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50 YEARS OF THE CATALYSIS SCIENCE IN SIBERIA Valentin Parmon, Director of the Boreskov Institute of Catalysis SB RAS

The Boreskov Institute of Catalysis (BIC) has accomplished 50 years. BIC is the largest chemical institute in Russia east of ral and one of !orld"s largest research centers speciali#ed in catalysis. The Institute is a uni$ue team!ork of e%perts in various fields of science and engineering !ho are capa&le of solving any catalytic pro&lems from fundamentals to design of industrial catalysts and processes. 'n e%tremely !ide R() activities area of the Institute em&races pro&lems from fundamentals of catalysis to innovative catalytic technologies and large*scale production of catalysts and chemicals. +ore than ,0 catalysts and catalytic technologies have &een created &y BIC and implemented into various industries. Catalysis and catalytic technologies are key factors in &uilding*up modern energetic- oil processing and chemical industries in Russia. In the recent years- revival of the Russian economy has provoked updating of the range and an increase in the output of Russian catalysts !ith their parameters superior or corresponding to the !orld level. .e do hope that the economic &oom in the country !ill strengthen BIC contacts !ith industrial enterprises and allo! our innovative products to &e industrially implemented.

CATALYSIS IN YOUR HOUSE Z.R. Ismagilov, Boreskov Institute of Catalysis SB RAS Boreskov Institute of Catalysis, 5, Pr. Lavrentieva, Novosibirsk !""#", $ri%&atalysis.ru +ore than /00 of processes in the chemical industry use catalysts. Catalyst sales in 1005 !ere estimated to &e !orth around 2344 &illion. In period 1005*100, the gro!th in catalyst sales !as estimated to &e increasing at a&out 5.50 per year. In a recently pu&lished BCC Research report- Catalysts for 6nergy and 6nvironmental 'pplications- the glo&al market for energy and environmental catalysts !as !orth an estimated 347.0 &illion in 100, and 34/.5 &illion in 1041 at a compound annual gro!th rate (C'8R) of ,.50 from 100, to 1041. In e%cess of 237 trillion in goods and services in !orld*!ide 8ross )omestic 9roduct annually can &e attri&uted to catalysts. The conversion of crude oil- coal or natural gas to all do!nstream products uses a catalyst. The importance of industrial catalysis in development and progress in society is pronounced through environmentally clean motor fuels- plastics- synthetic ru&&er- ne! fi&erscomposite materials- pharmaceutics and many others. The !idely used automo&ile catalytic converters and diesel o%idation catalysts could &e considered as a linkage &et!een industrial catalysis and our everyday life. In addition there are a num&er of efficient uses of catalysts in household appliances. The market of these devices is less than of industrial catalysts- &ut they are in houses around us or have a potential to &e in future.

