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PP-V-21KINETICS OF THE HYDROXYMATAIRESINOL HYDROGENOLYSISOVER PALLADIUM CATALYSTSHeidi Bernas, Dmitry Yu. MurzinLaboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre,Åbo Akademi University, Biskopsgatan 8, FI-20500 Turku, FinlandIntroductionKnots, e.g. the part of the branch that is embedded in the tree, are harmful in pulp andpaper manufacturing and should be removed before pulping [1]. Some years ago, largequantities of the lignan hydroxymatairesinol (HMR) were discovered in Norway spruce(Picea abies) knots [2]. Since lignans have anticarcinogenic [3] and antioxidative [4] effects,the waste material from pulping industry can be used for synthesis of pharmaceuticals andtechnical antioxidants. No other lignan has been found in substantial amounts in nature,therefore other lignans that are of great interest and importance should be synthesized startingfrom HMR. The lignan matairesinol (MAT) has high application potential. In our previousstudies related to HMR hydrogenolysis, we have investigated the influence of support acidityfor palladium catalysts supported on carbon [5], zeolites [6] and carbon nanofibres (CNF) [7].It was concluded that the acidity of the support material has a great influence on the activity;for carbon and CNF supported palladium catalysts, the activity increased when the acidityincreased. For palladium supported by H-Beta zeolites, having higher concentration of acidsites than carbon materials, the activity decreased with the acidity increase. Since the choiceof catalyst support and the concentration of acid sites on the support have a great influence onthe hydrogenolysis to HMR, it is important to study the effect of reaction conditions. Theinfluence of mass transfer, temperature, reactant concentration and hydrogen pressure wasstudied.Results and discussionThe main reaction network is presented in Fig. 1. There are two diastereomers of HMR,the isomer with RRR configuration (HMR 1) and the one with RRS configuration (HMR 2).The influence of hydrogen pressure was studied using a 5% Pd/C catalyst (Degussa) in anautoclave at hydrogen pressures from 5 to 40 bars. At low pressures the reaction rateincreased, but at pressures higher than 25 bar the reaction rate decreased dramatically. It canbe concluded that there is an optimum in activity not only as a function of acid siteconcentration but also as a function of hydrogen concentration. These observations are inagreement with the reaction mechanism presented in [5], where the first step is protonation of496
PP-V-21the hydroxyl group (with proton coming from the support material) followed by waterabstraction and a hydride addition (hydrogen adsorbed on the catalyst surface) resulting inMAT. Too high concentration of acid sites or excess hydrogen retards the reaction.H 3 COHOHOOOOHHMR 1OCH3H 3 COOOHOH 3 COHOHOOOOHMATOCH3OCH 3OHHMR 2Fig. 1. The main reaction, hydrogenolysis of hydroxymatairesinol (HMR) to matairesinol (MAT).References1. B. Holmbom, C. Eckerman, P. Eklund, J. Hemming, L. Nisula, M. Reunanen, R. Sjöholm, A. Sundberg,K. Sundberg and S. Willför, Phytochem. Rev. 2 (2003) 331.2. S. Willför, J. Hemming, M. Reunanen, C. Eckerman and B. Holmbom, Holzforschung 57 (2003) 27.3. H. Adlercreutz, Lancet 3 (2002) 364.4. S.M. Willför, M.O. Ahotupa, J.E. Hemming, M.H.T. Reunanen, P.C. Eklund, R.E. Sjöholm,C.S.E. Eckerman, S.P. Pohjamo and B.R. Holmbom, J. Agric. Food Chem. 51 (2003) 7600.5. H. Markus, P. Mäki-Arvela, N. Kumar, N.V. Kul’kova, P. Eklund, R. Sjöholm, B. Holmbom, T. Salmi andD.Yu. Murzin, Catal. Lett. 103 (2005) 125.6. H. Markus, P. Mäki-Arvela, N. Kumar, T. Heikkilä, V-P. Lehto, R. Sjöholm, B. Holmbom, T. Salmi andD.Yu. Murzin, J. Catal. 238 (2006) 301.7. H. Markus, A.J. Plomp, P. Mäki-Arvela, J.H. Bitter and D.Yu. Murzin, Catal. Lett. 113 (2007) 141.497
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Boreskov Institute of Catalysis of
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Mikhail G. Slinko,Honour ChairmanVa
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PLENARY LECTURES
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PL-1built up from an intrinsic cont
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PL-3DEVELOPMENT OF ZEOLITE-COATED M
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PL-4processes in order to evaluate
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PL-5CATALYTIC PARTIAL OXIDATION OF
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KEY-NOTE PRESENTATIONS
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KN-2GETTING TO THE POINT: FROM MOLE
