Fe-Zn基废脱硫剂制备铁碳材料及其对废水微电解性能

doi:10.11949/0438-1157.20190832

摘要/Abstract

摘要：

以Fe-Zn基废脱硫剂、煤、Na ₂CO ₃为原料进行高温炭热还原反应，制备了铁碳材料，实现了Zn和S的分离，有望能实现废脱硫剂的综合利用。考察不同工艺条件（配比，温度，时间）对铁碳材料品质，Zn单质分离效率和Na ₂S的收率影响。结果表明：反应温度≥900℃，煤∶废脱硫剂≥1，Na ₂CO ₃∶废脱硫剂≥1.5，反应时长≥2 h，Zn、S的分离回收效率可达到95%以上。且900℃制备的铁碳材料比表面高达193.6 m ²/g，介孔孔体积为0.028 cm ³/g，炭均匀附着于铁骨架。微电解-芬顿联用降解有机废水实验表明：仅微电解或微电解-芬顿联用（H ₂O ₂=COD=1500 mg/L）时，自制铁碳材料的稳定化学需氧量（COD）去除效率（41.78%、73.56%）都高于商业铁碳（8.43%、48.43%)。本文实验结果表明废脱硫剂与煤和碳酸钠混烧可实现废脱硫剂中Zn与S的分离回收，成功获得了比表面高、去除COD性能好的铁碳材料。

关键词: Fe-Zn基废脱硫剂, 炭热还原, 微电解-芬顿, COD

Abstract:

The Fe-Zn-based waste desulfurizer, coal and Na ₂CO ₃ were used as raw materials to carry out high-temperature carbon thermal reduction reaction, and iron-carbon materials were prepared to realize the separation of Zn and S. It is expected to realize the comprehensive utilization of waste desulfurizer. The effect of different preparation parameters ( e. g., ratios, temperature, time) were investigated to improve the removal efficiency of Zn/S and obtain high-quality Fe-C materials. The best results can be achieved with separation efficiency of Zn and S above 95% with the ratio of 1/1/1.5 for coal/waste desulfurizer/Na ₂CO ₃ at 900℃ for 2 h. Moreover, the specific surface area of the prepared Fe-C material can reach as high as 193.6 m ²/g with the mesoporous volume of 0.028 cm ³/g. In addition, the micro-electrolysis-Fenton test showed the removal efficiency of COD for the as-prepared Fe-C material are 41.78% and 73.56% without/with H ₂O ₂ (H ₂O ₂=COD=1500 mg/L), respectively, which is much better than commercial Fe-C material with the removal efficiency of 8.43% and 48.43% on the same condition. These results demonstrate the heat treatment process of waste desulfurizer with Buliangou-coal and Na ₂CO ₃ may be an effective way for its resource utilization to separate Zn and S as well as produce Fe-C material.

Key words: Fe-Zn-based waste desulfurizer, carbothermal reaction, micro-electrolysis-Fenton, COD

中图分类号:

TQ 420.6

张霄玲, 于凤芹, 皇甫林, 王超, 李长明, 高士秋, 余剑. Fe-Zn基废脱硫剂制备铁碳材料及其对废水微电解性能[J]. 化工学报, 2020, 71(2): 788-798.

Xiaoling ZHANG, Fengqin YU, Lin HUANGFU, Chao WANG, Changming LI, Shiqiu GAO, Jian YU. Utilization of Fe-Zn-based waste desulfurizer to produce Fe-C materials for removing COD from waste water[J]. CIESC Journal, 2020, 71(2): 788-798.

图/表 12

图1 废脱硫剂XRD谱图

Fig.1 XRD pattern of waste desulfurizer

表1 不连沟煤的工业分析和元素分析

Table 1 Proximate and ultimate analysis of Buliangou coal

Proximate analysis/%(mass)			Ultimate analysis/%(mass)
Ash	Volatile	Fixed carbon	C	H	O	N	S
19.56	29.46	50.98	62.38	3.68	12.46	1.09	1.02

图2 废脱硫剂制备铁碳材料及分离Zn工艺流程图

Fig.2 Schemtic diagram for preparation of Fe-C materatial and separation of Zn

表2 废脱硫剂及经过不同热处理样品的XRF分析结果

Table 2 Main chemical composition of waste desulfurizer and samples through different thermal processes

