Zeolite Catalysis with a Focus on Downstream Refining Applications

2017 Spring Symposium

C.Y. Chen, Chevron Ener­gy Tech­nol­o­gy Com­pa­ny, Rich­mond, CA

Abstract — Zeo­lites have been impor­tant cat­a­lysts for the refin­ing and petro­chem­i­cal indus­tries and oth­er appli­ca­tions. The use of organo-cation tem­plate mol­e­cules to pro­vide struc­ture direc­tion has giv­en rise to a num­ber of nov­el zeo­lites in recent years, lead­ing to break­throughs in zeo­lite syn­the­sis and pro­vid­ing an impe­tus in devel­op­ing new process chem­istry. As a con­se­quence, the under­stand­ing of zeo­lite struc­tures and the struc­ture-prop­er­ty rela­tion­ships has become not only of basic aca­d­e­m­ic inter­est but also one of the most crit­i­cal tasks in bring­ing the indus­tri­al appli­ca­tions of these mate­ri­als to suc­cess­ful fruition.

In this paper I will first present a brief overview of Chevron’s zeo­lite R&D. Then the empha­sis will be placed on zeo­lite catal­y­sis for down­stream refin­ing appli­ca­tions such as hydro­c­rack­ing, hydroi­so­mer­iza­tion and MTO (methanol to olefins). Here the char­ac­ter­i­za­tion of zeo­lites via cat­alyt­ic test reac­tions and physisorp­tion plays an impor­tant role. The hydro­c­rack­ing and hydroi­so­mer­iza­tion of paraf­fins such as n-hexa­ne, n-decane and n-hexa­de­cane as well as MTO will be dis­cussed as exam­ples for the inves­ti­ga­tion of the cat­alyt­ic prop­er­ties of a series of zeo­lites (e.g., Y, mor­den­ite, fer­rierite, ZSM-5, ZSM-12, ZSM-22, ZSM-48, TNU-9, SSZ-25, SSZ-26, SSZ-32, SSZ-33, SSZ-56, SSZ-57, SSZ-75, SSZ-87 and SSZ-98) and some new exam­ples of shape selec­tiv­i­ties of zeo­lite catal­y­sis will be demon­strat­ed. Fur­ther­more, our stud­ies on the vapor phase physisorp­tion of a series of hydro­car­bon adsor­bates with vary­ing mol­e­cule sizes for a wide spec­trum of zeo­lite struc­tures will be report­ed. Cat­alyt­ic test reac­tions and vapor phase hydro­car­bon adsorp­tion togeth­er also pro­vide use­ful infor­ma­tion for the deter­mi­na­tion of zeo­lite struc­tures.

The author thanks Chevron Ener­gy Tech­nol­o­gy Com­pa­ny for sup­port of zeo­lite R&D, espe­cial­ly S.I. Zones, R.J. Sax­ton and G.L. Scheuer­man.

Biog­ra­phy — C.Y. Chen is a senior staff sci­en­tist and tech­ni­cal team leader in the Catal­y­sis Tech­nol­o­gy Depart­ment of Chevron Ener­gy Tech­nol­o­gy Com­pa­ny locat­ed in Rich­mond, Cal­i­for­nia. He is a zeo­lite sci­en­tist by train­ing and has been work­ing at Chevron for the past 22 years in zeo­lite research projects involv­ing syn­the­sis, mod­i­fi­ca­tion, char­ac­ter­i­za­tion, catal­y­sis, adsorp­tion and com­mer­cial­iza­tion. He received his Diplom in Chem­i­cal Engi­neer­ing from the Uni­ver­si­ty of Karl­sruhe, Ger­many and Ph.D. in Chem­istry from the Uni­ver­si­ty of Old­en­burg, Ger­many with Prof. Jens Weitkamp. Then he was a post­doc at Vir­ginia Tech and Cal­tech with Prof. Mark Davis. He is also an adjunct pro­fes­sor in the Depart­ment of Chem­i­cal Engi­neer­ing at the Uni­ver­si­ty of Cal­i­for­nia at Davis.

