基于新型微通道分离技术的甲醇制烯烃废水处理

doi:10.16085/j.issn.1000-6613.2022-0658

摘要/Abstract

摘要：

甲醇制烯烃（MTO）开辟了一条制取低碳烯烃的新途径，但由于MTO反应器内旋风分离器分离精度的限制，微细催化剂颗粒会进入后续的水系统，从而产生大量废水。MTO急冷废水中微细颗粒的分离是实现废水回用的关键，针对目前MTO废水处理技术的不足，本文提出一种新型的旋流再生型微通道分离技术处理MTO废水，并建立了处理量为50t/h的工业级实验装置进行长周期分离实验。结果表明：该装置在处理MTO废水中具有较好的性能，平均悬浮物含量从143mg/L降至22mg/L，分离媒质的平均悬浮物残留率在2%以下。该技术具有运行周期长、对悬浮物去除效率高、运行压降低、分离媒质再生彻底等特点，技术的成功应用有效缓解了甲醇制烯烃装置水系统的堵塞，并极大地节约水资源和减少环境污染。

关键词: 甲醇制烯烃, 废水, 微通道型分离, 旋流再生, 催化剂

Abstract:

Methanol-to-olefin (MTO) opens up a new way to produce light olefins. Due to the limitation of the separation accuracy of the cyclone separator in the MTO reactor, the fine catalyst particles will enter the water system, resulting in large amounts of wastewater. The separation of fine particles in MTO quench wastewater is the key to realize wastewater reuse. In view of the shortcomings of the current MTO wastewater treatment technologies, a novel swirl regenerating microchannel separation technology was proposed to treat MTO wastewater, and an industrial-scale device with a treatment capacity of 50t/h was established. The device had good performance in the treatment of MTO wastewater, the average suspended solids content decreased from 143mg/L to 22mg/L, and the average suspended solids residual rate of the separation media was below 2%. The technology had a long operating cycle and high removal efficiency for suspended solids. The operating pressure was low, and the separation media were completely regenerated. The successful application of the technology had effectively alleviated the blockage of the water system of the methanol-to-olefins unit. Water resources were greatly saved and environmental pollution was reduced.

Key words: methanol to olefin, wastewater, microchannel separation, swirl regeneration, catalyst

中图分类号:

TQ051.8

黄起中, 刘冰, 马红鹏, 吕文杰. 基于新型微通道分离技术的甲醇制烯烃废水处理[J]. 化工进展, 2023, 42(2): 669-676.

HUANG Qizhong, LIU Bing, MA Hongpeng, LYU Wenjie. Methanol to olefin wastewater treatment based on a novel microchannel separation technology[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 669-676.

图/表 12

表1 MTO急冷水中微细催化剂特性

类别	数值
浓度/mg·L^-1	50~300
粒径/μm	0.1~10
堆积密度/g·cm^-3	约1.30
骨架密度/g·cm^-3	约2.23
比表面积/m²·g^-1	约1.05
化学成分	Al₂O₃/SiO₂/P₂O₅

图1 甲醇制烯烃急冷水微细颗粒物理分离方法示意图

图2 实验流程示意图1—反应器；2—水洗塔；3—换热器；4—急冷塔；4-1—急冷泵；4-2—换热器；4-3—空冷器；4-4—急冷泵；5—水洗塔；5-1—水洗泵；5-2—换热器；5-3—空冷器；5-4—换热器；5-5—换热器；6—旋流再生型微通道分离器；6-1，6-2—流量表；6-3，6-4—压力表

表2 实验流程设备及仪表阀门

名称	数量	规格	生产公司
旋流再生型微通道分离器	1	50t/h	自制
液体流量表	1	楔式流量计	江苏苏川仪表有限公司
气体流量表	1	孔板流量计	江苏苏川仪表有限公司
压力表	2	0~1.6MPa	北京布莱迪仪器仪表有限公司
闸阀	5	DN150	上海科科阀门集团有限公司
闸阀	1	DN80	上海科科阀门集团有限公司
闸阀	1	DN40	上海科科阀门集团有限公司

图3 实验装置

表3 三相分离器尺寸

符号	数值	符号	数值
H₁	220mm	Φ₁	800mm
H₂	600mm	Φ₂	1200mm
H₃	150mm	Φ₃	400mm
H₄	410mm	θ₁	90°
H₅	380mm	θ₂	45°
H₆	200mm	θ₃	90°

