低阶煤原位制备ZnO基活性炭脱硫剂

doi:10.11949/0438-1157.20210041

化工学报 ›› 2021, Vol. 72 ›› Issue (9): 4921-4930.DOI: 10.11949/0438-1157.20210041

低阶煤原位制备ZnO基活性炭脱硫剂

演康^1,³(),杨颂^1,³,刘守军^1,^2,³(),杨超²,樊惠玲^2,³,上官炬^2,³

^1.太原理工大学化学化工学院，山西太原 030024
^2.太原理工大学，煤科学与技术教育部和山西省重点实验室，山西太原 030024
^3.山西省民用洁净燃料工程研究中心，山西太原 030024

收稿日期:2021-01-08 修回日期:2021-04-23 出版日期:2021-09-05 发布日期:2021-09-05
通讯作者: 刘守军
作者简介:演康（1995—），男，硕士研究生，1310333755@qq.com
基金资助:
国家自然科学基金项目(22078223);山西省高等学校科技创新项目(2019L0313);山西省专利推广实施资助计划(20200719)

In-situ preparation of ZnO-based activated carbon desulfurizer from low-rank coal

Kang YAN^1,³(),Song YANG^1,³,Shoujun LIU^1,^2,³(),Chao YANG²,Huiling FAN^2,³,Ju SHANGGUAN^2,³

^1.College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^3.Shanxi Engineering Center of Civil Clean Fuel, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2021-01-08 Revised:2021-04-23 Online:2021-09-05 Published:2021-09-05
Contact: Shoujun LIU

摘要/Abstract

摘要：

将金属氧化物活性组分通过浸渍负载的方式分散到多孔载体上，是制备高活性金属氧化物脱硫剂的常用方法。然而，由于活性组分的负载易使载体孔隙率下降，导致活性组分的脱硫能力不能充分发挥。本文直接以廉价的低阶煤为原料，经过预处理后在煤中加入硝酸锌，通过物理-化学活化法一步制备ZnO基活性炭常温脱硫剂，即将活性炭的制备与活性组分的负载一步完成。研究了硝酸锌加入量、活化温度和活化时间对脱硫剂脱硫性能的影响。结果表明：当硝酸锌加入量为20%（质量），活化温度为850℃，活化时间为1 h时，脱硫剂的穿透时间为210 min，其对应的穿透硫容为71.4 mg/g，其脱硫性能是同等实验条件下商业活性炭负载ZnO脱硫剂的5.3倍，较高的脱硫性能主要归因于其发达的介孔孔隙，不仅有利于传质，而且有利于硫化产物的存储。

关键词: 原位制备, 活性炭, 脱硫剂, 吸附, H₂S

Abstract:

Dispersing the metal oxide active component on the porous carrier by impregnation and loading is a common method for preparing highly active metal oxide desulfurizers. However, due to the decrease of porosity of the carrier due to the loading of active components, the desulfurization capacity of active components cannot be fully utilized. In this study, cheap low-rank coal was directly used as raw material. After pretreatment, zinc nitrate was added into the coal to prepare ZnO based activated carbon desulfurizer at room temperature in one step through physical-chemical activation method. The preparation of activated carbon and the loading of active components were completed in one step. The effects of zinc nitrate immersion amount, activation temperature and activation time on desulfurization performance of desulfurizer were studied. The results showed that when the immersion amount was 20%(mass), the activation temperature was 850℃, and the activation time was 1 h, the breakthrough time of desulfurizer was 210 min, and its sulfur capacity was 71.4 mg/g. Its desulfurization performance was 5.3 times that of commercial activated carbon supported ZnO desulfurizer under the same experimental conditions. The high desulfurization performance is mainly attributed to its developed mesoporous pores, which is not only conducive to mass transfer, but also beneficial to the storage of sulfide products.

Key words: in-situ preparation, activated carbon, desulfurizer, adsorption, hydrogen sulfide

中图分类号:

O 643.3

演康, 杨颂, 刘守军, 杨超, 樊惠玲, 上官炬. 低阶煤原位制备ZnO基活性炭脱硫剂[J]. 化工学报, 2021, 72(9): 4921-4930.