Synthesis of Zincosilicate Catalysts for the Oligomerization of Propylene

2017 Spring Symposium

Mark Deimund, Exxon­Mo­bil Research and Engi­neer­ing Com­pa­ny, Annan­dale, NJ

Abstract — Two zin­cosil­i­cate mol­e­c­u­lar sieves (CIT-6 and Zn-MCM-41) were syn­the­sized and ion-exchanged with nick­el, allow­ing them to act as cat­a­lysts for the oligomer­iza­tion of propy­lene into C3n prod­ucts (pri­mar­i­ly C6 and C9 species). For per­for­mance com­par­i­son to alu­mi­nosil­i­cate mate­ri­als, two zeo­lites (high-alu­minum beta and zeo­lite Y) were also nick­el exchanged and uti­lized in the oligomer­iza­tion reac­tion.

CIT-6 and the high-alu­minum zeo­lite beta (HiAl-BEA) both have the *BEA frame­work topol­o­gy, allow­ing for com­par­i­son between the zinc and alu­minum het­eroatoms when exchanged with nick­el, as the for­mer gives two frame­work charges per atom, while the lat­ter gives only one. Ni-CIT-6 and Ni-Zn-MCM-41 enable the com­par­i­son of a micro­p­orous and a meso­porous zin­cosil­i­cate. The Ni2+ ion exchanged onto zeo­lite Y has been pre­vi­ous­ly report­ed to oligomer­ize propy­lene and is used here for com­par­i­son.

Reac­tion data are obtained at 180°C and 250°C, atmos­pher­ic pres­sure, and a WHSV = 1.0 h-1 in a feed stream con­sist­ing of 85mol% propy­lene, with the bal­ance inert. At these con­di­tions, all cat­a­lysts are active for propy­lene oligomer­iza­tion, with steady-state con­ver­sions rang­ing from 3–16%. With the excep­tion of Ni-HiAl-BEA, all cat­a­lysts exhib­it high­er propy­lene con­ver­sions at 250°C than 180°C. Both *BEA topol­o­gy mate­ri­als exhib­it sim­i­lar propy­lene con­ver­sions at each tem­per­a­ture, but Ni-HiAl-BEA is not as selec­tive to C3n prod­ucts as Ni-CIT-6. Zin­cosil­i­cates demon­strate high­er aver­age selec­tiv­i­ties to C3n prod­ucts than the alu­mi­nosil­i­cates at both reac­tion tem­per­a­tures test­ed. Hex­ene prod­ucts oth­er than those expect­ed by sim­ple oligomer­iza­tion are also present, like­ly formed by dou­ble-bond iso­mer­iza­tion cat­alyzed at acid sites.

Addi­tion­al­ly, both of the alu­mi­nosil­i­cate mate­ri­als cat­alyzed crack­ing reac­tions, form­ing non-C3n prod­ucts. The reduced acid­i­ty of the zin­cosil­i­cates rel­a­tive to the alu­mi­nosil­i­cates like­ly accounts for the high­er C3n prod­uct selec­tiv­i­ty of the zin­cosil­i­cates. Zin­cosil­i­cates also exhib­it­ed high­er lin­ear-to-branched hex­ene iso­mer ratios when com­pared to the alu­mi­nosil­i­cates. The meso­porous zin­cosil­i­cate exhibits the best reac­tion behav­ior (includ­ing C3n prod­uct selec­tiv­i­ty: approx­i­mate­ly 99% at both tem­per­a­tures for Ni-Zn-MCM-41) of the cat­alyt­ic mate­ri­als test­ed here.

From Deimund, MA, et al. ACS Catal., 2014, 4 (11), pp 4189–4195. DOI: 10.1021/cs501313z

Biog­ra­phy — Orig­i­nal­ly from Okla­homa City, Okla­homa, Mark attend­ed Texas A&M Uni­ver­si­ty where he earned his under­grad­u­ate degree in chem­i­cal engi­neer­ing. He then attend­ed the Uni­ver­si­ty of Cam­bridge for his MPhil, con­duct­ing research into the for­ma­tion of pro­tein deposits in brain cells as a means to bet­ter under­stand the onset of Alzheimer’s and oth­er neu­rode­gen­er­a­tive dis­eases. Upon com­ple­tion of this degree, he began his PhD work at the Cal­i­for­nia Insti­tute of Tech­nol­o­gy in the area of mol­e­c­u­lar sieve syn­the­sis and reac­tion test­ing under Pro­fes­sor Mark E. Davis. Cur­rent­ly, he works as a researcher at Exxon­Mo­bil Research and Engi­neer­ing Com­pa­ny in Annan­dale, NJ.

