生物乙醇制高级醇催化剂研究进展

王文文; 逯炀炀; 李治宇; 张玉春; 付鹏

doi:10.19906/j.cnki.JFCT.2023061

生物乙醇制高级醇催化剂研究进展

doi: 10.19906/j.cnki.JFCT.2023061

山东理工大学农业工程与食品科学学院, 山东淄博 255000

基金项目: 国家自然科学基金(51976112,52206264), 山东省高等学校青年创新团队发展计划(2023KJ333)和山东省属普通本科高校教师访学研修经费资助

详细信息

通讯作者:
Tel: 15689002285,15064314128, E-mail: lizhiyu@sdut.edu.cn

fupengsdut@163.com

中图分类号: O643.3
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- 被引次数: 0
出版历程
- 收稿日期: 2023-07-13
- 修回日期: 2023-08-19
- 录用日期: 2023-08-21
- 网络出版日期: 2023-09-18
- 刊出日期: 2024-04-03

Research progress in catalysts for producing higher alcohols from bioethanol

School of Agricultural Engineering and Food Science, Shandong University of Technology, Zibo 255000, China

Funds: The project was supported by the National Natural Science Foundation of China (51976112, 52206264), Youth Innovation Support Program of Shandong Colleges and Universities (2023KJ333), the visiting Training Funds for Teachers from Ordinary Undergraduate Colleges and Universities in Shandong Province.

摘要

摘要: 与乙醇相比，高级醇具有高的十六烷值、高能量密度、对发动机部件无腐蚀性、与水不混溶、稳定性好等直接作为燃料或燃料添加剂的优势，将发酵产生的生物乙醇转化为更有价值的高级醇受到了广泛关注。本工作综述了近年来世界各国有关生物乙醇制高级醇的研究进展，包括金属氧化物、羟基磷灰石（HAP）和负载型金属催化剂的研究开发现状，并比较了不同类型催化剂参与下的乙醇转化率和高级醇选择性，结合乙醇经缩合反应制备高级醇的机理进行了讨论，最后对当前生物乙醇制高级醇的挑战以及未来研究趋势进行了总结与展望，指出多功能催化剂的开发是未来研究重点，羟醛缩合是进一步提高生物乙醇制高级醇转化率与选择性的有效策略。
- 生物乙醇 /
- 高级醇 /
- 催化剂 /
- 反应机理
Abstract: Compared with ethanol, higher alcohols have the advantages of high cetane number, high energy density, non corrosiveness to engine parts, immiscibility with water, good stability, and other advantages as fuel or fuel additive directly. The conversion of fermentation bioethanol into more valuable higher alcohols has attracted widespread attention. This paper reviewed the research progress of bioethanol to higher alcohols at home and abroad in recent years, including the research and development of metal oxides, hydroxyapatite (HAP) and supported metal catalysts. Finally, the current challenges and future research trends of bioethanol to higher alcohols are summarized and prospected, pointing out that the development of multifunctional catalysts is the focus of future research, and Aldol condensation is an effective strategy to further improve the conversion and selectivity of bioethanol to higher alcohols.
- bioethanol /
- higher alcohol /
- catalysts /
- reaction mechanism

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FIG. 3072. FIG. 3072.

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图 1 乙醇的转化途径^[11]

Figure 1 Conversion pathway of ethanol^[11] (with permission from Springer Nature Publications)

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图 2 木质纤维素生物质发酵制生物乙醇^[14]

Figure 2 Fermentation of lignocellulose biomass to produce bioethanol^[14] (with permission from Elsevier Publications)

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图 3 采用CO₂/NH₃-TPD对催化剂的酸碱度进行表征^[21]

Figure 3 Characterization of the acidity and alkalinity of the catalyst using CO₂/NH₃-TPD^[21]

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图 4 Co_0.15Mg_2.85AlO_x催化剂的催化性能^[23]

Figure 4 Catalytic performance of Co_0.15Mg_2.85AlO_x catalyst^[23] (with permission from RSC Publications)

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图 5 OM-Cu_xLa_yAl₁₀₀催化剂的反应路径和机理^[24]

Figure 5 Reaction path and mechanism of OM-Cu_xLa_yAl₁₀₀ catalyst^[24] (with permission from Elsevier Publications)

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图 6 Cu-HAP催化剂的催化性能和反应路径^[29]

Figure 6 Catalytic performance and reaction pathway of Cu HAP catalyst^[29] (with permission from ACS Publications)

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图 7 (a)多孔BAP-Ni上的反应途径; (b)无孔BAP-Ni催化剂^[30]

Figure 7 Reaction pathway on (a) porous BAP-Ni; (b) nonporous BAP-Ni catalyst^[30] (with permission from ACS Publications)

