NECZA Conference - December 11, 1998Goodstay Center - Wilmington, Delaware

Program

9:15 A.M. S tu d e n t/Po s te r Presenter Talks

10:15 A.M. C o f f e e Break

10:30 A.M. Sp e a ke r : T h o m a s F. Degnan, Jr., Mobil Technology Company"The History of ZSM-5 FCC Additive Developmentat Mobil"

Moderator: Bonnie Marcus, PQ Corporation

11:30 A.M. Sp e a ke r : M i c h a e l Tsapatsis, University of Massachusetts (Amherst)"Zeolite Membranes"

Moderator: Chuck Coe, Air Products and Chemicals, Inc.

12:30 P.M. L u n c h

1:30 P.M. P o s t e r s

2:30 P.M. S p e a k e r : R i c h a r d Hinchev, PQ Corporation"The Epistemology of Zeolite Synthesis: How Does theGel 'Know' What To Do?"

Moderator: John Parise, SUNY (Stony Brook)

3:30 P.M. B u s i n e s s Meeting(Coffee and cookies will be available in the hallway for those whowish to take a break.)

3:45 P.M. S p e a k e r : Y u e j i n Lin, Engelhard CorporatioB.,"Ammoxidation of t o Acetronite on Cobalt-Exchanged Zeolites"

Moderator: Todd Ballinger, Johnson Matthey

4:45 P.M. C l o s i n g RemarksInformal Poster Session

5:45 P.M. D i n n e r at a local restaurant—if you wish to attend, please addyour name to the sign-up sheet at the registration table. We need tomake reservations!

Program Organizers: Raul Lobo, Beatrice Gooding, Clare Grey, Scott Auerbach

Name

Accardi, RobynBallinger, ToddBennett, MikeBordawekar, ShailendraBorghard, WilliamBulanin, KiriIIBulow, MartinBurton, AllenCahill, ChristopherCao, Guang

Ciraolo, MichaelCoe, ChuckCorbin, DavidCorcoran, NedDadachov, Mike

•Degnan, TomDoskocil, EricEhland, ErikaFlanigen, Edith

.Gooding, BeatriceGrey, ClareGuo, Ming

Hanson, JonHasse, DavidHinchey, RichardHuessner, RalfJale, SudhakarJaramillo, EugenioJuttu, GopalKalyanaraman, MohanKirchner, RichardKuehl, Guenter

Larese, JohnLi, Hong-XinLi, YuejinLiu, HaimingLobo, RaulMaesen, TheoMarcus, BonnieMicco, DanMoini, Ahmad

Parise, JohnPatel, AspiPeters, Alan

NECZA ConferenceGoodstay Center - Wilmington, Delaware

December 11, 1998

Affiliation

University of DelawareJohnson MattheyPQ CorporationUniversity of VirginiaMobil Technology CompanyUniversity of DelawareBOCUniversity of DelawareSUNY (Stony Brook)Exxon R(StE Company

SUNY (Stony Brook)Air Products (Sr Chemicals, Inc.DuPont CompanyExxonMSTMobil Technology CompanyUniversity of VirginiaPQ CorporationUOPCollege of Staten IslandSUNY (Stony Brook)Pennsylvania State University

Brookhaven National LaboratoryMedalPQ CorporationUniversity of PennsylvaniaBOCUniversity of Massachusetts (Amherst)University of DelawareMobil Technology CompanyManhattan CollegeUniversity of Pennsylvania

Brookhaven National LaboratoryPQ CorporationEngelhard CorporationSUNY (Stony Brook)University of DelawarePQ CorporationPQ CorporationPQ CorporationEngelhard Corporation

SUNY (Stony Brook)DuPont CompanyW. R. Grace Co mp a n y

Name

Ray, GayatriRaybold, TroySaxton, RobertShantz, DanielShen, DongminStrohmaier, KarlToby, BrianTsapatsis, MichaelWeston, SimonWolf, RudyXiao, Yi

VaiithA 1 .Polv•41

Ps-u,

Affiliation

PQ CorporationUniversity of DelawareMobil Technology CompanyUniversity of DelawareBOCExxon MEE CompanyNISTUniversity of Massachusetts (Amherst)Mobil Technology CompanyBOCSUNY (Stony Brook)

NECZA ConferenceDecember 11, 1998

Posters

L " N e w Force Field for Cations in Dry Zeolites," Eugenio Jaramillo andScott M. Auerbach, Departments of Chemistry and Chemical Engineering,University of Massachusetts, Amherst, MA 01003.

