Research progress of hydrate separation technology for biogas purification

doi:10.16085/j.issn.1000-6613.2017-0798

Abstract

Abstract: Biogas is an important renewable energy source, and the full use of biogas is of great significance to alleviate energy demand and environmental pressure. Biogas must be purified by decarbonization before high value utilization. A new technology——hydrate-based separation technology, for the biogas purification is introduced. The basic theories of hydrate-based separation technology were introduced, and the research progress of hydrate-based separation technology biogas (CH₄/CO₂)was summarized, including phase equilibrium research, thermodynamic promotors, kinetic promotors, mechanical strengthening, field strengthening, adding porous media/nano-fluids, and using oil/water emulsion. Various technologies of hydrate-based separation were analyzed. Phase equilibrium study provided the theoretical basis for the purification of biogas by hydrate method. Reasonable selection of thermodynamic and kinetic promoters could effectively improve gas hydrate phase equilibrium conditions, promote hydrate formation, increase gas storage effect and improve separation efficiency. Mechanical strengthening and field action promoted hydrate formation by enhancing the mass and heat transfer effect in the hydration process. Adding porous media/nano-fluids could increase the gas-liquid contact area and promote the hydration process. The use of oil/water emulsion not only strengthened the gas-liquid contact, but also improved the fluidity of the hydrate in the microemulsion state with a good industrial application prospects. Finally, the application of hydrate-based biogas purification technology was proposed. The hydrate purification biogas research is still in the early stage. This technology has the advantages of mild operation conditions, low requirement for raw biogas, simple and flexible operation, high safety, and environmental protection without pollution. It will certainly play an important role in the development of biogas industry in China.

Key words: hydrate, biogas, separation, purification, methane, carbon dioxide

摘要： 沼气是一种重要的可再生能源，对沼气进行充分高值利用对于缓解我国能源需求和环境压力具有重要意义。沼气在高值利用前必须进行脱碳提纯处理，本文介绍了一种可用于沼气提纯的新技术——水合物分离技术。介绍了水合物分离技术的基本理论，调研总结了水合物法提纯沼气和可用于沼气体系（CH₄/CO₂）的水合物分离技术研究进展，包括相平衡研究、热力学促进剂、动力学促进剂、机械强化、外场强化、添加多孔介质/纳米流体等和采用油/水乳液促进技术，并对各种水合物分离促进技术进行了分析：相平衡研究为水合物法提纯沼气提供了理论基础；合理地选用热力学和动力学促进剂能够有效改善气体水合物相平衡条件，促进水合物生成，增加储气效果和提高分离效率；机械强化及外场作用通过强化水合反应过程的传质传热效果促进水合物生成；添加多孔介质和纳米流体等能够增大气液接触面积，对水合过程发挥促进作用；采用油/水乳液不但能够强化气液接触，而且微乳状态下的水合物具有很好的流动性，具有良好工业应用前景。最后对水合物法提纯沼气技术进行了展望，水合物提纯沼气研究虽处在起步阶段，但随着研究的不断深入，该技术凭借操作条件温和，对原料气要求低，并且具有操作简单灵活、安全性高、环保无污染等优点，必将在我国沼气产业发展过程中发挥作用。

关键词: 水合物, 沼气, 分离, 提纯, 甲烷, 二氧化碳

CLC Number:

TQ028.8

MENG Fanfei, WANG Haibo, LIAO Changjian. Research progress of hydrate separation technology for biogas purification[J]. Chemical Industry and Engineering Progress, 2018, 37(01): 68-79.

孟凡飞, 王海波, 廖昌建. 水合物法提纯沼气技术研究进展[J]. 化工进展, 2018, 37(01): 68-79.

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