The list of household catalytic appliances includes: Carbon mono'i(e (ete&tor Self &leaning &atalysts in )ome in&inerators an( &ooking a**lian&es +as &atalyti& furna&e +as &atalyti& s*a&e )eater Catalyti& t)ermoele&tri&ity generator Catalyti& o$one (estroyer P)oto&atalyti& air &leaner Portable *o&ket ,armer Cor(less &atalyti& )air &urler Catalyti& igniters in kerosene s*a&e )ater Catalyti& gas lig)ter Catalyti& mos-uito killer Catalyti& lam* Catalyti& fragran&e lam* .uel Cells Batteries /ater *urifier0 1 2omesti& *urifier 1 (e&)lorination on *o,(ere( a&tivate( &)ar&oal, Cl3 3Cl 11 1 .e34 an( 5n34 removal 2ome e%amples of these appliances manufactured !orld!ide and principles of advanced catalyst development at BIC and their performance !ill &e presented in this lecture. Carbon monoxide detectors development !as stimulated &y increasing a!areness of the dangers of car&on mono%ide in homes and urgent need of sensors to detect the poisonous gas. Car&on mono%ide can accumulate gradually from poorly maintained heaters due to incomplete com&ustion of fuels. The most modern car&on mono%ide detectors are &attery po!ered electrochemical devices. 9orous platinum electrodes catalyse electrode reactions of car&on mono%ide and o%ygen as the gases diffuse into the sensor. The car&on mono%ide sensor is &ased on an electrochemical cell. The electrolytic solution is held in a semi permea&le container !ith a polymer mem&rane e%posed to the air. Car&on mono%ide molecules can pass through this mem&rane and react at the anode. This frees electrons !hich are pushed around the circuit to the cathode. The current flo!ing &et!een the anode and the cathode is proportional to the concentration of car&on mono%ide in the air and is set to trigger an alarm !hen it reaches a set value. In some parts of the 2' all ne! houses are re$uired &y la! to install a car&on mono%ide detector. uel cells are attracting a great deal of interest in the search for alternative energy supplies to fossil fuels- since they are very efficient and virtually pollution free. In a fuel cell a fuel gas such as hydrogen is com&ined !ith o%ygen to produce electricity. This conversion happens at electrodes that are coated !ith catalysts. nlike an ordinary &attery !hich has a fi%ed life spanthe fuel cell !ill continue to function for as long as the fuel gases are supplied to it. 2ome consumers use gasoline or methanol as the fuel. This is first catalytically converted (reformed) into hydrogen for use in the fuel cell. Catalytic combustion and catalytic furnaces and s!ace heaters"
The first catalytic com&ustion devices ; miners safety lamps !ere designed &y 2ir. <umphry )avy in 4/45. 2i% years later =ohann .olfgang )oe&ereiner invented a catalytic lamp- in !hich a light caused &y a >et of hydrogen passing over spongy platinum. ?or some 50 years )@&ereinerAs lighter served as an important source for household and industrial fire lighting. .ithin five years of its discovery 10-000 )@&ereinerAs lamps !ere in use in 8ermany and 6ngland. It entered the middle*class home as !ell.. In

4/1B a Berlin manufacturer could offer CD as a pleasant and useful Christmas present a lighting machineoutfitted !ith platinum- elegant- clean- and sturdily constructed- !ith Chinese and other decorationinsensitive to !etness and coldD.C In 4B4E !as &orn the first catalytic heater. The ?rench !ar ministry re$uired to Fuis Fumiere(already famous for the cinefilm invention)- the solution- that !ould allo! to preheat the engines of the military aeroplanes !ithout any risk of fire neither e%plosion !hen in contact !ith petrol stored in the hangars. Fumiere created a heat appliance- &ased on the principle of catalytic com&ustion- achieving to maintain the engines of the aeroplanes !arm and avoiding the risk of fire- since the heat !as produced to a temperature lo!er than the inflammation point of petrol. Thanks to this invention- the !ar +inistry could maintain his air force on full efficiency and it reached such a &ig success that a lot of other models !ere developed- so as to e$uip the rest of the army.

In 4B4B- Fuis Fumiere founded a civil company in order to e%ploit the registered patents. <e manufactured and marketed an important range of heating appliances for catalysis under ThermG% &rand- such as: +adam !arm hands- !arm feet- lu%urious appliances for detached and semidetached houses- appliances for aeroplanes- ships- trains- etc... ?or the past 10 ; 70 years e%tensive R() !ork on catalytic fuel com&ustion for energy efficiency and &etter environment in household appliances have &een performed. Catalytic com&ustion is proved effective techni$ue for clean com&ustion of fuels. It is fundamentally different from traditional flame com&ustion &ecause fuels are o%idi#ed flamelessly on the surface of catalysts at relatively lo! temperatures: 500*4000 HC. In many la&oratories the fundamental research !as conducted in follo!ing main directions: study of kinetics and mechanism of catalytic com&ustion of organic compounds of various nature (hydrocar&ons- alcohols- amines- etc)I synthesis and characteri#ation of novel efficient com&ustion catalysts containing &oth transition metal o%ides and no&le metals. +ethods of catalyst preparation in shape of granulated- honeycom&- fi&rous- foam material supported- etc. have &een developed. modeling of catalytic com&ustion development of technologies for practical application ' very attractive feature of catalytic com&ustion is the possi&ility to reduce drastically CJ and KJ% emissions. Rather lo! temperature of catalytic com&ustion allo!s nearly complete elimination of thermal KJ%. GolfCat Catalytic Heater includes a holder that conveniently fits in most golf cart cup holders ; Continually provides !hisper $uiet heat * 7-000 BT s of heat !ithout flame raises the cart temperature from 40*15 degrees. <eater head is angled to ma%imi#e heat direction to!ards those in the cart. This catalytic heater can also &e used a!ay from the golf course- in your shopgarage- &all and etc. Catalytic hair curlers or stylers have &een designed for use !hen an electricity supply is not availa&le. They carry their o!n fuel supply- for e%ample methanol or F98- in a cartridge !ithin the handle. The vapori#ed fuel is mi%ed !ith air and passes into a com&ustion cham&er !hich makes up the core of the curling part of the device. .ithin the com&ustion cham&er is a catalyst of $uart# !ool coated !ith platinum in the shape of a stocking- !hich specially designed for flameless o%idation of fuel to car&on dio%ide and !ater. .hen a &utton is pressed on the outside of the hair curler- the fuel gasLair mi%ture is ignited &y the creation of sparks or &y electrically

