生物油电催化加氢提质技术研究进展

doi:10.11949/0438-1157.20210732

摘要/Abstract

摘要：

生物油是一种可再生的碳中和有机资源，在液体燃料和高值化学品生产中显示出较大的潜力，对其大规模利用有助于实现碳中和目标。生物油因其固有的腐蚀性和化学不稳定性而需要提质以提高其应用价值。电催化加氢能够在常温常压下实现生物油加氢提质，该方法反应条件温和、操作简单、能源效率高，具有碳中和属性，为生物油提质提供了新的选择。综述了近年来生物油电催化加氢的研究进展，分析了不同生物油模型化合物在电催化加氢过程中的作用机理。讨论了真实生物油样品的电催化加氢实例，以证明电催化应用于生物油提质的可行性。最后，针对生物油电催化加氢提质技术面临的困难和挑战，提出了该领域未来的研究方向和重点，并展望了生物油电催化加氢提质工业化应用的前景。

关键词: 生物油, 电化学, 电催化, 加氢, 提质, 还原反应

Abstract:

Bio-oil is a renewable carbon-neutral resource that has shown great potential in the production of liquid fuels and value-added chemicals. Large-scale use of bio-oil could help achieve carbon neutrality. Bio-oil requires upgrading to improve its application value because of its inherent corrosion and chemical instability. Electrocatalytic hydrogenation (ECH) can realize the bio-oil hydrogenation under atmosphere temperature and pressure. ECH can be easily controlled by regulating the potential, and have a high energy efficiency. It is a carbon neutral process which provides a new option for bio-oil upgrading. The research progress of ECH of bio-oil in recent years was reviewed, and the mechanisms of different bio-oil model compounds in the ECH process were analyzed. The examples of ECH of real bio-oil samples were also discussed to prove the feasibility of electrocatalytic application in bio-oil upgrading. Finally, in view of the difficulties and challenges faced by ECH of bio-oil, the research direction and focus in this field in the future were proposed. The prospects of industrial application of the electrocatalytic hydrogenation upgrading of bio-oil are prospected.

Key words: bio-oil, electrochemistry, electrocatalysis, hydrogenation, upgrading, reduction reaction

中图分类号:

TK 6

邓伟,林镇浩,熊哲,汪雪棚,徐俊,江龙,苏胜,汪一,胡松,向军. 生物油电催化加氢提质技术研究进展[J]. 化工学报, 2021, 72(10): 4987-5001.

Wei DENG,Chunho LAM,Zhe XIONG,Xuepeng WANG,Jun XU,Long JIANG,Sheng SU,Yi WANG,Song HU,Jun XIANG. Research progress in electrocatalytic hydrogenation upgrading of bio-oil[J]. CIESC Journal, 2021, 72(10): 4987-5001.

图/表 12

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化合物	相对含量/ %	化合物	相对含量/ %
酸	5~10	酚	20~30
甲酸	0.3~9.1	苯酚	0.1~3.8
乙酸	0.5~12	二乙酰基苯酚	0.1~1.3
丙酸	0.1~1.8	对羟基苯酚	0.1~1.9
乙酰丙酸	0.1~0.3	甲基苯酚	0.1~5
醇	0~5	愈创木酚	2~14
甲醇	0.4~2.4	2-甲氧基苯酚	0.1~1.1
乙醇	0.6~1.4	4-甲基愈创木酚	0.1~1.9
乙二醇	0.7~2	异丁子香酚	0.1~7.2
酮	0~10	丁子香酚	0.1~2.3
丙酮	2.8	丁香酚	2~8
羟基丙酮	0.7~7.4	2,6-二甲氧基苯酚	0.7~4.8
醛	5~20	丙基丁香酚	0.1~1.5
甲醛	0.1~3.3	丁香醛	0.1~1.5
乙醛	0.1~8.5	呋喃	0~12
乙二醛	0.9~4.6	呋喃酮	0.1~1.1
羟基乙醛	0.9~13	糠醛	0.1~1.1
糖	5~30	糠醇	0.1~5.2
D-木糖	0.1~3.2	5-羟甲基糠醛	0.3~2.2
左旋葡聚糖	0.4~1.4	其他	—
葡萄糖	0.4~1.3	甲基环戊烯酮	0.1~1.9
果糖	0.7~2.9	3-甲氧基苯甲醛	0.1~1.1
聚纤维二糖	0.6~3.2	低聚物	0~20
1,6-脱水呋喃葡萄糖	0.1~3.1	水	15~30

