CN110339856A - 一种以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂及其制备方法与应用 - Google Patents
一种以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂及其制备方法与应用 Download PDFInfo
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
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- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
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- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种以介孔SiO2分子筛KIT‑6为载体的镍基甲烷化催化剂,以介孔SiO2分子筛KIT‑6为载体,以金属Ni为活性组分;其中,以100重量份的催化剂为基准,以金属元素计,镍的含量为3~10重量份,余量为介孔SiO2分子筛KIT‑6。本发明还公开了一种所述以介孔SiO2分子筛KIT‑6为载体的镍基甲烷化催化剂的制备方法及在合成气制甲烷中的用途。本发明的以介孔SiO2分子筛KIT‑6为载体的镍基甲烷化催化剂,是以化学性质稳定、比表面积大和热传导性质好的介孔SiO2分子筛KIT‑6为载体,制备的催化剂具有金属分散度高、催化活性高、热稳定性好以及催化剂寿命较长等优点。
Description
技术领域
本发明属于精细化工技术领域,涉及一种以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂及其制备方法与应用。
背景技术
近年来,随着石油燃料的日益枯竭以及工业上大量排放污染物造成生态环境问题日益严重,将煤炭、生物质的合成气进行甲烷化技术越来越受到人们的关注。合成气可以通过净化、调节氢碳比后进行甲烷化过程制备甲烷及代用天然气(SNG)。煤制天然气技术是将高碳能源向低碳、富氢能源转化,这样既提高了热能有效利用率(53%),也对煤炭资源的高效洁净综合利用具有重要的意义。
Ni基催化剂由于其价格相对适宜、催化活性较高,成为煤气化制备代用天然气甲烷化反应的主要催化剂。目前镍基催化剂的制备方法通常是以其盐类与其它金属盐进行共沉淀或者将其盐溶液浸渍多孔性载体,然后进行焙烧和还原得到催化剂样品。采用这些方法,活性组分Ni不易高度分散,且在后续的高温处理和还原过程中易造成金属Ni微晶的团聚,从而进一步降低分散度,影响催化活性。
此外,对于高温甲烷化反应***,稳定的载体是非常关键的。有序介孔材料以其高比表面积、热稳定性较好、易于修饰和对金属活性组分较好的分散作用等特性,已在催化化学领域中被广泛应用。由于介孔分子筛多是纯SiO2,不具有催化活性,因此在这些分子筛中掺入金属/金属氧化物或对它们进行表面改性是目前将这些分子筛用于催化领域的有效方法。通过浸渍法可将金属/金属氧化物负载到介孔分子筛上,但是金属/金属氧化物大多分布于介孔分子筛表面且很难分散均匀。有研究表明,采用浸渍法制备Ni/Al2O3时,表面活性剂的加入有效地抑制了金属的蛋壳型分布,从而使金属在载体表面的分布更加均匀。此外,还有很多学者研究了表面活性剂对于金属催化剂中金属分散及催化性能的影响,但大多运用的是沉积沉淀法制备催化剂,这种方法相较浸渍法来说,制备过程较繁琐,成本较高。因此,需要寻找一种简单易操作的方法制备高分散镍基甲烷化催化剂,在保证高活性的同时,还需要具备优良的耐高温性能和稳定性。
发明内容
为了克服现有技术中活性组分在载体表面分散性差的缺陷,本发明的目的在于提供一种分散性好、具有优良合成气甲烷化活性的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂。
本发明的另一个目的是提供一种所述以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂的制备方法,该方法简单方便。
本发明的再一个目的是提供一种所述以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂的应用。
为了实现上述目的,本发明采用的技术方案如下:
本发明的一个方面提供了一种以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂,以介孔SiO2分子筛KIT-6(Ia3d)为载体,以金属Ni为活性组分;其中,以100重量份的催化剂为基准,以金属元素计,镍的含量为3~10重量份,余量为介孔SiO2分子筛KIT-6。
所述以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂的比表面积为500~1000m2/g,优选为835m2/g,孔径为3~12nm,优选为6.0nm,孔体积为0.4~1.4m3/g,优选为1cm3/g。
