CN113289625B - 基于反应物富集的二氧化碳制液体燃料催化剂及其制备方法 - Google Patents
基于反应物富集的二氧化碳制液体燃料催化剂及其制备方法 Download PDFInfo
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- CN113289625B CN113289625B CN202110599239.5A CN202110599239A CN113289625B CN 113289625 B CN113289625 B CN 113289625B CN 202110599239 A CN202110599239 A CN 202110599239A CN 113289625 B CN113289625 B CN 113289625B
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Abstract
本发明属于催化剂技术领域,公开了一种基于反应物富集的二氧化碳制液体燃料催化剂及其制备方法,它是由均匀分布的过渡金属氧化物CuxFe2‑xOy作催化活性中心和多孔杂原子掺杂中空碳壳组成的过渡金属氧化物担载量为10‑40%的中空核壳结构电催化剂,通过制备CuxFe2‑xOy/SiO2中间体及CuxFe2‑xOy/SiO2@PHC中间体最终制得CuxFe2‑xOy@PHC催化剂。本发明的制备方法操作简便,成本低,所制得的CuxFe2‑xOy@PHC催化剂表现出优异的稳定性、活性、产物选择性和转化率。本发明适用于作为催化剂应用于二氧化碳催化加氢反应和电催化还原二氧化碳反应。
Description
技术领域
本发明属于液体燃料催化剂技术领域,涉及二氧化碳制液体燃料催化剂,具体地说是一种基于反应物富集的二氧化碳制液体燃料催化剂及其制备方法。
背景技术
随着全球变暖加剧,将二氧化碳转化为高附加值化学品和液体燃料,可从根本上实现碳的循环利用,有望帮助解决人类面临的日益严重的能源危机及温室效应问题。
二氧化碳催化加氢反应是在较温和条件下将二氧化碳转化为高附加值化学品和液体燃料的一种有效策略,近年来被广泛研究,但仍面临许多问题:例如,二氧化碳直接加氢的产物大多局限于C1-C4的低分子量短链烃类或CO、CH3OH、HCOOH、CH3OCH3等含氧化合物,而不是理想的长链液态烃燃料;同时,二氧化碳加氢过程中二氧化碳的转化率较低,即催化二氧化碳加氢反应的催化剂活性低,经济效益差,且反应条件较苛刻,也增加了生产成本;此外,催化二氧化碳加氢反应的催化剂选择性差,二氧化碳加氢的产物较分散,使产品需进一步分离,也增加了成本。
近年来,国内外针对二氧化碳加氢反应催化剂的活性和选择性做了大量的研究,名称为《Directly converting CO2 into a gasoline fuel》的文章报道了一种多活性位点Na-Fe3O4/HZSM-5催化剂,该催化剂可使二氧化碳加氢生成C5-C11碳氢燃料的选择性达到78%,但二氧化碳转化率仅有22%。
为提高二氧化碳的转化率,名称为《Transforming carbon dioxide into jetfuel using an organic combustion-synthesized Fe-Mn-K catalyst》的文章报道了Mn和K掺杂的块状Fe基催化剂Fe-Mn-K,可催化碳碳偶联反应进而生成长链液态烃燃料,但Fe-Mn-K催化剂对目标产物的选择性较低,仅为47.8%,二氧化碳的转化率也不高,为17.2%,同时该反应在1MPa、320℃条件下进行,反应条件苛刻,大大增加了生产成本。
为了提高催化剂对目标产物的选择性,名称为《Carbon dioxide Fischer-Tropsch synthesis:A new path to carbon-neutral fuels》的文章报道了铜铁矿型CuFeO2催化剂,通过在催化剂中引入Cu来催化CuFeO2中Fe3+的还原速率和碳碳偶联反应速率,从而使CuFeO2催化剂对液体燃料目标产物的选择性提高至65%,但二氧化碳的转化率仅为13.3%,同时该反应也是在1MPa条件下进行,反应条件较为苛刻,成本高。
