CO2辅助好氧菌煤炭脱硫工艺的实验

doi:10.16085/j.issn.1000-6613.2020-0416

摘要/Abstract

摘要：

生物脱硫技术具有环境和过程友好等特点，在煤炭脱硫领域具有重要的应用开发前景。本文主要研究了嗜酸氧化亚铁硫杆菌（Acidithiobacillus ferrooxidans）和嗜酸氧化硫硫杆菌（Acidithiobacillus thiooxidans）混合菌群对高硫煤生物的脱硫工艺，分别考察了空气氧化环境、CO₂辅助气氛下的脱硫效果。实验结果表明，A. ferrooxidans和A. thiooxidans混合菌群在空气氧化环境下具有良好的脱硫能力，两种嗜酸好氧菌表现出一定的协同作用，无机硫脱除率可达70%；而CO₂辅助能够显著提高有氧条件下菌群的脱硫效率，无机硫脱除率可达90%以上。通过扫描电镜（SEM）、红外光谱（FTIR）、X射线衍射（XRD）、X射线光电子能谱技术（XPS）等表征手段对脱硫后的煤炭结构变化和发酵脱硫机制进行研究，引入的CO₂一方面为两种好氧菌在发酵条件下提供碳源，促使菌群快速生长增殖；另一方面部分CO₂溶于水使发酵溶液中碳酸根离子浓度发生改变，实现降低发酵脱硫产物黄钾铁矾在煤粒表面的沉积密度，促进生物脱硫过程的进行。

关键词: 生物脱硫, 氧化亚铁硫杆菌, 氧化硫硫杆菌, 二氧化碳, 混合共培养, 煤

Abstract:

Biodesulfurization technology is environmentally and process-friendly, which has important application and development prospect in the field of coal desulfurization. This paper studied the biological desulfurization process of high sulfur coal by the mixed flora of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans, and examined the desulfurization effects under air oxidation environment and CO₂ auxiliary atmosphere. The results showed that the mixed flora of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans had good desulphurization ability in air oxidation environment, the two aerobic eosinophilic bacteria showed certain synergistic effect, and the inorganic sulfur removal rate reached 70%. However, CO₂-assisted atmosphere significantly improved the desulfurization efficiency of bacteria under aerobic (air oxidation environment) conditions, which increased the removal rate of inorganic sulfur by 20%, and the removal rate of inorganic sulfur reached more than 90%. SEM, FTIR, XRD, XPS and other characterization methods were used to study the structural changes of coal desulfurization. It was speculated that the introduced CO₂ provided sufficient carbon source for the growth of the two bacteria, which promoted the rapid growth and proliferation of the two bacteria. At the same time, the solution ion concentration changed due to the CO₂ dissolved in water, which reduced the adsorption density of jarosite precipitation on the surface of coal particles, and promoted the process of biodesulfurization.

Key words: biological desulfurization, Acidithiobacillus thiooxidans, Acidithiobacillus thiooxidans, carbon dioxide, mixed co-culture, coal

中图分类号:

Q939.9

王瑞, 刘自勇, 王琪, 彭翠娜, 陈中合, 李福利, 王晓龙, 杨成. CO₂辅助好氧菌煤炭脱硫工艺的实验[J]. 化工进展, 2021, 40(1): 526-533.

Rui WANG, Ziyong LIU, Qi WANG, Cuina PENG, Zhonghe CHEN, Fuli LI, Xiaolong WANG, Cheng YANG. Experimental on CO₂-assisted aerobic-bacteria coal desulfurization process[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 526-533.

