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PP-IV-20FORMALDEHYDE FORMATION DURING NON-OXIDATIVEDEHYDROGENATION OF METHANOLV.F. Tretyakov, A.M. Ilolov, R.M. Talyshinskiy, T.N. Burdeynaya, A.S. LermontovA.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Leninsky pr. 29E-mail: tretjakov@ips.ac.ruFormaldehyde is one of important chemicals with annual production of 27 million tonnes,which are used for the synthesis of polymers, resins, paints and explosives. Currently, the mostwidely used technology for formaldehyde production is the partial oxidation of methanol (1):2 CH 3 OH + O 2 2 CH 2 =O + 2 H 2 O (1)The main drawback of this technology is water produced during synthesis leading to formalinproduction instead of pure formaldehyde. Production of pure formaldehyde from formalinneeds a complicated distillation procedure which increases its overall cost. The side reactionsleading to formic acid are also not favorable from process organization and equipment.Non-oxidative methanol dehydrogenation (2) gives a mixture of formaldehyde andhydrogen which is easy separable. Moreover, this method also produces hydrogen – clean fuelCH 3 OH CH 2 =O + H 2 (2)of XXI century, which could be used for heating the rector for formaldehyde productionpreventing toxic exhausts.The catalyst based on modified silica (K-1) was developed for this process and tested atvarious conditions for methanol dehydrogenation. The results are presented in Table 1.Table 1. Experimental data for formaldehyde production on K-1 catalyst at different reactionconditionsCatalystsCH Yield, %WHSV,CHh –1 T, C volume, N 2 , l/min 3 OH,3 OHCH 2 =Oconversion,selecti-vity,cm 3ml/minCH%2 O CO CH 4%0,141 900 0,326 0,35 85,4 1,8 83,6 ~ 2,130,315 7500,326 0,335 23,5 4,16 19,34 ~ 17,71,19 900 1,4 2,8 +5%H 2 O 45,4 12,6 32,8 ~ 27,72,02 900 0,7 2,8 50,5 21,3 29,2 ~ 42,3201,59 900 0,7 2,8 48,0 16,8 31,2 ~ 35,02,12 9001,4 5,6 40,6 11,2 25,9 3,5 27,7Thermodynamic calculation shows that the desired reaction (2) starts only from 500 °C,but the typical catalysts (sodium-containing solids) performance starts near 900 °C. Thecurrent opinion is that active centers of catalysts for non-oxidative methanol to formaldehydeconversion are sodium atoms evaporated from the surface of catalysts. Gaseous state of activeparticles and gas-phase catalysis leads to extremely high sensitivity of the reaction to large432
PP-IV-20amount of parameters: WHSV, catalysts loading and sodium content, impurities, dilution gas,temperature profile of reactor and even its form.Using continuous-flow fixed-bed reactor we have achieved conversion value 50% withformaldehyde selectivity near 42 % on catalyst K-1 at 900 °C. Further efforts for improvingconversion parameters are in progress and mainly connected with the form of reactor andcatalysts loading to prevent further dehydrogenation of formaldehyde with CO formation.433
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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
Page 382 and 383: PP-III-41MODELLING AND DESIGN OF TH
Page 384 and 385: PP-III-42COMPLEX TECHNOLOGY OF TREA
Page 386 and 387: PP-III-43PHOTO ELECTROCHEMISTRY APP
Page 388 and 389: PP-III-45MODELING OF CATALYTIC α-O
Page 390 and 391: PP-III-46steady states. It was show
Page 392 and 393: PP-III-47Results and discussion:The
Page 394 and 395: PP-III-49FIBROUS PALLADIUM-SUPPORTE
Page 396 and 397: Section 4.Catalytic technologies in
Page 398 and 399: PP-IV-1method is adiabatic or autot
Page 400 and 401: PP-IV-2It had been established that
Page 402 and 403: PP-IV-4INTERACTION OF ACTIVATED ALU
Page 404 and 405: PP-IV-5ENVIRONMENTALLY FRIENDLY PRO
Page 406 and 407: PP-IV-6THE 5%Ni-2%Au/Al 3 CrO 6 SYS
Page 408 and 409: PP-IV-7MESOPOROUS ANODES BASED ON Y
Page 410 and 411: PP-IV-8ADVANCED OXIDATION PROCESS F
Page 412 and 413: PP-IV-9PROCESSING OF POLYMERIC CORD
Page 414 and 415: PP-IV-10EFFECT OF SULPHUR ON THE CA
Page 416 and 417: PP-IV-11OXIDATIVE CONVERSION OF MET
Page 418 and 419: PP-IV-13CATALYTIC FLUE GAS CONDITIO
Page 420 and 421: PP-IV-14RIBBON POROUS NICKEL BASED
Page 422 and 423: PP-IV-15ETHANOL CONVERSION TO HYDRO
Page 424 and 425: PP-IV-16A HIGH-EFFICIENT MICROREACT
Page 426 and 427: PP-IV-17DIRECT DECOMPOSITION OF NIT
Page 428 and 429: PP-IV-18NICKEL CATALYSTS BASED ON P
Page 430 and 431: PP-IV-19SELECTION OF FAVOURABLE FEE
Page 434 and 435: PP-IV-21PRODUCTION OF HYDROGEN-RICH
Page 436 and 437: PP-IV-22INFLUENCE OF COMPOSITION OF
Page 438 and 439: PP-IV-24ONE-STAGE CATALYTIC CONVERS
Page 440 and 441: PP-IV-25THE STUDY OF METHANE DEHYDR
Page 442 and 443: PP-IV-26MCM-41-SUPPORTED PdNi CATAL
Page 444 and 445: 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
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PP-V-13catalysts (e.g. Pt or Pd), t
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PP-V-14Alkali catalyst. For a basic
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PP-V-15obtaining the related profil
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PP-V-16reaction parameters, not rep
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PP-V-18STUDY OF THE CATALYTIC ACTIV
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PP-V-19BIOMORPHIC CATALYSTS ON THE
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PP-V-20Al,Cu-PILLARED CLAYS AS CATA
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PP-V-21KINETICS OF THE HYDROXYMATAI
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PP-V-22THE NEW METHOD OF OBTAINING
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PP-V-23containing mono- and di-subs
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AUTOCLAVE ENGINEERS COMPANYSYSTEMAT
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CATACON CATACON CATACON CATACON CAT
Page 506 and 507:
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George AvgouropoulosFoundation for
Page 512 and 513:
Leonid BykovJSC «Chemphyst-Alloy L
Page 514 and 515:
Debora FinoPolitecnico di TorinoCor
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Jenő HancsókUniversity of Pannoni
Page 518 and 519:
Andrey KhudoshinLomonosov Moscow St
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Cristian LedesmaEnergetic Technique
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Uri Matatov-MeytalDepartment of Che
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Karina OjedaIndustrial University o
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Yuri PyatnitskyPisarzhevsky Institu
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Vera ScmachkovaBoreskov Institute o
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Peter StrizhakPisarzhevsky Institut
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Nadezhda VernikovskayaBoreskov Inst
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Nataliya ZubritskayaRSC «Applied C
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ORAL PRESENTATIONS.................
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OP-I-21Saeedizad M., Sahebdelfar S.
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OP-III-9Nekhamkina O., Sheintuch M.
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OP-IV-5Hernández L., Kafarov V.V.M
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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
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XVIII International Conference on C
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