Waste sponge derived carbon-based solid acids for levoglucosanone production via cassava residue pyrolysis

doi:10.11949/0438-1157.20230997

Abstract

Abstract:

In this paper, waste sponges were used as carbon material precursors, and a series of sulfonic acid functionalized carbon-based solid acids were synthesized through inert atmosphere carbonization and grafting of sulfonic acid groups, which were used for rapid pyrolysis of cassava residue to prepare LGO. The as-prepared waste sponge derived carbon-based solid acids were systematically analyzed by using various physicochemical characterizations, including X-ray diffraction (XRD), infrared spectroscopy (FT-IR), liquid nitrogen adsorption and desorption, and scanning electron microscopy (SEM), and so on, so as to identify the structural characteristics. The experimental results indicated that waste sponge derived carbon-based solid acid prepared at 500℃ and carbon-to-acid ratio of 1 g∶0.5 ml had rich porous structures and sulfonic acid groups, thus facilitating the selective pyrolysis of cassava residue into LGO. Under the catalysis of above mentioned carbon-based solid acid, the mass yield of LGO achieved 12.93% from cassava residue pyrolysis. This study presents a new idea for the resource utilization of waste sponges, which also promoted the application of solid wastes derived carbon materials for high-value transformation of agricultural and forestry wastes.

Key words: biomass, catalyst, pyrolysis, organic compounds, chemical analysis

摘要：

以废弃海绵作为碳材料前体，通过惰性气氛碳化和接枝磺酸基团，合成了系列磺酸功能化碳基固体酸，用于木薯渣快速热解制备左旋葡萄糖酮（LGO）。研究采用多种物理化学表征手段，如X射线衍射、红外光谱、液氮吸脱附、扫描电镜等，系统分析了制备的废弃海绵衍生碳基固体酸物化特性。结果表明，废弃海绵衍生碳基固体酸具有较丰富的孔道结构，其表面接枝了丰富的磺酸基团，因而有利于木薯渣选择性热解转化获得LGO。其中，在碳化温度500℃、碳/酸比1 g∶0.5 ml时，废弃海绵衍生碳基固体酸展现出较优的催化热解性能，产物中LGO质量收率可达12.93%。本文研究将为废弃海绵资源化利用提供新的思路，同时又能够促进固废衍生碳材料在农林废弃物高值转化方面应用。

关键词: 生物质, 催化剂, 热解, 有机化合物, 化学分析

CLC Number:

TQ 352.4

Shengliang ZHONG, Jun ZHANG, Rui SHAN, Yong SUN. Waste sponge derived carbon-based solid acids for levoglucosanone production via cassava residue pyrolysis[J]. CIESC Journal, 2023, 74(11): 4559-4569.

钟声亮, 张军, 单锐, 孙勇. 废海绵衍生碳基固体酸催化热解木薯渣制备左旋葡萄糖酮[J]. 化工学报, 2023, 74(11): 4559-4569.

Figures/Tables 12

Fig.1 XRD patterns of as-prepared carbon-based solid acid catalysts

Fig.2 N2 adsorption-desorption curves of carbon-based solid acids

Table 1 Pore structure parameters of catalysts with different carbonization temperatures

碳化温度/℃	比表面积/ (m²/g)	孔体积/ (cm³/g)	孔径/nm
300	4.99	0.02	18.94
500	13.93	0.07	16.55
700	23.13	0.10	13.67

Fig. 3 SEM images of carbon-based solid acid catalysts

Table 2 Sulfonic acid group loading for different chlorosulfonic acid additions

催化剂	磺酸基团负载量/(mmol/g)
500WS-S0.1	0.24
500WS-S0.25	2.73
500WS-S0.5	3.87
500WS-S1	4.19
500WS-S2	3.39

Fig. 4 XPS spectra of 500WS-S0.5

Fig. 5 FT-IR spectra of carbon-based solid acid catalysts

Fig. 6 TG-DTG curves of catalytic pyrolysis of cassava residues

Fig. 7 TG/MS curves of catalytic pyrolysis of cassava residues

Fig. 8 The results of Py-GC/MS experiments

Fig. 9 GC-MS spectra for pyrolytic products in the case of using 500WS-S0.5 as catalyst