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KN-3PROBLEMS AND PROSPECTS FOR IMRO
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KN-4remain out of the sight of rese
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KN-5SSITKA allows to study not only
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KN-6individual reaction stages with
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Section 1.Kinetics of catalytic rea
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OP-I-1-specialthat Г s /f changed
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OP-I-3-specialKINETIC MODELING OF L
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OP-I-4PARTIAL OXIDATION OF TOLUENE
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OP-I-5Also, the approach to modelin
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OP-I-6starch granules, but after a
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OP-I-8KINETICS OF CARBON MONOXIDE O
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OP-I-9CHAOTIC DYNAMICS IN THE THREE
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OP-I-10ADSORPTION OF COMPLEX MOLECU
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OP-I-11KINETIC ASPECTS OF METHANE O
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OP-I-12KINETIC STUDIES IN STRUCTURE
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OP-I-13A STUDY ON THERMAL COMBUSTIO
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OP-I-14KINETICS OF THE CONVERSION O
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OP-I-15HYDROCRACKING OF LONG CHAIN
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OP-I-16KINETICS IN THE HYDROGENATIO
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OP-I-17MECHANISM OF FORMATION OF ET
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OP-I-18KINETIC STUDIES OF PROPANE D
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OP-I-19ACTIVITY AND DEACTIVATION OF
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OP-I-20GAS PHASE OXIDATION OF FORMA
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OP-I-21Where k A is the rate consta
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OP-I-22al., 2008; Monolith, 2008).
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OP-I-23Fig. 1. Scheme of the FIM ma
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OP-I-24Θ DZ centersdeactivationr D
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OP-I-25equation [2] to nitrogen iso
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OP-II-1CHEMICAL NANOREACTORS AS BAS
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OP-II-2gas model use, there is no n
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OP-II-3Taking into account these pr
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OP-II-4WATER2METH1STEAM2AOFF3AIR10O
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OP-II-5completely dry, at the same
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OP-II-6Many factors have been found
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OP-II-7mechanistic and kinetic stud
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OP-II-9MODELLING OF DIESEL PARTICUL
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Section 3.Catalytic processesí dev
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OP-III-1BIC’s catalyst for N 2 О
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OP-III-2powder sample with the same
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OP-III-3Analysis of the results sho
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OP-III-4Exhaustaftertreatmenttechno
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OP-III-6SOME PROPERTIES OF PEROVSKI
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OP-III-7with the conventional react
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OP-III-8resistance is the membrane
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OP-III-9mass dispersion and to anal
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OP-III-11PROCESS INTENSIFICATION US
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OP-III-12ETHYL ACETATE SYNTHESIS BY
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OP-III-12products are vaporized and
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OP-III-13The reforming reaction was
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OP-III-14reactivity (compared to ot
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OP-III-15Fig. 2. The spent Smopex-1
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OP-III-16Numbers of curves are acco
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OP-III-17perimeter were determined.
