煤基富氮层级多孔碳制备及其催化脱硫性能

doi:10.11949/0438-1157.20190998

化工学报 ›› 2020, Vol. 71 ›› Issue (2): 660-668.DOI: 10.11949/0438-1157.20190998

• 催化、动力学与反应器 • 上一篇下一篇

煤基富氮层级多孔碳制备及其催化脱硫性能

孙明慧^1,²(),陈静圆²,肖南^1,²,陈奥博²,王旭珍^1,²(),邱介山^1,^2,³()

^1.精细化工国家重点实验室，辽宁大连 116024
^2.大连理工大学化工学院，辽宁省功能材料化工重点实验室，辽宁大连 116024
^3.北京化工大学化学工程学院，北京 100029

收稿日期:2019-09-03 修回日期:2019-11-08 出版日期:2020-02-05 发布日期:2020-02-05
通讯作者: 王旭珍,邱介山
作者简介:孙明慧（1993—），女，硕士研究生，smh1105@mail.dlut.edu.cn
基金资助:
国家自然科学基金项目(U1610105)

Preparation of hierarchical nitrogen-rich porous carbon from coal tar for catalytic desulfurization

Minghui SUN^1,²(),Jingyuan CHEN²,Nan XIAO^1,²,Aobo CHEN²,Xuzhen WANG^1,²(),Jieshan QIU^1,^2,³()

^1.State Key Laboratory of Fine Chemical Engineering, Dalian 116024, Liaoning, China
^2.School of Chemical Engineering & Liaoning Key Laboratory for Energy Materials and Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
^3.School of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2019-09-03 Revised:2019-11-08 Online:2020-02-05 Published:2020-02-05
Contact: Xuzhen WANG,Jieshan QIU

摘要/Abstract

摘要：

以煤加工副产物煤焦油中蒽油馏分为碳源、多巴胺为氮源，基于纳米碳酸钙球模板在碳化过程中发生的诱导自活化作用，一步共碳化制得氮掺杂多孔碳（NPCs）材料。通过元素分析、低温氮气吸附-脱附测试、扫描及透射电镜表征，结果表明，NPCs材料的氮元素掺杂量高，且具有发达的微孔-介孔梯级孔道结构。结合室温下催化硫化氢选择性氧化为单质硫的反应性能评价，发现改变模板剂用量、碳/氮源投料比和碳化温度，可调控NPCs材料的氮掺杂量（质量分数6.4%~21.3%）、比表面积、孔道结构发达程度及相应的定向转化硫容，最佳工艺条件下合成样品的饱和硫容高达5.8 g H₂S/(g催化剂)。

关键词: 碳材料, 煤焦油, 氮掺杂, 纳米结构, 催化, 氧化脱硫

Abstract:

Nitrogen-doped porous carbon (NPCs) were prepared by one-step co-carbonization used the anthracene oil fraction form coal taras the carbon source and dopamine as the nitrogen source, based on the induced self-activation of the nano-calcium carbonate template in the carbonization process. The results from element analyses, cryogenic nitrogen adsorption-desorption test, scanning and transmission electron microscopy characterization show that NPCs have a high level of doping nitrogen and the developed micro-mesoporous hierarchical structure. Combined with the evaluation for catalytic oxidation of hydrogen sulfide to elemental sulfur at room temperature, it is found that the doped-nitrogen amount (6.4%－21.3%,mass fraction), the specific surface area, the channel texture and the corresponding desulfurization performance of NPCs can be controlled by changing the dosage of template agent, the feeding ratio of carbon/nitrogen source and the carbonization temperature. And the saturated sulfur capacity of NPCs can be up to 5.8 g H₂S/(g cat.) when synthesized under the optimal process conditions.

Key words: carbon material, coal tar, nitrogen doped, nanoscale structure, catalysis, oxidative desulfurization

中图分类号:

TQ 127.1

孙明慧, 陈静圆, 肖南, 陈奥博, 王旭珍, 邱介山. 煤基富氮层级多孔碳制备及其催化脱硫性能[J]. 化工学报, 2020, 71(2): 660-668.

Minghui SUN, Jingyuan CHEN, Nan XIAO, Aobo CHEN, Xuzhen WANG, Jieshan QIU. Preparation of hierarchical nitrogen-rich porous carbon from coal tar for catalytic desulfurization[J]. CIESC Journal, 2020, 71(2): 660-668.

图/表 7

图1 氮掺杂层级多孔碳材料（NPCs）的形成机理

Fig.1 Schematic diagram for formation of nitrogen-doped hierarchical porous carbons (NPCs)

图2 不同样品的电镜图像

Fig.2 Electron microscope images of different samples

表1 不同实验参数制备的不同系列 NPCs 样品的元素分析结果

Table 1 Elemental analysis results of various NPCs prepared at different experiment conditions

Sample	Elemental analysis /%
Sample	N	C	N/C
NPC-1/5-2-700	6.4	69.9	0.09
NPC-1/5-1-700	10.2	63.3	0.16
NPC-1/5-1/4-700	16.3	52.4	0.31
NPC-1/5-1/2-400	21.3	49.9	0.43
NPC-1/5-1/2-600	18.7	56.4	0.33
NPC-1/5-1/2-700	12.5	58.3	0.21
NPC-1/5-1/2-800	9.0	67.3	0.13

图3 不同条件下制备样品的低温N2吸附测试结果

Fig.3 Low temperature N2 adsorption test results

表2 不同实验参数制备的不同系列 NPCs 样品的BET测试结果

Table 2 BET test results of various NPCs prepared at different experiment conditions

Sample	Pore structures
Sample	S_BET/(m²/g)	V_tot/(cm³/g)	V_mic/(cm³ /g)
NPC-2-1/2-700	307. 8	0.2	0.1
NPC-1-1/2-700	465.5	0.4	0.2
NPC-1/3-1/2-700	666.5	0.5	0.3
NPC-1/10-1/2-700	339.3	0.3	0.1
NPC-1/5-1/2-400	286.2	0.4	0.1
NPC-1/5-1/2-600	480.6	0.8	0.2
NPC-1/5-1/2-700	811.6	0.8	0.2
NPC-1/5-1/2-800	941.3	0.6	0.4

图4 不同条件下制得的NPCs样品用于室温下催化脱硫性能结果

Fig.4 Desulfurization performances of NPCs samples prepared under different conditions (room temperature)

图5 NPC-1/5-1/2-700催化剂脱硫前后的系列表征

Fig.5 Characterization results of NPC-1/5-1/2-700 catalyst before and after desulfurization

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煤基富氮层级多孔碳制备及其催化脱硫性能

Preparation of hierarchical nitrogen-rich porous carbon from coal tar for catalytic desulfurization

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