Direct Decomposition of Nitric Oxide by Copper Containing ZSM-5 Citation Seidel, Peter Robert (1996) Direct Decomposition of Nitric Oxide by Copper Containing ZSM-5. Master's thesis, California Institute of Technology. doi:10.7907/ab1s-x455. https://resolver.caltech.edu/CaltechTHESIS:03242025-182317095 Abstract Currently there is an enormous demand for nitric oxide decomposition catalysts and hydrocarbon-based selective catalytic reduction catalysts to eliminate NO. The incorporation of copper atoms into the pores of ZSM-5 has endowed this solid with the catalytic ability for the direct decomposition of NO to N 2 and O 2 . This report describes the synthesis, characterization, ion-exchange, and reactivity of several ZSM-5 samples prepared by various methods. ZSM-5 is prepared using TPA and also by template-free synthesis methods. Ion-exchange was performed using copper acetate and a copper ethylene complex. Reaction studies include determining rates and turnover frequencies for certain ZSM-5 samples. It was found that ion-exchange with copper ethylene almost doubled the copper weight percent and the reaction rate compared to samples exchanged with copper acetate, however, the turnover frequencies were similar. Item Type: Thesis (Master's thesis) Subject Keywords: (Chemical Engineering) Degree Grantor: California Institute of Technology Division: Chemistry and Chemical Engineering Major Option: Chemical Engineering Thesis Availability: Public (worldwide access) Research Advisor(s): Davis, Mark E. Thesis Committee: Unknown, Unknown Defense Date: 1996 Record Number: CaltechTHESIS:03242025-182317095 Persistent URL: https://resolver.caltech.edu/CaltechTHESIS:03242025-182317095 DOI: 10.7907/ab1s-x455 Default Usage Policy: No commercial reproduction, distribution, display or performance rights in this work are provided. ID Code: 17089 Collection: CaltechTHESIS Deposited By: Ben Maggio Deposited On: 25 Mar 2025 18:03 Last Modified: 25 Mar 2025 18:04 Thesis Files PDF - Final Version See Usage Policy. 22MB Repository Staff Only: item control page

Direct Decomposition of Nitric Oxide By Copper Containing ZSM-5 Peter R. Seidel Research Report Submitted In Partial Fulfillment of the Requirements for the Degree of Masters of Science California Institute of Technology Pasadena, Califomia 1996 11 Acknowledgments I would like to thank Professor Mark E. Davis for his guidance and support in the completion of this project. I would also like to thank Dr. Jay Labinger for his interest and many suggestions. I want to thank all the members of the Davis research group, both past and present for being excellent labmates and friends. Dr. Clemens Freyhardt spent a lot of time with me discussing my project and future options. Dr. Chris Dartt, Dr. John Lewis and John Nagel helped me during my first year in lab. Dr. Larry Beck would always take the time to discuss my project and advise me on NMR. Alex Katz, Dave Foss, Wayez Ahmad, Shervin Khodabandeh, and the rest of my ChE class have made the past two years very entertaining. Tara Weiscarger deserves special credit for putting up with me through some very stressful times. She never lost faith in me and was always there when I needed someone to lean on. Finally, I want to thank my mom, dad, and brother for all their help and support. My student career has been long and expensive, and I thank you for everything you have done to make it possible. 111 Abstract Currently there is an enormous demand for nitric oxide decomposition catalysts and hydrocarbon-based selective catalytic reduction catalysts to eliminate NO. The incorporation of copper atoms into the pores of ZSM-5 has endowed this solid with the catalytic ability for the direct decomposition of NO to N2 and 0 2 . This report describes the synthesis, characterization, ionexchange, and reactivity of several ZSM-5 samples prepared by various methods. ZSM-5 is prepared using TPA and also by template-free synthesis methods. Ion-exchange was performed using copper acetate and a copper ethylene complex. Reaction studies include determining rates and turnover frequencies for certain ZSM-5 samples. It was found that ion-exchange with copper ethylene almost doubled the copper weight percent and the reaction rate compared to samples exchanged with copper acetate, however, the turnover frequencies were similar. IV Table of Contents Acknowledgments ...........................................................................................ii Abstract .......................................................................................................... iii Table of Contents ........................................................................................... iv List of Tables .................................................................................................. vi List of Figures .............................................................................................. vii 1. Introduction ................................................................................................. I 1.1 Zeolites ................... ............................. ............................................................. 2 1.2 NOx Catalysis ................................................................................................... 4 1.2.1 Direct NO Decomposition ................................................................................... 4 1.2.2 Selective Catalytic Reduction of NOx with CH4........ ... .... ... ...... ... ....................... 5 1.3 Objectives .............................................................. .:......................................... 5 2. Experimental ............................................................................................... 7 2.1 Samples Preparation ........................................ ................................................. 7 2.2 Characterization ............................................................................................... 8 2.3 Ion Exchange ..................................................................................... .. ........... 10 2.4 Catalytic Reactions ......................................................................................... 11 3. Results and Discussion ............................................................................. 13 3.1 ZSM-5 Samples ......................... ...... ...................................... ......................... 13 3.2 Ion-Exchange Isotherms ................................................................................. 17 3.2.1 Copper Acetate Exchange ... ... ........... ... ...... ......................................... ...... ... ...... 17 3.2.2 Copper Ethylene Complex Exchange ......................................... ................... .... 21 3.3 Catalytic Studies on Cu-ZSM-5 ................... .... ............................. ................. 22 ~.3.1 Sample Reactivity .............................................................................................. 22 3.3.2 Differential Reactor Regime ...................... .................................................. .. .... 23 4. Conclusions and Future Directions ......................................................... 29 4.1 Conclusions .................................................................................................... 29 4.2 Future Directions ................................... ......................................................... 29 4.2.1 Exchange on Different Si/Al Samples .................................................. .. ........... 29 4.2.2 Temperature Programmed Desorption of Isopropylamine (IPA) ................... ... 30 4.2.3 Activity of Other Copper Ion-Exchanged Zeolites ...... ...................................... 31 5. References ...................................................................................._.............. 32 V A ppendices ..................................................................................................... 33 Appendix I. List of Chemicals Used ............... ..................................................... 33 Appendix II. List of Samples .................................. ............................................. 34 Appendix III. Characterization of Samples ........................................................ .. 35 Appendix IV. X-ray Powder Diffraction Patterns ............................................... . 36 Appendix V. Thermogravimetric Analyses ............................... ....... ................... 57 Appendix VI. NMR Spectra .............. ......................... ........ .................................. 73 Appendix VII. Conversion versus WIF Plots for VA W sample 1. .. .................... 99 vi List of Tables Table 1 Synthesis conditions for ZSM-5 zeolites with varying Si/Al and Defects ... ... .... 8 Table 2 Characterization Data for ZSM-5 Zeolites ... .. ... ........... ..... .. ... ...... ...... ....... ...... .. 15 Table 3 Elemental Analysis on Copper Exchanged Samples .............. .............. ............. 22 Table 4 Reaction conversions .. ....... ............ ........... ... ... .......... .... .......... ..... ....... .............. . 23 Table 5 Reaction Rates and Turnover Frequencies .. .. ... .... ...... .... ................. .. ....... .... ..... 25 Table 6 Activation Energies .. ... .... ....... ......... ........ ............... .... ..... ........ ....... ............ ....... 27 List of Figures Figure I Tetrahedral building units in zeolites (adapted from ref.[5]) ..... .... ....... ............. 2 Figure 2 Structure of ZSM-5 . ........ ........... .. ..... ......................... ........ ............... .... ... ....... ... 3 Figure 3 Setup for copper ethylene complex exchange ....................... .................. ..... ... . 11 Figure 4 Setup of catalytic reactor. Can monitor all exit gases with a mass spectrometer. ........... ....... .... .. ..... ..... .... ... .. ... .. .. .. ....... ..... ..... ..... ................. ........ .. 12 Figure 5 29 Si MAS NMR spectra of ZSM-5 sample 2 (top) and 4 (bottom) with deconvolution peaks .. .. .... ................................................ ........................... ..... . 16 Figure 6 Copper acetate ion-exchange data for YAW NH/ ZSM-5 ..... .. ..... ..... ...... ....... 17 Figure 7 Copper acetate ion-exchange data for YAW H+ ZSM-5 ...................... ...... ... ... 18 Figure 8 Copper acetate ion-exchange data for YAW Na+ ZSM-5 ........ ... ..... .......... ...... 18 Figure 9 Copper acetate ion-exchange data for sample 2 from the Na+ form ....... .. .. ... ... 20 Figure 10 Copper acetate ion-exchange data for sample 4 from the Na+ form ....... .......... 20 Figure 11 Reaction run for sample 1, ion-exchanged with the copper ethylene complex ..... .. ... ... ........ ........... ...... ......... ............ ..... ....... ... ... .. ... .. ...... ...... ..... .. ... ... 23 Figure 12 Conversion versus WIF for YAW sample 1. Temperature was 502°C .. .. ..... .. 24 Figure 13 Turnover frequency versus temperature for YAW sample I exchanged with copper acetate ................................... ..... ....... ... ....... .............. ..... ....... .. ... .... ....... 26 Figure 14 Turnover frequency versus temperature for YAW sample 1 exchanged with copper ethylene .......................... .............. ........ .. ... ...... ...... ......... .. ... ..... ....... .... .. 26 Figure 15 Arrhenius plot for YAW sample 1 exchanged with copper acetate .......... ...... . 28 Figure 16 Arrhenius plot for YAW sample 1 exchanged with copper ethylene ........ ....... 28 Vlll Appendices Figure VII-I Sample I ion-exchanged with copper acetate, T=526 c c. . .. . .. ....... .. .. ... .. . . . . . . 99 Figure VII-2 Sample I ion-exchanged with copper acetate, T=500 cc. . . . .. . . . . ... . . . ... . . .. . . . . .. 99 Figure VII-3 Sample I ion-exchanged with copper acetate, T=473 cc ........ .. .. .. .. ....... .... 100 Figure VII-4 Sample I ion-exchanged with copper acetate, T=447 cc. . . . . . .. . .... . . . ..... .. . ... 100 Figure VII-5 Sample I ion-exchanged with copper acetate, T=422 c c. .... . . . . .................. 101 Figure VII-6 Sample I ion-exchanged with copper ethylene complex, T=525 c c. . .... .... 101 Figure VII-7 Sample I ion-exchanged with copper ethylene complex, T=500 cc .. ... . . .. . 102 Figure VII-8 Sample I ion-exchanged with copper ethylene complex, T=477 c c. ......... 102 Figure VII-9 Sample I ion-exchanged with copper ethylene complex, T=450 cc .... . ... .. 103 Figure VII-IO Sample I ion-exchanged with copper ethylene complex, T=425 c c .. . ..... 103 1. Introduction The removal of nitric oxide from combustion exhaust streams has become increasingly important as NO has been linked to smog formation, acid rain, ozone effects and other harmful consequences. 1 In the future, stricter federal and state emissions regulations will dramatically increase gas equipment operating costs. The outlay of ammonia-based selective catalytic reduction (SCR) is currently very high, and noncatalytic processes perform inefficiently at relevant operating temperatures. As automobile manufactures move toward more efficient "lean burn" engines, an additional catalytic converter will be required to handle the increased levels of NO production. There is clearly a growing need for NOx decomposition or hydrocarbon-based SCR catalysts to eliminate nitric oxides. Thermodynamically, nitric oxide is unstable to its molecular elements 0 2 and N2 , except at very high temperatures.2 2NO ~ N 2 +0 2 ~0°= -20.7 kcal/ mo! @ T = 298 K Therefore, NO decomposition is thermodynamically favorable. The equilibrium for this reaction lies far to the right up to high temperatures, as characterized by the following expression. 3 K=[N 2 ][02 2 ] [NO] with logK=-l.63+9452/T This reaction, however, is very slow from a kinetic standpoint. In the absence of a catalyst, several days are required to establish equilibrium even at I000°C. 4 This data supports the need for NOx decomposition catalysts. 2 1.1 Zeolites Zeolites are microporous crystalline aluminosilicates that are constructed from T04 tetrahedra (T represents a tetrahedral atom such as Si or Al.) These tetrahedral atoms are the primary building blocks in the formation of zeolites. 5 Each oxygen atom bridges two neighboring T-atoms and shares its two negative charges equally. This causes each Si04 unit to become electronically neutral as a result of the +4 charge of Si and the four -1 charges from the oxygen atoms (see Figure 1). An Al04 unit will therefore have a -1 charge. A framework made up entirely of Si04 units will contain no charge, and a material containing Si and Al atoms will be negatively charged. 0 0 0 I +4 J- Si•. cl \''''O o 0 -1 0 cl 0 '-----si_..,..- - - s · / O 0 I '·O 0 ~ I +3 A\.,,,,,,0 0 Figure 1 Tetrahedral building units in zeolites (adapted from ref.[5]) Since zeolites are crystalline, all the pores, cages, and channels have exactly the same dimensions. Some zeolite frameworks form independently of a structure directing agent (an organic molecule which creates a cage or channel by crystallizing T04 units around itself.) Other zeolites cannot form without a structure directing agent. Some 3 zeolites can be synthesized both ways, such as ZSM-5. Most ZSM-5 produced today is made by a template-free method6 . It can also be made using tetrapropylammonium ions (TPA+) as a structure-directing agent. Both preparation methods lead to the same framework structure, but the ordering of aluminum in the zeolite and the number of defects sites (silanol groups SiO3OH and siloxy groups SiO3O-) will differ. Figure 2 shows the structure of ZSM-5. It has IO membered rings with intersecting channels. The channels which lie in the plane of the paper are sinusoidal. Figure 2 Structure of ZSM-5. During synthesis of an aluminosilicate there must be a cation present to balance the negative charge of the AlO 4 unit. After synthesis this cation can be replaced by 4 performing an ion-exchange. ZSM-5 prepared by a template-free method will have Na+ balancing the negatively charged aluminum in the framework, but the Na+ can then be replaced with copper by ion-exchanging with a copper acetate solution. As previously mentioned, the ordering of the aluminum in a zeolite, and thus the cation balancing this charge, is dependent upon the synthesis method. 1.2 NOx Catalysis Currently, the most active catalyst reported for the direct decomposition of NO to 0 2 and N 2 is ZSM-5 which has been excessively copper ion-exchanged. 7 It is also well known that in the presence of additional species (H 2O, SO 2, 0 2), the ability of Cu-ZSM-5 to catalyze this reaction greatly decreases. 8•9 Selective catalytic reduction of NOx with hydrocarbons is becoming a popular option as a possible replacement to current ammoniabased SCR processes. Cobalt ion-exchanged ferrierite (FER) catalysts show the greatest activity for SCR of NO with methane, especially in the presence of water. 10 1.2.1 Direct NO Decomposition Most studies on NO decomposition have investigated Cu-ZSM-5 synthesized by the template-free method with Si/Al around 15-20.7•9•10•11 •12 The number of aluminum per intersection in ZSM-5 prepared by this method is unknown. Other studies report ZSM-5 preparations with no mention of the synthesis method. The literature reports ion-exchange levels of 100% and more, termed "over exchanged." For a divalent ion, 100% exchange would give M+ 2/Al = 0.5. However, the exchange of M+ 2 implies a paired Al center (AlO-Si-O-Al), unlikely for high Si/Al ZSM-5 unless there is very strong Al zoning within 5 the crystal. Transition-metal ions can hydrolyze water to lower their effective charge. Copper could then ion-exchange as [Cu 2\H 2O) 5Offt. The definition of over exchange hinges upon what copper species ion-exchanges into ZSM-5. Another possible explanation for reaching overexchange is that for exchange levels up to 70% (100% = Cu/Al = 0.5) [Cu 2+Offt exchanges for Na+. 7 At higher levels of exchange Larsen et al. speculate that Cu 2+ or H+ exchange as well. Valyon and Hall showed that ion-exchanging copper into ZSM-5 at pH ~6 yields higher copper loadings than at pH ~4. 12 This is also consistent with Larsen et al. in that [Cu 2+Offt forms more readily as the pH is raised. One certain observation is that high levels of copper exchange in ZSM-5 are necessary for maximum activity. 1.2.2 Selective Catalytic Reduction of NOx with CH4 Li and Armor have shown that Cu-ZSM-5 is a very poor catalyst for NO reduction in the presence of 0 2 . 9•10•13 •14 They found that Co-ZSM-5 performed better than Cu-ZSM5 for SCR of NO with CH4 in the presence of 0 2 and occasionally H 2O. However, CoZSM-5 is a very poor catalyst for the direct decomposition of NO to N 2 and 0 2. The best catalyst for SCR of NO with CH4 , in the presence or absence of H2O, is Co-FER. Similar to Cu-ZSM-5, Co-FER and Co-ZSM-5 are highly ion-exchanged with cobalt to achieve maximum activity. Although these trends have been verified by other studies, it is not understood why they exist. 1.3 Objectives Currently, little is known about the features of metal-loaded zeolites which endow them with their catalytic properties for NOx reactions. Our first objective is to synthesize a 6 broad spectrum of zeolite samples. This includes the synthesis of ZSM-5 by three different procedures, with Si/Al ratios ranging from 15 to 40. Next, these samples will be characterized by several techniques. Some of the characterization techniques to be used are powder x-ray diffraction (XRD), nuclear magnetic resonance (NMR), temperature program desorption (TPD), thermogravimetric analysis (TGA), ultraviolet spectroscopy (UV), infrared spectroscopy (IR), and Far IR spectroscopy. Full ion-exchange isotherms will be generated for some samples to give insight into how copper ion-exchanges into ZSM-5. The catalytic activity of certain samples will be tested in a packed bed reactor for direct decomposition of NO. Rates and turnover frequencies will be calculated for these samples. 7 2. Experimental 2.1 Samples Preparation ZSM-5 was prepared by three different methods. The synthesis of all ZSM-5 samples were conducted in Teflon-lined, stainless steel reactors. Fumed SiO 2 from CabO-Sil, Grade M5 was used as the silicon source. The fluid gel was heated statically and at autogenous pressure for 6 to 14 days, depending on the synthesis method used. The three synthesis methods used are summarized in Table 1. In addition to the samples prepared in our lab, experiments were performed using a ZSM-5 sample produced by VAW. 6 This sample had a Si/Al= 11 and was made using a continuous template-free method. The Na+ method corresponds to samples 2 and 3 in Table 1. TPABr was used as a structure directing agent and hydroxide from NaOH as a mineralizing agent. The F method corresponds to samples 4-6 in Table 1. TPABr was again used as a structure directing agent, but the fluoride ion from NH 4F was the mineralizing agent. The templatefree method corresponds to sample 7 in Table 1. No template was used in this synthesis, though a few crystals of ZSM-5 were added as seeds for nucleation. 