图（右）。
具体实施方式
下面通过实施例对本发明进行具体描述。有必要在此指出的是以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，在不背离本发明精神和实质的情况下，对本发明方法、步骤或条件所作的修改或替换，均属于本发明的范围。
实施例1
将2.5 g 六水硝酸钴、0.0416 g 三水硝酸铜、0.7739 g 尿素溶于86 mL去离子水，常温搅拌3 h，形成均相溶液。均相溶液在微波条件于160 °C反应处理15 min，冷却至室温、过滤、干燥，400 °C焙烧4 h，获得催化剂2Cu-Co3O4-MW。
壬醇合成催化活性评价：催化剂与原料1-辛烯质量比=8.4%，催化剂用量为0.1445g，1-辛烯用量为1.68 g，溶剂四氢呋喃用量为10.65 g，合成气CO/H2=1，反应温度150 °C，反应压力7 MPa，搅拌速度700 r.m.p.，反应时间4 h。反应结果参见表1。
实施例2
将2.5 g 六水硝酸钴、0.0694 g 九水硝酸铁、0.0415 g 六水硝酸钴、0.7739 g尿素溶于86 mL去离子水，常温搅拌3 h，形成均相溶液。均相溶液在微波条件于160 °C反应处理15 min，冷却至室温、过滤、干燥，400 °C焙烧4 h，获得催化剂2Fe2Cu-Co3O4-MW。活性评价同实施例1。反应结果参见表1。
实施例3
将2.5 g 六水硝酸钴、0.0500 g 六水硝酸镍、0.0415 g 三水硝酸铜、0.7739 g尿素溶于86 mL去离子水，常温搅拌3 h，形成均相溶液。均相溶液在微波条件于160 °C反应处理15 min，冷却至室温、过滤、干燥，400 °C焙烧4 h，获得催化剂2Ni2Cu-Co3O4-MW。活性评价同实施例1。反应结果参见表1。
实施例4
将2.5 g 六水硝酸钴、0.0694 g 九水硝酸铁、0.0415 g 三水硝酸铜、0.7739 g尿素溶于86 mL去离子水，常温搅拌3 h，形成均相溶液。均相溶液在水热条件于160 °C晶化反应18 h，冷却至室温、过滤、干燥，400 °C焙烧4 h，获得催化剂2Fe2Cu-Co3O4-HT。活性评价同实施例1。反应结果参见表1。
对比实施例1
将2.5 g Co(NO3)2×6H2O、0.0694 g Fe(NO3)3×9H2O、0.7739 g CO(NH2)2尿素溶于86 mL去离子水，常温搅拌3 h，形成均相溶液。均相溶液在微波条件下160 °C反应处理15min，冷却至室温、过滤、干燥，400 °C焙烧4 h，获得催化剂2Fe-Co3O4-MW。活性评价同实施例1。反应结果参见表1。
对比实施例2
将2.5 g Co(NO3)2×6H2O、0.0500 g Ni(NO3)2×6H2O、0.7739 g CO(NH2)2尿素溶于86 mL去离子水，常温搅拌3 h，形成均相溶液。均相溶液在微波条件下160 °C反应处理15min，冷却至室温、过滤、干燥，400 °C焙烧4 h，获得催化剂2Ni-Co3O4-MW。活性评价同实施例1。反应结果参见表1。
对比实施例3
将2.5 g Co(NO3)2·6H2O和0.7739 g CO(NH2)2尿素溶于86 mL去离子水，常温搅拌3 h，形成均相溶液。均相溶液在微波条件下160 °C反应处理15 min，冷却至室温、过滤、干燥，400 °C焙烧4 h，获得催化剂Co3O4-MW样品。活性评价同实施例1。反应结果参见表1。
表1 1-辛烯与合成气反应制壬醇催化活性
实施例5