Sample	Main elements/%
Sample	O	Fe	Zn	Al	Ti	Si	Na	Ca	S	Cl	其他
waste desulfurizer	36.11	21.69	10.75	0.105	0.156	0.770	2.570	2.860	13.48	9.980	1.529
W-C900-3	34.37	25.77	14.48	0.145	0.210	1.160	2.675	3.170	10.01	6.830	1.180
WC-C900-3	41.51	18.09	8.015	4.274	0.468	3.064	1.204	3.492	14.15	3.798	1.935
WCN-C900-3	36.31	9.950	0.060	4.350	0.290	3.280	29.88	2.620	8.160	4.120	0.980
Fe-C material	36.23	28.77	0.232	5.342	0.752	7.698	1.770	6.464	0.804	0.372	11.56
commercial Fe-C	36.61	44.11	0.046	3.823	0.251	9.515	0.275	2.678	0.918	0.043	1.728
C-C900-3	47.87	1.450	0.063	21.83	2.250	13.41	0.270	6.510	0.866	0.160	5.318

图3 不同热处理样品XRD谱图及空气热重分析

Fig.3 XRD patterns and TG analysis of samples through different thermal processes

图4 不同工艺参数对废脱硫剂中Zn、S分离效率的影响

Fig.4 Separation rate of Zn and S from waste desulfurizer under different preparation processes

图5 不同样品的扫描电镜图

Fig.5 SEM images of W,W-C900-3, WC-C900-3 and Fe-C material

图6 不同样品N 2等温线及孔径分布曲线

Fig.6 Nitrogen adsorption isotherms and pore size distribution of different samples

表3 不同样品的比表面，孔容及孔径结果

Table 3 Specific surface area and pore size distribution of different samples

Sample	S_BET/ (m ²/g)	Pore volume/(cm ³/g)		Pore size/nm
Sample	S_BET/ (m ²/g)	V_total	V_meso	Pore size/nm
waste desulfurizer	75.08	0.068	0.092	9.446
W-C900-3	12.38	0.012	0	3.915
WC-C900-3	84.97	0.108	0.009	16.39
WCN-C900-3 Fe-C material	84.36 193.6	0.102 0.186	0.008 0.028	15.34 8.281
commercial Fe-C	9.371	0.006	0.001	10.17

图7 铁碳微电解-联用处理有机废水过程的工作特性

Fig.7 Changing rules of disposing waste water by micro-electrolysis-Fenton technology

表4 初始pH对铁碳材料微电解-芬顿联用处理有机废水的影响

Table 4 Effect of original pH on removal rate of COD via micro-electrolysis-Fenton in waste water

Original pH	pH(Fe-C 1.5 h)	Fe ²⁺concentration/ (mg/L)	COD removal rate/%
1.5	1.83	471.2	82.68
2.0	2.57	204.6	72.15
2.5	4.00	85.74	59.56
3.0	5.42	27.89	39.69
5.0	6.30	0.2659	15.36
6.5	7.80	0.008412	14.56

图8 铁碳材料/商业铁碳的重复使用性能及铁的溶出特性

Fig.8 Cyclic utilization performance of Fe-C/commercial Fe-C and dissolution of corresponding Fe element