Science and Technology of Framework Metal-Containing Molecular Sieves Catalysts

2017 Spring Symposium

Las­z­lo Nemeth, Depart­ment of Chem­istry and Bio­chem­istry, Uni­ver­si­ty of Neva­da Las Vegas

Abstract — Since the dis­cov­ery of tita­ni­um sil­i­calite (TS-1) more than 30 years ago frame­work met­al-con­tain­ing mol­e­c­u­lar sieves have become an impor­tant class of cat­a­lyst, find­ing appli­ca­tion in sev­er­al indus­tri­al process­es. Incor­po­ra­tion of tita­ni­um, gal­li­um, iron, tin and oth­er ele­ments into mol­e­c­u­lar sieves frame­works has led to both sci­en­tif­ic progress and engi­neer­ing inno­va­tions in catal­y­sis. As a result of these devel­op­ments, frame­work met­al-con­tain­ing zeo­lites have been imple­ment­ed in the pre­ced­ing decade in new com­mer­cial, byprod­uct-free green process­es, which have improved sus­tain­abil­i­ty in the chem­i­cal indus­try. Based on a com­pre­hen­sive analy­sis of the recent lit­er­a­ture includ­ing patents, this review is a sum­ma­ry of the cur­rent knowl­edge of the sci­ence and tech­nol­o­gy of frame­work met­al-con­tain­ing mol­e­c­u­lar sieves. The syn­the­sis of these mate­ri­als is sum­ma­rized, fol­lowed by an account of state-of-the-art char­ac­ter­i­za­tion meth­ods. The key cat­alyt­ic chemistries, which can be clas­si­fied into oxi­da­tion reac­tions such as olefin epox­i­da­tion, aro­mat­ic hydrox­y­la­tion and ammox­i­ma­tion, and Lewis acid-cat­alyzed reac­tions, are dis­cussed. Mech­a­nisms pro­posed for these trans­for­ma­tions are reviewed, togeth­er with the the­o­ret­i­cal and mod­el­ing tools applied in this con­text. An overview of the com­mer­cial tech­nolo­gies asso­ci­at­ed with the use of frame­work met­al-con­tain­ing mol­e­c­u­lar sieves ( Tita­ni­um and Gal­li­um Mol­e­c­u­lar sieves) mate­ri­als will be pre­sent­ed. The paper will be dis­cuss the cur­rent activ­i­ty on frame­work Tin Beta Zeo­lite, which shown unique “Zeoen­zyme” selec­tiv­i­ties in mul­ti­ple appli­ca­tions. Some new chem­istry using Sn-zeo­lites will be pre­sent­ed also to pro­duce new prod­uct from bio­mass.

Biog­ra­phy — Las­z­lo Nemeth earned a Bachelor’s Degree in Chem­istry and Doc­tor of Sci­ence in chem­i­cal engi­neer­ing from Uni­ver­si­ty of Debre­cen, Hun­gary.

Upon grad­u­a­tion he was assis­tant pro­fes­sor in Depart­ment of Chem­i­cal Tech­nol­o­gy at same Uni­ver­si­ty and lat­er scientist/ man­ag­er at Hun­gar­i­an High Pres­sure Insti­tute, Hun­gary.

UOP invit­ed him to join to Cor­po­rate Research in Des Plaines, IL, He worked for UOP LLC a Hon­ey­well Com­pa­ny 23 years as senior research asso­ciate, with joint appoint­ment as an adjunct pro­fes­sor at Chem­i­cal Engi­neer­ing Depart­ment of Uni­ver­si­ty of Illi­nois at Chica­go.

Dur­ing his research career at UOP he was prin­ci­pal inves­ti­ga­tor of mul­ti­ple suc­cess­ful projects in the area of mate­r­i­al sci­ence, adsorp­tion and catal­y­sis. His exper­tise also includes zeo­lite appli­ca­tion for UOP’s cat­alyt­ic process­es, met­al-zeo­lites, sol­id and liq­uid superacids, hydro­gen per­ox­ide syn­the­sis and new appli­ca­tions.

