Directional synthesis of bio-based light olefins has great significance for promoting sustainable development of chemical industry. Present work proves that light olefins can be selectively prepared from the cellulose-derived acetone-butanol-ethanol. This transformation has been achieved by coupling cellulose fermentation and acetone-butanol-ethanol catalytic dehydration over the Ce@SAPO-34 catalyst. The active sites and reusability of the catalyst were investigated. High acetone-butanol-ethanol conversion (91.9%) and high olefin selectivity (86.1%) are achieved. Based on the study of the individual components in acetone-butanol-ethanol, the reaction pathways are put forward.
Biomass has been demonstrated to be a sustainable carbon resource for the preparation of renewable fuels and chemicals [1-4]. The important intermediate of ABE (acetone-butanol-ethanol) can be obtained from the biomass hydrolysis/fermentation [5-11]. The ABE yield mainly depends on raw materials, fermentation strains, and fermentation conditions [5-11]. Some high-value chemicals (such as butanol and acetone) can be directly obtained from ABE fermentation by using the product recall technology [5, 6, 8].
Considering that ABE fermentation products mainly contain short chain alcohols and acetone, ABE fermentation broth cannot fully meet the requirements of conventional transportation fuels [5, 6, 8]. However, ABE can be used as intermediates to produce transportation fuels by the alkylation/hydrotreating reactions [8, 12] or dehydration/olefin polymerization processes [13, 14]. Research shows that lower alcohol has two dehydration channels: intramolecular dehydration to light olefin and intermolecular dehydration to ether [15, 16]. Obviously, the ABE intramolecular dehydration is beneficial for the synthesis of transportation fuel through olefin polymerization [13, 14].
Light olefins are fundamental building block chemicals and important precursors for the synthesis of hydrocarbon fuels [17-24]. Currently, light-olefins are produced primarily by thermal cracking of naphtha [17]. The growing demand for light olefins and carbon emission reduction has stimulated the production of light olefins using renewable biomass [1, 22]. The MTO (methanol-to-olefins) has been demonstrated to be a successful way for light olefin preparation, and methanol can be produced from biomass [1, 18, 24]. Besides, bio-ethanol based on cellulose-fermentation can be converted to ethylene [5, 22]. Bio-butanol derived from cellulose-fermentation can be converted to butenes, which can be used as chemicals or synthesis of transportation fuel [5-11].
Generally, the concentration of alcohols in bio-based ABE is low, because it contains a lot of water and other impurities [5, 6, 8]. If light olefins are produced from ABE fermentation broth without purification, it will help to reduce energy consumption and simplify process. This work shows that light olefins can be selectively synthesized through coupling cellulose fermentation and catalytic dehydration of unpurified ABE. The role of the active center of catalyst was investigated. High ABE conversion and high olefin selectivity were achieved under mild reaction condition.
II.
EXPERIMENTS
A
Materials
In this work, ABE (acetone-butanol-ethanol) was produced by the hydrolysis/fermentation of cellulose, as described in the previous work [8]. The element composition of cellulose contained 45.04 wt% C, 6.21 wt% H and 48.01 wt% O. The fermentation intermediates obtained from the cellulose fermentation mainly contained 1-butanol (61.3 wt%), ethanol (10.5 wt%), acetone (19.7 wt%) and other fermentation products (8.5 wt%).
B
Catalyst preparation and characterization
Zeolites (including HZSM-5, Hβ, Al-MCM41, and SAPO-34) were ordered from Nankai university catalyst company (Tianjin, China). The Ce/SAPO34 catalyst (typically containing 2 wt% Ce) was synthesized by incipient wetness impregnation [25]. The catalyst characterization method was described in details in Supplementary materials (SM). Briefly, pyridine Fourier transform infrared (Py-FTIR) and NH3-TPD (NH3 temperature programmed desorption) were used to analyze the acid nature of the catalyst [26, 27]. X-ray diffraction (XRD) was used to analyze crystal phase [28, 29]. Transmission electron microscope (TEM ) was used to obtain the morphology characteristics of catalysts [30].
