Author Archives: Edrick Morales

Search for a better water gas shift catalyst

2008 Spring Symposium

 
Luis Boll­mann, Joshua L. Ratts, W. Damion Williams, Jorge Pazmino,Jeffrey T. Miller1, W. Nicholas Del­gass, Fabio H. Ribeiro
School of Chem­i­cal Engi­neer­ing
Pur­due Uni­ver­si­ty
480 Sta­di­um Mall Dri­ve
West Lafayette, IN 47907–2100

1BP Research Cen­ter
E-1F, 150 W.Warrenville Rd.
Naperville, IL 60563

Abstract — We are attempt­ing to syn­the­size a cat­a­lyst for the WGS reac­tion that has the high­turnover rate (TOR) of the Cu-based sys­tem and the capa­bil­i­ty typ­i­cal of noble met­al­sys­tems to recov­er from oper­a­tional upsets. The kinet­ic mea­sure­ments were car­ried out­at 300 °C, 1 bar, 6.8% CO, 22% H2O, 8.5% CO2, 37.3% H2, and bal­ance Argon. As aref­er­ence, the TOR for a Cu based cat­a­lyst at these con­di­tions was about 2 s-1. Wes­t­ud­ied cat­a­lysts based on Pd and Pt. For Pt on alu­mi­na, par­ti­cle size (2–15 nm) caused­no change in the TOR, which was about 1 s-1 for Pt on CeO2, TiO2, and ZrO2 supports,implying that these sup­ports do not influ­ence the reac­tiv­i­ty.

How­ev­er, cat­a­lysts sup­port­e­don sil­i­ca and alu­mi­na showed a TOR about 10 times low­er than those on these three­sup­ports. The addi­tion of, for exam­ple, Mo, Fe, and Zn to Pd and Pt cat­a­lysts on alu­mi­nasig­nif­i­cant­ly increased the rate (up to a fac­tor of 100), but only up to the rate on the non­in­ter­act­ing­sup­ports. The rates of Pd and Pt cat­a­lysts sup­port­ed on the non-inter­act­ing­sup­ports CeO2, TiO2, and ZrO2 could not be fur­ther increased by any of these additives.For a series of Pd-Zn cat­a­lysts rang­ing from 2 to 19 wt% Zn on Al2O3, it was observed byEX­AFS and DRIFTS of CO that Pd alloyed with Zn, and that the alloy exhib­it­ed anin­creased TOR of up to 20 times as com­pared to Pd on Al2O3. The pres­ence of zin­ca­lu­mi­nate was also observed. The addi­tion of 2 wt% Zn to Pd cat­a­lysts sup­port­ed onTiO2, CeO2 and ZrO2 did not enhance the WGS rate, although alloy­ing was ver­i­fied byEX­AFS and DRIFTS of CO. The TORs of Pd on these three sup­ports were as high as theTOR on the best PdZn on alu­mi­na. One expla­na­tion of the results is that Zn forms ana­lu­mi­nate and pre­vents a dele­te­ri­ous inter­ac­tion between Pd and alu­mi­na. Zinc is thus­not a true pro­mot­er for WGS, although it decreased the unde­sir­able metha­na­tion reac­tion­to below detec­tion lim­its. While we have found ways to mit­i­gate the dele­te­ri­ous effect­sof alu­mi­na and sil­i­ca on the WGS rate, we have not yet found a pro­mot­er that will­increase the TOR sig­nif­i­cant­ly for Pd or Pt on non-inter­act­ing sup­ports.

Speaker’s BioBiog­ra­phy — Dr. Ribeiro is Pro­fes­sor at the School of Chem­i­cal Engi­neer­ing, Pur­due­U­ni­ver­si­ty. His research inter­est is in kinet­ics of het­ero­ge­neous cat­alyt­ic processes.Before start­ing on acad­e­mia, Dr. Ribeiro has worked in indus­try and in research using­mod­el cat­a­lysts and sur­face sci­ence tech­niques.