Las­z­lo joined the Chem­istry and Bio­chem­istry Depart­ment of Uni­ver­si­ty of Neva­da Las Vegas in 2015 as a research pro­fes­sor. Cur­rent­ly he is work­ing on bimetal­lic-zeo­lite syn­the­sis and appli­ca­tions, Lithi­um Ion Bat­tery recir­cu­la­tion, and devel­op new Ther­mochromic nano­ma­te­ri­als.

He spent his sab­bat­i­cal with George Olah (Nobel Lau­re­ate) and Aveli­no Cor­ma (ITQ Spain).

Dr. Nemeth was award­ed with Stein Star award and Honeywell’s excel­lence in Inno­va­tion. He pub­lished 50+ papers and 90+ patents.

Emerging Challenges in Catalysis for Sustainable Production of Transport Fuels: An Industrial View

2017 Spring Symposium

John Shabak­er, BP Group Research, Naperville, IL

Abstract — Pri­ma­ry ener­gy demand has grown tremen­dous­ly over the past cen­tu­ry, and despite the recent eco­nom­ic down­turn, it is pre­dict­ed to increase anoth­er 37% over the peri­od from 2013–20351. Dri­ven by glob­al pop­u­la­tion growth and ris­ing stan­dards of liv­ing, this rapid increase in demand has dri­ven inno­va­tion in the devel­op­ment of new ener­gy sup­plies and high­light­ed envi­ron­men­tal impacts of ener­gy pro­duc­tion & con­sump­tion. In this sem­i­nar, we will explore how these broad changes have in turn affect­ed the trans­porta­tion fuels sec­tor, great­ly influ­enc­ing the price and avail­abil­i­ty of feed­stocks, as well as the desired mix and qual­i­ty of prod­ucts. We will focus on the tech­no­log­i­cal chal­lenges aris­ing for today’s trans­port fuels indus­try, and pro­vide com­men­tary on the role of catal­y­sis research to help address them.

1 BP Ener­gy Out­look 2035 (2017)

Biog­ra­phy — John is cur­rent­ly Tech­nol­o­gy Strate­gist in BP Group Research, where he pro­vides tech­ni­cal input into strate­gic ini­tia­tives across the com­pa­ny.  For­mer­ly, he was US Sci­ence Team Leader in the BP Cen­ter of Excel­lence for Applied Chem­istry & Physics, also part of Group Research that sup­ports busi­ness­es in refin­ing, petro­chem­i­cals, lubri­cants, and upstream pro­duc­tion, as well as man­ages glob­al uni­ver­si­ty pro­grams. From 2007–2011 John led the imple­men­ta­tion of new bio­fu­els path­ways in Refin­ing Tech­nol­o­gy, rang­ing from biobu­tanol process devel­op­ment to renew­able diesel co-pro­cess­ing in refin­ery hydrotreaters.   He was also active in con­ven­tion­al hydropro­cess­ing tech­nol­o­gy, includ­ing pilot plant oper­a­tions and mod­el­ling.

Pri­or to join­ing BP, John was a reac­tion engi­neer­ing spe­cial­ist at Bris­tol-Myers Squibb, apply­ing in-situ spec­troscopy, kinet­ics, and safe­ty stud­ies to phar­ma­ceu­ti­cal process devel­op­ment.  He received his PhD in chem­i­cal engi­neer­ing in 2004 from the Uni­ver­si­ty of Wis­con­sin-Madi­son.  He holds bach­e­lor degrees in chem­i­cal engi­neer­ing and chem­istry from Lehigh Uni­ver­si­ty.

Solid Catalysts Design: From Fundamental Knowledge To Catalytic Application

Meeting Program — April 2017

Professor Avelino Corma
Pro­fes­sor Aveli­no Cor­ma
Pro­fes­sor and founder of the Insti­tu­to de Tec­nología Quími­ca (UPV-CSIC)
Valen­cia, Spain


Abstract — The key point in catal­y­sis is to define and syn­the­size the spe­cif­ic active site that will min­i­mize the acti­va­tion ener­gy of the reac­tion, while form­ing selec­tive­ly the desired prod­uct.