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图 8 （a） 8 h 后的产物选择性：使用MgAl（2/1）负载量分别为 2.5 g/L（白色）和 10 g/L（紫色）或HAP 2.5 g/L（黄色）和10 g/L（棕色）；（b） 8 h 后的产物分布：MgAl (2/1) (白色)；Cu/MgAl （蓝色）；Ru/MgAl （黄色）；Pd/MgAl （绿色）；Pt/MgAl （灰色）^[42]

Figure 8 (a) Product selectivity after 8 h: Using MgAl (2/1) with loading amounts of 2.5 g/L (white) and 10 g/L (purple) or HAP 2.5 g/L (yellow) and 10 g/L (brown); (b) Product distribution after 8 h: MgAl (2/1) (white); Cu/MgAl (blue); Ru/MgAl (yellow); Pd/MgAl (green); Pt/MgAl (gray)^[42] (with permission from RSC Publications)

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图 9 催化剂的制备工艺示意图和SEM图像^[50]

Figure 9 Schematic diagram of catalyst preparation process and SEM diagram (a) NiSn@C-5/1-500, (b) NiSn@C-1/2-500, (c) NiSn@C-1/5-500, (d) NiSn@C-1/2-300, (e) NiSn@C-1/2-600, (f) NiSn@C-1/2-800^[50] (with permission from Elsevier Publications)

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图 10 Ni₂₀Sn₁@NC催化剂的催化性能^[51]

Figure 10 Ni₂₀Sn₁@NC catalytic performance of catalysts^[51] (with permission from ACS Publications)

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图 11 催化剂制备示意图和表征分析^[52]

Figure 11 Schematic diagram and characterization analysis of catalyst preparation^[52] (with permission from ACS Publications)

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图 12 乙醇在Ni和Sn-Ni上解离的结构图以及偶联机制^[53]

Figure 12 Structure diagram and coupling mechanism of ethanol dissociation on Ni and Sn-Ni^[53] (with permission from Elsevier Publications)

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图 13 电荷密度分布以及Bader电荷转移^[54]

Figure 13 Charge density distribution and Bader charge transfer^[54] (with permission from Elsevier Publications)

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图 14 不同碳化温度下的XRD谱图以及演化示意图^[55]

Figure 14 XRD patterns and evolution diagrams at different carbonization temperatures^[55] (with permission from Elsevier Publications)

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图 15 （a）乙醇生成正丁醇的直接机理; （b）间接机理示意图; （c）主要机理; （d）和（e）次要机理

Figure 15 (a) Direct mechanism of ethanol producing n-butanol; (b) Schematic diagram of indirect mechanism; (c) Main mechanism; (d) and (e) Secondary mechanisms

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表 1 金属氧化物催化剂

Table 1 Metal oxide catalysts

Catalyst	Reaction conditions	Conv./%	Sel./%	Reference
MgO	450 ℃, 0.5 g catalyst, N₂ 10 mL/min, 7 h	56.1	32.7	[15]
MgO	400 ℃, 0.2 g catalyst, 6% ethanol, 1.3 atm	23.0	34.0	[16]
Mg-ZrO₂	400 ℃	52.0	35.0	[17]
Mg-Al(Mg/Al=3)	350 ℃, 0.3 g catalyst, 12% ethanol, atmospheric pressure, 12 h	35.0	40.0	[18]
Cu₁MgAl₃O	200 ℃, 0.5 g catalyst, 39.5 g ethanol, autogenic pressure, 5 h	2.5	43.0	[20]
Cu₅MgAl₃O	200 ℃, 0.5 g catalyst, 39.5 g ethanol, autogenic pressure, 5 h	4.1	40.0	[20]
Cu₁₀MgAl₃O	200 ℃, 0.5 g catalyst, 39.5 g ethanol, autogenic pressure, 5 h	4.5	28.0	[20]
Cu₂₀MgAl₃O	200 ℃, 0.5 g catalyst, 39.5 g ethanol, autogenic pressure, 5 h	3.8	18.0	[20]
Pd₅MgAlO	200 ℃, 0.5 g catalyst, 39.5 g ethanol, autogenic pressure, 5 h	3.8	72.7	[20]
Ag₅MgAlO	200 ℃, 0.5 g catalyst, 39.5 g ethanol, autogenic pressure, 5 h	1.6	38.8	[20]
Mn₅MgAlO	200 ℃, 0.5 g catalyst, 39.5 g ethanol, autogenic pressure, 5 h	0.7	53.3	[20]
Fe₅MgAlO	200 ℃, 0.5 g catalyst, 39.5 g ethanol, autogenic pressure, 5 h	0.3	39.2	[20]
Sm₅MgAlO	200 ℃, 0.5 g catalyst, 39.5 g ethanol, autogenic pressure, 5 h	1.3	66.3	[20]
Yb₅MgAlO	200 ℃, 0.5 g catalyst, 39.5 g ethanol, autogenic pressure, 5 h	1.2	53.0	[20]
CuMgAlO_x	260 ℃, 0.1 MPa, GHSV=750 mL/(g·h), LHSV=2 mL/(g·h)	43.9	48.0	[21]
CuMgAlO_x	350 ℃, 0.15 g catalyst, 5 h	79.6	32.0	[22]
Co_0.15Mg_2.85AlO_x	250 ℃, 0.1 MPa, 0.2 g catalyst, WHSV=0.96 h⁻¹	32.9	95.4	[23]
OM-Cu₄La_2.6Al₁₀₀	260 ℃, 3 MPa (N₂), LHSV=2 mL/(h·g), 12 h	52.2	72.2	[24]
Conv.: conversion of ethanol; Sel.: selectivity of higher alcohol.