化合物	相对含量/ %	化合物	相对含量/ %
酸	5~10	酚	20~30
甲酸	0.3~9.1	苯酚	0.1~3.8
乙酸	0.5~12	二乙酰基苯酚	0.1~1.3
丙酸	0.1~1.8	对羟基苯酚	0.1~1.9
乙酰丙酸	0.1~0.3	甲基苯酚	0.1~5
醇	0~5	愈创木酚	2~14
甲醇	0.4~2.4	2-甲氧基苯酚	0.1~1.1
乙醇	0.6~1.4	4-甲基愈创木酚	0.1~1.9
乙二醇	0.7~2	异丁子香酚	0.1~7.2
酮	0~10	丁子香酚	0.1~2.3
丙酮	2.8	丁香酚	2~8
羟基丙酮	0.7~7.4	2,6-二甲氧基苯酚	0.7~4.8
醛	5~20	丙基丁香酚	0.1~1.5
甲醛	0.1~3.3	丁香醛	0.1~1.5
乙醛	0.1~8.5	呋喃	0~12
乙二醛	0.9~4.6	呋喃酮	0.1~1.1
羟基乙醛	0.9~13	糠醛	0.1~1.1
糖	5~30	糠醇	0.1~5.2
D-木糖	0.1~3.2	5-羟甲基糠醛	0.3~2.2
左旋葡聚糖	0.4~1.4	其他	—
葡萄糖	0.4~1.3	甲基环戊烯酮	0.1~1.9
果糖	0.7~2.9	3-甲氧基苯甲醛	0.1~1.1
聚纤维二糖	0.6~3.2	低聚物	0~20
1,6-脱水呋喃葡萄糖	0.1~3.1	水	15~30

序号	提质方法	方法描述	优点	缺点	文献
1	催化加氢	高温（300~600℃）高压条件下，有机组分加氢提高氢碳比	易于与传统石油提质工艺整合；非均相催化；高脱氧率；可生产高热值产品	高温导致催化剂积炭；需消耗氢气；可能产生甲烷；高温加速生物油聚合	[11, 44]
2	加氢裂解	高温高压（500~700℃，0.7~13.8 MPa）条件下，有机组分加氢提高氢碳比，同时生成轻质芳烃	生成小分子加氢产物；积炭率低于催化加氢；能分解高沸点芳烃原料	工况更苛刻；氢气消耗更多；加工成本高；积炭不可避免	[45-46]
3	催化裂解	在高温（300~800℃）下，利用催化剂通过脱羰和脱羧反应以CO₂和水的形式脱除氧	在常压下反应；不需要氢气；能耗低、成本低；催化剂改性用于特定用途	烃类产率低；结焦率高；催化剂积炭失活	[47]
4	酯化	将腐蚀性羧酸转化为中性酯作为燃料添加剂，通过稳定反应中间体来降低生物油聚合的趋势	可由固体酸或液体酸催化；通过去除反应活性化合物（例如糖和呋喃类）来提升生物油稳定性；反应工况比催化加氢温和，不需要氢气	生物油中的氧含量不会降低，因此热值不会提高；酯化过程中糖脱水和醚化反应会产生较多的水；醇之间的分子间醚化会消耗醇；无法避免积炭；醇回收较难	[48-49]
5	超临界流体提质	将生物油置于超临界溶剂介质中，如甲醇、乙醇、异丙醇、水、丙酮、二氧化碳等	超临界甲醇中酯化率高；燃料的产率和质量较高	实现超临界工况能量成本高；溶剂成本高；溶剂脱除成本高	[50-51]
6	乳化	在表面活性剂的作用下将生物油与另一种有机溶剂混合	降低生物油的黏度；促进生物油酸性组分与（醇）溶剂的酯化反应；简单、成本低廉；提高生物油储存稳定性	表面活性剂选择要求高；无法实现脱氧	[52]
7	蒸汽重整	促进蒸汽重整，在高温（500~800℃）下将生物油转化为CO和H₂合成气	利用生物油生产氢气，用于生物油加氢；氢气产率比由生物质气化产氢更容易调节	聚合导致快速积炭；重质有机组分难以重整；高黏度导致进料困难	[53]
8	催化转移氢化	以有机物（醇类、甲酸等）为氢供体，对生物油中氢受体进行催化转移氢化的还原反应	反应温度、压力范围广；无须外部氢气源	常温常压下加氢效率低、反应速率低；供氢体转化为不饱和产物	[54-55]
9	光催化重整	通过半导体催化剂利用太阳能将生物油转化为H₂和碳基化学品	反应条件温和	生成强氧化性自由基中间体，导致聚合；太阳能利用率低	[56-57]
10	电催化加氢	对生物油中的反应活性物进行电化学加氢，以防止其发生聚合	反应条件温和，常温常压实现加氢；无须外部氢气源	需添加支持电解质以提高反应液体导电性	[21, 58]

