CN110180592B - 一种用于二氧化碳加氢反应的催化剂的制备方法 - Google Patents
一种用于二氧化碳加氢反应的催化剂的制备方法 Download PDFInfo
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- CN110180592B CN110180592B CN201910566290.9A CN201910566290A CN110180592B CN 110180592 B CN110180592 B CN 110180592B CN 201910566290 A CN201910566290 A CN 201910566290A CN 110180592 B CN110180592 B CN 110180592B
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Abstract
本发明公开了一种用于二氧化碳加氢反应的催化剂的制备方法,以层状铜铝水滑石(简称CuAl‑LDH)为固体前驱体,利用CuAl‑LDH的阴离子交换性质,在惰性气体气氛下将基于TCPP或含有过渡金属离子的TCPP(简称TCPP(M))的阴离子配体(即Na‑TCPP或Na‑TCPP(M))插层于二维层状水滑石的层间区域,再经过高温空气焙烧处理和氢气还原处理后,获得应用于二氧化碳气相加氢反应的催化剂。该制备方法工艺简单、重复性好,所制备得到的催化剂具有均匀组成、高活性组分分散度、高稳定性和高二氧化碳转化率等优点。
Description
技术领域
本发明属于催化剂制备领域,具体涉及一种用于二氧化碳加氢反应的催化剂的制备方法。
背景技术
随着全球人口和经济规模的不断增长,人类活动带来的环境问题越来越突出。最为突出的是大量化石能源被开采利用,导致大气中排放的温室气体越来越多,随之引起全球气候变暖和极端气候问题。二氧化碳(CO2)作为主要的温室气体之一,如何处理大气中日渐增多的CO2已是世界各国亟需解决的一个重要问题。据相关资料统计,全球每年排放CO2约250多亿吨,其中我国排放量达60多亿吨,位居世界第一。我国是世界上能源消耗量最大的国家之一,其能源结构仍然以煤为主体,石油、天然气、水、核电仅占25%左右,这决定了我国CO2排放量持续增长的趋势在短期内难以改善。因此,开发有关CO2的捕集、储存及综合利用的新技术已是我国研究的热点之一。除了将CO2直接深埋入地下或注入海洋封存外,研究学者已经将捕获后的浓缩二氧化碳用于制造新材料、化学品和燃料,实现CO2资源化。例如,从大气中捕获的二氧化碳可进行气相催化加氢得到甲醇、甲烷、一氧化碳、二甲醚和甲酸等燃料和化学品。这些燃料和化学品燃烧后,被释放到大气中的二氧化碳又可以再次被捕获并加氢转化为燃料和化学品。例如,通过碳捕获和催化加氢生产甲醇是诺贝尔奖得主George A.Olah倡导的“甲醇经济”概念的重要组成部分。
而催化剂是实现上述二氧化碳气相加氢工艺的核心技术。铜基催化剂具有比表面积大、高活性组分分散度等优点,是目前国内外研究最多的催化剂。自20世纪60年代起,以英国卜内门化学工业有限公司(ICI公司)为代表生产的Cu-ZnO-Al2O3催化剂就已成为合成气(CO/H2混合气)制甲醇的商用催化剂。目前很多研究者也对铜基催化剂及其改性催化剂进行大量研究,其活性体系主要有Cu/ZnO/Al2O3、Cu/ZnO、Cu/ZnO/ZrO2、Cu/ZnO/SiO2、Cu/NiO、Cu/NiO2/TiO2等。其中,黄树鹏等(石油化工,2009,38(5),480-484)采用共沉淀法制备CuO-ZnO-Al2O3催化剂,研究了分别添加ZrO2和Ag2O助剂对二氧化碳加氢合成甲醇反应性能的影响。中国发明专利CN106423175A公开了一种采用球磨的方法制备铜基催化剂,虽然该方法可掺杂不同结构助剂和其它金属离子,但是该方法难以对催化剂的微观形貌进行精确调控。
