Progress in heterogeneous catalyst for ethanol upgrading to higher (C6+) alcohols

doi:10.16085/j.issn.1000-6613.2022-0507

Abstract

Abstract:

Conversion of ethanol to other high value-added chemicals has attracted extensive attention recently, especially upgrading to higher alcohols (C₆₊) through Guerbet reaction. The research and development status of several typical heterogeneous catalysts, including hydroxyapatite (HAP), hydrotalcite (LDHs) and supported metal catalysts, for the conversion of ethanol to higher alcohols in recent years are reviewed in this paper. Their advantages and disadvantages are comprehensively compared and analyzed. The reasons for the low selectivity for higher alcohols of current catalysts are discussed based on the reaction mechanism. The design and improvement to obtain an ideal catalyst are prospected. It is pointed out that the higher alcohols selectivity could be improved by promoting the aldol reaction step in Guerbet reaction. The metal-supported catalyst can accelerate the rate-limiting step significantly. Fine regulation of metal, acid and base active sites distribution on the support surface and the controlled synthesis of catalyst with specific structures will be the focus of future research in this field.

Key words: higher alcohols, biofuel, heterogeneous reaction, catalyst, Guerbet reaction

摘要：

以乙醇为原料制备其他高附加值化工产品近期得到了广泛关注，特别是乙醇基于Guerbet反应缩合制备高碳醇（C₆₊）的过程更成为这一领域的研究热点。本文着重报道了近年来乙醇转化为高碳醇过程的几种典型的多相催化剂，包括羟基磷灰石（HAP）、类水滑石（LDHs）以及各种负载型金属催化剂的研究开发现状，分析比较了各类催化剂的优势与不足，结合反应机理针对催化剂对高碳醇选择性不高的原因进行了讨论，对理想催化剂的设计和改进进行了展望，指出应该通过促进Guerbet反应中的羟醛缩合过程增加高碳醇的选择性。金属负载型催化剂对该反应控制步骤的加速作用显著，而金属位点和载体表面酸碱活性位点的精细调控以及特定催化剂形貌结构的控制合成则是该领域未来的研究重点。

关键词: 高碳醇, 生物燃料, 多相反应, 催化剂, Guerbet反应

CLC Number:

TQ032.4

XUE Machen, YANG Bolun, XIA Chungu, ZHU Gangli. Progress in heterogeneous catalyst for ethanol upgrading to higher (C₆₊) alcohols[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 194-203.

薛马晨, 杨伯伦, 夏春谷, 朱刚利. 乙醇缩合制高碳醇（C₆₊醇）多相催化剂研究进展[J]. 化工进展, 2023, 42(1): 194-203.