因此,设计一种结构稳定的二氧化碳制液体燃料催化剂来提高二氧化碳加氢反应催化剂的活性和选择性,提高转化率,对实现“碳达峰碳中和”目标和利用二氧化碳生产高附加值液体燃料具有重要意义。
发明内容
本发明的一个目的,是要提供一种基于反应物富集的二氧化碳制液体燃料催化剂,由催化活性中心和多孔杂原子掺杂中空碳壳组成中空核壳结构催化剂,以达到解决解决现有二氧化碳加氢催化剂反应条件苛刻、活性不高和选择性差等问题的目的;
本发明的另外一个目的,是要提供上述基于反应物富集的二氧化碳制液体燃料催化剂的一种制备方法。
为实现上述目的,本发明采用的技术方案是:
一种基于反应物富集的二氧化碳制液体燃料催化剂,它是由催化活性中心和多孔杂原子掺杂中空碳壳组成的中空核壳结构催化剂,催化活性中心是过渡金属氧化物CuxFe2-xOy,x为0-2;y为2-3;过渡金属氧化物担载量为10-40%,多孔杂原子掺杂中空碳壳的直径为5nm-200nm。
作为一种限定,所述中空核壳结构催化剂为CuxFe2-xOy@PHC催化剂,其中,CuxFe2- xOy的粒径小于多孔杂原子掺杂中空碳壳的直径为1nm-100nm。
其中,PHC为Porous Heteroatom-doped Carbon,即多孔杂原子掺杂中空碳壳。
本发明还提供了上述基于反应物富集的二氧化碳制液体燃料催化剂的一种制备方法,包括依次进行的以下步骤:
S1.制备CuxFe2-xOy/SiO2中间体
取球状纳米二氧化硅载体与过渡金属前驱体溶液,经混匀得悬浮液,加入还原剂和碱溶液,经加热,反应,冷却,抽滤干燥,得CuxFe2-xOy/SiO2中间体;
S2.制备CuxFe2-xOy/SiO2@PHC中间体
将CuxFe2-xOy/SiO2中间体、含杂原子有机物、碳源有机物和结构助剂混匀,聚合反应,抽滤得固体,干燥,研磨,在惰性气体保护下,加热,冷却,得CuxFe2-xOy@PHC中间体;
S3.制备CuxFe2-xOy@PHC催化剂
将CuxFe2-xOy/SiO2@PHC中间体与碱性水溶液混匀,过滤,将滤液干燥,得固体,研磨,在惰性气体保护下,加热,刻蚀,得CuxFe2-xOy@PHC催化剂。
作为一种限定,步骤S1中,所述球状纳米二氧化硅载体由化学沉淀法制得;
所述过渡金属前驱体溶液中过渡金属前驱体和去离子水的重量比为1:1-50;
所述过渡金属为Fe和Cu中的至少一种;
所述过渡金属前驱体为过渡金属的硝酸盐、硫酸盐、乙酸盐、盐酸盐和氯酸盐中的至少一种;
所述球状纳米二氧化硅载体、过渡金属前驱体、还原剂和碱溶液的重量体积比为1g:0.1-20g:0.1-20mL:0.1-20mL。
作为另一种限定,步骤S1中,所述还原剂为甲醛、乙醛、丙醛、乙二胺、柠檬酸、抗坏血酸或葡萄糖中的至少一种;所述碱溶液中OH-的浓度为0.05-0.2mol/L;
所述加热的温度为60-220℃,时间为0.5-24h;冷却至室温。
作为第三种限定,步骤S2中,所述CuxFe2-xOy/SiO2中间体、含杂原子有机物、碳源有机物和结构助剂的重量比为1:1-100:1-100:1-20;
所述含杂原子有机物为多巴胺、尿素、硫脲、乙二胺、L-半胱氨酸、氰胺、双氰胺和三聚氰胺中的至少一种;
所述碳源有机物为多巴胺、壳聚糖、葡萄糖、间苯二酚、四氯化碳、乙二胺四乙酸和甲醛中的至少一种;
所述结构助剂为间苯二胺和对氨基苯酚中的至少一种。
作为第四种限定,步骤S2中,步骤S2中,所述加热的温度为300-1000℃,时间为0.5-24h;所述冷却为冷却至18-26℃。
作为第五种限定,步骤S3中,步骤S3中,所述CuxFe2-xOy/SiO2@PHC中间体与碱性水溶液的质量体积比为1g:0.5-20mL;
所述加热的温度为300-1000℃,时间为0.5-24h。
作为第六种限定,步骤S3中,所述碱性水溶液中OH-的浓度为0.2-20mol/L。
