CN107469802B - 一种用于生产富芳烃生物燃油的催化剂及其制备方法 - Google Patents
一种用于生产富芳烃生物燃油的催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于生产富芳烃生物燃油的催化剂及其制备方法,包括:微波热解木质素形成木质素生物炭原料。将称取好的锌盐溶于过量去离子水中,在搅拌时加入粉碎、洗涤、干燥后的生物炭粉末;将溶液在60℃水浴中利用磁力搅拌器连续搅拌6h;然后抽滤、成型,在105℃烘箱中烘干15h;接着在以氮气和氢气的混合气氛围(99:1)的管式炉中550℃结晶、成型,制成改性后的锌‑生物炭催化剂。本发明改性后的催化剂能够提高木质素催化热解所得到生物油产率及芳烃的选择性,可应用于相关的催化热解转化技术中。
Description
技术领域
本发明属于生物质催化热解技术领域,具体涉及一种用于生产富芳烃生物燃油的催化剂及其制备的方法。
背景技术
现今化石燃油已渐渐不能满足人类的需要,急需发现可替代的新型能源,来缓解日益紧张的能源危机问题和环境污染问题。我国作为农业大国生物质能资源广泛,包括玉米、小麦、水稻等农作物秸秆及稻谷壳、甘蔗农产品加工剩余物,每年可达几亿吨。生物质已被确定为用于生产可再生能源最有前途的原料。但是在生物质转化为液体燃油过程中仍然存在很多问题,如:所得液体油产率和品质较低,选择性较差,催化剂活性较低、易失活等,因此必须提高生物质热解液体产物的产率和品质。另外,热解过程中除了获得生物油,还会产生大量的生物炭,生物炭是由于生物质在无氧获缺氧状态下,经高温热解后形成的固体产物,其本身含有一些矿物元素如Ca, Mg, Zn等碱金属元素,此外,生物炭具有发达的空隙和比表面积,因此,本研究拟以微波热解生物质形成的生物炭产物为基础,经过过渡金属氧化物对其进行改性,制备一种生物炭催化剂,以这种生物炭催化剂来解决热解实验中生物油产率和品质等问题。
生物质主要有纤维素、半纤维素和木质素组成。在木本植物中,木质素占25%,是世界上第二位最丰富的有机物(纤维素是第一位)。木质素是由三种醇单体(对香豆醇、松柏醇、芥子醇)形成的一种复杂酚类聚合物。近年来利用木质素热解生产生物油已经得到许多关注。但利用微波热解木质素生成的固体产物(生物炭)来制备催化剂还鲜有报道。因此,本研究拟通过微波辅助热解制备木质素衍生生物炭,并在所生成的生物炭表面负载过渡金属氧元素以调节木质素衍生生物炭催化剂的理化性质,在微波热解木质素制备生物燃料过程中提高原料转化率,减少积炭的形成,提高催化剂的活性、选择性及使用寿命。
发明内容
本发明的目的在于提供一种用于生产富芳烃生物燃油的催化剂及其制备方法,以得到改性后的催化剂,从而提高生物质催化热解反应中液体产率和品质,具体体现在提高原料转化率及生物油的化学组分选择性,减少催化剂积炭的形成,提高催化剂的活性及选择性。
为了解决上述技术问题,本发明以木质素微波热解衍生生物炭为催化剂载体原料,揭示负载过渡金属氧化物对所制备生物炭催化剂的影响,通过XRD、SEM等分析手段分析所制备的过渡金属改性生物炭催化剂微观形态变化、活性组分与载体的结合方式以及分布状态,具体技术方案如下:
一种用于生产富芳烃生物燃油的催化剂的制备方法,其特征在于包括以下步骤:
步骤一,微波热解木质素获得生物炭;将木质素原料根据需用量称重并放置在石英烧瓶反应器内,将微波热解参数设定为反应温度500℃,微波功率为750W,为使木质素热解反应发生较完全,从而获得较纯净的生物炭,反应时间设定为30分钟;
步骤二,生物炭粉末的制备:将所述生物炭从石英烧瓶反应器中倒出并冷却至室温;由于木质素在微波热解时,容易形成粘结在一起块状生物炭产物。为了制备经过渡金属改性的生物炭催化剂,先要将微波热解生成的木质素衍生生物炭粉碎成细粉,然后筛分以确保尺寸的均匀性,从而获得生物炭粉末;
步骤三,用去离子水反复洗涤所述生物炭粉末,以从生物炭粉末结构中除去污染物并且打开生物炭表面孔,得纯净的生物炭粉末;
步骤四,将所述纯净的生物炭粉末在105℃的烘箱中干燥15h以除去多余水分,得干燥生物炭粉末;
步骤五,将称取好的锌盐溶于去离子水中,得到溶液A,在不断搅拌的情况下向溶液A中加入所述干燥生物炭粉末,得溶液B;所述锌盐中金属元素的质量比含量为所选择的生物炭的5%;
步骤六,利用磁力搅拌器连续搅拌所述溶液B,得溶液C;
