1

Desilication: Novel Technique to Enhance Catalytic Activity

2 Abstract Catalytic activities as well as hierarchal properties of various species of zeolites used commercially were investigated after alkali treating at various treatment conditions and compared with parent. In some cases vide array of parameters like alkali concentrations, temperature of bath, time of bath as well as Si/Al ratios were used to study dominating parameter. These results were linked with original species to find out better. Various cases were studied and finally it was inferred that Alkali treatment resulted to selective removal of silica from catalyst framework which generated mesopores, conserving the acidity of catalysts. The generation of mesopores created scope in reaction kinetics, iomerizations, cracking, diffusivity and in overcoming restricted access of discriminated species.

1. Introduction to Zeolites and their Properties

Zeolites can be referred chemically as alumino-silicates with well organized spatial arrangement of ions. Cronstedt was the person who discovered in 1756 the first naturally
occurring mineral stilbite that lost a substantial amount of steam upon heating. Accordingly, he named the material zeolite after the Greek zeo (to boil) and lithos (stone). In 1948 the first synthetic zeolite was successfully prepared by Richard Barrer [1]. Approximately there exist over 40 natural and 100 synthetic zeolites, whereas many of the synthetic zeolites do not have natural counterparts.

Compositionally, zeolites are similar to clay minerals. More specifically, both are alumino-silicates. They differ, however, in their crystalline structure. Many clays have a layered crystalline structure (similar to a deck of cards) and are subject to shrinking and swelling as water is absorbed and removed between the layers. In contrast, zeolites have a rigid, 3-dimensional crystalline structure (similar to a honeycomb) consisting of a network of interconnected tunnels and cages. Water moves freely in and out of these pores but the zeolite framework remains rigid. Another special aspect of this structure is that the pore and channel sizes are nearly uniform, allowing the crystal to act as a molecular sieve [2]. Some properties of zeolites can be studied as follows. 1.1. Ion Exchange Ingredients of zeolite include cations (e.g., Na+, K+, or NH4+) after the synthesis. These cations are required to balance the negative netcharge caused by trivalent aluminum cations which are coordinated tetrahedrally by oxygen anions. By exposing a sodium containing zeolite to a solution containing other cations, the sodium ions can be Na + K + NH4 + exchanged by these other cations provided they areFig 1. A typical Zeolitic Structure, with Si-O-Si bond.
Si Al

4 not excluded from the pores due to their size (including the water molecules coordinating the respective cations). 1.2. Molecular Sieve Effect The pore sizes of zeolites are determined by their structures and may be varied slightly by ion-exchanging the zeolite. By this process smaller cations can be positioned in windows making them wider. Specific cations may also be positioned on other sites than in the windows, thus leading to even larger open windows. The window sizes determine the accessibility of the zeolite pore system for other (e.g. organic) molecules.

Window Opening

Species larger than window opening dimensions are discriminated using sieving effect.

Fig 2. Zeolite Window size Figure Courtesy: http://www.co2crc.com.au/images/imagelibrary/cap_diag/zeolites._adsorption_media.jpg

1.3. Acidity As already mentioned, protonated zeolites have acidic properties. The protons which balance the negative charge of a zeolite framework are not strongly bound to the framework and are able to move within the pores and react with molecules which penetrate into the zeolite pore system. A protonated zeolite thus can act as a Bronsted acid. Furthermore, Lewis acidity can be caused by cations within the pores. Bronsted Acidity

5 Al OH Si Terminal Silanol group Lewis Acidity AlO+ , Al(OH)3 x H2O Metal Cations [3] Significance of zeolites is held in their appreciable morphological characteristics. Some of the promising properties of zeolites includes : High surface area Uniform micropore size High Hydro thermal stability Intrinsic acidity Ability to accommodate active metal species Introducing constraints to undesired species by molecular sieving effect ( Shape Selectivity) [4] Environmentally harmless Non-corrosive Show ease of separation from reaction mixture compared with homogeneous catalysts [5] Due to such properties zeolites have increased attention in commercial application for several Petrochemical and Industrial processes. But theses benefits associated with zeolites are accompanied with some drawbacks like intraparticular diffusional constraints, geometrical constraints, coking or carbon deposits etc. To overcome these drawbacks or even to alter post synthesis properties some modifications are done, of which includes desilication, dealumination and carbon templating. Theses three strategies are widely used to improve transport properties of zeolites to overcome mentioned constraints. A comprehensive description of former method will be followed after briefing of all three methods. Carbon templating: A hydrothermal zeolite synthesis is carried out in the presence of an additional carbon source, e.g. carbon black or carbon nanofibers [6]. Extra voids are formed due to combustion, after it is calcined in presence of this extra source of carbon

