Modification & Application of Borate Zirconia Catalyst

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Information about Modification & Application of Borate Zirconia Catalyst
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Published on November 17, 2008

Author: ran_nwd

Source: slideshare.net

Description

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.

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

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

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

Overall catalyst market is around $10 bn. And revenue generated by processes using catalysts exceeds the catalyst market probably by factor between 100 and 1000, i.e. is somewhere between $1.000 and 10.000 billion Fig: 1. Catalyst market total around $10 bn and its division into different application Slight improvement in catalyst performance can lead to big saving in RM & energy.

Overall catalyst market is around $10 bn.

And revenue generated by processes using catalysts exceeds the

catalyst market probably by factor between 100 and 1000, i.e. is

somewhere between $1.000 and 10.000 billion

Importance of Alkylation Reactions Used in Pharmaceuticals, Agrochemicals, Resins, Additives, Polymerization inhibitors, Antioxidants Petroleum refining

Used in

Pharmaceuticals, Agrochemicals,

Resins, Additives,

Polymerization inhibitors, Antioxidants

Petroleum refining

Heavy environment pollution Troublesome product recovery & purification Catalysts cannot be reused Lower stability at higher temperature . Poor selectivity Use of expensive acid-resistant MOC Alkylation reaction with solid catalysts are becoming emerging field in catalysis Problems with Friedel-Craft alkylation---

Heavy environment pollution

Troublesome product recovery & purification

Catalysts cannot be reused

Lower stability at higher temperature .

Poor selectivity

Use of expensive acid-resistant MOC

Objective:- To search an environmental friendly process to produce ortho -alkylates with high selectivity >> OPTIONS ARE:- ZEOLITES CATION EXCHANGE REGINS unstable at higher temperature ZIRCONIA CATALYST its high acidity favors C-alkylation.

>> OPTIONS ARE:-

ZEOLITES

CATION EXCHANGE REGINS

unstable at higher temperature

ZIRCONIA CATALYST

its high acidity favors C-alkylation.

Borate zirconia B 2 O 3 /ZrO 2 catalyst (30mol% B) is reported as a superacid catalyst suitable for isomerization of butane & pentanes. AlCl 3 and borate zirconia had shown comparable performance for Friedel-Craft acylation & beckman rearrangement of cyclohexanone oxime. Comparable performance with heterogeneous catalysts like zeolite H-beta and sulphated zirconia.

B 2 O 3 /ZrO 2 catalyst (30mol% B) is reported as a superacid catalyst suitable for isomerization of butane & pentanes.

AlCl 3 and borate zirconia had shown comparable performance for Friedel-Craft acylation & beckman rearrangement of cyclohexanone oxime.

Comparable performance with heterogeneous catalysts like zeolite H-beta and sulphated zirconia.

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

Literatures on BZ No literature is available for preparation of ortho-xylene using heterogeneous catalysts Activity & selectivity of zirconia based catalysts are very sensitive to the method of preparation & heat treatments. Most of the studies have been carried out using large quantities of the catalyst, and the effect of parameters need to be addressed.

No literature is available for preparation of ortho-xylene using heterogeneous catalysts

Activity & selectivity of zirconia based catalysts are very sensitive to the method of preparation & heat treatments.

Most of the studies have been carried out using large quantities of the catalyst, and the effect of parameters need to be addressed.

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

ZrOCl 2 + H 2 O . . .. 8 ZrOCl 2 clear solution Addition of NH 3 8 Till pH = 10 Precipitate of Zr(OH) 4 Zirconium hydroxide was filtered Washed with hot water Zr(OH) 4 was then dried Immersed in boric acid solution Heated to dryness Calcined Preparation of BZ

Zirconium hydroxide was filtered

Washed with hot water

Zr(OH) 4 was then dried

Immersed in boric acid solution

Heated to dryness

Calcined

ZrOCl 2 + H 2 O . . .. 8 ZrOCl 2 clear solution Addition of NH 3 8 Till pH = 10 Precipitate of Zr(OH) 4 Zirconium hydroxide was filtered Washed with hot water Zr(OH) 4 was then dried Immersed in sulfuric acid solution filtered Dried Calcined Preparation of SZ

Zirconium hydroxide was filtered

Washed with hot water

Zr(OH) 4 was then dried

Immersed in sulfuric acid solution

filtered

Dried

Calcined

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

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

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

Alkylated product may increase by modifying reaction conditions. Max temp is main constraint, reacton time may be increased to get good result. Catalyst may be unsuitable for the desired reaction. Catalysts prepared above were microporous and may be unsuitable for large molecule like benzene or phenol. Microporous materials – pore size less than 2 nm (20 A ° ) Reasons for low conversion may be

Alkylated product may increase by modifying reaction conditions.