heating a filament in the com&ustion cham&er. The e%othermic flameless reaction heats up the curler and !ill continue until the supply of fuel is turned off. Catalytic stoves rely on a catalyst to help &urn smoke &efore it leaves the appliance. The catalyst in a !ood*&urning appliance is a coated ceramic honeycom&*shaped device through !hich the e%haust gas is routed. The catalytic coating lo!ers the ignition temperature of the com&ustion gases as they pass through it. This allo!s catalytic appliances to &urn cleanly at lo! heat output settings. ' revie! of main types of processes and apparatuses for catalytic fuel com&ustion developed at BIC !ill &e follo!ed: Catalytic heat generators (C<8) &ased on the use of fluidi#ed &ed of granulated spherical catalyst particles !ith a capacity of 40*4000 k.. The C<8s provide high heat efficiency due to the use of fluidi#ed &ed and catalysts !ith high performance. 9ilot and industrial C<8s !ere tested !ith various fuels: natural gas- diesel fuel- residual oil- etc. They !ere sho!n to &e efficient for heat production- &iomass gasification- drying and thermal treatment of po!der materials- treatment of dust loaded off*gases- treatment of !aste !ater containing organic admi%tures and ha#ardous organic !astes. ?luidi#ed &ed com&ustion has preference in com&ustion of lo! grade fuels and organic !astes at residences and farms. The &iomass gasification for cogeneration of heat and electricity is a entirely ne! application of fluidi#ed &ed com&ustion. Catalytic #as combustion air heaters" The outstanding environmentally clean performance of air heater is &ased on t!o*stage com&ustion. 't the first stage flame com&ustion proceeds under fuel rich conditions at M0.B5*0.B/. Then the com&ustion products !ith additionally in>ected air pass into the second cham&er e$uipped !ith an assem&ly of honeycom& monolithic catalyst. The catalyst provides total o%idation of CJ and <C and reduction of KJ%. The purified flue gas is further diluted !ith air &ehind the monolithic catalyst and e>ected from the apparatus to heat premises- such as greenhouses- garages- hangars and etc Catalytic #as burnin# s!ace heaters" T!o types of heaters !ith a capacity of 1*7 k. !ere developed: for com&ustion of city gas from cylinders and natural gas. The active component comprising com&ination of transition metal o%ides and 9t is supported on silica*alumina fi&er mat (Termocat*4)- or on multichannel ceramic plates (Termocat*1- 7). The original construction and use of high performance catalytic materials provides complete &urning of fuel and concentrations of KJ% and CJ in flue gases completely fulfill re$uirements of sanitary standards. Catalytic $ater%heatin# boiler. The main feature of this appliance is the foam structured ceramic catalysts and it has a capacity of 10 k. ; for on residence. The &oiler !orks !ith natural gas. It operates !ith original catalysts supported on highly porous foam materials and catalytic heat e%changers. The heat efficiency of the &oiler is //*B50. The concentrations of CJ and KJ% in the flue gas are &elo! 5 ppm. The lecture !ill &e decorated !ith a num&er of schemes and photos of catalytic household appliances. The most interesting of our results in development of catalyst support design of variety of materials and geometry !ill &e demonstrated. In addition some fundamental results of catalyst development for fuel cells and catalytic com&ustion !ill &e presented.