发明内容
有鉴于此,本发明的目的在于解决CO2温室效应问题,将CO2资源化,提供一种用于二氧化碳加氢反应的催化剂的制备方法,其制备的催化剂具有均匀组成、高活性组分分散度、高稳定性和高二氧化碳转化率等优点。
为了达成上述目的,本发明的技术方案是:
一种用于二氧化碳加氢反应的催化剂的制备方法,包括以下步骤:
(1)将TCPP或TCPP(M)放置于容器中,加入去离子水和氢氧化钠固体,在20~50℃下和惰性保护气氛中搅拌,反应24小时后,将所得固体产物经过离心、洗涤、干燥,得到阴离子配体Na-TCPP或Na-TCPP(M);
(2)取一定量CuAl-LDH和步骤(1)的阴离子配体Na-TCPP(M)或Na-TCPP放置于容器中,往容器中加入去离子水,在惰性保护气氛和60~100℃下充分搅拌,反应6~12小时,待反应结束后,所得固体产物经过离心、洗涤、干燥、高温焙烧和氢气还原处理,得到用于二氧化碳气相加氢反应的催化剂。
进一步地,步骤(1)中,将TCPP(M)放置于容器中,TCPP(M)的制备方法包括如下步骤:
步骤a:将一定量的TCPP和醋酸盐固体放置于容器中,并在该容器中通入保护气体,营造惰性保护气氛;
步骤b:往步骤a中的容器中加入有机溶剂,搅拌至溶解后,得到混合溶液,然后混合溶液在惰性保护气氛和80~200℃条件下反应3~10小时,待反应结束后,将所得固体产物经过离心、洗涤、干燥后,得到含过渡金属离子的TCPP,记为TCPP(M)。
进一步地,步骤(a)中醋酸盐为过渡金属离子醋酸盐,包括醋酸锌、醋酸钴、醋酸镍、醋酸铁和醋酸亚铁中的其中一种或多种混合。
进一步地,步骤(b)中所用有机溶剂为N,N-二甲基甲酰胺、N,N-二乙基甲酰胺中、N,N-二丁基甲酰胺和N,N-二甲基丙酰胺中的一种或多种混合。
进一步地,步骤(1)、步骤(2)、步骤a和步骤b中,惰性保护气氛均为氮气气氛。
进一步地,步骤(2)中,CuAl-LDH与阴离子配体Na-TCPP(M)的质量比为1:0.25~2,或者,CuAl-LDH与阴离子配体Na-TCPP的质量比为1:0.25~2。
进一步地,步骤(2)中,高温焙烧过程中焙烧温度为200~500℃,焙烧时间为1~10小时。
进一步地,步骤(2)中,氢气还原过程中还原温度为250~350℃,还原时间为1~5小时。
进一步地,步骤(2)中,CuAl-LDH通过共沉积法、沉积沉淀法、溶胶凝胶法或水热法制备获得。
采用上述技术方案后,本发明一种用于二氧化碳加氢反应的催化剂的制备方法,具有以下有益效果:以层状铜铝水滑石(简称CuAl-LDH)为固体前驱体,利用CuAl-LDH的阴离子交换性质,在惰性保护气体气氛下将基于TCPP或含有过渡金属离子的TCPP(简称TCPP(M))的阴离子配体(即Na-TCPP或Na-TCPP(M))插层于二维层状水滑石的层间区域,再经过高温空气焙烧处理和氢气还原处理后,获得应用于二氧化碳气相加氢反应的催化剂。该制备方法工艺简单、重复性好,所制备得到的催化剂具有均匀组成、高活性组分分散度、高稳定性(即可以较长时间使用,实验室可以连续测试2-4天活性没有下降)和高二氧化碳转化率等优点。
可通过调控TCPP所负载的过渡金属离子种类(比如Zn2+、Co2+、Ni2+、Fe2+或Fe3+)来控制催化反应过程中的产物种类。
利用二维层状水滑石(Layered Double Hydroxide,LDH)的阴离子交换性质和“限域空间”效应,在铜铝水滑石(CuAl-LDH)中引入不同的过渡金属离子(如Zn2+、Co2+、Ni2+、Fe2+和Fe3+等),通过改变Na-TCPP(M)的质量,可以调控比例和分散度,通过焙烧处理温度和时间,也可以调控微观形貌和活性组分分散度。因此,在催化剂制备过程中可对催化剂的微观形貌与活性组分的分散度进行精准调控,从而增强温室气体二氧化碳加氢反应性能。
附图说明
图1为本发明中TCPP(Zn)@CuAl-LDH催化剂的透射电镜图。
