CN112452328A - NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法 - Google Patents
NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种NiO@SiO2@CoAl‑LDH多级核壳催化剂的制备方法,其特征在于,将镍源与聚乙烯吡咯烷酮溶解于醇溶液中反应,得到NiO纳米颗粒;加入到乙醇、去离子水、氨水和十六烷基三甲基溴化铵的混合溶液中,再加入正硅酸乙酯,得到NiO@SiO2,将其分散在铝溶胶中,重复多次,得到不同铝溶胶包裹厚度的NiO@SiO2@AlOOH;将钴源与NH4F溶解于去离子水中,加入NiO@SiO2@AlOOH,反应;干燥、焙烧、还原后,即得Ni@SiO2@Co‑Al2O3多级核壳催化剂。本发明具有多级核壳结构,能够更大程度地提高Ni的抗积碳以及抗烧结能力,极大提高催化剂的稳定性以及寿命。
Description
技术领域
本发明属于能源利用和环境技术领域,涉及一种NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法及其在甲烷二氧化碳重整反应中的应用。
背景技术
为解决温室气体(CH4、CO2)浓度上升引起的全球变暖问题,CH4和CO2的去除、处理和化学利用已成为研究的重点。甲烷二氧化碳干重整(DRM)不仅能够将这两种主要的温室气体转化为具有工业价值的合成气(VH2/VCO≈1),且该合成气可用于长链烃或含氧化合物的合成。Ni基催化剂由于其低的经济成本和高的活性被认为是最有工业化前景的催化剂。但在苛刻的重整条件下,Ni基催化剂容易因烧结和积碳而失活。因此,开发出一种高稳定且抗积碳、抗烧结的Ni催化剂是本文的主要的研究目标。
改进的途径主要为以下几个方面:减小Ni颗粒的尺寸、提高Ni颗粒的分散性、控制催化剂的酸碱性、选择性钝化活性金属Ni、设计并调控催化剂的结构等。近年来新型多功能核壳型复合材料因其独特的结构和性质而被广泛应用于催化领域的研究,核壳催化剂由于其纳米金属活性粒子被外层包覆而起到一定的保护作用,在催化反应的过程中,尤其是高温反应中能够有效抑制活性金属纳米粒子的长大。因此,设计并合成核壳结构的纳米Ni基催化剂,将会有望解决催化剂积炭和烧结这两大限制Ni基催化剂在甲烷二氧化碳反应中应用的关键问题。
专利CN107262097A公开了一种NiCo/SiO2核壳催化剂的制备方法。其先制备了NiCo合金纳米粒子,然后加入硅源,再搅拌反应,用甲醇沉降固体产物,并离心洗涤,洗涤后样品经干燥后,高温焙烧后得到NiCo/SiO2核壳催化剂。其反应活性较高,但是其反应寿命还不够长,Ni颗粒尺寸不可控,并且NiCo合金的协同作用需要一定的间距才能最大程度地发挥其作用。
发明内容
本发明所要解决的技术问题是:如何提高现有Ni活性中心的抗烧结以及抗积碳能力。
为了解决上述技术问题,本发明提供了一种NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法,其特征在于,包括以下步骤:
步骤1):将镍源与聚乙烯吡咯烷酮溶解于醇溶液中,搅拌至溶解后转移入聚四氟乙烯内衬的水热釜中进行水热反应,反应完毕后,过滤,洗涤干燥后得到NiO纳米颗粒;
步骤2):配制乙醇、去离子水、氨水和十六烷基三甲基溴化铵的混合溶液,然后向该混合溶液中投入步骤1)所得NiO纳米颗粒,超声分散10-60min,室温下继续搅拌0.5-3h,使NiO纳米颗粒均匀分散在溶液中;在剧烈搅拌下向NiO溶液中缓慢加入正硅酸乙酯,于室温下反应,将所得产物用乙醇洗涤,然后干燥、焙烧后得到NiO@SiO2;