Fig. 10 Possible pathway for CR pyrolysis over carbon-based solid acids

References 49

1	Lazaroiu G C, Putrus G. Renewable energy generation driving positive energy communities[J]. Renewable Energy, 2023, 205: 627-630.
2	Velvizhi G, Jacqueline P J, Shetti N P, et al. Emerging trends and advances in valorization of lignocellulosic biomass to biofuels[J]. Journal of Environmental Management, 2023, 345: 118527.
3	Kiehbadroudinezhad M, Merabet A, Hosseinzadeh-Bandbafha H, et al. Environmental assessment of optimized renewable energy-based microgrids integrated desalination plant: considering human health, ecosystem quality, climate change, and resources[J]. Environmental Science and Pollution Research, 2023, 30(11):29888-29908.
4	Amjith L R, Bavanish B. A review on biomass and wind as renewable energy for sustainable environment[J]. Chemosphere, 2022, 293: 133579.
5	Moradian J M, Fang Z, Yong Y C. Recent advances on biomass-fueled microbial fuel cell[J]. Bioresources and Bioprocessing, 2021, 8(1): 14.
6	Qi W, Feng Q F, Wang W, et al. Combination of surfactants and enzyme cocktails for enhancing woody biomass saccharification and bioethanol production from lab-scale to pilot-scale[J]. Bioresource Technology, 2023, 384: 129343.
7	Faizan M, Song H. Critical review on catalytic biomass gasification: state-of-art progress, technical challenges, and perspectives in future development[J]. Journal of Cleaner Production, 2023, 408: 137224.
8	Manikandan S, Subbaiya R, Biruntha M, et al. Recent development patterns, utilization and prospective of biofuel production: emerging nanotechnological intervention for environmental sustainability—a review[J]. Fuel, 2022, 314: 122757.
9	Qiu B B, Tao X D, Wang J H, et al. Research progress in the preparation of high-quality liquid fuels and chemicals by catalytic pyrolysis of biomass: a review[J]. Energy Conversion and Management, 2022, 261: 115647.
10	Dorleku W P, Bayitse R, Hansen A C H, et al. Response surface optimisation of enzymatic hydrolysis of cassava peels without chemical and hydrothermal pretreatment[J]. Biomass Conversion and Biorefinery, 2022, 1-14.
11	Egbune E O, Ezedom T, Orororo O C, et al. Solid-state fermentation of cassava (Manihot esculenta Crantz): a review[J]. World Journal of Microbiology and Biotechnology, 2023, 39(10): 259.
12	Aduba C C, Ndukwe J K, Onyejiaka C K, et al. Integrated valorization of cassava wastes for production of bioelectricity, biogas and biofertilizer[J]. Waste and Biomass Valorization, 2023, 14(12): 4003-4019.
13	Li Z Y, Lan W, Liu C F. Biomass derived bifunctional catalyst for the conversion of cassava dreg into sorbitol[J]. Industrial Crops and Products,2023, 197: 116493.
14	Chen H P, Liu Z H, Chen X, et al. Comparative pyrolysis behaviors of stalk, wood and shell biomass: correlation of cellulose crystallinity and reaction kinetics[J]. Bioresource Technology,2020, 310: 123498.
15	Hassan N S, Jalil A A, Hitam C N C, et al. Biofuels and renewable chemicals production by catalytic pyrolysis of cellulose: a review[J]. Environmental Chemistry Letters,2020, 18(5): 1625-1648.
16	Sharifzadeh M, Sadeqzadeh M, Guo M, et al. The multi-scale challenges of biomass fast pyrolysis and bio-oil upgrading: review of the state of art and future research directions[J]. Progress in Energy and Combustion Science, 2019, 71: 1-80.