Figures/Tables 12

References 40

1	XU Di, YANG Hengquan, HONG Xinlin, et al. Tandem catalysis of direct CO₂ hydrogenation to higher alcohols[J]. ACS Catalysis, 2021, 11(15): 8978-8984.
2	LIANG Ning, ZHANG Xiaolong, AN Hualiang, et al. Direct synthesis of 2-ethylhexanol via n-butanal aldol condensation-hydrogenation reaction integration over a Ni/Ce-Al₂O₃bifunctional catalyst[J]. Green Chemistry, 2015, 17(5): 2959-2972.
3	ATABANI A E, Al KULTHOOM S. Spectral, thermoanalytical characterizations, properties, engine and emission performance of complementary biodiesel-diesel-pentanol/octanol blends[J]. Fuel, 2020, 282: 118849.
4	GUERBET Marcel. Guerbet reaction[J]. Comptes Rend, 1899, 128: 511.
5	WU Xianyuan, FANG Geqian, TONG Yuqin, et al. Catalytic upgrading of ethanol to n-butanol: Progress in catalyst development[J]. ChemSusChem, 2018, 11(1): 71-85.
6	WANG S C, CENDEJAS M C, HERMANS I. Insights into ethanol coupling over hydroxyapatite using modulation excitation operando infrared spectroscopy[J]. ChemCatChem, 2020, 12(16): 4167-4175.
7	CARVALHO D L, DE AVILLEZ R R, RODRIGUES M T, et al. Mg and Al mixed oxides and the synthesis of n-butanol from ethanol[J]. Applied Catalysis A: General, 2012, 415/416: 96-100.
8	NDOU A S, PLINT N, COVILLE N J. Dimerisation of ethanol to butanol over solid-base catalysts[J]. Applied Catalysis A: General, 2003, 251(2): 337-345.
9	TSUCHIDA， SAKUMA S, TAKEGUCHI T, et al. Direct synthesis of n-butanol from ethanol over nonstoichiometric hydroxyapatite[J]. Industrial & Engineering Chemistry Research, 2006, 45(25): 8634-8642.
10	TSUCHIDA T, KUBO J, YOSHIOKA T, et al. Reaction of ethanol over hydroxyapatite affected by Ca/P ratio of catalyst[J]. Journal of Catalysis, 2008, 259(2): 183-189.
11	OGO S, ONDA A, IWASA Y, et al. 1-Butanol synthesis from ethanol over strontium phosphate hydroxyapatite catalysts with various Sr/P ratios[J]. Journal of Catalysis, 2012, 296: 24-30.
12	MOTEKI T, FLAHERTY D W. Mechanistic insight to C—C bond formation and predictive models for cascade reactions among alcohols on Ca- and Sr-hydroxyapatites[J]. ACS Catalysis, 2016, 6(7): 4170-4183.
13	HANSPAL S, YOUNG Z D, SHOU H, et al. Multiproduct steady-state isotopic transient kinetic analysis of the ethanol coupling reaction over hydroxyapatite and magnesia[J]. ACS Catalysis, 2015, 5(3): 1737-1746.
14	HO C R, SHYLESH S, BELL A T. Mechanism and kinetics of ethanol coupling to butanol over hydroxyapatite[J]. ACS Catalysis, 2016, 6(2): 939-948.
15	WANG Qingnan, ZHOU Baichuan, WENG Xuefei, et al. Hydroxyapatite nanowires rich in [Ca-O-P] sites for ethanol direct coupling showing high C_6-12 alcohol yield[J]. Chemical Communications (Cambridge, England), 2019, 55(70): 10420-10423.
16	BRASIL H, BITTENCOURT A F, YOKOO K C, et al. Synthesis modification of hydroxyapatite surface for ethanol conversion: The role of the acidic/basic sites ratio[J]. Journal of Catalysis, 2021, 404: 802-813.
17	RAMASAMY K K, GRAY M, JOB H, et al. Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds[J]. Catalysis Today, 2016, 269: 82-87.
18	BENITO P, VACCARI A, ANTONETTI C, et al. Tunable copper-hydrotalcite derived mixed oxides for sustainable ethanol condensation to n-butanol in liquid phase[J]. Journal of Cleaner Production, 2019, 209: 1614-1623.
19	SUMMA P, SAMOJEDEN B, MOTAK M, et al. Investigation of Cu promotion effect on hydrotalcite-based nickel catalyst for CO₂ methanation[J]. Catalysis Today, 2022, 384/385/386: 133-145.
20	JIANG Dahao, WU Xianyuan, MAO Jun, et al. Continuous catalytic upgrading of ethanol to n-butanol over Cu-CeO₂/AC catalysts[J]. Chemical Communications (Cambridge, England), 2016, 52(95): 13749-13752.
21	EAGAN N M, LANCI M P, HUBER G W. Kinetic modeling of alcohol oligomerization over calcium hydroxyapatite[J]. ACS Catalysis, 2020, 10(5): 2978-2989.
