(Preeti  Aghalayam,  Jan  2014)  

Sir  Humphrey  Davy:  1817    

• Demonstrated  reaction  of  coal  gas  with  oxygen  on  a  glowing  Pt  wire    

Berzelius:  1836    

• Defined  the  term  ‘catalysis’  

Faraday:  1834  

• Proposed  that  reactants  have  to  adsorb  simultaneously  at  catalyst  surfaces  

(Catalysts  were  being  used  inadvertently,  for  making  beer,  wine,  &  cheese,  in  earlier  times)    

Ostwald (1900s)

• Catalysis, Equilibria

Haber (1905)

• Ammonia Production Catalyst

Langmuir (1920s)

• Surface Chemistry

Bosch (1931)

• High pressure reactor for ammonia

Hinshelwood & Semenov (1956)

• Reaction Mechanisms

Catalysis  began  by  helping  make  bulk  basic  &  inorganic  chemicals,  several  centuries  ago      

It  transitioned  to  a  huge  volumes  and  investments  business  with  the  advent  of  the  oil  economy  and  the  need  for  petroleum  re<ining  

Further  impetus  was  achieved  via  the  petrochemicals  industy  

Soon,  specialty  chemicals  production  and  environmentally  relevant  catalysis  became  the  exciting  new  trend  

Today,  in  addition  to  being  a  mainstay  in  the  chemicals  industry,  catalysts  are  expected  to  charter  new  directions  for  the  world  economy!  

¡  80  –  90%  of  current  day  products  emerge  from  some  or  the  other  catalytic  process  

¡  As  our  focus  shifts  in  the  21st  century,  the  challenges,  especially  in  petro  industry,  are  remarkable  

New  materials:  Catalytic  membranes,  hydrogen  storage  

Cheaper  catalysts  for  pollution  control  

Biocatalysts  for  re<ining  of  petroleum  

Fundamental  studies:  kinetics,  characterisations  

The  petroleum  economy  especially  can  expect  widespread  changes  

(from  Marcilly,  2003)  

(from  Vlachos  &  Caratzolous,2010)  

ARTICLE IN PRESS

up to two orders of magnitude higher than that of Li-basedbatteries (Vlachos, 2009).

The above applications underscore the need for developingsmall and efficient chemical plants. While smaller scales canstill be described with the core reaction engineering models,downscaling imposes new challenges that have been detailedelsewhere (Norton et al., 2005; Vlachos, 2009) and are onlybriefly mentioned here. Reactors need to be designed to ensurefast mixing, low pressure drop, high catalyst area for highconversions, and minimal transport (external and internal)resistances. In addition, catalyst requirements, such as activity,selectivity, safety (non-pyrophoric materials), and stability intransient operation, become more stringent. Integration of micro-units into compact, energy-efficient, self-sustained systems iscrucial given the lack of large heat and process integration withnearby plants.

4. Hydrogen economy, green hydrogen, and remote/offshoreutilization of natural gas

The concept of hydrogen economy has frequently been in therecent news and a DOE report has been published (Dresselhauset al., 2003; NRC, 2004). The ideal hydrogen cycle entails splittingof H2O to produce (green) hydrogen followed by its electro-chemical (green) combustion. The challenge, like CO2 utilization,is that H2O split is very hard to achieve at reasonable rates andefficiencies.

Hydrogen is the cleanest burning fuel. The much higherefficiency (compared with the current ICEs) and zero emissionsmake the PEM fuel cell running on H2 an appealing technology.Hydrogen addition to fossil fuels can stabilize combustion ofextra-lean mixtures (below their fuel lean flammability limit) inICEs, and thus, it could allow for reduction of temperatures andNOx emissions. Despite these obvious advantages, hydrogen is notavailable as a natural reserve, i.e., hydrogen is not an energysource but rather an energy carrier. It is currently produced andused in chemical industry for, among others, production ofammonia, methanol, and various refinery processes, such assulfur removal.

The strong opposition against a hydrogen economy from someof the scientific community arises in part from the fact that thereis no hydrogen surplus to realize a hydrogen economy and watersplit is too difficult to achieve. However, even if a hydrogeneconomy is never realized, increased hydrogen production fromalternative and renewable sources is still compelling sincehydrogen finds many industrial uses. For instance, the risingprices of crude oil and of natural gas have led to an increased priceof hydrogen. As a result, the price of diesel has increased over thatof gasoline due to more stringent regulations for sulfur removal.These problems can be mitigated if additional hydrogen produc-tion routes are developed.