Max temp is main constraint, reacton time may be increased to get good result.

Catalyst may be unsuitable for the desired reaction.

Catalysts prepared above were microporous and may be unsuitable for large molecule like benzene or phenol.

Mesoporous catalyst with wider opening may be more suitable for alkylation of phenol & toluene. Forward path >>> Table - 2,IUPAC definition for materials on the basis of pore size macroporous >50 nm mesoporous >2 nm & < 50 nm microporous < 2 nm Type of material Pore size

Mesoporous catalyst with wider opening may be more suitable for alkylation of phenol & toluene.

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

Literatures on Mesoporous zirconia catalyst No literature is available on mesoporous borate zirconia. Mesoporous sulphated zirconia and other mesoporous catalysts are reported and are useful for alkylation reactions. [7], [8], [9], [11].

No literature is available on mesoporous borate zirconia.

Mesoporous sulphated zirconia and other mesoporous catalysts are reported and are useful for alkylation reactions. [7], [8], [9], [11].

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

Preparation of Mesoporous BZ Co-operative nucleation of molecular inorganic solution (I), with surfactant molecules (S). Two different surfactants were selected for searching/standardizing the preparation method --- 1) sodium lauryl sulfate (C 12 H 25 NaO 4 S) (SLS) 2) tetradecyltrimethylammonium bromide (C 17 H 38 BrN) (TTBr or Cetrimide) Acid percolation in mesoporous materials, neutral templating are other methods for mesoporous catalyst preparation

Co-operative nucleation of molecular inorganic solution (I), with surfactant molecules (S).

Two different surfactants were selected for searching/standardizing the preparation method ---

1) sodium lauryl sulfate (C 12 H 25 NaO 4 S) (SLS)

2) tetradecyltrimethylammonium bromide (C 17 H 38 BrN)

(TTBr or Cetrimide)

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

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 :

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 :

Trials were done by changing surfactant, instead of SLS, cetrimide was used. Instead of calcinations extraction of aged precipitate with ethanol plus sodium acetate solution was done. Aging hours were increased from 72 hours to 120 hours. Instead of making one solution of S & I, two separate solutions were prepared and mixed drop wise.

Trials were done by changing surfactant, instead of SLS, cetrimide was used.

Instead of calcinations extraction of aged precipitate with ethanol plus sodium acetate solution was done.

Aging hours were increased from 72 hours to 120 hours.

Instead of making one solution of S & I, two separate solutions were prepared and mixed drop wise.

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

Elemental analysis of prepared catalyst Energy Dispersive X-Ray Spectrometer (EDS) was done in CRF lab – >>Test confirmed the presence of Zr, O. It failed to detect the presence of B. >>> Presence of B was confirmed by Atomic Absorption Spectrometry

Energy Dispersive X-Ray Spectrometer (EDS) was done in CRF lab –

>>Test confirmed the presence of Zr, O.

It failed to detect the presence of B.

>>> Presence of B was confirmed by Atomic Absorption Spectrometry

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

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

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

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.

Reaction was carried out in a flow reactor at 450 °C over MBZ catalyst, reactants were toluene and methanol. Reaction mixture was analyzed in GC, retention time of product confirmed presence of o-xylene. Conversion of methanol was about 30%. Reaction with MBZ . >>>>

Reaction was carried out in a flow reactor at 450 °C over MBZ

catalyst, reactants were toluene and methanol.

Reaction mixture was analyzed in GC, retention time of

product confirmed presence of o-xylene.

Conversion of methanol was about 30%.

