2011 Spring Symposium

 
Kevin Bakhmut­sky¹, Noah Wieder¹, Thomas Bal­das­sare², Michael A. Smith² and Ray­mond J. Gorte^1
1Depart­ment of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing
Uni­ver­si­ty of Penn­syl­va­nia
²Depart­ment of Chem­i­cal Engi­neer­ing
Vil­lano­va Uni­ver­si­ty

Abstract — High demand for petro­le­um and the ris­ing costs of the crude oil feed­stock have spurred a great deal of inter­est in the con­ver­sion of nat­ur­al gas into liq­uid fuels via the gas-to-liq­uids (GTL) process. As a key step in the process, the Fis­ch­er-Trop­sch syn­the­sis (FTS) con­verts syn­gas (CO and H2) to pro­duce hydro­car­bons. Cobalt cat­a­lysts are pref­er­en­tial­ly used in the low tem­per­a­ture Fis­ch­er-Trop­sch syn­the­sis because of their high activ­i­ty, paraf­fin selec­tiv­i­ty and rel­a­tive resis­tance to oxi­da­tion [1,2]. How­ev­er, stud­ies have shown that dis­persed cobalt on cat­a­lyst sup­ports tends to deac­ti­vate into sta­ble cobalt (II) oxide or irre­ducible cobalt sup­port mixed com­pounds [3–5]. This decrease of active cobalt met­al sites has pri­mar­i­ly been attrib­uted to oxi­da­tion by water. Ther­mo­dy­nam­ic data for bulk cobalt sug­gests oth­er­wise, as oxi­da­tion of cobalt at FTS oper­at­ing con­di­tions would not be expect­ed. Coulo­met­ric titra­tion was used to exam­ine redox char­ac­ter­is­tics of cobalt sup­port­ed on meso­porous sil­i­ca and zir­co­nia. Exper­i­men­tal data of cobalt con­strained by pore size in a meso­porous sil­i­ca sup­port sug­gests that oxi­da­tion ener­get­ics of Co nanopar­ti­cles are near­ly iden­ti­cal to those of bulk par­ti­cles [6]. How­ev­er, ther­mo­dy­nam­ic mea­sure­ments of cobalt sup­port­ed on zir­co­nia revealed that low cobalt load­ing sam­ples do appear to under­go par­tial oxi­da­tion at FTS con­di­tions, unlike bulk cobalt and high­er cobalt load­ing sam­ples. Fur­ther exper­i­ments have sug­gest­ed that the appar­ent dis­tinc­tion in redox prop­er­ties is like­ly due to sup­port inter­ac­tions of cobalt oxide with the zir­co­nia rather than an inher­ent dif­fer­ence in ther­mo­dy­nam­ics of bulk and dis­persed cobalt.

Speaker’s Biog­ra­phy – Kevin Bakhmut­sky com­plet­ed his under­grad­u­ate stud­ies at the Johns Hop­kins Uni­ver­si­ty, obtain­ing a B.S. in Chem­i­cal Engi­neer­ing in 2007. Kevin has since worked on his doc­tor­al research at the Uni­ver­si­ty of Penn­syl­va­nia and is present­ly in his fourth year of study as a mem­ber of Dr. Ray­mond J. Gorte’s research group. Kevin’s the­sis research focus­es on catal­y­sis and reac­tion engi­neer­ing, with an empha­sis on a ther­mo­dy­nam­ic approach to met­al-sup­port inter­ac­tions.

2011 Spring Symposium

 
Deng-Yang Jan
UOP-LLC-A Hon­ey­well Com­pa­ny.
© 2011 UOP LLC, All Rights Reserved

Abstract — UZM-5 (UFI frame­work type) has 2-dimen­sion­al, chan­nel sys­tem con­nect­ing alpha cages through 8-MR pores with no con­nec­tiv­i­ty along the [001] axis. The active sites with­in the micro­p­orous struc­ture are not read­i­ly acces­si­ble to aro­mat­ic mol­e­cules. How­ev­er, UZM- 5 (UFI) based cat­a­lysts is shown to be effec­tive in the alky­la­tion of ben­zene with light olefin under the liq­uid phase test con­di­tion. The good cat­alyt­ic per­for­mance sug­gests that there are abun­dant active sites exter­nal to the micro­p­orous struc­ture of UZM-5 and is con­sis­tent with struc­tur­al char­ac­ter­i­za­tion using DIF­Fax and HR-TEM. In con­trast the dis­pro­por­tion­a­tion and trans alky­la­tion reac­tion of alkyl­ben­zene over zeo­lite beta (BEA) is car­ried out by acid sites in zeo­lite micro­p­ores and is sen­si­tive to acid­i­ty irre­spec­tive of the vary­ing mor­pholo­gies achieved by var­i­ous syn­the­sis approach­es. As shown by the EB dis­pro­por­tion­a­tion reac­tion in vapor phase and acid­i­ty mea­sure­ment by FTIR, the max­i­mal activ­i­ty coin­cides with max­i­mal acid­i­ty. Fur­ther­more, the activ­i­ty of the cat­a­lyst in liq­uid phase trans-alky­la­tion of di-iso­propy­l­ben­zene with ben­zene is shown to require both frame­work and non-frame­work alu­minum to achieve max­i­mal reac­tiv­i­ty.