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OP-III-18of 2. MSR has been coupled
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OP-III-19chemisorption heat and pro
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OP-III-20In the experiments, total
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OP-III-21obtained by the new techno
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OP-III-22reactor wall from the two-
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OP-III-23and parameters of synthesi
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OP-III-24Results and discussionThe
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OP-IV-1DEEP DESULPHURIZATION OF PET
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OP-IV-2LACTIC ACID AS A BACKGROUND
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OP-IV-3CO REMOVAL FROM H 2 -rich GA
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OP-IV-4REFORMING OF ETHANOL OVER ME
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OP-IV-5MODELING OF HYDROGEN PRODUCT
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OP-IV-6PRODUCTION OF HYDROGEN FROM
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OP-IV-7SYNTHESIS GAS PRODUCTION FRO
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OP-IV-8HYDROGEN PRODUCTION FROM MET
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OP-IV-9A NEW GENERATION OF SUPER-TH
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OP-IV-10EXERGY ANALYSIS OF ENZYMATI
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OP-IV-11ADVANCEMENT OF SLURRY BUBBL
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OP-IV-12Pd-DOPED PEROVSKITE CATALYS
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OP-IV-13HYDROGEN PRODUCTION VIA MET
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Section 5.Catalytic processing of r
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OP-V-1Scheme 1. The developing path
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OP-V-2An example of the model compo
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OP-V-3catalysts were shown to be su
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OP-V-4Catalyst deactivation was mor
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OP-V-53) Study of the FFAs esterifi
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OP-V-6In the present work, a compre
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OP-V-7Ca 2 Fe 2 O 5 , MgFe 2 O 4 an
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OP-V-8cellulose components decompos
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OP-V-9sintering a couple of spirale
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OP-V-10Catalyst preparationA series
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OP-V-11Catalysts characterizationIn
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OP-V-12Kinetic ExperimentsHexadecan
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OP-V-13DESIGN OF PILOT REACTOR AND
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OP-V-14DEVELOPMENT OF A LAB SCALE C
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OP-V-15DEVELOPMENT OF TWO-STAGE PRO
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OP-V-15The data of Table 2 show, th
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OP-V-17ENERGY PRODUCTION FROM BIOMA
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OP-V-18CATALYTIC PARTIAL OXIDATION
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OP-V-19A PHOTOCATALYTIC REACTOR FOR
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OP-V-20BIOMASS GASIFICATION IN A CA
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OP-V-21ESTIMATION OF OPTIMAL REACTO
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POSTER PRESENTATIONSSection 1. Kine
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PP-I-1CONVERSION OF ETHANOL OVER CO
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PP-I-2LATERAL INTERACTIONS, FINITE
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PP-I-3UTILIZATION OF TAFT EQUATION:
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PP-I-4SELECTIVE HYDROGENATION OF CI
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PP-I-5NON OXIDATIVE REGENERATION ME
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PP-I-6Table 1. Parameters in kineti
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PP-I-7where: k nc , k 1 , k a , k b
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PP-I-8After each adsorption or deso
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PP-I-9The increase in pressure, in
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PP-I-10The analysis of the composit
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PP-I-11The network of βP oxidation
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PP-I-12order of magnitude lower. Th
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PP-I-13ab1,01,0Isotope fraction0,5[
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PP-I-14Relations ‘rate vs alcohol
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PP-I-15[EEAA] t , M[EEAA] t -1 , M
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PP-I-17NEW OSCILLATING REACTION:CAR
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PP-I-18NEW OSCILLATING REACTIONS OF
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PP-I-19KINETICS OF GAS-LIQUID PROCE
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PP-I-20COMPLETE OXIDATION OF HARMFU
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PP-I-21THEORETICAL RESEARCH OF SURF
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PP-I-22INFLUENCE OF ORGANIC HELATES
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PP-I-23The equation of the reaction
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PP-I-25SELECTIVE OXIDATION OF METHA
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PP-I-26coefficients of the equation
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PP-I-27into propionic acid. The giv
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PP-I-28In the studied range of temp
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PP-I-29Table. Reaction temperature
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PP-I-30other in both direction of t
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PP-I-31Reynolds number. The boundar
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PP-I-32NANOPARTICLES AND CATALYSISI
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Section 2.Physico-chemical and math
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PP-II-1For investigation, we used n
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PP-II-2criterion «Zn dissolved in
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PP-II-3exist around the steady stat
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PP-II-4in range 0-1. In our case n
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PP-II-5at comparable activity, the
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PP-II-7CFD-CALCULATION OF MALDISTRI
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PP-II-8INVESTIGATION OF NONLINEAR P
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PP-II-8reactivity. There is a small
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PP-II-10CALCULATION OF INDUSTRIAL C
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PP-II-11type of reactors a catalyst
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PP-II-13MATHEMATTICAL MODELLING OF
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PP-II-13where I Э , M 1Э , M 2Э
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PP-II-14where TOC 0 is the initial
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PP-II-16AUTOCATALYTIC REACTION FRON
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Section 3.Catalytic processesí dev
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PP-III-1for the traditional scheme
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PP-III-2Initial conditions: С i (0
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PP-III-3Afterward, a 30% aqueous hy
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PP-III-4The influence of the water
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PP-III-5Vanadium oxide was grafted
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PP-III-6(T p ) was taken as an inde
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PP-III-7dCdτLABdCNABdτdCdτdCdτd
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PP-III-8O 2 , balanced by He, at a
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PP-III-9Solution of system (3) for
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PP-III-10HDT330ºCHDT350ºCHDT370º
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PP-III-11The activity of Au/support
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PP-III-1249775 m 3 /h0,65Initial te
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PP-III-13through one layer of ACC w
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PP-III-14the runs was always higher
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PP-III-15The experimental data for
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PP-III-16Catalytic hydrogenation of
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PP-III-17The following parameters a
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PP-III-18Figure 1 - Dependence of t
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PP-III-19Our method has some advant
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PP-III-20Furthermore, Ayude et al.