步骤3):将步骤2)所得NiO@SiO2分散在铝溶胶中,剧烈搅拌,过滤,然后用无水乙醇洗涤,并在室温下干燥,完成第一次铝溶胶包裹,得到NiO@SiO2@AlOOH;将得到的NiO@SiO2@AlOOH再次分散在铝溶胶中,根据需要重复上述操作多次,得到不同铝溶胶包裹厚度的NiO@SiO2@AlOOH;
步骤4):将钴源与NH4F溶解于去离子水中配成溶液,再将步骤3)所得NiO@SiO2@AlOOH加入到该溶液中,然后将所得到的溶液转移至聚四氟乙烯内衬的水热釜中,于烘箱中反应;然后将所得到的产物离心洗涤至中性,并在烘箱中干燥,最后得到NiO@SiO2@CoAl-LDH;
步骤5):将步骤4)所得NiO@SiO2@CoAl-LDH在马弗炉中焙烧得到氧化物催化剂,然后在反应器中经H2气还原后,即制得Ni@SiO2@Co-Al2O3多级核壳催化剂。
优选地,所述步骤1)中镍源为乙酸镍;醇溶液为甲醇、乙醇、丙醇和乙二醇中至少一种的水溶液,所述醇与水的体积比为1:(0.1~1);乙酸镍与聚乙烯吡咯烷酮的比例为1mmol:(1~8g);镍与醇溶液的比例为1mmol:(50~400)mL;聚乙烯吡咯烷酮的分子量为54,000。
优选地,所述步骤1)中水热反应的温度为100~180℃,时间为6~16h。
优选地,所述步骤2)中镍与乙醇和去离子水体积之和的比例为1mmol:(50~300)mL;混合溶液中乙醇、去离子水、氨水的体积比为50:50:(1~8);十六烷基三甲基溴化铵与Ni的摩尔比为(1~10):1;正硅酸乙酯使用量以Si与Ni的摩尔比(0.5~4):1为准。
优选地,所述步骤2)中反应的时间为12~36h,焙烧的温度为400~700℃。
优选地,所述步骤3)中铝溶胶为AlOOH,NiO@SiO2与AlOOH的比例为1mmol:10~50mL;重复的次数为2~20次。
优选地,所述步骤3)中剧烈搅拌的时间为1h;干燥的时间为1h。
优选地,所述步骤4)中钴源为硝酸钴;NiO@SiO2@AlOOH、钴、NH4F的摩尔比为(0.3~1.5):1:1.5;钴与去离子水的比例为1mmol:20~60mL。
优选地,所述步骤4)中反应的温度为80~150℃,时间为12~60h。
优选地,所述步骤5)中焙烧的温度为400~800℃,时间为4~12h。
与现有技术相比,本发明具有如下优点:
(1)水热法可以通过控制反应温度,反应时长等条件较容易地控制Ni的尺寸大小,保证Ni具有较小的颗粒尺寸,因此具有更好的催化性能和稳定性。
(2)催化剂具有多级核壳结构,能够更大程度地提高Ni的抗积碳以及抗烧结能力,极大提高催化剂的稳定性以及寿命。
(3)催化剂的制备方法每一步都可以实现工业化放大,并且制备催化剂的收率较高,不会造成资源浪费。
(4)催化剂中含有磁性金属Co,因此对于催化剂的回收可以使用磁铁,更为便利地实现工业上的催化剂回收问题。
附图说明
图1为本发明提供的催化剂的合成示意图。
具体实施方式
为使本发明更明显易懂,兹以优选实施例,并配合附图作详细说明如下。
对实施例中制得的NiO@SiO2@CoAl-LDH催化剂以及对比例中制备的NiO,Co3O4以及Al2O3负载在SiO2载体上的催化剂用于甲烷二氧化碳重整反应评价过程如下:
称取0.1g(80-100目)催化剂与石英砂0.9g(80-100目)混合均匀,于H2/N2气氛(体积百分比各50%,流速120mL/min)、700℃预还原2h。还原完毕后,反应温度为850℃,原料气中甲烷和二氧化碳比为1.2,N2作为内标占3%。原料气流速为141.7mL/min,空速为85000mL/(gh),原料气直接经过催化剂床层。通过气相色谱TCD采用内标法计算即可得到CH4,CO2转化率以及产物CO与H2的比值。在所有实施例中所展示的评价数据均为评价反应500h后的评价数据。
