合成气乙醇发酵技术研究进展

doi:10.16085/j.issn.1000-6613.2018-1129

摘要/Abstract

摘要：

采用合成气发酵生产燃料乙醇具有反应条件温和、产物耐受性好、原料来源丰富等优点，是燃料乙醇生产的一种新型工艺。文章综述了国内外合成气厌氧发酵的微生物种类，常见合成气乙醇发酵微生物的生长、代谢特点以及底物利用范围；分析了合成气乙醇发酵的Wood-Ljungdahl代谢途径，以及Wood-Ljungdahl代谢途径中涉及的关键酶类甲酸脱氢酶和CO脱氢酶/乙酰辅酶A合成酶；探讨了过程工艺参数如培养介质、还原剂、pH、气体组成、终产物、培养基和培养方法对合成气发酵的影响；比较了不同反应器在体积传质系数等方面的差异，并重点分析了搅拌罐式反应器和柱式反应器等的反应特点。同时，对合成气发酵的未来发展方向进行了展望。

关键词: 合成气, 乙醇, 发酵, 代谢机理, 生物反应器

Abstract:

Bioethanol production through syngas fermentation has many advantages, such as mild reaction conditions, higher end-product tolerance, rich source of raw carbon materials and so on, which is a novel method for fuel ethanol productions. In this paper, the types of microorganisms for syngas fermentation, the characteristics of growth, metabolism and substrate utilization of the main microorganisms, Wood-Ljungdahl pathways, the key enzymes of formate dehydrogenase and carbon monoxide dehydrogenase/acetyl-CoA synthase, the influence factors of culture medium, reducing agent, pH, gas composition, products, medium composition and culture methods on syngas fermentation, and the types of syngas fermentation reactor were reviewed. The prospect of future development direction of syngas fermentation was proposed.

Key words: syngas, ethanol, fermentation, metabolic mechanism, bioreactor

中图分类号:

TK6
TQ517.43

许敬亮, 常春, 韩秀丽, 韩一帆. 合成气乙醇发酵技术研究进展[J]. 化工进展, 2019, 38(01): 586-597.

Jingliang XU, Chun CHANG, Xiuli HAN, Yifan HAN. Research progress on bioethanol production technologies through syngas fermentation[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 586-597.

图/表 11

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微生物	分离地点	最适温度 /℃	最适pH	倍增时间 /h	产物
Acetobacterium woodii	黑色沉积物	30	6.8	13	乙酸
Alkalibaculum bacchi	牧场土壤	37	8.0～8.5	—	乙酸、乙醇
Archaeoglobus fulgidus	—	83	6.4	—	乙酸、甲酸、H₂S
Butyribacterium methylotrophicum	下水道污泥	37	6	12~20	乙酸、乙醇、丁酸、丁醇
Clostridium aceticum	—	30	8.5	—	乙酸
Clostridium autoethanogenum	兔粪	37	5.8～6.0	—	乙酸、乙醇
Clostridium carboxidivorans	污水池沉积物	38	6.2	6.25	乙酸、乙醇、丁酸、丁醇
Clostridium drakei	沉积物	30～37	5.5～7.5	—	乙醇
Clostridium ljungdahlii	鸡粪	37	6.0	3.8	乙酸、乙醇
Clostridium ragsdalei P11	鸭塘底泥	37	6.3	—	乙醇
Desulfotomaculum kuznetsovii	—	60	7	—	乙酸、H₂S
Desulfotomaculum thermobenzoicum subsp. thermosyntrophicum	—	55	7	—	乙酸、H₂S
Eubacterium limosum	绵羊食物	38～39	7.0～7.2	7	乙酸
Eubacterium limosum KIST612	厌氧消化液	37	7.0	—	乙酸、丁酸
Mesophilic bacterium P7	泻湖	37	5.7～5.8	—	乙醇
Methanosarcina acetivorans C2A	—	37	7.0	24	乙酸、甲酸、甲烷
Moorella sp. HUC22-1	地下热泥浆	55	6.3	—	乙醇
Moorella thermoacetica (原Clostridium thermoaceticum)	—	55	6.5～6.8	10	乙酸
Moorella thermoautotrophica (原Clostridium thermoautotrophicum)	—	58	6.1	7	乙酸
Oxobacter pfennigii	食物	36～38	7.2	13.9	乙酸、正丁酸
Peptostreptococcus productus	—	37	7	1.5	乙酸

