微藻/核桃壳混合热解需热量及制备芳烃研究

doi:10.11949/j.issn.0438-1157.20171298

化工学报 ›› 2018, Vol. 69 ›› Issue (5): 2137-2148.DOI: 10.11949/j.issn.0438-1157.20171298

微藻/核桃壳混合热解需热量及制备芳烃研究

苗鹏¹, 常国璋¹, 燕希敏¹, 胡修德², 郭庆杰^1,2

1. 青岛科技大学化工学院清洁化工过程山东省高校重点实验室, 山东青岛 266042;
2. 宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室, 宁夏银川 750021

收稿日期:2017-09-27 修回日期:2017-10-19 出版日期:2018-05-05 发布日期:2018-05-05
通讯作者: 郭庆杰
基金资助:
山东省研究生教育创新计划项目（SDYC13010）；省部共建煤炭高效利用与绿色化工国家重点实验室开放基金项目（2017-K22）；山东省自然科学基金重点项目（ZR2015QZ02）；宁夏回族自治区重点研发计划项目（2016BY005）；宁夏回族自治区引进科技创新团队。

Experimental study on thermal demanding and preparation of aromatics of mixed pyrolysis of Nannochloropsis sp./walnut shell

MIAO Peng¹, CHANG Guozhang¹, YAN Ximin¹, HU Xiude², GUO Qingjie^1,2

1. Key Laboratory of Clean Chemical Processing of Shandong Province, College of Chemical Engineering, Qingdao University of Science & Technology, Qingdao 266042, Shandong, China;
2. State Key Laboratory of High-efficiency Utilization of Coal & Green Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China

Received:2017-09-27 Revised:2017-10-19 Online:2018-05-05 Published:2018-05-05
Supported by:
supported by the Innovation Project of Graduate Education in Shandong Province(SDYC13010), the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (2017-K22), the Key Project of the Natural Science Foundation of Shandong Province (ZR2015QZ02), the Ningxia Hui Autonomous Regionkey R & D Project(2016BY005) and the Ningxia Hui Autonomous Region Introduction of Scientific and Technological Innovation Team.

摘要/Abstract

摘要：

利用热重分析仪（TG）、气相色谱-质谱联用仪（GC/MS）与固定床反应器，考察了微藻、核桃壳及混合物主要热解阶段的需热量特性，以及混合比、温度、催化剂种类对二者混合热解制备芳烃的影响规律。结果表明：在不同升温速率下，核桃壳热解在180～270℃和380～485℃处存在两个吸热峰，整体表现为吸热效应（378.56～596.45 kJ·kg^-1）；微藻热解在280～450℃处存在一个放热峰，整体表现为放热效应（-814.76～-1191.52 kJ·kg^-1）。微藻/核桃壳热解呈现较低的放热效应（-99.05～-158.04 kJ·kg^-1），表明二者混合热解可以实现一定程度的热量耦合。微藻/核桃壳热解在制备芳烃上表现出明显的协同效应，且芳烃相对含量在600℃、混合比1：1下达到最大值，为20.51%；加入Cu/HZSM-5可进一步提高混合热解的芳烃相对含量，达到35.74%。为微藻与核桃壳的高值化利用提供了新思路。

关键词: 生物能源, 热解, 热量耦合, 分子筛, 芳烃

Abstract:

In this study, Nannochloropsis sp. (NS) and walnut shell (WS) were used as raw materials for mixed pyrolysis, and the characteristics of thermal demanding during pyrolysis of NS, WS and NS/WS were initially investigated by a thermogravimetric analyzer and a fixed-bed reactor. Then the effects of mass ratio, reaction temperature, and catalysts on the preparation of aromatic hydrocarbons from NS/WS mixed pyrolysis were studied by a GC/MS method. Results showed that the two endothermic peaks were observed from WS pyrolysis at 180-270℃ and 380-485℃, the overall performance of WS pyrolysis took on the endothermic effect with thermal demanding values of 378.56-596.45 kJ·kg^-1 under different heating rates. An endothermic peak was obtained from NS pyrolysis at 280-450℃, the overall performance of NS pyrolysis took on exothermic effect with thermal demanding values of -814.76——1191.52 kJ·kg^-1. The pyrolysis of NS/WS presented low exothermic effect with thermal demanding values of -99.05——158.04 kJ·kg^-1, indicating that the mixed pyrolysis achieved a certain degree of thermal coupling. The mixed pyrolysis of NS/WS demonstrated a synergistic effect in the preparation of aromatic hydrocarbons. The optimum condition for aromatics preparation with a value of 20.51% was achieved at a temperature of 600℃ and a NS/WS mass ratio of 1:1. By introducing Cu/HZSM-5 catalyst, the relative content of aromatics was further improved (35.74%). This study provided a new approach for high-value utilization of NS and WS.

Key words: bioenergy, pyrolysis, thermal coupling, moleclar sieves, aromatic hydrocarbons

中图分类号:

苗鹏, 常国璋, 燕希敏, 胡修德, 郭庆杰. 微藻/核桃壳混合热解需热量及制备芳烃研究[J]. 化工学报, 2018, 69(5): 2137-2148.

MIAO Peng, CHANG Guozhang, YAN Ximin, HU Xiude, GUO Qingjie. Experimental study on thermal demanding and preparation of aromatics of mixed pyrolysis of Nannochloropsis sp./walnut shell[J]. CIESC Journal, 2018, 69(5): 2137-2148.

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微藻/核桃壳混合热解需热量及制备芳烃研究

Experimental study on thermal demanding and preparation of aromatics of mixed pyrolysis of Nannochloropsis sp./walnut shell

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