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表 2 羟基磷灰石（HAP）催化剂

Table 2 Hydroxyapatite (HAP) catalyst

Catalyst	Reaction conditions	Conv./%	Sel./%	Reference
HAP Ca/P=1.64	320 ℃, 0.21 g catalyst, GHSV=10000 h⁻¹	22.7	62.4	[26]
HAP (Ca+Sr)/P=1.67	400 ℃, flow=50 mL/min, GHSV=5000 mL/(g·h), 4 h	13.0	76.4	[27]
Ca-HAP-1(1.59)	400 ℃, atmospheric pressure, GHSV=10000 h⁻¹	16.2	22.2	[28]
Ca-HAP-2(1.62)	400 ℃, atmospheric pressure, GHSV=10000 h⁻¹	20.8	50.4	[28]
Ca-HAP-3(1.65)	400 ℃, atmospheric pressure, GHSV=10000 h⁻¹	21.2	62.4	[28]
Ca-HAP-4(1.67)	400 ℃, atmospheric pressure, GHSV=10000 h⁻¹	15.8	56.2	[28]
Sr-HAP-1(1.58)	300 ℃, atmospheric pressure, W/F_ethanol=130 (h·g)/mol	1.1	69.0	[28]
Sr-HAP-2(1.64)	300 ℃, atmospheric pressure, W/F_ethanol=130 (h·g)/mol	5.9	78.1	[28]
Sr-HAP-3(1.67)	300 ℃, atmospheric pressure, W/F_ethanol=130 (h·g)/mol	7.9	81.7	[28]
Sr-HAP-4(1.70)	300 ℃, atmospheric pressure, W/F_ethanol=130 (h·g)/mol	11.3	86.4	[28]
Cu-HAP	250 ℃, 0.1 g catalyst, H₂ or N₂ 30 mL/min, 0.5 h	36.6	86.7	[29]
Ni-HAP	400 ℃, 0.25 g catalyst, 0.5 mL ethanol, 0.1 MPa N₂, 24 h	55.6	67.7	[30]
Conv.: conversion of ethanol; Sel.: selectivity of higher alcohol.

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表 3 单金属负载催化剂

Table 3 Monometal Supported Catalysts

Catalyst	Reaction conditions	Conv./%	Sel./%	Reference
5%Ru/Al₂O₃	300 ℃, 0.01−0.05 g catalyst, 1.2 g ethanol, autogenic pressure, 3 h	12.0	9.0	[34]
5%Rh/Al₂O₃	300 ℃, 0.01−0.05 g catalyst, 1.2 g ethanol, autogenic pressure, 3 h	5.0	35.0	[34]
5%Pd/Al₂O₃	300 ℃, 0.01−0.05 g catalyst, 1.2 g ethanol, autogenic pressure, 3 h	9.0	21.0	[34]
5%Pt/Al₂O₃	300 ℃, 0.01−0.05 g catalyst, 1.2 g ethanol, autogenic pressure, 3 h	3.0	37.0	[34]
0.8%Au/Al₂O₃	300 ℃, 0.01−0.05 g catalyst, 1.2 g ethanol, autogenic pressure, 3 h	6.0	35.0	[34]
6%Ag/Al₂O₃	300 ℃, 0.01−0.05 g catalyst, 1.2 g ethanol, autogenic pressure, 3 h	2.0	20.0	[34]
Ag/Mg-Al	250 ℃	53.7	13.8	[35]
Ni/γ-Al₂O₃	230 ℃, WHSV=1.42 h⁻¹, 100 bar, 10 h	41.0	47.5	[36]
Ni/γ-Al₂O₃	240 ℃, 2 g catalyst, 70 bar, LHSV=0.1 h⁻¹, 10 h	14.0	69.0	[37]
Cu/γ-Al₂O₃	240 ℃, 2 g catalyst, 70 bar, LHSV=0.1 h⁻¹, 10 h	14.0	64.0	[37]
Cu/CeO₂	260 ℃, 1 mL/min CO₂ and 0.05 mL/min EtOH, LHSV=1.97 h⁻¹	39.0	35.0	[38]
Ru/MgO	400 ℃	43.0	9.0	[39]
Au/mTiO₂	250 ℃	74.0	10.0	[40]
Co/MgAlO	350 ℃	55.0	33.0	[41]
Cu/MgAl	230 ℃, 0.5 or 2 g catalyst, 200 mL ethanol, 30 bar N₂, 8 h	−	81.9	[42]
Ru/Mg₃Al₁-LDO	350 ℃, 0.5 g catalyst, p(N₂)=0.1 MPa, WHSV=3.2 h⁻¹	29.6	82.6	[43]
Ni@C	0.5 g catalyst, 5 MPa H₂ initial pressure, 10 h	61.7	85.7	[44]
Conv.: conversion of ethanol; Sel.: selectivity of higher alcohol.