图2为本发明中TCPP(Co)@CuAl-LDH催化剂的透射电镜图。
图3为本发明中TCPP(Ni)@CuAl-LDH催化剂的透射电镜图。
图4为本发明中TCPP(Fe)@CuAl-LDH催化剂的透射电镜图。
具体实施方式
为了进一步解释本发明的技术方案,下面通过具体实施例来对本发明进行详细阐述。
实施例1
一种用于二氧化碳加氢反应的催化剂的制备方法,包括以下步骤:
(1)先称量45mg的中-四(4-羧基苯基)卟吩(meso-Tetra(4-carboxyphenyl)porphine,简称TCPP)固体加入15mL的去离子水和14mg的氢氧化钠,在氮气气氛下和30℃条件下充分搅拌、反应24h,然后将所得固体再进行离心、洗涤、干燥,后得到阴离子配体Na-TCPP;
其中,TCPP从郑州如科生物科技有限公司购买。
(2)称量20mg的CuAl-LDH和5mg的Na-TCPP到玻璃容器中,在氮气气氛下,往玻璃容器中加入15mL的去离子水,然后在60℃下反应12h,所得固体产物依次经过离心、洗涤、干燥后,得到固体粉末。将所得干燥后的固体粉末置于马弗炉中以2℃/min加热速率从室温加热至200℃,并在此温度下保持10h。然后再以2℃/min的升温速率升温到250℃,在氢气环境下还原处理5h,得到TCPP@CuAl-LDH催化剂。
其中,本发明中,CuAl-LDH与阴离子配体Na-TCPP的质量比为1:0.25~2。
其中,CuAl-LDH可通过共沉积法、沉积沉淀法、溶胶凝胶法、水热法制备或从商业市场上购买获得。
本实施例中,CuAl-LDH的制备方法如下:以去离子水为溶剂,分别配制0.4mol/L的硝酸铜、0.2mol/L的硝酸铝和0.2mol/L的尿素溶液。然后上述三种溶液分别取20mL加入到100mL的聚四氟乙烯内衬中,在室温下搅拌30min后,放入不锈钢反应釜中,在130℃水热条件下反应8h。反应结束后,所得固体依次经离心、洗涤、干燥,得到CuAl-LDH。
进一步地,量取50mg催化剂(即TCPP@CuAl-LDH催化剂)放入固定床反应器中进行CO2加氢反应性能测试,反应气体浓度为CO2/H2/N2=24%/72%/4%,反应气体流速为20mL/min,反应压力为3MPa。在反应温度250℃下,CO2转化率为3.2%,甲醇的选择性为39.3%,甲烷的选择性为0.4%,一氧化碳的选择性为60.3%。该催化剂经过48h的加氢反应在线测试,催化活性无明显变化。
实施例2
一种用于二氧化碳加氢反应的催化剂的制备方法,包括以下步骤:
(1)将TCPP(Zn)放入容器中,加入15mL的去离子水和14mg的氢氧化钠,在25℃、氮气气氛下充分反应24h,然后将所得固体再依次进行离心、洗涤、干燥,得到阴离子配体Na-TCPP(Zn);
其中,TCPP(Zn)的制备方法如下:
步骤a:先称量45mg的TCPP固体和120mg的醋酸锌(即醋酸盐)固体添加到玻璃容器中,并且通入氮气营造氮气气氛,TCPP从郑州如科生物科技有限公司购买,醋酸盐为过渡金属离子醋酸盐,包含醋酸锌、醋酸钴、醋酸镍、醋酸铁、醋酸亚铁中的其中一种或多种混合;
步骤b:加入20mL的有机溶剂,有机溶剂优选为N,N-二甲基甲酰胺,然后在120℃下搅拌6h,所得固体产物依次经过离心分离、洗涤、干燥,得到含Zn2+的TCPP,记为TCPP(Zn),有机溶剂除了采用上述N,N-二甲基甲酰胺外,还可采用N,N-二甲基甲酰胺、N,N-二乙基甲酰胺中、N,N-二丁基甲酰胺和N,N-二甲基丙酰胺中的一种或多种混合;
(2)称量20mg的CuAl-LDH和15mg的Na-TCPP(Zn)置于玻璃容器中,在氮气气氛下,往玻璃容器中加入15mL的去离子水,然后在80℃下反应10h,所得固体产物依次经过离心、洗涤、干燥后得到固体粉末。将所得干燥后的固体粉末置于马弗炉中以2℃/min加热速率从室温加热至350℃,并在此温度下保持3h。然后再以2℃/min的升温速率升温到300℃,在氢气环境下还原处理3h,得到TCPP(Zn)@CuAl-LDH催化剂。催化剂的TEM图如图1所示,图中标尺100nm,可见TCPP(Zn)@CuAl-LDH催化剂呈现二维纳米片结构;另外,TEM图中无明显大颗粒存在,证明了催化剂的活性组分分布均匀。