所述介孔SiO2分子筛KIT-6的比表面积为500~1000m2/g,优选为600~835m2/g,孔径为3~12nm,优选为4~10nm,孔壁为2~6nm,孔体积为0.4~1.4cm3/g,优选为0.8~1cm3/g;
所述活性组分Ni以NiO、Ni2O3的形式存在。
本发明的另一个方面提供了一种所述以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂的制备方法,包括以下步骤:
将镍盐溶于溶剂中,并加入添加剂配成镍盐的溶液,然后加入干燥的介孔SiO2分子筛KIT-6,采用等体积浸渍法将介孔SiO2分子筛KIT-6浸渍于镍盐的溶液中,搅拌后静置、真空干燥、焙烧、磨碎、筛分,得到所述以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂。
所述镍盐为氯化镍、硫酸镍、醋酸镍、草酸镍、硝酸镍中的至少一种。
所述溶剂为去离子水、甲醇、乙醇、乙酸、乙酸乙酯、氯仿、丙酮中的至少一种。
所述添加剂为柠檬酸、葡萄糖、乙二醇、甘油、山梨醇等有机小分子添加剂中的至少一种。
所述添加剂与所述镍盐的质量比为(0.3~1.5):1;并会在催化剂焙烧过程中除去,不在催化剂成分中。在催化剂制备过程中,通过加入这些添加剂,可以减小活性组分颗粒的尺寸大小,使其均匀的分散于载体的孔道内,同时由于分子筛孔道具有限域作用,在催化剂还原过程中也能防止其烧结,进而提高催化剂中活性组分镍的分散度,最终影响催化剂的活性和稳定性。
所述镍盐与介孔SiO2分子筛KIT-6的质量比为(0.1~0.6):1。
所述等体积浸渍法的温度为室温,时间为2~12h,优选为4~6h。
所述真空干燥的温度为30~80℃,优选为50~70℃,时间为1~12h,优选为2~6h。
所述焙烧的温度为400~800℃,优选为400~600℃,时间为0.5~10h,优选为0.5~2h。
所述筛分是通过200目的分样筛筛分。
所述干燥的介孔SiO2分子筛KIT-6是在温度为50~200℃的条件下干燥,时间为2~24h。
本发明的再一个方面还提供了一种所述以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂在合成气制甲烷中的用途。
所述合成气制甲烷的条件如下:合成气体积空速为3000~30000h-1,压力为常压至3.0MPa,温度为300~500℃,合成气中H2/CO比值为2~4。
由于采用上述技术方案,本发明具有以下优点和有益效果:
本发明的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂,在合成气制甲烷反应中显示出优越的活性和甲烷选择性,在300~500℃的温度区间内都有活性,其中300~400℃的温度范围内,催化剂的活性最好,CO转化率可以达到100%,甲烷选择性达到99.9%,极具工业化前景。
本发明的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂,是以化学性质稳定、比表面积大和热传导性质好的介孔SiO2分子筛KIT-6为载体,制备的催化剂具有金属分散度高、催化活性高、热稳定性好(经过700℃高温煅烧2h催化活性不下降)以及催化剂寿命较长(100h寿命实验催化活性无下降)等优点,该催化剂不含有贵金属组分,制备方法简单易行,Ni含量低,且催化性能较高,在性价比上有较大的优势。
本发明的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂,镍颗粒尺寸小,分散均匀,金属比表面积大,且金属组分进入分子筛孔道内部,用于合成气制甲烷这一强放热反应中,具有催化活性高、甲烷选择性好、热稳定性好、催化剂寿命较长等优点。
本发明的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂,介孔分子筛载体KIT-6是三维柱状SiO2分子筛材料,孔径大小介于较传统的MCM-41和SBA-15之间,三维结构使物料传质效果更好,克服了活性组分堵塞分子筛孔道问题,分子筛壁中含有次级介孔和微孔,可以起到活性组分陷域效果,防止高温下活性组分热迁移烧结。其在吸附、生物医药、新材料加工尤其催化等领域都展现出广泛的潜在应用前景。
附图说明
图1为实施例1中5Ni-KIT-6-CA的TEM图。
图2为实施例8中5Ni-KIT-6-CA经过原料气氛围下650℃焙烧2h后的TEM图。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
下列实施例中未注明具体条件的实验方法,通常按照常规条件或按照制造厂商所建议的条件。除非另外说明,否则所有的百分数、比率、比例或份数按重量计。
本发明中的重量体积百分比中的单位是本领域技术人员所熟知的,例如是指在100毫升的溶液中溶质的重量。
如本文所用,“室温”是指15-30℃,优选20-25℃。
如本文所用,“常压”是指0.1MPa。
如本文所用,若无特别指出,介孔SiO2分子筛KIT-6的合成方法如下:水热合成温度100℃时间24h,80℃干燥12h,550℃煅烧5h。