Molecular Basket Sorbents as a Novel Approach to CO2 Capture and Separation

2008 Spring Symposium

 
Chun­shan Song
Direc­tor, EMS Ener­gy Insti­tute and Pro­fes­sor of Fuel Sci­ence
Depart­ment of Ener­gy and Min­er­al Engi­neer­ing
The Penn­syl­va­nia State Uni­ver­si­ty
209 Aca­d­e­m­ic Projects Build­ing
Uni­ver­si­ty Park, PA 16802, USA
Tel: 814–863-4466
csong@​psu.​edu

Abstract — This lec­ture will begin with an overview of ener­gy-relat­ed cap­ture, sequestration,conversion, and uti­liza­tion of car­bon diox­ide (CO2) [C.S. Song, Catal. Today, 115 (2006)2–32]. Car­bon cap­ture and seques­tra­tion (CCS) is con­sid­ered as one of the key options for mit­i­gat­ing the emis­sions of CO2 from ener­gy sys­tems. Accord­ing to stud­ies by U.S. Depart­ment of Ener­gy, CO2 cap­ture by cur­rent com­mer­cial tech­nol­o­gy using aque­ous solu­tions of liq­uid alka­nolamines is ener­gy inten­sive and con­tributes to as much as two thirds of the total cost for CO2 seques­tra­tion. We have pro­posed a new design con­cept of “mol­e­c­u­lar bas­ket sor­bent (MBS)” as a nov­el approach to CO2 cap­ture and sep­a­ra­tion using selec­tive sol­id sor­bent [X. Xu et al., Micro­p­or. Meso­por. Materi., 62 (2003) 29–45]. CO2 “mol­e­c­u­lar bas­ket” is nano-porous, CO2-selec­tive high-capac­i­ty sor­bent for adsorp­tion sep­a­ra­tion of CO2 from var­i­ous gas mix­tures.

We have explored a num­ber of new MBS for­mu­la­tions. An exam­ple of the MBS-CO2 is a nano-porous com­pos­ite of poly­eth­yl­eneimine and a meso­porous moec­u­lar sieve MCM-41. PEI-MCM-41 type sor­bents have been found to be effec­tive for remov­ing CO2 from flue gas and oth­er gas streams with high capac­i­ty and selec­tiv­i­ty at 20–100 °C under atmos­pher­ic pres­sure. The CO2 adsorp­tion capac­i­ty and CO2 sep­a­ra­tion selec­tiv­i­ty of MCM-41 were great­ly improved by load­ing PEI into its nano-sized pore chan­nels (about 3 nm), which made the result­ing sor­bent oper­at­ing like a “mol­e­c­u­lar bas­ket” for CO2 (MBS-CO2). The influ­ence of mois­ture con­cen­tra­tions in the sim­u­lat­ed flue gas on the CO2 adsorp­tion sep­a­ra­tion per­for­mance was also exam­ined. CO2 adsorp­tion capac­i­ty of the MCM-41-PEI adsor­bent for the sim­u­lat­ed moist flue gas was high­er than that for the sim­u­lat­ed dry flue gas. The cap­tured CO2 can be eas­i­ly and com­plete­ly recov­ered by using a purge gas or a vac­u­um sys­tem at 75–100 °C. The mul­ti-cycle exper­i­ments have shown that the MBS-CO2sor­bents have very good regen­er­a­bil­i­ty and sta­bil­i­ty [C. S. Song et al., Stud. Surf, Sci.Catal., 153 (2004) 411–416]. With the MBS, CO2 cap­ture from flue gas can be con­duct­ed in a sol­vent-free and com­pact sol­id sor­bent sys­tem more ener­gy effi­cient­ly, eco­nom­i­cal­ly and envi­ron­men­tal­ly friend­ly. The MBS-CO2 con­cept has also been found applic­a­ble to cap­ture and sep­a­ra­tion of hydro­gen sul­fide H2S in gas mix­tures [X.Wang et al., Green Chem­istry, 9 (2007) 695–702]. Results of ana­lyt­i­cal char­ac­ter­i­za­tion of MBS will also bedis­cussed to shed light on why and how these nov­el sor­bents work under real­is­tic con­di­tions.

Speaker’s Biog­ra­phy — Dr. Chun­shan Song is a Pro­fes­sor of Fuel Sci­ence and the Direc­tor of the EMS Ener­gy Insti­tute at the Penn­syl­va­nia State Uni­ver­si­ty. His research inter­ests include catal­y­sis and adsorp­tion for fuel pro­cess­ing, adsorp­tion desul­fu­r­iza­tion of fuels and reform­ing of hydro­car­bons and bio­fu­els for fuel cells, shape-selec­tive catal­y­sis for chem­i­cals, CO2 cap­ture and uti­liza­tion, heavy oil upgrad­ing, and con­ver­sion of coal and bio­mass to liq­uid fuels and chem­i­cals.