C
Experimental method for production of light olefins from ABE
In this work, the production of light olefins from cellulose-based ABE or its individual components was conducted by using a flowing fixed bed reactor [31]. Both the aqueous ABE (water content: 97.8%) and the dehydrated ABE (water content: 5.8%) were tested for production of light olefins. Prior to the reactions, the mixture of the catalyst and quartz sand (1:10) was added to the catalytic reactor. When heated to the set temperature, cellulose-based ABE was added to the reactor using TS260 liquid injection pump (Baoding, China). Typical reaction conditions were: 2.0 g ABE, 2.0 g catalyst, temperature (250–500 °C) and reaction time (1 h). After the reactions, the gas products were detected by a GC-SP6890 gas chromatograph (Tengzhou, China). Liquid products were detected by Thermo-Trace 1300 chromatography-mass spectrometry (GC-MS, Wilmington, USA). The conversion, products selectivity, and olefins yield were evaluated based on our previous work [32].
III.
RESULTS AND DISCUSSION
A
Preparation of light olefins from bio-based ABE with different catalysts
As displayed in Table I, all tested catalysts have high activity for the conversion of ABE at 350 °C. The complex products such as light olefins, aromatics, light alkanes, and oxygenates have been detected in the ABE conversion (Table S1 in SM). The Ce/SAPO-34 catalyst shows the highest olefin selectivity and olefin yield (Table I). With the Ce/SAPO-34 catalyst, the primary reaction is the catalytic transformation of ABE to form n-butenes and iso-butylene (Table S1 in SM). Considering that n-butanol is a main constituent in the cellulose-dervied ABE, n-butenes (major products) should be attributed to catalytic dehydration of n-butanol.
Table
I.
Production of light-olefins from the dehydrated ABE using different catalysts. C: conversion, Solefin: olefin selectivity, Saromatics: aromatics selectivity, and Yolefin: olefin yield. Reaction conditions: 2 g catalyst, 2 g dehydrated ABE, T=350 °C.
Unlike Ce/SAPO-34, catalysts with larger pores (like Al-MCM-41, HZSM-5 and Hβ) form more aromatics and oxygenates (Table S1 in SM). The HZSM-5 catalyst has the highest aromatics selectivity (Table I). This is due to that HZSM5 catalyst has high content of Brønsted acid (Table II), which may promote olefin aromatization to form aromatics [33, 34]. The catalysts with larger pore size also form more oxygenated compounds, such as dibutyl ether, diacetone alcohol, and high-carbon alkyl ketones (Table S1 in SM). Dibutyl ether is formed from intermolecular dehydration of n-butanol [16]. Alkyl ketones (mainly C7 alkyl-ketones) may come from the alkylation of acetone with n-butanol [8]. However, Ce/SAPO-34 with small pore size forms trace amounts of dibutyl-ether and alkyl-ketones (Table S1 in SM), suggesting that the shape selectivity of the catalyst inhibits the ABE dehydration to ether and the alkylation reactions. In addition, adding a small amount of Ce into SAPO-34 is beneficial to reduce the formation of coke (Table S1 in SM). Previous work also showed that Ce/Mg-modified SAPO-34 reduced carbon deposition for ethanol catalytic conversion [35-36].
Table
II.
Main characteristics of catalysts. SBET: Brunauer-Emmet-Teller surface area in m2/g, Vp: pore-volume in cm3/g, Total acidity in µmol NH3/g, B/L: Bronsted/Lewis acid ratio and S/W: strong/weak acid ratio.
B
Effect of reaction condition on production of light olefin from ABE
As shown in FIG. 1(a), the ABE conversion shows an upswing trend as temperature increases, suggesting that increasing temperature promotes ABE dehydration. On the other hand, the selectivity of products is also influenced by temperature (FIG. 1(b)). The formation of oxygen-containing by-products (such as butyl ether and ketones) mainly occurrs at lower temperature below 300 °C (FIG. 1(b)). The selectivity of oxygenates decreases with increasing temperature, suggesting high temperature promotes ABE catalytic deoxygenation to hydrocarbons (mainly light olefins). In the lower temperature region (below 300 °C), C4+ higher olefins caused by olefin polymerization are also observed (FIG. 1(b)). The aromatic selectivity increases with increasing temperature, since high temperature enhance olefins aromatization [32, 33]. As a result, the olefin selectivity shows a maximum value at about 350 °C (FIG. 1(a)).