Dealumination: It is selective removal of aluminium from the zeolite framework, which is an established post-synthesis treatment to stabilize zeolites [7]. Dealumination can be done by acid treating or steam treating the zeolite. Dealumination is mainly employed to improve mesoporosity in matrix, to improve acidity and to stabilize the catalyst. Desilication: It is selective removal of framework silica from zeolite matrix. Usually most of the zeolite frameworks contain a higher concentration of silicon than aluminium and accordingly formation of extra pores can be conveniently achieved. It is known that treatment in alkaline and even acidic medium can be used to dissolve amorphous silica [8]. Many references proved with compared to dealumination, silica removal is affordable if acidic properties are not to be changed. With the help of these references we are able to conclude that desilication is opted when mesoporosity is to be altered but not at the cost of significant acidity changes, while dealumination is opted when acidity is to be altered [9].

2. Desilication Methodology
In precise, desilication is achieved by treating the parent zeolite in bath of basic chemicals (mainly alkali) with different concentrations. A generalized method can be described as follows. Alkali solution is prepared in water either at room temperatures or at elevated ones, well stirring ensures uniform distribution of alkali over solution. Then, catalyst is introduced in this solution and stirred for several hours. This catalyst-alkali solution is cooled, filtered, washed neutralized and dried over long duration (generally overnight) at ambient or elevated temperatures. Then finally daughter catalyst is exchanged with ammonium nitrate if desired [4] [9] [10] [11]. So we can thus conclude that governing parameters which decides amount of silica to be extracted are alkali concentration, temperature of bath and time in bath. Severity in conditions will lead to more difference in properties.

3. Characterization
Various characterizations includes following parameters crystallinity, morphology, Si/Al or SAR, porosity, diffusion, acidity, microporous and mesoporous surface area per weight of catalyst, microporous and mesoporous volume respectively. Following table will help us to select method for particular characterization. Characterizations can be summarized. 3.1 Hierarchal Properties Hierarchal properties mainly include morphology of the zeolitic framework and its crystallinity. Study of these properties of zeolites reveals crystal structure of geometry of zeolite and crystallinity gives us information on stability of framework. Crystallinity can be studied on X-Ray Diffraction Patterns by comparing Intensity of peaks w.r.t. 2 . Morphological studies are done with the help of Scanning Electron Microscopic (SEM) or Transmission Electron Microscope (TEM). 3.2 Si/Al or SAR Silicon to Aluminum Ratio is a very important parameter to be characterized in desilication. This ratio gives amount of Silicon per Aluminum. This ratio helps us to decide extent of desilication. Various methods are employed for its characterization such as X-Ray Flourescence (XRF), Inductively Coupled Plasma individually and combined with Optical Emission Spectroscopy and Atomic Emission Spectroscopy (ICP, ICP-OES, ICP-AES), as well as Nuclear Magnetic Resonance (NMR) as well as some other techniques are also employed.

9 3.3 Porosimetry N2 Adsorption and Desorption isotherms are mainly used to study pore size as well as pore size distribution. Amount of N2 desorbed is related with saturation pressure. Some conclusions can be made from the relations such as, a vertical hystersis loop indicates cylindrical mesopores, while horizontal hysteresis loop indicates ink bottle type mesopoers. 3.4 Acidity Acidity of the zeolite samples can be measured by adsorbing a basic compound such as NH3 or Pyridine adsorption. Acidity characterizes amount of catalyst activity by giving us information on acidic sites. 3.5 Diffusivity Diffusivity of various probe molecules can be studied with the help of Thermo Gravimetric Analysis, Intelligent Gravimetric Analysis, DRIFTS Diffuse Refluctance Infrared Fourier Transform Spectroscopy. 3.6 Aluminum Characterization Aluminum Characterization is performed with the help of Fourier Transform Infrared Spectroscopy (FT-IR), Argon Adsorption Desorption. 3.7 Coke Characterizations Coke characterizations are also performed to compare and measure amount of coke formed for different species of catalysts.

