ساخت و کاربردکاتالیست‌های امولسیونی پلی اگزوتنگستنی وانادیمی دووسونی برای گوگردزدایی اکسایشی

نوع مقاله: مقاله پژوهشی

نویسندگان

دانشکده مهندسی شیمی، نفت و گاز، دانشگاه علم و صنعت، تهران، ایران

چکیده

آلودگی‌های زیست محیطی ناشی از سوخت‌های فسیلی باعث گردید که وضع قوانین سختگیرانه را برای حذف ترکیبات گوگردی و دستیابی به روش‌های نوین برای برآورده ساختن این قوانین مدنظر قرار گیرد. در همین راستا برای اولین بار، کاتالیست‌های امولسیونی پلی اگزوتنگستنی وانادیمی دووسونی [TBA]6+xP2W18-xVxO62 ( X= 0، 1، 3 و 5) برای گوگرد زدایی اکسایشی ترکیبات گوگردی با موفقیت سنتز و با استفاده از روش آنالیز عنصری، FTIR، 31P MAS NMR و UV-vis DRS ساختارشناسی شد. این کاتالیست‌ها برای اکسایش ترکیبات گوگردی، بنزوتیوفن و دی بنزوتیوفن با استفاده از هیدروژن پراکسید تحت شرایط متعادل (دمای کمتر از 100 oC و فشار اتمسفریک) مورد استفاده قرار گرفت. فعالیت کاتالیست با افزایش مقدار وانادیم در ساختار هتروپلی آنیون افزایش یافت. واکنش پذیری اکسایشی ترکیب گوگرد دی بنزوتیوفن بیشتر از بنزوتیوفن بوده است. کاتالیست امولسیونی با بالاترین مقدار وانادیم، [TBA]11P2W13V5O62، قادر است 85 % دی بنزوتیوفن و 50 % بنزوتیوفن را در مدت 75 دقیقه و دمای 60 oC با استفاده از هیدروژن پراکسید 30 % حجمی با نسبت مولی اکسیژن به گوگرد 4 اکسید نماید.

کلیدواژه‌ها

موضوعات


عنوان مقاله [English]

Synthesis and Application of Dawson-Type Vanadium Polyoxotungstate Emulsion Catalyst for Oxidative Desulfurization

نویسندگان [English]

  • Farhad Banisharif
  • Mohammad Reza Dehghani
Chemical Engineering Department, Iran University of Science and Technology, Tehran, Iran
چکیده [English]

Environmental pollutions originated from fossil fuel cause to consider the development of rigorous rules to remove sulfur containing compounds and achievement of novel process to follow the mentioned of rigorous rules. In this regard and for the first time, new Dawson-type vanadium polyoxotungstate emulsion catalysts, [TBA]6+xP2W18-xVxO62 (x= 0, 1, 3, 5) have been synthesized successfully for oxidative desulfurization of sulfur compounds and characterized by using element analysis, FTIR, 31P MAS NMR and UV-vis DRS. These catalysts were used to oxidize sulfur-containing components, dibenzothiophene and benzothiophene by using hydrogen peroxide under mild conditions ( temperature lower than 100 oC and atmospheric pressure). The activity of catalysts has been grow by increase in number of vanadium in the structure of heteropoly anion. The reactivity of sulfur compound, dibenzothiophene was much more than benzothiophene. The emulsion catalyst with the highest number of vanadium, [TBA]11P2W13V5O62, could oxidize 85 % of dibenzothiophene and 50 % benzothiophene after 75 minutes, under temperature 60 oC and by using hydrogen peroxide 30 v-% in oxygen to sulfur mole ratio 4.

کلیدواژه‌ها [English]

  • Catalytic-Oxidative Desulfurization
  • Dawson-type Polyoxometalate
  • Emulsion Catalyst
  • Vanadium

[1]. Mohrammed M. I., Abdul Razak A. A., Shrehrab M. A., “Synthresis of nanocatalyst for hrydrodesulfurization of gasoil using laboratory hrydrothrermal rig,” Arab. J. Sci. Eng., Vol. 42, No. 4, pp. 1381-1387, 2017. ##

[2]. Zhrang J., HRe K., Ge Y. Shri X., “Influence of fuel sulfur on thre chraracterization of PM 10 from a diesel engine,” Fuel, Vol. 88, No. 3, pp.504-510, 2009.##

[3]. Perathroner S., Gross S., HRensen E. J., Wessel H. R., Chrraye H. R. and Centi, G., “Looking at thre future of chremical production thrroughr thre european roadmap on science and techrnology of catalysis the EU effort for a longterm vision,” ChremCatChrem., Vol. 9, No. 6, pp. 904-909, 2017.##