Figure
1.
Influence of temperature on production of light-olefins from dehydrated ABE. Reaction conditions: 2 g Ce/SAPO-34 catalyst, 2 g dehydrated ABE. (a) conversion, olefin yield, olefin selectivity, and carbon balance; (b) selectivity of different products.
Next, we investigated the effect of water on the catalytic conversion of cellulose-based ABE to light olefins. FIG. 2 shows the difference about light olefins production from two different reactants (aqueous ABE and dehydrated ABE). For the catalytic conversion of the dehydrated ABE, the conversion is 91.9% with Ce/SAPO-34 catalyst at 350 °C. The main product derived from the dehydrated ABE is olefins (86.1%), together with a small amount of the by-products (aromatics, alkanes and oxygenates). Compared to the dehydrated ABE, the catalytic conversion of the aqueous ABE shows higher ABE conversion under the same reaction condition. Especially, higher olefins selectivity (93.1%) is obtained through catalytic conversion of aqueous ABE with the Ce/SAPO-34 catalyst (FIG. 2). The undesired by-products (aromatics and coke) for aqueous ABE are negligible. This suggests that water molecules in the ABE mixture may occupy the parts of the acidic sites in the catalyst and thus limit the secondary reactions, such as the dissociation of the olefins, alkylation and aromatization reactions [8, 32, 33]. As shown in FIG. 2, the by-product of alkyl ketone is observed, which is attributed to the alkylation reaction of acetone with butanol [8]. This indicates that there is interaction among different components in the catalytic conversion of cellulose-based ABE.
Figure
2.
Production of light olefins from two cellulose derived ABE. (a) Aqueous ABE (water content: 97.8%); (b) dehydrated ABE (water content: 5.8%). Reaction conditions: 2 g Ce/SAPO-34 catalyst, 2 g ABE, T=350 °C.
C
Catalytic transformation of n-butanol to light olefins
It is worth noting that n-butanol and acetone are two main components in the bio-based ABE fermentation broth. FIG. S1(a, b) in SM shows the catalytic performance of different catalysts for producing light alkenes from 1-butanol. All tested acid catalysts have high catalytic activity at 350 °C (FIG. S1(a) in SM). However, different acid catalysts show significant differences in the product distribution and the olefins selectivity. Ce/SAPO-34 with smaller pores shows the highest olefins selectivity (FIG. S1(b) in SM). When using the Ce/SAPO-34 catalyst, main reaction is n-butanol intramolecular dehydration to form n-butenes, while ether selectivity by intermolecular dehydration is very low. Iso-butene is also observed, which is attributed to isomerization of n-butene [33]. A small amount of C4+ olefins are formed by polymerization of light olefins [34, 37]. Unlike the Ce/SAPO-34 catalyst, the acid catalysts with larger pores (like Al-MCM-41) produce more by-products (alkanes, aromatics dibutyl ether and coke), resulting in olefin selectivity decrease (FIG. S1(b) in SM). As a result, the pore size and the acidity of the acid catalysts have important impact on the products selectivity.
FIG. S1(c, d) in SM shows temperature effect on production of light olefins from n-butanol. The n-butanol conversion reaches almost complete conversion over 350 °C (FIG. S1(c) in SM). The yield of olefins shows the maximum value at about 350 °C. The primary reaction is n-butanol dehydration to n-butenes at 350 °C. Subsequently, a part of butenes are further converted into iso-butylene through isomerization process (FIG. S1(d) in SM). The dibutyl ether selectivity decreases with increasing temprature (FIG. S1(d) in SM), because it is an exothermic reaction [16]. When the temperature rises above 350 °C, the selectivity to light olefins displays a decline trend, while the selectivity to aromatics increases (FIG. S1(d) in SM). This suggests that higher temperature enhance the olefins aromatization [33]. The gas alkanes also increased with increasing temperature, since high temperature promote the dissociation of butenes [23, 33].