本发明由于采用了上述技术方案,其与现有技术相比,所取得的技术进步在于:
本发明的基于反应物富集的二氧化碳制液体燃料催化剂中CuxFe2-xOy@PHC催化剂具有稳定结构:CuxFe2-xOy为催化活性中心,粒径均一且均匀分布在PHC内表面,金属氧化物担载量高达10-40%;PHC为多孔杂原子掺杂中空碳壳,作为外围组织,具有富集反应物、稳定反应中心和提供活性表面区域的功能;PHC空腔内的高浓度二氧化碳会增加二氧化碳与CuxFe2-xOy活性中心的碰撞频率,既增加了二氧化碳的转化率,又提高了催化剂表面的碳碳耦合反应速率,利于C5-C20液体烃类组分的生成,提高催化剂的活性与催化产物的选择性;同时,在PHC壳层的保护下,能有效抑制CuxFe2-xOy活性中心的溶解、聚集和迁移,大大提高了催化剂的整体稳定性。
本发明的制备方法简单易操作,反应条件易达,成本低,适于工业生产,所制得的基于反应物富集的二氧化碳制液体燃料催化剂稳定性、活性、选择性和转化率高,适于作为催化剂应用于二氧化碳催化加氢反应和电催化还原二氧化碳反应。
附图说明
图1为本发明实施例1中制备的CuxFe2-xOy@PHC催化剂J1的结构示意图;
图2为本发明实施例1中制备的CuxFe2-xOy@PHC催化剂J1的高倍透射电镜照片;
图3为本发明实施例9中CuxFe2-xOy@PHC催化剂J1和对比样品CuxFe2-xOy/C的二氧化碳流出曲线图;
图4为本发明实施例9中CuxFe2-xOy@PHC催化剂J1和对比样品CuxFe2-xOy/C的二氧化碳加氢催化性能测试结果图;
图5为本发明实施例9中CuxFe2-xOy@PHC催化剂J1和对比样品CuxFe2-xOy/C的催化稳定性测试结果图。
具体实施方式
下面通过具体实施例对本发明做进一步详细说明,应当理解所描述的实施例仅用于解释本发明,并不限定本发明。
如果实施例中未注明的实验具体条件,通常按照常规条件,或者按照试剂公司所推荐的条件;下述实施例中所用的试剂、耗材等,如无特殊说明,均可通过商业途径获得,所用工艺如无特殊说明,均为本领域常规工艺方法。
实施例1一种基于反应物富集的二氧化碳制液体燃料催化剂的制备方法
实施例1的制备方法,包括依次进行的以下步骤:
化学沉淀法制备球状纳米二氧化硅载体:
取10L乙醇和40L去离子水,混合均匀后加入0.5L硅酸四甲酯和0.1kg十六烷基三甲基氯化铵(CTAC)表面活性剂,室温下搅拌0.5h后,逐滴加入0.5L重量分数为25%的氨水溶液,在室温条件下搅拌处理3h,先后使用去离子水和乙醇将过滤所得产物洗涤、70℃干燥,再于空气中600℃下加热6h,制到球状纳米二氧化硅载体,备用。
其中,球状纳米二氧化硅载体也可通过商业途径获得。
S1:制备CuxFe2-xOy/SiO2中间体:
按过渡金属氧化物CuxFe2-xOy担载量为12%,称取2kg球状纳米二氧化硅载体与453g三水合硝酸铜和868g九水合硝酸铁,按照过渡金属前驱体和去离子水的重量比(标记为:比例1)为1:20,溶解得过渡金属前驱体溶液;
将球状纳米二氧化硅载体与过渡金属前驱体溶液超声波分散0.5h,机械搅拌0.5h,混匀得悬浮液,加入8L、0.1mol/L的NaOH溶液和5L的丙醛,转入反应釜,将反应釜加热至160℃,反应8h后,自然冷却,抽滤,干燥得CuxFe2-xOy/SiO2中间体。
其中,球状纳米二氧化硅载体、过渡金属前驱体、还原剂和碱溶液的重量体积比为2g:1.3g:5mL:8mL,标记为比例2。
S2:制备CuxFe2-xOy/SiO2@PHC中间体:
将1kg的CuxFe2-xOy/SiO2中间体加入到2kg间苯二胺(结构助剂)中,依次加入2kg乙二胺(含杂原子有机物)和4kg四氯化碳(碳源有机物),搅拌混匀,在100℃和冷凝回流的条件下,聚合反应4h,抽滤得固体,干燥、研磨。将所得固体粉末置于管式炉中,在氮气保护下,600℃加热5h,冷却至室温,得到CuxFe2-xOy/SiO2@PHC中间体;
其中,CuxFe2-xOy/SiO2中间体、含杂原子有机物、碳源有机物和结构助剂的重量比为1:2:4:2(标记为:比例3)。
