Solid catalysts are of great advantages in alkylation reaction due to heterogenous reaction which makes separation of catalysts very easy and environment friendly. Here, sulfated and borate zirconia catalysts are used to search for ortho-xylene with Toluene & methanol. To find a new path to get o-xylene, catalysts surface was studied and a new mesoporous borate zirconia catalyst was prepared. Mesoporous Borate Zirconia had showed a very efficient path to manufature o-xylene.

1. MODIFICATION & APPLICATION OF BORATE ZIRCONIA CATALYST Ranjeet Kumar 04CH6022 Under the guidance of Dr. Sonali Sengupta Department of Chemical engineering IIT Kharagpur

2. Contents…. Introduction Literature survey Experiments Mesoporous borate zirconia Characterization Conclusion References

3. Contents…. Introduction Literature survey Experiments Mesoporous borate zirconia Characterization Conclusion References

9. Contents…. Introduction Literature survey Experiments Mesoporous borate zirconia Characterization Conclusion References Introduction Literature survey

11. Contents…. Introduction Literature survey Experiments Mesoporous borate zirconia Characterization Conclusion References Introduction Literature survey

14. Two different systems of reactions were investigated in batch reactor :- 1) Phenol + MeOH – 2) Toluene + MeOH – Reaction temp was 250 °C % conversion of MeOH 5.577 2.205 14.186 BZ 4 hours Toluene + methanol BZ 8 hours Phenol + methanol BZ 4 hours Phenol + methanol Catalyst Reaction hr. Reactants

15. Maximum temp attainable in this reactor is 300°C Reactor set-up Fig.- 1, reactor and controller

16. Fig.-2, stirrer & vessel Reactor set-up… Capacity of the vessel is 260 ml

19. Contents…. Introduction Literature survey Experiments Mesoporous borate zirconia Characterization Conclusion References Introduction Literature survey

21. Contents…. Introduction Literature survey Experiments Mesoporous borate zirconia Characterization Conclusion References

23. Preparation of Mesoporous BZ In this case I = Zirconium Oxychloride + Water + Borax S = SLS / TTBr + Water Steps of preparation: - a) preparation of solution b) aging c) filtration d) washing e) calcinations/extraction More the hours of aging better is the catalyst

24. Trials for standardizing the preparation method Trial 1:- 86.70 1500 0.05 0.3 1 NA 1250 0.05 0.3 1 83.26 1000 0.05 0.3 1 NA 750 0.05 0.3 1 75.53 500 0.05 0.3 1 SA m 2 /g H 2 O B : SLS : Zr :

25. Trial 2 :- Since the range of surface area was not so wide so Zr : Sufactant : B : H 2 O :: 1 : 0.3 : 0.05 : 1000 was taken as base for further trials. 85.53 1500 0.05 0.2 1 NA 1250 0.05 0.2 1 NA 1000 0.05 0.2 1 43.80 750 0.05 0.2 1 37.00 500 0.05 0.2 1 SA m 2 /g H 2 O B : SLS : Zr :

27. Contents… Introduction Literature survey Experiments Mesoporous borate zirconia Characterization Conclusion References

29. XRD Fig.:- XRD pattern of MBZ shows a peak at 3 ° .

30. Reading from pore size analyzer 100 0.06069 100 0.06699 TOTAL 5.64 0.00342 6.85 0.00459 Above 80 24.45 0.01484 21.72 0.01455 20-80 6.98 0.00424 5.73 0.00384 16-20 6.06 0.00368 5.66 0.00379 12-16 4.51 0.00274 5.18 0.00347 10-12 5.24 0.00318 4.60 0.00308 8-10 9.21 0,00559 8.37 0.00561 6-8 37.91 0.02301 41.89 0.02806 Under 6 % Pore vol, ml/g % Pore vol, ml/g pore dia, nm A dsorption Desorption

31. Adsorption isotherm The adsorption isotherm is type IV IUPAC classification with hysteresis, which Indicate a mesoporous material.

32. Surface area & pore size distribution Apparatus used was – Coulter’s SA3100 for SA & pore size analysis. SMARTSORB-90 for SA M esoporous Microporous SA – 310 m 2 /g 85-115 m 2 /g Pore volume – 0.23 cm 3 /g 0.09-0.12 cm3/g >>> An excellent surface area (310 m2/g) was obtained by using separate solution of S ( Cetrimide ) & I, 72 hr aging, and extraction.

34. Flow reactor >>>>> preheater reactor condenser

37. [8] Yinyong Sun, Lina Yuan , Shengqian Ma, Yu Han, Lan Zhao, Wei Wang, Chang-Lin Chen, Feng-Shou Xiao(2004), Improved catalytic activity and stability of mesostructured sulfated zirconia by Al promoter , Applied Catalysis A: General, vol 268, p 17-24 [9] Cornelia Breitkopf , Arnd Garsuch, Helmut Papp (2005), “Structure– activity relationships for sulfated zirconias — comparison of mesoporous samples based on organic precursors”, Applied Catalysis. A: General, vol 296 , p 148-156. [10] Huiyuan Gao, Jerry Y. S. Lin, Baoquan Zhang (2005), “Electroless plating synthesis, characterization & permeation of Pd-Cu membranes supported on ZrO2 modified porous stainless steel”, Journal of Membrane Science , Vol 265, Issues 1-2, p 142-152 [11] Yinyong Sun, Lei Zhu, Huijuan Lu, Runwei Wang, Sen Lin, Dazheng Jiang, Feng-Shou Xiao (2002), “Sulfated zirconia supported in mesoporous materials”, Applied Catalysis. A: General, vol 237 p 21–31. [12] Daniela Terribile, Alessandro Trovarelli,*, Jordi Llorc, Carla de Leitenburg, Giuliano Dolcetti (1998) “The preparation of high surface area CeO2±ZrO2 mixed oxides by a surfactant- assisted approach”, Catalysis Today, vol 43, p 79-88. [13] G. Pacheco , E. Zhao , E. Diaz Valdes, A. Garcia, J.J. Fripia (1999), “Microporous zirconia from anionic and neutral surfactants”, Microporous and Mesoporous Materials, vol 32 p 175–188. [14] Debra J. McIntosh, Ronald A. Kydd(2000), “Tailoring the pore size of mesoporous sulfated Zirconia” Microporous and Mesoporous Materials , vol 37, p 281–289 References…..

38. Thanks