实施例1
首先将1.25g四水乙酸镍与10g聚乙烯吡咯烷酮溶解于丙醇溶液中,醇与水的体积比为1:1。搅拌至溶解后转移入聚四氟乙烯内衬的水热釜中进行水热反应,丙醇溶液体积为1500mL,水热反应温度为120℃,水热反应时长为16h。过滤洗涤后得到NiO纳米颗粒。
NiO纳米颗粒超声60min后,使其均匀分散在溶液中,依次向其中加入乙醇,去离子水,氨水,以及十六烷基三甲基溴化铵(CTAB);乙醇、去离子水、氨水混合溶液体积分别为250mL、250mL、10mL;十六烷基三甲基溴化铵加入量为7.29g;室温下继续搅拌3h,使NiO纳米颗粒均匀分散在溶液中。然后向其中缓慢加入正硅酸乙酯,正硅酸乙酯使用量为3.12g。然后室温下伴随剧烈搅拌反应24h,将所得产物用乙醇洗涤,然后在烘箱中干燥,700℃下焙烧6h最终得到NiO@SiO2。
NiO@SiO2分散在AlOOH溶胶并在烧杯中剧烈搅拌1h,AlOOH体积为250mL;然后用无水乙醇洗涤,并在空气中干燥,完成第一次铝溶胶包裹;重复上述操作10次,得到NiO@SiO2@AlOOH。
然后继续加入六水硝酸钴与NH4F溶解于去离子水中配成溶液,将NiO@SiO2@AlOOH均匀分散在溶液中,六水硝酸钴和NH4F分别加入2.43g和0.46g。去离子水体积为200mL;溶液在烘箱中进行水热反应。反应温度为100℃,反应时间为12h。产物经过离心洗涤,干燥,400℃下焙烧4h后得到多级核壳结构催化剂。在反应器中的还原温度为700℃,还原时间为2h。
通过XRD,TEM等表征结果可以发现Ni颗粒的平均粒径为13.6nm。再将其装入甲烷重整评价装置中,评价结果表明其CO2转化率为78.56%,CH4转化率为81.73%,H2/CO为0.80。
实施例2
首先将1.25g四水乙酸镍与5g聚乙烯吡咯烷酮溶解于甲醇溶液中,醇与水的体积比为1:0.3。搅拌至溶解后转移入聚四氟乙烯内衬的水热釜中进行水热反应,甲醇溶液体积为2000mL,水热反应温度为100℃,水热反应时长为8h。过滤洗涤后得到NiO纳米颗粒。
NiO纳米颗粒超声60min后,使其均匀分散在溶液中,依次向其中加入乙醇,去离子水,氨水,以及十六烷基三甲基溴化铵(CTAB);乙醇、去离子水、氨水混合溶液体积分别为750mL、750mL、15mL;十六烷基三甲基溴化铵加入量为3.65g;室温下继续搅拌3h,使NiO纳米颗粒均匀分散在溶液中。然后向其中缓慢加入正硅酸乙酯,正硅酸乙酯使用量为2.60g。然后室温下伴随剧烈搅拌反应12h,将所得产物用乙醇洗涤,然后在烘箱中干燥,500℃下焙烧6h最终得到NiO@SiO2。
NiO@SiO2分散在AlOOH溶胶并在烧杯中剧烈搅拌1h,AlOOH体积为100mL;然后用无水乙醇洗涤,并在空气中干燥,完成第一次铝溶胶包裹;重复上述操作5次,得到NiO@SiO2@AlOOH。
然后继续加入硝酸钴与NH4F溶解于去离子水中配成溶液,将NiO@SiO2@AlOOH均匀分散在溶液中,六水硝酸钴和NH4F分别加入1.46g和0.28g。去离子水体积为150mL;溶液在烘箱中进行水热反应。反应温度为150℃,反应时间为12h。产物经过离心洗涤,干燥,400℃下焙烧8h后得到多级核壳结构催化剂。在反应器中的还原温度为700℃,还原时间为2h。