步骤七,对溶液C进行抽滤、成型,得成型的柱状颗粒物质,然后在烘箱中烘干,得产物一;
步骤八,在氮气和氢气的混合气氛围中通过高温管式炉对产物一进行焙烧,使其结晶、成型,从而制备得到最终产物,即改性后的负载有过渡金属的生物炭催化剂;所述混合气中氮气和氢气的体积比为99:1。
步骤一所述木质素原料为一种商业化木质素。
步骤五中所述锌盐为Zn(NO3)2.6H2O,锌盐与干燥生物炭粉末质量比为5%。
步骤六具体为将溶液B放在磁力搅拌器上,在溶液中加入磁力搅拌子,在60℃的水浴中连续搅拌6h。
所述步骤七具体为:抽滤、成型是在布氏漏斗中放一层滤纸然后将布氏漏斗连接真空泵,将溶液C在准备好的布氏漏斗中进行抽滤,抽滤完后保留滤纸上的残渣,然后使用塑料管将抽滤后的残渣 制成直径5毫米、长7毫米的柱状颗粒,以方便做实验时使用。
步骤七烘干条件具体为105℃的电烘箱中真空干燥15h。
所述步骤八中在管式炉内,用流速为60mL / min的混合气来维持缺氧气氛,以550℃的温度进行结晶4h。
一种用于生产富芳烃生物燃油的催化剂,其特征在于:利用上述方法制备而得。
本发明具有有益效果。本发明中制备的过渡金属改性后的生物炭催化剂,样品保持了生物炭拓扑结构的特征模式,经改性后的生物炭催化剂仍保持规整的结构形态。说明改性后的生物炭催化剂的分散性仍较好。以锌盐改性的生物炭的XRD图与没有改性的生物炭催化剂相比,它具有一个较为突出的峰,这是生成了由骨架物质之外物质所形成的高结晶,也表明该峰是由锌的加入引起的,而其他峰则与生物炭催化剂的峰一致。从SEM分析可以得到主要晶体颗粒及其附聚物在样品中随添加锌盐略有变化,与未添加金属的生物炭相比,经过加锌的样品的单晶尺寸稍有减小,且表面更为光滑。
附图说明
图1为本发明锌盐对改性生物炭催化剂的影响的XRD衍射图;
图2为本发明锌盐对改性生物炭催化剂的影响的SEM图;
图3为本发明加入改性后催化剂和未加催化剂木质素/PE微波共热解反应产物生物油组分分析图;
图4为本发明的方法流程图。
具体实施方式
下面结合附图和具体实施例,对本发明的技术方案做进一步详细说明。
实施例一
本发明的方法流程图如图4所示。将40g木质素生物质原料称重并放置在反应烧瓶内,不加入加热剂,使得所得的焦炭尽可能纯。实验开始前通入氮气15min以保持无氧的氛围。将微波热解参数设定为反应温度500℃,微波功率为750W,为使木质素热解反应发生较完全,从而获得较纯净的生物炭,反应时间设定为30分钟。由于木质素在微波热解时,容易形成粘结在一起块状生物炭产物。为了制备经过渡金属改性的生物炭催化剂,先要将微波热解生成的木质素衍生生物炭粉碎成细粉,然后筛分以确保尺寸的均匀性。然后,用去离子水反复洗涤生物炭粉末。洗涤后,在105℃的烘箱中干燥15h以除去多余水分。这就得到了制备催化剂的生物炭原料。将称取好的10.13g的Zn(NO3)2.6H2O溶于过量去离子水中,在不断搅拌的情况下向其中加入生物炭原料40g。将溶液放在磁力搅拌器上,在60℃的水浴中连续搅拌6h。抽滤、成型,将成型的物质在105℃的电烘箱中真空干燥15h。然后以流速为60mL /min的氮气氢气混合气氛(99:1)来维持缺氧气氛,以550℃的温度进行结晶4h,制成负载金属锌的生物炭催化剂。为了对比金属锌改性后的催化剂和未经处理的催化剂的晶体特征进行了XRD表征,如图1所示。改性后的分子筛催化剂保持了原催化剂的拓扑结构的特征模式,但出现一个由金属锌加入形成的突出峰,说明改性后的金属锌负载到了生物炭催化剂中。如图2所示的负载锌的生物炭催化剂和生物炭催化剂的SEM对比图。说明负载金属锌的催化剂的单晶尺寸稍有减小,且表面更为光滑。
实施例二
为了验证所改性后的催化剂对生物质热解转化的影响,采用催化固定床反应器与微波热解装置联用进行了催化热解实验。试验所用的原料为木质素:首先称取20g的木质素和5g的PE作为原料放于容量为500ml的石英烧瓶反应器中,然后加入1g的活性炭作为微波吸收材料与木质素/聚乙烯(PE)混合,再将石英烧瓶反应器置于微波炉中,在催化固定床反应器中放置1g的所制备的催化剂。设置微波热解的反应温度为500℃,时间为8min,微波功率为750W;热解气通过微波热解反应后经过催化固定床进行催化重整反应,再经快速冷凝后收集生物油,收集反应后的生物油有机组分及催化剂经GC/MS、SEM、XRD等表征手段进行分析。