Study on separation of mixed alcohol from water phase by-product in the F-T synthesis by pervaporation technology

doi:10.16085/j.issn.1000-6613.2017.06.017

Abstract

Abstract: This article aimed at studying the separation of water phase by-products produced by slurry bed process with cobalt-based catalyst in Fischer-Tropsch synthesis. A separation project about pervaporation and distillation was put forward to instead of the multi-columns distillation technology which was high energy consumption to separate alcohol and water. The new technology remained dehydrating tower and crude distillation tower in multi-columns distillation technology,while C₁—C₃ alcohol-water mixture was dehydrated by pervaporation technology,replacing the traditional distillation technology. The results showed that NaA zeolite molecular sieve permeable membrane was a suitable material for separation,and the permeation flux can reach 2.4 kg/(m²·h). The water content of water phase by-products in Fischer-Tropsch synthesis was reduced from 17.09% to below 0.5% by pervaporation-distillation process. In addition,the energy consumption between pervaporation-distillation process and multi-columns distillation process was compared. It was found that the energy consumption of pervaporation and distillation coupling process can save approximately 24%.

Key words: Fischer-Tropsch synthesis, alcohol, pervaporation, separation

摘要： 对以钴基催化剂、浆态床工艺为核心的费托合成中试装置产生的水相副产物的分离提纯过程进行了研究，针对目前混合醇多塔精馏回收工艺能耗高的问题，提出了渗透蒸发与精馏耦合的分离提纯工艺。新工艺保留传统多塔精馏回收工艺中的脱水塔和粗分塔，对原工艺中C₁～C₃混合醇-水的分离提纯采用渗透蒸发技术替代传统的精馏技术。研究结果表明：NaA型沸石分子筛渗透膜是混合醇渗透蒸发脱水适宜的膜分离材料，该渗透膜的渗透通量可达2.4 kg/（m²·h），粗分塔塔顶产品C₁～C₃混合醇-水混合物经过渗透蒸发，混合醇中含水量由17.09%降低到0.5%以下。费托合成水相副产物混合醇经渗透蒸发-精馏耦合工艺可得到含水量低于0.5%的醇产品，与传统多塔精馏回收工艺相比，渗透蒸发-精馏耦合工艺可节能24%，节能效果显著。

关键词: 费托合成, 醇, 渗透蒸发, 分离

CLC Number:

TQ028

LI Ling, CHAI Shiyang, LIU Laichun, HUANG Dan, YE Changshen. Study on separation of mixed alcohol from water phase by-product in the F-T synthesis by pervaporation technology[J]. Chemical Industry and Engineering Progress, 2017, 36(06): 2086-2093.

李玲, 柴士阳, 刘来春, 黄丹, 叶长燊. 费托合成水相副产物混合醇渗透蒸发分离工艺[J]. 化工进展, 2017, 36(06): 2086-2093.

References

[1] 杨霞珍,刘化章,唐浩东,等.Fe、Co基费托合成催化剂助剂研究进展[J].化工进展,2006,25(8):867-870. YANG X Z,LIU H Z,TANG H D,et al.Research progress of promoters for Fe, Co-based Fischer-Tropsch synthesis catalysts[J]. Chemical Industry and Engineering Progress,2006,25(8):867-870.
[2] VAN DIJK H A J.The Fischer-Tropsch synthesis:a mechanistic study using transient isotopic tracing[M].Eindhoven:Technische Universiteitndhoven,2001.
[3] 张华松.煤直接液化工艺条件对液化反应的影响[J].化工技术与开发,2011,40(7):36-38. ZHANG H S.Effect of direct coal liquefaction process variables on reaction unit[J].Technology & Development of Chemical Industry,2011,40(7):36-38.
[4] 周辉.煤化工废水处理现状及“零排放”重要性[J].化工管理,2016(14):257. ZHOU H.Coal chemical industry of waste water treatment status and the importance of“zero emissions”[J].Chemical Enterprise Management,2016(14):257.
[5] 马爱华,云志. 费托合成水相副产物中具有共沸组成的低碳混合醇-水体系分离方法研究进展[J].石油学报,2013,29(4):739-742. MA A H,YUN Z.Research progress of separation technologies for azeotropic mixture of lower alcohols-water system of the by-product in water of Fischer-Tropsch synthesis[J].Petroleum Processing Section,2013,29(4):739-742.
[6] KOCH K, GORAK A. Pervaporation of binary and ternary mixtures of acetone,isopropyl alcohol and water using polymeric membranes:experimental characterisation and modelling[J]. Chemical Engineering Science,2014.115:95-114.
[7] KONDO M,KITA H.Permeation mechanism through zeolite NaA and T-type membranes for practical dehydration of organic solvents[J].Journal of Membrane Science,2010,361(1):223-231.
[8] 肖佩佩,韩笑颜,曾楚怡,等.聚乙烯醇/二氧化硅杂化膜的制备及渗透蒸发分离环己醇(酮)/环己烷[J]. 化工进展,2014,33(10):2693-2699. XIAO P P,HAN X Y,ZENG C Y,et al.Pervaporation separation of cyclohexanol(cyclohexanone)/cyclohexane mixture by polyvinyl alcohol(PVA)/silica(SiO₂) hybrid membrane[J]. Chemical Industry and Engineering Progress,2014,33(10):2693-2699.
[9] 陈翠仙,李继定,潘健,等.我国渗透汽化技术的工业化应用[J].膜科学与技术,2007,27(5):1-4. CHEN C X,LI J D,PAN J,et al.Industrial application of pervaporation membrane technology in China[J].Membrane Science and Technology,2007,27(5):1-4.
[10] VAN BAELEN D,REYNIERS A,VAN DER BRUGGEN B,et al.Pervaporation of binary and ternary mixtures of water with methanol and/or ethanol[J].Separation Science and Technology,2005,39(3):563-580.
[11] 李云华,李永红.费托合成水相副产物馏分切割工艺开发[D].天津:天津大学,2003. LI Y H,LI Y H.Technology exploitation of cutting the by-product in water of Fischer-Tropsch synthesis[D].Tianjin:The University of Tianjin,2003.
[12] 吴流芳.费托合成工艺中水相副产物的分离[D].太原:中国科学院山西煤炭化学研究所,2007. WU L F.The separation of the water phase by-products in Fischer-Tropsch synthesis process[D].Taiyuan:Institute of Coal Chemistry,Chinese Academy of Sciences,2007.
[13] OKAMOTO K,KITA H,HORII K,et al.Zeolite NaA membrane:preparation,single-gas permeation,and pervaporation and vapor permeation of water/organic liquid mixtures[J].Industrial & Engineering Chemistry Research,2001,40(1):163-175.
[14] 日本膜学会编.膜分离过程设计法[M].王志魁,译.北京:科学技术文献出版社,1988. The Japanese Membrane Association.Design method of membrane separation process[M]. WANG Z K,trans.Beijing:Science and Technology Literature Press,1988.