The hydrogen economy consists of three legs: hydrogenproduction, storage, and use. The CRE community has tradition-ally been involved with the production of hydrogen (Figs. 2 and 3).Fuel cells (use) and catalytic storage/release offer newopportunities. The current production relies mainly on steamreforming of natural gas followed by two (high and lowtemperature) water gas shift (WGS) reactors. Depending on thepurity of hydrogen needed, a final stage of pressure swingadsorption or selective oxidation of CO or methanation may beneeded. This last process is deemed necessary in the case of PEMfuel cells to avoid poisoning of the Pt catalyst by COchemisorption. Coal gasification is another route for H2

production and is currently utilized to a less extent due to coalbeing the least clean fossil fuel. Given the huge coal reserves in the

US, it is expected that coal gasification to syngas and eventually tohydrogen or chemicals will gain substantial momentum in thenear future.

4.1. Green hydrogen production

The exploration of renewables for hydrogen production hasintroduced new processes to produce syngas. One such process isthe short contact time catalytic partial oxidation (CPOX) of liquid(oil) and solid lignocellulosic materials (e.g., wood chips) on Rh-based catalysts (Dauenhauer et al., 2006; Salge et al., 2006; Wanatet al., 2005). As elaborated further in the section on renewables, amajor advantage of this reforming technology is the minimizationor elimination of coke formation. An alternative to this reformingis the aqueous phase reforming (APR) of various oxygenatedmolecules to H2 (Cortright et al., 2002; Davda et al., 2005; Huberand Dumesic, 2006; Huber et al., 2003), e.g.,

C6HxO6(l)+6H2O(l)-6CO2(g)+(12+x)/2H2(g); x=12 or 14 (APR)

Under certain conditions (Davda and Dumesic, 2003), H2/CO2

mixtures (with fractions of CO as low as 100 ppm) are produceddue to the enhanced contribution of the water gas shift (WGS)reaction during low-temperature (!500 K) operation. The low COcontent makes purification of H2 from CO2 (with a membrane) forfuel cells very feasible but is disadvantageous for Fisher–Tropschsynthesis. The CO:H2 ratio can be tuned by changing the support(Chheda et al., 2007a).

Fuel

+ Air

Fuel

Steam

Pure H 2Combustor

Fuel + Air

Fuel

Steam

Pure H2

SR

WGSPSA, PROX, methanation

Fig. 2. Schematic of the flow sheet for syngas and H2 production.

Steam reforming CO

H2

CH 4

CO 2

H2O

CHO

H2OSteam reforming

Water-gas shift

H2O

CO

Water-gas shift

CO

H2

CO

H2

CO

H2

O2

O2

Partial o

xidation

Partial oxidation

CH 4

CO 2

H2O

CHO

Dry

ref

orm

ing

Dry reform

ing

CO2

CO2

CH4

CO2

H2OO2

O2

O2

O2

CHO

CH3O

CH2O

CH3OH

CHO

H2O

Combustion

Combustion

Oxidation

Oxidation

Fig. 3. Schematic of the reaction network in converting natural gas to syngas (seeFig. 2). In most of these reactions, more than one overall reactions happen. In CPOXand ATR, combustion, steam reforming, water gas shift, and direct formation ofsyngas are all possible depending on operating conditions and mass transferlimitations.

D.G. Vlachos, S. Caratzoulas / Chemical Engineering Science 65 (2010) 18–2920

The  Hydrogen  Economy  has  to  rely  heavily  on  catalysts  

ARTICLE IN PRESS

This paper focuses mainly on select emerging technologies andprocesses where the CRE community can significantly contributein solving the energy problem, mainly through innovation inheterogeneous catalysis and reactors. Topics touched uponinclude process intensification (PI) and efficiency, hydrogeneconomy, offshore and remote natural gas utilization, andrenewables, such as biomass utilization and transformation ofvarious waste streams. As underscored herein, a crosscuttingtheme emerging for future power generation is processing atscales smaller than those of the conventional refinery andpetrochemical plants. Future research needs are finally outlined.

2. Improving process efficiency

While the quest for alternative and renewable energy sourceswill be very important in meeting the increasing energy needs, akey aspect in overcoming the energy and environmental chal-lenges is to improve process efficiency of existing and newprocesses (Nat.Acad.Press, 2008). This is particularly importantsince fossil fuels will continue to constitute the backbone of ourenergy supply.

Several processes exhibit low energy efficiency. For example,the overall efficiency in converting chemical energy, starting froma power plant running on coal, and ending with light is just 2%:62% of the initial energy is lost in the power plant, 2% intransmission lines, and 34% as heat in light lumps (Nat.Acad.Press,2008). As another example, the efficiency of a typical internalcombustion engine (ICE) is of the order of !20%. This low fractionis despite the progress made in fuel efficiency of automobiles from18 mpg (1978) to 27.5 mpg (1985) to an imposed average of35 mpg (2030) for all cars, SUVs, and light trucks (Nat.Acad.Press,2008), due mainly to improvements in light materials.

