酶催化固碳过程及其强化技术研究进展

doi:10.16085/j.issn.1000-6613.2023-1677

摘要/Abstract

摘要：

全球范围迅猛发展的工业生产导致温室气体CO₂的排放，引发人们对全球气候变化的普遍关切。在发展清洁能源、工业流程再造等减少碳排放的同时，开发高效、经济的CO₂捕集、利用与储存（CCUS）技术显得尤为迫切。本文基于CO₂资源化利用的目的，对生物体外酶催化固碳过程及其强化技术的研究进展进行综述。首先，介绍了CO₂转化过程中涉及的关键催化酶及其优化，阐述了CO₂资源化利用的具体策略，涵盖了将CO₂催化转化为甲酸、甲醇、甲烷、淀粉以及L-乳酸、丙酮酸等特定产物分子。进而，重点阐述了辅因子的原位再生、酶的固定化、反应系统的优化设计、反应条件优化（pH、温度、底物浓度）以及产物原位分离等技术对CO₂生物酶催化反应过程的强化，实现CO₂的高效固定与资源化利用。旨在通过多方面交叉论述，为生物酶催化过程及路线设计包括固定化酶催化剂的制备、反应器选择设计与开发、酶催化过程调控、高值化产品定向合成等提供有益的启发和思考。最后，总结了酶催化固碳过程存在的问题和挑战，并对其未来值得研究的方向进行了展望。

关键词: 酶催化固碳, CO₂资源化, 生物催化, 酶, 强化技术

Abstract:

The rapid expansion of the global industrial production has led to a sharp increase in the emission of the greenhouse gas CO₂, triggering widespread concern about global climate change. While developing clean energy sources and industrial process reengineering to reduce carbon emissions, there is an urgent need to develop highly efficient and economical carbon capture, utilization, and storage (CCUS) technologies. This article provides a comprehensive overview of the research progress on the extracellular enzyme-catalyzed carbon sequestration and its enhancement technologies bases on the purpose of CO₂ resource utilization. Firstly, it introduces the key biocatalytic enzymes involved in the CO₂ conversion process and their optimization. It elaborates on the specific strategies for CO₂ resource utilization, encompassing the catalytic transformation of CO₂ into specific product molecules such as formic acid, methanol, methane, starch, L-lactide and pyruvic acid. The article further focused on the enhancement of the CO₂ enzyme catalysis reaction processes through in-situ regeneration of cofactors, enzyme immobilization, optimization of reaction system design, optimization of reaction condition such as pH, temperature, substrate concentration, and in situ product separation. These measures aim to achieve efficient sequestration and resource utilization of CO₂.The intention is to provide valuable insights and considerations for the design of enzyme catalysis processes and routes, encompassing the preparation of immobilized enzyme catalysts, reactor selection and design, regulation of enzyme catalysis processes, and targetes synthesis of high-value products through a comprehensive and interdisciplinary approach. Finally, the problems and challenges existing in the enzyme-catalyzed carbon sequestration processes are summarized, and the future research directions are prospected.

Key words: enzyme-catalyzed carbon sequestration, CO₂ resource utilization, biocatalysis, enzyme, enhancement technologies

中图分类号:

Q814

王玉杰, 张艳梅, 栾金义, 赵之平. 酶催化固碳过程及其强化技术研究进展[J]. 化工进展, 2024, 43(1): 232-245.

WANG Yujie, ZHANG Yanmei, LUAN Jinyi, ZHAO Zhiping. Enzyme-catalyzed carbon sequestration processes and enhancement technologies[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 232-245.

图/表 4

表1 不同酶催化CO2转化

酶	产物	反应	优势	参考文献
甲酸脱氢酶	甲酸盐（HCOO^-）	$C O 2 + N A D H ⇌ H C O O - + N A D +$	易获取增值产品、底物广泛	[14-16]
碳酸酐酶	碳酸氢盐（ $H C O 3 -$ ）	$C O 2 + H 2 O ⇌ H C O 3 - + H +$	快速催化CO₂水合反应、低能耗	[17-19]
重塑固氮酶	甲烷（CH₄）	$C O 2 + 8 H + + 8 e - → C H 4 + 2 H 2 O$	H₂无抑制作用	[7, 20]
一氧化碳脱氢酶	一氧化碳（CO）	$C O 2 + 2 H + + 2 e - → C O + H 2 O$	大气氛围下稳定、独特的催化活性中心、反应产物易转化为增值产品	[21-24]
多重脱氢酶	甲醇（CH₃OH）	$C O 2 + 6 H + + 6 e - ⇌ C H 3 O H + H 2 O$	易获取增值产品	[25-26]
丙酮酸脱羧酶	羧酸类化合物	$C O 2 + C H 3 C H O → C H 3 C O C O O H$	对环境友好	[27]

表1 不同酶催化CO2转化

酶	产物	反应	优势	参考文献
甲酸脱氢酶	甲酸盐（HCOO^-）	$C O 2 + N A D H ⇌ H C O O - + N A D +$	易获取增值产品、底物广泛	[14-16]
碳酸酐酶	碳酸氢盐（ $H C O 3 -$ ）	$C O 2 + H 2 O ⇌ H C O 3 - + H +$	快速催化CO₂水合反应、低能耗	[17-19]
重塑固氮酶	甲烷（CH₄）	$C O 2 + 8 H + + 8 e - → C H 4 + 2 H 2 O$	H₂无抑制作用	[7, 20]
一氧化碳脱氢酶	一氧化碳（CO）	$C O 2 + 2 H + + 2 e - → C O + H 2 O$	大气氛围下稳定、独特的催化活性中心、反应产物易转化为增值产品	[21-24]
多重脱氢酶	甲醇（CH₃OH）	$C O 2 + 6 H + + 6 e - ⇌ C H 3 O H + H 2 O$	易获取增值产品	[25-26]
丙酮酸脱羧酶	羧酸类化合物	$C O 2 + C H 3 C H O → C H 3 C O C O O H$	对环境友好	[27]

表2 固定化方法优缺点

固定化方法	具体策略	优点	缺点	参考文献
吸附法	主要分为表面吸附和孔道吸附两类，通过弱相互作用力（如氢键、范德华力、亲疏水作用和静电作用等）实现酶的固定化	操作简单载体种类广泛酶构象变化小	酶与载体间的结合力较弱，易发生酶泄露	[67-68]
共价结合法	改性载体表面的胺基、羟基、羧基或环氧基等官能团和酶的氨基酸残基之间可以形成共价键	酶与载体间作用力强，基本不发生酶泄露	操作相对复杂易影响酶的构象	[69-70]
包埋法	将载体与酶“一锅反应”，通过机械搅拌、加入交联剂等将酶包裹在凝胶等材料中	操作简单不涉及酶的构象转变	酶被限制在载体中，存在扩散受限、传质受阻	[71]
交联法	利用酶自身的双官能团结构或者加入一些交联剂（如戊二醛、甲苯二异氰酸酯等）连接起来形成酶聚集体	不需要载体	机械强度差	[72]
原位合成法	将酶的溶液与合成MOF的前体溶液（金属和配体溶液）混合在一起，诱导MOF晶核生成、晶体生长，同时实现酶的包覆	酶的固定与载体的制备同时发生，结合牢固	易影响酶的构象反应不易控制	[73-74]

图1 游离酶和固定化酶膜反应器示意图[87]

图2 中空纤维膜反应器CO2通入方式示意图[93-94]1—PE中空纤维膜；2—FDH-PE；3—反应溶液；4—水浴；5—吸收溶液；6—冰浴

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