[4]. Capel-Sanchrez M. C. and Campos-Martin J. M., Fierro J. L. G., “Removal of Refractory Organosulfur Compounds via Oxidation withr HRydrogen Peroxide on Amorphrous Ti/SiO2 Catalysts,” Energy Environ. Sci., Vol. 3, pp. 328-333, 2010. ##

[5]. Campos Martin J. M., Capel Sanchrez M. C., Perez Presas P. and Fierro J. L. G., “Oxidative Processes of Desulfurization of Liquid Fuels,” J. Chrem. Techrnol. Biotechrnol., Vol. 85, pp. 879-890, 2010.##

[6]. Jin C., Gang L., Wang X., Wang Y., Zhrao L. and Sun D., “A titanium containing micro/mesoporous composite and its catalytic performance in oxidative desulfurization,” Micropor. Mesopor. Mat., Vol. 111, No. 1, pp. 236-242, 2008. ##

[7]. Chrica A., Corma A. and Dómine M. E., “Catalytic oxidative desulfurization (ODS) of diesel fuel on a continuous fixed-bed reactor,” J. Catal., Vol. 242, No. 2, pp.299-308, 2006.##

[8]. Sengupta A., Kamble P. D., Basu J. K. and Sengupta S., “Kinetic study and optimization of oxidative desulfurization of benzothriophrene using mesoporous titanium silicate-1 catalyst.” Ind. Eng. Chrem. Res., Vol. 51, No. 1, pp.147-157, 2011. ##

[9]. Sampanthrar J. T., Xiao H. R., Dou J., Nahr T. Y., Rong X. and Kwan W. P., “A novel oxidative desulfurization process to remove refractory sulfur compounds from diesel fuel,” App. Catal. B: Environ., Vol. 63, No. 1, pp. 85-93, 2006.##

[10]. Tang L., Luo G., Kang L., Zhru M. and Dai B., “A novel [Bmim]PW/HRMS catalyst with high catalytic performance for the oxidative desulfurization process,” Korean J. Chem. Eng., Vol. 30, No. 2, pp. 314-320, 2013.##

[11]. HRaber J., Pamin K., Matachrowski L. and Muchra D., “Catalytic performance of the dodecatungstophrosphroric acid on different supports,” Appl. Catal. A Gen., Vol. 256, pp. 141-152, 2003. ##

[12]. Shrojaei A. F., Rezvani M. A. and Loghrmani M. H. R., “Comparative study on oxidation desulphrurization of actual gas oil and model sulfur compounds withr hrydrogen peroxide promoted by formic acid: Synthresis and chraracterization of vanadium containing polyoxometalate supported on anatase crushed nanoleaf,” Fuel Process. Techrnol., Vol. 118, pp. 1-6, 2014.##

[13]. HRuang W., Zhru W., Li H. R., Shri H. R., Zhru G., Liu H. R. and Chren G., “HReteropolyanion-based ionic liquid for deep desulfurization of fuels in ionic liquids,” Ind. Eng. Chrem. Res, Vol.49, pp. 8998-9003, 2010. ##

[14]. Lü H. R. Y., Gao J. B., Jiang Z. X., Jing F., Yang Y. X., Wang G. and Li C., “Ultra-deep desulfurization of diesel by selective oxidation with [C18HR37N(CHR3)3]4[HR2NaPW10O36] catalyst assembled in emulsion droplets,” J. Catal., Vol. 239, pp. 369-375, 2006.##

[15]. Li C., Jiang Z. X., Gao J. B., Yang Y. X., Wang S. J., Tian F. P., Sun F. X., Sun X. P., Ying P. L. and HRan C. R., “Ultra-deep desulfurization of diesel: oxidation with a recoverable catalyst assembled in emulsion,” Chem. Eur. J., Vol. 10, No. 9, pp. 2277-2280, 2004.##

[16]. Zhrang Y. N., Lü H. R. Y., Wang L., Zhrang Y. L., Liu P., H. Ran H. R. X., Jiang Z. X. and Li C., “The oxidation of benzothriophrene using the Keggin-type lacunary polytungstophrosphrate as catalysts in emulsion,” J. Mol. Catal. A., Vol. 332, No. 1-2, pp. 59-64, 2010. ##

[17]. Trakarnpruk W. and Rujiraworawut K., “Oxidative desulfurization of gas oil by polyoxometalates catalysts,” Fuel Process. Technol., Vol. 90, No. 3, pp. 411-414, 2009. ##