Automotive Emission Control: Past, Present and Future

2008 Spring Symposium

 
Robert J. Far­rauto
Research Fel­low
BASF Cat­a­lysts
Iselin, New Jer­sey
Bob.​Farrauto@​BASF.​com

Adjunct Pro­fes­sor, Earth and Envi­ron­men­tal Engi­neer­ing
Colum­bia Uni­ver­si­ty
City of New York

Abstract — The first auto­mo­bile cat­a­lysts, for gaso­line fueled inter­nal com­bus­tion engines(IC) were intro­duced in 1975. They were designed to facil­i­tate the reduc­tion of car­bon­monox­ide (CO) and unburned gaso­line derived hydro­car­bons (HC). The cat­a­lyst had tocon­tin­ue to func­tion with a approx­i­mate reduc­tion of 90% (rel­a­tive to an uncontrolled1970 vehi­cle) for 50,000 miles. The auto­mo­bile indus­try was skep­ti­cal since the suc­ces­sof the cat­a­lyst was depen­dent on the dri­ving and main­te­nance cycles of the aver­age­con­sumer. Since that time we have seen one of the most suc­cess­ful appli­ca­tions ofcatal­y­sis for clean­ing emis­sions from IC engines includ­ing gaso­line, diesel, two and 4cycle engines, pow­er plants, chem­i­cal plants, restau­rants, and wide body air­craft to namea few. Today we see the three way cat­a­lyst (TWC) as the heart of a closed loop enginecon­trol strat­e­gy suc­cess­ful­ly reduc­ing emis­sions of CO, HC and oxides of nitro­gen (NOx)to near zero for 150,000 miles. This has clear­ly been an achieve­ment of epic pro­por­tion­swith a pos­i­tive impact on the envi­ron­ment and the health of the world.

Now cat­alyt­ic sci­en­tists and engi­neers are faced with new chal­lenges for­con­trol­ling diesel engine emis­sions for trucks, bus­es and pas­sen­ger cars. As we approach2010 Fed­er­al Stan­dard emis­sions of CO, HC, NOx and par­tic­u­lates must approach zerolevels. This is still not the end because we are now see­ing the emer­gence ofen­vi­ron­men­tal emis­sion con­trol with the need to uti­lize more renew­able sources oftrans­porta­tion fuels. Catal­y­sis is already tak­ing on the chal­lenges of gen­er­at­ing alter­na­tivesources of ener­gy while pre­serv­ing the world’s envi­ron­ment.

Today’s talk will pro­vide a brief his­to­ry of some of the accom­plish­ments incon­trol­ling emis­sions from the gaso­line and diesel engines and point to alter­na­tivetech­nolo­gies under inves­ti­ga­tion includ­ing advanced NOx reduc­tion tech­nolo­gies, newengine con­cepts and the fuel cell as the end game in the hydro­gen econ­o­my.

Speaker’s Biog­ra­phy — Dr. Far­rauto is a Research Fel­low at the Cor­po­rate Research­Lab­o­ra­to­ries of BASF Cat­a­lysts (for­mer­ly Engel­hard) in Iselin, New Jer­sey, USA. His­ma­jor respon­si­bil­i­ties have includ­ed the devel­op­ment of advanced auto­mo­bile emis­sion­con­trol cat­a­lysts and cat­a­lysts for the chem­i­cal indus­try. He man­aged an Engel­hardresearch team that devel­oped and com­mer­cial­ized diesel oxi­da­tion cat­a­lysts for theEu­ro­pean, North Amer­i­can and Asian mar­kets for pas­sen­ger cars and heavy duty trucks.Currently he man­ages a research team devel­op­ing new cat­a­lyst tech­nol­o­gy for the­hy­dro­gen econ­o­my includ­ing hydro­gen refu­el­ing sta­tions and fuel cells for stationary,portable pow­er and vehic­u­lar appli­ca­tions. He is also Adjunct Pro­fes­sor in the Earth andEn­vi­ron­men­tal Engi­neer­ing Depart­ment of Colum­bia Uni­ver­si­ty, in the City of NewYork where he teach­es course in catal­y­sis.

Elected Officers for the 2008–2009 Season

Elec­tions for the 2008–2009 offi­cers were held on Thurs­day, April 24, 2008. The elect­ed offi­cers are: Michael Smith, Chair-Elect (Vil­lano­va Uni­ver­si­ty); Steve Harries,Treasurer (Lyon­dell­Basell Indus­tries); Joe Fedeyko, Direc­tor (John­son Matthey); Haim­ing Liu, Direc­tor (Arke­ma Inc.); and Eliz­a­beth Ross-Medgaar­den, Direc­tor (Lyon­dell­Basell Indus­tries). Con­grat­u­la­tions!

