CN108295834B - 一种高效稳定的生产生物柴油的核壳型CeO2@CaO催化剂及其应用 - Google Patents
一种高效稳定的生产生物柴油的核壳型CeO2@CaO催化剂及其应用 Download PDFInfo
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Abstract
本发明公开了一种高效稳定的生产生物柴油的核壳型CeO2@CaO催化剂及其应用,该催化剂是以CeO2为核、CaO为壳,其中CeO2核的直径为100~300nm,CaO壳层的厚度为50~400nm,CaO占催化剂质量的20%~70%,其是以纳米氧化钙和七水氯化铈、尿素为原料,十六烷基三甲基溴化铵为表面活性剂,经水热反应后煅烧制备而成。本发明催化剂用于催化生产生物柴油的效率高,多次循环使用之后仍具有很高的催化活性,稳定性好,易分离,便于多次回收利用,使用成本低。
Description
技术领域
本发明属于生物柴油制备技术领域,具体涉及一种生产生物柴油的核壳型 CeO2@CaO催化剂及应用。
背景技术
进入21世纪以来,石油资源日益减少,而其需求量却逐年递增。同时化石燃料的燃烧导致生态环境遭到破坏,产生雾霾、温室效应、环境污染等问题严重影响着人们的生活和健康。能源危机和环境污染已经成为全人类面临的重大课题,人们开始寻找新的清洁、环保、绿色的可再生能源。生物柴油是以可再生的油脂资源(如动植物油脂、微生物油脂以及餐饮废油等)为原料制得的主要成分为长链脂肪酸甲酯的液体燃料,具有与石油柴油相近的性能,生物柴油因具有可再生性、环境友好性、不含硫和芳香烃化合物、无毒、可降解性、高十六烷值、良好燃料性、安全性、便于运输和储存、润滑性优良等诸多优点越来越受到人们的关注,素有“绿色柴油”之称,是优质的石化燃料替代品。
生物柴油的制备方法分为物理法和化学法,物理法包括直接使用法、混合法和微乳液法;化学法包括高温热裂解法和酯交换法。目前工业上生产生物柴油的主要方法是酯交换法,即用各种动植物油脂、微生物油脂以及餐饮废油等与甲醇等低碳醇类物质在催化剂作用下反应而生成。酯交换法包括:酸或碱催化法、生物酶法、工程微藻法和超临界法。固体碱金属催化法生产生物柴油,采用的催化剂价格低廉,且可重复回收利用,反应装置简单,操作方便,反应条件温和,是近年来研究的热点。
现有技术催化制备生物柴油用的固体碱催化剂主要为CaO,其价格低廉,操作方便,在生物柴油生产上具有广泛的应用前景,然而单纯的CaO使用后容易失活,重复利用性不好。因此,对CaO的改性研究成为人们关注的重点。文献(Y.C. Wong,Y.P.Tan,Y.H.Taufiq-Yap,I.Ramli,H.S.Tee.Biodiesel production via transesterificationof palm oil by using CaO-CeO2mixed oxide catalysts[J]. Fuel,2015,162.)报道了一种复合型CaO-CeO2催化剂,它与CaO相比,提高了循环过程中的收率,但在循环六次后,与CaO一样活性骤降至30%以下。
发明内容
本发明的目的在于针对现有生物柴油固体碱催化剂存在的稳定性差、收率低等不足,提供一种具有核壳结构的稳定性更好和收率更高的固体碱催化剂。该催化剂可用于催化制取生物柴油并实现催化剂的高效循环利用。
针对上述目的,本发明提供的催化剂是以CeO2为核、CaO为壳,其中CeO2核的直径为100~300nm,CaO壳层的厚度为50~400nm,CaO占催化剂质量的 20%~70%。
本发明催化剂中,优选CaO占催化剂质量的40%~60%,其中CeO2核的直径为150~200nm,CaO壳层的厚度为250~350nm。