采用实施例3催化剂，活性评价参照实施例1，反应时间为5 h，反应结果参见表2。
实施例6
采用实施例3催化剂，活性评价参照实施例1。反应时间为7 h，反应结果参见表2。
表2 不同反应条件催化剂的制醇反应活性
实施例7
采用实施例3催化剂。实活性评价参照实施例1。原料为1-己烯，反应时间为7 h，产物为庚醇和庚醛，反应结果参见表3。
实施例8
活性评价参照实施例1。原料为1-十二烯，产物为十三醇和十三醛，反应结果参见表3。
表3不同碳数直链α烯烃制醇反应活性
| 实施例 | α-烯烃 | 转化率/% | 醇选择性/% | 醛选择性/% |
| 实施例7 | 1-己烯 | 98.40 | 52.51 | 9.21 |
| 实施例8 | 1-十二烯 | 99.97 | 32.59 | 45.17 |
从表1-3可见，Cu掺杂有利于提高Co3O4氢甲酰化反应活性，Fe掺杂有利于提高产物醇选择性；以1-辛烯为底物时，在150 °C、7 MPa、5 h时，以2Fe2Cu-Co3O4-HT为催化剂催化氢甲酰化反应，壬醇选择性最高为67.87%；2Fe2Cu-Co3O4-HT催化剂可有效催化C6～C12直链α-烯烃制醇，特别地，以1-辛烯作为原料时，获得醇选择性最高，其他碳数的醇(C7，C8，C9～C13)，随着碳数的增加，醇选择性降低。
图1和图2分别为实施例2和实施例4制备催化剂样品的高倍率透射电子显微镜(TEM)照片。可以证实催化剂材料主要暴露晶面为(111)晶面和(220)晶面。
图3为实施例2制备催化剂样品(微波法)的扫面电子显微镜(SEM)照片和TEM照片。可以证实微波法制备催化剂呈棒状结构。
图4为实施例4制备催化剂样品(水热法)的SEM照片和TEM照片。可以证实水热法制备催化剂呈层状纳米片堆叠结构。
Claims (5)
1.一种金属掺杂自组装催化剂，其特征在于，所述催化剂为过渡金属TM掺杂氧化钴材料，表述为xTM1yTM2-Co3O4，其中TM2为过渡金属铜，TM1为过渡金属铁或镍；氧化钴暴露晶面(111)和(220)；催化剂制备方法通过引入尿素和过渡金属盐，采用微波法或者水热法制备；其中微波法制备催化剂呈棒状结构；水热法制备催化剂呈层状纳米片堆叠结构；所述催化剂应用于醇的制备，原料底物为长链烯烃，含有α-辛烯，溶剂为四氢呋喃，合成气体积比CO/H2=1，催化剂与α-辛烯质量比为1～5%，反应温度为140～160℃；反应压力5～7 MPa，反应时间4～7h，长链烯烃与合成气在所述催化剂的催化作用下制备得到醇；长链烯烃包括C6～C12直链α-烯烃，目标产物醇包括C7～C13醇。
2.根据权利要求1所述的一种金属掺杂自组装催化剂，其特征在于，微波法制备催化剂粒径为190 nm～1.5 μm，长度不一，比表面积≥20 m2/g；水热法制备催化剂比表面积≥30m2/g。
3.一种如权利要求1所述催化剂的制备方法，其特征在于，催化剂制备方法包括将硝酸钴、尿素溶解，尿素与硝酸钴摩尔比为1～5；加入过渡金属硝酸盐，搅拌混匀为混合溶液；混合溶液通过微波法或者水热法获得固液混合物，冷却至室温、过滤、干燥得催化剂前驱体，进一步将催化剂前驱体焙烧，获得目标催化剂。
4.根据权利要求3所述的制备方法，其特征在于，水热法晶化温度为140～200℃，晶化时间为16～20h。
5.根据权利要求3所述的制备方法，其特征在于，微波法反应温度为100～180℃，反应时间为0.25～1h。
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