تبدیل متانول به آروماتیک های سبک با استفاده از نانوزئولیت HZSM5 : اثرات شرایط عملیاتی

نوع مقاله : مقاله پژوهشی

نویسندگان
1 کارشناسی ارشد، گروه مهندسی شیمی، دانشکده مهندسی، دانشگاه کردستان، سنندج، ایران
2 دانشیار، گروه مهندسی شیمی، دانشکده مهندسی، دانشگاه کردستان، سنندج، ایران
20.1001.1/ijge.2026.2084516.1117
چکیده
این مطالعه درباره استفاده از نانوزئولیت HZSM5 از شرکت زئوکیم برای تولید آروماتیک‌های سبک از متانول است. اثر مقدار نسبت Si/Al بررسی شد و کاتالیست HZSM5 با نسبت Si/Al برابر با 50 انتخاب شد. کاتالیست‌های HZSM5 به‌وسیله روش‌های تخلخل سنجی و تعیین مساحت سطح ویژه، پراش پرتو ایکس و دفع برنامه‌ریزی شده با دمای NH3 تعیین مشخصات شدند. روش طرح مرکب مرکزی برای بررسی اثرات شرایط عملیاتی شامل دمای کوره، مقدار کاتالیست، سرعت جریان‌های متانول و نیتروژن بر روی مقدار متانول باقیمانده در محصول و تولید BTX به‌کاربرده شدند. مقادیر F برای مدل‌های متانول در محصول و تولید BTX به ترتیب برابر با 21/1233 و 77/14971 بودند. مقادیر p برای هر دو مدل کوچک‌تر از 0001/0 بودند. نتایج تجزیه و تحلیل‌های آماری نشان دادند که سرعت جریان نیتروژن تأثیرگذارترین عامل بر تبدیل متانول و تولید BTX است. علاوه بر این‌ها، جملات برهم‌کنش بین عوامل تأثیرات اساسی بر تبدیل متانول و تولید BTX داشتند. شرایط عملیاتی برای حداکثر کردن مصرف متانول و تولید BTX بهینه شدند. عملکرد راکتور در شرایط عملیاتی بهینه؛ موجب حداکثر شدن بازده تولید BTX و متعاقباً فرآیند اقتصادی‌تر می‌شود.
کلیدواژه‌ها
موضوعات

عنوان مقاله English

Methanol Conversion to Light Aromatics Using HZSM5 Nano Zeolite: Effects of Operating Conditions

نویسندگان English

Meysam Mostafaei 1
Faranak Akhlaghiantab 2
1 M.Sc., Position, Department of Chemical Engineering, Faculty of Engineering, University of Kurdistan, Sanandaj, Iran
2 Associate Professor, Department of Chemical Engineering, Faculty of Engineering, University of Kurdistan, Sanandaj, Iran
چکیده English

This study employed HZSM5 nano zeolite from Zeochem to produce light aromatics from methanol. The influence of the Si content of the HZSM5 catalysts was investigated, and the HZSM5 catalyst with a Si/Al ratio of 50 was selected. The HZSM5 catalysts were characterized using porosimetry and determination of specific surface area, X-ray diffraction, and NH3 temperature-programmed desorption techniques. The central composite design method was employed to investigate the effects of the operating conditions, including furnace temperature, catalyst dosage, methanol, and nitrogen flow rates, on the methanol in the product and BTX production. The F-values were 1233.21 and 14971.77 for methanol in product and BTX production model; respectively. The p-values were less than 0.0001 for both models. Statistical analysis revealed that the nitrogen flow rate was the most significant factor affecting methanol in the product and BTX production. Furthermore, the interaction between these factors exerted a more substantial influence on methanol in the product and BTX production. The performance of the reactor in the optimized operating conditions causes maximum BTX yield and consequently more economic process.