上述催化剂由下述方法制备得到:按照催化剂中CaO的质量百分含量为20~ 70%称取纳米氧化钙和七水氯化铈,将纳米氧化钙和七水氯化铈加入蒸馏水中,并加入十六烷基三甲基溴化铵和尿素,混合均匀后加入水热釜中,在80~100℃下反应12~24小时,反应完后抽滤、洗涤、烘干、800~900℃煅烧3~6小时,得到核壳型CeO2@CaO催化剂。
上述制备方法中,优选七水氯化铈与十六烷基三甲基溴化铵的质量比为 1:0.2~0.3,七水氯化铈与尿素的摩尔比为1:2.5~3.5。
上述制备方法中,所述纳米氧化钙的粒径为40~60nm。
本发明核壳型CeO2@CaO催化剂在催化生产生物柴油中的用途,具体使用方法与现有技术公开的方法相同。
本发明所制备的核壳型氧化钙包覆氧化铈的催化剂用于生产生物柴油,催化效率高,多次循环使用之后仍具有很高的催化活性,稳定性好,易分离,便于多次回收利用,使用成本低。与现有技术公开的复合型CaO-CeO2相比,本发明催化剂不仅增加了催化剂的循环使用次数,同时也大大提高了催化剂的收率。
附图说明
图1是实施例1制备的20%CeO2@CaO催化剂的透射电镜图。
图2是实施例1制备的20%CeO2@CaO催化剂中Ca元素的能谱图。
图3是实施例1制备的20%CeO2@CaO催化剂中Ce元素的能谱图。
图4是实施例1制备的20%CeO2@CaO催化剂的能谱图。
图5是20%CeO2@CaO催化剂和20%CeO2-CaO催化剂的循环使用效果图。
图6是40%CeO2@CaO催化剂和40%CeO2-CaO催化剂的循环使用效果图。
图7是60%CeO2@CaO催化剂和60%CeO2-CaO催化剂的循环使用效果图。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明,但本发明的保护范围不仅限于这些实施例。
实施例1
在200mL水热反应釜中加入0.375g粒径为50nm的纳米氧化钙和3.25g七水氯化铈,再向其中加入0.725g十六烷基三甲基溴化铵、1.572g尿素、100mL蒸馏水,搅拌均匀后,然后在密闭条件下,90℃静置反应24h。将反应后的混合液进行抽滤、洗涤,所得固体100℃干燥6小时后,置于马弗炉内3℃/min升温至850℃,恒温煅烧6h,得到CaO质量百分含量为20%的核壳型CeO2@CaO(记为20%CeO2@CaO) 催化剂。由图1可见,所得催化剂为核壳结构,核的直径为200nm,壳层厚度为50nm。由图2~4可见,所得催化剂是以CeO2为核,CaO为壳。
对比例1
采用等体积浸渍法,将2.844g二氧化铈、3g硝酸钙置于蒸发皿内,然后加入蒸馏水,120℃搅拌至水分完全蒸发,再置于马弗炉内3℃/min升温至850℃,恒温煅烧6小时,得到CaO质量百分含量为20%的CeO2-CaO(记为20%CeO2-CaO) 催化剂。
实施例2
在200mL水热反应釜中加入1.00g粒径为50nm的纳米氧化钙和3.25g七水氯化铈,再向其中加入0.725g十六烷基三甲基溴化铵、1.572g尿素、100mL蒸馏水,搅拌均匀后,然后在密闭条件下,90℃静置反应24h。将反应后的混合液进行抽滤、洗涤,所得固体100℃干燥6小时后,置于马弗炉内3℃/min升温至850℃,恒温煅烧6h,得到CaO质量百分含量为40%的核壳型CeO2@CaO(记为40%CeO2@CaO) 催化剂。所得催化剂为核壳结构,核的直径为180nm,壳层厚度为80nm。
对比例2
采用等体积浸渍法,将1.0665g二氧化铈、3g硝酸钙置于蒸发皿内,然后加入蒸馏水,120℃搅拌至水分完全蒸发,再置于马弗炉内3℃/min升温至850℃,恒温煅烧6小时,得到CaO质量百分含量为40%的CeO2-CaO(记为40%CeO2-CaO) 催化剂。
