Catalytic fast pyrolysis of walnut shell for alkylphenols production with nitrogen-doped activated carbon catalyst

Highlights

• N-doped activated carbon was prepared for catalytic pyrolysis of walnut shell.

• Alkylphenols were selectively produced from catalytic pyrolysis process.

• The alkylphenols yield increased by 8.5 times under the optimal conditions.

• Formation mechanism of alkylphenols was proposed.

Abstract

Alkylphenols are a group of valuable phenolic compounds that can be derived from lignocellulosic biomass. In this study, three activated carbons (ACs) were prepared for catalytic fast pyrolysis (CFP) of walnut shell to produce alkylphenols, including nitrogen-doped walnut shell-derived activated carbon (N/WSAC), nitrogen-doped rice husk-derived activated carbon (N/RHAC) and walnut shell-derived activated carbon (WSAC). Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments were carried out to reveal the influences of AC type, pyrolytic temperature, and AC-to-walnut shell (AC-to-WS) ratio on the product distributions. Results showed that with nitrogen doping, the N/WSAC possessed stronger capability than WSAC toward the alkylphenols production, and moreover, the N/WSAC also exhibited better effects than N/RHAC to prepare alkylphenols. Under the catalysis of N/WSAC, yields of alkylphenols were significantly increased, especially phenol, cresol and 4-ethylphenol. As the increase of pyrolytic temperature, the alkylphenols yield first increased and then decreased, while high selectivity could be obtained at low pyrolytic temperatures. Such a trend was also observed as the AC-to-WS ratio continuously increased. The alkylphenols production achieved a maximal yield of 44.19 mg/g with the corresponding selectivity of 34.7% at the pyrolytic temperature of 400°C and AC-to-WS ratio of 3, compared with those of only 4.67 mg/g and 6.1% without catalyst. In addition, the possible formation mechanism of alkylphenols was also proposed with the catalysis of N/WSAC.

Graphical abstract

Keywords

Pyrolysis / Walnut shell / Alkylphenols / Nitrogen-doped activated carbon

References

[1] Açıkalın K, Karaca F (2017). Fixed-bed pyrolysis of walnut shell: Parameter effects on yields and characterization of products. Journal of Analytical and Applied Pyrolysis, 125: 234–242

[2] Babu N S, Sree R, Prasad P S S, Lingaiah N (2008). Room-temperature transesterification of edible and nonedible oils using a heterogeneous strong basic Mg/La catalyst. Energy & Fuels, 22(3): 1965–1971

[3] Bai X, Kim K H, Brown R C, Dalluge E, Hutchinson C, Lee Y J, Dalluge D (2014). Formation of phenolic oligomers during fast pyrolysis of lignin. Fuel, 128: 170–179

[4] Britt P F, Buchanan A C III, Thomas K B, Lee S K (1995). Pyrolysis mechanisms of lignin: Surface-immobilized model compound investigation of acid-catalyzed and free-radical reaction pathways. Journal of Analytical and Applied Pyrolysis, 33: 1–19

[5] Cao Z, Engelhardt J, Dierks M, Clough M T, Wang G H, Heracleous E, Lappas A, Rinaldi R, Schüth F (2017). Catalysis meets nonthermal separation for the production of (Alkyl)phenols and hydrocarbons from pyrolysis oil. Angewandte Chemie International Edition, 56(9): 2334–2339

[6] Chen W, Fang Y, Li K, Chen Z, Xia M, Gong M, Chen Y, Yang H, Tu X, Chen H (2020). Bamboo wastes catalytic pyrolysis with N-doped biochar catalyst for phenols products. Applied Energy, 260: 114242

[7] Deng Y, Peng S , Liu H, Li S , ChenY (2019). Mechanism of dichloromethane disproportionation over mesoporous TiO₂ under low temperature. Frontiers of Environmental Science & Engineering, 13(2): 21

[8] Elkasabi Y, Mullen C A, Boateng A A (2015). Aqueous extractive upgrading of bio-oils created by tail-gas reactive pyrolysis to produce pure hydrocarbons and phenols. ACS Sustainable Chemistry & Engineering, 3(11): 2809–2816

[9] Geng J, Wang W L, Yu Y X, Chang J M, Cai L P, Shi S Q (2017). Adding nickel formate in alkali lignin to increase contents of alkylphenols and aromatics during fast pyrolysis. Bioresource Technology, 227: 1–6

[10] Guo X, Wang Q, Xu T, Wei K, Yin M, Liang P, Huang X, Zhang X (2020). One-step ball milling-prepared nano Fe₂O₃ and nitrogen-doped graphene with high oxygen reduction activity and its application in microbial fuel cells. Frontiers of Environmental Science & Engineering, 14(2): 30

[11] Gupta S, Gupta G K, Mondal M K (2019). Slow pyrolysis of chemically treated walnut shell for valuable products: Effect of process parameters and in-depth product analysis. Energy, 181: 665–676

[12] Hao X, Wang G, Chen S, Yu H, Quan X (2019). Enhanced activation of peroxymonosulfate by CNT-TiO₂ under UV-light assistance for efficient degradation of organic pollutants. Frontiers of Environmental Science & Engineering, 13(5): 77

[13] Jiang X, Lu Q, Hu B, Liu J, Dong C, Yang Y (2017). A comprehensive study on pyrolysis mechanism of substituted b-O-4 type lignin dimers. International Journal of Molecular Sciences, 18(11)

[14] Kim J S (2015). Production, separation and applications of phenolic-rich bio-oil–A review. Bioresource Technology, 178: 90–98

[15] Li K, Chen W, Yang H, Chen Y, Xia S, Xia M, Tu X, Chen H (2019). Mechanism of biomass activation and ammonia modification for nitrogen-doped porous carbon materials. Bioresource Technology, 280: 260–268

[16] Li K, Wang Z X, Zhang G, Cui M S, Lu Q, Yang Y P (2020). Selective production of monocyclic aromatic hydrocarbons from ex situ catalytic fast pyrolysis of pine over the HZSM-5 catalyst with calcium formate as a hydrogen source. Sustainable Energy & Fuels, 4(2): 538–548

[17] Li X, Su L, Wang Y, Yu Y, Wang C, Li X, Wang Z (2012). Catalytic fast pyrolysis of Kraft lignin with HZSM-5 zeolite for producing aromatic hydrocarbons. Frontiers of Environmental Science & Engineering, 6(3): 295–303

[18] Lu Q, Ye X N, Zhang Z X, Wang Z X, Cui M S, Yang Y P (2018a). Catalytic fast pyrolysis of sugarcane bagasse using activated carbon catalyst in a hydrogen atmosphere to selectively produce 4-ethyl phenol. Journal of Analytical and Applied Pyrolysis, 136: 125–131

[19] Lu Q, Zhang Z B, Ye X N, Li W T, Hu B, Dong C Q, Yang Y P (2017). Selective production of 4-ethyl guaiacol from catalytic fast pyrolysis of softwood biomass using Pd/SBA-15 catalyst. Journal of Analytical and Applied Pyrolysis, 123: 237–243

[20] Lu Q, Zhou M X, Li W T, Wang X, Cui M S, Yang Y P (2018b). Catalytic fast pyrolysis of biomass with noble metal-like catalysts to produce high-grade bio-oil: Analytical Py-GC/MS study. Catalysis Today, 302: 169–179

[21] Mullen C A, Tarves P C, Boateng A A (2017). Role of potassium exchange in catalytic pyrolysis of biomass over ZSM-5: formation of alkyl phenols and furans. ACS Sustainable Chemistry & Engineering, 5(3): 2154–2162

[22] Shafaghat H, Rezaei P S, Daud W (2015). Effective parameters on selective catalytic hydrodeoxygenation of phenolic compounds of pyrolysis bio-oil to high-value hydrocarbons. RSC Advances, 5(126): 103999–104042

[23] Sing K S W (1985). Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure and Applied Chemistry, 57(4): 603– 619

[24] Totong S, Daorattanachai P, Quitain A T, Kida T, Laosiripojana N (2019). Catalytic depolymerization of alkaline lignin into phenolic-based compounds over metal-free carbon-based catalysts. Industrial & Engineering Chemistry Research, 58(29): 13041–13052