2. "A l ka l i Occlusion in Zeolite Cages: Investigation of Catalyst Basicity,"Eric J. Doskocil and Robert J. Davis, Department of Chemical Engineering,University of Virginia, Charlottesville, VA 22903.

3. "Evaluation of Base Strength and Activity of Alkali-Modified ZeoliteCatalysts," Shailendra Bordawekar and Robert J. Davis, Department ofChemical Engineering, University of Virginia, Charlottesville, VA 22903.

4. "Structural Diversity Within Open Framework Indium-SulfideCompounds," Christopher Cahill and John Parise, Department ofChemistry, State University of New York at Stony Brook, Stony Brook,NY 11794.

5. "Incorporation of Zirconium into Microporous Silicates by Gas PhaseTreatment," Gopal Juttu and Raul F. Lobo, Department of ChemicalEngineering, Center for Catalytic Science and Technology, University ofDelaware, Newark, DE 19716.

6. "Superstructure of Silica Sodalite: Progress Report," Jon Hanson and JohnLarese, Chemistry Department, Brookhaven National Laboratory, UptonNY 11792.

7. "Structural Characterization and Reactivity of HCFC 124a over Cation-Exchanged Faujasites," Michael Ciraolo and Clare Grey, Department ofChemistry, State University of New York at Stony Brook, Stony Brook,NY 11794.

8. "Solid-State NMR Study of the Reaction of Hydrofluorocarbon-143 on BasicZeolites," Yi Xiao and Clare Grey, Department of Chemistry, StateUniversity of New York at Stony Brook, Stony Brook, NY 11794.

9. "Multinuclear NMR Studies of the Ethylene Adsorption on a-CuA1C14,"Haming Liu and Clare Grey, Department of Chemistry, State University ofNew York at Stony Brook, Stony Brook, NY 11794.

10. "Studies of Diatomic Molecules in X Zeolites at 77 K," Kiri11 Bulanin andRaul F. Lobo, Department of Chemical Engineering, Center for CatalyticScience and Technology, University of Delaware, Newark, DE 19716.

NECZA ConferenceDecember 11, 1998

Poster Abstracts

New Force Field For Cations In Dry Zeolites

Eugenio Jaramillo and Scott M. AuerbachDepartments of Chemistry and Chemical Engineering

University of MassachusettsAmherst, MA 01003

Zeolites have been used recently for the separation of hydrofluorocarbon (HFC)mixtures, such as HFC-134 (CF2HCF2H) and HFC-134a (CF3CF1-12). Studies ofHCF-134 in zeolite Na-Y suggest that the interaction of HCF-134 with Na cationsis so strong, that the HFC induces significant migration of Na(I1) c a t i o n s i n t o t h eNa-Y supercage to maximize favorable interactions with the HFC. In order to betterunderstand the dynamics underlying these studies, we have initiated a programmodeling cation transport in dry zeolites, focusing on determining whether thisinvolves correlated motion of different cations. A new force has been developed andtested for cations in zeolites X and Y. The model yields cation site occupancies andatomic distances consistent with X-Ray diffraction data. This model has the advantageof explicitly distinguishing the T-atoms (Si from Al) and the oxygens (Si-O-Si fromAI-0-Si) instead of using an average site for these atoms. Another important feature isthat the model makes no initial assumptions about the occupancies, leaving all cationsfree to move. We present here preliminary results on calculating cation diffusivitiesusing various dynamical methods.

Alkali Occlusion in Zeolite Cages: Investigation of Catalyst Basicity

Eric J. Doskocil and Robert J. DavisDepartment of Chemical Engineering

University of VirginiaCharlottesville, VA 22903

Solid base catalysts are an important alternative to homogeneous systems currentlyused in industry. Not only does replacement of homogeneous bases allow for easierdownstream processing of the product, but in many cases the basic solids are moreselective. For example, alkali-exchanged zeolites are effective for side-chain alkylationof toluene with methanol to form styrene and ethylbenzene. Occlusion of alkali speciesin zeolite cages beyond the ion-exchange capacity increases the base strength of thesecatalysts. However, the nature of the supported alkali is not completely understood. Inthis work, the structure and basicity of various alkali-modified zeolites wereinvestigated to elucidate the role of alkali species on catalytic activity. The electronicstructure near the alkali was investigated using x-ray absorption spectroscopy.Molecular adsorption of carbon dioxide and iodine was investigated using infrared andUV-visible spectroscopy, respectively. The dehydrogenation of 2-propanol and the side-chain alkylation of o-xylene with 1,3-butadiene were used as probes for catalyticactivity. Correlations between structure and reactivity will be presented.