How do we improve process efficiency? Improved efficiencyusually entails catalyst and/or reactor/flow sheet optimization.Selectivity is, by and large, the single most important factor.Improved selectivity implies reduced waste and reduction orelimination downstream of the energy-intensive separation units.High throughput experiments and insights gained from computa-tional catalysis promise the development of more selectivecatalysts. An example is the epoxidation of ethylene to ethyleneoxide on Ag-based bimetallic and doped catalysts (Dellamorte etal., 2007) and many more are emerging. Catalyst design willunquestionably play a key role in both conventional processes andbiomass conversion.

Process intensification (PI) entails the enhancement of theeffective rate by increasing transport rates and/or impartingmultifunctionality into devices (Stankiewicz, 2007). The net resultcan be improvement of process efficiency, reduction in size (withan associated reduction in capital cost), and/or in operation cost.Several concepts for PI have been developed over the past fewyears. The overall idea of multifunctional reactors was madepopular about two decades ago (Agar and Ruppel, 1988; Wester-terp, 1992). A popular example of PI is reactive separation, withthe reactive distillation (Malone et al., 2003) of MTBE by EastmanChemicals being a successful commercial test bed. Membranereactors for equilibrium-limited reactions or for selectivelyremoving a product that inhibits catalysts is another example ofreactive separation (Harale et al., 2007). Reactive adsorption forCO2 capture during the water gas shift reaction is a recentlyexplored application (Dadwhal et al., 2008; Martavaltzi andLemonidou, 2008). Miniaturization of chemical processes leadsto enhanced transport rates and concomitant size reduction. Asdiscussed further below, this size reduction is deemed essentialfor smaller or distributed scale (remote, offshore, transportation,portable power) applications. Integration of heat exchangers with

reactors in making efficient, compact systems has also beenintensively studied (Kolios et al., 2005, 2007). The parallel-platecatalytic reactor (where an endothermic and an exothermicreaction take place on opposite sides of a wall that serves as aheat exchanger) is a fairly common configuration of spatialcoupling (Fig. 1). Heat recuperation strategies via recirculationor regeneration are essential strategies (Federici and Vlachos,2008; Jones et al., 1978; Lloyd and Weinberg, 1974; Matros andBunimovich, 1996; Neumann and Veser, 2005) for energy lossminimization. Additional examples of PI will be discussed below.

3. Distributed power generation and downscaling ofchemical processes

In a recent report, it was suggested that ‘building small plantsnear customers, known as distributed generation, may becomemore important in order to meet demand and maintain reliability’(Nat.Acad.Press, 2008). Processing at smaller scales can meetmultiple objectives, namely increased reliability, overcomingexpensive or impossible transportation from remote and offshorelocations, improved PI and enhanced efficiency, and the need forH2 production for PEM fuel cells for transportation and portabledevices.

Miniaturization will be central to several energy efforts in thefuture. As discussed below, if we were to realize a hydrogeneconomy in the short term, we would need onboard reforming.This will entail !108 reactors to runs all cars in the US alone. Inthe mid term, and assuming that suitable nanomaterials forhydrogen storage are developed, hydrogen may be produced ingas stations (!105 in the US) to take advantage of the liquid fueldistribution infrastructure. When compared with the operating149 refineries in the US, the aforementioned numbers indicatereduction in reactor volume and increase in the number ofreactors needed for H2-based transportation economy.

Remote and offshore utilization of natural gas will requiresmaller-scale systems (Lerou, 2006). One could envision futuresupertankers, being filled offshore with crude oil, to be smallchemical plants transforming natural gas into liquids via gas toliquids (GTL) or easy-to-liquefy gases, e.g., ammonia, which arethen transported to mainland. Achieving this goal will requiredownscaling the currently bulky steam reforming process. In thecase of biomass, feedstock utilization will be localized. This is dueto the large water content of biomass, which makes thetransportation cost high. It is anticipated that the optimal scaleplants (biorefineries) will be of the order of !1000 barrels perday, much smaller than the current refinery and petrochemicalplants.

Electronics (1–100 W) currently rely on batteries whoseefficiency is low and their weight is high (their mass energydensity is low). One could replace batteries with microchemicalsystems since the mass energy density of common liquid fuels is

catalyst

Fuel + O2 ! CO2 + H2O

CH4 + H2O ! CO+3H2

Wall

Fig. 1. Schematic of multifunctional catalytic parallel-plate microreactor. Catalyticcombustion occurs on a Pt washcoat catalyst in one channel and steam reformingof methane on a Rh washcoat catalyst in the other channel. The (thin) separatingwall serves as a compact and efficient heat exchanger.

