Production of bio-ethanol by consecutive hydrogenolysis of corn-stalk cellulose

doi:10.1016/S1872-2067(20)63709-3

Abstract

Abstract:

Current bio-ethanol production entails the enzymatic depolymerization of cellulose, but this process shows low efficiency and poor economy. In this work, we developed a consecutive aqueous hydrogenolysis process for the conversion of corn-stalk cellulose to produce a relatively high concentration of bio-ethanol (6.1 wt%) without humin formation. A high yield of cellulose (ca. 50 wt%) is extracted from corn stalk using a green solvent (80 wt% 1,4-butanediol) without destroying the structure of the lignin. The first hydrothermal hydrogenolysis step uses a Ni-WO_x/SiO₂ catalyst to convert the high cumulative concentration of cellulose (30 wt%) into a polyol mixture with a 56.5 C% yield of ethylene glycol (EG). The original polyol mixture is then subjected to subsequent selective aqueous-phase hydrogenolysis of the C-O bond to produce bioethanol (75% conversion, 84 C% selectivity) over the modified hydrothermally stable Cu catalysts. The added Ni component favors the good dispersion of Cu nanoparticles, and the incorporated Au³⁺ helps to stabilize the active Cu⁰-Cu⁺ species. This multi-functional catalytic process provides an economically competitive route for the production of cellulosic ethanol from raw lignocellulose.

Key words: Corn-stalk, Cellulose, Aqueous-phase hydrogenolysis, Bio-ethanol, Ni-WO_x catalyst, Cu⁰-Cu⁺ species, C-C bond cleavage

Dawang Chu, Yingying Xin, Chen Zhao. Production of bio-ethanol by consecutive hydrogenolysis of corn-stalk cellulose[J]. Chinese Journal of Catalysis, 2021, 42(5): 844-854.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63709-3

https://www.cjcatal.com/EN/Y2021/V42/I5/844

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References

[1]	N. Wei, J. Quarterman, S. R. Kim, J. H. Cate, Y.-S. Jin, Nat. Commun., 2013,4, 2580.
[2]	M. E. Himmel, S.-Y. Ding, D. K. Johnson, W. S. Adney, M. R. Nimlos, J. W. Brady, T. D. Foust, Science, 2007,315, 804-807.
[3]	S. Dutta, K. C.-W Wu, Green Chem., 2014,16, 4615-4626.
[4]	G. Xu, A. Q. Wang, J. F. Pang, X. C. Zhao, J. M. Xu, N. A. Lei, J. Wang, M. Y. Zheng, J. Z. Yin, T. Zhang, ChemSusChem, 2017,10, 1390-1394.
[5]	C. Yang, Z. Miao, F. Zhang, L. Li, Y. Liu, A. Wang, T. Zhang, Green Chem., 2018,20, 2142-2150.
[6]	M. Yang, H. Qi, F. Liu, Y. Ren, X. Pan, L. Zhang, X. Liu, H. Wang, J. Pang, M. Zheng, A. Wang, T. Zhang, Joule, 2019,3, 1937-1948.
[7]	H. Song, P. Wang, S. Li, W. Deng, Y. Li, Q. Zhang, Y. Wang, Chem. Commun., 2019,55, 4303-4306.
[8]	C. Li, G. Xu, C. Wang, L. Ma, Y. Qiao, Y. Zhang, Y. Fu, Green Chem., 2019,21, 2234-2239.
[9]	Q. Liu, H. Wang, H. Xin, C. Wang, L. Yan, Y. Wang, Q. Zhang, X. Zhang, Y. Xu, G. W. Huber, L. Ma, ChemSusChem, 2019,12, 3977-3987.
[10]	S. -F. Chen, R. A. Mowery, C. J. Scarlata, C. K. Chambliss, J. Agri. Food Chem., 2007,55, 5912-5918.
[11]	A. Rodríguez, L. Serrano, A. Moral, L. Jiménez, Biochem. Eng. J., 2008,42, 243-247.
[12]	L. Jiménez, A. Pérez, M. J. de la Torre, A. Moral, L. Serrano, Bioresource Technol., 2007,98, 3487-3490.
[13]	N. Ji, T. Zhang, M. Zheng, A. Wang, H. Wang, X. Wang, J. G. Chen, Angew. Chem. Inter. Ed., 2008,47, 8510-8513.
[14]	Z. Tai, J. Zhang, A. Wang, J. Pang, M. Zheng, T. Zhang, ChemSusChem, 2013,6, 652-658.
[15]	M. Y. Zheng, A. Q. Wang, N. Ji, J. F. Pang, X. D. Wang, T. Zhang, ChemSusChem, 2010,3, 63-66.
[16]	Y. Liu, C. Luo, H. Liu, Angew. Chem. Inter. Ed., 2012,51, 3249-3253.
[17]	Y. Zhang, A. Wang, T. Zhang, Chem. Commun., 2010,46, 862-864.
[18]	N. Ji, M. Zheng, A. Wang, T. Zhang, J. G. Chen, ChemSusChem, 2012,5, 939-944.
[19]	J. Chai, S. Zhu, Y. Cen, J. Guo, J. Wang, W. Fan, RSC Adv., 2017,7, 8567-8574.
[20]	N. Li, Y. Zheng, L. Wei, H. Teng, J. Zhou, Green Chem., 2017,19, 682-691.
[21]	Y. Cao, J. Wang, M. Kang, Y. Zhu, J. Mol. Catal. A, 2014,381, 46-53.
[22]	D. Chu, C. Zhao, Catal. Today, 2020,351, 125-132.
[23]	L. Wu, B. Li, C. Zhao, ChemCatChem, 2018,10, 1140-1147.
[24]	L. Wu, L. Li, B. Li, C. Zhao, Chem. Commun., 2017,53, 6152-6155.
[25]	H. Zhao, Y. Jiang, P. Chen, J. Fu, X. Lu, Z. Hou, Green Chem., 2018,20, 4299-4307.
[26]	L. Zheng, H. Zhao, J. Fu, X. Lu, Z. Hou, Appl. Clay Sci., 2018, 54-60.
[27]	Z. Ren, M. N. Younis, H. Zhao, C. Li, X. Yang, E. Wang, G. Wang, Chin. J. Chem. Eng., 2020,28, 1612-1622.
[28]	J. Gong, H. Yue, Y. Zhao, S. Zhao, L. Zhao, J. Lv, S. Wang, X. Ma, J. Am. Chem. Soc., 2012,134, 13922-13925.
[29]	S. C. Larsen, A. Aylor, A. T. Bell, J. A. Reimer, J. Phys. Chem., 1994,98, 11533-11540.