D
Catalytic transformation of acetone to light olefins
In this work, the acetone content in the dehydrated ABE is 19.7%, which is produced by the cellulose fermentation. FIG. S2(a, b) in SM shows catalytic performance of different catalysts for producing light-alkenes from acetone. Compared to n-butanol, acetone shows a lower conversion under the same reaction condition. Catalytic conversion of acetone forms complex products, such as olefins, aromatics, alkanes, oxygenates and coke (FIG. S2(b) in SM). Iso-butylene is one of the main products in the catalytic conversion of acetone. The Ce/SAPO-34 catalyst shows higher selectivity to iso-butylene. Another major product in acetone conversion is aromatics, which may come from olefins aromatization or acetone trimerization/deoxidation over the catalysts [38, 39]. Compared to the Ce/SAPO-34, the catalyst with a larger pore (like Al-MCM-41) produces more aromatics (FIG. S2(b) in SM).
As shown in FIG. S2(c) in SM, higher temperature is profited to acetone conversion. The primary product is iso-butene in acetone conversion below 350 °C (FIG. S2(d) in SM). At 250 °C, diacetone-alcohol is observed, which may be formed by acetone dimerization [38, 39]. Diacetone alcohol decreases with increasing temprature, probably because acetone dimerization is an exothermic reaction [38, 39]. The selectivity of butenes over 350 °C declines, while aromatics selectivity increases (FIG. S2(d) in SM). Different from n-butanol, a large number of aromatics and coke are formed in catalytic transformation of acetone (FIG. S2 in SM). Therefore, it is necessary to consider other ways of using acetone in the ABE mixtures. For example, acetone can be directly separated from ABE, which can be used as a high-value chemical. Alternatively, the alkylation reaction between acetone and butanol in ABE can be further converted into fuels [8].
E
Characterization of catalysts
In this work, the acid catalysts have been picked out for production of light olefins using cellulose-derived ABE. Main properties of these catalysts are shown in Table II. The nitrogen adsorption/desorption isotherm analysis was also conducted for pore characteristics of catalyst (FIG. 3 (a, b)). As shown in Table II, adding Ce to SAPO-34 leads to slight decrease of surface area. The porous volume of Ce/SAPO-34 is smaller than that of SAPO-34, which may be due to the factor that doped-oxides may block the channels of the catalyst [25, 32]. As can be seen from FIG. 3(c, d), the typical image of the Ce/SAPO-34 catalyst exhibits the non-uniform block structure.
Figure
3.
Catalyst characterization of Ce/SAPO-34 catalyst. (a) N2 adsorption-desorption isotherms, (b) pore distribution, (c) SEM image, (d) TEM image.
FIG. S3(a) in SM shows representative py-FTIR spectrum obtained from the acid catalyst. The absorption bands of 1540 cm−1 and 1450 cm−1 belong to Bronsted acid site and Lewis acid site, respectively [34]. Py-FTIR is not appropriate for detecting the SAPO-34 catalyst, since pyridine probe molecule is too large to fit into its pores [33, 35-36]. Thus, we adopted NH3-FTIR to analyze acid sites of SAPO-34 [36]. As displayed in FIG. S3(b) in SM, 1455 cm−1 and 3400 cm−1 bands are depicted to Bronsted and Lewis acid sites respectively [36]. NH3-TPD was also used to analyze the nature of the catalyst. FIG. S3(c) in SM shows NH3 desorption peaks near 220 °C and 430 °C, which are depicted as weak and strong acids, respectively [25]. FIG. S3(d) in SM shows representative XRD spectrum of Ce/SAPO-34, containing crystalline phase of SAPO-34 [35, 24]. It is noteworthy that the Ce-modified SAPO-34 shows a lower ratio of strong acid to weak acid than the parent SAPO-34 (Table II), which is conducive to reduce the coke formation during the catalytic conversion of ABE (Table S1 in SM).