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PP-III-22OPTIMIZATION OF THE METHAN
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PP-III-23EXPERIMENTAL INVESTIGATION
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PP-III-24CATALYTIC REACTORS WITH HY
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PP-III-25ACTIVITY OF Cu/ZSM-5 CATAL
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PP-III-26SIMULATION AND OPTIMISATIO
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PP-III-27model of plug flow reactor
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PP-III-28Calculations were experime
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PP-III-29continuous and pressurized
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PP-III-30adequacy of multistage mod
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PP-III-31+CH 3 OHH 2 O + HO-(CH(CH
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PP-III-32procedure presented by Mar
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PP-III-33HPA-x + 2 H + + Pd 0 ⎯
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PP-III-34of the process as well as
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PP-III-35This study was financially
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PP-III-36phase. Peroxopolyoxometall
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PP-III-37performed under atmospheri
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PP-III-38orders of magnitude larger
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PP-III-39CATALYTIC REACTORS WITH ST
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PP-III-40THE OXIDATIVE DEHYDROGENAT
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PP-III-41MODELLING AND DESIGN OF TH
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PP-III-42COMPLEX TECHNOLOGY OF TREA
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PP-III-43PHOTO ELECTROCHEMISTRY APP
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PP-III-45MODELING OF CATALYTIC α-O
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PP-III-46steady states. It was show
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PP-III-47Results and discussion:The
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PP-III-49FIBROUS PALLADIUM-SUPPORTE
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Section 4.Catalytic technologies in
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PP-IV-1method is adiabatic or autot
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PP-IV-2It had been established that
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PP-IV-4INTERACTION OF ACTIVATED ALU
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PP-IV-5ENVIRONMENTALLY FRIENDLY PRO
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PP-IV-6THE 5%Ni-2%Au/Al 3 CrO 6 SYS
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PP-IV-7MESOPOROUS ANODES BASED ON Y
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PP-IV-8ADVANCED OXIDATION PROCESS F
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PP-IV-9PROCESSING OF POLYMERIC CORD
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PP-IV-10EFFECT OF SULPHUR ON THE CA
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PP-IV-11OXIDATIVE CONVERSION OF MET
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PP-IV-13CATALYTIC FLUE GAS CONDITIO
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PP-IV-14RIBBON POROUS NICKEL BASED
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PP-IV-15ETHANOL CONVERSION TO HYDRO
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PP-IV-16A HIGH-EFFICIENT MICROREACT
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PP-IV-17DIRECT DECOMPOSITION OF NIT
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PP-IV-18NICKEL CATALYSTS BASED ON P
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PP-IV-19SELECTION OF FAVOURABLE FEE
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PP-IV-20FORMALDEHYDE FORMATION DURI
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PP-IV-21PRODUCTION OF HYDROGEN-RICH
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PP-IV-22INFLUENCE OF COMPOSITION OF
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PP-IV-24ONE-STAGE CATALYTIC CONVERS
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PP-IV-25THE STUDY OF METHANE DEHYDR
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PP-IV-26MCM-41-SUPPORTED PdNi CATAL
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PP-IV-27IMPROVING THE FLOW SHEET OF
Page 446 and 447: PP-IV-29THE PARTIAL OXIDATION OF CH
Page 448 and 449: PP-IV-30PRODUCTION OF CO-FREE HYDRO
Page 450 and 451: PP-IV-31PHOTOCATALYTICAL ACTIVITY O
Page 452 and 453: PP-IV-32NEW ELECTRODE MATERIALSFOR
Page 454 and 455: PP-IV-33THE CATALYTIC HYDROGENATION
Page 456 and 457: PP-IV-34W 0, μmol O 2/min0,25 1. 1
Page 458 and 459: PP-V-1INFLUENCE OF ICE ON MEAs OF P
Page 460 and 461: PP-V-2DIRECT OILS HYDROGENATION TO
Page 462 and 463: PP-V-3DEVELOPMENT OF Pd/SIBUNIT CAT
Page 464 and 465: PP-V-4Pt NANOPARTICLE-HOLLOW POROUS
Page 466 and 467: PP-V-5THE PROCESS FOR PRODUCING ORG
Page 468 and 469: PP-V-6water removing. This method p
Page 470 and 471: PP-V-7ResultsThe presented technolo
Page 472 and 473: PP-V-8the most effective catalysts.