Feedstock	Catalyst	Yield (%)
Feedstock	Catalyst	Cellulose	Lignin	Hemicellulose
Corn stalk	Blank	49.8	8.7	Dissolved
Corn stalk	0.1% NaOH	49.2	Dissolved	Dissolved
Corn stalk	0.5 g HUSY	46.2	7.2	Dissolved
Corn stalk	0.5 g ZSM-5	51.4	9.2	Dissolved
Corn stalk	0.1% HCl	35.0	6.6	Dissolved
Sawdust	Blank	51.9	18.8	Dissolved
Sawdust	0.1% HCl	10.0	19.1	Dissolved
Corn cob	Blank	53.3	6.6	Dissolved
Corn cob	0.1% HCl	24.6	14.7	Dissolved

Feedstock	Catalyst	Yield (%)
Feedstock	Catalyst	Cellulose	Lignin	Hemicellulose
Corn stalk	Blank	49.8	8.7	Dissolved
Corn stalk	0.1% NaOH	49.2	Dissolved	Dissolved
Corn stalk	0.5 g HUSY	46.2	7.2	Dissolved
Corn stalk	0.5 g ZSM-5	51.4	9.2	Dissolved
Corn stalk	0.1% HCl	35.0	6.6	Dissolved
Sawdust	Blank	51.9	18.8	Dissolved
Sawdust	0.1% HCl	10.0	19.1	Dissolved
Corn cob	Blank	53.3	6.6	Dissolved
Corn cob	0.1% HCl	24.6	14.7	Dissolved

Entry	Feedstock	Catalyst	Conc. (wt%)	Conv. (C %)	Yield (C %)
Entry	Feedstock	Catalyst	Conc. (wt%)	Conv. (C %)	EG	1,2-PDO	1,2-BDO	Sorbitol	Others
1	Cellulose	5%Ni-50%WO_x/SiO₂	1	100	30.3	2.3	2.7	3.2	9.1
2	Cellulose	10%Ni-50%WO_x/SiO₂	1	100	70.6	5.2	1.8	3.3	5.3
3	Cellulose	15%Ni-50%WO_x/SiO₂	1	100	72.0	4.1	3.6	5.8	7.1
4	Cellulose	25%Ni-50%WO_x/SiO₂	1	100	47.1	1.8	2.0	19.9	10.8
5	Cellulose	50%Ni-50%WO_x/SiO₂	1	100	33.8	2.0	3.3	28.3	12.5
6	Cellulose	15%Ni-50%WO_x/SiO₂	0.5	100	71.8	4.1	3.3	7.2	6.6
7	Cellulose	15%Ni-50%WO_x/SiO₂	5	100	70.5	5.4	6.6	3.6	6.0
8	Cellulose	15%Ni-50%WO_x/SiO₂	10	100	55.2	8.6	10.6	11.3	7.1
9	Cellulose *	15%Ni-50%WO_x/SiO₂	1	100	72.4	1.5	2.6	8.0	7.5
10	Cellulose *	15%Ni-50%WO_x/SiO₂	1	100	52.4	18.1	10.5	7.1	4.9
11	Cellulose *	15%Ni-50%WO_x/SiO₂	1	100	37.0	2.3	8.6	4.5	20.9