试验中对比了未添加催化剂与添加金属锌改性后生物炭催化剂的微波热解实验,发现使用催化剂明显比未加催化剂获得的生物油多,催化剂对生物油产率的影响为:锌-生物炭催化剂>无催化剂。催化剂对合成气产率的影响与它对生物油产率的影响一致。发现添加催化剂可以获得更多的生物燃油。由GC/MS分析微波共热解木质素、木质素/PE以及木质素/PE+锌-生物炭所得到的生物油的组分分析图,如图3所示,它的主要化学化合物是醛/酮、酚类、有机酸、醇、糖、酯及烃。其中添加锌-生物炭催化剂与其他两个相比,有机酸的含量明显降低了(由5.23%降到0%),并且它富芳烃的含量所占比例最多,高达49%,而木质素/PE富芳烃的含量为23.33%,木质素富芳烃的含量几乎为零。说明锌-生物炭催化剂的使用提高了生物油的中芳烃的选择性和生物油的品质,可用于生产富芳烃生物燃油。
Claims (8)
1.一种用于生产富芳烃生物燃油的催化剂的制备方法,其特征在于:通过微波辅助热解制备木质素衍生生物炭,并在所生成的生物炭表面负载过渡金属元素以调节木质素衍生生物炭催化剂的理化性质,在微波热解木质素制备生物燃料过程中提高原料转化率,以这种生物炭催化剂来解决热解实验中生物油产率和品质问题,具体包括以下步骤:
步骤一,微波热解木质素获得生物炭;将木质素原料根据需用量称重并放置在石英烧瓶反应器内,将微波热解参数设定为反应温度500℃,微波功率为750W,为使木质素热解反应发生较完全,从而获得较纯净的生物炭,反应时间设定为30分钟;
步骤二,生物炭粉末的制备:将所述生物炭从石英烧瓶反应器中倒出并冷却至室温;由于木质素在微波热解时,容易形成粘结在一起块状生物炭产物;
为了制备经过渡金属改性的生物炭催化剂,先要将微波热解生成的木质素衍生生物炭粉碎成细粉,然后筛分以确保尺寸的均匀性,从而获得生物炭粉末;
步骤三,用去离子水反复洗涤所述生物炭粉末,以从生物炭粉末结构中除去污染物并且打开生物炭表面孔,得纯净的生物炭粉末;
步骤四,将所述纯净的生物炭粉末在105℃的烘箱中干燥15h以除去多余水分,得干燥生物炭粉末;
步骤五,将称取好的锌盐溶于去离子水中,得到溶液A,在不断搅拌的情况下向溶液A中加入所述干燥生物炭粉末,得溶液B;所述锌盐中金属元素的质量比含量为所选择的生物炭的5%;
步骤六,利用磁力搅拌器连续搅拌所述溶液B,得溶液C;
步骤七,对溶液C进行抽滤、成型,得成型的柱状颗粒物质,然后在烘箱中烘干,得产物一;
步骤八,在氮气和氢气的混合气氛围中通过高温管式炉对产物一进行焙烧,使其结晶、成型,从而制备得到最终产物,即改性后的负载有过渡金属的生物炭催化剂;所述混合气中氮气和氢气的体积比为99:1。
2.根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法,其特征在于:步骤一所述木质素原料为一种商业化木质素。
3.根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法,其特征在于:步骤五中所述锌盐为Zn(NO3)2.6H2O,锌盐与干燥生物炭粉末质量比为5%。
4.根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法,其特征在于:步骤六具体为将溶液B放在磁力搅拌器上,在溶液中加入磁力搅拌子,在60℃的水浴中连续搅拌6h。
5.根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法,其特征在于所述步骤七具体为:抽滤、成型是在布氏漏斗中放一层滤纸然后将布氏漏斗连接真空泵,将溶液C在准备好的布氏漏斗中进行抽滤,抽滤完后保留滤纸上的残渣,然后使用塑料管将抽滤后的残渣 制成直径5毫米、长7毫米的柱状颗粒,以方便做实验时使用。
6.根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法,其特征在于:步骤七烘干条件具体为105℃的电烘箱中真空干燥15h。
7.根据权利要求1所述的一种用于生产富芳烃生物燃油的催化剂的制备方法,其特征在于:所述步骤八中在管式炉内,用流速为60mL / min的混合气来维持缺氧气氛,以550℃的温度进行结晶4h。
8.一种用于生产富芳烃生物燃油的催化剂,其特征在于:利用权利要求1-6中任一权利要求的方法制备而得。
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