Page 474 and 475: PP-V-9Neither the low sulphur conte
Page 476 and 477: PP-V-10composition (methyl esters,
Page 478 and 479: PP-V-11reactor we can see that its
Page 480 and 481: PP-V-12Recent studies lead in this
Page 482 and 483: PP-V-13catalysts (e.g. Pt or Pd), t
Page 484 and 485: PP-V-14Alkali catalyst. For a basic
Page 486 and 487: PP-V-15obtaining the related profil
Page 488 and 489: PP-V-16reaction parameters, not rep
Page 490 and 491: PP-V-18STUDY OF THE CATALYTIC ACTIV
Page 492 and 493: PP-V-19BIOMORPHIC CATALYSTS ON THE
Page 494 and 495: PP-V-20Al,Cu-PILLARED CLAYS AS CATA
Page 498 and 499: PP-V-22THE NEW METHOD OF OBTAINING
Page 500 and 501: PP-V-23containing mono- and di-subs
Page 502 and 503: AUTOCLAVE ENGINEERS COMPANYSYSTEMAT
Page 504 and 505: CATACON CATACON CATACON CATACON CAT
Page 510 and 511: George AvgouropoulosFoundation for
Page 512 and 513: Leonid BykovJSC «Chemphyst-Alloy L
Page 514 and 515: Debora FinoPolitecnico di TorinoCor
Page 516 and 517: Jenő HancsókUniversity of Pannoni
Page 518 and 519: Andrey KhudoshinLomonosov Moscow St
Page 520 and 521: Cristian LedesmaEnergetic Technique
Page 522 and 523: Uri Matatov-MeytalDepartment of Che
Page 524 and 525: Karina OjedaIndustrial University o
Page 526 and 527: Yuri PyatnitskyPisarzhevsky Institu
Page 528 and 529: Vera ScmachkovaBoreskov Institute o
Page 530 and 531: Peter StrizhakPisarzhevsky Institut
Page 532 and 533: Nadezhda VernikovskayaBoreskov Inst
Page 534 and 535: Nataliya ZubritskayaRSC «Applied C
Page 536 and 537: ORAL PRESENTATIONS.................
Page 538 and 539: OP-I-21Saeedizad M., Sahebdelfar S.
Page 540 and 541: OP-III-9Nekhamkina O., Sheintuch M.
Page 542 and 543: OP-IV-5Hernández L., Kafarov V.V.M
Page 544 and 545: OP-V-13Sadykov V., Mezentseva N., V
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PP-I-15PP-I-16PP-I-17PP-I-18PP-I-19
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PP-II-9 Nikiforov A., Paek U-Hyon,
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PP-III-17 Vernikovskaya N.V., Kashk
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PP-III-42 Goshu Y.W., Tsaryov Y.V.,
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PP-IV-17 Ohnishi C.H., Yoshino H.,
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PP-V-9 Hancsók J., Magyar S., Kall
Page 558:
XVIII International Conference on C
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