序号	提质方法	方法描述	优点	缺点	文献
1	催化加氢	高温（300~600℃）高压条件下，有机组分加氢提高氢碳比	易于与传统石油提质工艺整合；非均相催化；高脱氧率；可生产高热值产品	高温导致催化剂积炭；需消耗氢气；可能产生甲烷；高温加速生物油聚合	[11, 44]
2	加氢裂解	高温高压（500~700℃，0.7~13.8 MPa）条件下，有机组分加氢提高氢碳比，同时生成轻质芳烃	生成小分子加氢产物；积炭率低于催化加氢；能分解高沸点芳烃原料	工况更苛刻；氢气消耗更多；加工成本高；积炭不可避免	[45-46]
3	催化裂解	在高温（300~800℃）下，利用催化剂通过脱羰和脱羧反应以CO₂和水的形式脱除氧	在常压下反应；不需要氢气；能耗低、成本低；催化剂改性用于特定用途	烃类产率低；结焦率高；催化剂积炭失活	[47]
4	酯化	将腐蚀性羧酸转化为中性酯作为燃料添加剂，通过稳定反应中间体来降低生物油聚合的趋势	可由固体酸或液体酸催化；通过去除反应活性化合物（例如糖和呋喃类）来提升生物油稳定性；反应工况比催化加氢温和，不需要氢气	生物油中的氧含量不会降低，因此热值不会提高；酯化过程中糖脱水和醚化反应会产生较多的水；醇之间的分子间醚化会消耗醇；无法避免积炭；醇回收较难	[48-49]
5	超临界流体提质	将生物油置于超临界溶剂介质中，如甲醇、乙醇、异丙醇、水、丙酮、二氧化碳等	超临界甲醇中酯化率高；燃料的产率和质量较高	实现超临界工况能量成本高；溶剂成本高；溶剂脱除成本高	[50-51]
6	乳化	在表面活性剂的作用下将生物油与另一种有机溶剂混合	降低生物油的黏度；促进生物油酸性组分与（醇）溶剂的酯化反应；简单、成本低廉；提高生物油储存稳定性	表面活性剂选择要求高；无法实现脱氧	[52]
7	蒸汽重整	促进蒸汽重整，在高温（500~800℃）下将生物油转化为CO和H₂合成气	利用生物油生产氢气，用于生物油加氢；氢气产率比由生物质气化产氢更容易调节	聚合导致快速积炭；重质有机组分难以重整；高黏度导致进料困难	[53]
8	催化转移氢化	以有机物（醇类、甲酸等）为氢供体，对生物油中氢受体进行催化转移氢化的还原反应	反应温度、压力范围广；无须外部氢气源	常温常压下加氢效率低、反应速率低；供氢体转化为不饱和产物	[54-55]
9	光催化重整	通过半导体催化剂利用太阳能将生物油转化为H₂和碳基化学品	反应条件温和	生成强氧化性自由基中间体，导致聚合；太阳能利用率低	[56-57]
10	电催化加氢	对生物油中的反应活性物进行电化学加氢，以防止其发生聚合	反应条件温和，常温常压实现加氢；无须外部氢气源	需添加支持电解质以提高反应液体导电性	[21, 58]