[25] Uzun B B, Sarioğlu N (2009). Rapid and catalytic pyrolysis of corn stalks. Fuel Processing Technology, 90(5): 705–716

[26] Vispute T P, Zhang H, Sanna A, Xiao R, Huber G W (2010). Renewable chemical commodity feedstocks from integrated catalytic processing of pyrolysis oils. Science, 330(6008): 1222–1227

[27] Wang C, Luo Z, Diao R, Zhu X (2019). Study on the effect of condensing temperature of walnut shells pyrolysis vapors on the composition and properties of bio-oil. Bioresource Technology, 285: 121370

[28] Wang K, Zhang J, Shanks B H, Brown R C (2015). Catalytic conversion of carbohydrate-derived oxygenates over HZSM-5 in a tandem micro-reactor system. Green Chemistry, 17(1): 557–564

[29] Wang S, Dai G, Yang H, Luo Z (2017). Lignocellulosic biomass pyrolysis mechanism: A state-of-the-art review. Progress in Energy and Combustion Science, 62: 33–86

[30] Wang S, Li Z, Bai X, Yi W, Fu P (2018). Catalytic pyrolysis of lignin with red mud derived hierarchical porous catalyst for alkyl-phenols and hydrocarbons production. Journal of Analytical and Applied Pyrolysis, 136: 8–17

[31] Wu X, Zhu F, Qi J, Zhao L, Yan F, Li C (2017). Challenge of biodiesel production from sewage sludge catalyzed by KOH, KOH/activated carbon, and KOH/CaO. Frontiers of Environmental Science & Engineering, 11(2): 3

[32] Yahya M A, Al-Qodah Z, Ngah C W Z (2015). Agricultural bio-waste materials as potential sustainable precursors used for activated carbon production: A review. Renewable & Sustainable Energy Reviews, 46: 218–235

[33] Yakout S M, Sharaf El-Deen G (2016). Characterization of activated carbon prepared by phosphoric acid activation of olive stones. Arabian Journal of Chemistry, 9: S1155–S1162

[34] Yang Z, Lei H, Zhang Y, Qian K, Villota E, Qian M, Yadavalli G, Sun H (2018). Production of renewable alkyl-phenols from catalytic pyrolysis of Douglas fir sawdust over biomass-derived activated carbons. Applied Energy, 220: 426–436

[35] Zhang H, Chen S, Zhang H, Fan X, Gao C, Yu H, Quan X (2019a). Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants. Frontiers of Environmental Science & Engineering, 2019, 13 (2): 18

[36] Zhang Y, Lei H, Yang Z, Duan D, Villotaa E, Ruan R (2018). From glucose-based carbohydrates to phenol-rich bio-oils integrated with syngas production via catalytic pyrolysis over an activated carbon catalyst. Green Chemistry, 20(14): 3346–3358

[37] Zhang Y, Zhu X, Zhang L, Zhu X (2019b). Preparation and characterization of microemulsion fuels from diesel and model compound of walnut shell pyrolysis oil. Fuel, 243: 478–484

[38] Zhang Z B, Lu Q, Ye X N, Li W T, Hu B, Dong C Q (2015). Production of phenolic-rich bio-oil from catalytic fast pyrolysis of biomass using magnetic solid base catalyst. Energy Conversion and Management, 106: 1309–1317

[39] Zou K, Deng Y, Chen J, Qian Y, Yang Y, Li Y, Chen G (2018). Hierarchically porous nitrogen-doped carbon derived from the activation of agriculture waste by potassium hydroxide and urea for high-performance supercapacitors. Journal of Power Sources, 378: 579–588

Acknowledgements

The authors thank the National Natural Science Foundation of China (Grant Nos. 51922040 and 51821004), Grants from Fok Ying Tung Education Foundation (No. 161051) and Fundamental Research Funds for the Central Universities (Nos. 2020DF01, 2019QN002, and 2018ZD08) for financial support.

RIGHTS & PERMISSIONS

2020 Higher Education Press