Adva ced !eo"etric for"# i cataly#i# Bair Bal"#hinimaev Boreskov Institute of Catalysis, Lavrentieva 5, Novosibirsk !""#", Russia .a' number0467 !8!9!!"8!5 , :1mail a((ress0 bal$)%&atalysis.ru It is !ell kno!n that catalysts !ith ne! geometric form like ceramic- metal monoliths or metalceramics composites !ith supported thin films of active components are successfully used in purification of various gaseousLli$uid emissions. The novel geomentric forms provide the improved hydrodynamic properties- improved heat* and mass*transfer- as !ell as possi&ility to make ne! design of catalytic reactors !ith structured catalyst &ed. The present lecture is devoted to study the silicate glass fi&er materials in order to reveal their molecular structure and to evaluate their potentiality in catalysis. The effective procedures for introduction of metal comple%es (mostly- 9t- 9d) into the &ulk of glassmatri% (up to 400 ' in depth) and for further redo% treatments to form highly dispersed metal species !ere developed. The capa&ility of glass to sta&ili#e the metal clusters (up to 40 ' in si#e)- as !ell as to a&sor& predominantly the polar or polari#a&le molecules from gas or li$uid is responsi&le for its high performance in many reactions like deKJ%- 2J 1 o%idation- NJC removal- selective hydrogenation of acetylenic hydrocar&ons etc. In conclusion some e%amples of fi&erglass &ased catalysts testing in pilot plants are given.

Na o#i$e Effect# i Cataly#i#


%alerii I& B'()tiyarov Boreskov Institute of Catalysis, Lavrentieva 5, Novosibirsk !""#", Russia .a' number0467 !8!9!!"8!5 , :1mail a((ress0 vib%&atalysis.ru In this lecture I !ill present the data of BIC recent investigations of the si#e effects in lo! temperature o%idation of CJ over 'uL'l1J7 catalysts- in C<5 o%idation over 9tL'l1J7 catalysts and in ethylene epo%idation over 'gL'l1J7 catalysts. The catalysts !ere prepared &y deposition precipitation ('uLO*'l1J7)- &y incipient !etness impregnation (9tLO*'l1J7 and 'gL*'l1J7) and &y physical vapor deposition ('gL<J98 M highly oriented pyrolitic graphite). The model 'gL<J98 samples !ere used to study the reasons of si#e effects in ethylene epo%idation over silver. The preparation of the catalysts !ith narro! and varia&le particle si#e distri&ution allo!ed us to sho! that the reduction of metallic particle si#es to nanometer range can increase not only activity (C<5 and CJ o%idation)- &ut also selectivity (ethylene epo%idation) in the target reactions. 's conse$uence- !e conclude that the si#e effects can &e applied for developing the