如本文所用,若无特别指出,浸渍溶剂一般采用去离子水。
除非另行定义,文中所使用的所有专业与科学用语与本领域技术人员所熟悉的意义相同。此外,任何与所记载内容相似或均等的方法及材料皆可应用于本发明方法中。文中所述的较佳实施方法与材料仅作示范之用。
本发明实施例中所用溶剂和材料如表1所示:
表1
实施例1
称取0.26g六水合硝酸镍溶于1.9mL去离子水中,并添加0.18g一水合柠檬酸,配制成硝酸镍的水溶液。然后称取1g比表面积为835m2/g的介孔SiO2分子筛KIT-6(介孔SiO2分子筛KIT-6的孔径尺寸为6nm,孔壁为4nm,孔体积为1cm3/g),介孔SiO2分子筛KIT-6是在温度为100℃的条件下干燥,时间为12h,在常温下采用等体积浸渍法将载体KIT-6浸渍于上述硝酸镍的水溶液中,搅拌后室温静置6h,烘箱中80℃干燥12h。将所得固体产物在马弗炉中焙烧,焙烧的温度为500℃,时间为5h,研钵磨碎后,用200目分样筛筛分,即可得到镍负载量为5wt%的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂,记为5Ni/KIT-6-CA,TEM图片如图1所示,图1为实施例1中5Ni-KIT-6-CA的TEM图片,以方便直观认识催化剂负载后活性组分分散情况及其对载体有序性的影响。从图1中可以看出,负载金属后载体的孔道结构依然清晰可见,其中镍颗粒大小约2-4nm,Ni分散度得到了极大提高。
以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂的比表面积为835m2/g,孔径为6.0nm,孔体积为1cm3/g。
实施例2
制备方法同实施例1,所不同之处在于:添加剂为葡萄糖,所得催化剂记为5Ni/KIT-6-Gl。
实施例3
制备方法同实施例1,所不同之处在于:添加剂为山梨醇,所得催化剂记为5Ni/KIT-6-So。
实施例4
制备方法同实施例1,所不同之处在于:以0.3g四水合醋酸镍取代实施例1中的0.26g六水合硝酸镍,本实施例制备得到的催化剂记为5Ni/KIT-6-CA/AC。
实施例5
制备方法同实施例1,所不同之处在于:六水合硝酸镍的添加量为0.15g,所得催化剂的镍负载量为3%,记为3Ni/KIT-6-CA。
实施例6
制备方法同实施例1,所不同之处在于:六水合硝酸镍的添加量为0.55g,所得催化剂的镍负载量为10%,记为10Ni/KIT-6-CA。
实施例7
分别将实施例1~6制得的催化剂装填在内径为8mm的固定床微型反应器中,反应前先用N2吹扫空气,再在500℃下,通入纯H2还原催化剂2小时。然后用还原后得到的催化剂对原料气的甲烷化反应进行催化。原料气的组成和催化反应条件如下:
原料气组成:CO:20%,H2:60%,N2:20%;
催化剂装填量:200mg;
反应温度:300~500℃;
反应压力:0.1MPa;
反应空速:15,000h-1。
本发明的催化剂适用的原料气的组成和催化反应条件还可以为:合成气体积空速为3000~30000h-1,压力为常压至3.0MPa,温度为300~500℃,合成气中H2/CO比值为2~4。
按照如下方法测定并计算CO转化率和CH4收率:
CO转化率:XCO=(1-产物中含有的CO量/原料气中含有的CO量)×100%
CH4收率:SCH4=(转化成CH4的CO量/原料气中含有的CO量)×100%
实施例8
实施例8用于说明实施例1~6制得的催化剂在合成气制甲烷反应中的耐高温性能。
将实施例1~6制得的催化剂装填在内径为8mm的固定床微型反应器中,反应前先用N2吹扫空气,再用纯H2还原催化剂,原料气由CO和H2混合经过滤后进入反应器,先在最优温度下测得催化剂活性,再将催化剂在原料气氛围下650℃煅烧2h,再将反应温度降回最优温度考察催化剂活性。反应所得气体经气相色谱在线分析,并按照与实施例7相同的方法计算CO转化率和CH4选择性,结果列于表1。
测试条件为:温度T=350℃,原料气H2:CO=3:1,空速15,000h-1。以5Ni/KIT-6-CA为例,其焙烧后的催化剂TEM图片如图2所示,图2为实施例8中5Ni-KIT-6-CA经过原料气氛围下650℃焙烧2h后的TEM图,以方便对比焙烧对活性组分团聚与否及其对载体有序性的影响。图2中负载金属后的载体的孔道结构依然清晰可见,其中镍颗粒大小仍约2-4nm,并无明显的Ni团聚现象,这说明KIT-6分子筛的热稳定性较好,且小颗粒的Ni耐热性较好,不易团聚。
对比例
本对比例用于说明现有技术的甲烷化催化剂及其在合成气制甲烷反应中的应用。
分别以KIT-6、MCM-41、Al2O3和SiO2为载体,按照过量浸渍法得到催化剂,记为5Ni/KIT-6、5Ni/MCM-41、5Ni/Al2O3、5Ni/SiO2,并按照与实施例6相同的方法将制得的催化剂应用于合成气甲烷化反应,结果列于表2。
表2