通过XRD,TEM等表征结果可以发现Ni颗粒的平均粒径为12.1nm。再将其装入甲烷重整评价装置中,评价结果表明其CO2转化率为80.12%,CH4转化率为84.37%,H2/CO为0.81。
实施例3
首先将1.25g四水乙酸镍与20g聚乙烯吡咯烷酮,溶解于乙醇溶液中,醇与水的体积比为1:0.5。搅拌至溶解后转移入聚四氟乙烯内衬的水热釜中进行水热反应,乙醇溶液体积为500mL,水热反应温度为140℃,水热反应时长为8h。过滤洗涤后得到NiO纳米颗粒。
NiO纳米颗粒超声60min后,使其均匀分散在溶液中,依次向其中加入乙醇,去离子水,氨水,以及十六烷基三甲基溴化铵(CTAB);乙醇、去离子水、氨水混合溶液体积分别为250mL、250mL、20mL;十六烷基三甲基溴化铵加入量为9.11g;室温下继续搅拌3h,使NiO纳米颗粒均匀分散在溶液中。然后向其中缓慢加入正硅酸乙酯,正硅酸乙酯使用量为2.08g。然后室温下伴随剧烈搅拌反应24h,将所得产物用乙醇洗涤,然后在烘箱中干燥,500℃下焙烧6h最终得到NiO@SiO2。
NiO@SiO2分散在AlOOH溶胶并在烧杯中剧烈搅拌1h,AlOOH体积为100mL;然后用无水乙醇洗涤,并在空气中干燥,完成第一次铝溶胶包裹;重复上述操作10次,得到NiO@SiO2@AlOOH。
然后继续加入硝酸钴与NH4F溶解于去离子水中配成溶液,将NiO@SiO2@AlOOH均匀分散在溶液中,六水硝酸钴和NH4F分别加入1.46g和0.28g。去离子水体积为250mL;溶液在烘箱中进行水热反应。反应温度为100℃,反应时间为48h。产物经过离心洗涤,干燥,700℃下焙烧8h后得到多级核壳结构催化剂。在反应器中的还原温度为700℃,还原时间为2h。
通过XRD,TEM等表征结果可以发现Ni颗粒的尺寸很小,其平均粒径为7.4nm。再将其装入甲烷重整评价装置中,评价结果表明其CO2转化率为90.36%,CH4转化率为94.51%,H2/CO为0.89,其在评价1000h内,未见其失活,具有非常良好的催化性能。
实施例4
首先将1.25g四水乙酸镍与40g聚乙烯吡咯烷酮溶解于乙二醇溶液中,醇与水的体积比为1:0.1。搅拌至溶解后转移入聚四氟乙烯内衬的水热釜中进行水热反应,乙二醇溶液体积为250mL,水热反应温度为180℃,水热反应时长为6h。过滤洗涤后得到NiO纳米颗粒。
NiO纳米颗粒超声60min后,使其均匀分散在溶液中,依次向其中加入乙醇,去离子水,氨水,以及十六烷基三甲基溴化铵(CTAB);乙醇、去离子水、氨水混合溶液体积分别为125mL、125mL、20mL;十六烷基三甲基溴化铵加入量为18.22g;室温下继续搅拌3h,使NiO纳米颗粒均匀分散在溶液中。然后向其中缓慢加入正硅酸乙酯,正硅酸乙酯使用量为0.52g。然后室温下伴随剧烈搅拌反应36h,将所得产物用乙醇洗涤,然后在烘箱中干燥,400℃下焙烧6h最终得到NiO@SiO2。
NiO@SiO2分散在AlOOH溶胶并在烧杯中剧烈搅拌1h,AlOOH体积为50mL;然后用无水乙醇洗涤,并在空气中干燥,完成第一次铝溶胶包裹;重复上述操作20次,得到NiO@SiO2@AlOOH。
然后继续加入硝酸钴与NH4F溶解于去离子水中配成溶液,将NiO@SiO2@AlOOH均匀分散在溶液中,六水硝酸钴和NH4F分别加入0.97g和0.19g。去离子水体积为300mL;溶液在烘箱中进行水热反应。反应温度为80℃,反应时间为60h。产物经过离心洗涤,干燥,800℃下焙烧12h后得到多级核壳结构催化剂。在反应器中的还原温度为700℃,还原时间为2h。