F. Reaction pathways in preparation of light olefins from bio-based ABE
FIG. 4 depicts the possible reaction pathways for the production of light olefins from cellulose-derived ABE, based on the present and previous work [5-8, 33, 37-39]. The predominant reaction paths include ABE dehydration to light-olefins, olefins polymerization, olefins aromatization, and acetone alkylation [5-8, 33, 37-39].
Figure
4.
Possible reaction pathways for production of light olefins from cellulose-based ABE.
Light olefins are basic chemicals and key precursors for the fuels synthesis [17-23]. Main factors affecting the catalytic performance in the conversion of cellulose-based ABE to light olefins are the catalyst’s nature and reaction conditions. The Ce/SAPO-34 shows higher olefin selectivity and olefin yield (Table I). Research shows that lower alcohol has two dehydration ways: intramolecular dehydration to lower olefin and intermolecular dehydration to ether [15, 16]. For the acid catalyst with smaller pores, intermolecular dehydration of alcohol is effectively suppressed (FIG. S1 in SM), suggesting that bio-based ABE can be dehydrated to light olefins by using shape selectivity of Ce/SAPO-34 [33]. Different from the Ce/SAPO-34 catalyst, the acid catalysts with larger pores (like Al-MCM-41) produce more aromatics, dibutyl ether and coke, resulting in the decrease of olefin selectivity (Table S1 in SM). The pore size and acidity of catalysts play an important role in the selective conversion of cellulose-based ABE to olefins. Compared to 1-butanol (FIG. S1 in SM), the products from the catalytic transformation of acetone are more complicated (FIG. S2 in SM). Acetone catalytic conversion with Ce/SAPO-34 catalyst mainly yields olefins and aromatics, along with a small amount of alkanes and oxygenates (FIG. S2 in SM). Existence of iso-butene/diacetone alcohol shows that an acid-catalyzed aldol condensation could be an important reaction [38, 39]. Aromatics from acetone may come from olefins aromatization or acetone trimerization/deoxidation [38, 39]. In addition, alkyl ketone may be formed by the alkylation of acetone with butanol [38, 39].
G. Stability of catalysts in synthesis of light olefins
The stability/reusability of representative Ce/SAPO-34 in production of light olefins from the cellulose-based ABE was tested by the cycle experiments. As displayed in FIG. 5, the catalyst deactivation leads to the decrease of the ABE conversion and olefin yield after four cycles. To investigate the catalyst reusability, the used Ce@SAPO-34 catalyst was regenerated by the coke-burning method. The regenerated catalyst also shows a high ABE conversion and good olefin selectivity (FIG. 5). Considering that the activity of deactivated catalyst can almost be recovered by coke combustion (FIG. 5), the deposition of coke (or some heavy oligomer products) on the active acid sites may be the main factor of catalyst deactivation in the ABE conversion [32]. Moreover, according to the preliminary evaluation, the maximum olefin yield is 10.4 wt% (based on dry biomass raw material). Definitely, it is necessary to improve olefin yield through catalyst optimization and process integration in our future work.
Figure
5.
Catalyst stability and reusability in the production of light olefins from the dehydrated ABE. Reaction condition: 2 g Ce/SAPO-34 catalyst, 2 g dehydrated ABE, T=350 °C. Regeneration condition: T=550 °C, t=2 h. (a) Conversion, olefin yield and carbon balance, (b) selectivity of different products.
Present work reports that light olefins can be selectively produced from the cellulose-based ABE. This transformation has been achieved by coupling cellulose fermentation to ABE and the selective catalytic dehydration of ABE to light olefins. The Ce/SAPO-34 catalyst has superior performance in the synthesis of light olefins from the cellulose-derived ABE. The ABE dehydration to ethers is suppressed by using the shape selectivity of the catalyst. High ABE conversion (91.9%) and high olefin selectivity (86.1%) are obtained under the mild condition. Based on the study of the individual components in ABE, the reaction pathways are put forward.