Speaker’s Biog­ra­phy – Deng-Yang Jan has been work­ing in cat­a­lyst and prod­uct devel­op­ment at UOPHoney­well since 1986. He received his Ph. D. in Inor­gan­ic Chem­istry from The Ohio State Uni­ver­si­ty in 1985.

2011 Spring Symposium

 
Mike Harold
Depart­ment of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing
Uni­ver­si­ty of Hous­ton

Abstract — Cat­alyt­ic tech­nolo­gies are crit­i­cal to reduc­ing NOx and par­tic­u­late soot from diesel exhaust. In this talk an overview will be pro­vid­ed of efforts span­ning exper­i­men­tal stud­ies of NOx stor­age and reduc­tion and selec­tive cat­alyt­ic reduc­tion, mod­el­ing of mono­lith reac­tors, and dynamome­ter test­ing of fuels and aftertreat­ment tech­nolo­gies. The effec­tive­ness and spa­tio-tem­po­ral fea­tures of the “lean NOx trap” (LNT) will be described based on our com­bined exper­i­men­tal and mod­el­ing stud­ies. Our recent work focused on the gen­er­a­tion and reac­tiv­i­ty of NH3 has sig­nif­i­cance in NSR/SCR appli­ca­tions. Exper­i­ments in both bench-scale and Tem­po­ral Analy­sis of Prod­ucts (TAP) reac­tors reveal a com­plex cou­pling between the stor­age chem­istry and trans­port process­es. Mea­sure­ments of the con­cen­tra­tion fronts show that a major route to N2 for­ma­tion is via NH3. Sys­tem­at­ic vari­a­tion of the Pt dis­per­sion results in a sig­nif­i­cant vari­a­tion in stor­age and reduc­tion activ­i­ty as well as the prod­uct dis­tri­b­u­tion. Iso­topic TAP exper­i­ments reveal the exis­tence of gra­di­ents in the stored NOx in the vicin­i­ty of the Pt crys­tal­lites. The trans­port of the stored NOx can lim­it the regen­er­a­tion rate under some con­di­tions. Glob­al kinet­ic and micro­ki­net­ic mod­els are devel­oped that pre­dict most of the obser­va­tions and direct ongo­ing design and opti­miza­tion efforts. Stud­ies of selec­tive cat­alyt­ic reduc­tion of NOx with NH3 on Fe- and Cu-based zeo­lite coat­ed mono­liths will be also be high­light­ed described. Steady-state kinet­ics exper­i­ments reveal sev­er­al com­pet­ing reac­tions. The NOx con­ver­sion is shown to be a non­lin­ear func­tion of the NO: NO2 feed ratio and is under­mined by the com­pet­ing reac­tions of NH3 and NO oxi­da­tion. Trans­port lim­i­ta­tions become prob­lem­at­ic when NO2 is present.

Speaker’s Biog­ra­phy — Mike Harold is the M.D. Ander­son Pro­fes­sor of Chem­i­cal & Bio­mol­e­c­u­lar Engi­neer­ing at the Uni­ver­si­ty of Hous­ton. He received his B.S. in Chem­i­cal Engi­neer­ing from Penn State in 1980 and his PhD in Chem­i­cal Engi­neer­ing from the Uni­ver­si­ty of Hous­ton in 1985. Mike joined the fac­ul­ty of the Chem­i­cal Engi­neer­ing Depart­ment at the Uni­ver­si­ty of Mass­a­chu­setts at Amherst, where he became Asso­ciate Pro­fes­sor in 1991. In 1993 Mike joined DuPont Com­pa­ny where he held sev­er­al research and super­vi­so­ry posi­tions. In 1999 Mike was appoint­ed Research Man­ag­er of the Chem­i­cal Process Fun­da­men­tals Group in the Cen­tral Research Depart­ment of the DuPont Com­pa­ny. Mike returned to acad­e­mia as the Dow Chair of the UH Depart­ment of Chem­i­cal Engi­neer­ing, which lat­er became the Depart­ment of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing. He served this post until fall 2008.