7 NaOH was used for mineralizing. All of the above samples were calcined in a muffle furnace. The samples were first dehydrated by being heated to 250°C and held for an hour. The temperature was then raised to 580°C, and held steady for 8 hours. During the first two heating steps, nitrogen was flowed over the samples. For the last 7 hours at 580°C, air was passed over the samples. 8 Table 1 Synthesis conditions for ZSM-5 zeolites with varying Si/Al and Defects. gel composition gel Si/Al mineralizing agent T {°C) VAW unknown, but has NH4+ balancing Ar, no template --------- --------- --------- 2 0.1 TPABr: SiO2 : 36 H2O: 0.25 NaOH : 0.05 Al(NO3) 3 20 OH- 150 3 0.1 TPABr: SiO2 : 36 H2O: 0.25 NaOH : 0.025 Al(NO3) 3 40 OH- 150 4 0.1 TPABr: SiO 2 : 25 H2O : 0.5 NH4F : 0.067 Al(NO 3) 3 14.9 F 175 5 0.1 TPABr: SiO 2 : 25 H2O : 0.5 NH 4F : 0.042 Al(NO 3) 3 23.8 F 175 6 0.1 TPABr: SiO 2 : 25 H2O : 0.5 NH4F : 0.025 Al(NO 3) 3 40 F 175 7 SiO 2 : 19.5 H2O: 0.21 NaOH: 0.054 Al(OH) 3 : seeds 18 OH- 175 No 2.2 Characterization X-ray powder diffraction (XRD) patterns were collected for all samples on a Scintag XDS-2000 diffractometer equipped with a liquid-nitrogen-cooled germanium solid state detector using Cu-Ka radiation. Data were acquired using a Digital Instruments Micro Vax 3100 system. Thermogravimetric analyses (TGA) were performed in air at a constant heating rate of 10 K/min from 298 K to 1173 K on a DuPont 951 TGA. All NMR spectra were collected at room temperature on a Bruker AM 300 spectrometer equipped with a high-power assembly for solids. Sample holders were 7 mm ZrO 2 rotors. The magic angle spinning (MAS) technique was used for 29 Si, 27 Al and 13 C 9 NMR spectra with recycle delays between 10 and 60 s to avoid relaxation effects in the signal intensities. The chemical shift for 29 Si and 13 C were referred to tetramethylsilane and adamantane respectively. For 27 Al NMR spectra, a IM solution of Al(NO 3h was used as reference. Elemental analysis was performed by Galbraith Laboratories Inc., Knoxville, TN, and on campus using a single amu resolution quadropole Elan 5000 Inductively Coupled Plasma Mass Spectrometer (ICP-MS). ICP standards from VWR and Aldrich were used for calibration, and scandium was used as an internal standard to correct for drift during sampling. To prepare a sample for ICP analysis, the zeolite must be dissolved into an aqueous solution. One way to do this is to digest the zeolite with HF/HNO 3 in Teflon-lined, Parr autoclaves. 15 •16 The difficulty with this method is that silicon tetraflouride forms as a gas, and one can not accurately determine silicon values. Another method is to mix 20 mg of zeolite with 2 g of lithium metaborate and heat in a platinum crucible until a clear melt forms. 17 A pinch of cesium iodide is then added, and the melt is poured into a beaker of water containing 15% concentrated nitric acid and a teaspoon of tartaric acid. The melt dissolves and is ready for ICP analysis. This technique enables one to measure silicon and therefore calculate Si/Al. However, this technique deposits significant amounts of lithium into the ICP-MS, so a variation of this procedure was implemented. The zeolite was mixed with 2 g of potassium carbonate and heated in a platinum crucible until a clear melt formed. The crucible was cooled and then placed in water with stirring. 10 ml of concentrated nitric acid and additional water were added to reach 100 ml total volume. The solution was diluted and elements measured with an ICP-MS. 2.3 Ion Exchange All samples were ion exchanged two times with 0. lM NaCl for 24 hours at 80°C, unless otherwise stated. Copper acetate exchange was carried out at room temperature in 0.0013M solutions. The maximum copper exchange of a zeolite was controlled by varying the volume of the exchange solution, holding the copper concentration constant. The extent of exchange was determined by measuring the amount of NH/ or Na+ that came out of the sample during exchange and the amount of copper that was removed from the solution. NH/ and Na+ were measured by an ion chromatograph and copper by a UV spectrometer. A copper(!) ethylene complex [Cu(C 2H4 )(H 20)xt was generated and exchanged into samples 1, 2, and 4 by a multi-step process. The ethylene complex was generated by flowing ethylene through a reaction vessel containing copper(m perchlorate hexahydrate and copper powder 18 (see Figure 3). Methanol was then added through a serum cup to avoid exposure to air. The solution turned clear within an hour indicating that the copper(!) complex had formed. The reaction vessel was tilted, enabling the solution to filter through a frit and mix with the already dehydrated zeolite. The exchange and drying of the zeolite were performed under an ethylene atmosphere. 11 methanol f vacuum tilt Serum cup glass frit tilt Figure 3 Setup for copper ethylene complex exchange. 2.4 Catalytic Reactions Figure 4 shows the setup of the packed bed reactor that was constructed for catalytic testing. Mass flow controllers regulated the inlet gas flow rate, and an Aero Vac 2900 mass spectrometer system equipped with an electron multiplier was used to monitor the exit gases. Standard gas mixtures from Matheson were used to calibrate the mass spectrometer. The zeolite catalysts were compacted without binder into pellets which were subsequently crushed and size separated. The resulting particle size was -60/+80 mesh. Sample weights ranged from 20 to 150 mg. Catalyst pretreatment consisted of activation at 500°C under flowing helium for 3 hours. Reactions were run at 425°C to 525°C with flow rates from 25 to 120 ml/min, all containing 4% NO in helium. In order to eliminate the effects of mass diffusion in the reactor bed, reaction rates and turn over frequencies were measured for sample 1, ion-exchanged with copper acetate and copper ethylene. The reactor was operated as a differential bed, and the rate of NO decomposition was assumed to be independent of conversion. By using 20 mg of catalyst 12 (W) and varying the total flow rate (F), the conversion was decreased into the differential regime. NO, N 2, and 0 2 concentrations were monitored and used to calculate conversion. NOx REACTOR NO REACTOR APPARATUS © FUME Reaction Gos HOOD thermocouple lJ filter sample ~ moss flow controller t:kJ manual valve @ pinvolve lf NOsensor 0 3-woy valve reactor feed NO Furnace controller reactor product • vti t-AodEil · • : : : : :AV-2900 :. He Magnetic Sector Mass Spectrometer PC using AEROSCAN mass spec software to Serial Port 11 111, 1111111111 11 VTI 5.3 -7 1S -2 11 ■ ■• Q] AERO VAC ~ass Spec 35 oven 80 temp Figure 4 Setup of catalytic reactor. Can monitor all exit gases with a mass spectrometer. □ 111 13 3. Results and Discussion 3.1 ZSM-5 Samples For the Na+ method, TPA+ and Na+ balance the negative charge from the AIO4 units. The aluminum therefore need not be evenly distributed throughout the framework, because the Na+ ions are not confined to the pore intersections, like the TPA+ ions. Thus it is possible for several Na+ ions to balance aluminum atoms in one unit cell, while another unit cell may not contain any aluminum. For the F method only TPA+ balance the AIO 4 units, because NH4+ is the only other cation present and it has never been found to balance charges inside a zeolite during synthesis. In this situation, the aluminum must be evenly distributed throughout the framework, because the TPA+ ions are only located in pore intersections of the zeolite. This method also produces nearly defect free crystals. For the template-free method Na+ balance the negative charge from the AlO4 units, so again, uniform distribution of the aluminum throughout the framework may not occur. The multi-step calcination procedure reduced the extent of dealumination during calcination. Two steps are involved in the removal of an organic template. First, the organic turns to coke, and then, in the presence of oxygen, it oxidizes and burns out of the pores. The oxidation process is very exothermic, and although the oven is at 580°C, the temperature inside a pore of the zeolite may be much higher. This high temperature tends to drive aluminum out of the framework and create defect sites. So by first heating the samples in a nitrogen rich environment, the oxidation process is slowed down, keeping the pore temperature lower. dealumination still occurs. Yet even with this multi-step calcination process, some 14 XRD data show that all the samples are very crystalline before and after calcination and have the MFI structure. The high peak intensities for the F method samples are caused by the preferred orientation of the extra large crystals that this method produces. The weight loss in the TGA plots show removal of water and bulk removal of TP A, followed by removal of occluded organic species. The water content for most samples was 3% to 4% of the initial sample weight. The amount of TPA+ per unit cell was determined from the weight loss above 300°C (see Table 2). The samples containing TPA had between 2.7 and 4.1 TPA+ per unit cell, which is reasonable, as there are four channel intersections per unit cell. TGA was also run after calcination to determine the dehydrated weight of the calcined zeolites. All the samples, regardless of the synthesis method, had a dehydrated weight of 88% to 91 %. From the 29 Si MAS NMR spectrum the framework Si/Al was determined. The NMR data shown were taken by Hubert Koller. 19 Figure 5 shows the deconvolution of the NMR spectrum for samples 2 and 4. There are two Q4 peaks which represent silicon tetrahedra with no aluminum. The next Q4 peak corresponds to silicon tetrahedra with an aluminum [(Si-O) 3-Si-O-AI ]. Finally, there is a Q 3 peak which represents a silicon with a silanol or siloxy group [(Si-O)3-Si-OH or -0-]. This peak denotes the number of defect sites in the framework. From the figure it is evident that the fluoride sample has little or no Q3 peak, which corresponds to very few defect sites. The data for elemental analysis are shown in Table 2. The values with an asterisk were measured on campus and those without an asterisk were measured by Galbraith Laboratories Inc. Elemental analysis is another way to determine the Si/Al. However, this 15 technique does not differentiate between aluminum m the framework versus in the channels. The Si/Al values for elemental analysis are usually lower than those determined by NMR. Sample 4 and 6 after calcination is an exception with Si/Al = 36 and 69 determined by elemental analysis verses 32.5 and 56.3 determined by NMR. The reason for this exception is that these samples were calcined and ion-exchanged before elemental analysis. So any aluminum which came out of the framework during calcination was washed out of the zeolite during ion-exchange. Table 2 No I 2 Characterization Data for ZSM-5 Zeolites. 