图4 连续操作装置对悬浮物的分离效果

图5 MTO废水中悬浮物粒径

图6 不同pH下悬浮物分离效率

图7 不同pH下MTO废水中悬浮物粒径

图8 悬浮物的zeta电位与pH关系

图9 旋流再生型微通道分离器中分离媒质再生性能

参考文献 16

1	SUN Qiming, XIE Zaiku, YU Jihong. The state-of-the-art synthetic strategies for SAPO-34 zeolite catalysts in methanol-to-olefin conversion[J]. National Science Review, 2017, 5(4): 542-558.
2	ZHANG Shihong, YANG Mingfa, SHAO Jingai, et al. The conversion of biomass to light olefins on Fe-modified ZSM-5 catalyst: Effect of pyrolysis parameters[J]. Science of the Total Environment, 2018, 628/629: 350-357.
3	TIAN Peng, WEI Yingxu, YE Mao, et al. Methanol to olefins (MTO): From fundamentals to commercialization[J]. ACS Catalysis, 2015, 5(3): 1922-1938.
4	Wenjie LYU, CHEN Jianqi, CHANG Yulong, et al. UU-type parallel mini-hydrocyclone group separation of fine particles from methanol-to-olefin industrial wastewater[J]. Chemical Engineering and Processing-Process Intensification, 2018, 131: 34-42.
5	Wenjie LYU, YANG Qiang, MA Liang, et al. Application of minihydrocyclones in methanol-to-olefin process wastewater treatment[J]. Chemical Engineering & Technology, 2015, 38(3): 504-510.
6	YANG Qiang, LI Zhiming, Wenjie LYU, et al. On the laboratory and field studies of removing fine particles suspended in wastewater using mini-hydrocyclone[J]. Separation and Purification Technology, 2013, 110: 93-100.
7	YANG Qiang, Wenjie LYU, SHI Lei, et al. Treating methanol-to-olefin quench water by minihydrocyclone clarification and steam stripper purification[J]. Chemical Engineering & Technology, 2015, 38(3): 547-552.
8	孙保全, 夏季, 吕文杰, 等. 液-固微旋流分离技术脱除水中催化剂颗粒[J]. 化工进展, 2011, 30(10): 2173-2177.
	SUN Baoquan, XIA Ji, Wenjie LYU, et al. Liquid-solid micro hydrocyclone separation technology in removing catalyst particle from water[J]. Chemical Industry and Engineering Progress, 2011, 30(10): 2173-2177.
9	CHEN Jianqi, WANG Lu, MA Shihao, et al. Separation of fine waste catalyst particles from methanol-to-olefin quench water via swirl regenerating micro-channel separation (SRMS): A pilot-scale study[J]. Process Safety and Environmental Protection, 2021, 152: 108-116.
10	郭瑜, 汪强兵, 李烨, 等. 金属微孔膜在甲醇制烯烃(MTO)急冷水过滤中的试验研究[J]. 粉末冶金工业, 2018, 28(1): 45-49.
	GUO Yu, WANG Qiangbing, LI Ye, et al. Experimental research of metal microporous membranes in filtration of methanol to olefins(MTO) chilled water[J]. Powder Metallurgy Industry, 2018, 28(1): 45-49.
11	赵宜江, 张艳, 钟璟, 等. 无机分离膜及其在微米与亚微米级固液分离中的应用[J]. 现代化工, 2000, 20(1):22-26.
	ZHAO Yijiang, ZHANG Yan, ZHONG Jing, et al. Inorganic separation membrane and its application in the liquid-solid separation of micron and submicron particles[J]. Modern Chemical Industry, 2000, 20(1):22-26.
12	Tănase DOBRE, ZICMAN Laura Ruxandra, PÂRVULESCU Oana Cristina, et al. Species removal from aqueous radioactive waste by deep-bed filtration[J]. Environmental Pollution, 2018, 241: 303-310.
13	LI Jianping, YANG Xuejing, MA Liang, et al. The enhancement on the waste management of spent hydrotreating catalysts for residue oil by a hydrothermal-hydrocyclone process[J]. Catalysis Today, 2016, 271: 163-171.
14	HUANG Yuan, LI Jianping, ZHANG Yanhong, et al. High-speed particle rotation for coating oil removal by hydrocyclone[J]. Separation and Purification Technology, 2017, 177: 263-271.
15	LI Jianping, WANG Yao, CHANG Yulong, et al. Cold model testing of in situ catalyst activation by swirling self-rotation in ebullated bed reactor for biomass pyrolysis oils hydrogenation[J]. Chemical Engineering Journal, 2021, 406: 126909.
16	李闯. 水处理滤料表面的zeta电位及其过滤除油性能研究[D]. 兰州: 兰州交通大学, 2009.
	LI Chuang. The study of zeta potential and oil-removal efficiency of water treatment filter media[D]. Lanzhou: Lanzhou Jiatong University, 2009.

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