10 Characterizations can be summarized. Parameter Crystallinity Morphology Si/Al or SAR Porosity Acidity microporous per weight of catalyst Diffusivity Aluminum Characterization Avaliable methods XRD SEM, TEM, XRF, ICP, ICP-OES, ICP-AES, NMR N2 Adsorption Desorption, Ar Adsorption Desorption NH3-TPD, Pyridine IR and BET method, t-plot

mesoporous surface area TGA, IGA, DRIFTS FT-IR, Ar Adsorption Desorption

11

4. Application to Catalysis
A) Advantages 4.1. Hydroxylation of Benzene to Phenol Cumene process is conventionally used for hydroxylation of benzene to phenol [12]. But researchers proved that Fe-HZSM-5 was one of its alternatives [12,13]. Also for the catalyst to be effective Fe species are prerequisite [14-16]. On the contrary, some drawbacks accompanied by these catalysts are rapid deactivation of catalyst, consequently leading to lower yield [17]. Main reaction involving in process is Benzene (C6H6) + N2O Phenol (C6H6O) Main drawbacks involving hindered activity of catalyst is limited diffusion due to geometrical constraints. This can be overcome by introducing mesoporosity in catalyst by treating it with 0.2 M NaOH solution (full procedure mentioned in [11]). Comparing the results obtained for hydroxylation with the help of graphs and charts.

Fig 3 conv. of benzene temp

12

a)
Fig. 4 a) Yield of phenol TOS, b) Selectivity of phenol TOS

b)

From these statistics we can come to a conclusion that after 360 min TOS yield of phenol was 1 % for parent and 22 % for desilicated species. While selectivity didnt changed markably for daughter while for parent, it reduced to 10 % from 70 % . Conversion can also be studied as a function of temperature, and it is clear that it is directly related with temperature i.e. as temperature increases conversion also increases. Desired results can justified by following facts i) changes in active sites ii) mesopore formation [15-17]. 4.2. Benzene Alktylation [5]

13 This text describes that how reaction performance is enhanced after, selective removal of silica from catalyst. Due to low micropore size, mass transport of bulky hydrocarbon experience restricted access in the catalyst for reaction this directly affects the reaction kinetics [18]. Reaction undergoing in the process in presence of mordenite is Benzene + Ethane (Alkane) Ehtylbenzene As in above case this reaction is also affected by diffusional limitations due to geometrical constraints. So catalyst is treated with 0.2 M NaOH (full procedure mentioned in [5]). The improved kinetics can be studied as follows. After treating the catalyst with alkali, benzene is more likely to reach upto intrapore active sites. Also since residence time is reduced, so further alkylation of benzene is suppressed hence increase in Ethylbenzene yield is obvious. 4.3 Butene aromatization [23] Mobil Oil disclosed that ZSM-5 was apt catalyst for transformation of light hydrocarbons to aromatics due to promising properties discussed above [19-22]. But together with these benefits, the catalyst enhances coke production which is undesired for reaction kinetics. For treating the catalyst, it was introduced in the bath of low solutions of different alkali concentration 0.1M (AT1) and 0.1 M (AT2). To monitor coke formation qualitatively and quantitatively FT-IR and TG profiles were used respectively. Reaction undergoing in presence of ZSM-5 catalyst: Butene (C4H8) Aromatics 4.3.1 Conversion
Fig. 5 comparsion of yield and selectivity parent and treated species with time.

14 Conversion decreased to around 93.5 % while it as not issue in case of alkali treated catalysts after 34hr TOS which is evident form fig 6.

Fig 6 Benzene Conv. TOS

4.3.2. Selectivity of aromatics Selectivity of aromatics during the reaction is important aspect. For parent catalyst initial selectivity was noted as 61.9 % which decreased to 19.1 % after 34 hr TOS. While same thing for treated samples remained nearly constant, this can be studied from fig 7
Fig 7 aromatics selectivity TOS

4.3.3 Coking Coking was found to be decreased in treated samples. Characterization of coke revealed that treated samples had 149 and 147 152 mg/g mg/g cat. cat. for AT1 and AT2 are respectively. While same for parent was These evidences insufficient to prove that enhanced catalyst activity is due to less coking, so it is

Fig 8 TPO of coked samples

15 important to know the location of the coke in the catalyst as this will provide that extra coke deposited in the parent catalyst was covering the active site due to which reaction kinetics were apparent. Fig 8 helps us to find the location of coke with TPO.