29SiMASNMR QJ / % Si/ Al QJ / % Si/ Al (as made) (calcined) ~3 11.5 16.5 22 11 3 4 ~23-30 <0.5 5 6 7 ~35-45 <0.5 29 6 29 4.6 32.5 <0.5 40.8 <0.5 56.3 <0.5 elemental analysis Si/ Al Si/ Al Al/ (calcined) u.c. 7.4* 12.( TPA+ I u.c. ----- 22* 4.4 4.2* 4.8* 3.1 3.7 2.6* 2.5* 3.9 2.3 1.4* 3.7* 3.9 3.7-4.1 ----- ----- 21 19* 25 36* 37* 41 25* *Elemental analysis performed on campus using ICP-MS . 69* TGA TPA+/ u.c. ----2.7 3.22 3.5-3.9 3.6-4.0 16 Si/Al~ 29 OH- mediated Q4 (OAI) Q3 (0A -90 -100 -110 6/ppm -120 -130 Si/Al~ 33 F- mediated -90 Figure 5 29 -100 -110 6/ppm -120 -130 Si MAS NMR spectra of ZSM-5 sample 2 (top) and 4 (bottom) with deconvolution peaks. 17 3.2 Ion-Exchange Isotherms 3.2.1 Copper Acetate Exchange The VAW sample was ion-exchanged with copper acetate from three forms: NH/, H\calcined), and Na+ (see Figures 6-8). This first test was performed to see if ionexchange depends on the cation being replaced. As shown in Figure 8, the maximum loading of copper is the point at which 0.85 of the aluminum sites have copper exchanged. The figures also imply that one copper atom exchanges for two NH/, H+, or Na+ ions, since the maximum Cu/Al is 0.41. We suspect that a copper complex of the form [Cu 2\H 2O) 5Offt---H+ is actually what ion-exchanged into the zeolite. In the VAW sample there are on average two aluminum atoms per intersection. So a copper complex of the above form could bridge two aluminum sites in a single intersection. --cu (determined by UV) . • • + • • NH4+ (determined by IC) C11 .. 1 ·. .. 0.8 • 0.8 ;!:: ~ C 0Cl) m .c u N >< -=<t 0.6 •• Cl) - 0.6 ~ 0Cl) N C = Cl) (U =:m 0CII C N ·= 0.4 0.4 .2 :i <i: 0 II) ::, -= 0 +,. ::c: 0.2 .. 0.2 z 0+---+----+----+----+-----+----+----+-~o 0 0.2 0.4 0.6 0.8 1.2 1.4 Cu in solution / Al in zeolite Figure 6 Copper acetate ion-exchange data for VA W NH4+ ZSM-5 18 1-+- Cu (determined bu UV) I 0.9 • 0.8 .. Cl) ::: 0.7 0Cl) N C 0.6 • -;; 0.5 ~ 0 :!l 0.4 C 0.3 ::I (.) 0.2 • 0.1 0 ·1 - - - - - + - - - + - - - - - + - - - - + - - - - f - - - - - + - - - - + - - - - ' 0.2 0 0.4 0.6 0.8 1.2 1.4 Cu in solution/ Al in zeolite Figure 7 Copper acetate ion-exchange data for VAW u+ ZSM-5 ----- Cu (dtermined by UV) • - + - • Na (determined by IC) 0.9 0Cl) N ·=ci: ~ 0Cl) N C . ... ..... .. . - ··· ····--•················· · 0.8 · Cl) ~ .. 0.9 ..•· ··· 0.7 . .. 0.8 • Cl) 0.7 Cl C CII fl 0.6 0.6 .c c., >< ... ~ CII N C 0 ·= Cl) , 0.5 . . Cl) 0.5 0.4 0.4 • ::, 0.3 0.3 (.) :;::: ::, ci: 0II) C + CII 0.2 • · · 0.2 0.1 0.1 0 z 0 0 0.2 0.4 0.6 0.8 1.2 1.4 Cu in solution/ Al in zeolite Figure 8 Cl) ;::: 0Cl) Copper acetate ion-exchange data for VAW Na+ ZSM-5 19 In the next step, copper acetate exchange isotherms were generated for samples 2 and 4 starting from the Na+ form. The Na+ form was chosen as the standard exchange state, because after calcination the samples made with TPA have Na+ and H+ balancing the Ar sites. Figures 9 and 10 show the isotherms for samples 2 and 4 respectively. It is clear that very little copper exchanges into the samples made with TPA, especially the fluoride method sample. The maximum loading of copper for samples 2 and 4 is the point at which Cu/Al was 0.18 and 0.12, respectively. In these samples, it appears that one copper atom exchanges for one Na+ ion. As mentioned in the introduction, transition-metals can hydrolyze water. So we suspect that a copper complex of the form [Cu 2+(H 2O)sOfft is what ion-exchanged into these zeolites. A zeolite with Si/Al ~ 24 has one or less aluminum atoms per intersection. So a copper complex of the form [Cu 2\H 2O) 5Offt--H+ could not bridge two aluminum sites because the aluminum atoms are too far apart. One problem with comparing these samples is that their Si/Al are not exactly the same. These particular samples were chosen because they have the closest Si/Al of the samples synthesized. However, in the calcined material, the VAW sample 1 has Si/Al ~ 16, the Na+ method sample 2 has Si/Al ~22, and the F method sample 4 has Si/Al ~33. Unfortunately it is not possible to synthesize samples by templated methods with Si/Al below 20 or so. For the F method it is difficult to make samples with Si/Al below 30. 20 1,;::=========;------------------,---- Cu (dterrnined by UV) o.9 . . 1·· + ·· Na (determined by IC) ~ 0 :!l .!: I 0.9 0.8 0.8 0.7 0.7 0.6 • 0.6 Cl) Cl C Cll .c ~ ... ::: 0.5 £ °g Cll N Cl) '; 0.5 :!:: 0 :!l 0.4 0.4 C 0.1 g ·= ~ ct 0 8 0.3 . 0.2 • Cl) 0.3 ~ + Cll - - •····· ···· ··• ··· ·· · · · ··· ....... . . . . . .. . . . .. . . .. ./ ··· · > ····· ·· ·< ·· . •····· · 0.2 Z 0.1 0t----+----+----+----+----+----+----+--~o 0 0.2 0.4 0.6 0.8 ·1.2 1.4 Cu in solution/ Al in zeolite Figure 9 Copper acetate ion-exchange data for sample 2 from the Na+ form. ---- Cu (determined by UV) · · + ·· Na (determined by IC) .. 0.9 0.8 .. . . 0.8 0.7 • 0.7 0Cl) N C 0.6 • 0.6 - ~ ... ::: 0.5 £ g Cll N Cl) 0.5 • 0.4 . 0.4 ·=::s 0.3 .. 0.3 0.2 • 0.2 N C Cll :!:: 0Cl) Cl .c ct Cl) Cl) Cl) :!:: Cl) g ·= ~ ct 0 0 Ill ·= + Cll ,..,_.....-,----.:.·· · ·· -· •··· · ·· - - -• 0.1 Z 0.1 • -- - - -- --- --♦- - -· 0 +-----+----+-----+----+-----+----+-----+--~o 0.2 0 0.4 0 .6 0.8 1.2 1.4 Cu in solution/ Al in zeolite Figure 10 Copper acetate ion-exchange data for sample 4 from the Na+ form. 21 3.2.2 Copper Ethylene Complex Exchange One observation worth noting about sample 1 after copper ethylene exchange is that when the dried zeolite was removed from the flask, its color was white, and a few hours after contact with air, it turned yellowish-green. This probably has to do with the removal of ethylene from the copper complex. 13 C NMR did not indicate the presence of ethylene inside the zeolite after exchange and exposure to air. A sample was also prepared for NMR in a glove box directly after ion-exchange. This spectrum, which was taken under a nitrogen spinning environment, showed the presence of methanol, but no significant amount of ethylene. Ethylene desorption was also checked for during activation by mass spectrometry, but no increase in ion current for masses 28, 27, 26, and 14 were observed up to 500 °C. Elemental analysis was performed on samples, exchanged with the copper ethylene complex and with copper acetate, to determine the extent of exchange (Table 3). A Cu/Al of 0.74 for the VAW sample 1 exchanged with the copper ethylene complex is almost twice the Cu/Al value of 0.41 obtained by ion-exchange with copper acetate. The same is true for sample 2. Thus higher copper loadings are attainable by exchanging with the ethylene complex ·because copper is in an oxidation state of one. To balance the charge from the same number of aluminum atoms, it takes twice as many copper ethylene molecules as copper acetate molecules. The very low values for Na/Al led us to believe that total sodium exchange was not taking place. For high silicon content zeolites, it is very difficult to ion-exchange certain cations. However, elemental analysis before copper exchange showed that the Na/Al was 22 0.75 or higher. Sodium exchange with O. lM NaOH (pH=13) was also tried, but gave Na/Al values much greater than one, indicating that NaOH had been occluded in the zeolite pores. Copper acetate exchange data from elemental analysis is consistent with the results found from the ion-exchange isotherms shown previously. Table 3 Elemental Analysis on Copper Exchanged Samples Sample exchange method Si/Al Cu/Al Na/Al 1 (YAW) ethylene complex 12.3 0.74 0.0 ... 1...(VAW) ............................copper.acetate ......................... 1.1_.8 ............................. 0.4} .................................0.05 .................. 2 (Na+ method) ethylene complex 22.1 0.38 0.0 ... 2...(Na+. method) .............copper.acetate ........................ 23.4 .............................0._16 ................................0.33 .................. 4 (F method) ethylene complex 35.8 0.0 0.07 4 (F method) copper acetate 32.8 0.0 0.93 3.3 Catalytic Studies on Cu-ZSM-5 3.3.1 Sample Reactivity Samples 1, 2, and 4 were tested for catalytic activity in the packed bed reactor. Figure 11 shows the reaction run for sample 1 after exchange with the copper ethylene complex. The conversion was calculated from the decrease in NO concentration during the reaction. Table 4 lists the conversion, the copper weight percent, and the conversion per mole of copper in the zeolite. The conversion per mole ofcopper is on the same order of magnitude for all the samples that were reactive. It is clear that samples 2 and 4 take in little or no copper during exchange and therefore have very low conversions. 23 1.00E-10 N2 02 1.00E-11 H20 C 1.00E-12 Cl) ,_ ,_ ::::J 0 C: _2 1.00E-13 N02 1.00E-14 - 1.00E-15 + - - - ½ - - - - - + - - - - - - + - - - - - - - + - - - - - - 1 - - ¼ - - - - - j 0 50 Reaction Started 100 150 200 Time (minutes) 250 Reaction Stopped Figure 11 Reaction run for sample 1, ion-exchanged with the copper ethylene complex. Table 4 Reaction conversions Sample 1 (VAW) 1 (VAW) 2 (Na+ method) 4 (F- method) Ion-Exchange Method copper acetate ethylene complex copper acetate coeeer acetate Conversion 24 29 2 0 Cu wt% 3.3 5.5 0.7 0 Conversion/ mole Cu x10" 5 3.1 2.2 1.2 3.3.2 Differential Reactor Regime Figure 12 plots conversion versus W/F for three different weights of sample 1 ionexchanged with copper acetate. It was necessary to decrease the sample weight because even with a catalyst weight of 20 mg and a flow rate of 125 ml/min, a conversion of 4% 24 was obtained. Samples weighing 20 mg were used to determine rates and turnover frequencies for sample 1 exchanged with copper acetate and copper ethylene, see Table 5. Reaction rates were determined from the decrease in NO concentration and also from the increase in N2 and 0 2 concentration. The rates were calculated by finding the slope of the best fit line through the origin and the three lowest W/F data points (F = 80, 100, and 120 ml/min), see Appendix VII. Turnover frequencies were calculated from the rate data using the Cu/Al values from elemental analysis. The turnover frequencies are plotted versus temperature in Figures 13 and 14. The TOP passes through a maximum as a function of reaction temperature, which is in agreement with plots reported in the Iiterature. 