序号	化合物	实验条件	电解质	催化剂	产物	法拉第效率/%	转化频率/ h^-1	文献
1	苯甲醛 (20 mmol/L)	-0.9 V(vs Ag/AgCl),pH = 5, 25℃	乙酸缓冲液	5% Ni/C	苯甲醇	35	约5000	[99]
				5% Pt/C		约39	2189
				5% Rh/C		约65	2267
				5% Pd/C		99	3899
2	苯甲醛( 80 mmol/L)	-0.8 V(vs Ag/AgCl), pH<7, 常温	47.5%异丙醇 47.5%去离子水 5.0%乙酸	0.5% Pd/碳毡	苯甲醇	80~85^①	3.6 mmol/ (g cat·h)	[63]
2	苯甲醛( 80 mmol/L)	-0.8 V(vs Ag/AgCl), pH<7, 常温	47.5%异丙醇 47.5%去离子水 5.0%乙酸	0.5%Cu/碳毡	苯甲醇	60~65^①	2.4 mmol/ (g cat·h)	[63]
3	羟丙酮 (50 mmol/L)	-1.5 V(vs Ag/AgCl), pH=2, 常温	0.5 mol/L Na₂SO₄	1 mg/cm² Cu/C	丙二醇	11	420	[61]
				1 mg/cm² Ni/C		17	498
				1 mg/cm² CuNi/C		16	534
				1 mg/cm² Pt/C		20	516
				1 mg/cm² Ru/C		22	840
				1 mg/cm² PtRu/C		22	282
4	糠醛(5%)	-1.1~1.8 V(vs Ag/AgCl),pH<7, 30℃	0.5 mol/L H₂SO₄	1 mg/cm² Pd/C	FA, THFA, MF, MTHF	54	400^①	[62]
5	糠醛 (100 mmol/L)	-1.1~1.8 V(vs Ag/AgCl),pH<7, 常温	20%（体积）乙腈 0.5 mol/L H₂SO₄	Cu	FA，MA	52.2	N.A	[76]
			20%（体积）乙腈 0.1 mol/L H₂SO₄			43.2
			20%（体积）乙腈 0.2 mol/L NH₄Cl			47.2
6	糠醛(50 mmol/L)	-0.55 V(vs Ag/AgCl),pH<2, 23℃	0.5 mol/L H₂SO₄	Cu	FA，MA	55^*	N.A	[78]
			0.05 mol/L H₂SO₄			47^*
			0.01 mol/L H₂SO₄			45^*
7	5-羟甲基糠醛 (50 mmol/L)	-1.5~0 V(vs Ag/AgCl),pH<7, 常温	0.5 mol/L H₂SO₄	Fe, Ni, Cu, Pb	DHMF	N.A	N.A	[83]
				Co, Ag, Au,Cd, Sb, Bi	DHMF, DHMTHF
				Pd, Pt, Al, Zn, In, Sb	DMDHF
8	5-羟甲基糠醛 (10 mmol/L)	20 mA, pH<7, 常温	0.2 mol/L HClO₄	Pd/VN空心纳米球	DHMTHF	86	N.A	[68]
9	乙酰丙酸 (200 mmol/L)	-1.3 V(vs RHE),pH=0, 常温	0.5 mol/L H₂SO₄	Pb	γ-戊内酯，戊酸	84	N.A	[68]
9	乙酰丙酸 (200 mmol/L)	-1.3 V(vs RHE), pH=7.5, 常温	K₂HPO₄/KH₂PO₄ 缓冲液	Pb	γ-戊内酯	6	N.A	[68]
10	葡萄糖 (100 mmol/L)	-1.5~0 V(vs Ag/AgCl),pH<7, 常温	0.1 mol/L Na₂SO₄	Ni, Fe, Co, Cu, Pd, Au, Ag	山梨醇	N.A	N.A	[69]
				Pb, Zn,Cd, Sn, In, Sb, Bi	山梨醇，2-脱氧山梨醇
				Ti, V, Cr, Mn, Zr, Nb, Mo, Hf, Ta, We, Re, Ru, Rh, Ir, Pt	2-脱氧山梨醇
11	苯酚(20 mmol/L)	-0.28 V(vs NHE), pH<1, 55℃	0.1 mol/L 硅钨酸水溶液	10% Pd/C	环己烷	98	N.A	[86]
12	苯酚(16 mmol/L)	-0.9 V(vs Ag/AgCl), pH=5, 常温	异丙醇中30%（体积）乙酸盐缓冲液	5 % Rh/C	环己酮环己醇	68	629	[87]