4.3. Production of propylene from methanol [27] Propylene has many industrial applications some of which includes as a raw material for production of polypropylene, polyacrylonitrile, acrolein and acrylic acid. Propylene is mainly obtained as a byproduct of petroleum refining and by naphtha cracking. But, due to increased demand of this alkane a promising process emerged known as Methanol to Propylene (MTP) [24-26]. For this task ZSM-5 was most effective catalyst. Main reaction undergoing in the process in presence of ZSM-5. Methanol Propylene 0.45 M Na2CO3 solution was used as alkaline media for four different catalysts differing in Si/Al ratio denoted as S1-S6. From fig 9 it is clear that as Si/Al increased the conversion also increased. Also, from fig. 10 selectivity of S5 is displayed. Black triangle at topmost position represents propylene, throughout process it remains constant.

Fig. 9. Conv. of MeOH TOS

Fig. 10. Selectivity of HC over S5 TOS

4.4 Conversion of n-Octene [30]

16

Amount alkenes in the fuel have become a big question for environment so their conversion to aromatics has become inevitable; also that octane no. will be retained [28, 29]. Present text describes us how n-octene is converted in presence of ZSM-5 at different temperatures. 4.5 Mesoporosity development in ZSM-5 [31] Due to magnificent acidic properties ZSM-5 has attracted many industrial processes. But, these acidic properties are of no use if reactants could not access them. Present text will relate dependence of mesoporosity developed on couple of parameters, temperature of bath and treatment time. Here alkali, concentration is 0.2M NaOH kept constant throughout the treatment. Initially let us study effect of temperature. Following results were obtained when time was kept constant for 30 min and temperature in the range of 308-358 K at 10 K interval. Table 4.5.1.1 Influence of temperature on hierarchal properties. T (K) SBET a (m2/g) Untreated 308 318 328 338 348 358 430 440 455 520 550 520 495 Vtotal b (cm3/g) 0.26 0.3 0.33 0.41 0.53 0.58 0.68 Vmicro c (cm3/g) 0.17 0.16 0.16 0.15 0.13 0.13 0.13 Smicro c (m2/g) 390 385 385 360 325 320 315 Smeso c (m2/g) 40 55 70 160 225 200 180
Fig. 11. Product Selectivity of HC T

17 Now, focus on time on mesoporosity development. In this temperature is kept at 338 K for 0.2 M NaOH for 4 ranges of time. Table 4.5.1.2 Influence of alkali bath time on hierarchal properties. T (K) SBET a (m2/g) Untreated 15 30 60 120
a BET

Vtotal b (cm3/g) 0.26 0.42 0.53 0.58 0.59

Vmicro c (cm3/g) 0.17 0.14 0.13 0.12 0.13

Smicro c (m2/g) 390 325 325 300 310

Smeso c (m2/g) 40 180 225 215 200

430 505 550 515 510

method. adsorbed at p/p0 = 0.99. method.

b Volume c t-plot

Fig. 12. Smeso %,( full triangles) Smeso %,( full triangles) Vmicro(hollow Fig. 13. Vmicro(hollow triangles) T (K) triangles) t (min)

Grey lines represent optimum mesoporous values and corresponding temperature and time associated with it. So thus form this we can infer that controlled time and temperature selection leads to optimum mesoporosity values.

18 4.6 Alkali bath time dependence on Mesoporosity development [32]. In this text time dependence on hierarchal properties will be the subject of interest. Here, ZSM-5 with Si/Al ratio of 24 is selected as a parent catalyst. It is treated with 0.5 M NaOH at 325 K. Table 4.6.2.1 Influence of alkali bath time on hierarchal properties time (h) SBET (m2/g) 4 2 1.5 0.5 0.25 Untreated
70 % change in mesopore volume 60 50 40 30 20 10 0 0 0 1 2 time (h) 3 4 5 0.5 0.25 1.5 2 4

Size micro nm 0.55 0.55 0.55 0.55 0.55 0.55

Vmicro (cm3/g) 0.16 0.16 0.16 0.16 0.16 0.16

Size meso nm 2-25 2-25 10-20 2-35 2-35 2-30

Vmeso

329 342 328 336 339 336

0.12 0.12 0.14 0.06 0.1 0.05

Fig. 14. Vmeso %, t (h)