Supplementary materials: The selectivity of the detailed products in the ABE catalytic conversion using different catalysts is shown in Table S1. The catalytic performance of different catalysts for the production of light olefins from n-butanol is shown in FIG. S1. The catalytic performance of different catalysts for the production of light olefins from acetone is shown in FIG. S2. Py-FTIR spectrum of the Hβ catalyst is shown in FIG. S3, NH3-FTIR spectrum, NH3-TPD profile, and XRD spectrum of the Ce@SAPO-34 catalyst are also shown in FIG. S3.
ACKNOWLEDGEMENTS
This work was supported by the National Natural Science Foundation of China (No.21978280 and No.U21A20288).
J. P. Ma, S. Shi, X. Q. Jia, F. Xia, H. Ma, J. Gao, and J. Xie, J. Energy Chem. 36, 74 (2019). doi: 10.1016/j.jechem.2019.04.026
[2]
L. F. Zhu, X. Fu, Y. X. Hu, and C. W. Hu, ChemSusChem 13, 4812 (2020). doi: 10.1002/cssc.202001341
[3]
X. Liu, T. F. Li, S. B. Wu, H. Ma, and Y. H. Yin, Bioresour. Technol. 310, 123460 (2020). doi: 10.1016/j.biortech.2020.123460
[4]
Z. Y. Li, Z. P. Zhong, B. Zhang, W. Wang, G. V. S. Seufitelli, and F. L. P. Resende, Waste Manage. 102, 561 (2020). doi: 10.1016/j.wasman.2019.11.012
[5]
S. K. Bhatia, S. H. Kim, J. J. Yoon, and Y. H. Yang, Energy Convers. Manage. 148, 1142 (2017). doi: 10.1016/j.enconman.2017.06.073
[6]
Y. Guo, Y. Liu, M. D. Guan, H. C. Tang, Z. L. Wang, L. H. Lin, and H. Pang, RSC Adv. 12, 18848 (2022). doi: 10.1039/D1RA09396G
[7]
P. X. Wang, J. Zhang, J. Feng, S. J. Wang, L. Guo, Y. F. Wang, Y. Y. Lee, S. Taylor, T. McDonald, and Y. Wang, Bioresour. Technol. 281, 217 (2019). doi: 10.1016/j.biortech.2019.02.096
[8]
C. Xue, M. Liu, X. W. Guo, E. P. Hudson, L. J. Chen, F. W. Bai, F. F. Liu, and S. T. Yang, Green Chem. 19, 660 (2017). doi: 10.1039/C6GC02546C
[9]
Z. Q. Wen, R. Ledesma-Amaro, M. R. Lu, M. J. Jin, and S. Yang, ACS Synth. Biol. 9, 304 (2020). doi: 10.1021/acssynbio.9b00331
J. W. Wu, L. L. Dong, B. F. Liu, D. F. Xing, C. S. Zhou, Q. Wang, X. K. Wu, L. P. Feng, and G. L. Cao, Environ. Res. 186, 109580 (2020). doi: 10.1016/j.envres.2020.109580
[12]
P. Anbarasan, Z. C. Baer, S. Sreekumar, E. Gross, J. B. Binder, H. W. Blanch, D. S. Clark, and F. D. Toste, Nature 491, 235 (2012). doi: 10.1038/nature11594
B. H. H. Goh, C. T. Chong, H. C. Ong, T. Seljak, T. Katrasnik, V. Jozsa, J. H. Ng, B. Tian, S. Karmarkar, and V. Ashokkumarh, Energy Convers. Manage. 251, 114974 (2022). doi: 10.1016/j.enconman.2021.114974
[15]
Y. Chen, Y. L. Wu, L. Tao, B. Dai, M. D. Yang, Z. Chen, and X. Y. Zhu, J. Ind. Eng. Chem. 16, 717 (2010). doi: 10.1016/j.jiec.2010.07.013
[16]