2011 Spring Symposium

 
Robert McIn­trye
Mil­len­ni­um Inor­gan­ic Chem­i­cals a Cristal Com­pa­ny

Abstract — Pho­to­cat­alyt­ic prod­ucts have been around for many years with use in numer­ous appli­ca­tions. Pho­to­cat­alyt­ic TiO2 is being used today in air purifi­ca­tion devices and as sur­face treat­ment and addi­tive in ceram­ics, cement, trans­porta­tion infra­struc­ture and glass. These prod­ucts are being uti­lized or eval­u­at­ed for their de-pol­lu­tion, self-clean­ing, anti-fun­gal, and envi­ron­men­tal improve­ment attrib­ut­es. Pho­to­cat­alyt­ic coat­ings are one of the tools we have which can be used to com­bat the air qual­i­ty issues. Many tri­als have been car­ried out using pho­to­cat­alyt­ic prod­ucts. For the first time, tri­als have shown, quan­ti­ta­tive­ly, the de-pol­lu­tion effect using chemil­lu­mi­nes­cence mon­i­tors over extend­ed peri­ods. This allows unam­bigu­ous sta­tis­ti­cal analy­sis which proves the tech­nol­o­gy is a cost effec­tive prac­ti­cal solu­tion to inner city pol­lu­tion prob­lems. In this pre­sen­ta­tion we eval­u­ate the effi­cien­cy of two types of pho­to­cat­alyt­ic prod­ucts with respect to the removal of haz­ardous NOx pol­lu­tion: pho­to­cat­alyt­ic paints and trans­par­ent clear coat­ings for con­crete sur­faces. The set­ting of impor­tant field test tri­als and the cor­re­spond­ing results are ana­lyzed and pre­sent­ed in details in this lec­ture.

Speaker’s Biog­ra­phy – Robert McIn­trye is cur­rent­ly the Glob­al Research Direc­tor for Mil­len­ni­um Inor­gan­ic Chem­i­cals a Cristal Com­pa­ny. Pri­or to join­ing Mil­le­ni­um, Robert was a research man­ag­er for ICI (’92 – ’97) and Sur­face Chem­istry Cour­taulds (’87 – ’92).

2011 Spring Symposium

 
John L. Cas­ci
John­son Matthey

Abstract — Feed­stocks for Chem­i­cals and Fuels are chang­ing, with an increas­ing empha­sis on coal and bio-mass along­side the move to heav­ier, and dirt­i­er, sources of oil. One tech­nol­o­gy plat­form that cuts across these diverse feed­stocks is based on Syn­the­sis Gas (Syn­Gas). Each feed­stock, how­ev­er, pos­es spe­cif­ic chal­lenges: chal­lenges that occur across the flow-sheet par­tic­u­lar­ly in purifi­ca­tion and Syn­Gas gen­er­a­tion. The glob­al oper­at­ing envi­ron­ment requires new tech­nolo­gies to be robust and cap­i­tal inten­sive while increas­ing the aware­ness of, and empha­sis on, sus­tain­abil­i­ty requir­ing inno­v­a­tive solu­tions to min­i­mize emis­sions of green­house gas­es. The pro­duc­tion of liq­uid hydro­car­bons from Syn­Gas is com­mon­ly referred to by
the names of the inven­tors, Fis­ch­er and Trop­sch, and hence as Fis­ch­er-Trop­sch (FT) catal­y­sis. FT tech­nol­o­gy dates back to the ear­ly 20th cen­tu­ry but is being “re-invent­ed” for 21st cen­tu­ry needs and mar­kets.

This pre­sen­ta­tion will pro­vide a brief overview of key tech­nolo­gies across the Syn­Gas flow­sheet: cat­a­lysts and process and the require­ment to inte­grate. Fis­ch­er- Trop­sch catal­y­sis will be high­light­ed and a his­toric per­spec­tive pre­sent­ed. Final­ly, using exam­ples from our own lab­o­ra­to­ries, the key role of advanced char­ac­ter­i­za­tion, and diag­nos­tic tools, in the elu­ci­da­tion of cat­a­lyst struc­ture across the length scales will be high­light­ed.