4.7 Isomerization of -Pinene [33] Present text will cover the reaction proceeding over ZSM-5, ZSM-12, MCM-22 their parent and subsequent treated species. Applications of Pinene isomerization is that its isomers such as camphene, limonene, p-cymene and Pinene itself are very crucial for chemical and pharmaceutical industries [55]. A very wide range of options were tried for catalyzing the reaction, some of which are oxides[34-35], oxides treated with acids

19 [36], zeolites [37-44], mesoporous materials [4446], activated clays [4751], resins [52, 53] and heteropolyacids [54]. Table 4.7.1 Result table for Isomerization including selectivity
Sample NaOH (M) ZSM-5 unmod d500585 d50185 d50585 d5185 ZSM-12 unmod d0185 d0585 d185 d01A 0.1 0.5 1.0 0.1 0.05 0.1 0.5 1.0 T (C) 75 90 75 90 75 90 75 90 75 75 90 75 90 75 75 75 90 MCM-22 unmod d00585 d0185 d01A 0.05 0.1 1.0 75 90 75 75 75 X (%) 11.4 10.0 14.7 8.7 9.3 9.5 17.1 17.2 27.5 43.0 7.0 36.0 42.0 69.0 41.0 23.0 15.0 77.0 70.0 37.0 59.0 47.0 Scam (%) 33.6 33.6 32.6 27.5 31.4 29.3 33.7 34.6 34.4 43.0 35.0 38.0 38.0 39.0 37.0 45.0 31.0 35.0 36.0 35.0 38.0 36.0 Slim (%) 34.3 34.5 32.3 34.9 30.8 30.3 33.1 32.0 34.1 31.0 25.0 35.0 35.0 34.0 35.0 32.0 32.0 45.0 50.0 47.0 47.0 48.0 Ycam (%) 3.8 3.3 4.8 2.4 2.9 2.8 5.8 5.9 9.5 18.5 2.4 13.7 16.0 26.9 15.2 10.4 4.7 26.9 25.2 12.9 22.4 16.9 Ylim (%) 3.9 3.4 4.7 3.0 2.9 2.9 5.7 5.5 9.4 13.3 1.7 12.6 14.7 23.5 14.4 7.4 4.8 34.6 35.0 17.4 27.7 22.6

X-conversion, Scam, selectivity to camphene; Slim, selectivity to limonene; Ycam, yield of camphene; Ylim, yield of limonene; T, reaction temperature. Samples labeling: d0585, desilicated with 0.5 M NaOH at 85 C; d01A, desilicated with 0.1 M NaOH under hydrothermal conditions at 100 C. Product distribution is given in mol%

20

Fig 15 Catalyst activity of ZSM12 (left) and MCM-22 (right)

Different parameters were changed to give best selectivity values and ZSM-12 at optimum parameters was found to give best selectivity value of 70% ,which was recorded highest among all the zeolites observed up to now. 4.8. Improved heavy oil conversion and diffusional properties [56]. Diffusional properties can be improved directly by introducing mesopores in the catalyst, which also results in better catalytic results like improved conversion, selectivity, increased TOS etc. Properties of heavy oil feed stocks are tabled. Table 4.8.1 Properties of heavy oil feedstock Items Density (g/cm3) (293 K) Viscosity (Pas) (323 K) Carbon residue (wt %) Mn (g/mol) H (wt %) C (wt %) H/C Saturated carbons Daqing heavy oil 0.913 0.213 4.3 577 12.87 86.77 1.78 59.2

21 Aromatics Resins and asphaltenes Mn: average molecular weight. Various treatments with alkali solution can also be represented as follows. Table 4.8.2 Treatment parameters Sample OZ5 AZ5-1 AZ5-2 AZ5-3 Si/Al molar ratio 30 29 24 22 Treatment time (min) 120 300 300 Temp water bath (K) 333 353 343 Conc. of NaOH solution (mol/L) 0.25 0.20 0.25 29.1 11.7

Also the results obtained after treatment can be summarized in below table. 4.8.3 Hierarchal properties of catalysts. Sample OZ5 AZ5-1 AZ5-2 AZ5-3 Daver SBET (nm) 2.2 2.4 3.5 4.0 380 383 414 427 Smicro 358 347 283 252 Smeso m2/g 22 36 131 175 Vp Vmicro m3/g 0.212 0.171 0.231 0.167 0.357 0.144 0.431 0.130 Vmeso m3/g 0.042 0.064 0.213 0.300 (m2/g )