In the case of homo­ge­neous catal­y­sis, high­ly selec­tive mol­e­c­u­lar cat­a­lysts can be designed and/or opti­mized from the fun­da­men­tal knowl­edge accu­mu­lat­ed on chem­i­cal reac­tiv­i­ty, and the pos­si­bil­i­ties offered by mol­e­c­u­lar mod­el­ling, in situ or operan­do spec­troscopy, kinet­ics and advanced cat­a­lyst syn­the­sis. Then, when the cat­alyt­i­cal­ly active cen­ters are defined, and their inter­ac­tion with reac­tants and prod­ucts can be ratio­nal­ized, it could, in prin­ci­ple, be pos­si­ble to pre­dict and pre­pare more active and selec­tive cat­a­lysts. In the case of sol­id cat­a­lysts it becomes more dif­fi­cult to define and specif­i­cal­ly build the active sites due to sur­face het­ero­geneities present in most of the solids. Indeed, one should con­sid­er that the pres­ence of non-con­trol­lable sur­face defects and the fact that sur­face recon­struc­tion may occur dur­ing the cat­alyt­ic reac­tion, makes the iden­ti­fi­ca­tion and syn­the­sis of the active sites in sol­id cat­a­lysts a big chal­lenge.

From the point of view of max­i­miz­ing active sites, and since catal­y­sis with solids is a sur­face phe­nom­e­non, high sur­face sol­id cat­a­lysts are most of the times pre­ferred. In this case it is not a sim­ple task to iden­ti­fy the assem­bly of atoms, and there­fore to estab­lish the enthalpy and entropy effects at the inter­face of the sol­id-gas or sol­id-liq­uid, that will be respon­si­ble for the cat­alyt­ic effect at the mol­e­c­u­lar lev­el. More­over, even when the above is achieved, to syn­the­size the solids with well defined, homo­ge­neous sin­gle or mul­ti­ple cat­alyt­i­cal­ly active sites it is a dif­fi­cult task. Notice that reac­tion selec­tiv­i­ty will depend on the capac­i­ty to pre­pare the sol­id avoid­ing the pres­ence of sites oth­er than the desired ones.

It was our objec­tive, since the first moment, to design and syn­the­size sol­id cat­a­lysts in where we could build with­in the struc­ture (almost like in a lego), on the bases of the knowl­edge devel­oped on reac­tion mech­a­nisms, adsorp­tion inter­ac­tions and mate­ri­als syn­the­sis pro­ce­dures, the poten­tial cat­alyt­ic active sites. We expect­ed that, if suc­cess­ful, this could be one way to achieve sol­id cat­a­lysts with well defined, uni­form sin­gle or mul­ti­ple active sites. It also appeared to us that work­ing in that way it should be pos­si­ble to build bridges between the homo­ge­neous and het­ero­ge­neous catal­y­sis. We are aware that in the case of the sol­id cat­a­lysts would not be pos­si­ble to achieve the fine tun­ing of elec­tron­ic, geo­met­ric and chi­ral effects obtained by means of the lig­ands and mol­e­c­u­lar struc­ture, with tran­si­tion met­al com­plex­es, and organ­ic mol­e­cules in homo­ge­neous catal­y­sis. Nev­er­the­less, we attempt­ed to use the sur­face topol­o­gy, tex­tur­al char­ac­ter­is­tics and chem­i­cal com­po­si­tion of the sol­id to mas­ter mol­e­c­u­lar dif­fu­sion and adsorp­tion of reac­tants, while select­ing one among the dif­fer­ent pos­si­ble tran­si­tion states.

We will present what has been our evo­lu­tion on the design of three types of sol­id cat­a­lysts in where we fol­lowed the method­ol­o­gy describe above. They are:

  1. High sur­face area hybrid organ­ic-inor­gan­ic cat­a­lysts in where we attempt to reg­u­late the char­ac­ter­is­tics of the active sites and the geo­met­ri­cal flex­i­bil­i­ty to max­i­mize dis­per­sion forces.
  2. Ful­ly inor­gan­ic high­ly ther­mi­cal­ly sta­ble micro and meso­porous mate­ri­als with well defined sin­gle sites, while con­trol­ling mol­e­c­u­lar dif­fu­sion and adsorp­tion to achieve remark­able selec­tiv­i­ty effects.
  3. Gen­er­at­ing and sta­bi­liz­ing from sin­gle met­al atoms to clus­ters with a few atoms to nanopar­ti­cles, with reac­tiv­i­ties so high that remind those of enz­imes.