Speaker’s Biog­ra­phy – John Cas­ci is cur­rent­ly the Tech­nol­o­gy Man­ag­er at the John­son Matthey Tech­nol­o­gy Cen­tre at Chilton man­ag­ing Cat­a­lyst Research, Man­u­fac­tur­ing Sci­ence, Cat­a­lyst Engi­neer­ing and Zeo­lite teams. From 2002–2006, John was the Catal­y­sis R&D Direc­tor at Chilton focused on Fis­ch­er-Trop­sch cat­a­lysts. Pri­or to 2002, John had mul­ti­ple roles in ICI focus­ing on cat­a­lyst and zeo­lite research, devel­op­ment and scale­up.

2011 Spring Symposium

 
Lynne B. McCusker and Chris­t­ian Baer­locher
Lab­o­ra­to­ry of Crys­tal­log­ra­phy
ETH Zurich

Abstract — Struc­tur­al infor­ma­tion is essen­tial to the under­stand­ing of zeo­lite chem­istry. Whether it is the syn­the­sis process, the adsorp­tion prop­er­ties, the ion-exchange selec­tiv­i­ty, or the cat­alyt­ic activ­i­ty that is of inter­est, the key lies in the struc­ture. How­ev­er, zeolitic mate­ri­als tend to be poly­crys­talline, so stan­dard sin­gle-crys­tal meth­ods of struc­ture analy­sis can­not be applied. For­tu­nate­ly, pow­der dif­frac­tion meth­ods have devel­oped enor­mous­ly in the last 20 years, and as a result, struc­ture analy­sis using pow­der dif­frac­tion data has become almost rou­tine. Nev­er­the­less, zeo­lite struc­tures often pose a chal­lenge to these meth­ods.

For struc­ture solu­tion, i.e. when the zeo­lite frame­work struc­ture is not known, the prob­lems to be over­come are twofold: (1) the basic phase prob­lem, which is cen­tral to all crys­tal­lo­graph­ic struc­ture analy­ses (includ­ing sin­gle crys­tals), and (2) the reflec­tion over­lap prob­lem, which is spe­cif­ic to pow­der dif­frac­tion data. Over the years, our group has devel­oped sev­er­al dif­fer­ent approach­es to these prob­lems, and a few of these (the use of chem­i­cal infor­ma­tion to sup­ple­ment the pow­der dif­frac­tion data, the adap­ta­tion of the charge-flip­ping algo­rithm to accom­mo­date pow­der dif­frac­tion data, and the use of elec­tron microscopy data to com­ple­ment the pow­der dif­frac­tion data) will be described.

Once the basic frame­work struc­ture is known, inves­ti­ga­tion of the details of the struc­ture can begin. Where is the struc­ture direct­ing agent? Where are the iso­mor­phous­ly sub­sti­tut­ed atoms in the frame­work? What hap­pens upon cal­ci­na­tion? Where are the ions before and after ion exchange? Where are the sorbed mol­e­cules? Under favor­able cir­cum­stances, these ques­tions can be addressed by gen­er­at­ing dif­fer­ence elec­tron den­si­ty maps using the mea­sured pow­der dif­frac­tion pat­tern and the frame­work struc­ture mod­el. How­ev­er, not all prob­lems are amenable to this tech­nique and even when they are, the inter­pre­ta­tion of the maps still requires con­sid­er­able patience and per­se­ver­ance. The pos­si­bil­i­ties and lim­i­ta­tions will be dis­cussed.

Speaker’s Biog­ra­phy — Lynne McCusker has been study­ing zeo­lite crys­tal struc­tures since she start­ed her doc­tor­al research with Karl Seff at the Uni­ver­si­ty of Hawaii in 1976. After spend­ing three years as a post­doc in the group of Wal­ter Meier at the ETH in Zurich, Switzer­land learn­ing pow­der dif­frac­tion tech­niques from Chris­t­ian Baer­locher, she moved on to Texas A&M Uni­ver­si­ty to put these new­ly acquired skills into prac­tice. In 1985, she moved back across the Atlantic for anoth­er post­doc, this time at Oxford Uni­ver­si­ty in Mike Glazer’s group. There she learned the val­ue of syn­chro­tron radi­a­tion and solved her first nov­el zeo­lite frame­work struc­ture (Sig­ma 2). For this work, she received the Bar­rer Award from the British Zeo­lite Asso­ci­a­tion in 1987 and the Phys­i­cal Crys­tal­log­ra­phy Award from the British Crys­tal­lo­graph­ic Asso­ci­a­tion in 1989. In 1988, she returned to the ETH and for the last 20 years has head­ed a group, togeth­er with Chris­t­ian Baer­locher, devot­ed to the devel­op­ment of method­ol­o­gy for solv­ing zeo­lite frame­work struc­tures from pow­der dif­frac­tion data. In 2007, they received the Breck Award of the IZA (togeth­er with Osamu Terasa­ki) for their zeo­lite struc­tur­al work. In 2010, she received the IZA award for the research she has done with Chris­t­ian and for her ser­vice to the IZA com­mu­ni­ty.