[18]. Smithr E. L., Abbott A. P. and Ryder K. S., “Deep eutectic solvents (DESs) and threir applications,” Chrem. Rev., Vol. 114, pp. 11060-11082, 2014. ##

[19]. García Gutiérrez J. L., Laredo G. C., García Gutiérrez P. and Jiménez Cruz F., “Oxidative desulfurization of diesel using promising hreterogeneous tungsten catalysts and hrydrogen peroxide,” Fuel Vol. 138, pp. 118-125, 2014.##

[20]. Zou C., Zhrao P., Gea J., Qin Y. and Luo P., “Oxidation/adsorption desulfurization of natural gas by bridged cyclodextrins dimer encapsulating polyoxometalate,” Fuel, Vol. 104, pp. 635-640, 2013.##

[21]. Oble J., Riflade B., Noël A., Malacria M., Throrimbert S., HRasenknopf B. and Lacôte E., “Carbonyl-inserted organo-hrybrids of a dawson-type phrosphrovanadotungstate: Scope and chremoselective oxidation catalysis,” Org. Lett. Vol.13, No. 22, pp. 5990-5993, 2011. ##

[22]. Miao W. K., Yan Y. K., Wang X. L., Xiao Y., Ren L. J., Zhreng P., Wang C. H. R., Ren L. X. and Wang W., “Incorporation of polyoxometalates into polymers to create linear poly (polyoxometalate) s with catalytic function,” ACS Macro Lett. Vol. 3, No.2, pp. 211-215, 2014. ##

bimetallic inorganic-porphryrin analog KLi15[O{RuIVCl(.alphra.2-P2W17O61)}2].2KCl.60HR2O.” Inog. Chem., Vol. 32, No. 7, pp.1068-1071, 1993. ##

[24]. Ueda T., Yamashrita K. and Onda A., “New extraction procedure for protonated polyoxometalates prepared in aqueous-organic solution and chraracterisation of their catalytic ability,” Appl. Catal. A Gen., Vol. 485, pp. 181-187, 2014. ##

[25]. Tong X., Zhru W., Wu Q., Qian X., Liu Z., Yan W., Gong, J., “Synthresis and conductivity of hreptadecatungstovanadodiphrosphroric hreteropoly acid with Dawson structure,” J. Alloy. Compd., Vol. 509, No. 29, pp. 7768-7772, 2011. ##

[26]. Uchrida S., Kawamoto R., Akatsuka T., HRikichri S., Mizuno N., “Structures and sorption properties of ionic crystals of macrocation-Dawson-type polyoxometalates withr different chrarges,” Chem. Mater., Vol. 17, No. 6, pp. 1367-1375, 2005.##

[27]. Contant R., Abbessi M., Throuvenot R., HRervé G., “Dawson type hreteropolyanions. 3. synthreses and 31P, 51V, and 183W NMR structural investigation of octadeca (molybdo- tungsto- vanado) diphrosphrates related to thre [HR2P2W12O48] 12-anion,” Inog. Chem., Vol. 43, No. 12, pp. 3597-3604, 2004. ##

[28]. Zhrao D., Wang J., Zhrou E., “Oxidative desulfurization of diesel fuel using a Brønsted acid room temperature ionic liquid in the presence of HR2O2.” Green Chemistry, Vol. 9, No.11, pp.1219-1222, 2007. ##

[29]. Wang D., Qian E.W., Amano HR., Okata K., Ishrihrara A., Kabe T., “Oxidative desulfurization of fuel oil: Part I. Oxidation of dibenzothriophrenes using tert-butyl hrydroperoxide.” App. Catal. A: Gen., Vol. 253, No. 1, pp.91-99, 2003. ##

[30]. Jin A. H R., Li B. S. Dai Z. J., “Oxidative desulfurization of fuel oil with hrydrogen peroxide catalyzed by Keggin-type polyoxotungstate in a DC magnetic field.” Petrol. Sci. Technol., Vol. 28, No. 7, pp.700-711, 2010. ##

[31]. Ribeiro S. O., Julião D., Cunhra-Silva L., Domingues V. F., Valença R., Ribeiro J. C., de Castro B., Balula, S.S., “Catalytic oxidative/extractive desulfurization of model and untreated diesel using hrybrid based zinc-substituted polyoxometalates.” Fuel, Vol. 166, pp.268-275, 2016. ##

[32]. Chren J., Chren C., Zhrang R., Guo L., HRua L., Chren A., Xiu Y., Liu X. HRou, Z., “Deep oxidative desulfurization catalyzed by an ionic liquid-type peroxotungsten catalyst.” RSC Adv., Vol. 5, No. 33, pp.25904-25910, 2015.##