M. A. Perez, R. Bringue, M. Iborra, J. Tejero, and F. Cunill, Appl. Catal. A Gen. 482, 38 (2014). doi: 10.1016/j.apcata.2014.05.017
[17]
K. Cheng, B. Gu, X. Liu, J. Kang, Q. Zhang, and Y. Wang, Angew. Chem. Int. Ed. 55, 4725 (2016). doi: 10.1002/anie.201601208
[18]
S. X. Bai, F. F. Liu, B. L. Huang, F. Li, H. P. Lin, T. Wu, M. Z. Sun, J. B. Wu, Q. Shao, Y. Xu, and X. Q. Huang, Nat. Commun. 11, 954 (2020). doi: 10.1038/s41467-020-14742-x
[19]
S. W. Koh, J. Hu, J. Hwang, P. Yu, Z. Sun, Q. Liu, W. Hong, J. Ge, J. Fei, and B. Han, Mater. Chem. Front. 5, 4970 (2021). doi: 10.1039/D0QM01113D
[20]
J. S. Lopez, R. A. Dagle, V. L. Dagle, C. Smith, and K. O. Albrecht, Catal. Sci. Technol. 9, 1117 (2019). doi: 10.1039/C8CY02297F
[21]
X. Y. Guo, X. S. Guo, and Y. Suzuki, ChemistrySelect 5, 528 (2020). doi: 10.1002/slct.201903665
[22]
J. Y. Zhang, E. Yoo, B. H. Davison, D. Liu, J. A. Schaidle, L. Tao, and Z. L. Li, Green Chem. 23, 9534 (2021). doi: 10.1039/D1GC02854E
[23]
X. Y. Guo, L. S. Guo, Y. Zeng, R. Kosol, X. H. Gao, Y. Yoneyama, G. H. Yang, and N. Tsubaki, Catal. Today 368, 196 (2021). doi: 10.1016/j.cattod.2020.04.047
Y. T. He, L. J. Zhu, Y. H. Luo, M. H. Fan, M. Y. Yang, Y. H. Zhang, and Q. X. Li, Fuel Process. Technol. 213, 106674 (2021). doi: 10.1016/j.fuproc.2020.106674
[26]
Y. T. He, Y. H. Luo, M. Y. Yang, Y. H. Zhang, L. J. Zhu, M. H. Fan, and Q. X. Li, Appl. Catal. A Gen. 630, 118440 (2022). doi: 10.1016/j.apcata.2021.118440
[27]
X. J. Niu, J. Gao, Q. Miao, M. Dong, G. F. Wang, W. B. Fan, Z. F. Qin, and J. G. Wang, Microporous Mesoporous Mater. 197, 252 (2014). doi: 10.1016/j.micromeso.2014.06.027
[28]
L. J. Zhu, Y. H. Luo, Y. T. He, M. Y. Yang, Y. H. Zhang, M. H. Fan, and Q. X. Li, Mol. Catal. 517, 112063 (2022). doi: 10.1016/j.mcat.2021.112063
[29]
Y. H. Luo, L. J. Zhu, Y. T. He, M. Y. Yang, Y. H. Zhang, M. H. Fan, and Q. X. Li, Cellulose 29, 303 (2022). doi: 10.1007/s10570-021-04285-9
[30]
Y. H. Zhang, X. P. Wu, Y. T. He, Y. H. Luo, M. Y. Yang, M. H. Fan, and Q. X. Li, J. Chem. Technol. Biotechnol. 97, 2068 (2022). doi: 10.1002/jctb.7077
[31]
M. Y. Yang, X. P. Wu, Y. T. He, Y. H. Luo, Y. H. Zhang, M. H. Fan, and Q. X. Li, Cellulose 29, 5557 (2022). doi: 10.1007/s10570-022-04625-3
[32]
Y. T. He, Y. H. Luo, M. Y. Yang, Y. H. Zhang, M. H. Fan, and Q. X. Li, Catal. Sci. Technol. 12, 4524 (2022). doi: 10.1039/D2CY00382A
[33]
C. P. Nash, A. Ramanathan, D. A. Ruddy, M. Behl, E. Gjersing, M. Griffin, H. D. Zhu, B. Subramaniam, J. A. Schaidle, and J. E. Hensley, Appl. Catal. A Gen. 510, 110 (2016). doi: 10.1016/j.apcata.2015.11.019
[34]
A. Martinez, M. A. Arribas, P. Concepcion, and S. Moussa, Appl. Catal. A Gen. 467, 509 (2013). doi: 10.1016/j.apcata.2013.08.021