2011 Spring Symposium

 
John N. Armor
Glob​al​Catal​y​sis​.com
Ore­field, PA, USA

Abstract — Ener­gy is one of the biggest busi­ness­es in the world, and catal­y­sis plays a big part in mak­ing this hap­pen. For 2010, the pro­ject­ed mar­ket for cat­a­lysts for ener­gy and envi­ron­men­tal seg­ments exceed­ed $16. bil­lion (Bharat Book Bureau, June 2010). This pre­sen­ta­tion will describe the impor­tance of under­stand­ing how cur­rent and future ener­gy needs and usage fit inti­mate­ly into catal­y­sis and chem­istry. Ener­gy needs and con­sump­tion impact economies world­wide, glob­al envi­ron­men­tal con­cerns, and also the chem­i­cal indus­try. Catal­y­sis plays a piv­otal role in cre­at­ing new, more effi­cient routes to chem­i­cals and adding flex­i­bil­i­ty to our spec­trum of ener­gy sources, ener­gy car­ri­ers, and ener­gy conversion/production, while offer­ing a green­er more sus­tain­able solu­tion to future ener­gy demands. Thus, catal­y­sis is fun­da­men­tal to gen­er­at­ing cur­rent and future ener­gy solu­tions, and new ener­gy effi­cient sys­tems. Catal­y­sis has and will con­tin­ue to play a key role in the gen­er­a­tion of envi­ron­men­tal­ly friend­ly, sus­tain­able, and clean­er sources of ener­gy. The pre­sen­ta­tion will look anew at glob­al ener­gy sup­plies and focus on the com­po­nents and the increas­ing role of nat­ur­al gas (rel­a­tive to petro­le­um and coal), renew­ables, gas purifi­ca­tion, and how all this pro­vides mul­ti­ple oppor­tu­ni­ties for catal­y­sis, espe­cial­ly with regard to envi­ron­men­tal con­cerns. What is impres­sive is the past and pro­ject­ed growth of the world’s demand for ener­gy. Over the last 30 years, all of the major fuel options have shown mod­est growth, but these growth rates are pro­ject­ed to increase sig­nif­i­cant­ly over the next 20 years. World ener­gy demand is expect to expand by almost 45% between 2010 and 2030. It is clear that this demand is dri­ven not only by sus­tained growth in the US and Europe, but by rapid growth in Chi­na, India, and oth­er parts of Asia. The key is that demand will remain tight and very sus­cep­ti­ble to unpre­dictable events which can cre­ate hav­oc in the com­modi­ties mar­kets. When cou­pled with increas­ing pop­u­la­tions and people’s nat­ur­al quest to improve lifestyles, the price of oil (and ener­gy) is pro­ject­ed to only go high­er and high­er. The demands on ener­gy sup­ply will con­tin­ue to push nations to retrieve dirt­i­er sources of oil (oil shale and tar sands) and impure nat­ur­al gas. Those mar­ket forces and envi­ron­men­tal pres­sures, through tougher emis­sions con­trols and purifi­ca­tion stan­dards, will con­tin­ue to dri­ve con­tin­u­ing growth in cat­a­lysts as well as purifi­ca­tion meth­ods and mate­ri­als.

Speaker’s Biog­ra­phy — John N. Armor, PhD, has oper­at­ed his own inter­na­tion­al catal­y­sis con­sult­ing com­pa­ny, Glob​al​Catal​y​sis​.com L.L.C., since retir­ing from Air Prod­ucts, Inc in 2004 (after 19 years). Before serv­ing as the leader of the Catal­y­sis Research Cen­ter at Air Prod­ucts, he was a group leader at Allied Chem­i­cal (11 years), and an Assis­tant Pro­fes­sor of Chem­istry at Boston Uni­ver­si­ty (4 years). He is a past Pres­i­dent of the North Amer­i­can Catal­y­sis Soci­ety (2001–2009) and active­ly involved in oth­er pro­fes­sion­al orga­ni­za­tions, served as an edi­tor of Applied Catal­y­sis and CATTECH, and also has served on sev­er­al edi­to­r­i­al boards. He has pub­lished over 125 arti­cles in catal­y­sis and been a co-inven­tor on over 50 US patents, and he has been inter­na­tion­al­ly rec­og­nized by sev­er­al pres­ti­gious awards (includ­ing the Houdry and Mur­phree Awards and the Excel­lence in Catal­y­sis Award of the Philadel­phia Catal­y­sis Club).