12 45 • 40 • 35 • slope= -rA 30 • y C: 0 "iii 25 • ... Cl) > C: 0 • W=0.15 20 (.) 15 • • 10 5 0 ----+---+-------<----+---+-----+----+-------<----+-----< 7.00 9.00 10.00 0.00 1.00 2.00 3.00 4.00 5.00 6.00 8.00 W/F (g*s/ml) Figure 12 Conversion versus WIF for VA W sample 1. Temperature was 502°C 25 It is clear from Table 5 that the rate for the copper ethylene exchanged sample is almost double that of the copper acetate exchanged sample. frequencies are very similar. However, the turnover This shows that although the copper ethylene exchange method greatly increases the copper weight percent in the sample, the activity of each copper atom toward the decomposition of nitric oxide is the same. Table 5 Reaction Rates and Turnover Frequencies 525 500 475 450 425 Rate x 106 (moles NO I g cat* s) Copper Copper Acetate Ethylene Decrease in NO Concentration 5.98 12.4 5.98 13.1 5.72 10.6 4.12 8.98 3.98 6.63 Copper Copper Acetate Ethylene Decrease in NO Concentration 1.21 1.39 1.22 1.48 1.16 1.19 0.837 1.01 0.809 0.747 525 500 475 450 425 Increase in N2 Concentration 5.13 8.30 4.48 7.98 3.83 6.39 3.42 4.69 3.04 3.78 Increase in N2 Concentration 1.04 0.934 0.910 0.899 0.720 0.778 0.528 0.696 0.425 0.618 525 500 475 450 425 Increase in 0 2 Concentration 1.93 4.94 1.29 4.25 0.775 2.56 0.445 1.18 0.341 0.557 Increase in 0 2 Concentration 0.392 0.557 0.262 0.479 0.288 0.157 0.0904 0.133 0.0627 0.0693 Temperature (OC) TOFx 102 (s-1) 26 1.60E·02 1.40E·02 NO ♦ 1.20E·02 ♦ ♦ ■ N2 - 1.00E-02 1n ~ 8.00E-03 0 I- • 6.00E-03 • ♦ ♦ • • 4.00E-03 • 0 2 • 2.00E-03 • 0.00E+OO 500 550 600 650 • 700 • 750 800 850 900 Temperature (K) Figure 13 Turnover frequency versus temperature for VA W sample 1 exchanged with copper acetate. 1.60E·02 ♦ 1.40E-02 ♦ 1.20E-02 --en u. ♦ NO ♦ 1.00E-02 • • 8.00E-03 ♦ 0 N2 • I6.00E-03 • • 4.00E-03 2.00E-03 0.00E+OO 500 550 600 650 700 750 800 850 900 Temperature (K) Figure 14 Turnover frequency versus temperature for VAW sample 1 exchanged with copper ethylene. 27 The temperature dependence of the activities was determined by generating arrenhius plots (ln(rate) versus lff), see Figures 15 and 16. The activation energy of the reaction can be calculated from the slope of the best fit line. 20 The data point at 525 °C was not used in the line fit because the rate started to decrease with temperature at this point and therefore departs from arrenhius behavior. The values for the activation energies are reported in Table 6. It should be noted that these activation energies are two to three times lower than expected. One possible explanation is that the experimental data used to calculate these values were taken at temperatures near the reaction rate maximum and were not in the arrenhius region. Another point worth addressing is why the rates calculated from the decrease in NO do not match those calculated from the increase in N 2 and 0 2. From Figure 11 it is seen that N 2 and 0 2 are not the only products of the decomposition reaction. Nitrous oxide (N 2O) and nitrogen dioxide (NO2) also form in significant quantities. It appears that more NO 2 forms than N 2O which would explain why the conversions calculated from N2 are higher than for 0 2. In order to quantitatively confirm this the mass spectrometer needs to be calibrated for N 2O and NO2. Table 6 Activation Energies (kcal/mole) Copper Acetate Copper Ethylene Decrease in NO Concentration 6.36 9.41 Increase in N2 Concentration 5.21 10.8 Increase in 0 2 Concentration 18.6 29.3 28 -0.5 -1 -1.5 - NO ♦ -2 Q) ~ -2.5 •• .5 -3 • ♦ • -3.5 -4 -4.5 • -5 ·I - - - - - + - -- + - - - + - - - - + - - - + - - - > - - - - - + - - - + -- - - + - - - - - - < 1.24 1.26 1.28 1.3 1.32 1.34 3 1.36 1.38 1.4 1.42 1.44 1 1/T X 10 (K" ) Figure 15 Arrhenius plot for VA W sample 1 exchanged with copper acetate. 0 -0.5 -1 . ♦ -1 .5 -- -2 Q) A • I ll ,!::. -2.5 • .5 -3 -3.5 -4 -4.5 -5 1.24 1.26 1.28 1.3 1.32 1.34 1.36 1.38 1.4 1.42 1.44 Figure 16 Arrhenius plot for VA W sample 1 exchanged with copper ethylene. 29 4. Conclusions and Future Directions 4.1 Conclusions Direct decomposition of nitric oxide by copper ion-exchanged ZSM-5 was investigated. It was found that ion-exchanging with a copper ethylene complex doubles the copper content in the zeolite because copper is in an oxidation state of one, and can only balance the charge from one aluminum atom. The reaction rates also double for these samples, however, the turnover frequencies are similar to those obtained by samples exchanged with copper acetate. Samples prepared using TPA were found to have poor ion-exchange properties and therefore low activities toward the decomposition of NO. It is probable that TPA forces the aluminum in the framework of ZSM-5 to be more uniformly distributed than in a template free synthesis. It is possible that in the template free samples there is a high concentration of aluminum near the outside of the crystal. Copper can then easily exchange onto these sites, whereas aluminum in the center of the crystal are much harder to ion-exchange with copper. 4.2 Future Directions 4.2.1 Exchange on Different Si/Al Samples All the ion-exchanges performed have been on samples with Si/Al between 16 and 32. If the charge on a Cu +2 ion is balanced by charges created by two framework aluminum atoms, then a sample with a Si/Al = 40 should result in very little or no ion- 30 exchange. A sample with Si/Al ~ 40, prepared by each of the three methods, could be ionexchanged and tested for activity. Since high copper loadings are attainable in the VAW sample, it would be desired to attempt ion-exchange on other samples with Si/Al= 12, but it is not possible to synthesize these samples via the Na+ or F templated method. 4.2.2 Temperature Programmed Desorption of Isopropylamine (IPA) TPD experiments are another method for determining the amount of aluminum in a zeolite and could be conducted in the same fixed-bed reactor described above. TPD is performed on the acid form (H+) of a zeolite. IP A is chemisorbed onto all the acid sites (Ar and defect sites SiO-) and quantitatively measured as it desorbs from these sites during heating. From past experience by Kam-to Wan in our lab, it is known that IP A desorbs from Ar and SiO- sites at different temperatures. Thus, TPD will accurately determine both the number of aluminum sites and defect sites in ZSM-5. This technique combined with Si NMR should produce reliable data for defect concentrations. The procedure is to activate 50-100 mg of sample by heating under a flow of dry He to 300°C at 10°C/min. Next, the sample is cooled to 35°C. 75-150 µI IP A is introduced into the helium stream and the He flow continues over the catalyst for 1.5 hours to allow removal of any physisorbed IP A. The TPD is conducted by elevating the temperature at a rate of l 0°C/min to 630°C. The desorbed gases are analyzed by a mass spectrometer. 31 4.2.3 Activity of Other Copper Ion-Exchanged Zeolites It was found that NU-87 is active for the direct decomposition of NO. It would be helpful to test other zeolites with similar structure-property relationships for NO reactivity. The objective would be to try and predict which zeolites will be NO active before testing. Another experiment would be to try and ion-exchange copper onto defect sites. ZSM-5 can be prepared with born-silicate. The boron can be removed by treatment with HCl, creating a defect site. Sodium can then be exchanged onto the defect sites by exchanging with sodium hydroxide. Copper can be exchanged by the usual procedure. The activity of this sample might determine whether a copper atom must be coordinated with an aluminum atom for the site to be active. 32 5. References Li, Y.; Hall, W. K. J. Phys.Chem. 1990, 94, 6145. 2 Sandler, S. I. Chemical and Engineering Thennodynamics, Wiley: New York, NY, 1989, 604. 3 Moelwyn-Hughes, E. A. Physical Chemistry, Pergamon: London, 1961, 989. 4 Winter, E. R. S. J. of Cata!. 1971, 22, 158. 5 Davis, M. E. Ind. Eng. Chem. Res. 1991, 30, 1675. 6 Thome, R.; Schmidt, H.; Tissler, A. U.S. Patent No. 5,089,243 1992. 7 Larsen, S. C.; Aylor, A.; Bell, A. T.; Reimer, J. A. J. Phys. Chem . 1994, 98, 11533. 8 Iwamoto, M.; Yahiro, H.; Tanda, K. ; Mizuno, N.; Mine, Y.; Kagawa, S. J. Phys. Chem . 1991, 95, 3727. • 9 Li, Y.; Armor, J. N. Appl. Cata!. B 1993, 2, 239. 10 Li, Y.; Armor, J. N. Appl. Cata!. B 1993, 3, LI. II Shpiro, E. S.; Grunert, W.; Joyner, R. W. ; Baeva, G. N. Cata!. Lett. 1994, 24, 159. 12 Valyon, J.; Hall, W. K. Cata! Lett. 1993, 19, 109. 13 Li, Y.; Armor, J. N. Appl. Cata!. B 1992, I, L31. 14 Li, Y.; Armor, J. N. Appl. Cata!. B 1993, 3, L55. 15 Bernas, B. Anal. Chem. 1968, 40, 1968. 16 Corbin, D.R.; Burgess Jr. , B. F.; Vega, A. J.; Farlee, R. D. Anal. Chem. 1987, 59, 2722. 17 Feldman, C. Anal. Chem. 1983, 55, 2451. 18 Ogura, T. Inorg. Chem. 1976, 15, 2301. 19 Koller, H.; Lobo, R. F.; Burkett, S. L; Davis, M. E. J. Phys. Chem. 1995, 99, 12588. 20 Hathaway, P. E.; Davis, M. E. J. of Cata!. 1989, I 16, 263. 33 Appendices Appendix I. List of Chemicals Used Aluminum hydroxide: Reheis Inc. Aluminum nitrate nonahydrate: 98+%, Aldrich Ammonium fluoride: 97%, Aldrich Cesium iodide: 99.999%, Aldrich Colloidal silica (SiO2): Ludox AS-40, 40% SiO 2 in aq. solution, DuPont Copper powder - 150 mesh: 99.5%, Aldrich Copper(II) perchlorate hexahydrate: 98%, Aldrich Cupric acetate monohydrate: EM Science Fumed-silica (SiO 2): 99.8%, Cab-O-Sil MS, Cabot Corp. ICP Standards: aluminum, calcium, copper, scandium, silicon, sodium 1000 PPM, VWR L-Tartaric acid: 99.5%, Aldrich Lithium Metaborate: 99.995%, Aldrich Methyl alcohol anhydrous: 99.9%, Mallinckrodt Nitric Acid: 69.6%, Mallinckrodt Nitric oxide: 14.8% balance helium, Matheson Potassium carbonate: 99.99%, Aldrich Sodium chloride: 99+%, Em Science Sodium hydroxide: 50% (w/w), Mallinckrodt Sodium hydroxide: Em Science Tetrapropylammonium bromide (TPABr): 98%, Aldrich Water: distilled and deionized 34 Appendix II. List of Samples psa Samples HKb Gel Si/Al 1 Synthesis Method YAW 2 Na+/TPA 20 PS00l PS007 PS013 PS015 HK113 3 Na+/TPA 40 PS003 PS008 HK114 4 F-/TPA 14.9 PS005 PS009 PS014 PS016 HK109 5 F-/TPA 23.8 PS004 PS0l0 HK108 6 F-/TPA 40 PS006 PS0ll HKll0 7 Na+ template free 18 PS012A Sample No aSamples prepared by Peter Seidel bSamples prepared by Hubert Koller Samples 35 Appendix III. Characterization of Samples XRD Sample as made VAW PS00l PS003 PS004 PS005 PS006 PS007 PS008 PS009 PS0IO PS0l 1 PS012 PS013 PS014 PS015 PS016 X HK113 HKl 14 X X Cale after TGA X X X X X X X X NMR TGA as made Calcined 7 Elemental Analysis Galb Peter Seidel as made Cale• Na+ z9Si "''AI -"YSi X X X X X X X X X X X X X X X X X X X X X X X X X "' Al as made X Cale· Na+ X X X X X X X X X X X X X X X X X X X X X X X X X CP HK109 HK108 HKllO as made X X X X X X X X X X X X X X X X X X X X *samples were calcined and ion-exchanged with sodium chloride X X 36 Appendix IV. X-ray Powder Diffraction Patterns VAWNH4+ PS00 1 as made PS00 1 Calcined PS00 1 after TGA PS003 as made PS004 as made PS005 as made, PS006 as made PS007 as made PS008 as made PS009 as made PS0 10 as made PS0 11 as made PS0 12 as made PS0 13 as made PS0 14 as made PS0 15 as made PS0 16 as made PS004 after TGA PS005 Calcined 2.976 2.562 2.252 2. 