CN108144615A - 一种高分散度蒙脱石基金属镍催化剂及其制备方法和应用 - Google Patents
一种高分散度蒙脱石基金属镍催化剂及其制备方法和应用 Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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Abstract
本发明公开一种高分散度蒙脱石基金属镍催化剂及其制备方法和应用,属于化工技术领域。该催化剂载体为蒙脱石,活性组分为平均粒径小于3.0nm的金属镍颗粒,金属镍的质量不低于催化剂总质量的7.0%。其制备方法是:将蒙脱石与镍盐和水充分搅拌混合,通过用水热合成方法将镍物种引入到分散于水溶液中的蒙脱石纳米片骨架中,高度分散的镍物种经高温还原制得高分散度蒙脱石基金属镍催化剂。本发明高分散度蒙脱石基金属镍催化剂对芳烃化合物加氢反应具有很高的催化活性及金属镍利用效率,同时该催化剂制备方法简单、成本低廉,很适合于工业化生产。
Description
技术领域:
本发明属于化工技术领域,具体涉及一种高分散度蒙脱石基金属镍催化剂、水热合成的制备方法及其在芳烃化合物催化加氢方面的应用。
背景技术:
金属催化剂分散度的改善是提高金属活性组分利用效率及其催化性能的有效手段。前期研究发现蒙脱石基金属镍催化剂表现出较为优异的芳烃加氢性能(中国专利ZL201410632565.1、ZL201310142076.3),采用合适的制备方法以提高金属镍分散度,不仅可促进蒙脱石基金属镍催化剂中金属镍的利用效率和催化剂的芳烃加氢性能,而且利于蒙脱石基金属镍催化剂实现工业化应用。离子交换是制备高分散度沸石分子筛负载金属催化剂的有效方法,尤其是在沸石分子筛负载贵金属催化剂方面得到广泛应用。与沸石分子筛负载金属催化剂相似,蒙脱石(MMT)是层状结构粘土矿物,其层间域存在可交换性水合阳离子,因此,通过离子交换亦是获得高分散度蒙脱石负载金属催化剂的有效制备方法。但是,离子交换法所制催化剂的金属负载量不高,在实际应用中受到了很大限制。本发明采用水热合成的方法制备了高分散度蒙脱石基金属镍催化剂,该制备方法操作过程简单,很适合于工业化生产。
发明内容:
本发明的目的是提供一种高分散度蒙脱石基金属镍催化剂,本发明的另一目的是提供一种成本较低、工艺简单的方法来制备上述催化剂,本发明的另一目的是提供上述催化剂在芳烃化合物加氢反应中的应用。
本发明提供的一种高分散度蒙脱石基金属镍催化剂的制备方法,其步骤如下:
(A)将蒙脱石与水按质量比1:(20~100)混合,室温搅拌2~4h后得到充分水化的蒙脱石水溶液;
(B)将步骤A得到的充分水化的蒙脱石水溶液置于内衬为聚四氟乙烯的不锈钢水热合成釜中,按照与蒙脱石质量比为0.1~0.3:1向所述蒙脱石水溶液分别加入镍盐并搅拌0.5~1小时,在200℃进行水热反应24~72小时,冷却至室温后离心洗涤3次,在100~120℃下干燥8~16小时后得到高分散度蒙脱石基金属镍催化剂前体;
(C)将步骤B得到的高分散度蒙脱石基金属镍催化剂前体通氢气于450~650℃还原3~6小时,在氢气氛围下冷却至室温,通入O2/N2体积比为0.5~1.0%的混合气钝化2~4小时,得到能够直接在空气中保存的所述高分散度蒙脱石基金属镍催化剂。
所述金属镍催化剂的载体为蒙脱石,活性组分为平均粒径小于3.0nm的金属镍颗粒,金属镍的质量不低于催化剂总质量的7.0%。
所述催化剂能够应用在芳烃化合物加氢反应中,所述芳烃化合物为萘。
所述制备方法,其中,步骤A中所述蒙脱石优选为钠基蒙脱石,所用镍盐为硝酸镍、氯化镍、硫酸镍、乙酸镍和甲酸镍中的任一种,优选硝酸镍。
本发明所述的高分散度蒙脱石基金属镍催化剂可以在芳烃化合物(萘)催化加氢方面得到应用。芳烃加氢反应是在40mL不锈钢高压釜中进行。具体步骤和条件如下:依次向高压釜中加入0.05g蒙脱石基金属镍纳米片催化剂、6g质量浓度为20.0wt%萘正十二烷溶液,密封后,先用H2置换3次以除去釜内空气,然后将釜内H2调整到所需压力,在300℃、4.4MPa下反应2.0h,反应产物冷却至室温后取出用气相色谱进行分析。