catalysts !ith improved performance. The prepared samples have &een studied &y physical methods ( N*Nis- P92- 2'P2- 6P'?2- P'K62 spectroscopy- T6+ and 2T+). The results of this study !ere used for discussion the reasons of the si#e effects in the reactions studied. ECOLOGICAL CATALYSIS *rof& A&S& No#(ov Boreskov Institute of Catalysis Novosibirsk, Russia e1mail0 noskov%&atalysis.ru Implementation of the Qyoto 9rotocol makes it necessary to pay particular attention to treatment of industrial !aste gases (neutrali#ation of nitrous o%ide- K 1J) and vent gases from coal mining (removal of methane). )ecomposition of nitrous o%ide in industrial !aste gases is proposed to achieve over BIC"s proprietary #eolite catalysts at 550;E00 HC. In comparison to the traditional process of non*catalytic high*temperature decomposition- the proposed process allo!s economy of fuel (natural gas) up to 15 to 70 m7 per 4000 m7 of treated gas. In coal mining- methane- prefera&ly in the form of vent gases !ith the methane concentration ca. 4 vol 0- is evolved in amount of ca. 40 m 7 per 4 ton of coal. Catalytic technologies can &e used for utili#ation of the vent gases to generate heat. ?or e%ample- a catalytic unit can utili#e up to 15-000 m7Lh of gas to produce up to 50 tLh of hot !ater. Customers of these units are coal mines or energy producers. 'pplication of a com&ination of adsor&ents and catalysts allo!s the solution of pro&lems of human and environmental protection from emergency escape of to%ic compounds (for e%ampleammonia- chlorine)- hydrocar&ons- evil*smelling matters. The treatment installation comprises t!o units: one for adsorption and another for catalytic transformations. 6mergence to%ic !astes are trapped in the adsorption unit- then desor&ed in controlled manner and catalytically transformed (neutrali#ed) in the catalytic unit. The installations are mainly used &y enterprises !here tanks !ith to%ic compounds are employed (chemical plants- industrial refrigerators etc.). ?or hydrosphere protection- a li$uid*phase adsorptive catalytic process is proposed to treat !aste !ater containing lo!*concentrated organic contaminants (phenol- aromatic compounds in amounts of 40;400 mgLl). The process is &ased on t!o alternating stages: a) sorption and &) regeneration*o%idation. 2tage (a) takes 70 to /0 hours depending on the contaminant concentration. The !aste !ater to &e treated is passed through a catalyst*adsor&ent &ed at am&ient pressure and temperature in the reactor. 's soon as the contaminants are detected in the treated !ater- it is stopped passing- the temperature and pressure are increased (up to 450R0100 HC and 70;50 atm) and hot air is fed to the reactor. The sor&ed impurities are completely o%idi#ed in 1;1.5 hours and the sor&ent*catalyst &ed can &e used again. ?or the atmosphere and hydrosphere protection- BIC can provide: )evelopment of processes for neutrali#ation of industrial !aste !ater and gas under customer"s re$uestI In cooperation !ith BIC"s partners- supply of facilities and catalysts for neutrali#ation of particular gases and li$uid !astes.

Hydro!e a d tra #+ort i t)e f't're


Nladimir '. 2o&yanin- Nalerii '. Qirillov

Boreskov Institute of Catalysis Kovosi&irsk 2tate niversity In recent years- research institutions and industrial companies all over the !orld have &een focusing considera&le efforts on the development of technologies and infrastructure for hydrogen energy. 2pecial attention is targeted at the development of the fuel*cell*&ased engine for vehicle applications- alternative to conventional internal com&ustion engines. ?uel*cell*&ased engines are fed &y hydrogen- !hich is most reasona&ly to generate on*&oard a vehicle from conventional fuel. The present report presents the results of studies on: * the development of nano*structured catalysts and compact on*&oard reactors for conversion (using these catalysts) of fossil- synthetic and rene!a&le fuels to hydrogen*rich gasI * nontraditional use of hydrogen*rich gas generated on*&oard a vehicle- namely- as an additive to the primary fuel (&en#ene- natural gas- etc.) supplied to IC6- and as a KJ% reducer in the car e%haust converters.

Cataly#i# a d re e,a-le feed#toc(


)r. Sakovlev N.'. Boreskov Institute of Catalysis, Lavrentieva 5, Novosibirsk !""#", Russia .a' number0467 !8!9!!"8!5 , :1mail a((ress0 yakovlev%&atalysis.ru The consumption of petroleum has surged during the 10th century- at least partially &ecause of the rise of the automo&ile industry. Today- fossil fuels such as coal- oil- and natural gas provide more than three $uarters of the !orld"s energy. <o!ever at present rene!a&le feedstock attracts attention due to increasing of fossil fuels cost and its graceful irretrieva&le consumption. 't that- no! the technologies level of &iomass processing into engine fuels is lo!er than oil*refinery industry. This is a main reason of higher prime cost of &io*fuels production. Bioethanol and &iodiesel are produced from food ra! materials. Bio*fuels competition !ith food sector plays negative role for &ioenergetics progress. 2o- for &io*fuels production increasing scientific society has to not only improve present &iotechnologies- &ut develop ne! &iomass processing technologies !ith !idening of rene!a&le feedstock list- including !ood and agricultural !aste. The ne! catalytic technologies of &iomass processing should play a key role in the &ioenergetics evolution. In Boreskov Institute of Catalysis the intensive investigations are carried out in the field of &iodiesel production in the presence of heterogeneous catalysts- high* cetane fuels production from &iodiesel and plant oils directly- upgrading of &io*oil ; product of !ood flash pyrolysis- production of &io*syn*gas and car&onaceous materials.