参考文献 32

1	白静怡, 凌开成. 处理废脱硫剂的可行性研究[J]. 煤炭转化, 2002, 25( 3): 17- 20.
	Bai J Y, Ling K C. Feasibility study on disposal of waste desulfurizer [J]. Coal Conversion, 2002, 25( 3): 17- 20.
2	Wang M M, Li T, Li H Y, et al. Desulfurization of hot coal gas over regenerable low-cost Fe ₂O ₃/mesoporous Al ₂O ₃ prepared by the sol gel method [J]. Energy & Fuels, 2017, 31( 12): 13921- 13932.
3	Lin C F, Qin W, Dong C Q. H ₂S adsorption and decomposition on the gradually reduced alpha-Fe ₂O ₃(001) surface: a DFT study [J]. Applied Surface Science, 2016, 387: 720- 731.
4	刘焕群. 氧化锌脱硫剂的回收利用[J]. 中国资源综合利用, 2001, ( 9): 12- 15.
	Liu H Q. Recovery and utilization of zinc oxide desulfurizer[J]. Comprehensive Utilization of Chinese Resources, 2001, ( 9): 12- 15.
5	马孟臣, 刘自民, 饶磊, 等. 烧结处理焦炉煤气废脱硫剂的研究与应用[J]. 烧结球团, 2017, 42( 1): 54- 57.
	Ma M C, Liu Z M, Rao L, et al. Study and application on the treatment of waste desulfurization for coke oven gas by sintering[J]. Sintering and Pelletizing, 2017, 42( 1): 54- 57.
6	Ma J R, Liu Z Y, Liu S J, et al. A regenerable Fe/AC desulfurizer for SO ₂ adsorption at low temperatures [J]. Applied Catalysis B-Environmental, 2003, 45( 4): 301- 309.
7	陈燕彬. 国内外锌冶炼技术的现状及发展动向[J]. 世界有色金属, 2018, ( 15): 5- 6.
	Chen Y B. Present situation and development trend of zinc smelting technology at home and abroad[J]. Metallurgical Smelting, 2018, ( 15): 5- 6.
8	田秋月, 李聚. 常温氧化铁废脱硫剂回收处理方法的可行性研究[J]. 公用科技, 1995, ( 4): 14- 17.
	Tian Q Y, Li J. Feasibility study on utilization of waste iron oxide desulfurizer at room temperature[J]. Public Science and Technology, 1995, ( 4): 14- 17.
9	丁明雷, 刘建周, 段利叶, 等. 中温氧化锌脱硫剂再生及其织构研究[J]. 天然气化工(C1化学与化工), 2013, 38( 5): 67- 70.
	Ding M L, Liu J Z, Duan L Y, et al. Study on regeneration and texture of a mid-temperature zinc oxide desulfurizer[J]. Natural Gas Chemical Industy(C1 Chemistry and Chemical Engineering), 2013, 38( 5): 67- 70.
10	杨文刚. 废脱硫剂高温焙烧制酸技术的应用[J]. 燃料与化工, 2005, ( 1): 33.
	Yang W G. Application of high temperature roasting of waste desulfurizer to produce acid[J]. Fuel and Chemical Processes, 2005, ( 1): 33.
11	秦亚平. 用氮肥厂的废氧化锌脱硫剂生产七水硫酸锌[J]. 化工环保, 1997, ( 5): 31- 34.
	Qing Y P. Production of ZnSO ₄•7H ₂O from spent ZnO desulfurizer in nitrogen fertilizer plant [J]. Chemical Industry and Environmental Protection, 1997, ( 5): 31- 34.
12	Guo Z Q, Pan J, Zhang F. Green and efficient utilization of waste ferric-oxide desulfurizer to clean waste copper slag by the smelting reduction-sulfurizing process[J]. Journal of Cleaner Production, 2018, 199: 891- 899.
13	Liang M S, Kang W K, Xie K C. Comparison of reduction behavior of Fe ₂O ₃, ZnO and ZnFe ₂O ₄ by TPR technique [J]. Journal of Natural Gas Chemistry, 2009, 18( 1): 110- 113.
14	蒋洪静, 郭满囤. 我国表面活性剂LAS废水的处理技术进展[J]. 山西化工, 2008, 28( 1): 28- 31+51.
	Jiang H J, Guo M T. Development of treatment technology on LAS wastewater[J]. Shanxi Chemical Industry, 2008, 28( 1): 28- 31+51.
15	周丹, 张涛, 呼世斌. 水性油墨废水的活性炭吸附特性研究[J]. 环境科学与技术, 2007, ( 3): 85- 86.
	Zhou D, Zhang T, Hu S B. Adsorbing properties of activated carbon for treating water-based ink-manufacturing wastewater [J]. Environmental Science and Technology, 2007, ( 3): 85- 86.
16	冷彩凤, 王崟, 任龙飞. 光催化氧化法处理胶印油墨废水的研究[J]. 包装工程, 2016, 37( 23): 181- 185.
	Leng C F, Wang Y, Ren L F. Treatment of offset printing ink wastewater by photocatalytic oxidation process[J]. Packing Engineering, 2016, 37( 23): 181- 185.
17	Wu B T, He C H, Yuan S J, et al. Hydrogen enrichment as a bioaugmentation tool to alleviate ammonia inhibition on anaerobic digestion of phenol-containing wastewater[J]. Bioresource Technology, 2019, 276: 97- 102.