کلیدواژه‌ها English

Light Aromatics
Methanol to Aromatics
HZSM5 Nano Zeolite
Response Surface Method
Si/Al Ratio
Operating Conditions
[1] Xi Z, Zhou B, Jiang B, Wang J, Liao Z, Huang Z, Yang Y. Efficient conversion of methane to aromatics in the presence of methanol at low temperature. J Mol Catal 2019;475:110493.
[2] Liu Y, Kooli F, Borgna A. Tandem dual bed Mo/HZSM-5 and Mo/HMCM-22 catalysts with enhanced catalytic performance for natural gas conversion to aromatics. Catal. Today, 2020;357:392-398.
[3] Schwach, P., Pan, X., & Bao, X. (2017). Direct conversion of methane to value-added chemicals over
heterogeneous catalysts: challenges and prospects. Chemical Reviews, 2017;117:8497-8520.
[4] http://profsite.um.ac.ir/~fanaei/_private/Methanol%20production.pdf, Available in 22 May (2024).
[5] Yaripour F, Shariatinia Z, Sahebdelfar S, Irandoukht A. Conventional hydrothermal synthesis of nanostructured H-ZSM-5 catalysts using various templates for light olefins production from methanol. J Nat Gas Sci Eng 2015;22:260-269.
[6] Zahara Z, Krisnandi Y K, Wibowo YW, Nurani D A, Rahayu DUC, Haerudin H. Synthesis and characterization of hierarchical ZSM-5 zeolite using various templates as cracking catalysts. AIP Con 2023;020088:1-6.
[7] Cheng C, Li G, Ji D, Zhao Y, Shen J. Regulating hierarchical structure and acidity of HZSM-5 for methanol to aromatics via protective desiliconization and external surface modification. Microporous Mesoporous Mater 2021;312:110784.
[8] Pérez-Ramírez J, Christensen, CH, Egeblad K, Christensen C, Green J. Hierarchical zeolites: enhanced utilization of microporous crystals in catalysis by advances in material design. Chem Soc Rev 2008;37:2530-2542.
[9] Tian P, Wei Y, Ye M, Liu Z. Methanol to olefins (MTO): from fundamentals to commercialization. ACS Catal 2015;5:1929-1938.
[10] Vicente H, Liu C, Gayubo AG, Castano P, Pidko EA. Improving the dehydrogenation function and stability of 20-modified ZSM-5 catalyst in methanol-to-aromatics reaction by Ca addition. Appl Catal A: Gen 2024;683:119854.
[11] Liu C, Uslamin EA, Khramenkova E, Sireci E, Ouwehand LTLJ, Ganapathy S, Kapteijn F, Pidko EA. High stability of methanol to aromatic conversion over bimetallic Ca, Ga-modified ZSM 5. ACS Catal 2022;12:3189-3200.
[12] Freeman D, Wells RPK, Hutchings, JG. Conversions of methanol to hydrocarbons over Ga2O3/HZSM5 and Ga2O3/WO3 catalysts. J Catal 2020;205:358-365.
[13] Wang C, Si Z, Wu X, Lv W, Bi K, Zhang X, Chen L, Xu Y, Zhang Q, Ma L. Mechanism study of aromatics production from furans with methanol over zeolite catalysts. J Anal Appl Pyrolysis 2019;139:87-95.
[14] Li H, Li XG, Xiao WD. Deactivation kinetics of individual C6–C9 aromatics' generation from methanol over Zn and P co-modified HZSM-5. RSC Adv 2019;9:22327-22355.
[15] Chotiwan S, Somwongsa P, Lao-Ubol S, Lao-Auyporn P, Attanatho L, Laosombut T, Larpkiattaworn S. Improvement of HZSM-5 catalytic performance by rice husk ash addition for methanol to hydrocarbons. Mater Today 2019;17:1354-1361.