Cumene molecule was taken as probe molecule for of studying different diffusional properties

catalysts Fig 16 helps us to compare performance of original and treated catalyst. The initial adsorption rate of cumene on OZ5 was 48% of the maximum adsorption amount was after 32 min.
Fig 16 Adsorption amount time (min)

Then, the adsorption rate declined, indicating that with the increase in the amount of

22 cumene adsorbed, it becomes more difficult for cumene to diffuse into the micropore of OZ5 zeolite channels. However, it was different for AZ5-3. It is clear that there were many steps when cumene adsorbed on/into AZ5-3. At the beginning the cumene molecules adsorbed and diffused quickly on the outside surface of AZ5-3 with a high adsorption rate, this phenomenon was similar to that of OZ5. The cumene molecules also diffused easily into the mesopores and/or super-micropore of AZ5-3 at a high adsorption rate, and the amount of adsorption became higher than that on OZ5 because of the existence of mesopores. When sufficient cumene molecules were adsorbed on the mesopore and/or super-micropore of AZ5-3, the interaction between molecules became dominant. Consequently, a phase transition could occur, which means, the adsorption of cumene molecules changed from monolayer adsorption to multilayer adsorption or condensation. At this time, due to the balance adsorption, the rapid decrease of adsorption rate is observed. After that, the cumene molecules commenced to diffuse into micropores via rearrangement. In this step the diffusion rate was low due to the limitation of pore size and interaction between molecules and zeolite walls. The increased adsorption amount can also be observed with smaller slope comparing to the very beginning. Cumene molecules could not enter the intersection of two different size pores and/or between straight channel and zig-zag channel until re-arrangement occurred. The re-arrangement of molecules resulted in an increase of adsorption amount and rate.

23 Table 4.8.4 Product distribution of cumene cracking Catalyst Yields of gas products (wt%) Methane Ethane Ethene Propene Butene Yields of liquid products (wt%) Benzene Toluene Ethylbenzene Styrene Methyl-styrene Propylbenzene Cumene Yields of solid products (wt%) Coke Cumene conversion (%) 0.34 30.71 0.36 66.35 16.12 0.18 0.32 0.40 1.19 0.21 69.29 36.58 0.23 0.50 0.46 1.39 0.62 33.65 0.30 0.31 1.01 9.75 0.58 0.38 0.40 1.04 23.52 0.88 OZ5 catalyst AZ5-3 catalyst

Cumene cracking generally occurs in Bronsted acid sites, so more Bronsted acid sites will result into more catalytic activity. But, on the contrary Pyridine-IR revealed that there was subsequent decrease in acid sites after alkali treatment but still catalyst performance was enhanced. This can be justified as follows, treated catalyst leads to lower adsorption activation energy also the diffusivity of catalyst is better than parent.

24 Table 4.8.5 Product distribution of heavy oil cracking Catalyst Yields of products (wt%) Dry gas LPG Liquid Coke Yields of olefins (wt%) Ethene Propene Ethene + propene Butene Total light olefins 13.82 14.90 28.72 4.74 33.46 13.18 16.84 30.02 5.91 35.93 33.46 22.49 31.93 12.12 29.58 25.65 31.58 13.19 OZ5 catalyst AZ5-3 catalyst

4.9 Diffusivity of neo-Pentane over ZSM-5 [57] In this, neo-Pentane was used as a probe molecule to investigate diffusional properties of parent and desilicated zeolite. Enhanced diffusional results cannot be always directly attributed to mesopores formation in catalyst. Catalyst was treated with 0.2 M NaOH solution at 338 K for 120 min subsequent hierarchal properties can be tabled as below. Table 4.9.1 Hierarchal properties of catalysts. molar SBET b sample calcined alkaline Si/Al a (m2 /g) 30 24 350 415 Smeso c (m2/g) 5 120 Vmicro c (cm3/g) 0.14 0.12 VmesoN2 d (cm3/g) 0.01 0.16 Vmeso,Hg e (cm3/g) 0.00 0.13

a ICP-OES. b BET method. c t-plot. d Pore volume in the range of 4-100 nm derived from N2 adsorption. e Pore volume in the range of 4-100 nm

25 derived from Hg intrusion curve.