18	唐文伟, 曾新平, 胡中华. 芬顿试剂和湿式过氧化氢氧化法处理乳化液废水研究[J]. 环境科学学报, 2006, 26( 8): 1265- 1270.
	Tang W W, Zeng X P, Hu Z H. Study of Fenton’s reagent and wet hydrogen peroxide oxidation for treatment of emulsified wastewater[ J]. Acta Scientiae Circumstantiae, 2006, 26( 8): 1265- 1270.
19	Liu W W, Tu X Y, Wang X P, et al. Pretreatment of coking wastewater by acid out, micro-electrolysis process with in situelectrochemical peroxidation reaction [J]. Chemical Engineering Journal, 2012, 200( 202): 720- 728.
20	华松林, 何淦锋, 何明, 等. 线路板废水处理工艺的探讨[J]. 工业安全与环保, 2002, 28( 8): 15- 16.
	Hua S L, He G F, He M, et al. An approach to the wastewater treatment process of circuit board production[J]. Industrial Safety and Environmental Protection, 2002, 28( 8): 15- 16.
21	Chao H, Fen P, Hai J G, et al. Efficient COD degradation of turpentine processing wastewater by combination of Fe-C micro-electrolysis and Fenton treatment: long-term study and scale up[J]. Chemical Engineering Journal, 2018, 351: 697- 707.
22	宋忠忠, 李杰, 孙静. 铁碳微电解填料的研究及应用现状[J]. 绿色科技, 2017, ( 6): 48- 50+55.
	Song Z Z, Li J, Sun J. Research and application of iron carbon micro electrolysis filler[J]. Journal of Green Science and Technology, 2017, ( 6): 48- 50+55.
23	Liu G D, Liu K, Zhang H T. Study of desulfurization with magnesite desulfurized under hot metal pretreatment[J]. Metalurgija, 2018, 57( 1/2): 35- 38.
24	Abramowitz H, Rao Y K. Direct reduction of zinc-sulfide by carbon and lime[J]. Mineral Processing and Extractive Metallurgy, 1978, 87: 180- 188.
25	时永辉, 苏建文, 陈建华, 等. 微电解-Fenton 深度处理制药废水影响因素与参数控制[J]. 环境工程学报, 2014, 8( 3): 1106- 1112.
	Shi Y H, Su J W, Chen J H, et al. Influencing factors and parameters control on advanced treatment of pharmaceutical wastewater by micro-electrolysis-Fenton process[J]. Chinese Journal of Environmental Engineering, 2014, 8( 3): 1106- 1112.
26	仇雅丽, 李长明, 王德亮, 等. 赤泥/煤基铁炭材料的制备及其脱除废水Cr(Ⅵ)的性能[J]. 化工学报, 2018, 69( 7): 3216- 3225.
	Qiu Y L, Li C M, Wang D L, et al. Preparation of red mud/coal based material and its performance to remove Cr(Ⅵ) in waste water[J]. CIESC Journal, 2018, 69( 7): 3216- 3225.
27	Yesiltepe S, Bugdayci M, Yucel O, et al. Recycling of alkaline batteries via a carbothermal reduction process [J]. Batteries, 2019, 5( 1): 35.
28	Liu W, Han J W, Qin W Q, et al. Reduction roasting of high iron bearing zinc calcine for recovery of zinc and iron[J]. Canadian Metallurgical Quarterly, 2014, 53( 2): 176- 182.
29	Holloway P C, Etsell T H, Murland A L. Roasting of La Oroya zinc ferrite with Na ₂CO ₃ [J]. Metallurgical and Materials Transactions B-Process Metallurgy and Materials Processing Science, 2007, 38( 5): 781- 791.
30	高爱舫, 吴财松, 高鹏, 等. Fenton 试剂氧化处理油墨废水的条件优化[J]. 湖北农业科学, 2012, 51( 18): 3999- 4013.
	Gao A F, Wu C S, Gao P, et al. Optimization of treatment condition of printing-ink wastewater by Fenton’s reagent[J]. Hubei Agricultural Sciences, 2012, 51( 18): 3999- 4013.
31	沈欣军, 邹成龙, 孙美芳. 铁碳微电解技术处理实际印染废水[J]. 沈阳工业大学学报, 2018, 40( 4): 397- 401.
	Shen X J, Zou C L, Sun M F. Treatment of actual dyeing wastewater with iron-carbon micro-electrolysis technology[J]. Journal of Shenyang University of Technology, 2018, 40( 4): 397- 401.
32	许杰, 董岁明, 柴丽红, 等. 新型铁炭微电解材料的制备研究[J]. 应用化工, 2016, 45( 8): 1482- 1484+1487.
	Xu J, Dong S M, Chai L H, et al. Preparation research of micro-electrolysis material[J]. Applied Chemical Industry, 2016, 45( 8): 1482- 1484+1487.