Flow reactor >>>>> preheater reactor condenser

conclusions Surface area of prepared catalyst is 310 m 2 /g, it is highest among mesoporous zirconia catalysts. Conversion of methanol is about 30% which may be increased by searching optimum reaction conditions. Large pores will allow the use of bulky oxidants in fine chemical preparation. Catalyst has shown its activity in alkylation reaction. It may open a path to produce many fine chemicals.

Surface area of prepared catalyst is 310 m 2 /g, it is highest among mesoporous zirconia catalysts.

Conversion of methanol is about 30% which may be increased by searching optimum reaction conditions.

Large pores will allow the use of bulky oxidants in fine chemical preparation.

Catalyst has shown its activity in alkylation reaction.

It may open a path to produce many fine chemicals.

[1] Sonali Sengupta, G. D. Yadav, Yogeeta B. Jadhav (2003), “Novelties of kinetics and mechanism of liquid–liquid phase transfer catalysed reduction of p-nitroanisole to p-anisidine”, Chemical Engineering Science , vol 58 , p 2681-1689. [2] Sonali Sengupta, G. D. Yadav, Yogeeta B. Jadhav, (2003), “Selectivity engineered phase transfer catalysis in the synthesis of fine chemicals: reactions of p-chloro- nitrobenzene with sodium sulphide”, Journal of molecular Catalysis A: Chemical , vol 200, p 117-129. [3] Kusum M. Malshe, Pratap T. Patil, Shubhangi B. Umbarkar, Mohan K. Dongare (2004), “Selective C-methylation of phenol with methanol over borate zirconia solid catalyst”, Journal of Molecular Catalysis A : Chemical, vol 212, p 337–344. [4] Ullman’s Encyclopedia of Industrial chemistry, vol. A 19, fifth ed.,(1989), p313. [5] S. Velu, C.S. Swamy, (1996), “Selective C-alkylation of phenol with methanol over catalysts derived from copper-aluminium hydrotalacite”, Applied Catalysis A : General, vol 145, p 141-154. [6] Takako Funamoto, Takamasa Nakagawa, Kohichi Segawa, (2005), “Isomerization of n-butane over sulfated zirconia catalyst under supercritical conditions”, Applied Catalysis A:General, vol 286, p 79-84. [7] Yin-Yan Huang, Timothy J. McCarthy, Wolfgang M.H. Sachtler(1996),”Preparation and catalytic testing of mesoporous sulfated zirconium dioxide with partially tetragonal wall structure” Applied Catalysis A:General, vol 148 (1996) p 135-154. References

[1] Sonali Sengupta, G. D. Yadav, Yogeeta B. Jadhav (2003), “Novelties of kinetics and mechanism of liquid–liquid phase transfer catalysed reduction of p-nitroanisole to p-anisidine”, Chemical Engineering Science , vol 58 , p 2681-1689.

[2] Sonali Sengupta, G. D. Yadav, Yogeeta B. Jadhav, (2003), “Selectivity engineered phase transfer catalysis in the synthesis of fine chemicals: reactions of p-chloro- nitrobenzene with sodium sulphide”, Journal of molecular Catalysis A: Chemical , vol 200, p 117-129.

[3] Kusum M. Malshe, Pratap T. Patil, Shubhangi B. Umbarkar, Mohan K. Dongare (2004), “Selective C-methylation of phenol with methanol over borate zirconia solid catalyst”, Journal of Molecular Catalysis A : Chemical, vol 212, p 337–344.

[4] Ullman’s Encyclopedia of Industrial chemistry, vol. A 19, fifth ed.,(1989), p313.

[5] S. Velu, C.S. Swamy, (1996), “Selective C-alkylation of phenol with methanol over catalysts derived from copper-aluminium hydrotalacite”, Applied Catalysis A : General, vol 145, p 141-154.

[6] Takako Funamoto, Takamasa Nakagawa, Kohichi Segawa, (2005), “Isomerization of n-butane over sulfated zirconia catalyst under supercritical conditions”, Applied Catalysis A:General, vol 286, p 79-84.

[7] Yin-Yan Huang, Timothy J. McCarthy, Wolfgang M.H. Sachtler(1996),”Preparation and catalytic testing of mesoporous sulfated zirconium dioxide with partially tetragonal wall structure” Applied Catalysis A:General, vol 148 (1996) p 135-154.

[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…..

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