Kang YAN, Song YANG, Shoujun LIU, Chao YANG, Huiling FAN, Ju SHANGGUAN. In-situ preparation of ZnO-based activated carbon desulfurizer from low-rank coal[J]. CIESC Journal, 2021, 72(9): 4921-4930.

图/表 15

表1 WM的工业分析及元素分析

Table 1 Industrial analysis and elemental analysis of WM

工业分析/%					元素分析/%
V_ad	M_ad	A_ad	FC_ad		C_ad	H_ad	O_ad^①	N_ad	S_ad
31.57	22.16	7.24	39.03		47.54	4.61	16.97	0.61	0.87

图1 样品制备示意图

Fig.1 Schematic diagram of sample preparation

图2 脱硫实验流程图

Fig.2 Flow chart of desulfurization experiment

图3 不同硝酸锌加入量所制备脱硫剂的穿透曲线(a)和对应的穿透硫容(b)

Fig.3 The breakthrough curves (a) and the breakthrough sulfur capacity (b) of the adsorbents prepared with different Zn(NO3)2 impregnation content

图4 不同活化温度所制备脱硫剂的穿透曲线(a)和对应的穿透硫容(b)

Fig.4 The breakthrough curves (a) and the breakthrough sulfur capacity (b) of the adsorbents prepared with different activation temperature

图5 不同活化时间所制备脱硫剂的穿透曲线(a)和对应的穿透硫容(b)

Fig.5 The breakthrough curves (a) and the breakthrough sulfur capacity (b) of the adsorbents prepared with different activation time

图6 商业活性炭负载ZnO脱硫剂和原位制备ZnO活性炭脱硫剂的穿透曲线(a)和对应的穿透硫容(b)

Fig.6 The breakthrough curves (a) and the breakthrough sulfur capacity (b) of the commercial activated carbon supported ZnO adsorbent and in-situ prepared ZnO activated carbon adsorbent

图7 AC-20和WM-850-1-20的XRD谱图

Fig.7 XRD patterns of samples AC-20 and WM-850-1-20

图8 AC-20和WM-850-1-20的N2吸脱附等温线(a)及孔径分布(b)

Fig. 8 The adsorption and desorption isotherms (a) and the pore size distribution (b) of AC-20 and WM-850-1-20

表2 AC-20和WM-850-1-20的织构性质

Table 2 Textural properties of AC-20 and WM-850-1-20

样品	比表面积/(m²/g)	总孔/(cm³/g)	微孔/(cm³/g)	介孔/(cm³/g)	介孔/总孔
AC-20	913	0.47	0.37	0.10	0.21
WM-850-1-20	355	0.25	0.08	0.17	0.68

图9 AC-20 (a)和WM-850-1-20 (b) 的扫描电镜图和对应的Zn元素分布图

Fig. 9 SEM images and the corresponding Zn mapping of AC-20 (a) and WM-850-1-20 (b)

图10 ACE-20 (a)和WME-850-1-20 (b)的S 2p XPS谱图

Fig. 10 S 2p XPS spectra of ACE-20 (a) and WME-850-1-20 (b)

图11 ACE-20和WME-850-1-20的N2吸脱附等温线(a)及孔径分布(b)

Fig. 11 The N2 adsorption and desorption isotherms (a) and the pore size distribution (b) of ACE-20 and WME-850-1-20

表3 ACE-20和WME-850-1-20的织构性质

Table 3 Textural properties of ACE-20 and WME-850-1-20

样品	比表面积/(m²/g)	总孔/(cm³/g)	微孔/(cm³/g)	介孔/(cm³/g)	介孔/总孔
ACE-20	854	0.44	0.35	0.09	0.20
WME-850-1-20	302	0.20	0.05	0.15	0.75

图12 原位ZnO基活性炭脱硫剂的制备和吸附机理

Fig. 12 Preparation and adsorption mechanism of in-situ ZnO activated carbon adsorbents

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低阶煤原位制备ZnO基活性炭脱硫剂

In-situ preparation of ZnO-based activated carbon desulfurizer from low-rank coal

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