通过XRD,TEM等表征结果可以发现Ni颗粒的平均粒径为15.4nm。再将其装入甲烷重整评价装置中,评价结果表明其CO2转化率为75.12%,CH4转化率为78.51%,H2/CO为0.80。
实施例5
首先将1.25g四水乙酸镍与20g聚乙烯吡咯烷酮,溶解于乙醇溶液中,醇与水的体积比为1:0.7。搅拌至溶解后转移入聚四氟乙烯内衬的水热釜中进行水热反应,乙醇溶液比例为500mL,水热反应温度为120℃,水热反应时长为8h。过滤洗涤后得到NiO纳米颗粒。
NiO纳米颗粒超声60min后,使其均匀分散在溶液中,依次向其中加入乙醇,去离子水,氨水,以及十六烷基三甲基溴化铵(CTAB),乙醇、去离子水、氨水混合溶液体积分别为500mL、500mL、40mL;十六烷基三甲基溴化铵加入量为12.75g;室温下继续搅拌3h,使NiO纳米颗粒均匀分散在溶液中。然后向其中缓慢加入正硅酸乙酯,正硅酸乙酯使用量为4.16g。然后室温下伴随剧烈搅拌反应24h,将所得产物用乙醇洗涤,然后在烘箱中干燥,500℃下焙烧6h最终得到NiO@SiO2。
NiO@SiO2分散在AlOOH溶胶并在烧杯中剧烈搅拌1h,AlOOH体积为100mL;然后用无水乙醇洗涤,并在空气中干燥,完成第一次铝溶胶包裹;重复上述操作2次,得到NiO@SiO2@AlOOH。
然后继续加入硝酸钴与NH4F溶解于去离子水中配成溶液,将NiO@SiO2@AlOOH均匀分散在溶液中,六水硝酸钴和NH4F分别加入2.43g和0.46g。去离子水体积为250mL;溶液在烘箱中进行水热反应。反应温度为120℃,反应时间为48h。产物经过离心洗涤,干燥,600℃下焙烧8h后得到多级核壳结构催化剂。在反应器中的还原温度为700℃,还原时间为2h。
通过XRD,TEM等表征结果可以发现Ni颗粒的平均粒径为9.7nm。再将其装入甲烷重整评价装置中,评价结果表明其CO2转化率为82.11%,CH4转化率为85.86%,H2/CO为0.82。
实施例6
首先将1.25g四水乙酸镍与20g聚乙烯吡咯烷酮,溶解于乙醇溶液中,醇与水的体积比为1:0.9。搅拌至溶解后转移入聚四氟乙烯内衬的水热釜中进行水热反应,乙醇溶液比例为1000mL,水热反应温度为160℃,水热反应时长为8h。过滤洗涤后得到NiO纳米颗粒。
NiO纳米颗粒超声60min后,使其均匀分散在溶液中,依次向其中加入乙醇,去离子水,氨水,以及十六烷基三甲基溴化铵(CTAB),乙醇、去离子水、氨水混合溶液体积分别为250mL、250mL、30mL;十六烷基三甲基溴化铵加入量为16.40g;室温下继续搅拌3h,使NiO纳米颗粒均匀分散在溶液中。然后向其中缓慢加入正硅酸乙酯,正硅酸乙酯使用量为1.04g。然后室温下伴随剧烈搅拌反应24h,将所得产物用乙醇洗涤,然后在烘箱中干燥,600℃下焙烧6h最终得到NiO@SiO2。
NiO@SiO2分散在AlOOH溶胶并在烧杯中剧烈搅拌1h,AlOOH体积为100mL;然后用无水乙醇洗涤,并在空气中干燥,完成第一次铝溶胶包裹;重复上述操作2次,得到NiO@SiO2@AlOOH。
然后继续加入硝酸钴与NH4F溶解于去离子水中配成溶液,将NiO@SiO2@AlOOH均匀分散在溶液中,六水硝酸钴和NH4F分别加入1.46g和0.28g。去离子水体积为100mL;溶液在烘箱中进行水热反应。反应温度为100℃,反应时间为48h。产物经过离心洗涤,干燥,700℃下焙烧6h后得到多级核壳结构催化剂。在反应器中的还原温度为700℃,还原时间为2h。
通过XRD,TEM等表征结果可以发现Ni颗粒的平均粒径为8.3nm。再将其装入甲烷重整评价装置中,评价结果表明其CO2转化率为84.24%,CH4转化率为86.68,H2/CO为0.82。