D.G. Vlachos, S. Caratzoulas / Chemical Engineering Science 65 (2010) 18–29 19

Energy  ef<icient  processes  will  require  new  ideas-­‐  such  as  this  combined  reactor/heat  exchanger  in    micro-­‐scale  

The  current  challenge  is  to  design  catalysts  to  explore  these  new  vistas  

First  implemented  in  the  USA  in  1975  

In  Japan  &  Europe  in  1986  

Currently,  all  over  the  world!  

Challenges  today:  •  Selectivity  •  Cold  start  emissions  •  Fuel-­‐lean  engine  •  Biofuel  engines  •  CO2  &  PM    •  Bi-­‐functional  catalysts  

This  catalyst  can  reduce  NO  in  fuel-­‐lean  engines  without  problems  of  

NH3  slip  

New  age  engines  and  new  age  ground  rules  have  kept  researchers  on  their  toes!  (from  Schauer  et  al.,2012)  

¡  Picture  this:  metallic  gold  is  typically  chemically  inert.  But  prepared  in  a  special  way  –  depositing  only  particles  that  are  a  few  nanometers  in  size  –  makes  it  a  viable  catalyst  for  several  reactions!  

settled, it appears that mild reduction treatments may be

preferred in many instances, even if those leave some ofthe organic matter behind [30]. In fact, it is possible that

the remaining carbonaceous deposits may actually help

with the performance of the catalyst, at least in the pro-motion of mild reactions such as olefin hydrogenations

[37]. Access to the metal inside dendritic or colloidal

structures may also be possible in liquid solutions [38], inwhich case the catalyst may not even require special acti-

vating treatments. The issue of the activation of heteroge-

neous catalysts prepared by these new self-assemblymethodologies requires further studies.

When considering nanoparticle size in heterogeneous

catalysts, one extreme is catalysis by one single atom, orperhaps by a small number of atoms in a well-defined

molecular cluster. The behavior of the catalyst in suchcases may resemble more closely that of homogeneous

catalysts, where selectivity can sometimes be controlled at

a molecular level. In fact, the heterogeneous catalysts canbe prepared by starting with the corresponding discrete

molecular clusters [39]. However, the interaction of the

atoms of the catalytic phase with the support is rarelynegligible, and needs to be considered. The final structure

of the surface species may also dynamically change as the

pretreatment or reaction conditions are changed, and thefinal active phase may exhibit very different characteristics

to those of the original organometallic precursors. An

interesting example of a change in the structure of thecatalyst leading to changes in reaction selectivity has been

recently reported for the conversion of ethylene on sup-

ported rhodium catalysts [40]. In that case, the initialRh(C2H4)2 complexes bonded to a crystalline zeolite HY

support could be made to remain isolated and to display

high selectivity for the dimerization of ethylene to butenesand butane under most conditions, except upon exposure to

highly reducing environments, after which they were seen

to form small metal clusters and to preferentially promotehydrogenation to ethane instead. Curiously, this transfor-

mation was shown to be reversible: the isolated-Rh

dimerization sites could be regenerated upon exposure ofthe catalyst to ethylene-rich mixtures. In general, the use of

small molecular clusters as precursors for the preparation

of heterogeneous catalyst could be quite useful if issues ofstability and selectivity can be worked out.

3 Nanoparticle Shape

Perhaps more interesting than controlling the performanceof catalysts by controlling the size of the nanoparticles of

the active phase is the idea of exerting that control via theselection of their shape. It has been long known that some

catalytic processes are structure sensitive, which in tradi-

tional catalysis has come to mean that their performance interms of activity or selectivity changes significantly with

the method used for their preparation. However, this

behavior has been justified on the basis of the associatedchanges in the distribution of particle size in the resulting

catalysts [41]. It has only been recently, with the incor-

poration of methods to better control particle size andshape independently of each other, that the effects of those

two parameters have started to be untangled.

In surface science studies using model system, structuresensitivity has traditionally been probed by comparing

chemical reactivity on single crystals exposing surfaces

with different orientations [5, 8]. Initial studies on chemi-sorption were later extended to catalytic rate measurements

using so-called ‘‘high pressure cells’’ [42–44]. Those

studies have been quite useful, but also revealed someintrinsic limitations, in particular the fact that they cannot

Fig. 2 Pyrrole hydrogenation selectivity at 413 K (4 torr pyrrole,400 torr H2, 2 % conversion) as a function of the size of the Ptnanoparticles, dispersed on a HY zeolite, used as catalysts [32].Hydrogenation to pyrrolidine is facile in all cases, but further

hydrogenolysis to n-butylamine can only be partially avoided if smallnanoparticles, of diameters on the order of *1 nm, are used. Figurecourtesy of Jeong Park and Gabor Somorjai, reproduced fromRef. [32] with permission. Copyright 2009 American Chemical Society

504 F. Zaera

123

We  are  now  able  to  really  control  size  of  the  catalyst  particles  we  make  (from  Zaera,2012)  

¡  How  does  Zeolite  microporosity  control  reactivity?      àby  selectively  allowing  access  to  an  active  site  within  the  zeolite  cavity!  