[1]	王聪, 王淑莹, 张淼, 彭永臻, 曾薇. 多因素对反硝化除磷过程中COD、N和P的去除分析[J]. 化工学报, 2015, 66(4): 1467-1475.
[2]	昌盛, 李建政, 付青, 赵兴茹, 郑国臣. ACR在不同进水COD浓度下的产氢性能与菌群结构[J]. 化工学报, 2015, 66(3): 1156-1162.
[3]	昌盛, 刘枫. 对比分析进水基质浓度对乙醇型和丁酸型发酵制氢系统的影响[J]. 化工学报, 2015, 66(12): 5111-5118.
[4]	尹志轩, 谢丽, 王蕊, 周琪. 亚硝酸盐对厌氧产酸耦合反硝化工艺的影响[J]. 化工学报, 2014, 65(9): 3640-3646.
[5]	尹志轩, 谢丽, 王蕊, 周琪. 亚硝酸盐对厌氧产酸耦合反硝化工艺的影响[J]. 化工学报, 2014, 65(9): 0-0.
[6]	柯蓝婷, 王海涛, 王远鹏, 何宁, 李清彪. 不同来源家庭户用沼气池沼液成分分析及风险评价[J]. 化工学报, 2014, 65(5): 1840-1847.
[7]	秦娟辛寅昌马德华. 微乳液的油水分离和机理探讨及应用[J]. CIESC Journal, 2013, 64(5): 0-0.
[8]	秦娟, 辛寅昌, 马德华. 微乳液的油水分离和机理探讨及应用[J]. 化工学报, 2013, 64(5): 1797-1802.
[9]	祁佩时, 赵俊杰, 刘云芝, 李立君. Fenton试剂深度处理稠油石化废水的反应动力学 [J]. 化工学报, 2011, 62(2): 490-494.
[10]	陈伟林，邱文杰，陈伟丽，林津冰. 催化湿式氧化法处理垃圾渗滤液 [J]. CIESC Journal, 2010, 29(9): 1775-.
[11]	陈捷, 冯威, 刘延, 王丽, 田斌. 有机膨润土的制备与表征及吸附港口含油废水性能 [J]. 化工学报, 2008, 59(1): 228-231.
[12]	刘越男，金栋，吕效平，韩萍芳. 超声波内环流气升式反应器处理印染废水 [J]. CIESC Journal, 2007, 26(12): 1808-.
[13]	范晓丹，张襄楷，杨虹莹. 污泥活性炭的制备及其脱色性能 [J]. CIESC Journal, 2007, 26(12): 1804-.
[14]	RafDewila,JanBaeyensandRebeccaGoutvrindc. The Use of Ultrasonics in the Treatment of Waste Activated Sludge[J]. CIESC Journal, 2006, 14(1): 105-113.
[15]	李清彪, 廖鑫凯, 吴志旺, 邓旭, 黄益丽, 卢英华, 孙道华, 洪铭嫒, 王琳. 高浓度淀粉废水水解——好氧循环一体化处理工艺的初步研究[J]. CIESC Journal, 2004, 12(1): 108-112.