实施例7
首先将1.25g四水乙酸镍与20g聚乙烯吡咯烷酮,溶解于乙醇溶液中,醇与水的体积比为1:0.5。搅拌至溶解后转移入聚四氟乙烯内衬的水热釜中进行水热反应,乙醇溶液比例为500mL,水热反应温度为140℃,水热反应时长为8h。过滤洗涤后得到NiO纳米颗粒。
NiO纳米颗粒超声60min后,使其均匀分散在溶液中,依次向其中加入乙醇,去离子水,氨水,以及十六烷基三甲基溴化铵(CTAB),乙醇、去离子水、氨水混合溶液体积分别为250mL、250mL、35mL;十六烷基三甲基溴化铵加入量为9.11g;室温下继续搅拌3h,使NiO纳米颗粒均匀分散在溶液中。然后向其中缓慢加入正硅酸乙酯,正硅酸乙酯使用量为2.08g。然后室温下伴随剧烈搅拌反应24h,将所得产物用乙醇洗涤,然后在烘箱中干燥,700℃下焙烧6h最终得到NiO@SiO2。
NiO@SiO2分散在AlOOH溶胶并在烧杯中剧烈搅拌1h,AlOOH体积为100mL;然后用无水乙醇洗涤,并在空气中干燥,完成第一次铝溶胶包裹;重复上述操作10次,得到NiO@SiO2@AlOOH。。
然后继续加入硝酸钴与NH4F溶解于去离子水中配成溶液,将NiO@SiO2@AlOOH均匀分散在溶液中,六水硝酸钴和NH4F分别加入4.85g和0.93g。去离子水体积为250mL;溶液在烘箱中进行水热反应。反应温度为100℃,反应时间为48h。产物经过离心洗涤,干燥,700℃下焙烧8h后得到多级核壳结构催化剂。在反应器中的还原温度为700℃,还原时间为2h。
通过XRD,TEM等表征结果可以发现Ni颗粒的平均粒径为7.9nm。再将其装入甲烷重整评价装置中,评价结果表明其CO2转化率为86.51%,CH4转化率为88.97,H2/CO/为0.84。
对比例1
将硝酸镍,硝酸钴以及硝酸铝按Ni:Co:Al摩尔比为1:1:1溶解于50mL的去离子水中,然后通过等体积浸渍法将上述溶液浸渍到商用SiO2载体上,SiO2与Ni的摩尔比为1:1。上述操作可以将Ni,Co,Al三种元素均匀的负载在SiO2载体上。再使其在静态空气下马弗炉中700℃焙烧4h得到NiO,Co3O4以及Al2O3负载在SiO2载体上的催化剂。
通过XRD,TEM等表征结果可以发现Ni颗粒的尺寸非常不均一,并且存在团聚现象,其平均颗粒尺寸为25nm。再将上述催化剂装入甲烷重整评价装置中,评价结果表明其CO2转化率仅为50.48%,CH4转化率为55.89%,H2/CO为0.73,其在评价50h内,活性不断降低,最后积碳严重导致反应管堵死,说明其催化性能以及稳定性不佳。
Claims (10)
1.一种NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法,其特征在于,包括以下步骤:
步骤1):将镍源与聚乙烯吡咯烷酮溶解于醇溶液中,搅拌至溶解后转移入聚四氟乙烯内衬的水热釜中进行水热反应,反应完毕后,过滤,洗涤干燥后得到NiO纳米颗粒;
步骤2):配制乙醇、去离子水、氨水和十六烷基三甲基溴化铵的混合溶液,然后向该混合溶液中投入步骤1)所得NiO纳米颗粒,超声分散10-60min,室温下继续搅拌0.5-3h,使NiO纳米颗粒均匀分散在溶液中;在剧烈搅拌下向NiO溶液中缓慢加入正硅酸乙酯,于室温下反应,将所得产物用乙醇洗涤,然后干燥、焙烧后得到NiO@SiO2;
步骤3):将步骤2)所得NiO@SiO2分散在铝溶胶中,剧烈搅拌,过滤,然后用无水乙醇洗涤,并在室温下干燥,完成第一次铝溶胶包裹,得到NiO@SiO2@AlOOH;将得到的NiO@SiO2@AlOOH再次分散在铝溶胶中,根据需要重复上述操作多次,得到不同铝溶胶包裹厚度的NiO@SiO2@AlOOH;