¡  para-­‐xylene  can  gain  access  to  the  inside  of  the  zeolite  channel,  whereas  the  meta-­‐  and  ortho-­‐  forms  of  xylene  are  sterically  hindered  from  doing  so.  

We  are  now  able  to  really  understand  how  these  magical  things  work!  (from  Bill  Vining’s  work)  

New  experimental  techniques  help  us  with  molecular  level  pictures!    (from  Somorjai  &  Wang  1997,)  

Electron  based  microscopy  

Molecule/ion  based  spectroscopy  

Photo-­‐mediated  spectroscopy  

Scanning  tunneling  microscopy  

( )G.A. Somorjai, M.X. YangrJournal of Molecular Catalysis A: Chemical 115 1997 389–403 393

� .Pt 110 surface exposed to ambient pressures ofhydrogen, oxygen and carbon monoxide at 425K. Under 1.6 atm of hydrogen pressure, thesurface presents various sizes of missing-rowreconstruction. In 1 atm of oxygen, however,

� .enlarged 111 microfacets can be observed.The surface in 1 atom of carbon monoxideappears to have large scale terraces separated bymultiple height steps.The surface reconstruction is a reversible

process. The platinum surface was exposed todifferent gases alternatively and the surface

w xstructure changed accordingly 18 . In 1.6 atmH , chemisorbed oxygen reacts to form water2and desorbs from the surface. In CO environ-ment, the binding energy of hydrogen atoms onthe surface is reduced and surface hydrogens arereplaced by CO molecules. Under atmosphericoxygen pressure, surface CO molecules are oxi-dized to CO and the surface is switched to be2covered by oxygen. The conversion of surfacestructures is indicative of the adsorbate compo-sition change on the surface.

2.1.2. Coadsorption-induced reconstruction ofadsorbate oÕerlayerAdsorbate overlayer as well as substrate

atoms can be rearranged by adsorption of coad-sorbates. Surface species are highly mobile onthe surface. In many cases, adsorbate structuresare reorganized in order to accommodate othersurface species. A reconstruction of adsorbateoverlayers by coadsorption has been demon-strated in a STM and LEED study of sulfur

� . � .chemisorption on Re 0001 and Pt 111 sur-w xfaces 19 . Surface structures imaged by STM

are consistent with electron diffraction patternsobtained in complementary LEED studies. At a

�sulfur coverage of 0.25 monolayer one atom. � .per four substrate metal atoms , a 2=2 or-

dered sulfur structure can be observed, as shown� . � . � .in Fig. 4 a . On either Re 0001 and Pt 111

surfaces, coadsorption of carbon monoxidemolecules induces a reordering of sulfur struc-ture. The sulfur overlayer is compressed, creat-ing empty space on the surface for carbon

� . � .Fig. 4. STM images a before and b after the reordering of� . � .sulfur overlayer on Re 0001 induced by CO exposure. a The

� .round maxima are due to individual p 2=2 ordered sulfur atomsadsorbed at the hcp hollow site of the surface. Image size: 40=40˚ � . � .A. b A hole has formed in the p 2=2 layer where CO has

�adsorbed CO molecules are not visible in the STM images,.presumably due to their facile diffusion on the surface . The sulfur

atoms which resided previously in the hole have been compressedto form trimers of three atoms which appear as bright spots

˚surrounding the hole. Image size: 55=55 A.

monoxide adsorption. The new sulfur overlayer� .presents a 3 63= 363 R308 structure on

� . � � .. � .Re 0001 Fig. 4 b and a 63=63 R308 struc-� .ture on Pt 111 . The CO molecules have a high

mobility on the surface and are not visible inSTM experiments. The change of sulfur over-layer structure is reversible and the original� .2=2 sulfur structure can be restored afterdesorbing CO molecules at high temperature.Competitive adsorption and mobility of ad-

sorbates on the surface attribute to the coadsorp-tion-induced reconstruction of adsorbate over-layers. If surface species are immobile becauseof a high activation energy for surface diffusion,coadsorption cannot take place. On the other

( )G.A. Somorjai, M.X. YangrJournal of Molecular Catalysis A: Chemical 115 1997 389–403400

catalyst. An optimization of catalyst perfor-mance can be accomplished.UV light and X-ray radiation have also been

used in lithography studies. The main advantageof electron beam lithography over the othertechniques is its exceptional high resolution. Itcan generate features as small as a few nanome-

w xters 30 . Notice that the average particle size ofindustrial catalysts is 1–100 nm, electron beamlithography is, at present, the best choice inmodel catalyst preparation.