[35]
S. X. Tian, S. F. Ji, D. D. Lu, B. Y. Bai, and Q. Sun, J. Energy Chem. 22, 605 (2013). doi: 10.1016/S2095-4956(13)60079-0
[36]
D. Z. Zhang, Y. X. Wei, L. Xu, F. X. Chang, Z. Y. Liu, S. H. Meng, B. L. Su, and Z. M. Liu, Microporous Mesoporous Mater. 116, 684 (2008). doi: 10.1016/j.micromeso.2008.06.001
[37]
A. G. Popov, V. S. Pavlov, and I. I. Ivanova, J. Catal. 335, 155 (2016). doi: 10.1016/j.jcat.2015.12.008
[38]
H. Konno, T. Tago, Y. Nakasaka, G. Watanabe, and T. Masuda, Appl. Catal. A Gen. 475, 127 (2014). doi: 10.1016/j.apcata.2014.01.031
[39]
T. Tago, H. Konno, M. Sakamoto, Y. Nakasaka, and T. Masuda, Appl. Catal. A Gen. 403, 183 (2011). doi: 10.1016/j.apcata.2011.06.029
Zhang, R., Zhu, C., Jiang, Y. et al. An eco-friendly catalytic pretreatment using recyclable CuFeO2 catalyst for enhancing the production of bio-based ethanol and jet fuel. Biomass and Bioenergy, 2025.
DOI:10.1016/j.biombioe.2025.107668
2.
Hong, J., Chen, B., Wang, T. et al. A promising technical route for converting lignocellulose to bio-jet fuels based on bioconversion of biomass and coupling of aqueous ethanol: A techno-economic assessment. Fuel, 2025.
DOI:10.1016/j.fuel.2024.133670
3.
Jing, Y., Liu, M., Peng, S. et al. Strategies for enhanced acetone-butanol-ethanol production by Clostridium beijerinckii Y10 from glucose and xylose and exploration of its physiological mechanisms. Biochemical Engineering Journal, 2024.
DOI:10.1016/j.bej.2024.109518
4.
Zhang, R., He, Y., Zhu, R. et al. Enhancement of bio-jet fuel production from corncob by iron ion-catalyzed hydrogen peroxide pretreatment. Fuel, 2024.
DOI:10.1016/j.fuel.2024.132347
5.
Zhu, C., Zhang, R., Zhu, L. et al. A green biomass pretreatment using iron ion-catalyzed hydrogen peroxide for lignocellulose fermentation and biofuel production. Cellulose, 2024, 31(12): 7367-7384.
DOI:10.1007/s10570-024-06054-w
6.
Zhu, R., Zhang, R., He, Y. et al. Iron ion catalyzed hydrogen peroxide pretreatment for bio-jet fuel production from straw biomass. Journal of Chemical Technology and Biotechnology, 2024, 99(8): 1810-1820.
DOI:10.1002/jctb.7683
Table
I.
Production of light-olefins from the dehydrated ABE using different catalysts. C: conversion, Solefin: olefin selectivity, Saromatics: aromatics selectivity, and Yolefin: olefin yield. Reaction conditions: 2 g catalyst, 2 g dehydrated ABE, T=350 °C.
Table
II.
Main characteristics of catalysts. SBET: Brunauer-Emmet-Teller surface area in m2/g, Vp: pore-volume in cm3/g, Total acidity in µmol NH3/g, B/L: Bronsted/Lewis acid ratio and S/W: strong/weak acid ratio.
DownLoad:
