CN112090444A - 一种生物质热解用高芳构化性能催化剂及其制备方法 - Google Patents

一种生物质热解用高芳构化性能催化剂及其制备方法 Download PDF

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CN112090444A
CN112090444A CN202010824738.5A CN202010824738A CN112090444A CN 112090444 A CN112090444 A CN 112090444A CN 202010824738 A CN202010824738 A CN 202010824738A CN 112090444 A CN112090444 A CN 112090444A
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姚志通
罗琦予
唐俊红
黄进刚
韩伟
徐少丹
刘洁
吴卫红
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Hangzhou Dianzi University
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Abstract

本发明公开了一种生物质热解用高芳构化性能催化剂及其制备方法。主要包括如下步骤：1)将粉煤灰漂珠过100‑300目筛。2)将粉煤灰、过氧化氢和离子液体按一定质量比混合后置于水浴锅，在30‑60℃反应3‑5h后过滤分离得到催化剂。所述的离子液体为1‑乙基‑3‑甲基咪唑硫酸氢盐、1‑丁基‑3‑甲基咪唑硫酸氢盐、1‑己基‑3‑甲基咪唑硫酸氢盐、1‑丁基磺酸‑3‑甲基咪唑三氟甲烷磺酸盐、氯化胆碱‑甘油离子液体、氯化胆碱‑丙三醇离子液体、氯化胆碱‑尿素离子液体、氯化胆碱‑乙二醇离子液体中的一种或几种。所述的催化剂表面碱性常数Kb和酸性常数Ka之比为0.8‑1.4：1，具有10‑80nm孔径的多孔道结构。本发明利用粉煤灰漂珠天然的核壳结构，通过过氧化氢和离子液体对其进行扩孔改性，提高芳构化性能，具有制备工艺简单、催化效率高、绿色环保等优点，易于大规模生产。

Description

一种生物质热解用高芳构化性能催化剂及其制备方法
技术领域
本发明属于生物质再利用技术领域，特别涉及一种生物质热解用高芳构化性能催化剂及其制备方法。
背景技术
芳烃不仅可作为调和组分用于提高油品辛烷值，而且还是生产大宗石化产品的重要基础原料，其中苯、甲苯和二甲苯的应用最为广泛。我国芳烃市场长期供不应求，主要依赖进口，而国内以化石资源为原料的芳烃装置受环保压力很难立项。以生物质为原料制取芳烃技术因其环保、安全性不失为一条颇具潜力的芳烃生产替代路径，不仅可以降低对不可再生化石资源的依赖，还有利于碳减排，同时具有经济效益和社会效益。
生物质催化热裂解技术是诸多生物质制芳烃技术中最有工业化苗头的工艺。但是生物质氧含量高，氢含量低，在催化热裂解过程中容易生成大量的焦炭，这些焦炭容易沉积于分子筛的表面及孔道，导致分子筛快速失活。因此木质纤维素催化热裂解制备芳烃、烯烃效率差，不利于木质纤维素生物质资源的大规模利用。为了提高生物油产率和目标产物选择性，生物质供氢热解技术应运而生。该技术通过引入氢气或供氢剂，为生物质热解反应体系提供足够的供氢体，稳定自由基碎片，从而获得稳定的热解产物。目前采用的供氢剂主要有四氢萘、小分子醇类、甲酸盐和有机高分子聚合物。氢气和醇类化合物价格昂贵，为生物质提供氢源的经济性较差。此外，氢气在高温高压下操作危险性较大，对设备要求也较高。除了加入一种氢量高的原料，催化剂载体也是重要的影响因素，现有技术中的催化剂由于本身结构的限制，焦炭容易沉积于分子筛的表面及孔道，导致分子筛快速失活，从而影响芳烃的收率。因此，开发制备工艺简单、催化效率高的催化剂成为生物质催化热解的关键。
发明内容
本发明的一个目的在于克服现有技术的不足，提供一种生物质热解用高芳构化性能催化剂的制备方法。
本发明方法主要包括如下步骤：
1)将粉煤灰漂珠过100-300目筛。
2)2)将粉煤灰、过氧化氢和离子液体按一定质量比混合后置于水浴锅，在30-60℃反应3-5h后过滤分离得到催化剂。
所述的粉煤灰、过氧化氢和离子液体的质量比为1：0.02-0.5：1-5；
所述的离子液体为1-乙基-3-甲基咪唑硫酸氢盐、1-丁基-3-甲基咪唑硫酸氢盐、1-己基-3-甲基咪唑硫酸氢盐、1-丁基磺酸-3-甲基咪唑三氟甲烷磺酸盐、氯化胆碱-甘油离子液体、氯化胆碱-丙三醇离子液体、氯化胆碱-尿素离子液体、氯化胆碱-乙二醇离子液体中的一种或几种。
所述的催化剂表面碱性常数Kb和酸性常数Ka之比为0.8-1.4：1，具有10-80nm孔径的多孔道结构。
本发明的另一个目的是提供一种生物质热解用高芳构化性能催化剂，采用以上方法制备得到。
本发明以粉煤灰漂珠为基体材料，通过采用过氧化氢和离子液体对其扩孔改性制备高芳构化性能催化剂。粉煤灰漂珠通常内部包裹着更细小的玻璃微珠，为天然的核壳结构，可延长生物质裂解产物在催化剂内部的反应时间，同时通过扩孔改性获得10-80nm孔径的多孔道结构，提高了生物质热裂解大分子产物进入漂珠内部发生定向裁剪的几率。此外，催化剂表面碱性常数Kb和酸性常数Ka之比为0.8-1.4：1，酸碱性适宜，因此具有高芳构化反应活性，克服了传统沸石分子筛制备工艺复杂、催化性能低、易结焦失活等缺点。
具体实施方式
本发明结合以下实例作进一步的说明，但本发明的内容不仅限于实施例中所涉及的内容。
实施例1：
1)将粉煤灰漂珠过100目筛。
2)将100g粉煤灰、2g过氧化氢和100g1-乙基-3-甲基咪唑硫酸氢盐按1：0.02：1的质量比混合后置于水浴锅，在60℃反应3h后过滤分离得到表面碱性常数Kb和酸性常数Ka之比为0.8：1，具有10-45nm孔径的催化剂。
3)称量2g玉米芯和1g上述催化剂，然后将混合物料在400℃、氮气氛围下热解。通过气相色谱质谱分析，芳烃产率为16.4wt％。
实施例2：
1)将粉煤灰漂珠过300目筛。
2)将100g粉煤灰、50g过氧化氢和500g1-丁基-3-甲基咪唑硫酸氢盐按质量比1：0.5：5混合后置于水浴锅，在30℃反应5h后过滤分离得到表面碱性常数Kb和酸性常数Ka之比为1.4：1，具有20-60nm孔径的催化剂。
3)称量3g木屑和1.5g上述催化剂，然后将混合物料在500℃、氮气氛围下热解。通过气相色谱质谱分析，芳烃产率为17.2wt％。
实施例3：
1)将粉煤灰漂珠过150目筛。
2)将100g粉煤灰、5g过氧化氢和150g1-己基-3-甲基咪唑硫酸氢盐按质量比1：0.05：1.5混合后置于水浴锅，在35℃反应3.5h后过滤分离得到表面碱性常数Kb和酸性常数Ka之比为0.9：1，具有15-35nm孔径的多孔道结构催化剂。
3)称量4g稻壳和2g上述催化剂，然后将混合物料在550℃、氮气氛围下热解。通过气相色谱质谱分析，芳烃产率为17.5wt％。
实施例4：
1)将粉煤灰漂珠过200目筛。
2)将100g粉煤灰、10g过氧化氢和200g1-丁基磺酸-3-甲基咪唑三氟甲烷磺酸盐按质量比1：0.1：2混合后置于水浴锅，在40℃反应4h后过滤分离得到表面碱性常数Kb和酸性常数Ka之比为1.1：1，具有15-63nm孔径的催化剂。
3)称量5g麦秸和2.5g上述催化剂，然后将混合物料在500℃、氮气氛围下热解。通过气相色谱质谱分析，芳烃产率为18.6wt％。
实施例5：
1)将粉煤灰漂珠过250目筛。
2)将100g粉煤灰、30g过氧化氢和300g氯化胆碱-丙三醇按质量比1：0.3：3混合后置于水浴锅，在50℃反应3.5h后过滤分离得到表面碱性常数Kb和酸性常数Ka之比为1.2：1，具有20-70nm孔径的催化剂。
3)称量4g污泥和2g上述催化剂，然后将混合物料在400℃、氮气氛围下热解。通过气相色谱质谱分析，芳烃产率为15.3wt％。
实施例6：
1)将粉煤灰漂珠过300目筛；
2)将100g粉煤灰、50g过氧化氢和250g氯化胆碱-甘油、250g氯化胆碱-丙三醇按质量比1：0.5：2.5：2.5混合后置于水浴锅，在55℃反应5h后过滤分离得到表面碱性常数Kb和酸性常数Ka之比为1.25：1，具有12-78nm孔径的催化剂。
3)称量6g麦秸、稻壳与3g上述催化剂，然后将混合物料在600℃、氮气氛围下热解。通过气相色谱质谱分析，芳烃产率为19.4wt％。
上述实施例并非是对于本发明的限制，本发明并非仅限于上述实施例，只要符合本发明要求，均属于本发明的保护范围。