本发明提供的高分散度蒙脱石基金属镍催化剂,用水热合成方法将镍物种引入到分散于水溶液中的蒙脱石纳米片骨架中,高度分散的镍物种经高温还原制得高分散度蒙脱石基金属镍催化剂。
与现有技术相比,本发明具有以下技术效果:
1)以价廉易得的天然粘土蒙脱石为基体制得高分散度(平均镍粒径小于3.0nm)且镍负载量不低于7.0wt%的负载型金属镍催化剂;
2)催化剂制备方法操作过程简单,很适合于工业化生产;
3)不使用贵金属就可以制备出具有活性高且具有一定抗硫中毒性能的芳烃加氢催化剂。
附图说明:
图1为本发明高分散度蒙脱石基金属镍催化剂的透射电镜照片。
图2为常规浸渍法制备的蒙脱石负载镍催化剂的透射电镜照片。
具体实施方式:
为了进一步说明本发明,例举以下实施例,但它并不限制各权利要求所定义的发明范围。
一、高分散度蒙脱石基金属镍催化剂的制备
实施例1:
称取2g钠基蒙脱石置于200ml烧杯中,加入100ml水室温搅拌3小时获得到充分水化的蒙脱石水溶液,将充分水化的蒙脱石水溶液和3.2g硝酸镍(Ni(NO3)2·6H2O)置于100ml水热反应合成釜中室温搅拌1小时,将水热反应合成釜于200℃进行水热反应24小时,冷却至室温后离心洗涤3次,在100℃下干燥12小时后于450℃通氢气还原2小时,在氢气氛围下冷却至室温,通入O2/N2体积比为1.0%的混合气钝化3小时,得到可直接在空气中保存的蒙脱石基金属镍纳米片催化剂。以Ni/MMT(S)24表示。
使用透射电镜(日本电子株式会社,JEM-1200EX(120KV)),对蒙脱石基金属镍纳米片Ni/MMT(S)24催化剂进行了表征,见图1。为了对比,同时对常规浸渍法制备蒙脱石负载金属镍Ni/MMT催化剂进行了透射电镜表征,见图2。由图1可观察到Ni/MMT(S)24催化剂中金属镍粒子非常均一的分布于蒙脱石的整个表面,金属镍颗粒粒径非常小,通过统计平均粒径约为2.74nm。从局部放大的照片还可清晰地看到完全剥离的蒙脱石单层晶片。而图2中常规浸渍法制备Ni/MMT催化剂的上部金属镍粒子未分散开、团聚较严重;中部的金属镍负载较少,且镍粒子大小和分别很不均一;下部蒙脱石层层堆叠在一起,表面结构不规则,几乎未负载金属镍。这说明Ni/MMT催化剂中镍粒子数目少且粒子大小和分布皆非常不均一,也未观察到蒙脱石单层晶片的存在。
实施例2:
称取2g钠基蒙脱石置于200ml烧杯中,加入100ml水室温搅拌3小时获得到充分水化的蒙脱石水溶液,将充分水化的蒙脱石水溶液和3.2g氯化镍(NiCl2·6H2O)置于100ml水热反应合成釜中室温搅拌1小时,将水热反应合成釜于200℃进行水热反应48小时,冷却至室温后离心洗涤3次,在100℃下干燥12小时后于500℃通氢气还原2小时,在氢气氛围下冷却至室温,通入O2/N2体积比为1.0%的混合气钝化3小时,得到可直接在空气中保存的蒙脱石基金属镍纳米片催化剂。以Ni/MMT(S)48表示。
实施例3:
称取2g钠基蒙脱石置于200ml烧杯中,加入100ml水室温搅拌3小时获得到充分水化的蒙脱石水溶液,将充分水化的蒙脱石水溶液和3.2g甲酸镍(Ni(HCO2)2·2H2O)置于100ml水热反应合成釜中室温搅拌1小时,将水热反应合成釜于200℃进行水热反应72小时,冷却至室温后离心洗涤3次,在100℃下干燥12小时后于600℃通氢气还原2小时,在氢气氛围下冷却至室温,通入O2/N2体积比为1.0%的混合气钝化3小时,得到可直接在空气中保存的蒙脱石基金属镍纳米片催化剂。以Ni/MMT(S)72表示。
二、常规浸渍法制备的金属镍催化剂
对比实施例1:
常规浸渍法制备蒙脱石负载金属镍催化剂。称取2g蒙脱石,按金属镍负载量为10.0wt%取Ni(NO3)2·6H2O溶于60m水中,将蒙脱石缓慢加入其中,室温搅拌1小时,然后在85℃下搅拌蒸干,所得样品在100℃干燥12小时后于550℃通氢气还原4小时,在氢气氛围下冷却至室温,通入O2/N2体积比为1.0%的混合气钝化3小时,得到可直接在空气中保存的蒙脱石负载镍催化剂。以Ni/MMT表示。
三、本发明高度分散蒙脱石基金属镍催化剂对芳烃的催化加氢
实施例4:
Ni/MMT(S)24催化剂的萘加氢活性评价:Ni/MMT(S)24催化剂的萘加氢性能评价是在40mL不锈钢高压釜中进行。具体步骤和条件如下:依次向高压釜中加入0.05g Ni/MMT(S)24催化剂、6g质量浓度为20.0wt%萘正十二烷溶液,密封后,先用H2置换3次以除去釜内空气,然后将釜内H2调整到所需压力,在300℃、4.4MPa下反应2.0h,反应产物冷却至室温后取出用气相色谱进行分析。
Ni/MMT(S)48、Ni/MMT(S)72以及对比例1的Ni/MMT芳烃加氢活性评价与Ni/MMT(S)24一样。
反应结果见表1。
表1不同高度分散蒙脱石基金属镍催化剂的萘加氢性能比较
a催化剂中镍负载量根据元素分析(XRF)测定。
b TON是基于催化剂中单位质量金属镍所转化的萘质量进行计算
反应条件:6.0g萘正十二烷溶液(20.0wt%),0.05g催化剂,300℃,4.4MPa H2,2.0h。
表1结果表明,本发明水热合成所制备的高度分散蒙脱石基金属镍催化剂,与常规浸渍法所制Ni/MMT催化剂相比,不仅萘加氢活性显著提高,Ni/MMT催化剂萘转化率为10.5%,Ni/MMT(S)24催化剂的萘转化率提高至86.0%,约提高了7.2倍,更值得注意的是,其金属镍利用率得到大幅提高,Ni/MMT(S)24的TON值高达246.1,相比Ni/MMT催化剂的17.3,约提高了14.2倍。同时,水热反应时间延长到48和72小时,Ni/MMT(S)48及Ni/MMT(S)72的萘转化率分别为85.6%和54.8%,虽都远高于Ni/MMT催化剂,但催化剂并没有因为水热时间的延长而增加其镍负载量,且萘转化率也较Ni/MMT(S)24有所降低,因此,本发明水热合成催化剂制备方法的最优反应时间为24小时。实验表明:此类催化剂是芳烃加氢饱和以降低煤焦油、煤液化油品、轻质循环油以及生物质所制油品芳烃含量的理想催化剂。
Claims (5)
1.一种高分散度蒙脱石基金属镍催化剂的制备方法,其特征在于该方法具体步骤如下:
(A)将蒙脱石与水按质量比1:(20~100)混合,室温搅拌2~4h后得到充分水化的蒙脱石水溶液;
(B)将步骤A得到的充分水化的蒙脱石水溶液置于内衬为聚四氟乙烯的不锈钢水热合成釜中,按照与蒙脱石质量比为0.1~0.3:1向所述蒙脱石水溶液分别加入镍盐并搅拌0.5~1小时,在200℃进行水热反应24~72小时,冷却至室温后离心洗涤3次,在100~120℃下干燥8~16小时后得到高分散度蒙脱石基金属镍催化剂前体;
(C)将步骤B得到的高分散度蒙脱石基金属镍催化剂前体通氢气于450~650℃还原3~6小时,在氢气氛围下冷却至室温,通入O2/N2体积比为0.5~1.0%的混合气钝化2~4小时,得到能够直接在空气中保存的所述高分散度蒙脱石基金属镍催化剂。
2.根据权利要求1所述的高分散度蒙脱石基金属镍催化剂的制备方法,其特征在于所述步骤A中的所述蒙脱石为钠基蒙脱石。
3.根据权利要求1所述的高分散度蒙脱石基金属镍催化剂的制备方法,其特征在于所述步骤A中的所述镍盐为硝酸镍、氯化镍、硫酸镍、乙酸镍和甲酸镍中的任一种。
4.一种由权利要求1所述方法制备的高分散度蒙脱石基金属镍催化剂,其特征在于所述金属镍催化剂的载体为蒙脱石,活性组分为平均粒径小于3.0nm的金属镍颗粒,金属镍的质量不低于催化剂总质量的7.0%。
5.权利要求1所述高分散度蒙脱石基金属镍催化剂的应用,其特征在于所述催化剂能够应用在芳烃化合物加氢反应中,所述芳烃化合物为萘。
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