Fig 17 neo-pentane uptake time (min)

Actually in this case alkali treatment hardly contribute to micropore change, so enhanced diffusion in neo-Pentane can be credited to the fact that alkaline treated species of catalyst are successful in creating improved accessibility inside the pores as well as shorter diffusion path length due to selective extraction of silica from zeolite framework. 4.10 Diffusivity investigation in ZSM-12 [58] In case of ZSM-12 if comparison is done with ZSM-5 for pore window opening, slight increase in window size for former helps to use molecules slightly larger than window opening of latter for investigating diffusional properties and reaction kinetics [59]. Very wide arrays of parameters were used to find governing parameter for mesopore formation which will however decide diffusional properties. These can be tabled out.

26 Table 4.10.1 Influence of alkali concentration and temperature on hierarchal properties t=30 min, Si/Al = 58 CNaOH M 0.05 0.1 0.1 0.2 0.2 0.2 0.4 0.4 T C 95 65 95 35 65 95 35 65 dSBET a m2/g m 0 0 +12 0 +22 +19 +16 +17 dVmicro b cm3/g m 0 0 -0.01 0 -0.02 -0.04 -0.03 -0.05 dVmeso c cm3/g m 0 0 +0.05 0 +0.27 +0.31 +0.29 +0.61

Table 4.10.2 Influence of time on hierarchal properties Si/Al =58, 0.2 M NaOH at 65 C Time min 30 90 150 dSBET a m2/g +22 +16 +14 dVmicro b cm3/g m -0.02 -0.03 -0.03 dVmeso c cm3/g m +0.27 +0.34 +0.35

Table 4.10.3 Influence of Si/Al on hierarchal properties T=65C, t=30min Sample M ZSM-12-31 ZSM-12-45 ZSM-12-58 ZSM-12-80 0.1 0.1 0.1 0.1 CNaOH m2/g 0 0 0 +19 +17 +24 +20 +24 dSBET a 0 0 0 -0.02 -0.02 -0.03 -0.02 -0.02 dVmicro b cm3/g m 0 0 0 +0.16 +0.18 +0.24 +0.17 +0.19 dVmeso c cm3/g m

ZSM-12-140 0.1 ZSM-12-500 0.1 ZSM-12-31 ZSM-12-45 0.2 0.2

27 Sample M ZSM-12-58 ZSM-12-80 0.2 0.2 CNaOH m2/g +22 +36 +32 +21 dSBET a dVmicro b cm3/g m -0.02 -0.03 -0.04 -0.06 dVmeso c

cm3/g m +0.27 +0.32 +0.34 +0.51

ZSM-12-140 0.2 ZSM-12-500 0.2

a BET method. b V total = V ads p/p0=0:99. c t-plot method.

Table 4.10.4 Investigation of Diffusivity properties of various Hydrocarbon over parent and desilicated catalyst Hydrocarbon compound n-Heptane 1,3-Dimethylcyclohexane n-Undecane 15.410-10 5.910-10 2.610-10 Diffusivity (cm2/s-1) Alkali Treated ZSM-12 UntreatedZSM-12 7.410-10 2.110-10 0.710-10

Finally this text concluded with increase in diffusivity properties in probe molecules. Concentration of alkali was found to be controlling parameter in desilication process. Also it was inferred that Al content in catalyst proved resistance to silicon extraction, as Al content increases desilication became harder. 4.11 Methane Dehydroaromatization (MDA) [60] Gasoline is crucial fuel in modern transportation strategies. Considering its reducing stocks and mounting demand it has become important to develop new strategies for production of Gasoline. Mobil Oil explored Methanol to Hydrocarbon (MTH) technology over zeolites [61]. Main reaction undergoing in presence of ZSM-5 is Methanol C2, C3, C4, C5, C6

28 Parent catalyst is treated with 0.05 M, 0.2 M NaOH for 2 x 4 hr at 75 C and above reaction was investigated and results were compared with parent catalyst. Table 4.11.1 Sample PARENT 0.05M 0.20M a ICP-AES. b t-Method. c Volume adsorbed at p/p0 = 0.99. 4.11.1.1 Conversion Parent sample shows initial activity of 86% and rapidly reduces to 20% after 30 hr TOS. While for sample treated with 0.5 M NaOH showed 89% initially and came down to 20% after 70 hr TOS. For sample treated with 0.2M NaOH showed 92% initial activity and showed greater TOS than 0.05 M sample. Nearly same initial activities suggest that acidities for all samples are nearly same so the improved performance is attributed to newly formed surface areas and mesopores. 4.11.1.2 Selectivities Product Selectivities are also investigated for set of catalysts. For parent, C2 was recorded highest followed by C3 amongst all catalysts and they were found to be decreased with severity in alkali concentration. While in case of C5+ hydrocarbons,
Fig 18 Conversion TOS(hr) at 370 C and WHSV 8 g/g hr