Evaluation of Base Strength and Activity of Alkali-Modified Zeolite Catalysts

Shailendra V. Bordawekar and Robert J. DavisDepartment of Chemical Engineering

University of VirginiaCharlottesville, VA 22903

Alkali ion-exchanged zeolites as well as zeolites containing occluded alkali species arebasic materials with demonstrated activity for several reactions including double bondisomerization of olefins, side-chain alkylation of alkylaromatics, alcoholdehydrogenation and knoevenagel condensation. We have investigated the energetics ofbase sites in these materials using adsorption inicrocalorimety of carbon dioxide.Zeolites X and Y containing occluded Cs species formed via decomposition of cesiumacetate showed a linear increase in carbon dioxide adsorption capacity with theamount of occluded cesium. The activity of these materials for 1-butene isomerizationwas commensurate with their carbon dioxide uptakes. Stronger base sites were createdin zeolites through decomposition of impregnated alkali azides, presumably due to theformation of alkali metal species. These materials were active for the side-chainalkylation of toluene with ethylene.

Structural Diversity Within Open Framework Indium-Sulfide Compounds

Christopher L. Cahill and John B. PariseDepartment of Chemistry

State University of New York at Stony BrookStony Brook, NY 11794

Framework chalcogenide materials have generated considerable interest due to theirpotential applications in areas such as holography, recording media, solid-electrolytebatteries and semi-conductors. A new class of compounds based on indium-sulfurchemistry has emerged, exhibiting new structural features when compared to, forexample, the better known germanium sulfides. Discussed here are the building unitsalnlOS20110- [In6S11]4- [ I n 9 S1 7 - [In4S10]8- ) that comprise the structures ofthese materials and the synthetic conditions under which each is promoted.

Incorporation of Zirconium into Microporous Silicates by Gas Phase Treatment

Gopal Juttu and Raul LoboDepartment of Chemical Engineering

Center for Catalytic Science and TechnologyUniversity of Delaware

Newark, DE 19716

A method for the isomorphous incorporation of zirconium into microporous silicatesby a post-synthetic gas phase treatment is described. The boron form of zeolite Beta(B-Beta) is treated with vapors of ZrC14 in an attempt to substitute the frameworkboron for zirconium. The resulting material, Zr-Beta, is characterized by XRD, solidstate NMR, FUR and Raman spectroscopies. Based on the various characterizationtechniques, we conclude that Zr does not occupy a framework position but is grafted tothe zeolite framework. The acid nature of Zr-Beta was characterized by FUR ofadsorbed pyridine and Temperature programmed desorption of isopropyl amine.Based on these techniques we can say that Zr-Beta has a greatly enhanced Lewis aciditycompared to B-Beta and that Zr is molecularly dispersed.

Superstructure of Silica Sodalite: Progress Report

Jon Hanson and John LareseChemistry Department

Brookhaven National LaboratoryUpton, NY 11792

Silica socialite was synthesized by the nonaqueous method with ethylene glycol as thesolvent by Bibby and Dale (Nature 317 157-158 [1985]). The structure was determinedfrom laboratory single crystal data by Richardson, et al. (J. Phys. Chem 92, 243-247[1988]). New synchrotron data from a 30g2 c r y s t a l r e v e a l a s e t o f s u p e r s t r u c tu r e

reflections which may be indexed by doubling the cubic unit cell. The crystal structurein the doubled unit cell has two unique sodalite cavities that have different ethyleneglycol binding patterns. Attempts to determine the structure of the ethylene glycolusing X-ray data and molecular modeling tools will be shown. Low temperature datahave been collected from single crystals and time resolved powder diffraction. Thesedata show increases in the super-lattice reflections at lower temperature.

This work was supported under contract D E A C O 279 8 C H 1 0 8 8 6 w i t h t h e U . S . D e p a r t m e n t o f

Energy by its Division of Chemical Sciences, Office of Basic Energy Sciences.

N.B. Abstracts not available for nos. 7-10.