图/表 10

参考文献 22

1	张成桂, 夏金兰, 邱冠周. 嗜酸氧化亚铁硫杆菌亚铁氧化系统研究进展[J]. 中国有色金属学报, 2006, 16(7): 1239-1249.
	ZHANG Chenggui, XIA Jinlan, QIU Guanzhou. Progress in research on Fe²⁺ oxidation system of Acidithiobacillus ferrooxidans[J]. The Chinese Journal of Nonferrous Metals, 2006, 16(7): 1239-1249.
2	CARDONA I C, MARQUEZ M A. Biodesulfurization of two Colombian coals with native microorganisms[J]. Fuel Processing Technology, 2009, 90: 1099-1106.
3	刘玉娇, 杨新萍, 张德伟, 等. pH、接种量及固形物含量对氧化亚铁硫杆菌LX5煤炭生物脱硫的影响[J]. 环境工程学报, 2013, 7(2): 759-764.
	LIU Yujiao, YANG Xinping, ZHANG Dewei, et al. Effect of pH, inoculation and coal burden on bio-desulfurization of coal by Acidithiobacillus ferrooxidans LX5 [J]. Chinese Journal of Environmental Engineering, 2013, 7(2): 759-764.
4	张明旭, 孙剑峰. 球红假单胞菌用于煤炭生物浸出脱硫的研究[J]. 选煤技术, 2009(4): 6-11.
	ZHANG Mingxu, SUN Jianfeng. Study on the application of pseudomonas globulum in coal bioleach desulfurization[J]. Coal Preparation Technology, 2009(4): 6-11.
5	巩冠群, 陶秀祥. 煤炭生物脱硫的白腐菌浮选和浸滤研究[J]. 煤炭科学技术, 2006(2): 49-51, 56.
	GONG Guanqun, TAO Xiuxiang. Research on white decay bacterium flotation and leaching for coal biological desulphurization[J]. Coal Science and Technology, 2006(2): 49-51, 56.
6	AKHTAR N, GHAURI M A, AKHTAR K. Exploring coal biodesulfurization potential of a novel organic sulfur Metabolizing Rhodococcus spp. (Eu-32)—A case study[J]. Geomicrobiology Journal, 2016, 33(6): 468-472.
7	JUSZCZAK A, DOMKA F, KOZLOWSKI M, et al. Microbial desulfurization of coal with Thiobacillus ferrooxidans bacteria[J]. Fuel, 1995, 74(5): 725-728.
8	OHMURA N, SASAKI K, MATSUMOTO N, et al. Anaerobic respiration using Fe³⁺, S⁰, and H₂ in the chemolithoautotrophic bacterium Acidithiobacillus ferrooxidans[J]. Journal of Bacteriology, 2002, 184(8): 2081-2087.
9	OHMURA N, MATSUMOTO N, SASAKI K, et al. Growth of Thiobacillus ferrooxidans on hydrogen by the dissimilatory reduction of ferric iron under anaerobic conditions[J]. Process Metallurgy, 1999, 9: 767-775.
10	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 煤中各种形态硫的测定方法: [S]. 北京: 中国标准出版社, 2003.
	General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China. Determination of forms of sulfur in coal: [S]. Beijing: Standards Press of China, 2003.
11	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 煤的工业分析方法: [S]. 北京: 中国标准出版社, 2008.
	General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China, China National Standardization Management Committee. Proximate analysis of coal: [S]. Beijing: Standards Press of China, 2008.
12	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 煤的发热量测定方法: [S]. 北京: 中国标准出版社, 2008.
	General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China, China National Standardization Management Committee. Determination of calorific value of coal: [S]. Beijing: Standards Press of China, 2008.
13	刘相梅, 文晴, 王慧妍, 等. 一种筛选嗜酸性氧化硫硫杆菌无标记基因敲除菌株的方法: CN103232994A[P]. 2013-08-07.
	LIU Xiangmei, WEN Qing, WANG Huiyan, et al. Method for screening markerless gene knockout strains of Acidithiobacillus acidophilus: CN103232994A[P]. 2013-08-07.
14	刘相梅, 林建群, 田克立, 等. 极端嗜酸性专性化能自养硫细菌有机质代谢的研究进展[J]. 生物工程学报, 2008, 24(1): 1-7.
	LIU Xiangmei, LIN Jianqun, TIAN Keli, et al. Metabolism of organic compounds by extreme acidophilic, obligately chemolithoautotrophic Thiobacilli—A review[J]. Chinese Journal of Biotechnology, 2008, 24(1): 1-7.
15	FARMER V C. The infrared spectra of minerals: mineralogical society monograph (Vol.4)[M]. London: Mineralogical Society, 1974.
16	李梅, 杨俊和, 张启锋, 等. 用XPS研究新西兰高硫煤热解过程中氮、硫官能团的转变规律[J]. 燃料化学学报, 2013, 41(11): 1287-1293.
	LI Mei, YANG Junhe, ZHANG Qifeng, et al. XPS study on transformation of N- and S-functional groups during pyrolysis of high sulfur New Zealand coal[J]. Journal of Fuel Chemistry and Technology, 2013, 41(11): 1287-1293.
17	YAMASHITA T, HAYES P. Analysis of XPS spectra of Fe²⁺ and Fe³⁺ ions in oxide materials[J]. Applied Surface Science, 2007, 254(8): 2441-2449.
18	竺桦, 陈诵英. 煤的生物脱硫(Ⅰ)——脱黄铁矿硫[J]. 煤炭转化, 1990(2): 40-44.
	ZHU Hua, CHEN Songying. Biological desulfurization of coal (Ⅰ)—Desulfurization of pyrite[J]. Coal Conversion, 1990(2): 40-44.
19	刘欣伟, 冯雅丽, 李浩然, 等. 好氧和厌氧条件下Acidithiobacillus ferrooxidans菌对Fe³⁺氧化FeS₂的影响[J]. 中国有色金属学报, 2013, 23(1): 274-281.
	LIU Xinwei, FENG Yali, LI Haoran, et al. Effect of Acidithiobacillus ferrooxidans on pyrite oxidation by ferric iron under aerobic and anaerobic conditions[J]. The Chinese Journal of Nonferrous Metals, 2013, 23(1): 274-281.
20	SAND W, GEHRKE T, JOZSA P, et al. (Bio)chemistry of bacterial leaching-direct vs. indirect bioleaching[J]. Hydrometallurgy, 2001, 59: 159-175.
21	SCHIPPERS A, SAND W. Bacterial leaching of metal sulfides proceeds by two indirect mechanisms via thiosulfate or via polysulfides and sulfur[J]. Applied and Environmental Microbiology, 1999, 65: 319-321.
22	朱长见, 陆建军, 陆现彩, 等. 氧化亚铁硫杆菌作用下形成的黄钾铁矾的SEM研究[J]. 高校地质学报, 2005, 11(2): 234-238.
	ZHU Changjian, LU Jianjun, LU Xiancai, et al. SEM study of pyrite in the potassium ferrooxide formed by thiobacillus ferrooxidans[J]. Geological Journal of China Universities, 2005, 11(2): 234-238.