步骤4):将钴源与NH4F溶解于去离子水中配成溶液,再将步骤3)所得NiO@SiO2@AlOOH加入到该溶液中,然后将所得到的溶液转移至聚四氟乙烯内衬的水热釜中,于烘箱中反应;然后将所得到的产物离心洗涤至中性,并在烘箱中干燥,最后得到NiO@SiO2@CoAl-LDH;
步骤5):将步骤4)所得NiO@SiO2@CoAl-LDH在马弗炉中焙烧得到氧化物催化剂,然后在反应器中经H2气还原后,即制得Ni@SiO2@Co-Al2O3多级核壳催化剂。
2.如权利要求1所述的NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法,其特征在于,所述步骤1)中镍源为乙酸镍;醇溶液为甲醇、乙醇、丙醇和乙二醇中至少一种的水溶液,所述醇与水的体积比为1:(0.1~1);乙酸镍与聚乙烯吡咯烷酮的比例为1mmol:(1~8g);镍与醇溶液的比例为1mmol:(50~400)mL;聚乙烯吡咯烷酮的分子量为54,000。
3.如权利要求1所述的NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法,其特征在于,所述步骤1)中水热反应的温度为100~180℃,时间为6~16h。
4.如权利要求1所述的NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法,其特征在于,所述步骤2)中镍与乙醇和去离子水体积之和的比例为1mmol:(50~300)mL;混合溶液中乙醇、去离子水、氨水的体积比为50:50:(1~8);十六烷基三甲基溴化铵与Ni的摩尔比为(1~10):1;正硅酸乙酯使用量以Si与Ni的摩尔比(0.5~4):1为准。
5.如权利要求1所述的NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法,其特征在于,所述步骤2)中反应的时间为12~36h,焙烧的温度为400~700℃。
6.如权利要求1所述的NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法,其特征在于,所述步骤3)中铝溶胶为AlOOH,NiO@SiO2与AlOOH的比例为1mmol:10~50mL;重复的次数为2~20次。
7.如权利要求1所述的NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法,其特征在于,所述步骤3)中剧烈搅拌的时间为1h;干燥的时间为1h。
8.如权利要求1所述的NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法,其特征在于,所述步骤4)中钴源为硝酸钴;NiO@SiO2@AlOOH、钴、NH4F的摩尔比为(0.3~1.5):1:1.5;钴与去离子水的比例为1mmol:20~60mL。
9.如权利要求1所述的NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法,其特征在于,所述步骤4)中反应的温度为80~150℃,时间为12~60h。
10.如权利要求1所述的NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法,其特征在于,所述步骤5)中焙烧的温度为400~800℃,时间为4~12h。
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