22	PERRONE O M, SIQUEIRA M R, METZKER G, et al. Copper and lanthanum mixed oxides as catalysts for ethanol Guerbet coupling: The role of La³⁺ on the production of long-chain alcohols[J]. Environmental Progress & Sustainable Energy, 2020, 40(2): e13541.
23	WANG Dong, LIU Zhenyu, LIU Qingya. Efficient conversion of ethanol to 1-butanol and C₅-C₉ alcohols over calcium carbide[J]. RSC Advances, 2019, 9(33): 18941-18948.
24	WANG Dong, LIU Zhenyu, LIU Qingya. Synthesis of 1-butanol from ethanol over calcium ethoxide: Experimental and density functional theory simulation[J]. The Journal of Physical Chemistry C, 2019, 123(37): 22932-22940.
25	PANG Jifeng, ZHENG Mingyuan, WANG Zhinuo, et al. Catalytic upgrading of ethanol to butanol over a binary catalytic system of FeNiO _x and LiOH[J]. Chinese Journal of Catalysis, 2020, 41(4): 672-678.
26	ZHANG Qian, LIU Wenping, CHEN Bo, et al. Upgrading of aqueous ethanol to fuel grade higher alcohols over dandelion-like Ni-Sn catalyst[J]. Energy Conversion and Management, 2020, 216: 112914.
27	ZAFFRAN J, MICHEL C, DELBECQ F, et al. Trade-off between accuracy and universality in linear energy relations for alcohol dehydrogenation on transition metals[J]. The Journal of Physical Chemistry C, 2015, 119(23): 12988-12998.
28	JORDISON T L, LIRA C T, MILLER D J. Condensed-phase ethanol conversion to higher alcohols[J]. Industrial & Engineering Chemistry Research, 2015, 54(44): 10991-11000.
29	PANG Jifeng, ZHENG Mingyuan, HE Lei, et al. Upgrading ethanol to n-butanol over highly dispersed Ni-MgAlO catalysts[J]. Journal of Catalysis, 2016, 344: 184-193.
30	EARLEY J H, BOURNE R A, WATSON M J, et al. Continuous catalytic upgrading of ethanol to n-butanol and>C₄ products over Cu/CeO₂ catalysts in supercritical CO₂ [J]. Green Chemistry, 2015, 17 (5): 3018-3025.
31	ZHANG Jian, SHI Kai, AN Zhe, et al. Acid-base promoted dehydrogenation coupling of ethanol on supported Ag particles[J]. Industrial & Engineering Chemistry Research, 2020, 59(8): 3342-3350.
32	JIANG Dahao, FANG Geqian, TONG Yuqin, et al. Multifunctional Pd@UiO-66 catalysts for continuous catalytic upgrading of ethanol to n‑butanol[J]. ACS Catalysis, 2018, 8(12): 11973-11978.
33	WANG Zhinuo, PANG Jifeng, SONG Lei, et al. Conversion of ethanol to n-butanol over NiCeO₂ based catalysts: Effects of metal dispersion and NiCe interactions[J]. Industrial & Engineering Chemistry Research, 2020, 59(51): 22057-22067.
34	XUE Machen, YANG Bolun, XIA Chungu, et al. Upgrading ethanol to higher alcohols via biomass-derived Ni/bio-apatite[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(11): 3466-3476.
35	DONG Chao, YU Qun, YE Runping, et al. Hollow carbon sphere nanoreactors loaded with PdCu nanoparticles: Void-confinement effects in liquid-phase hydrogenations[J]. Angewandte Chemie International Edition, 2020, 59(42): 18374-18379.
36	ZHANG Jian, SHI Kai, ZHU Yanru, et al. Interfacial sites in Ag supported layered double oxide for dehydrogenation coupling of ethanol to n-butanol[J]. ChemistryOpen, 2021, 10(11):1095-1103.
37	NIKOLAEV S A, CHISTYAKOV A V, ZHAROVA P A, et al. Synergistic effect of gold and copper in the catalytic conversion of ethanol to linear α-alcohols[J]. Petroleum Chemistry, 2016, 56(8): 730-737.
38	NIKOLAEV S A, TSODIKOV M V, CHISTYAKOV A V, et al. PdCu nanoalloy supported on alumina: A stable and selective catalyst for the conversion of bioethanol to linear α‍-alcohols[J]. Catalysis Today, 2021, 379: 50-61.
39	NEZAM I, ZAK J, MILLER D J. Condensed-phase ethanol conversion to higher alcohols over bimetallic catalysts[J]. Industrial & Engineering Chemistry Research, 2020, 59(31): 13906-13915.
40	FEI Xing, XU Quanzhou, XUE Lijing, et al. Aqueous phase catalytic conversion of ethanol to higher alcohols over NiSn bimetallic catalysts encapsulated in nitrogen-doped biorefinery lignin-based carbon[J]. Industrial & Engineering Chemistry Research, 2021, 60(49): 17959-17969.