由表2的数据可知,在浸渍过程中添加有机小分子,以等积极浸渍法制备的催化剂在原料气氛围中650℃煅烧2h后,CO转化率和CH4收率基本保持不变,而对比例中的5Ni/KIT-6、5Ni/MCM-41、5Ni/Al2O3和5Ni/SiO2的活性分别下降了13.5%、26.8%、35.2%和31.7%,这说明采用加入添加剂的过量浸渍法制备的催化剂除了具有良好的催化活性外,还具有很好的耐高温性能。另外,以5Ni/KIT-6-CA为例,催化活性考评中反应压力为1MPa时,在最优反应条件下,CO转化率可达100%和CH4甲烷选择性可达99.9%,说明甲烷化反应中适当加压有利于甲烷选择性的进行。
本发明在传统甲烷化催化剂的制备方法(浸渍法)的基础上,通过在浸渍过程中加入有机小分子添加剂,并以化学性质稳定、热传导性能好、比表面积大的介孔SiO2分子筛KIT-6为载体,制备了活性组分高度分散于载体孔道内的镍基金属催化剂,所得催化剂具有催化活性高、甲烷选择性好、热稳定性好以及催化剂寿命较长等优点。该催化剂在最优条件下可以达到CO转化率100%,甲烷选择性99.9%,甲烷收率99.9%,极具工业化前景。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等同物界定。
Claims (10)
1.一种以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂,其特征在于:以介孔SiO2分子筛KIT-6为载体,以金属Ni为活性组分;其中,以100重量份的催化剂为基准,以金属元素计,镍的含量为3~10重量份,余量为介孔SiO2分子筛KIT-6。
2.根据权利要求1所述的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂,其特征在于:以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂的比表面积为500~1000m2/g,优选为835m2/g,孔径为3~12nm,优选为6.0nm,孔体积为0.4~1.4m3/g,优选为1cm3/g。
3.根据权利要求1所述的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂,其特征在于:所述介孔SiO2分子筛KIT-6的比表面积为500~1000m2/g,优选为600~835m2/g,孔径为3~12nm,优选为4~10nm,孔壁为2~6nm,孔体积为0.4~1.4cm3/g,优选为0.8~1cm3/g;
所述活性组分Ni以NiO、Ni2O3的形式存在。
4.一种权利要求1至3任一项所述的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂的制备方法,其特征在于:包括以下步骤:
将镍盐溶于溶剂中,并加入添加剂配成镍盐的溶液,然后加入干燥的介孔SiO2分子筛KIT-6,采用等体积浸渍法将介孔SiO2分子筛KIT-6浸渍于镍盐的溶液中,搅拌后静置、真空干燥、焙烧、磨碎、筛分,得到所述以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂。
5.根据权利要求4所述的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂的制备方法,其特征在于:所述镍盐为氯化镍、硫酸镍、醋酸镍、草酸镍、硝酸镍中的至少一种。
6.根据权利要求4所述的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂的制备方法,其特征在于:所述溶剂为去离子水、甲醇、乙醇、乙酸、乙酸乙酯、氯仿、丙酮中的至少一种;
所述添加剂为柠檬酸、葡萄糖、乙二醇、甘油、山梨醇中的至少一种。
7.根据权利要求4所述的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂的制备方法,其特征在于:所述添加剂与所述镍盐的质量比为(0.3~1.5):1;
所述镍盐与介孔SiO2分子筛KIT-6的质量比为(0.1~0.6):1。
8.根据权利要求4所述的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂的制备方法,其特征在于:所述等体积浸渍法的温度为室温,时间为2~12h,优选为4~6h;
所述真空干燥的温度为30~80℃,优选为50~70℃,时间为1~12h,优选为2~6h;
所述焙烧的温度为400~800℃,优选为400~600℃,时间为0.5~10h,优选为0.5~2h;
所述筛分是通过200目的分样筛筛分;
所述干燥的介孔SiO2分子筛KIT-6是在温度为50~200℃的条件下干燥,时间为2~24h。
9.一种权利要求1至3任一项所述的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂在合成气制甲烷中的用途。
10.根据权利要求9所述的以介孔SiO2分子筛KIT-6为载体的镍基甲烷化催化剂在合成气制甲烷中的用途,其特征在于:所述合成气制甲烷的条件如下:合成气体积空速为3000~30000h-1,压力为常压至3.0MPa,温度为300~500℃,合成气中H2/CO比值为2~4。
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