化工学报 ›› 2022, Vol. 73 ›› Issue (7): 3026-3037.doi: 10.11949/0438-1157.20220341

• 催化、动力学与反应器 • 上一篇    下一篇

磁性MgFe2O4及其核壳催化剂制备与煤热解性能研究

陈永安1,2(),周安宁1,2(),李云龙1,3,石智伟1,2,贺新福1,2,焦卫红1,2   

  1. 1.西安科技大学化学与化工学院，陕西 西安 710054
    2.自然资源部煤炭资源勘探与综合利用重点实验室，陕西 西安 710021
    3.陕西煤业化工集团神木天元化工有限公司，陕西 榆林 719319
  • 收稿日期:2022-03-06 修回日期:2022-04-24 出版日期:2022-07-05 发布日期:2022-08-01
  • 通讯作者: 周安宁 E-mail:2920452554@qq.com;psu564@139.com
  • 作者简介:陈永安（1997—），男，硕士研究生， 2920452554@qq.com
  • 基金资助:
    陕西省煤炭联合基金项目(2019JPL-10)

Preparation and coal pyrolysis performance of magnetic MgFe2O4 and its core-shell catalysts

Yong’an CHEN1,2(),Anning ZHOU1,2(),Yunlong LI1,3,Zhiwei SHI1,2,Xinfu HE1,2,Weihong JIAO1,2   

  1. 1.School of Chemistry and Chemical Engineering, Xi’an University of Science and Technology, Xi’an 710054, Shaanxi, China
    2.Key Laboratory of Coal Resources Exploration and Comprehensive Utilization, MNR, Xi’an 710021, Shaanxi, China
    3.Shaanxi Coal Industry Chemical Group, Shenmu Tianyuan Chemical Co. , Yulin 719319, Shaanxi, China
  • Received:2022-03-06 Revised:2022-04-24 Published:2022-07-05 Online:2022-08-01
  • Contact: Anning ZHOU E-mail:2920452554@qq.com;psu564@139.com

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摘要：

采用溶胶-凝胶法制得MgFe2O4前体，经焙烧得到MgFe2O4催化剂，再经St?ber法制得核壳结构催化剂MgFe2O4@SiO2和MgFe2O4@SiO2@HZSM-5(MSH)，利用VSM、XRD、SEM、FT-IR、N2物理吸附等手段研究了催化剂的磁性能和结构特征；在固定床反应器上，考察了N2气氛下磁性催化剂对补连塔富油煤的催化热解特性及回收再生性能。结果表明：MgFe2O4为立方尖晶石结构，饱和磁化强度达到181.50 emu/g，具有良好热稳定性能。上述系列磁性催化剂均呈现出良好的催化活性，其中MSH催化活性最好。与非催化热解相比，MSH催化热解焦油产率提高了57.7%，焦油中脂肪烃和苯类含量增加约2倍，稠环芳烃含量下降8.6%~9.8%。采用磁选方法可有效实现催化剂回收，经700℃下焙烧处理，可实现回收催化剂的再生。SiO2包覆有助于提高核壳结构催化剂的磁热稳定性和催化寿命。

关键词: 催化热解, 磁性MgFe2O4, 包覆, 焦油, 回收, 再生

Abstract:

The MgFe2O4 precursor was prepared by the sol-gel method, the MgFe2O4 catalyst was obtained by calcination, and the core-shell structure catalyst MgFe2O4@SiO2 and MgFe2O4@SiO2@HZSM-5 (MSH) were prepared by the St?ber method. The magnetic properties and structural characteristics of the catalysts were investigated by VSM, XRD, SEM, FT-IR, and N2 physical adsorption. In a fixed bed reactor, under an N2 atmosphere, the magnetic catalysts were investigated for the catalytic properties and recovery and regeneration of tar-rich coal from the Bulianta (BLT). The results show that the MgFe2O4 has a cubic spinel structure with a saturation magnetization of 181.50 emu/g and good thermal stability. The above series of magnetic catalysts all show good catalytic activity, among which MSH has the best catalytic activity. Compared with non-catalytic pyrolysis, the tar yield of MSH catalytic pyrolysis increased by 57.7%, the content of aliphatic hydrocarbons and benzene in the tar increased by about 2 times, and the content of polycyclic aromatic hydrocarbons decreased by 8.6%—9.8%. The magnetic separation method can effectively realize the recovery of the catalyst, and regeneration of the catalyst can be realized by roasting in 700℃. The SiO2 coating helps to improve the magnetocaloric stability and catalytic lifetime of the core-shell catalyst.

Key words: catalytic pyrolysis, magnetic MgFe2O4, coating, tar, recovery, regeneration

中图分类号: 

  • TQ 530.2

表1

补连塔煤的工业分析与元素分析"

Proximate analysis/%(mass，ad)Ultimate analysis/%(mass，ad)
MAVFC①CHNSO①
9.584.430.4255.682.425.161.230.2610.93

图1

MgFe2O4系列催化剂制备流程"

图2

实验装置"

图3

磁性催化剂催化热解回收再生过程概念流程图"

图4

磁性催化剂的SEM图"

图5

磁性催化剂的XRD谱图、 N2吸脱附等温曲线、FT-IR谱图和VSM磁化曲线"

表2

磁性催化剂的比表面积和孔结构参数"

催化剂SBET/(m2/g)DBJH/nmVtotal/(10-2 cm3/g)
MgFe2O49.9426.197.32
MgFe2O4@SiO235.3514.0114.82
MSH321.134.207.32

图6

MgFe2O4的XRD与VSM分析"

表3

磁性催化剂对热解产物分布的影响"

催化剂半焦产率/%焦油产率/%气体产率/%水产率/%
none

68.13

65.76

64.94

65.67

9.42

14.25

12.16

14.86

16.19

14.46

16.73

14.82

6.26

5.53

6.17

4.61

MgFe2O4
MgFe2O4@SiO2
MSH

表4

不同催化剂上BLT-coal热解焦油组分含量"

催化剂苯类/%酚类/%脂肪 烃类/%稠环芳 烃类/%其他/%
none1.3718.0412.8534.2233.52
MgFe2O44.1818.5818.2828.6730.29
MgFe2O4@SiO24.0218.2117.9828.9130.88
MSH4.1217.8423.5325.6329.88

图7

磁性催化剂催化热解机理① 煤常规裂解及油气内扩散过程;② 煤常规热解生成的自由基之间的缩聚脱氢形成半焦;③ 煤大分子界面催化裂解形成油气;④ 油气扩散与催化裂化反应形成轻质油及煤气;⑤ 裂解自由基二次缩聚形成半焦或在催化剂表面积炭"

图8

再生催化剂VSM磁化曲线"

表5

再生磁性催化剂对热解产物分布的影响"

催化剂半焦产率/%焦油产率/%气体产率/%水产率/%
1R-MgFe2O465.9713.2314.985.82
1R-MgFe2O4@SiO265.0111.5416.986.47
1R-MSH66.6313.0815.125.17
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