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

doi:10.11949/0438-1157.20190998

Abstract

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

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

CLC Number:

TQ 127.1

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.

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.

Figures/Tables 7

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

Fig.2 Electron microscope images of different samples

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

Fig.3 Low temperature N2 adsorption test results

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

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

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

References 31

1	Sun F G, Liu J, Chen H C, et al. Nitrogen-rich mesoporous carbons: highly efficient, regenerable metal-free catalysts for low-temperature oxidation of H₂S[J]. ACS Catal., 2013, 3: 862-870.
2	Adib F, Bagreev A, Bandosz T J. Analysis of the relationship between H₂S removal capacity and surface properties of unimpregnated activated carbons[J]. Environ. Sci. Technol., 2000, 34: 686-692.
3	Yuan W X, Bandosz T J. Removal of hydrogen sulfide from biogas on sludge-derived adsorbents[J]. Fuel, 2007, 86: 2736-2746.
4	Bandosz T J, Bagreev A, Adib F, et al. Unmodified versus caustics-impregnated carbons for control of hydrogen sulfide emissions from sewage treatment plants[J]. Environ. Sci. Technol., 2000, 34: 1069-1074.
5	Long D H, Chen Q J, Qiao W M, et al. Three-dimensional mesoporous carbon aerogels: ideal catalyst supports for enhanced H₂S oxidation[J]. Chem. Commun., 2009, 26: 3898-3900.
6	Yu Z F, Wang X Z, Song X D, et al. Molten salt synthesis of nitrogen-doped porous carbons for hydrogen sulfide adsorptive removal[J]. Carbon, 2015, 95: 852-860.
7	Seredych M, Bandosz T J. Desulfurization of digester gas on wood-based activated carbons modified with nitrogen: importance of surface chemistry[J]. Energy & Fuels, 2008, 22: 850-859.
8	Seredych M, Bandosz T J. Role of microporosity and nitrogen functionality on the surface of activated carbon in the process of desulfurization of digester gas[J]. J. Phys. Chem. C., 2008, 112: 4704-4711.
9	Xing W, Liu C, Zhou Z Y, et al. Superior CO₂ uptake of N-doped activated carbon through hydrogen-bonding interaction[J]. Energy Environ. Sci., 2012, 5: 7323-7327.
10	Bing X F, Wei Y J, Wang M, et al. Template-free synthesis of nitrogen-doped hierarchical porous carbons for CO₂ adsorption and supercapacitor electrodes[J]. J. Colloid Inter. Sci., 2017, 488: 207-217.
11	Shen W Z, Fan W B. Nitrogen-containing porous carbons: synthesis and application[J]. J. Mater. Chem., 2013, 1: 999-1013.
12	Machnikowski J, Grzyb B, Machnikowska H, et al. Surface chemistry of porous carbons from N-polymers and their blends with pitch[J]. Micropor. Mesopor. Mater., 2005, 82: 113-120.
13	Guo H S, Ding B, Wang J, et al. Template-induced self-activation route for nitrogen-doped hierarchically porous carbon spheres for electric double layer capacitors[J]. Carbon, 2018, 136: 204-210.
14	Gu Y, Wu H, Xiong Z G, et al. The electrocapacitive properties of hierarchical porous reduced graphene oxide templated by hydrophobic CaCO₃ spheres[J]. J. Mater. Chem. A, 2014, 2: 451-459.
15	Kim Y K, Park J H, Lee J W. Facile nano-templated CO₂ conversion into highly interconnected hierarchical porous carbon for high-performance supercapacitor electrodes[J]. Carbon, 2018, 126: 215-224.
16	Li S, Jiang T, Xu Z H, et al. The Mn-promoted double-shelled CaCO₃hollow microspheres as high efficient CO₂ adsorbents[J]. Chem. Eng. J., 2019, 372: 53-64.
17	徐春霞. 煤焦油的性质与加工利用[J]. 洁净煤技术, 2013, 5: 63-67.
	Xu C X. Properties, processing and utilization of coal tar[J]. Clean Coal Technology, 2013, 5: 63-67.
18	史晓斐, 杨思宇, 钱宇. 化学链技术在煤炭清洁高效利用中的研究进展[J]. 化工学报, 2018, 69(12): 4931-4946.
	Shi X F, Yang S Y, Qian Y. Research progress of chemical chain technology in clean and efficient utilization of coal[J]. CIESC Journal, 2018, 69(12): 4931-4946.
19	程炎, 颜彬航, 李天阳, 等. 煤/煤焦油/沥青质的热等离子体裂解特性比较分析[J]. 化工学报, 2015, 66(8): 3210-3217.
	Cheng Y, Yan B H, Li T Y, et al. Comparative analysis of thermal plasma cracking characteristics of coal/coal tar/asphaltene[J]. CIESC Journal, 2015, 66(8): 3210-3217.
20	Cui M J, Ren S M, Zhao H C, et al. Polydopamine coated graphene oxide for anticorrosive reinforcement of water-borne epoxy coating[J]. Chem. Eng. J., 2018, 335: 255-266.
21	Jiang H, Ren D Y, Hu H F, et al. 2D Monolayer MoS₂-carbon interoverlapped superstructure: engineering ideal atomic interface for lithium ion storage[J]. Adv. Mater., 2015, 27: 3687-3695.
22	Wang J, Tang J, Xu Y, et al. Interface miscibility induced double-capillary carbon nanofibers for flexible electric double layer capacitors[J]. Nano Energy, 2016, 28: 232-240.
23	Lin T, Chen I W, Liu F, Yet al. Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage[J]. Science, 2015, 350(6267): 1508-1513.
24	Guang P H, Wen C L, Dan Q, et al. Rapid synthesis of nitrogen-doped porous carbon monolith for CO₂capture[J]. Adv. Mater., 2010, 22: 853-857.
25	Shen F H, Liu J, Zhang Z, et al. Density functional study of hydrogen sulfide adsorption mechanism on activated carbon[J]. Fuel Process. Technol., 2018, 171: 258-264.
26	Mochizuki T, Kubota M, Matsuda H, et al. Adsorption behaviors of ammonia and hydrogen sulfide on activated carbon prepared from petroleum coke by KOH chemical activation[J]. Fuel Process. Technol., 2016, 144: 164-169.
27	Ozekmekci M, Salkic G, Fellah M F. Use of zeolites for the removal of H₂S: a mini-review[J]. Fuel Process. Technol., 2015, 139: 49-60.
28	Liu H, Jia M, Sun N, et al. Nitrogen-rich mesoporous carbon as anode material for high-performance sodium-ion batteries[J]. ACS Appl. Mater. Interfaces, 2015, 7(49): 27124-27130.
29	Zhao C, Wang W, Yu Z, et al. Nano-CaCO₃ as template for preparation of disordered large mesoporous carbon with hierarchical porosities[J]. J. Mater. Chem., 2010, 20(5): 976-980.
30	Yu C, Fan X M, Yu L M, et al. Adsorptive removal of thiophenic compounds from oils by activated carbon modified with concentrated nitric acid[J]. Energy & Fuels, 2013, 27: 1499-1505.
31	Zhang Z, Wang J, Li W, et al. Millimeter-sized mesoporous carbon spheres for highly efficient catalytic oxidation of hydrogen sulfide at room temperature[J]. Carbon, 2016, 96: 608-615.

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