13 0.0 344.8 689.6 1034.4 1379.2 1724.0 \J~ i I~ I 0 10 20 30 40 50 60 2068.8 I 70 2413.6 I I 1.823 % 100 80 3.559 I 4.436 2758.4 5.901 SCINTAG/USA WL: 1.54060 i- 90 8.838 STEP: 0.03000 I 17 66 ID: NH4ZSM-5 YAW SI/AL=11 TIME: 14: 46 PT: 0.45000 3103.2--t PS 3448.0 FN:HKAA102.RD DATE: 12/01/94 \.,.) -..) ~ 1 3.559 0 10 500.0 O I 1 1 1 1 1 1 1 I 1 1 1 1 1 1 1 1 q - r T n I I rrr-r, -----'5.___ J_o________J,_q ___ ____ _ao._________ 2_5____ __;3.Q _ _ 20 1000.0 -vv. 30 90 i 1.823 % I 1100 1500.0 2.y13 40 C. . /1 ,;J / /'. ,,.,1.,.,,,!fl'.Y(Y I 2.252 2000.0 I 2 . 562 50 I 2.976 2500.0 I 60 I 4.436 3000.0 I I 70 5.901 8.838 3500.0 17i66 STEP: 0 . 03000 SCINTAG/USA WL: 1 . 54060 80 I ID: PS001A AS MADE TIME: 15: 12 PT: 0 . 45000 4000.0 4500.0 PS 5000. 0 FN: PS001A.AD DATE:03/04/95 v.) 00 I 1 1 ; I n t 14 n t \, 1 . . . ~ ~vWVJJJ l Vt w~ 1 I ~ dJ 1 Pl~ I 2.562 __j_ 2.976 - 2.252 0. oJ I I I r T - r r r , r , - r , I I r-f"TTT71··-r,7-rrTTT-.-r7 I I I ' I I .___ _ ____,5,:__ __,,1_Q 15 ~o 25 ----~Q______ 35 ~- 336.8 1• j i I 11 1 11 - 1~ H11 i 1i I :, :i. jlI i_ t ~ i: ij l :1 '· il H r~ l1,, ~ ~ ,, I I I t i! I 3.559 l111n I 4.436 673.6 I 5.901 ·: :~i·-: q ,. Ii 1~ '1 ~ ilj 1 ll ~,. .. I 1 -- I 8.838 •l H 17(66 IO:PS001 AFTER CALINATION 560 C TIME: 12:40 PT: 0.45000 STEP:0.03000 1010.4 1347.2 1684.0 2020.8 2357.6 j 2694.4 3031.2 3368. O PS DATE:06/21/95 j FN: PS001C. RD L I 415 QQ O 10 20 30 40 50' 60 70 80 90 I % 100 1. 623 t I , I T~j M 2.013 SC INT A-G/USAJ WL: 1.54060 V,) \0 i l ,I 800. 0-1, 600 • O-f \ I ti li !~I ; Ii ii Ii 'I I· ,. -' 2.562 2.252 2.013 1.823 % 100 60 0 r 10 r 20 t- 30 t- 40 ~ 501 0.0 I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I 35 r~ I 1000 .o; 1200.0-f I 2.976 70 3.559 1400.0 4.436 80 5.901 WL: 1. 54060 1600.0 8.838 STEP: 0.03000 SCINTAG/USA 90 17.66 ID:PS001 TGA 900C TIME: 10: 49 PT: 0.45000 1800.0 PS 2000.0 FN:PS00.18.RD DATE:05/.11/95 ~ 0 FN:PS003A.AO DATE:05/10/95 IO:PS003 AS MADE TIME: 21:08 PT: 0.45000 STEP:0.03000 SCINTAG/USA WL: 1.54060 jl i 2.562 I I ' ; ; ,, I: !f i :: i l j j ; j I ; 1; ~ 2.252 I 2.013 I 1.823 % ~100 0 10 20 30 40 50 60 70 L-~L.._:_ WU 1 ~---~,,,.::t ... _ _ ..~v!..,__..t.-~ ... 2.976 I r1 I I 1 1 r ~ ,........__ -; \. ____o.o ___,_ _ 5 .10____ I I I I I r r·1 I I I I "T I 1 I 1 17 ...,,,.Q ___ ____zo.____ ~s a • 580.0 1160.0 1740.0 2320.0 2900.0 j' i\ ,I lj I, l! 13480.0 11 !; l 1: 1! !\ I 4060.0 Il. i; II 3.559 ! 80 4.436 4640.0 5.901 90 8.838 5220.0 PS 17[66 5800. 0 I ! - - -,_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ____ _ _ ___ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ , ~ - ID:PS004 AS MADE TIME: 21: 53 PT: 0.45000 STEP: 0.03000 ! 1 ,... 1 o. o-rn 2200.0 l 1 , 1 , · r r ,· rr r·.,-,rr r - -·- -----·6.. __--1.(L ___. _tel ___ _gp i lj • .....,.,v 1··1 ..,. 1 - ~~ ~ r r• rrf 2G.____~ - , r 7 - r - r r T r 1 45 i Ii ~ ~ l l 11rr I I _Q.. _____;,.5 40 .5 20 .I JJ 30 6600.0 4400.0 40 8800.0 I 501 j ~1000.0~ -~U\l'--"'1~1...HW 60 I h3200.o I 70 90 l % 100 1.823 r5400.0j ~~ 2. r7s __ :_:1s2 -=~~=- 2. o13 80 •J I a. ees- ·-~:.r~-~--~~f.3s ____ :.:.~-~~ SCINTAG/USA WL: 1.54060 17600.0j ! 1 . ,_:~ 1ss 00 0 ~saoo oJ l ~~~ il l l r-•- ·- •- --------~-· - --·- ·-·•· - - · - -· --··. .--.------·•·- ··•-·•·· · - -··--·- - rFN:PS004A.RD / DATE: 05/10/95 .p... N 40 30 20 10 0 2920.0 2190.0 1460.0 730.0 0.0 I 1.823 % 100 so· 2. 13 3650.0 2.252 60 2.562 4380.0 2.976 70 3.559 5110.0 4.436 80 5.901 5840.0 8.838 SCINTAG/USA WL: 1. 54060 90 17 66 ID:PS004 AFTER TGA TO 700 DEG C TIME: 15:32 PT: 0.45000 STEP: 0.03000 6570.0 PS 7300.0 FN:PS00481.AD DATE: 05/11/95 .J:::,. w I -- 4.436 I 3.559 1!111 I II 960. 0-1. 0.0 I m'!it ·i I ~ I 2.976 2.562 2.252 STEP:0.03000 M 2.013 0 t- 10 t- 20 t- 30 t- 40 ~ 50 t- 60 t- 70 t- 80 90 I 1.823 % 100 SCINTAG/USA WL: 1.54060 I, I~~,~~~~\ ( I I I I I I I I I I I I I I-,-, I I,-, I I I I I I I , -1 ~ 1 ..1v· ; 1 1'1 ~ I ... J ~~ ' 111 1920 . 07 1 I II ,I ~ 2880.07 3840.07 5760.07 li '11 5.901 4800.07 8.838 Ij 17.66 ID;PS005 AS MADE TIME:22: 13 PT: 0.45000 6720.07 7680.0 8640 . 0 9600.0 PS FN:PS005A.RD DATE:05/10/95 .p.. .p.. ' ! 10 15 20 .4!i 2.013 5 70 80 90 '·t ijll ii { ! i I ,ii, ,. l i, !. 2G 30 ~5 40 0 10 20 30 40 I I 1.823 % 100 50 2.252 11 2.962 60 2.~76 SCINTAG/USA WL: 1.54060 ~ ii ~t ii 3.Q59 JJJ1UU it\JWL.J.Jk-- ;, _ _ \.1 ' I ii I r 4.~36 0. 0 I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I 995 .17 1990. 27 2985.3 I ,j ;· ., 3980.4 ,l Iu'I 11 ft ~ ~ I ~ 1 .: l i 5.~01 ID:PS005 AFTER CALCINATION 560 TIME: 12:58 PT:0.45000 STEP:0.03000 8.838 4975.5 5 17,66 ~ 5970.6 6965.7 7960.8 8955.9 PS 9951.0 FN:PS005C.RD DATE:06/21/95 +"VI FN: PS006A. RD 17 .66 I ! . I /'. ~ . ;t . I 4 l'Ui 2.y13 ~ 1, ~ I 2.252 ~ J j 70 80 90 1.823 ~ I -r-100 0. 0 I • I • 1, i 1 I t i.• ' ~ t •' • • i • '; : • ,i:• .i ' ' i 1 \,.Ju,_ , I i I I ,-rTTTT-ra7-rT·-r--r,-,-r-r I I I I r 1··1-n-T,Tl I I I I I I I I I I I I I I 1•• 5 1o..._____-3..5 _ ___ __~_ZQ ___ ,____.2_~------~.Q__~ 4 0 4~. ~JL. ~ v \J....J\.1.JJJ,e_J.Jv,,,JVJ ' 1', .h l•...,M1,.,.....1c..}V 990 • 0 i:.~ ;;;_-'1. i;•• •' •· _:.· ii I 1eeo.o I• :. , ~i I, 1 l' · l. jf,'· I :,·: ,::: 0 10 20 30 40 f_ 2.562 3960.0 4 2.976 50 lt 3.559 ' 2970 . 0 j 1 I 4.436 4950.0 i} L_,_ 5.901 SC INT AG/USA WL: 1. 54060 60 I 8.f38 TIME: 21: -~-~ ____ PT: 0. 45000 _____S_TE~~-· 03000 ID: PS006 AS l'-·IAOE 5940.0 6930.0 I 7920.01 0910.0-, Ieeoo.orl--, bps I l If DATE: 05/10/95 .+:>,. O'I 17.66 B.838 i l I II I I I l 2.552 • •r- · ·• • 2.252 • • • 2.013 , 1.s23 60 70 80 90 % I 313. 31' i I ~I j I 10\ I I ~ 20 30 L .......... ~---·~ _--~~~:_r·~.ls~~:1_~~~~-~-l~~~-~-.-~:~ :r:;i~~~1·:1 --·~-·~~1··.~-r .~1·~-;~.~~.~-~--j;~~-=~~~~.~l-~jlQ'_~..-~...'. J.i_'.._.~ .. '..d Q ~ : I I I I 626.6~ 939.9 40 2.976 1?.53,2 3.559 r ·- L ·- · · · · · L. ··- ··----· L .. ·-·-·• ---1 .•••.•.•..--L--.-·------··•J.•r100 501 4.136 . ·-- I . . I 1566.0j ! 1s·/9. s-; I : 12193.!~ ..') • ,--l i I I. 2 i··os i i 2f.H9. 77 • 5.901 j 3133. O,' .... -.1 ... .... _...... L ..... -.. . l . . bPs I .. SCINTAG/USA STEP:0.03000 WL: 1.54060 • · .. . . . . ........ .. ... ............. .. • - - - - - · · · " • ..... ... ...... ·- ··-· .. . .• -- .. ----··--·····-··•--············· ···-····- -· ·-· ...... ... ..... ...... .......... ... ..... -·· .... ......... . ........ ··-··· ... ........ ....... ·--·-···•·--··•·---·........-.........-·-----·--·. ·•··-·----1 ! FN: PS007A.R0 ID: PS007 AS MADE :'-··-·-·DATE:07/31/95 TIME: 16:04 PT: 0.45000 ... . · --- ... .. ·· ·- -·· ........ . .. ... . ..... . . . . . .j::.. -..I 17.66 8,838 I -- 2.~52 - .. J - 2.252 2.013 1.823 %l I I i , t..-::>oo 6. • a -7I 5 10 15 ?O 25 30 3~1 . ...4.0_. ·- ...... .. ~5. . ·--·-·· . ~0 ···-··--·· 0 r- 10 i i l t- 20 I I I i ~ 30 o.o~-- r··r· 1 r-,-r - ,·-,T ,-r , - , · I ·1 r ·1 I I r·1 T("T i 1· ,-, r ·r ·rTTTT"177"TT I I I I I I I I i I i br.)1.77 1003. ,1 i I 150fa.1-j I l i 40 i I II 60 70 ~ 50 i I 250A • 5~I i 3010.27 i II 3511. g-i I I 1 I I I - ··· ·-J·•--··-·-··--j_--- -·-·--·-.J·-r1oo l J I 80 2. □76 -1013.oi I 3.559 I . WW -- . 1.54060 . ·· ij 90 I I -· I . STE~ 0.03000 : 4515.3~ 1.~36 I p~ 0.45000 5.901 TIM~ 1~23 0017.0•, ·· ······ I -·-· .._ I . .. . .. CPS DAT~07/31/95 FN:-Psooai~Ro··· •· · . .. ---- -• 'io:.Ps·ooa···As· MADE - -· • • - ••• - ·····-- • •••• --·-· •••• -· -·· ··-------·-sc:"1NTAG/USA-1 +:- 00 0.0 I 1066.2 2132.4 3198.6 . , :: ' I ., i( " • ~ .. 1 • ' ,, ' I'I • ·• ' I ' \ ~ -' I 11 : , ;'·i 'I j; I' I [ 'j i)[ ; II' qi ! •·,1 •' i""t~ ·~ ,v.r~t.'·~. v··~ . ~'i'1:;:C;::;::1 ·1 :''I --- ,i •• I I . I 1 / J11 ' , ·----- ~ .,,;-".';-''.'"~-7 -,'.'l' ,~__,v-: . · ,--r~ : i· J ;: ' l ' , ,. \i I ., I I/ :i 0 10 20 30 40 4264.8 1.823 1 100 50 2.013 5331.0 2.~52 60 2.~62 6397.2 2.~76 70 a.~59 7463.4 4.~36 80 s.eo1 WL: 1. 54060 SCINTAG/USA 8529.6 8.838 STEP: 0.03000 90 17.66 PT: 0.45000 ID: PS009 AS ~ADE TIME: 13: 05 9595.8 PS 0662.0 FN: PS009A.AD DATE: 08/08/95 ~ \0 - r".)'' .v 2~·i 11; 2.252 2.013 1.823 l l % . . -· . -1 .. ... .. ···-L--- · .... Lr• 00 I ,l 2.56? I .. ···· - . l. 2.876 i i 2173.i': , 43 °17. -<17 I I 6521. 11 i I i a-t I ; 1086t~. 07 i 130'1?.27 I II I •::, ;I. ~J. r.;: n--1i ... l. . J 1 f, i l ::.17]f1!3. E,·...; , I . I I I ! • o I ~ ,'-i"i l I '"l'T fft 'i'f'Y"I I cl . ~j~'j ~o .4 0... j 0i :- .10 ~ 20 ; j 1 I •10; i 30, . L I rI 5ol• I I lI I I i [" 60 \ l • I II (_ 70) l l l • l,... 80]l .. '.-3 . !.) ~) 8 I .. I 1 i) .. l : j. ,)3fi STEP: 0 . 03000 1- 90 1 / J 9~':i53. ~i7 : 8694. I ~j.901 PT:0.45000 , SCINT AG/USA l WL: 1 . 54060 l .... .. - ·-···· ·- · .... . -··•···· ... · · · ·•· · .. ! I I I 17.66 8.838 21"/31 .o ·, ·· ··-·I ·· · ········-1 •• CPS TIME: 10: 14 •• ID: PS()~S MADE 0 Vl i 1 1 ,~. ¥-: :::j I :•1. L>~ l ~ ) i - i. ,~ . L) f ;.:·: ~, c. o 13 1 . a') :1 - ~J , ~ .. L-. .... __ ____ ... L............ L.,. 100 'J -:-;c:; ~ • ~-~~~ I :. v I ! •;_ ~; • .., -1 (.J .v . I 1 ~~ :j C- . ~.i ,···-· ~; ;:,; .. ~ ~-• . ., ... I'!(.; a: (r.;i .!.' PQO ,.J • ~ ~7uv. o-\ 1 ! 1 ! 1 1 l t i "" ,~O I :➔ n (;Q. O--' ~j (j(;. i)- ... 30 : -'iL:00. ::r' ; . . 50 : ~w : 1 S"! OU. o-.; 601 i i 701 ! i ' l . \ -.➔ .::, Fi~➔ JC . (; -i I - ·, . r·; BO ;! I ~~ . ~j :) 1 /?vv. u· ... I. 8. 83£~ WL: 1 . 54060 : -- 90 ! ! ~ .11.6~ I STEP: 0.03000 ··· • · ·, SCINTAG/USA i .... . -~- --· -··. ~-- . ..... ·- - - --~. -·· -- • • c :ti.:O. 0-; q,);j(J. 0 {~P :; I D : ~ A S MADE PT:0.45000 TIME: 1 ~ (' <.1',Vec-t VI - I I 10 0 o.o 60 70 80 400.0 [ ~ 90 l 1.823 % 11100 20 2.y13 800.0 2.T52 30 I 2.562 1200.0 I 2.976 3.559 40 f 4.436 SCINTAG/USA WL: 1.54060 1600.0 I f f STEP: 0.03000 50 / 5.901 8.838 ID:PS012A AS MADE TIME: 09:08 PT: 0.45000 2000.0 2400.0 2800 .OJ 3200.0 3600.0] PS 17[66 4000.0 I FN:PS012A.RD DATE: 09/28/95 N Vl 50 40 30 20 10 0 484.0 387.2 290.4 193.6 96 . 