3.2. ReactiÕity tests

An initial reactivity test of metal clustersprepared by electron beam lithography has

w xyielded encouraging results 31 . A metal clustersample was prepared by Dr. S.J. Wind at IBMresearch center, Yorktown Heights. Platinumparticles of 50 nm diameter and 15 nm heightwith 200 nm periodicity have been prepared ona 0.5=0.8 cm oxidized silicon wafer. Scanning

� .electron microscopy SEM pictures of the metalcluster array are shown in Fig. 15.The cluster sample shows a remarkable sta-

bility upon annealing and exposure to ions andelectrons. It allows us to remove surface con-taminants by low energy ion sputtering andoxygen treatment. The sample can be character-ized by electron- and ion-scattering surface sci-ence spectroscopies. AFM studies indicate thatthe sample structure remains intact after surfacecleaning, catalytic reaction and sample charac-terization.The rate of ethylene hydrogenation over this

new model catalyst was measured in aUHVrhigh pressure system. The surface area ofmetal cluster arrays is one to two orders ofmagnitude smaller than a single crystal surfaceof comparable sample size. Fig. 16 shows theethane yield as a function of time at roomtemperature, along with a background signaltaken on a blank silicon wafer. The measuredturnover rate is in good agreement with previ-ous results obtained on conventional supportedcatalysts and single crystals. As shown in Fig.

Fig. 15. SEM micrographs of platinum cluster array fabricated byelectron beam lithography. The sample has a cluster size of 50 nmand a periodicity of 200 nm.

16, an increase of reaction rate is also observedupon increasing sample temperature.The saturation coverage of adsorbates on the

platinum cluster sample can be determined frompeak areas in thermal desorption studies. Thethermal desorption spectra of D and 13C18O2from the cluster sample are displayed in Fig. 17,along with reference spectra collected on a plat-inum foil. The ratio of deuterium desorbingfrom the cluster sample to that desorbing fromthe reference foil sample is 2–4 times greaterthan the same ratio for carbon monoxide. Thisindicates a spillover of deuterium from platinummetal clusters onto silicon oxide support, whichis a characteristic of dispersed metal catalysts.Through the collaboration with IBM, we have

accumulated valuable experience on electronbeam lithography, sample handling, surfacecleaning and reactivity studies of nanoscale

STM  &  SEM  images  of    catalyst  surfaces  

¡  Catalysis  is  old  science    §  Industrial  catalysis  is  even  older!  

¡  Nevertheless,  its  contextually  immensely  relevant  today  in  several  walks  of  life  

HOME  ASSIGNMENT:  Identify  a  scientist  working  in  catalysis.    Read  some  abstracts/summaries  of  their  work.  Note  down  the  source  of  your  information.      I  will  upload  a  template  on  the  web-­‐page.  Fill  in  details  there  and  email  to  preeti  <at>  iitm.ac.in  with  CH4170:Assignment  2  as  subject  line  by  Monday  27  Jan  5  pm  for  discussion  in  class  on  Tuesday  28  Jan.    

The  Nobel  Prize  in  Chemistry  1909  was  awarded  to  Wilhelm  Ostwald  "in  recognition  of  his  work  on  catalysis  and  for  his  investigations  into  the  fundamental  principles  governing  chemical  equilibria  and  rates  of  reaction".  

Long  road  ahead  -­‐  At  present  the  main  task  is  still  essentially  to  discover  and  scientifically  to  establish  the  various  cases  of  catalysis.  For  the  moment  it  is  still  scarcely  possible  to  summarize  these  cases  systematically…  

Holding  catalysis  close  to  his  heart  -­‐  It  has  pleased  no  less  than  surprised  me  that  of  the  many  studies  whereby  I  have  sought  to  extend  the  field  of  general  chemistry,  the  highest  scientific  distinction  that  there  is  today  has  been  awarded  for  those  on  catalysis.    

A  man  of  varied  interests  -­‐  Ostwald  studied  colours  and  shapes,  in  the  endeavour  to  find  a  scientific  standardization  for  colours.  His  main  work  in  this  field  is  Die  Farbenfibel  (The  colour  primer)  

The  Nobel  Prize  in  Chemistry  1918  was  awarded  to  Fritz  Haber  "for  the  synthesis  of  ammonia  from  its  elements”.  (Fritz  Haber  received  his  Nobel  Prize  one  year  later,  in  1919).    

Haber  was  controversy’s  child.  His  nobel  lecture  was  nevertheless,  filled  with  humility  (and  he  only  talked  about  fertilizers,  and  not  explosives)...      …It  may  be  that  this  solution  is  not  the  final  one.  Nitrogen  bacteria  teach  us  that  Nature,  with  her  sophisticated  forms  of  the  chemistry  of  living  matter,  still  understands  and  utilizes  methods  which  we  do  not  as  yet  know  how  to  imitate.  Let  it  suffice  that  in  the  meantime  improved  nitrogen  fertilization  of  the  soil  brings  new  nutritive  riches  to  mankind  and  that  the  chemical  industry  comes  to  the  aid  of  the  farmer  who,  in  the  good  earth,  changes  stones  into  bread….    