序号	催化剂	反应条件	转化率/%	选择性/%		参考文献
序号	催化剂	反应条件	转化率/%	丁醇	C₆₊醇	参考文献
1	CaC₂	10%（摩尔分数）催化剂，6h，0.1MPa Ar，315℃	50	26.8	52.2	[23]
2	Ca(OCH₂CH₃)	10%（摩尔分数）催化剂，8h，0.1MPa Ar，315℃	28	34	47	[24]
3	FeNiO _x	1.25%（质量分数）催化剂，0.8% LiOH，24h，0.5MPa N₂，230℃	37	71	20	[25]
4	Ni-Sn	3.3%（质量分数）催化剂，NaOH，0.1MPa H₂，24h，250℃	46.6	23	53.6	[26]

序号	催化剂	反应条件	转化率/%	选择性/%		参考文献
序号	催化剂	反应条件	转化率/%	丁醇	C₆₊醇	参考文献
1	CaC₂	10%（摩尔分数）催化剂，6h，0.1MPa Ar，315℃	50	26.8	52.2	[23]
2	Ca(OCH₂CH₃)	10%（摩尔分数）催化剂，8h，0.1MPa Ar，315℃	28	34	47	[24]
3	FeNiO _x	1.25%（质量分数）催化剂，0.8% LiOH，24h，0.5MPa N₂，230℃	37	71	20	[25]
4	Ni-Sn	3.3%（质量分数）催化剂，NaOH，0.1MPa H₂，24h，250℃	46.6	23	53.6	[26]

序号	催化剂	反应条件	转化率/%	选择性/%		参考文献
序号	催化剂	反应条件	转化率/%	丁醇	C₆₊醇	参考文献
1	Ag/MgAl-LDO	LHSV=6h^-1，250°C，2MPa N₂	53.7	57.3	13.8	[31]
2	3Cu1Ce/AC	LHSV=4h^-1，250°C，2MPa N₂	46.2	41.3	19.7	[20]
3	3Cu1Ce/AC	4%（质量分数）催化剂，250℃，48h，0.1MPa N₂	39.1	55.2	20.3	[20]
4	Pd@UiO-66	LHSV=4h^-1，250°C，2MPa N₂	49.8	48.6	～20	[32]

序号	催化剂	反应条件	转化率/%	选择性/%		参考文献
序号	催化剂	反应条件	转化率/%	丁醇	C₆₊醇	参考文献
1	Ag/MgAl-LDO	LHSV=6h^-1，250°C，2MPa N₂	53.7	57.3	13.8	[31]
2	3Cu1Ce/AC	LHSV=4h^-1，250°C，2MPa N₂	46.2	41.3	19.7	[20]
3	3Cu1Ce/AC	4%（质量分数）催化剂，250℃，48h，0.1MPa N₂	39.1	55.2	20.3	[20]
4	Pd@UiO-66	LHSV=4h^-1，250°C，2MPa N₂	49.8	48.6	～20	[32]

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Progress in heterogeneous catalyst for ethanol upgrading to higher (C₆₊) alcohols

乙醇缩合制高碳醇（C₆₊醇）多相催化剂研究进展

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