8 0 .0 I I % 60 1.e23 580.8 2.013 70 2 . ~52 677.6 2.Q62 80 2.~76 774.4 3.Q59 90 4.436 SCINTAG/USA WL: 1. 54060 871.2 5.901 STEP: 0.03000 100 8.838 ID: PS013 AS MADE TIME: 16: 22 PT: 0.45000 PS 968.0 17.66 FN:PS013A.RD DATE: 02/14/96 I.>) Vl 40 30 20 10 0 1140.4 855.3 570 . 2 285.1 0.0 I 1.823 % 100 50 2.013 1425.5 2.252 60 2.562 1710.6 2.976 70 3.559 1995.7 4.436 80 5.901 SCINTAG/USA WL: 1. 54060 2280.8 8.838 STEP: 0.03000 90 17.66 ID: PS014 AS MADE TIME: 17: 08 PT: 0.45000 2565.9 PS 2851. 0 FN:PS014A.RD DATE:02/14/96 +:>,. Vl I 2.252 2.013 II ft l\ll 200.4-j 100. 2-1,.u I I . 300.6-j I J.I 111 I 400.8-j J 0 . 0 I I I I I I I I I I I I I I I i I • I I I I I I I I I ! I I I I I I I I I i I 0 1. I I I I • I I ·t I i •1 11 0 r 10 A. Jn • j I I I al I r 20 r 30 r 40 I- 50 111 In I 11111 II 501.0~ I I 1.823 % 100 60 2.562 601.2 2.976 70 3.559 701.4 4.436 80 5 . 901 SCINTAG/USA WL: 1. 54060 801.6 8.838 STEP: 0.03000 90 17.66 ID:PS015 AS MADE TIME: 16: 46 PT: 0.45000 901.8 PS 1002.0 FN:PS015A.AD DATE:02/14/96 Vl Vl 2.252 2.013 50 40 30 20 10 0 1302.0 1041. 6 781.2 520.8 260.4 0.0 I I 1.823 % 100 60 I 2.562 1562.4 2.976 70 3.559 1822.8 4.436 80 5.901 SCINTAG/USA WL: 1. 54060 2083.2 8.638 STEP: 0.03000 90 17,66 ID:PS016 AS MADE TIME: 17: 25 PT: 0.45000 2343.6 PS 2604.0 FN:PS016A.AD DATE: 02/14/96 °' v-, 57 Appendix V. Thermogravimetric Analyses VAWNH4+ VA W Na+ exchanged PS00I as made PS00I Calcined and Na+ exchanged PS003 as made PS003 Calcined and Na+ exchanged PS004 as made PS004 Calcined and Na+ exchanged PS005 as made PS005 Calcined and Na+ exchanged PS006 as made PS006 Calcined and Na+ exchanged PS007 Calcined and Na+ exchanged PS009 Calcined and Na+ exchanged PSO 12 as made 3: Q) Cl •rt .c .µ ~ -- 85-+---------~-----,----~-----,----..-------------1 200 400 600 0 800 Temperature (°C) General V4.0D DuPont 2100 90 95 100 TGA Sample: NH4-ZSM5 VAW 7461-05-43 File: A:HKVAW.002 Operator: HK Size: 11.3370 mg Method: 10 DEG C/MIN TO 700 DEG C Run Date: 10-Feb-95 09: 24 LOSS OF H20 AND NH4+ Comment:. ...:==--=~-=::......:~::......:_:_ ___________________________--, 105- Vl 00 Ql '"3: Cl .s::. M --..., I \ \ / \ \ X ., ---- / 0 20 40 oO 86-;---r--,-•-···- .,...-·-··- ·• ··r-··· ..., -,-.- ----- r · · ··-· ,.... 88____1 90~ 92~ 94 I 96J 98 100 12.1830 mg Size: Method: 5C/MIN 600 ISO 60 MIN Comment: LOSS OF WATER Sample: VAWZSMNA " / ;---•• 100 (min) .. .... ,.. .. ··• - . 1-· · ./ ' ·- 80 Time T "- ./ i \ ( • ·1 ; \ -r- .r -"\ JCL. 120 ·· 160 200 180 ··-··•--..·-·•-·---r 0 I '- Ql ~ 0 -u I- Ql E 1 r400 I I 600 800 General V4.0D DuPont 2100 140 · ......... ·· ···, ---· ···· --. --· ---··r - -- · "?'"........ , 87.67% Run Date: 26-Jun-95 22: 38 Operator: File: A: VAWZSMNA.001 VI \0 TGA X Q) .... Cl .c .µ ~ -- I 92-l " "'--.. I -, \ I\ I 471.15°C 92.33% A n Q) □ c.. ·rl 0.00 ~ 0.02 ~ o.o[ .c .µ ~ t- o .06' 0 u ~ I I '\ I I 370.19°C I- 0. 08 / I 0.10 884------.---~-----...-----r-----,----r-----,----r-----.----+--0.02 0 200 400 600 800 1000 Temperature {°C) General V4.0D DuPont 2100 _,·,,,(, 90 (\ 94~ 967 98~ 100 c;UJ~of File: C: PS001A Sample: PS001 NA-TPA-AL-ZSM-5 Operator: PS Size: 9.8390 mg Run Date: 10-May-95 22: 12 Method: 10 DEG C/MIN TO 900 DEG C Comment: LOSS OF WATER AND ?ORGANIC 1 0 2 - . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~ 0 .12 0\ 0 61 0 0 0 0 0 0 CD ...__ _ _ ~ C\J lO 0 0 _ _ ___,__ _ _ _.,___ _ _~ - - - - - - ' ' - - - - - _ . _ - - - ~ - - - - l - o \ :'; -' CD en 0 m ·.;; ;_ o =- 0 ).... ....... ·JJ •r t ., _ -. ~ i!.. :.::-. :°"- -__, L c: •M ~ .o§ , . ,._ -:--t i';t! .,... iO 0 0 ...-t ~•-; ~ 0 lO 0 CJ) a: w ~o ' lO Hf- < Ol O <t E Z o o <, . I O · t 3: i I.OIL , u "'l" z '<"1 -.:- ,-1 en l ' I I 00)~(!) 0 (!) a.. ..... ,:: C:0 0 Q)..t Q) 0 ~ .r. E N .µ E ~ i1) ..... fJ) I •'-,.0 0 U ...J 'I ..-t 1.') ..------,..----1,-----......- - - - - - - - - - - - - - - - - - - - - - - . . - - - - - - " 1 - 1 - o .µ(\J (l! Ul :-: u ~ .::= 0 0 ... m m CD m ru m 0 m 3: Q) .... Cl .c 4.J ~ -- 85 0 901 951 I 100--i I A ...__ 200 - 348.56°C 96.62% 451. 92°c 519.23°C 88.85% \ I I 400 600 Temperature (°C) I\ '' I I \ TGA t. 0.00 0.0~ ....> -0.02 1000 I General V4.0D DuPont 2100 800 .c 4.J ~ -' 0 0.0~ ,o.o: I - I I 0.08 File: C: PS003A Sample: PS003 NA-TPA-AL-ZSM-5 Operator: PS Size: 10. 7530 mg Method: 10 DEG C/MIN TO 800 DEG C Run Date: 11-May-95 08: 48 Comment: LOSS OF WATER AND ?ORGANIC 1 0 5 - , - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~ 0 .10 N 0\ 3: Q) C, .... .c .µ M -- I .J \ / / / / / Time (min) 90 + - · - - - - - - - - - - - - r - - " ' " T - -.............- - - - - p - - - - , - - -•- . --- - ~--. -< 0 20 40 60 80 100 120 92 94 I I I \ 1\ 961 98 100 102 TGA 160 180 200 0 c.. (ll E (ll I- General V4.0D DuPont 2100 140 90.87% u ~ 0 1 400 600 r I I I ~ File: A:PC003CNA.001 Sample: PC003CNA Operator: JCL 12.7990 mg Size: Run Date: 2-Jul-95 10:57 Method: 5C/MIN 600 ISO 60 MIN LOSS OF WATER AFTER NA EX __________ _ _ _ _ _ _ _ _ _ _ _ _ _ _-,- BOO Comment:•~=:~~~~:~~~~_:.::._::.:...:. l.,.) °' 3: Q) •r-1 C) .c .µ ii - 88 ,(I.; , 0 901 924 94 i 961 987 100 200 I\ _/ c;~ .c .µ ~ -' u 0 800 ~ -0.1 0.0 0 Q) c.. > •r-1 ,0.1: I I I 0.2 General V4.0D DuPont 2100 600 ~-~ 455.77°C 507.69°C 92.06% I \\ I \\ ~\ 400 Temperature (°C) A TGA File: C:PS004A.001 Sample: PS004 NA-TPA-AL-ZSM-5 Operator: PS Size: 15.9770 mg Run Date: 11-May-95 11:20 Method: 10 DEG C/MIN TO 700 DEG C LOSS OF WATER AND ?ORGANIC Comment:;~=:~~~~~~~~~~:.::::.=-------------------------,-0.3 102 .j:::,.. 0\ X Q) ....Cl .r:. M --..., \ \ 20 ·- -,- ' 92--t--'" o 94 9J I 98--t 100 -. 40 60 / 100 Time (min) 80 --,-.,.....- / / TGA Sample: PS004C Size: 12.3650 mg Method: 5C/MIN 600 ISO 60 MIN Comment: LOSS OF WATER -----·- ·- · ---.-------·-·- ···- - - - - 102 120 160 180 0 200 Q) I- General V4.0D DuPont 2100 140 93.71% '-- Q) u 0 - r400i I I 600 -----------~aoo File: A: PS004CNA.001 Operator: JCL Run Date: 11-Jul-95 22: 45 Vl 0\ - 3 Q) .,➔ Cl .c .µ ii I 200 I I I \\ I v'\ ' 513 . 46°C 92.70% 475 . 00°C 694.23°C 88.79% ~ File: C:PS005A Operator: PS Run Date: 12-May-95 21:06 ~\ 400 Temperature (°C) ~ 100 . 0% 378.85°C TGA u 0 o.o 800 r ~ .c .µ ~ -' 'Q) a > .,➔ 0.1: 1 I I I - 0.2 0.3 0 General V4 . 0D DuPont 2100 600 as--------------.....-----,,------.,------~-------- -o. 1 90~ 921 94~ 96 987 100 Sample: PS005A Size: 12.1000 mg Method: 10 DEG C/MIN TO 700 DEG C LOSS OF WATER ANO ORGANIC Comment: 102 0\ 0\ 11.4190 mg SC/MIN 600 ISO 60 MIN PS005CNA TGA Operator: Run Date: 5-Jul-95 JCL File: A:PS005CNA.001 10: 32 -..., X Q) ....Cl .c. ii I .J I I I \ ~ n,..-, ~no,, - 93.09.% / / / / / 91. 89% 600 Time (min) (I) c.. ~ u 0 ~ 200 General V4.0D DuPont 2100 I- (I) E r400t I I I ~ 90-+----r----T--~-~--,e---,----r--..----.-----.-~~-r----T"--r----------,.----+ 0 0 20 40 60 80 100 120 140 160 180 92 941 I 1\ 961 98 100 LOSS OF WATER C o102 m m e n t : . ~ ~ ~ ~ ~ ~ ~ ' . _ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - . 800 Sample: Size: Method: 'Si(4l ;:)_5 °'-....J X •rl Q) Cl .c ,µ ~ - 88 90 92 94 96 98 100 102 0 200 438 . 46°C Temperature (°C) 400 509.62°C 90.72% 390.38°C 99.73% TGA 800 -0.1 0.0 □ QI L > •r-1 X QI 0.1.~ .c ,µ ~ General V4.0D DuPont 2100 600 88.13% 696.15°C u 0 -' 0.2 Sample: PS006A File: C:PS006A Operator: PS Size: 13.3330 mg Run Date: 13-May-95 15:20 Method: 10 DEG C/MIN TO 700 DEG C LOSS OF WATER AND ORGANIC __________________;_______-r0.3 Comment:.~~~~:___::'..:.:,_=:~~~:...:::::::.:.:.:: 00 0\ - 3 Q) •r-t .c C, ..., !! I I \ / ,, TGA 95.07% Time (min) c.. Q) u 0 ...... 200 General V4.00 DuPont 2100 Q) E .... r400i I 600 ----------------800 Operator: JCL Run Date: 28-Jul-95 15:05 File: A:PS006CNA.001 94----------.-------.-- ----- -,---,-----· ···-r---------.------.------.----r--+ 0 0 20 40 60 80 100 120 140 160 180 96 981 100 Sample: PS006C Size: 10.3960 mg Method: 5C/MIN 600 ISO 60 MIN Comment: LOSS OF WATER 102 \0 °' -I-GA. - J: QJ C, •rl .s::. +' ii \ 1 \ 0 92 -t--- -·- -- 94 gJ I 987 100 50 / / 100 Time ·- •-~ - ---- · - ,-·--·- - ,, 200 150 250 QJ c.. QJ I- General V4.0D DuPont 2100 200 ·- --··r -···· --- ····r ---·---,---......,....·- - - - 0 (min) - r--- 92.27% ( .) 0 - 1 r400 I I 600 PC007C NAEXED (PS001) File: A: PS007CNA.001 Operator: JCL 11. 4500 mg Run Date: 10-Nov-95 14: 48 Method: 5C/MIN 600C ISO 120 MIN Comment: LOSS OF WATER, 11/4/95 102 ·- · - - - - -- ----~- -- -- - - - --··-··-- · - -·····- ·---···-··-- ·- "· ··-·--·-·- ··--·-·--·-··- - - - - - - - - - - r - 800 Sample: Size: -..) 0 TGA 3 Q) ....Cl .c ii -..., \ I I / / / 92.68% C. Q) u 0 - . 200 I- Q) 1 r400 I I 600 92-+----.-----,,-----r----~--~----..-----.----.-----,,-----rO 0 50 100 150 200 250 Time (min) General V4.0D DuPont 2100 94 9J I 98-' 100 File: A: PS009CNA.001 Sample: PS009C NA EXED (8/30/95) Operator: JCL Size: 10.7310 mg Run Date: 28-0ct-95 12:31 Method: 5C/MIN 600C ISO 120 MIN LOSS OF WATER C o102 m m e n t : • ~ ~ ~ ~ ~ ~ ~ ~ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - . 800 --.) 3: •r-i Q) C, .c .µ ~ - I .J I 0 90 I 92 94 \ \ \ \ 50 / , / Time (min) 150 200 90 . 85% 100 600 800 o 200 Q) I- E General V4.0D DuPont 2100 250 t. Q) u 0 -... 1 r400 I I I I I\ / File: A: PS012A Operator: JCL Run Date : 29-Sep-95 15: 56 I / TGA I\ 961 98 100 Sample: PS012A AS MADE WITH SI/AL=18 12.5490 mg Size: Method: 5C/MIN 600C ISO 120MIN Comment: LOSS OF WATER 102 N -.....l 73 Appendix VI. NMR Spectra YAW HKI 13 HK114 HK109 HK108 HKI 10 NH4+ 29 Si MAS 27 Al MAS calcined 29 Si MAS 27 Al MAS as made 29 Si MAS 27 Al MAS calcined 29 Si MAS 27 Al MAS as made 29 Si MAS 27 AI MAS calcined 29 Si MAS 27 AI MAS as made 29 Si MAS 27 Al MAS calcined 29 Si MAS 27 AI MAS as made 29 Si MAS 27 AI MAS calcined 29 Si MAS 27 AI MAS as made 29 Si MAS 27 AI MAS calcined 29 Si MAS 27 AI MAS 29 Si CPMAS ~~ t - ...... r , _ (. _\ -so 't--. . . .. . . -70 -eo -so .,.....~1 ....... ♦ -t.....--"t "9"111-,.-, .• -,~.._. ➔ 1-f; ·1 - 1•• ,f•.., 'f ... ~ . . . , ... f'l?1-! . .I ; _ ! , (' i ·. ,' ' 'i(7 ( c-· ,: '\ 1:' . ' ' ,·( , , -., -,_ ( \./ l /\ I ., ....... \ .. ~:, o f' j 'f.., -:120 ' -, • • ._ , , . , • --1:ao • -,.~,.~~-,, •-140 . ,....,.. ...... ~ . . . . , . . . . . . . , . . J I • \,,-,('-.-J"',.,'" '-.,,,./'1/·~ ~ \_ ', --,,.., ,.1 1"' .. '1 · 1~·• · • ·.. "T -y,o- '9' ..... I t,' -!oo . .. ' I ,.J:,' ,-. --""-'v,,~,.__,.--./\/',-,,,1\....