CHINESE JOURNAL OF CATALYSIS Volume 33, Issue 1, 2012 Online English edition of the Chinese language journal

Cite this article as: Chin. J. Catal., 2012, 33: 22–38.

Received 29 July 2011. Accepted 21 September 2011. *Corresponding author. Tel: +86-21-68462947; Fax: +86-21-68462283; E-mail: xzk@sinopec.com, xiezk2009@gmail.com This work was supported by the National Basic Research Program (973 Program, 2009CB623504, 2009CB623506). Copyright © 2012, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier BV. All rights reserved. DOI: 10.1016/S1872-2067(10)60299-9

REVIEW

Thoughts on the Future Development of Zeolitic Catalysts from an Industrial Point of View

LIU Zhicheng1, WANG Yangdong1, XIE Zaiku2,* 1Shanghai Research Institute of Petrochemical Technology, SINOPEC, Shanghai 201208, China 2SINOPEC, Beijing 100027, China

Abstract: Problems and challenges in the production and catalysis of zeolitic catalysts were addressed from an industrial point of view. The recent progress as well as discuss developments in zeolitic catalysts was reviewed. The highly efficient catalysis of zeolitic catalysts, the synthesis and application of novel zeolitic catalysts, the economic production of zeolites as well as the application of zeolites to environ-mental protection and green chemistry, etc., were covered. It is intended to stimulate thought and focus on the future development of zeolitic catalysts with regard to economic synthesis, catalyst design, high efficiency catalysis, green processes, new applications, etc.

Key words: zeolite; industrial catalyst; petrochemical industry; development; high efficiency catalysis; economic synthesis; green process

In the chemical industry most processes (more than 80%) involve catalysis especially in the petroleum and chemical industries. Catalysts are indispensable in many processes and zeolitic catalysts are important in these processes. The indus-trial application of zeolitic catalysts began in the 1960s when the FAU zeolite was the first to be used in the oil refining industry instead of the silica-alumina FCC catalyst by the former Mobil Company. Zeolitic catalysts are superior in terms of gasoline production and the utilization of crude oil com-pared to the conventional silica-alumina catalyst [1]. Currently, as a refinery catalyst, zeolitic catalysts occupy about 18.5% of the global catalyst manufacturing business [2]. Zeolitic cata-lysts have many distinctive advantages such as a regular pore system and a large inner micropore surface area, are compara-ble with H2SO4 and AlCl3, have molecular sieve or shape-selective properties, are amenable to modification or doping, etc. They have been widely used in many industrial catalysis processes including oil refinery and petroleum chemical processes such as catalytic cracking, hydrocracking, oligomerization, m-reforming, lube hydrotreating, dispropor-tionation, isomerization, alkylation, aromatics transalkylation, olefins catalytic cracking, methanol to gasoline, aromatization of olefins, alkylation of benzene, propylene or ethylene, and some fine chemical or coal chemical processes such as selec-

tive catalytic oxidation and methanol to olefins conversion (Table 1). The highly efficient catalysis of zeolitic catalysts has been very profitable for the petroleum and chemical industry.

However, with the increase in petroleum product consump-tion and the shortage of crude oil resources worldwide in ad-dition to changes in the composition and sources of raw mate-rials (increase in the heavy compositions in the crude oil), coal, natural gas, and bio-ethanol have become alternative resources, etc. Additionally, with the increased demand for energy saving and environment protection, improvements and innovation in the petrochemical industry technology are highly desirable. The development of new technologies such as heavy crude oil deep processing, coal or other alternative resources chemical processing, highly efficient transformation of low value side products, synthesis of high value special petroleum products, energy saving and consumption reducing technology, CO2 chemical utilization, etc. is in demand. Most of these new technologies should involve innovations in the development of catalysts and in the development of zeolitic catalysts. From an industrial point of view, to achieve industrial goals such as high efficiency or atomic economic utilization of resources, energy savings and a reduction in consumption as well as environ-mental friendliness, many problems and challenges exist for the future development of zeolitic catalysts such as maximizing

Journal of Catalysis 216 (2003) 47–62www.elsevier.com/locate/jcat

Present status and future trends in catalysis for refiningand petrochemicals

C. MarcillyInstitut Français du Pétrole, 1 & 4 av. de Bois Préau, 92500 Rueil-Malmaison, France

Received 10 July 2002; accepted 16 September 2002

Abstract

This article sets out to survey the remarkable development that has taken place in catalysis in the refining and petrochemical industriessince the middle of the 20th century, and more especially since the 1970s, highlighting what appears to be the most significant progress.It then attempts to outline the energy and environmental context for the coming decades which will govern the trend in industrial catalysisin the 21st century. Although the reduction of CO2 will eventually require the decarbonization of energy carriers, oil will still remain theprincipal source of liquid motor fuels for a long time. However, the share of gas will gradually increase and hydrogen is destined to play animportant part as an energy carrier. The use of biomass will develop, but at a modest level. Within this framework, catalysis will still play aleading role in technical and economic development in the 21st century, even though it is far from being an emerging discipline. 2003 Elsevier Science (USA). All rights reserved.