Si/Ala SBET m2/g 46 39 27 313 372 419

Sext b Smicro b 142 192 213 171 180 206

Vtotal c ml/g 0.28 0.39 0.37

Vmicro b 0.09 0.09 0.10

29 which can be considered approximately cut for gasoline, showed increase with increase in severity in alkali concentration.

Fig 19 Conversion TOS(hr) at 370 C and WHSV 8 g/g hr Fig 20 C4 HTI Conversion at 370 C and WHSV 8 g/g hr

4.11.1.3 Investigations on HTI (Hydrogen Transfer Index) C4 HTI is defined as combined yields of iso- and n- butanes over C4 alkanes and alkenes and comprises of Hydrogen transfer activity of catalyst [62]. From Fig. 20 0.05

30 M sample has bit higher HTI while that for 0.2 M sample was found to be considerably increased. Higher HTI indicates immense cyclization and aromatization reactions [63].

31 B) Drawbacks 4.12 Alkylation over Zeolite Beta [64] Zeolite Beta was treated with 0.2M NaOH at wide array of treatment conditions and their hierarchal properties can be studied for corresponding conditions. But an attention is made while performing desilication in case of BEA zeolites is that they should be performed under milder conditions than in MFI and MOR due to fact that framework of fromer is less stable. Table 4.12.1 Hierarchal properties of zeolite BEA after treatment. Sample NaOH B T K 318 318 298 308 318 328 338 B-at-1 0.2 B-at-2 0.2 B-at-3 0.2 B-at-4 0.2 B-at-5 0.2 B-at-6 0.2 B-at-7 0.2 b BET method. c t-plot method. Catalytic performance is studied with alkylation of Benzene and is compared with desilicated ZSM-5 to compare the results. From Fig 21 it is clear that as the Beta zeolite was treated with severe conditions the more apparent and undesired results were obtained. These apparent results can be directly related to loss of active sites in catalysts. Aluminum species are capable of shielding Silicon atoms in the framework, in case of BEA type zeolites aluminum is less stable in framework implies Aluminum provides less resistance for silicon extraction, so it was mentioned earlier that milder conditions were t min 10 60 30 30 30 30 30 35 30 23 20 615 680 675 650 595 695 705 705 Si/Ala SBET b Smeso c Vpore Vmicro c m2/g 60 125 305 70 80 250 300 370 cm3/gm 0.31 0.37 0.46 0.32 0.32 0.43 0.44 0.52 0.22 0.21 0.12 0.22 0.19 0.15 0.13 0.10

a ICP-OES of solid material.

32 used for desilication process. So, low stability of Aluminum is responsible for decline in catalyst activity with severity in conditions.

a)

b)

Fig 21 Catalytic performances of Zeolite Beta a) and ZSM-5 b)

33

5 Conclusion
Various conclusions can be made while performing selective removal of silica on zeolites. These can be summarized. Desilication does not affect acidic properties of catalyst, as in case of dealumination. Also, as Aluminum density increases they are more likely to shield Si atoms, so from this we can infer that as desilication progresses resistance for silicon extraction increases. Also stability of Aluminum in zeolites framework is important parameter, as it is deciding factor for conserving Bronsted Acidic sites. So catalyst activity is dependent on acidic sites. Stable sites results in enhanced activity, while on the contrary less stable sites lead to loss of activity and consequently apparent and undesired results are obtained. Parameters which affect desilication are mainly temperature of bath, time of bath, alkali concentration and Si/Al ratio. Desilication means selective removal of silicon from zeolite framework. So as silicon is removed, the formation of mesopores results. These formations of mesopores are likely to increase selectivity by discriminating undesired molecules due to their geometrical properties. It also discourages coking up to some extent and thus increases catalyst life. Formation of mesopores also in turn enhances diffusivity in the treated samples. Desilication also plays important role in Industrial cracking and fuel production. Because of shortened diffusion path length desired progressive cracking is avoided because of less residence time and thus giving desired fraction of hydrocarbons. Due to this advantage desilication has found many commercial processes.

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