We will show that by fol­low­ing the method­ol­o­gy: “under­stand­ing for design­ing and syn­the­siz­ing”, we could also achieve what it is always a desir­able objec­tive in catal­y­sis: “Design­ing for indus­tri­al appli­ca­tion”.

Biog­ra­phy — Aveli­no Cor­ma, Pro­fes­sor and founder of the Insti­tu­to de Tec­nología Quími­ca (CSIC-UPV) in Valen­cia (Spain), he has been car­ry­ing out research in het­ero­ge­neous catal­y­sis in acad­e­mia and in col­lab­o­ra­tion with com­pa­nies for near­ly 35 years. He has worked on fun­da­men­tal aspects of acid-base and redox catal­y­sis with the aim of under­stand­ing the nature of the active sites, and reac­tion mech­a­nisms. With these bases has devel­oped cat­a­lysts that are being used com­mer­cial­ly in sev­er­al indus­tri­al process­es. He is an inter­na­tion­al­ly rec­og­nized expert in sol­id acid and bifunc­tion­al cat­a­lysts for oil refin­ing, petro­chem­istry and chem­i­cal process, espe­cial­ly in the syn­the­sis and appli­ca­tion of zeo­lite cat­a­lysts. He has pub­lished more than 900 research papers, and inven­tor on more than 130 patents. Cor­ma earned his BS in Chem­istry at Valen­cia Uni­ver­si­ty, PhD at Madrid under direc­tion of Prof. Anto­nio Cortes, and spent two years post­doc at Queen ́s Uni­ver­si­ty. He has received the Dupont Award on “Mate­ri­als Sci­ence”, Cia­pet­ta and Houdry Awards of the North Amer­i­can Catal­y­sis Soci­ety, the F. Gault Award of the Euro­pean Catal­y­sis Soci­ety, the M. Boudart Award on Catal­y­sis by the North Amer­i­can and Euro­pean Catal­y­sis Soci­eties, the G. J. Somor­jai ACS Award on Cre­ative Catal­y­sis, the Breck Award of the Inter­na­tion­al Zeo­lite Asso­ci­a­tion, the Nation­al Award of Sci­ence and tech­nol­o­gy of Spain, “Rey Jaume I” Prize for New Tech­nolo­gies (2000), the ENI
Award on Hydro­car­bon Chem­istry, the Roy­al Soci­ety of Chem­istry Cen­te­nary Prize, Solvay Pierre-Gilles de Gennes Prize for Sci­ence and Indus­try and Gold Medal for the Chem­istry Research Career 2001–2010 in Spain, La Grande Médaille de l’Académie des sci­ences de France 2011 and Hon­our Medal to the Inven­tion from the Fun­dación Gar­cía Cabreri­zo in Spain. Gold Medal Foro QUÍMICA y SOCIEDAD to all his research career, Gran Medaille of the Sci­ence French Acad­e­my, Edith Flani­gen Lec­ture­ship, East­man Lec­ture, Direc­tor ́s Dis­tin­guished Lec­ture Series Pacif­ic North­west Nation­al Lab­o­ra­to­ry ́s. Prince of Asturias Award for Sci­ence & Tech­nol­o­gy 2014, 48th W. N. Lacey Lec­ture­ship in Chem­i­cal Engi­neer­ing-Cal­tech (2015) and The Jacobus van ‘t Hoff Lec­ture 2015 at TU Delft Process Tech­nol­o­gy Insti­tute (2015), The Hoyt C. Hot­tel Lec­tur­er in Chem­i­cal Engi­neer­ing at MIT Chem­i­cal Engi­neer­ing Depart­ment (2015), J.T. Don­ald Lec­ture series 2015–2016 at McGill Uni­ver­si­ty, Spiers Memo­r­i­al Award RSC (2016), IZA Award of the Inter­na­tion­al Zeo­lite Asso­ci­a­tion (2016), George C.A. Schuit Award lec­ture at the Uni­ver­si­ty of Delaware (2016).