DOE Catalysis for Energy Report Defines Future Research Directions

A recent­ly pub­lished report, Basic Research Needs: Catal­y­sis for Ener­gy, iden­ti­fies research oppor­tu­ni­ties for catal­y­sis to help meet the nation’s ener­gy needs, assess­es the cur­rent state of catal­y­sis sci­ence and tech­nol­o­gy, and rec­om­mends fun­da­men­tal research direc­tions to meet the goals described in the report. The report is based on a work­shop held in August, 2007, co-chaired by Alex­is Bell of the Uni­ver­si­ty of Cal­i­for­nia at Berke­ley, Bruce Gates of the Uni­ver­si­ty of Cal­i­for­nia at Davis, and Dou­glas Ray of the Pacif­ic North­west Nation­al Lab­o­ra­to­ry.

The report con­clud­ed that, on the basis of cur­rent trends, the Unit­ed States must seri­ous­ly reassess its ener­gy future. The urgent need for fuels in an era of declin­ing resources and press­ing envi­ron­men­tal con­cerns demands a resur­gence in catal­y­sis sci­ence, requir­ing a mas­sive com­mit­ment of pro­gram­mat­ic lead­er­ship and improved exper­i­men­tal and the­o­ret­i­cal meth­ods to make it pos­si­ble to fol­low, in real time, cat­alyt­ic reac­tions on an atom­ic scale on sur­faces that are nonuni­form and laden with large mol­e­cules under­go­ing com­plex com­pet­ing process­es. Ulti­mate­ly, a goal should be devel­op­ment of sus­tain­able tech­nolo­gies for con­vert­ing car­bon diox­ide and water into fuel feed­stocks. Until that future state is reached, new under­stand­ing of more tra­di­tion­al cat­a­lyst form and func­tion can ease the way to a more sus­tain­able ener­gy future.

Details are avail­able in the full 222-page report, which is acces­si­ble on line at www​.sc​.doe​.gov/​b​e​s​/​r​e​p​o​r​t​s​/​f​i​l​e​s​/​C​A​T​_​r​p​t​.​pdf.

Breaking the Chemical and Engineering Barriers to Lignocellulosic Biofuels

Work­shop Chair: George W. Huber, Uni­ver­si­ty of Mass­a­chu­setts-Amherst

Spon­sors:
Nation­al Sci­ence Foun­da­tion: Chem­i­cal, Bio­engi­neer­ing, Envi­ron­men­tal and Trans­port Sys­tems, John Regal­b­u­to
Depart­ment of Ener­gy: Office of the Bio­mass, Paul Grabows­ki
Amer­i­can Chem­i­cal Soci­ety-Green Chem­istry Insti­tute


A recent roadmap out­lines the vital impor­tance of cat­a­lysts for cel­lu­losic bio­fu­els. This roadmap is avail­able elec­tron­i­cal­ly at www​.ecs​.umass​.edu/​b​i​o​f​u​els and is the result of a 2 day work­shop spon­sored by the Nation­al Sci­ence Foun­da­tion and Depart­ment of Ener­gy. This work­shop brought togeth­er more than 70 par­tic­i­pants from acadamia, indus­try and gov­ern­ment agen­cies to pro­vide a uni­fied doc­u­ment on how cel­lu­losic bio­fu­els can become a prac­ti­cal real­i­ty. The roadmap artic­u­lates the cen­tral role of chem­istry, chem­i­cal catal­y­sis, ther­mal pro­cess­ing, and engi­neer­ing in the con­ver­sion of lig­no­cel­lu­losic bio­mass into liq­uid trans­porta­tion fuels includ­ing green gaso­line, green diesel and green jet fuel.

Six thrust areas are dis­cussed in the roadmap includ­ing:

  • Selec­tive Ther­mal Pro­cess­ing of Lig­no­cel­lu­losic Bio­mass
  • Uti­liza­tion of Petro­le­um Refin­ing Tech­nolo­gies for Bio­fu­el Pro­duc­tion
  • Aque­ous-phase Cat­alyt­ic Pro­cess­ing of Sug­ars and Bio-oils
  • Cat­alyt­ic Con­ver­sion of Syn-gas
  • Process Engi­neer­ing and Design
  • Cross Cut­ting 21st Cen­tu­ry Sci­ence, Tech­nol­o­gy, and Infra­struc­ture for a New Gen­er­a­tion of Bio­fu­el Research