Keywords: Catalysis; Refining; Petrochemicals; Fuels; Energy; Petroleum; Gas; Coal; Biomass; Sustainable development

1. Introduction

Since the middle of the 20th century, catalysis hasundergone remarkable development both from the pointof view of fundamental knowledge and from that of itsapplications. At the start of the 21st century, between 80and 90% of the products we use in our daily life have“seen” a catalyst at some point during their manufacture.What part will catalysis play in the 21st century now thatnew technologies are being born and developing at a fasterand faster pace? It would be presumptuous to make a long-term prediction, but it is nevertheless important to try tooutline the future of this discipline while limiting the scopeto the field of the oil industry and to a few decades. This isthe exercise that this article will undertake, after a look at themost significant progress that has marked the second half ofthe last century: on the one hand in the field of refining, withparticular stress on fuels and motor fuels, and on the otherhand in the field of the main first-generation petrochemicalintermediates. Although the environment is a major factorin the background to this article, the catalysis involved inthe depollution of exhaust gas from transport vehicles willnot be covered. Last, an attempt will be made, insofar as

E-mail address: christian.marcilly@ifp.fr.

possible, to evidence the contribution of Europe to catalysis,in the past and in the coming decades.

2. Salient factors in the development of industrialcatalysis in refining and petrochemicals in the secondhalf of the 20th century

2.1. The development of refining and petrochemicals: theimportance of the geopolitical context

The development of industrial catalysis in Europe in thelast three decades has been especially influenced by a seriesof political and economic events and situations that can besummed up as follows:

• The world oil crisis of the 1970s and the realizationthat fossil fuel resources were limited and concentratedgeographically in unstable areas of the world had thefollowing consequences:• With regard to energy in general, there was a searchfor substitutes for fossil fuels [1] and, in areas greatlydependent on energy, such as Europe, renewed inter-est in alternative fuels. But oil remained a strategic

0021-9517/03/$ – see front matter 2003 Elsevier Science (USA). All rights reserved.doi:10.1016/S0021-9517(02)00129-X

¡  J.  N.  Armor:  A  history  of  industrial  catalysis,  Catal.  Today  163  (2011)  3-­‐9  

¡  R.  A.  van  Santen  &  M.  Neurock:  Molecular  heterogeneous  catalysis.  Wiley-­‐VCH  

¡  http://nobelprize.org/nobel_prizes/chemistry/laureates/  

The  Nobel  Prize  in  Chemistry  2007  was  awarded  to  Gerhard  Ertl  "for  his  studies  of  chemical  processes  on  solid  surfaces".  

•  Studied  ammonia  synthesis  &  CO  oxidation  extensively  

•  Demonstrated  spatio-­‐temporal  patterns  and  oscillations  in  experiments  &  computer  simulations  

•  Paved  the  way  for  much  of  the  recent  advances  in  surface  chemistry  based  analysis  of  catalytic  reactions  

The  Nobel  Prize  in  Chemistry  1932  was  awarded  to  Irving  Langmuir  "for  his  discoveries  and  investigations  in  surface  chemistry".  

The  philosophical  underpinnings  of  their  science  was  an  important  part  of  the  thought  processes..    This  coupling  together  of  science  with  international  peace,  is,  I  think,  particularly  significant.  Science,  almost  from  its  beginnings,  has  been  truly  international  in  character.  National  prejudices  disappear  completely  in  the  scientist's  search  for  truth.  Medicine  also  disregards  national  boundaries.  And  literature  frequently  rises  to  heights  that  make  it  international.  (About  the  Nobel  Prize  itself,  in  the  banquet  lecture)    Langmuir  was  a  most  productive  scientist  of  his  times,  with  contributions  in  several  spheres  of  chemistry,  atmospheric  science  etc.  He  worked  at  the  General  Electric  (GE)  company,  and  was  involved  in  several  inventions.    

The  Nobel  Prize  in  Chemistry  2010  was  awarded  jointly  to  Richard  F.  Heck,  Ei-­‐ichi  Negishi  and  Akira  Suzuki  "for  palladium-­‐catalyzed  cross  couplings  in  organic  synthesis".  

The  applications  in  the  pharmaceutical  industry  of  such  C-­‐C  coupling  is  enormous