样品	热值/J·g^-1	硫化铁硫/%	工业分析			元素分析
样品	热值/J·g^-1	硫化铁硫/%	M_ad/%	V_ad/%	A_ad/%	C/%	H/%	N/%	S/%	O/%
原煤	25997	0.97	1.96	14.39	21.85	67.30	2.64	0.80	3.33	3.64
对照组	26393	0.77	1.78	11.95	18.81	70.36	2.84	0.86	3.37	3.42
实验组	26127	0.21	1.95	15.64	18.38	68.60	2.83	0.94	3.21	5.68

样品	热值/J·g^-1	硫化铁硫/%	工业分析			元素分析
样品	热值/J·g^-1	硫化铁硫/%	M_ad/%	V_ad/%	A_ad/%	C/%	H/%	N/%	S/%	O/%
原煤	25997	0.97	1.96	14.39	21.85	67.30	2.64	0.80	3.33	3.64
对照组	26393	0.77	1.78	11.95	18.81	70.36	2.84	0.86	3.37	3.42
实验组	26127	0.21	1.95	15.64	18.38	68.60	2.83	0.94	3.21	5.68

S 2p-结合能/eV			峰面积占比/%			赋存形态归属
原煤	空气-脱硫	CO₂-脱硫	原煤	空气-脱硫	CO₂-脱硫	赋存形态归属
170.10	170.18	170.03	30.10	43.36	62.43	硫酸盐
	169.10	168.84	30.10	43.36	62.43	硫酸盐
164.00	163.97	163.96	56.53	40.67	26.35	硫化物
163.73	163.67	163.53	56.53	40.67	26.35	硫化物

S 2p-结合能/eV			峰面积占比/%			赋存形态归属
原煤	空气-脱硫	CO₂-脱硫	原煤	空气-脱硫	CO₂-脱硫	赋存形态归属
170.10	170.18	170.03	30.10	43.36	62.43	硫酸盐
	169.10	168.84	30.10	43.36	62.43	硫酸盐
164.00	163.97	163.96	56.53	40.67	26.35	硫化物
163.73	163.67	163.53	56.53	40.67	26.35	硫化物

样品名	结合能/eV		Fe(Ⅲ)∶Fe(Ⅱ) 的峰面积比
样品名	Fe 2p_1/2	Fe 2p_3/2	Fe(Ⅲ)∶Fe(Ⅱ) 的峰面积比
原煤样	724.96	711.62	0
空气-脱硫	726.95	713.92	2.15
	725.24	712.10	2.5
CO₂-脱硫	726.59	713.47	1.49
	724.66	711.80	1.49

CO₂辅助好氧菌煤炭脱硫工艺的实验

Experimental on CO₂-assisted aerobic-bacteria coal desulfurization process

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