Claims (4)

1.一种生物质热解用高芳构化性能催化剂的制备方法，催化剂表面碱性常数Kb和酸性常数Ka之比为0.8-1.4：1，具有10-80nm孔径的多孔道结构；其特征在于具体是：
1)将粉煤灰漂珠过100-300目筛；
2)将粉煤灰、过氧化氢和离子液体按一定质量比混合后置于水浴锅，在30-60℃反应3-5h后过滤分离得到催化剂。
2.根据权利要求1所述的一种生物质热解用高芳构化性能催化剂的制备方法，其特征在于所述的粉煤灰、过氧化氢和离子液体的质量比为1：0.02-0.5：1-5。
3.根据权利要求1或2所述的一种生物质热解用高芳构化性能催化剂的制备方法，其特征在于所述的离子液体为1-乙基-3-甲基咪唑硫酸氢盐、1-丁基-3-甲基咪唑硫酸氢盐、1-己基-3-甲基咪唑硫酸氢盐、1-丁基磺酸-3-甲基咪唑三氟甲烷磺酸盐、氯化胆碱-甘油离子液体、氯化胆碱-丙三醇离子液体、氯化胆碱-尿素离子液体、氯化胆碱-乙二醇离子液体中的一种或几种。
4.一种生物质热解用高芳构化性能催化剂，表面碱性常数Kb和酸性常数Ka之比为0.8-1.4：1，具有10-80nm孔径的多孔道结构；采用权利要求1-3任一项所述的方法制备得到。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103272626A (zh) * 2013-05-31 2013-09-04 南京大学 一种以粉煤灰漂珠为基体固载杂多酸的复合催化剂、其制备方法和应用
CN104689844A (zh) * 2015-02-13 2015-06-10 北京神雾环境能源科技集团股份有限公司 一种煤焦油加氢催化剂载体酸性的调控方法
CN105623702A (zh) * 2014-10-28 2016-06-01 中国科学技术大学 一种利用木屑合成航空煤油环烷烃和芳香组分的方法
US20160207817A1 (en) * 2015-01-17 2016-07-21 Hamid Hojaji Fluid permeable and vacuumed insulating microspheres and methods of producing the same
CN106975514A (zh) * 2016-10-09 2017-07-25 张宗超 一种改性工业石油裂解催化剂、制法及其应用
CN108929426A (zh) * 2017-05-27 2018-12-04 科思创德国股份有限公司 一种聚氨酯预浸料及其制备方法与应用
CN109423148A (zh) * 2017-06-30 2019-03-05 翁秋梅 一种基于动态聚合物的吸能方法
CN111377460A (zh) * 2018-12-28 2020-07-07 中国石油化工股份有限公司 一种多级孔hzsm-5分子筛

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103272626A (zh) * 2013-05-31 2013-09-04 南京大学 一种以粉煤灰漂珠为基体固载杂多酸的复合催化剂、其制备方法和应用
CN105623702A (zh) * 2014-10-28 2016-06-01 中国科学技术大学 一种利用木屑合成航空煤油环烷烃和芳香组分的方法
US20160207817A1 (en) * 2015-01-17 2016-07-21 Hamid Hojaji Fluid permeable and vacuumed insulating microspheres and methods of producing the same
CN104689844A (zh) * 2015-02-13 2015-06-10 北京神雾环境能源科技集团股份有限公司 一种煤焦油加氢催化剂载体酸性的调控方法
CN106975514A (zh) * 2016-10-09 2017-07-25 张宗超 一种改性工业石油裂解催化剂、制法及其应用
CN108929426A (zh) * 2017-05-27 2018-12-04 科思创德国股份有限公司 一种聚氨酯预浸料及其制备方法与应用
CN109423148A (zh) * 2017-06-30 2019-03-05 翁秋梅 一种基于动态聚合物的吸能方法
CN111377460A (zh) * 2018-12-28 2020-07-07 中国石油化工股份有限公司 一种多级孔hzsm-5分子筛

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
PENGWEI HUO ET AL.: "H2O2 modified surface of TiO2/fly-ash cenospheres and enhanced photocatalytic activity on methylene blue", 《DESALINATION》 *
李尉卿等: "粉煤灰漂珠代替活性碳处理废水的技术研究", 《粉煤灰》 *
王洪志等: "离子液体改性漂珠对聚氨酯复合材料的燃烧及热解行为影响研究", 《青岛科技大学学报(自然科学版)》 *
甘攀学等: "酸性离子液体功能化MCM-36分子筛用于催化合成乙酸乙酯", 《石油化工》 *
黄正宏: "湿氧化改性多孔炭对低浓度苯和丁酮蒸汽的吸附", 《清华大学学报(自然科学版)》 *

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