其中,本发明中,CuAl-LDH与阴离子配体Na-TCPP(Zn)的质量比为1:0.25~2。
本实施例中,CuAl-LDH的制备方法如下:称量20mg的CuAl-LDH和15mg的Na-TCPP(Zn)置于玻璃容器中,在氮气气氛下,往容器中加入15mL的去离子水,然后在80℃下反应10h,所得固体产物经过离心、洗涤、干燥后得到固体粉末。将所得干燥后的固体粉末置于马弗炉中以2℃/min加热速率从室温加热至350℃,并在此温度下保持3h。然后再以2℃/min的升温速率升温到300℃,在氢气环境下还原处理3h,得到TCPP(Zn)@CuAl-LDH催化剂。催化剂的TEM图如图1所示,可见TCPP(Zn)@CuAl-LDH催化剂呈现二维纳米片结构。
进一步地,量取50mg催化剂(即TCPP(Zn)@CuAl-LDH催化剂)放入固定床反应器中进行CO2加氢反应性能测试,反应气体浓度为CO2/H2/N2=24%/72%/4%,反应气体流速为20mL/min,反应压力为3MPa。在反应温度250℃下,CO2转化率为8.5%,甲醇的选择性为58.5%,甲烷的选择性为0.3%,一氧化碳的选择性为41.2%。该催化剂经过48h的加氢反应在线测试,催化活性无明显变化。
实施例3
一种用于二氧化碳加氢反应的催化剂的制备方法,包括以下步骤:
(1)将TCPP(Co)放入玻璃容器中,加入15mL的去离子水和14mg氢氧化钠,在40℃、氮气气氛下充分反应24h,然后将所得固体再进行离心、洗涤、干燥,得到阴离子配体Na-TCPP(Co);
其中,TCPP(Co)的制备方法如下:
步骤a:先称量50mg的TCPP固体和135mg的醋酸钴固体置于玻璃容器中,并且通入氮气营造氮气气氛;
步骤b:随后加入20mL的N,N-二甲基丙酰胺,然后在120℃下搅拌6h。所得固体产物经过、洗涤、干燥,得到含Co2+的TCPP,记为TCPP(Co)
(2)称量20mg的CuAl-LDH和20mg的Na-TCPP(Co)到容器中,在氮气气氛下,往容器中加入15mL的去离子水,然后在70℃下反应8h,所得固体产物经过离心、洗涤、干燥,得到固体粉末。将所得干燥后的固体粉末置于马弗炉中以2℃/min加热速率从室温加热至400℃,并在此温度下保持10h。然后再以2℃/min的升温速率升温到350℃,在氢气环境下还原处理1h,得到TCPP(Co)@CuAl-LDH催化剂;
其中,CuAl-LDH的制备方法如下:称量20mg的CuAl-LDH和20mg的Na-TCPP(Co)到容器中,在氮气气氛下,往容器中加入15mL的去离子水,然后在70℃下反应8h,所得固体产物经过离心、洗涤、干燥,得到固体粉末。将所得干燥后的固体粉末置于马弗炉中以2℃/min加热速率从室温加热至400℃,并在此温度下保持10h。然后再以2℃/min的升温速率升温到350℃,在氢气环境下还原处理1h,得到TCPP(Co)@CuAl-LDH催化剂。TEM图(如图2所示,图中标尺20nm)中无明显大颗粒存在,证明了催化剂的活性组分分布均匀。钴离子在焙烧处理前处于LDH的二维层间,故焙烧过程中受到“限域空间“效应,使得最终钴活性组分在催化剂微观结构中可以很均匀分布。
进一步地,量取50mg催化剂(即TCPP(Co)@CuAl-LDH催化剂)放入固定床反应器中进行CO2加氢反应性能测试,反应气体浓度为CO2/H2/N2=24%/72%/4%,反应气体流速为20mL/min,反应压力为3MPa。在反应温度250℃下,CO2转化率为7.1%,甲醇的选择性为20.7%,甲烷的选择性为62.9%,一氧化碳的选择性为16.4%。该催化剂经过48h的加氢反应在线测试,催化活性无明显变化。