实施例3
在200mL水热反应釜中加入1.731g粒径为50nm的纳米氧化钙和2.50g七水氯化铈,再向其中加入0.558g十六烷基三甲基溴化铵、1.209g尿素、100mL蒸馏水,搅拌均匀后,然后在密闭条件下,90℃静置反应24h。将反应后的混合液进行抽滤、洗涤,所得固体100℃干燥6小时后,置于马弗炉内3℃/min升温至850℃,恒温煅烧6h,得到CaO质量百分含量为60%的核壳型CeO2@CaO(记为60%CeO2@CaO) 催化剂。所得催化剂为核壳结构,核的直径为160nm,壳层厚度为100nm。
对比例3
采用等体积浸渍法,将0.94g二氧化铈、6g硝酸钙置于蒸发皿内,然后加入蒸馏水,120℃搅拌至水分完全蒸发,再置于马弗炉内3℃/min升温至850℃,恒温煅烧6小时,得到CaO质量百分含量为60%的CeO2-CaO(记为60%CeO2-CaO)催化剂。
实施例4
实施例1~3的催化剂催化大豆油生成生物柴油的应用,具体方法如下:
向50mL烧瓶中加入10g大豆油和4.74g甲醇、0.3g催化剂,在70℃下搅拌反应8h,反应完后离心分离,上层溶液旋转蒸发除甲醇,得到生物柴油。下层沉淀作为催化剂重复使用。同时以对比例1~3得到的催化剂做对比试验。试验结果见表1 及图5~7。
表1不同催化剂催化大豆油生成生物柴油的结果对比
由表1及图5~7结果可见,催化剂中CaO质量百分含量相同时,实施例1~3 得到的核壳型CeO2@CaO催化剂催化大豆油生成生物柴油的循环使用性能明显高于对比例1~3采用等体积浸渍法得到的复合型CeO2-CaO催化剂,其中CaO质量百分含量为20%和40%时,核壳型CeO2@CaO催化剂循环反应6次,生物柴油的收率仍可达到92以上,循环反应7次,生物柴油的收率也可达到近70%,而复合型CeO2-CaO催化剂循环反应3次后,生物柴油的收率骤降至32%以下;CaO质量分数为60%时,核壳型CeO2@CaO催化剂循环反应8次,生物柴油的收率仍可达到98%以上,循环反应9次,生物柴油的收率为76.63%,而复合型CeO2-CaO催化剂循环反应至第6次时,生物柴油的收率已经骤降至37.04%。结果表明,本发明核壳型CeO2@CaO催化剂相比于现有技术公开的复合型CeO2-CaO催化剂,在催化大豆油生成生物柴油的过程中,更加高效、稳定。
Claims (5)
1.一种高效稳定生产生物柴油的核壳型CeO2@CaO催化剂,其特征在于:该催化剂是以CeO2为核、CaO为壳,其中CeO2核的直径为100~300nm,CaO壳层的厚度为50~400nm,CaO占催化剂质量的20%~70%;
按照催化剂中CaO的质量百分含量为20~70%称取纳米氧化钙和七水氯化铈,将纳米氧化钙和七水氯化铈加入蒸馏水中,并加入十六烷基三甲基溴化铵和尿素,混合均匀后加入水热釜中,在80~100℃下反应12~24小时,反应完后抽滤、洗涤、烘干、800~900℃煅烧3~6小时,得到核壳型CeO2@CaO催化剂。
2.根据权利要求1所述的核壳型CeO2@CaO催化剂,其特征在于:所述CeO2核的直径为150~200nm,CaO壳层的厚度为250~350nm,CaO占催化剂质量的40%~60%。
3.根据权利要求1所述的核壳型CeO2@CaO催化剂,其特征在于:所述七水氯化铈与十六烷基三甲基溴化铵的质量比为1:0.2~0.3,七水氯化铈与尿素的摩尔比为1:2.5~3.5。
4.根据权利要求1所述的核壳型CeO2@CaO催化剂,其特征在于:所述纳米氧化钙的粒径为40~60 nm。
5.权利要求1所述的核壳型CeO2@CaO催化剂在催化生产生物柴油中的用途。
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