Doc­tor Hon­oris Causa” by Utrecht Uni­ver­si­ty (2006), UNED (2008), München Tech­no­log­i­cal Uni­ver­si­ty (2008), Uni­ver­si­dad Jaime I de Castel­lón (2008), Uni­ver­si­dad de Valen­cia (2009), Bochüm Uni­ver­si­ty (2010), Uni­ver­si­dad de Ali­cante (2010), Ottawa Uni­ver­si­ty (2012) Delft Tech­no­log­i­cal Uni­ver­si­ty (2013) Jilin Uni­ver­si­ty (Chi­na) (2013), Uni­ver­si­ty of Bucarest (2014), Jaen (2016), Cantabria (2016).

Parallel between UOP’s Reforming and Dehydrogenation Technologies and Catalysts

Meeting Program — March 2017

Manuela Serban
Manuela Ser­ban
Prin­ci­pal Research Sci­en­tist,
Hon­ey­well UOP


Abstract — With sig­nif­i­cant expe­ri­ence in Con­tin­u­ous Cat­a­lyst Regen­er­a­tion (CCR) reform­ing tech­nol­o­gy, i.e., Plat­form­ing™ process, Honeywell’s UOP was unique­ly posi­tioned to invent, devel­op and com­mer­cial­ize 25 years ago, a CCR-type light paraf­fins dehy­dro­gena­tion tech­nol­o­gy, i.e., Ole­flex™ process, lever­ag­ing on the Plat­form­ing tech­nol­o­gy. These two tech­nolo­gies rep­re­sent two of UOP’s core tech­nolo­gies and togeth­er with their cat­a­lysts, are being con­tin­u­ous­ly improved and opti­mized to max­i­mize end-user prof­itabil­i­ty. Cur­rent­ly there are 300+ CCR Plat­form­ing units and 25+ Ole­flex units oper­at­ing world­wide, with more in con­struc­tion or in com­mis­sion. This pre­sen­ta­tion will high­light sim­i­lar­i­ties and dif­fer­ences between the Plat­form­ing and Ole­flex tech­nolo­gies and cat­a­lysts. We will dis­cuss the chem­i­cal and phys­i­cal require­ments and prop­er­ties for the two types of cat­a­lysts, the main cat­a­lysts deac­ti­va­tion routes, and high­light some of UOP’s char­ac­ter­i­za­tion tools and exper­tise used to devel­op new reform­ing and dehy­dro­gena­tion cat­a­lysts and diag­nose dif­fer­ent symp­toms relat­ed to aged com­mer­cial cat­a­lysts.

Biog­ra­phy — Manuela Ser­ban is a Prin­ci­pal Research Sci­en­tist in the Olefins and Deter­gents Devel­op­ment Group lead­ing teams respon­si­ble for the devel­op­ment of new Ole­flex cat­a­lyst gen­er­a­tions. Manuela has over 12 years of expe­ri­ence with UOP, includ­ing reform­ing tech­nol­o­gy and cat­a­lysts, cat­alyt­ic hydrodesul­fu­r­iza­tion, flue gas desul­fu­r­iza­tion for coal gasi­fi­ca­tion plants, break­through liq­uid fuels decon­t­a­m­i­na­tion tech­niques. She is the author of sev­er­al arti­cles in peer reviewed Chem­i­cal Engi­neer­ing jour­nals and has 38 US patents. She has a PhD in Chem­i­cal Engi­neer­ing from Worces­ter Poly­tech­nic Insti­tute and post-doc­tor­al expe­ri­ence at Argonne Nation­al Lab­o­ra­to­ry.

Biomass and Natural Gas Valorization by Zeolite Catalysis

Meeting Program — February 2017

Raul Lobo
Raul Lobo
Claire D. LeClaire pro­fes­sor of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing,
Uni­ver­si­ty of Delaware


Abstract — Prof. Lobo’s research group is inter­est­ed in devel­op­ing and under­stand­ing catal­y­sis sys­tems to enable the trans­for­ma­tion abun­dant, inex­pen­sive and—when possible—renewable car­bon sources into feed­stocks for the chem­i­cal indus­try. We com­bine exper­tise in mate­ri­als syn­the­sis, catal­y­sis and kinet­ics, and reac­tion engi­neer­ing to devel­op nov­el cat­a­lysts and cat­alyt­ic process­es that pro­duce valu­able prod­ucts.