This work­shop builds on the suc­cess of four pre­vi­ous NSF and DOE work­shops. The pre­vi­ous NSF work­shops include: “Catal­y­sis for Biore­new­ables Con­ver­sion (www​.egr​.msu​.edu/​a​p​p​s​/​n​s​f​w​o​r​k​s​hop)” and “Design of Cat­a­lyst Sys­tems for Biore­new­ables (www3​.cbe​.ias​tate​.edu/​n​s​f​b​i​o​r​en/)”. The pre­vi­ous DOE work­shops include: “Break­ing the Bio­log­i­cal Bar­ri­ers to Cel­lu­losic Ethanol” (genomic​s​gtl​.ener​gy​.gov/​b​i​o​f​u​e​l​s​/​b​2​b​w​o​r​k​s​h​o​p​.​s​h​tml) and “Ther­mo­chem­i­cal Con­ver­sion of Bio­mass” (www​.ther​mochem​.bio​mass​.gov​tools​.us/).

For cel­lu­losic bio­fu­els to real­ize their full poten­tial it is vital to over­come the chem­i­cal and engi­neer­ing bar­ri­ers. Recent advances in the­o­ret­i­cal chem­istry com­bined with new in-situ cat­a­lyst char­ac­ter­i­za­tion meth­ods allow us to under­stand chem­istry at a fun­da­men­tal­ly new lev­el. Com­bin­ing fun­da­men­tal chem­i­cal under­stand­ing with new meth­ods to syn­the­size nanos­truc­tured cat­alyt­ic mate­ri­als, the abil­i­ty to design and sim­u­late com­pli­cat­ed reac­tion net­works, and the abil­i­ty to per­form con­cep­tu­al design and opti­miza­tion prob­lems will allow us to engi­neer effi­cient and eco­nom­i­cal process­es for bio­fu­el pro­duc­tion.

Travel Grants for Participation in the 14th ICC

The North Amer­i­can Catal­y­sis Soci­ety, NACS, will dis­perse fund­ing from the Nation­al Sci­ence Foun­da­tion and the Depart­ment of Ener­gy to sup­port par­tic­i­pa­tion by US cat­alyt­ic sci­en­tist and engi­neers in the 14th Inter­na­tion­al Con­gress on Catal­y­sis, 14th ICC, to be held in Seoul, Korea from 13–18 July 2008. We hope to sup­port the air trav­el by US car­ri­ers for at least two dozen par­tic­i­pants.

Appli­ca­tions will be cho­sen based on sev­er­al cri­te­ria:

  • Young US fac­ul­ty and/or mem­bers of under­rep­re­sent­ed or minor­i­ty par­tic­i­pants active in catal­y­sis research.
  • Cho­sen pre­sen­ters of oral or poster pre­sen­ta­tions at the 14th ICC.
  • Par­tic­i­pants as ses­sion chairs or oth­er ICC or NACS pro­ceed­ings in Seoul.

Please apply to Wm. Cur­tis Con­ner (For­eign Sec­re­tary of NACS) before 15 May 2008 by email at wconner@​ecs.​umass.​edu, or by Fax to 413–545-0316 or by postal mail to:

Wm. Cur­tiss Con­nerx
For­eign Sec­re­tary of NACS
Dept. Chem. Engi­neer­ing
Uni­ver­si­ty of Mass­a­chu­setts
Amherst, MA 01003

Your one page appli­ca­tion should doc­u­ment your qual­i­fi­ca­tions as spec­i­fied in the cri­te­ria, 1–3, above and include:

  • Your posi­tion, includ­ing years in present posi­tion and activ­i­ty in catal­y­sis research in the last four years (pub­li­ca­tions, grants and pre­sen­ta­tions in catal­y­sis).
  • Your accept­ed par­tic­i­pa­tion in the 14th ICC: oral pre­sen­ta­tions and/or poster(s).
  • Oth­er par­tic­i­pa­tion such as ses­sion chair.
  • Any oth­er fac­tors the inde­pen­dent pan­el should con­sid­er.

The Inde­pen­dent pan­el will inform the appli­cants of their trav­el grants before 1 June 2008.

Again, young fac­ul­ty, par­tic­i­pat­ing stu­dents and under rep­re­sent­ed groups are encour­aged to apply and will be con­sid­ered pos­i­tive­ly! How­ev­er, these grants are restrict­ed pri­mar­i­ly to trav­el expens­es by US car­ri­er. Reg­is­tra­tion and hotel costs are not gen­er­al­ly to be cov­ered by these grants (oth­er spec­i­fied funds are required).