-r--,r,l',-~_,r,/\,,/V --r~ ~ r-v'---- t . ...,. .-...-. .._,,-. !1. n. ~r~ M NH4·7SM5 VAH ID:7461-05-43 SI/AL~11, 29SI ~~S. 7MM .015 5787.000 5t. ?0 640 289 OS NS RD PW UE Pi 01 P4 0 20.0000000 40.00 ,.~. 00 0.0 0.0 ,:o .00 3382 LB 0.0 GB 0.0 MI .05 HZ/CM 297.852 SR 27263.90 DP 02 AG AG iE Oi SF 59.628 22500.000 SI 2048 TO 500 S\'1 ~6666.667 HZ/PT ~6.276 DATE. 2?.-·:1-94 TIME 9: 25 SOLlDCYC.AU AU PBOG: HKZSM'✓ AW. 00 ~ ·...,. k. r~~..,.- ~ ('-8 -'· A a~(,'""~ ~ -....J ~ 150 r ···-,-···•, ·-··· ,· --- -r·· 7 ·-· -, •. ...,............ !00 ··""T ··· ·T ·· ...,, . ..., ~ ! ! I I ,,\ :.; ,;t U) "' P?M 50 · • ....,. •• . .. .., . •. 0 ·-1···--·1· . , . . . ..,. . . -- , - . .. . , . . -50 ··- 1 ·· r .. ··-....-··- "T - --r•··- ~v\/'..,~,,/w--~""1-J"A\.;v1"\~ \ - ""'T' ' ··- ·: ·•-· ·· ~)/\;v-J ~ ~ ' A ; - - ~ ~ Q.. ::c n. C\I c,-;· NH4-·2SK-5 ~AW ID:7 46!-05-~3 SI/AL~1!, 27 AL t,:;.S Bl<HZ, 4M}~ 78.206 38301.338 4096 i02-'< .005 DS NS Of: D1 p~ P1 RD P~i SR 0 .5000000 40.00 3.50 0.0 0.0 8.75 4355 34700 . 26 50.000 0.0 .02 19741.000 3L PO 640 289 .:B . B28 HZ/CM !.1?1E3 DP LB GB MI 02 AO AG TE HZ/PT sw rnoooo. ooo TD SI 0~ SF DATE 17-!1-94 TIME :18: 24 SOUDCYC . AU AU ?HOG: HKZSM5VA.001 '"';<:~ B;~~R Vl -..l ::.: a. I , / .l ~ r , 'Ii / , ... i ,;. , , ' I' .i I • r· I ! I ,: ~ ...., Cl[ m' M: N, -60 -70 -80 -90 -100 pp~ -110 -120 -130 -140 r·- ----r----r-·---r----r·- --,---,--··-,-··-- ·r· ----.-·- -- ·r ·-- .--- ·--T ··-··.- ----, -- ---·,··- ,------,--- a. ZSM-5 VAW CALC 550C, 29SI MAS 3KHZ, 7MM .015 5787.000 5L PO 640 289 RD PW DE NS OS Pi 01 P4 0 5.0000000 40.00 4 . 00 0.0 0.0 40.00 1145 LB 0.0 GB 0.0 MI . 04 HZ/CM 297.852 SR 29817.23 02 DP TE AG AG 59.631 26000.000 4096 500 SW 16666.667 HZ/PT 8 .138 SF 01 SI TD HKVAW.001 AU PROG: SOLIOCYC.AU DATE 25-1-95 TIME 17: 56 (.x~ s'i:@.~R °' ---.) r_,. ...,.....,...~-, -, . . a. a. ::,;:: "T" .. 100 1 + •. , . ~ ~ ~ ~ ~ . , . 150 ~ - -T· PPM 50 ·- r···1 -·"'---.,.. .,...~ _,. ·1··--- --~-·,--,· •- --·..,..-, M; in: ·' I'' Lil'. Lil: Mi VAW ZSM-5 CALC 550C, 27AL MAS 8KHZ, 4MM 0 .T ..,. .-.....---r-......-"T-,-· ! i ..-t! ., ,, ·I ~,: CTJ' ,q; '<I , -50 1.0000000 40.00 4.00 0.0 0.0 8.75 7263 0 D1 P4 OS NS PW DE RD Pi GB O .0 MI .03 HZ/CM 1.171E3 SR 38093.82 40.000 LB .005 19741.000 3L PO 200 289 02 DP TE RG AQ 78.209 38093.818 8192 TD 1024 SW 100000.000 HZ/PT 24.414 SF 01 SI SOL.IOCYC.AU DATE 20-1-95 TIME i5: 34 AU PROG: HKVAWZSM.001 I\,,.~ (;,i<g · R s~; -..) -..J 78 roo or·. ,1 :::nn -,cm C'.JO C.00 00 OC\! 0 O •1 ..-, U-rlO 010l000C\; .... :..- ! .. moe,oo~ >--iC:lLlCD('t') ,I)O(!)O L';Or.:l"'\'-i"'r-1 MC:.H ·ri r'\ __ ; it.! tLJ """i 0:-- - :l: ::L;:)(t) ... ::H :;:~, Ot- -~ - :n "" C'Jt- 0 0 0 OO'l ·:..: CD ' 0 o ·O . ,.-:_ OOOCOM 00 C\l (0 (\; ~"'-tHC:.<;•""J r---... , 01 C1 C\iW O'l :.:n; u n.. en o :.J') t-· CJ) :r: C\! r. :no C\i n. DO ~ m ~~ 0 000 000 0 .. 0 o.n • oo--: >C\!O Oi" , O 0~ 0 0 0 0 .. , (\;....-· ~ s,-1 ~~·r :::: .-ti, ~...... . w ' 0 ,-- ...., '"' 0 ,.. en 0 1- CO • i ;.. 0 !·- l.O i ;.. !50 r - . _ - - r • ..,.,-,---,--.,--1""-1···'1'- n. n. =,: ~ ~- - ~00 i .., ... .., .. "'Y ID '""' (Tl . •.f (Tl m' 4;4:;,: 50 :.l?1,: 1 ·-- · ·· .. . " 1" ' .... . ... . . .. 27AL 11.;l.S BKrE, ~ ·· "T·· - - · - . . ,,_. , . .. . HK1 ~3 TPA-·AL-ZSM--5, ·· - ... . ..,. • •• , . 0 ... . ..,. •• .,.. .,. ••• , . '1'" "· • ., ~ --r··-, · · r · ·r-...... ---.-.-, - ..... ~ -50 ·--r · · ""T • " ..- • -;- 3L PO .005 1974~.ooo 200 289 24.4i~ OS Pl~ OF. MS no P1 01 P4 ~.0000000 40.00 4.00 0.0 0.0 8.75 •~155 0 40.000 O .0 .09 HZ/CM 1. 171E3 SR 38093.82 LB GB MI DP 02 AQ RG TE HZ/PT 78.209 38093. 818 SI 8192 TD 1024 SI-/ 100000.000 SF Oi SOLIDCYC.;.U DATE 20-1-95 TIME 9: 55 HKU.3:0L.001 AU PrWG: (. O'--·"' -'·...~) c°'- "',....) BRlJ~R --.J \0 X r -•-..-· .. Q. n. (TPA) -AL-ZSM-5 CALC G00C, ~ I ~l/.S 3KHZ, I -.-1°. I ,.,= (\J , Ol (T')' ...,, 7t~i-' -·60 -70 ··BO ·-90 ··100 PPM ··U.O -120 -130 -140 -·-r·- ---..,... . -. -:-·-..··--r---T·-·· -·~--,,. · .. ,,, .. ·· ·, -· - - · , _,, .... ,,.,, ........ ,., . ,,.•.. , .• _....... T. · · -.---"T ,,......T.. --, - - · ,--- - - HKH3 ~ .031 5L PO 5787.000 640 289 P1 RD P~I DE NS OS P4 D1 LB GB 20.0000000 40.00 4.00 0.0 0.0 40.00 652 0 0.0 0.0 MI .02 HZ/CM 297.852 SR 29817.20 DP 02 AQ RG TE 01 SI TD SF 59.631 26000.000 4096 1024 SH 16666.667 HZ/PT B. 138 AU PROG: SOLIDCYC.AU DATE 28-1-95 TIME 17: 56 HK113SI. 002 '-..o-~·-~ B ( ~t1R , " ~ -) 0 00 6: 150 100 ...-1"' ....~ ~-..--1- ·.,......_.•• r~ ..,-~~._,.."("-r'j-...~......_...,.. ...., • !l. 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Dt: NS ~o r • '), 0.0 2~_50 .i. 00 0 i668 0.0 .-w.oo ~0.0000000 o:: p . ·; 29891.30 SR H?../Cl-'. 29:· . 852 MI ,~'... :}0 ~!3 Gd DP s:'a:·. ooo ?89 TE . 020 02 6,rn 12 . 207 RG AQ HZ/?T s:-: TD .~o9n ~02A 2sooo. 000 01 s: 53.G3:'.. 2,~500. 000 ,. S; · □ :,;· E ~8-1.-95 T:.~~t: ! ~·': 56 SO'....IDCYC.AU AU PiWG: H;<11~s:.oo~ l .O"' "' -.... _ _ l3~1)~~~R ( ' , ,,..._.... . . ! N 00 150 mo ' 1' '"1 ..... . .., 50 PP:•: ., .0 ,-, ~~ . (Tl 0 ctf -W!•! r · • . .,.. T 2:'AL t1'. AS BKH Z. r ··-,- -~- ---r__,........,... .._,. ___ .,...__ .,..-,-...~--r-.--T- ·T 1 -· -,. .,. a. a. :-.: HK114 TPA -AL-ZSM-5, T T .. .. ., ~ 0 ...,.. . T.,..""'r'"-T -· T -50 , ·---T ··· T·~-~T..,.-,, .-,---,---,-~,-~ .005 . 2i O .0 40.000 3L. PO 19741.000 200 289 OS Pi RD PW DE NS 01 P4 i.0000000 40.00 •! . 00 0.0 0.0 8.75 3435 0 HZ/CM 1.171E3 SR 38093.82 MI LB GB DP 02 T(.:" RG AQ O! SF 78.209 38093.818 SI 8i92 TD i024 S~i 100000. 000 HZ/PT 24.414 TIME i 1: 01 DATE 20-~-95 HK114AL.OO~ AU PROG: SOLIDCYC.AU sty}:~R ( o.,., ~) \.,.) 00 ~ / I C'l , CD t \ ~,· ~,- C\J tO . o' :-,1 "1" l"l u:i 600C, 29SI MAS 3~:H?: , 71-IM -60 ··7 0 -80 -90 PP1·1 --:i OO ·· :110 ··120 r· ··--,-···-··1 ·· - ·-,-•·•-·T. ···,- -- ·...,- ···-•-,-··-·· ... T .. ··· , ··•·· .T • . . , ·-·•····.-···· -----,- ... ... T ( I 1, a.in·. a.- X m' C\J o· HK11,t CALC -·DO - 140 ··-··,------T·- -·........-...,-----.--- '1 CD: .... (Tl " (T) ~ tO OS DE NS PW 01 P4 Pi RD 0 5.0000000 40. 00 4. 00 0.0 O.0 40. 00 479 MI . 01 HZ/CM 297.852 SR 298~'.'.20 GB 0.0 30.000 DP LS .018 5787.000 5L PO 640 289 02 TE AG RG SF 59.631 Of 26000.000 SI 4096 TO 600 SW 16666.667 HZ/PT 8.138 DATE 29-1-95 TIME i 1: 34 SOLIDCYC. AU AU PROG: HK114Sl.002 aRridH ~ .X,) 00 +'" r ·-- ··•· r ··· ...• 0. n. X -60 -70 i ·· ·---r ·- - ,- -80 -90 ···--r--· · ,-·- --,· • ···-- r .... 1 '<I' . ·• - ·- r ,· ,1: o i (TJ. 0 "I -· 1.00 PPM •..• ..,.. HK114 CALC 600C, 29SI CPMAS 3KHZ, 7MM -110 , ·· --- ·T I -120 I -130 ·····--,--· --, - - - · ·r ··- ·•· - -T'' - - - I I ~; 1' ~ - ~·~, ....; (Tl) -140 .015 5787.000 5L PO 640 289 03 NS OS DE P2 RD PW P1 01 P4 LB 5.0000000 40.00 8.50 3000.00 0.0 0.0 40.00 15327 0 . 0030000 30.000 GB 0.0 MI .08 HZ/CM 297.852 SR 29817.20 DP 02 RG TE AQ 01 SI 59.631 26000.000 4096 500 TD SW 16666.667 8 .138 HZ/PT SF HKi14SI.003 AU PROG: CPMAS.AU DATE 30-1-95 TIME 9: 13 ' -/ '\ ;,·-...._; Sc~?QR 00 V1 150 100 r- ,,__.,,_,....,.. ,. ....... T1'""~ · •· .--,-..'"1-1-"~• .., ... n. a. 2: ~ 27 Al . M;\S Br.Hi:, 11,: ..,. (T} m 10 r ,1 I.M ;I. 50 0 PPM ·- 50 ,.. .T... -150 · "I .... . ... .., ..... ., . ... "'T"', •.,"""' -~ - , . . . . . . . . - ·· i0O •• • •., .... .. .. ..... . 1'" - ~--., - ~ ·" 1 . .. ··• ... -... ·- 1 ·- ~ ..... 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X '1'' 0 . HK1 :l.O AL· ·ZSM··5 CALC 600C, 27 AL ~;,s BKHZ , 4:-,!M 00 \0 99 Appendix VII. Conversion versus WIF Plots for VA W sample 1. 25.00 ~ - - -- - - - - - - - - - - - - - -- - ---~ T=799 K ■ 20.00 15.00 C 0 'i?! ~ C 0 U • 10.00 ■ NO 5.00 N2 02 • • 0.00 ~::::::==--+----+-- - - - + - 0.4000 0.6000 0.0000 0.2000 0.8000 1.0000 1.2000 1.4000 W/F (g*s/ml) Figure VII-1 Sample 1 ion-exchanged with copper acetate, T=526 cc. 25.00 ~ - - - - - - - - - - -- - -- --------~ T:773 K ■ 20.00 .. C 0 -~ 15.00 Cl) > C 0 U • 10.00 ■ NO 5.00 • N2 02 • • 0.00 ,.::;..;;;::===+---=---+----+---0.0000 0.2000 0.4000 0.6000 0.8000 1.0000 1.2000 1.4000 W/F (g*s/ml) Figure VII-2 Sample 1 ion-exchanged with copper acetate, T=S00 cc. 100 25.00 - , - - - - - - - - - - - - - - - - - - - - - - - - - - ~ T:746 K 20.00 C 0 ■ 15.00 -~ Cl) > C 0 U 10.00 ♦ ■ NO 5.00 ♦ N2 02 . . 0.00 ,1,::::.::;;;;;:;,===+~~~'..+----+---0.0000 0.2000 0.4000 0.6000 0.8000 1.0000 1.2000 1.4000 W/F (g*s/ml) Figure VII-3 Sample 1 ion-exchanged with copper acetate, T=473 °C. 25.00 - , - - - - -- - - - - -- - - - -- - - - - - - - - - ~ T:720 K 20.00 ■ C 0 15.00 -~ Cl) > C 0 U 10.00 ♦ ■ 5.00 NO ♦ N2 02 . . 0.00 ,i.:::;;;::::::..~==-=~~'-+----+---0.0000 0.2000 0.4000 0.6000 0.8000 1.0000 1.2000 1.4000 W/F (g *s/ml) Figure VII-4 Sample 1 ion-exchanged with copper acetate, T=447 °C. 101 25.00 ~ - - - - - - - - - - - - - - -- - - -- - - - - ~ T:695 K 20.00 ■ C 15.00 0 -~ G) > C 0 U 10.00 ■ 5.00 NO N2 • • .. 02 0.00 ,..:::;=-==,~=--=4----"'+-------+----+----+------1 0.4000 0.0000 0.2000 0.6000 0.8000 1.0000 1.2000 1.4000 W/F (g*s/ml) Figure VII-5 Sample 1 ion-exchanged with copper acetate, T=422 °C. 25.00 ~ - - - - - - - - - - - - - - - - - - - - - - - - ~ ■ T=798 K 20.00 C -~ • 15.00 0 NO G) > C 0 u 10.00 • ■ • N2 5.00 02 .. . 0.00 i i " - - - - - + - - - - + - - - - - + - - - - - + - - - - + - - - - + - - - ~ 0.0000 0.2000 0.4000 1.0000 1.2000 1.4000 0.6000 0.8000 W/F (g*s/ml) Figure VII-6 Sample 1 ion-exchanged with copper ethylene complex, T=525 °C. 102 25.00 • T:773 K 20.00 ♦ C 0 15.00 -~ NO Cl) > ♦ C • • 0 (.) 10.00 ♦ N2 • 02 5.00 • 0.00 i f ' = - - - - - - + - - - - + - - - - + - - - - + - - - - + - - - - + - - - - - 1 0.8000 1.4000 0.0000 0.2000 0.4000 0.6000 1.0000 1.2000 W/F (g*s/ml) Figure VII-7 Sample 1 ion-exchanged with copper ethylene complex, T=S00 °C. 25.00 ~ - - - - - - - - - - - - - - - - - - - - - - - - - - , T:750 K • 20.00 C 0 ♦ 15.00 'i?! ~ ♦ C 0 U NO 10.00 ♦ • ♦ • 5.00 • 0.00 , . o : : : = - - - - - - - + - - - - + - - - - + - - - - + - - - - + - - - - + - - - - - 1 1.4000 0.0000 0.2000 0.4000 0.6000 0.8000 1.0000 1.2000 W/F (g*s/ml) Figure VII-8 Sample 1 ion-exchanged with copper ethylene complex, T=477 °C. 103 25.00 T=723 K 20.00 ■ C 0 15.00 "iii t> • C 0 (.) 10.00 • 5.00 NO • ■ N2 0 2 0.00 0.0000 0.2000 0.4000 . . 0.6000 0.8000 1.0000 1.2000 1.4000 W/F {g*s/ml) Figure VII-9 Sample 1 ion-exchanged with copper ethylene complex, T=450 °C. 25.00 . - - - - -- - - - - - - - - - -- - - - - - - - - - - T:698 K 20.00 ■ C 0 15.00 -~ Cl) > C • 0 (.) 10.00 NO • ■ 5.00 N2 0 2 0.00 0.0000 0.2000 0.4000 . . 0.6000 0.8000 1.0000 1.2000 1.4000 W/F {g*s/ml) Figure VII-10 Sample 1 ion-exchanged with copper ethylene complex, T=425 °C.