[1]	LI Mengyuan, GUO Fan, LI Qunsheng. Simulation and optimization of the third and fourth distillation columns in the recovery section of polyvinyl alcohol production [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 113-123.
[2]	SHENG Weiwu, CHENG Yongpan, CHEN Qiang, LI Xiaoting, WEI Jia, LI Linge, CHEN Xianfeng. Operating condition analysis of the microbubble and microdroplet dual-enhanced desulfurization reactor [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 142-147.
[3]	HE Meijin. Application and development trend of molecular management in separation technology in petrochemical field [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 260-266.
[4]	CUI Shoucheng, XU Hongbo, PENG Nan. Simulation analysis of two MOFs materials for O₂/He adsorption separation [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 382-390.
[5]	LI Shilin, HU Jingze, WANG Yilin, WANG Qingji, SHAO Lei. Research progress in separation and extraction of high value components by electrodialysis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 420-429.
[6]	GUO Qiang, ZHAO Wenkai, XIAO Yonghou. Numerical simulation of enhancing fluid perturbation to improve separation of dimethyl sulfide/nitrogen via pressure swing adsorption [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 64-72.
[7]	LIAO Zhixin, LUO Tao, WANG Hong, KONG Jiajun, SHEN Haiping, GUAN Cuishi, WANG Cuihong, SHE Yucheng. Application and progress of solvent deasphalting technology [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4573-4586.
[8]	PAN Yichang, ZHOU Rongfei, XING Weihong. Advanced microporous membranes for efficient separation of same-carbon-number hydrocarbon mixtures: State-of-the-art and challenges [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3926-3942.
[9]	ZHOU Longda, ZHAO Lixin, XU Baorui, ZHANG Shuang, LIU Lin. Advances in electrostatic-cyclonic coupling enhanced multiphase media separation research [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3443-3456.
[10]	HAN Hengwen, HAN Wei, LI Mingfeng. Research progress in olefin hydration process and the catalysts [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3489-3500.
[11]	CHEN Xiangli, LI Qianqian, ZHANG Tian, LI Biao, LI Kangkang. Research progress on self-healing oil/water separation membranes [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3600-3610.
[12]	LOU Baohui, WU Xianhao, ZHANG Chi, CHEN Zhen, FENG Xiangdong. Advances in nanofluid for CO₂ absorption and separation [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3802-3815.
[13]	ZHOU Lei, SUN Xiaoyan, TAO Shaohui, CHEN Yushi, XIANG Shuguang. Development and application of refinery short-cut column model [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2819-2827.
[14]	WU Heping, CAO Ning, XU Yuanyuan, CAO Yunbo, LI Yudong, YANG Qiang, LU Hao. Rapid separation of hydrofluoric acid and alkylated oil [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2845-2853.
[15]	SONG Minhang, ZHAO Lixin, XU Baorui, LIU Lin, ZHANG Shuang. Research progress of cyclone-enhanced separation based on disperse phase rearrangement at the inlet [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2219-2232.