S3:制备CuxFe2-xOy@PHC催化剂:
将1kg的CuxFe2-xOy/SiO2@PHC中间体与5L、6mol/L NaOH溶液混匀,搅拌6h,过滤以除去球状纳米二氧化硅载体,将滤液干燥,得固体,研磨固体,在氩气保护下,600℃加热2h,使残留的NaOH刻蚀杂原子掺杂碳壳,得CuxFe2-xOy@PHC催化剂为基于反应物富集的二氧化碳制液体燃料催化剂,标记为J1。
其中,CuxFe2-xOy/SiO2@PHC中间体与碱性水溶液的质量体积比为1g:5mL(标记为:比例4)。
图1为CuxFe2-xOy@PHC催化剂J1的结构示意图,它是由催化活性中心和多孔杂原子掺杂中空碳壳(PHC)组成的中空核壳结构催化剂,其中,催化活性中心是过渡金属氧化物CuxFe2-xOy,x为1;y为2.5;过渡金属担载量为12%,PHC形成的空腔提供活性表面区域,具有富集二氧化碳、稳定反应中心的功能。
图2为CuxFe2-xOy@PHC催化剂J1的高倍透射电镜照片,可以看出金属氧化物CuxFe2- xOy颗粒非常均匀分布在PHC壳空腔内壁,经测量,PHC壳的厚度为5nm。
实施例2-8基于反应物富集的二氧化碳制液体燃料催化剂的制备方法
实施例2-8分别为一种基于反应物富集的二氧化碳制液体燃料催化剂的制备方法,这些制备方法与实施例1基本相同,不同之处在于原料选择及其他工艺参数的调整,原料标记代码见表1,工艺参数调整见表2。
表1原料标记代码
表2实施例2-8工艺参数
所制得基于反应物富集的二氧化碳制液体燃料催化剂为CuxFe2-xOy@PHC催化剂,J2-J8均是由催化活性中心CuxFe2-xOy和多孔杂原子掺杂中空碳壳PHC组成的中空核壳结构电催化剂,其中,过渡金属担载量为10-40%,PHC形成的空腔提供活性表面区域,具有富集二氧化碳、稳定反应中心的功能。其中多孔杂原子掺杂中空碳壳的直径均为5nm-200nm;CuxFe2-xOy的粒径均小于多孔杂原子掺杂中空碳壳的直径为1nm-100nm。
实施例9基于反应物富集的二氧化碳制液体燃料催化剂的性能检测
对比实验材料为CuxFe2-xOy/C,商品名为XC-72,CuxFe2-xOy/C中CuxFe2-xOy催化活性中心担载在碳单质球表面。
一)CuxFe2-xOy@PHC催化剂J1和CuxFe2-xOy/C的二氧化碳流出曲线
检测方法:将100mg的CuxFe2-xOy@PHC放入U型管中,在300℃氩气下活化1h,降到室温后向U型管中通入二氧化碳1h,将二氧化碳切换成氩气吹扫,同时用质谱仪记录J1物理吸附二氧化碳的量,记录结果,绘制二氧化碳流出曲线;
取CuxFe2-xOy/C重复上述操作,绘制相应二氧化碳流出曲线。
检测结果:结果如图3所示,结果表明,相较于CuxFe2-xOy/C,CuxFe2-xOy@PHC催化剂J1的PHC壳层可以通过物理吸附,吸附更多二氧化碳,PHC空腔内的表面活性区域具有富集反应物二氧化碳的功能。
二)CuxFe2-xOy@PHC催化剂J1和CuxFe2-xOy/C二氧化碳加氢催化性能测试
检测方法:称取2g CuxFe2-xOy@PHC催化剂J1并置于固定床不锈钢反应器中,将J1在100sccm氢气、400℃下预还原2h,随后将J1冷却至180℃并将气体切换至CO2/H2=1:3的二氧化碳和氢气的混合气,气体流速设置为1800ml g-1h-1,气体压力为0.5MPa,进行二氧化碳催化加氢反应,反应结束后检测产物;
产物检测:采用气相色谱法、火焰离子化检测器分析C1-C4中的碳氢化合物,较重的烃产物在冷阱中收集后采用模拟蒸馏分析方法,以碳数的重量百分比计算烃产物的组成;绘制曲线图,结果如图4;
三)CuxFe2-xOy@PHC催化剂J1和CuxFe2-xOy/C的催化稳定性测试
检测方法:与一)中方法一致,记录液体燃料的产量,计算结果,绘制二氧化碳转化率与C5-C16液体燃料选择性曲线;结果如图5。
结果分析:
从图4和图5可以看出本发明的催化剂J1在活性组分担载量相同的情况下,CuxFe2-xOy@PHC的催化活性(即CO2转化率和C5-C20目标产物选择性)和稳定性均比对比样品CuxFe2-xOy/C有明显的提高,表明PHC壳内的高浓度二氧化碳增加了反应物与催化活性中心的碰撞频率,既能增加二氧化碳的转化率,又可提高催化剂表面的碳碳耦合反应速率,利于C5-C20液体烃类组分的生成;另一方面,PHC壳层的保护能有效抑制CuxFe2-xOy金属物的溶解、聚集和迁移,大大提高了催化剂的整体稳定性。
对实施例2-8制得的J2-J8均进行实施例9的性能检测,检测结果一致,均表明本发明的基于反应物富集的二氧化碳制液体燃料催化剂,表现出优异的稳定性、活性、产物选择性和转化率,本发明适用于作为催化剂应用于二氧化碳催化加氢反应和电催化还原二氧化碳反应。
需要注意,上述实施例,仅是本发明的较佳实施例,并非是对本发明所作的其他形式的限定,任何熟悉本专业的技术人员都可能利用上述技术内容作为启示加以变更或改型为等同变化的等效实施例,但凡是未脱离本发明权利要求的技术实质,对以上实施例所作出的简单修改、等同变化与改型,仍属于本发明权利要求保护的范围。
Claims (4)
1.一种基于反应物富集的二氧化碳制液体燃料催化剂的制备方法,其特征在于,包括依次进行的以下步骤:
S1.制备CuxFe2-xOy/SiO2中间体
取球状纳米二氧化硅载体与过渡金属前驱体溶液,经混匀得悬浮液,加入还原剂和碱溶液,经加热,反应,冷却,抽滤干燥,得CuxFe2-xOy/SiO2中间体;
S2.制备CuxFe2-xOy/SiO2@PHC中间体
将CuxFe2-xOy/SiO2中间体、含杂原子有机物、碳源有机物和结构助剂混匀,聚合反应,抽滤得固体,干燥,研磨,在惰性气体保护下,加热,冷却,得CuxFe2-xOy@PHC中间体;
S3.制备CuxFe2-xOy@PHC催化剂
将CuxFe2-xOy/SiO2@PHC中间体与碱性水溶液混匀,过滤,将滤液干燥,得固体,研磨,在惰性气体保护下,加热,刻蚀,得CuxFe2-xOy@PHC催化剂;
其中,步骤S1中,所述球状纳米二氧化硅载体由化学沉淀法制得;
所述过渡金属前驱体溶液中过渡金属前驱体和去离子水的重量比为1:1-50;
所述过渡金属为Fe和Cu中的至少一种;
所述过渡金属前驱体为过渡金属的硝酸盐、硫酸盐、乙酸盐、盐酸盐和氯酸盐中的至少一种;
所述球状纳米二氧化硅载体、过渡金属前驱体、还原剂和碱溶液的重量体积比为1g:0.1-20g:0.1-20mL: 0.1-20mL;
所述还原剂为甲醛、乙醛、丙醛、乙二胺、柠檬酸、抗坏血酸或葡萄糖中的至少一种;所述碱溶液中OH-的浓度为0.2-20mol/L;
所述加热是加热的温度为60-220℃,时间为0.5-24h;
步骤S2中,所述CuxFe2-xOy/SiO2中间体、含杂原子有机物、碳源有机物和结构助剂的重量比为1:0.2-20:0.2-40:0.2-20;
所述含杂原子有机物为多巴胺、尿素、硫脲、乙二胺、L-半胱氨酸、氰胺、双氰胺和三聚氰胺中的至少一种;
所述碳源有机物为多巴胺、壳聚糖、葡萄糖、间苯二酚、四氯化碳、乙二胺四乙酸和甲醛中的至少一种;
所述结构助剂为间苯二胺和对氨基苯酚中的至少一种。
2.根据权利要求1所述的基于反应物富集的二氧化碳制液体燃料催化剂的制备方法,其特征在于,步骤S2中,所述加热的温度为300-1000℃,时间为0.5-24h;所述冷却为冷却至18-26℃。
3.根据权利要求1所述的基于反应物富集的二氧化碳制液体燃料催化剂的制备方法,其特征在于,步骤S3中,所述CuxFe2-xOy/SiO2@PHC中间体与碱性水溶液的质量体积比为1g:0.5-20mL;
所述加热的温度为300-1000℃,时间为0.5-24h。
4.根据权利要求1所述的基于反应物富集的二氧化碳制液体燃料催化剂的制备方法,其特征在于,步骤S3中,所述碱性水溶液中OH-的浓度为0.2-20mol/L。
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