17	Rueangsan K, Kraisoda P, Heman A, et al. Bio-oil and char obtained from cassava rhizomes with soil conditioners by fast pyrolysis[J]. Heliyon, 2021, 7(11): e08291.
18	Liu J P, Chen X, Chen W, et al. Biomass pyrolysis mechanism for carbon-based high-value products[J]. Proceedings of the Combustion Institute, 2023, 39(3): 3157-3181.
19	Alhumade H, Alayed O S, Iqbal M W, et al. Exploration of the bioenergy potential of Dactyloctenium aegyptium through pyrolysis, kinetics, and thermodynamic parameters to produce clean fuels and biochemicals[J]. Fuel, 2023, 341: 127663.
20	Li X Q, Liu P, Yang Y T, et al. Pyrolysis behaviors of biomass tar-related model compounds catalyzed by Ni-modified HZSM-5 molecular sieve[J]. Industrial Crops and Products, 2023, 199: 116743.
21	Chen W H, Ghodke P K, Sharma A K, et al. Co-pyrolysis of lignocellulosic biomass with other carbonaceous materials: a review on advance technologies, synergistic effect, and future prospectus[J]. Fuel, 2023, 345: 128177.
22	Yuan H R, Li C Y, Shan R, et al. Aromatics production from catalytic pyrolysis of waste cassava residue using La and P modified ZSM-5: experimental and kinetic study[J]. Industrial Crops and Products, 2023, 198: 116753.
23	Eqbalpour M, Andooz A, Kowsari E, et al. A comprehensive review on how ionic liquids enhance the pyrolysis of cellulose, lignin, and lignocellulose toward a circular economy[J]. Wiley Interdisciplinary Reviews-Energy and Environment, 2023, 12(4): e473.
24	Liu Y, Wu S L, Zhang H Y, et al. Fast pyrolysis of holocellulose for the preparation of long-chain ether fuel precursors: effect of holocellulose types[J]. Bioresource Technology, 2021, 338: 125519.
25	Li C, Zhang J, Yuan H, et al. Advance on the pyrolytic transformation of cellulose[J]. Journal of Fuel Chemistry and Technology, 2021, 49: 1733-1751.
26	Li Y, Hu B, Fu H, et al. Catalytic fast pyrolysis of cellulose for the selective production of levoglucosenone using phosphorus molybdenum tin mixed metal oxides[J]. Energy & Fuels, 2022, 36(17): 10251-10260.
27	de Souza P M, de Sousa L A, Noronha F B, et al. Dehydration of levoglucosan to levoglucosenone over solid acid catalysts. Tuning the product distribution by changing the acid properties of the catalysts[J]. Molecular Catalysis, 2022, 529: 112564.
28	Allais F. Total syntheses and production pathways of levoglucosenone, a highly valuable chiral chemical platform for the chemical industry[J]. Current Opinion in Green and Sustainable Chemistry, 2023, 40: 100744.
29	Kudo S, Huang X, Asano S, et al. Catalytic strategies for levoglucosenone production by pyrolysis of cellulose and lignocellulosic biomass[J]. Energy & Fuels, 2021, 35(12): 9809-9824.
30	Wang B, Li K, Nan D H, et al. Enhanced production of levoglucosenone from pretreatment assisted catalytic pyrolysis of waste paper[J]. Journal of Analytical and Applied Pyrolysis, 2022, 165: 105567.
31	Huang W R, He X C, Wu J C, et al. The evaluation of deep eutectic solvents and ionic liquids as cosolvents system for improving cellulase properties[J]. Industrial Crops and Products, 2023, 197: 116555.
32	钱乐, 蒋丽群, 岳元茂, 等. 催化热解生物质生成左旋葡聚糖酮的研究进展[J]. 化工学报, 2020, 71(12): 5376-5387.
	Qian L, Jiang L Q, Yue Y M, et al. Research progress of catalytic pyrolysis of biomass to yield levoglucosenone[J]. CIESC Journal, 2020, 71(12): 5376-5387.