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表 4 多金属负载催化剂

Table 4 Multimetal supported catalysts

Catalyst	Reaction conditions	Conv./%	Sel./%	Reference
Cu-CeO₂/AC	250 ℃, 1.0 g catalyst, 2 MPa (N₂), LHSV=4 mL/(h·g)	39.1	55.2	[45]
5Cu1Ce/AC	250 ℃, 1.0 g catalyst, 2 MPa (N₂), LHSV=4 mL/(h·g)	46.2	61.8	[45]
4Cu1Ce/AC	250 ℃, 1.0 g catalyst, 2 MPa (N₂), LHSV=4 mL/(h·g)	45.6	62.7	[45]
3Cu1Ce/AC	250 ℃, 1.0 g catalyst, 2 MPa (N₂), LHSV=4 mL/(h·g)	46.2	60.0	[45]
2Cu1Ce/AC	250 ℃, 1.0 g catalyst, 2 MPa (N₂), LHSV=4 mL/(h·g)	46.3	58.7	[45]
1Cu1Ce/AC	250 ℃, 1.0 g catalyst, 2 MPa (N₂), LHSV=4 mL/(h·g)	44.0	45.5	[45]
3Cu1Ce/SiO₂	250 ℃, 1.0 g catalyst, 2 MPa (N₂), LHSV=4 mL/(h·g)	23.3	12.3	[45]
3Cu1Ce/A₂O₃	250 ℃, 1.0 g catalyst, 2 MPa (N₂), LHSV=4 mL/(h·g)	46.9	17.4	[45]
Ni-Cu/HT	310 ℃, Ni:Cu=1:1	62.4	34.8	[46]
Ni/La₂O₃/Al₂O₃	230 ℃, 30 g catalyst, reactor pressure=100 bar	41.0	74.0	[47]
Ni/Cu/La₂O₃/β-Al₂O₃	230 ℃, 30 g catalyst, WHSV=2.06 h⁻¹	15.0	78.0	[48]
NiSn/MgAlO	250 ℃, 1 g NaOH, 10 g H₂O, 10 g ethanol, 12 h	66.9	93.8	[49]
NiSn@C	250 ℃, 0.5 g catalyst, EtOH/H₂O=1, 24 h	47.0	36.0	[50]
NiSn@NC	250 ℃, 0.5 g catalyst, 15 g ethanol, 15 g H₂O, 1 g NaOH, 24 h	68.5	31.8	[51]
NiZn@NC	250 ℃, 0.5 g catalyst, 15 g ethanol, 15 g H₂O, 1 g NaOH, 24 h	75.2	−	[52]
Sn-Ni/CS	230 ℃, 0.3 g catalysts, 0.87 g NaOH, 10 g EtOH, 10 g H₂O, 12 h	60.0	85.0	[53]
NiMo@C	240 ℃, 0.6 g catalyst, 13.5 g C₂H₅OH, 1.5 g fusel, 15.0 g H₂O, 0.9 g NaOH, 12 h	89.4	44.7	[54]
NiSn@C-MgO	250 ℃, 0.5 g catalyst, 10 g ethanol, 10 g H₂O, 0.5 g NaOH, 12 h	73.3	60.9	[55]
Cu-La₂O₃/Al₂O₃	250 ℃, 1.0 g catalyst, 3 MPa (N₂), LHSV=2 mL/(g·h)	56.7	76.1	[9]
Conv.: conversion of ethanol; Sel.: selectivity of higher alcohol.

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