实施例4
一种用于二氧化碳加氢反应的催化剂的制备方法,包括以下步骤:
(1)将TCPP(Ni)放入玻璃容器中,加入15mL的去离子水和14mg氢氧化钠,在45℃和氮气气氛下充分搅拌24h,然后将所得固体再进行离心、洗涤、干燥,得到阴离子配体Na-TCPP(Ni);
其中TCPP(Ni)的制备方法如下:
步骤a:先称量40mg的TCPP固体和135mg的醋酸镍固体置于玻璃容器中,并且通入氮气营造氮气气氛;
步骤b:随后加入20mL的N,N-二丁基甲酰胺,然后在150℃下搅拌6h。所得固体产物经过离心、洗涤、干燥,得到含Ni2+的TCPP,记为TCPP(Ni)。
(2)称量20mg的CuAl-LDH和40mg的Na-TCPP(Ni)到玻璃容器中,在氮气气氛下,往玻璃容器中加入20mL的去离子水,然后在90℃下反应12h,所得固体产物经过离心、洗涤、干燥,得到固体粉末。将所得干燥后的固体粉末置于马弗炉中以2℃/min加热速率从室温加热至450℃,并在此温度下保持5h。然后再以2℃/min的升温速率升温到280℃,在氢气环境下还原处理3h,得到TCPP(Ni)@CuAl-LDH催化剂。TEM图(如图3所示,图中标尺50nm)中无明显大颗粒存在,证明了催化剂的活性组分分布均匀。镍离子在焙烧处理前处于LDH的二维层间,故焙烧过程中受到“限域空间“效应,使得最终镍活性组分在催化剂微观结构中可以很均匀分布。进一步地,量取50mg该催化剂放入固定床反应器中进行CO2加氢反应性能测试,反应气体浓度为CO2/H2/N2=24%/72%/4%,反应气体流速为20mL/min,反应压力为3MPa。在反应温度250℃下,CO2转化率为4.3%,甲醇的选择性为19.3%,甲烷的选择性为22.0%,一氧化碳的选择性为58.7%。该催化剂经过48h的加氢反应在线测试,催化活性无明显变化。
实施例5
一种用于二氧化碳加氢反应的催化剂的制备方法,包括以下步骤:
(1)将TCPP(Fe)放入玻璃容器中,加入15mL的去离子水和14mg氢氧化钠,在50℃、氮气气氛下充分反应24h,然后将所得固体再进行离心、洗涤、干燥,得到阴离子配体Na-TCPP(Fe);
其中,TCPP(Fe)的制备方法如下:
步骤a:先称量45mg的TCPP固体和95mg的醋酸亚铁固体置于玻璃容器中,并且通入氮气营造氮气气氛;
步骤b:随后加入20mL的N,N-二甲基甲酰胺,然后在80℃下搅拌10h。所得固体产物经过离心、洗涤、干燥,得到含Fe2+的TCPP,记为TCPP(Fe);
(2)称量20mg的CuAl-LDH和15mg的Na-TCPP(Fe)到玻璃容器中,在氮气气氛下,往玻璃容器中加入15mL的去离子水,然后在100℃下反应6h,所得固体产物经过离心、洗涤、干燥,得到固体粉末。将所得干燥后的固体粉末置于马弗炉中以2℃/min加热速率从室温加热至500℃,并在此温度下保持4h。然后再以2℃/min的升温速率升温到300℃,在氢气环境下还原处理2h,得到TCPP(Fe)@CuAl-LDH催化剂。TEM图(如图4所示,图中标尺20nm)中无明显大颗粒存在,证明了催化剂的活性组分分布均匀。铁离子在焙烧处理前处于LDH的二维层间,故焙烧过程中受到“限域空间“效应,使得最终铁活性组分在催化剂微观结构中可以很均匀分布。
进一步地,量取50mg该催化剂放入固定床反应器中进行CO2加氢反应性能测试,反应气体浓度为CO2/H2/N2=24%/72%/4%,反应气体流速为20mL/min,反应压力为3MPa。在反应温度250℃下,CO2转化率为11.1%,甲醇的选择性为41.3%,甲烷的选择性为5.8%,一氧化碳的选择性为52.9%。该催化剂经过48h的加氢反应在线测试,催化活性无明显变化。