33	Yuan H R, Li C Y, Shan R, et al. Municipal sludge derived solid acids for levoglucosenone production via cellulose fast pyrolysis[J]. Journal of Analytical and Applied Pyrolysis, 2022, 167: 105663.
34	Zhurinsh A, Dobele G, Pomilovskis R, et al. Evolution of 1,6-anhydrosugars in the pyrolysis of biomass with phosphoric acid and P-containing activated carbon[J]. Catalysis Today, 2021, 367: 51-57.
35	Çalışkan E, Çanak T Ç, Karahasanoğlu M, et al. Synthesis and characterization of phosphorus-based flame retardant containing rigid polyurethane foam[J]. Journal of Thermal Analysis and Calorimetry, 2022, 147(6): 4119-4129.
36	Jha A, Shaik K A, Bhardwaj Y K, et al. Electron beam assisted recycling of polyurethane (PU) sponge: turning it into a superabsorbent for wastewater treatment[J]. Journal of Applied Polymer Science, 2023, 140(9): e53545.
37	Li J H, Zhu H F, Fang D D, et al. Mechanochemistry recycling of polyurethane foam using urethane exchange reaction[J]. Journal of Environmental Chemical Engineering, 2023, 11(3): 110269.
38	Li C Y, Zhang J, Shan R, et al. Kinetic study for thermocatalytic degradation of waste mixed cloth over antibiotic residue derived carbon-based solid acids[J]. Fuel, 2023, 331: 125797.
39	Liu J, Xu J, Lin M, et al. Fabrication and modification research of namboo activated carbon[J]. New Chemical Materials, 2017, 45: 184: 1006-3536.
40	Hu M, Ma J J, Jiang Z R, et al. New insights into nitrogen control strategies in sewage sludge pyrolysis toward environmental and economic sustainability[J]. Science of the Total Environment, 2023, 882: 163326.
41	Mainali K, Mood S H, Pelaez-Samaniego M R, et al. Production and applications of N-doped carbons from bioresources: a review[J]. Catalysis Today, 2023, 423: 114248.
42	徐坤, 方阳, 宫梦, 等. 葡萄糖催化热解制备左旋葡萄糖酮特性研究[J]. 化工学报, 2020, 71(8): 3594-3601.
	Xu K, Fang Y, Gong M, et al. Study on the catalytic pyrolysis of glucose to prepare levoglucosenone[J]. CIESC Journal, 2020, 71(8): 3594-3601.
43	Yang H P, Lei S S, Xu K, et al. Catalytic pyrolysis of cellulose with sulfonated carbon catalyst to produce levoglucosenone[J]. Fuel Processing Technology, 2022, 234: 107323.
44	Zhang J, Li C Y, Gu J, et al. Synergistic effects for fast co-pyrolysis of strong-acid cation exchange resin and cellulose using Py-GC/MS[J]. Fuel, 2021, 302: 121232.
45	Zhang C T, Chao L, Zhang Z M, et al. Pyrolysis of cellulose: evolution of functionalities and structure of bio-char versus temperature[J]. Renewable and Sustainable Energy Reviews, 2021, 135: 110416.
46	Hu B, Lu Q, Wu Y T, et al. Insight into the formation mechanism of levoglucosenone in phosphoric acid-catalyzed fast pyrolysis of cellulose[J]. Journal of Energy Chemistry, 2020, 43: 78-89.
47	Wang B, Li K, Zhang C B, et al. Influence of cellulose ultrastructure on the catalytic pyrolysis for selective production of levoglucosenone[J]. Industrial Crops and Products, 2023, 192: 116072.
48	González Martínez M, Ohra-aho T, Tamminen T, et al. Detailed structural elucidation of different lignocellulosic biomass types using optimized temperature and time profiles in fractionated Py-GC/MS[J]. Journal of Analytical and Applied Pyrolysis, 2019, 140: 112-124.
49	Cao Q, Ye T, Li W H, et al. Dehydration of saccharides to anhydro-sugars in dioxane: effect of reactants, acidic strength and water removal in situ[J]. Cellulose, 2020, 27(17): 9825-9838.

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