[16] Shao J, Fu, T., & Li, Z. (2020). The selective and stable synthesis of aromatics from methanol via two-step route using light alkenes as intermediates, Fuel, 2020;280:118609.
[17] Wang Y, Zhao W-H, Yan X, Wang Q, Liang J, Zhao Y-P, Cao J, Zhu L. The application of Ni and Zr modified ZSM-5 nanosheet in upgrading of lignite pyrolysis volatiles coupling with methanol to light aromatics. J Anal Appl Pyrolysis 2024;180:106543.
[18] Wang Z, Zheng H, Meng F, Fu T, Li, Z. ZSM-5@Zn/ZSM-5 core@shell nanocrystals as integrated catalysts for efficient methanol conversion into aromatics. Fuel 2024;369:131728.
[19] Wang M, Liu N, Wu H, Dong Z, Wang J. Co-aromatization of methane and methanol over MoxZn/HZSM-5 to increase aromatic hydrocarbon yield: experimental and kinetic studies. J Mol Catal 2024;565:114366.
[20] Xu Q, Liang J, Chen Z, Guo J, Xia S, Zhao, Z, Zhu X, Zhao K, Cai P, Zheng A. Hierarchical zeolites promoting synergistic co-pyrolysis of biofuran and methanol for enhanced aromatic production. Ind Crops Prod 2025;236:121600.
[21] Wang Y, Gao H, Zhao W, Yan X, Liang J, Zhao Y, Cao J, Zhu, L. Catalytic upgrading of lignite pyrolysis volatiles to light aromatics under methanol atmosphere over Zr and/or Fe modified hollow ZSM-5 zeolites. Microporous Mesoporous Mater 2025;381: 113362.
[22] Guo Y, Wang R, Zhang L, Fu T, Li Z. Constructing hollow bivalve nanocomposite ZSM-5 with inverse Al zoned distribution to strengthen the stepwise conversion of methanol to aromatics. Appl Catal A: Gen 2025;689:120008.
 [23] Xue Y, Hao X, Li J, Mei Y, Zheng H, Cui X, Niu Y. Facile synthesis of hierarchical Zn@ZSM-5 zeolite with boosted aromatics selectivity for methanol to aromatics. Microporous Mesoporous Mater 2026;412:114250.
[24] Abbasi A, Pourabdollah K, Mokhtarani B. Tailoring hierarchical ZSM-5 with water-soluble polymers templates for BTX production in methanol-to-aromatics. RSC Adv 2026;16:7040-7056.
[25] Geng R, Niu X, Liu Y. Effect of extra-framework Ga2O3 species in Ga/ZSM-5 catalysts on methanol-to-aromatics reaction. Microporous Mesoporous Mater 2026;400:113907.
[26] Montgomery DC. Design and Analysis of Experiments. 5th ed., New York: John Wiley & Sons; 2001.
[27] Zhang GQ, Bai T, Chen TF, Fan WT, Zhang X. Conversion of methanol to light aromatics on Zn-modified nano-HZSM 5 zeolite catalysts. Ind Eng Chem Res 2014;53:14932-14940.
[28] Ayodele BV, Hossain SS, Lam SS, Osazuwa OU, Khan MR, Cheng CK. (2016). Syngas production from CO2 reforming of methane over neodymium sesquioxide supported cobalt catalyst. J Nat Gas Sci Eng 2016;34:873-885.
[29] Kim HS, Kang SK, Zhang H, Tikue ET, Lee JH, Lee PS. Al-ZSM-5 nanocrystal catalysts grown from silicalite-1 seeds for methane conversion. Energies, 2021;14:480.
[30] Shirazi L, Jamshidi E, Ghasemi MR. The effect of Si/Al ratio of ZSM-5 zeolite on its morphology, acidity and crystal size. Cryst Res Technol 2008;43:1300-1306.
[31] Kim J, Choi M, Ryoo R. Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process. J Catal 2010;269:219-228.