本发明公开了一种用于二氧化碳加氢反应的催化剂的制备方法,以层状铜铝水滑石(简称CuAl-LDH)为固体前驱体,利用CuAl-LDH的阴离子交换性质,在惰性保护气氛下将基于中-四(4-羧基苯基)卟吩(meso-Tetra(4-carboxyphenyl)porphine,简称TCPP)或含有过渡金属离子的TCPP(简称TCPP(M))的阴离子配体(即Na-TCPP或Na-TCPP(M))插层于二维层状水滑石的层间区域,再经过高温空气焙烧处理和氢气还原处理后,获得应用于二氧化碳气相加氢反应的催化剂。该制备方法工艺简单、重复性好,所制备的催化剂在温室气体二氧化碳加氢应用方面具有优越的催化性能,还可以通过调控TCPP所负载的过渡金属离子种类(Zn2+、Co2+、Ni2+、Fe2+或Fe3+)来控制催化反应过程中的产物种类(即产物选择性);并且所制备得到的催化剂具有均匀组成、高活性组分分散度、高稳定性和高二氧化碳转化率等优点。
上述实施例和附图并非限定本发明的产品的制备方法,任何所属技术领域的普通技术人员对其所做的适当变化或修饰,皆应视为不脱离本发明的专利范畴。
Claims (9)
1.一种用于二氧化碳加氢反应的催化剂的制备方法,其特征在于,包括以下步骤:
(1)将TCPP或TCPP(M)放置于容器中,加入去离子水和氢氧化钠固体,在20~50℃下和惰性保护气氛中搅拌,反应24小时后,将所得固体产物经过离心、洗涤、干燥,得到阴离子配体Na-TCPP或Na-TCPP(M);
(2)取一定量CuAl-LDH和步骤(1)的阴离子配体Na-TCPP(M)或Na-TCPP放置于容器中,往容器中加入去离子水,在惰性保护气氛和60~100℃下充分搅拌,反应6~12小时,待反应结束后,所得固体产物经过离心、洗涤、干燥、高温焙烧和氢气还原处理,得到用于二氧化碳气相加氢反应的催化剂。
2.如权利要求1所述的一种用于二氧化碳加氢反应的催化剂的制备方法,其特征在于:步骤(1)中,将TCPP(M)放置于容器中,TCPP(M)的制备方法包括如下步骤:
步骤a:将一定量的TCPP和醋酸盐固体放置于容器中,并在该容器中通入保护气体,营造惰性保护气氛;
步骤b:往步骤a中的容器中加入有机溶剂,搅拌至溶解后,得到混合溶液,然后混合溶液在惰性保护气氛和80~200℃条件下反应3~10小时,待反应结束后,将所得固体产物经过离心、洗涤、干燥后,得到含过渡金属离子的TCPP,记为TCPP(M)。
3.根据权利要求2所述的一种用于二氧化碳加氢反应的催化剂的制备方法,其特征在于:步骤(a)中醋酸盐为过渡金属离子醋酸盐,包括醋酸锌、醋酸钴、醋酸镍、醋酸铁和醋酸亚铁中的其中一种或多种混合。
4.如权利要求2所述的一种用于二氧化碳加氢反应的催化剂的制备方法,其特征在于:步骤(b)中所用有机溶剂为N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、N,N-二丁基甲酰胺和N,N-二甲基丙酰胺中的一种或多种混合。
5.如权利要求2所述的一种用于二氧化碳加氢反应的催化剂的制备方法,其特征在于:步骤(1)、步骤(2)、步骤a和步骤b中,惰性保护气氛均为氮气气氛。
6.如权利要求1所述的一种用于二氧化碳加氢反应的催化剂的制备方法,其特征在于:步骤(2)中,CuAl-LDH与阴离子配体Na-TCPP(M)的质量比为1:0.25~2,或者,CuAl-LDH与阴离子配体Na-TCPP的质量比为1:0.25~2。
7.如权利要求1所述的一种用于二氧化碳加氢反应的催化剂的制备方法,其特征在于:步骤(2)中,高温焙烧过程中焙烧温度为200~500℃,焙烧时间为1~10小时。
8.如权利要求1所述的一种用于二氧化碳加氢反应的催化剂的制备方法,其特征在于:步骤(2)中,氢气还原过程中还原温度为250~350℃,还原时间为1~5小时。
9.如权利要求1所述的一种用于二氧化碳加氢反应的催化剂的制备方法,其特征在于:步骤(2)中,CuAl-LDH通过共沉积法、沉积沉淀法、溶胶凝胶法或水热法制备获得。
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