微生物	分离地点	最适温度 /℃	最适pH	倍增时间 /h	产物
Acetobacterium woodii	黑色沉积物	30	6.8	13	乙酸
Alkalibaculum bacchi	牧场土壤	37	8.0～8.5	—	乙酸、乙醇
Archaeoglobus fulgidus	—	83	6.4	—	乙酸、甲酸、H₂S
Butyribacterium methylotrophicum	下水道污泥	37	6	12~20	乙酸、乙醇、丁酸、丁醇
Clostridium aceticum	—	30	8.5	—	乙酸
Clostridium autoethanogenum	兔粪	37	5.8～6.0	—	乙酸、乙醇
Clostridium carboxidivorans	污水池沉积物	38	6.2	6.25	乙酸、乙醇、丁酸、丁醇
Clostridium drakei	沉积物	30～37	5.5～7.5	—	乙醇
Clostridium ljungdahlii	鸡粪	37	6.0	3.8	乙酸、乙醇
Clostridium ragsdalei P11	鸭塘底泥	37	6.3	—	乙醇
Desulfotomaculum kuznetsovii	—	60	7	—	乙酸、H₂S
Desulfotomaculum thermobenzoicum subsp. thermosyntrophicum	—	55	7	—	乙酸、H₂S
Eubacterium limosum	绵羊食物	38～39	7.0～7.2	7	乙酸
Eubacterium limosum KIST612	厌氧消化液	37	7.0	—	乙酸、丁酸
Mesophilic bacterium P7	泻湖	37	5.7～5.8	—	乙醇
Methanosarcina acetivorans C2A	—	37	7.0	24	乙酸、甲酸、甲烷
Moorella sp. HUC22-1	地下热泥浆	55	6.3	—	乙醇
Moorella thermoacetica (原Clostridium thermoaceticum)	—	55	6.5～6.8	10	乙酸
Moorella thermoautotrophica (原Clostridium thermoautotrophicum)	—	58	6.1	7	乙酸
Oxobacter pfennigii	食物	36～38	7.2	13.9	乙酸、正丁酸
Peptostreptococcus productus	—	37	7	1.5	乙酸

底物	结果	底物	结果
H₂/CO₂	+	核糖	+
CO	+	木糖	+
甲酸钠	+/-	葡萄糖	+
甲醇	-	果糖	+
乙醇	+	半乳糖	-
丙酮酸钠	+	甘露糖	-
乳酸钠	-	山梨醇	-
甘油	-	蔗糖	-
柠檬酸钠	-	乳糖	-
琥珀酸钠	-	麦芽糖	-
富马酸钠	+	淀粉	-
苹果酸	-	阿魏酸	-
赤藓糖	+	三甲氧基苯甲酸	-
苏糖	+	酪蛋白氨基酸	+/-
阿拉伯糖	+	丙氨酸	-

底物	结果	底物	结果
H₂/CO₂	+	核糖	+
CO	+	木糖	+
甲酸钠	+/-	葡萄糖	+
甲醇	-	果糖	+
乙醇	+	半乳糖	-
丙酮酸钠	+	甘露糖	-
乳酸钠	-	山梨醇	-
甘油	-	蔗糖	-
柠檬酸钠	-	乳糖	-
琥珀酸钠	-	麦芽糖	-
富马酸钠	+	淀粉	-
苹果酸	-	阿魏酸	-
赤藓糖	+	三甲氧基苯甲酸	-
苏糖	+	酪蛋白氨基酸	+/-
阿拉伯糖	+	丙氨酸	-

反应模式	转速/r·min^-1	微生物	底物气体	体积传质系数K _L a/h^～1
滴流床	n/a	n/a	合成气	22
连续搅拌罐	n/a	n/a	合成气	38
连续搅拌罐	200	B.methylotrophicum	CO	14.2
连续搅拌罐	300	SRB混合培养	合成气	CO 31,H₂ 75
连续搅拌罐	300	C.ljungdahlii	合成气	CO 35
连续搅拌罐	300	R.rubrum	合成气	CO 28.1
连续搅拌罐	450	R.rubrum	合成气	CO 101
搅拌罐-微泡喷雾器	200	B．methylotrophicum	CO	90.6
搅拌罐-微泡喷雾器	300	SRB混合培养	合成气	CO 104, H₂ 190
填充柱气泡反应器	n/a	R.rubrum	合成气	2.1
滴流床	n/a	R.rubrum	合成气	55.5
滴流床	n/a	SRB混合培养	合成气	CO 121, H₂ 335
滴流床	n/a	C.ljungdahlii	合成气	CO 137
分批搅拌罐	n/a	P.productus	CO	7.15
搅拌罐	300	C.ljungdahlii	CO	14.9
搅拌罐	400	C.ljungdahlii	CO	21.5
搅拌罐	500	C.ljungdahlii	CO	22.8
搅拌罐	600	C.ljungdahlii	CO	23.8
搅拌罐	700	C.ljungdahlii	CO	35.5
气泡柱反应器	n/a	n/a	CO	72
搅拌罐	n/a	n/a	CO	10.8～155
搅拌罐	500	R.rubrum	合成气	71.8
柱状分散反应器	n/a	n/a	CO	2.5～40.0
20μm气泡分散器	n/a	n/a	CO	31.7～78.8
单喷式反应器	n/a	n/a	CO	29.5～50.4
机械混合喷雾反应器	150	n/a	CO	33.5～53.3
机械混合喷雾反应器	300	n/a	CO	34.9～55.8
浸没式复合中空纤维膜反应器	n/a	n/a	CO	0.4～1.1
气升式20μm气泡分散器	n/a	n/a	CO	49.0～91.1
单点输入气体气升式反应器	n/a	n/a	CO	16.6～45.0