[32] Al-Dughaither AS, de Lasa H. HZSM 5 zeolites with different SiO2/Al2O3 ratios. characterization and NH3 desorption kinetics. Ind Eng Chem Res 2014;53:15303-15316.
[33] Leofanti G, Padovan M, Tozzola G, Venturelli B. Surface area and pore texture of catalysts. Catal Today 1998;41:207-219.
[34] Gao Y, Zheng B, Wu G, Ma F, Liu C. Effect of the Si/Al ratio on the performance of hierarchical ZSM-5 zeolites for methanol aromatization. RSC Adv 2016;6:83581-83588.
[35] Liu J, Shen X, Lin L, Lu J, Zhou Y. Impact of the Al sites of ZSM-5 zeolite on product distribution in methanol to aromatics reaction. J Porous Mater 2025;32:1135-1147.
[36] Wang Y, An H, Ma H, Zhang X, Kang G, Cao J. Catalytic properties and deactivation behavior of modified H-ZSM-5 in the conversion of methanol-to-aromatics. Adv Powder Technol 2021;32:1869-1880.
[37] Li B-x, Wang W-c, Zhang X-p, Zhang D-x, Mu W, Liu F. Integrating uniform design and response surface methodology to optimize thiacloprid suspension. Sci Rep 2018;7:46018.
[38] Zaib Q, Park HS, Kyung D. Experimental modeling and optimization for the reduction of hexavalent chromium in aqueous solutions using ascorbic acid. Sci Rep 2021;11:13146.
[39] Echevskii CV, Ione KG, Nosyreva GN, Litvak GS. Effect of temperature regime on coking of zeolite catalyst and their regeneration. Appl Catal 1998;43:85-89.
 [40] Li T, Shoinkhorova T, Gascon J, Ruiz-Martínez J. Aromatics production via methanol-mediated transformation routes. ACS Catal 2021;11:7780-7819.
[41] García‑Ruiz M, Solís‑Casados DA, Aguilar‑Pliego J, Márquez‑Álvarez C, Sastre‑de Andrés E, Sanjurjo‑Tartalo D, Sáinz‑Vaque R, Grande‑Casas M. Synthesis of 10 and 12 ring zeolites (MCM‑22, TNU‑9 and MCM‑68) modified with Zn and its potential application in the reaction of methanol to light aromatics and olefins. Top Catal 2020;63:451-467.
[42] Chen Z, Song W, Hou Y, Wang H, Zhang C, Wang J, Yang Y, Qian W. Temperature-dependent secondary conversion of primary products from methanol aromatization in a two-stage fluidized bed. Fuel, 2020;267:117204.
[43] Karpe S, Veser G. Coke formation and regeneration during Fe-ZSM-5-catalyzed methane dehydro-aromatization. Catal 2024;14:292.
[44] Wan Z, Li GK, Wang C, Yang H, Zhang D. (2018). Relating coke formation and characteristics to deactivation of ZSM-5 zeolite in methanol to gasoline conversion. Appl Catal A: Gen 2018;549: 141-151.
[45] Qiao J, Wang J, Frenkel AI, Teng J, Chen X, Xiao J, Zhang T, Wang Z, Yuan Z, Yang W. Methanol to aromatics: isolated zinc phosphate groups on HZSM-5 zeolite enhance BTX selectivity and catalytic stability. RSC Adv 2020;10:5961-5971.
[46] Saber A, Jabbarpoor M, Safari N, Bahadoran F. Aromatic product selectivity of template-free and template-synthesized ZSM-5 catalysts in methanol to hydrocarbon conversion. Nanochem Res 2022;7:93-106.
[47] Fu T, Han Y, Li C, Guo M, Zhan G, Li Z. Self-assembly of hierarchical ZSM-5 particles on rice husk template as hybrid catalysts for boosting methanol aromatization. Chem Eng Sci 2024;284:119457.

  • تاریخ دریافت 14 بهمن 1404
  • تاریخ بازنگری 28 خرداد 1405
  • تاریخ پذیرش 30 خرداد 1405