Entry	Feedstock	Catalyst	Conc. (wt%)	Conv. (C %)	Yield (C %)
Entry	Feedstock	Catalyst	Conc. (wt%)	Conv. (C %)	EG	1,2-PDO	1,2-BDO	Sorbitol	Others
1	Cellulose	5%Ni-50%WO_x/SiO₂	1	100	30.3	2.3	2.7	3.2	9.1
2	Cellulose	10%Ni-50%WO_x/SiO₂	1	100	70.6	5.2	1.8	3.3	5.3
3	Cellulose	15%Ni-50%WO_x/SiO₂	1	100	72.0	4.1	3.6	5.8	7.1
4	Cellulose	25%Ni-50%WO_x/SiO₂	1	100	47.1	1.8	2.0	19.9	10.8
5	Cellulose	50%Ni-50%WO_x/SiO₂	1	100	33.8	2.0	3.3	28.3	12.5
6	Cellulose	15%Ni-50%WO_x/SiO₂	0.5	100	71.8	4.1	3.3	7.2	6.6
7	Cellulose	15%Ni-50%WO_x/SiO₂	5	100	70.5	5.4	6.6	3.6	6.0
8	Cellulose	15%Ni-50%WO_x/SiO₂	10	100	55.2	8.6	10.6	11.3	7.1
9	Cellulose *	15%Ni-50%WO_x/SiO₂	1	100	72.4	1.5	2.6	8.0	7.5
10	Cellulose *	15%Ni-50%WO_x/SiO₂	1	100	52.4	18.1	10.5	7.1	4.9
11	Cellulose *	15%Ni-50%WO_x/SiO₂	1	100	37.0	2.3	8.6	4.5	20.9

Entry	Catalyst	Preparation method	Reaction time (h)	Conv. (C%)	Selectivity (C%)		Ethanol yield (C%)
Entry	Catalyst	Preparation method	Reaction time (h)	Conv. (C%)	Acetaldehyde	Ethanol	Ethanol yield (C%)
1	20%Cu/SiO₂	AE	3	13.4	24.6	34.3	4.6
2	20%Cu-2%Ni/SiO₂	AE	3	35.3	5.7	73.4	25.9
3	20%Cu-2%Ni/SiO₂	AE	10	62.3	7.1	76.1	47.4
4	20%Cu-2%Ni/SiO₂	HT	3	26.6	10.2	60.2	16.0
5	20%Cu-2%Ni/SiO₂	HT	10	55.2	3.4	77.4	42.7
6	20%Cu-2%Co/SiO₂	AE	3	30.7	7.2	67.1	20.6
7	20%Cu-2%Co/SiO₂	AE	10	49.8	5.0	65.3	32.5
8	20%Cu-2%Co/SiO₂	HT	3	24.7	8.1	59.1	14.6
9	20%Cu-2%Co/SiO₂	HT	10	55.0	6.0	72.4	39.8
10	20%Cu-2%Mo/SiO₂	HT	3	30.1	6.0	68.4	20.6
11	20%Cu-2%Mo/SiO₂	HT	10	60.7	7.6	74.3	45.1
12	20%Cu-2%B/SiO₂	HT	3	24.0	1.3	74.2	17.8
13	20%Cu-2%B/SiO₂	HT	10	47.4	2.1	78.1	37.0
14	1%Ag-20%Cu/SiO₂	AE^*	3	13.3	11.3	56.4	7.5
15	1%Au-20%Cu/SiO₂	AE^*	3	28.7	8.7	64.5	18.5
16	1%Ru-20%Cu/SiO₂	AE^*	3	21.2	23.6	51.4	10.9
17	1%Au-(20%Cu-2%Co)/SiO₂	AE^*	3	29.7	6.7	69.4	20.6
18	1%Au-(20%Cu-2%Ni)/SiO₂	AE^*	3	39.7	4.3	74.1	29.4
19	1%Au-(20%Cu-2%Ni)/SiO₂	AE^*	10	73.1	5.0	85.1	62.2