In the first part I will focus on C-C bond form­ing reac­tions that are help­ful in the trans­for­ma­tion of furans (pro­duced from glu­cose or xylose by dehy­dra­tion) into valu­able com­mod­i­ty chem­i­cals. To this end we have devel­oped and opti­mized zeo­lite cat­a­lyst com­po­si­tions to form aro­mat­ic species out of the furans via Diels-Alder reac­tions and Friedel-Craft acy­la­tion reac­tions. We will describe efforts to pro­duc­ing ben­zoic acid and α-methyl­styrene from furans in high selec­tiv­i­ty and high yield, along with the elu­ci­da­tion of the reac­tion mech­a­nisms of these reac­tions.

In the sec­ond part I will dis­cuss on-going research direct­ed towards the devel­op­ment of cat­a­lysts for the selec­tive oxi­da­tion of methane into methanol. We will show that zeo­lites can serve as hosts of tran­si­tion met­als oxide clus­ters (cop­per or iron) that are anal­o­gous to met­al oxide clus­ters observed in a num­ber of impor­tant enzymes such as par­tic­u­late methane monooxy­ge­nase (pMMO). These clus­ters are capa­ble of oxi­diz­ing methane to methanol, car­bon monox­ide and CO2. By selec­tive­ly choos­ing mate­ri­als that com­part­men­tal­ize Cu-O clus­ters, we have iden­ti­fied zeo­lite struc­tures that are able to selec­tive­ly oxi­dize methane to methanol with very high selec­tiv­i­ty in a three-step cyclic process. We will describe the poten­tial and the draw­backs of trans­form­ing such cyclic process into a cat­alyt­ic process for methanol pro­duc­tion.

Despite the matu­ri­ty of the field of catal­y­sis this talk will show that tan­ta­liz­ing new oppor­tu­ni­ties emerge from the dis­cov­ery of new cat­a­lyst struc­tures and com­po­si­tions, and from improve­ments in our con­trol of the com­po­si­tion of met­al clus­ters in nanoscop­ic envi­ron­ments.

Biog­ra­phy — Raul F. Lobo is the Claire D. LeClaire pro­fes­sor of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing at the Uni­ver­si­ty of Delaware and Direc­tor of the Cen­ter for Cat­alyt­ic Sci­ence and Tech­nol­o­gy. His research inter­ests span the devel­op­ment of nov­el porous mate­ri­als for catal­y­sis and sep­a­ra­tions, the chem­istry of zeo­lites, catal­y­sis for ener­gy and the envi­ron­ment, and the sci­en­tif­ic aspects of cat­a­lyst syn­the­sis. He has pub­lished over one hun­dred fifty ref­er­eed reports and he is co-inven­tor in three US patents. He obtained his under­grad­u­ate degree in Chem­i­cal Engi­neer­ing at the Uni­ver­si­ty of Cos­ta Rica in 1989 and lat­er moved to Cal­i­for­nia to pur­sue grad­u­ate stud­ies in Chem­i­cal Engi­neer­ing at Cal­tech. He worked for one year at Los Alam­os Nation­al Lab­o­ra­to­ry, New Mex­i­co as a post­doc­tor­al fel­low and he start­ed his aca­d­e­m­ic career at the Uni­ver­si­ty of Delaware in 1995.

Prof. Lobo has con­duct­ed research in the use of zeo­lites for nitrogen/oxygen sep­a­ra­tions, and car­bon diox­ide sep­a­ra­tions from flue gas­es. He has con­tributed to the fun­da­men­tals of zeo­lite nucle­ation and crys­tal growth and to the appli­ca­tion of zeo­lites for a num­ber of cat­alyt­ic appli­ca­tions. In par­tic­u­lar his group research helped under­stand the mech­a­nisms of reac­tion and sta­bil­i­ty of zeo­lite cat­a­lysts used for the removal of NOx gas­es from com­bus­tion exhaust, devel­oped cat­alyt­ic mate­ri­als for the trans­for­ma­tion of bio­mass-derived furans into com­mod­i­ty aro­mat­ic mol­e­cules such as xylenes and ben­zoic acid and dis­cov­ered mate­ri­als for the selec­tive acti­va­tion of methane using cop­per oxide clus­ters.