Anda di halaman 1dari 5

Available online at www.sciencedirect.

com

Catalysis Communications 9 (2008) 18331837 www.elsevier.com/locate/catcom

Selective oxidation of methylal as a new catalytic route to concentrated formaldehyde: Reaction kinetic prole in gradientless ow reactor
J. ojewska a,*, J. Wasilewski b, K. Terelak b, T. ojewski a, A. Koodziej c
a w, Poland Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krako w, 47-225 Ke Institute of Heave Organic Synthesis Blachownia, Energetyko dzierzyn-Koz le, Poland c Institute of Chemical Engineering of the Polish Academy of Sciences, Batycka 5, 44-100 Gliwice, Poland b

Received 26 October 2007; received in revised form 13 February 2008; accepted 14 February 2008 Available online 23 February 2008

Abstract Catalytic selective oxidation of methylal (dimethoxy methane, DMM) was regarded as a new alternative for the production of highly concentrated formaldehyde. The aim of this work was to study the reaction kinetics in order to nd optimum reaction conditions. The reaction was tested on ironmolybdenum mixed oxide catalysts in gradientless stirred jet reactor operating at atmospheric pressure. The activity and selectivity of the catalyst prepared in our laboratory has proved similar to the industrial catalyst. It has been demonstrated that the highest selectivity towards formaldehyde 90% is achieved at a fairly narrow parameter window: temperature in the range 230260 C, at a contact time around 1 s, in the reaction mixture containing O2:N2:(CH3)2CH2O2:H2O = 0.08:0.76:0.11:0.05. 2008 Elsevier B.V. All rights reserved.
Keywords: Concentrated formalin; Formaldehyde; Methylal oxidation; Dimethoxy methane

1. Introduction Production of plastics, resins and adhesives usually requires highly concentrated formaldehyde. As we suggest in this work, it may be directly obtained by selective oxidation of methylal (dimethoxy methane, DMM). However, it should be noted that on industrial scale, formaldehyde is produced in catalytic selective oxidation of methanol: 1 CH3 OH O2 HCHO H2 O 2 which gives concentrations in water solutions not higher than 55%. Further increase in concentration can be achieved by distillation (physical or reactive), ruled by the subtle equilibrium in watermethanolformaldehyde systems [1]. In comparison with methanol oxidation, selective oxidation of methylal:
*

Corresponding author. Tel.: +48 1266322445. E-mail address: lojewska@chemia.uj.edu.pl (J. ojewska).

CH3 CH2 O2 2O2 3HCHO H2 O oers much better substrate/product ratio than oxidation of methanol as can be inferred from the simple stoichiometry. In this way energy consuming distillation step can be omitted. Till now, hardly any information can be found in the literature on selective oxidation of DMM. Partly because the idea may seem ridiculous at rst sight, because methylal is produced through condensation of methanol and formaldehyde [2,3]. The exceptions are the numerous patents, especially Japanese and Chinese, concerning the technology of this reaction [4]. Apparently, economic aspects and the energy balance are in favour of methylal oxidation. Some information on the reaction mechanism can be inferred from a study of Masamoto et al. [5] a recent study Daly et al. [6] dealing, however, with methylal combustion and giving the references of the work from seventies discussing the mechanism of methylal oxidation. Thus, the results on catalytic test of methylal selective oxidation presented in this work seem rather pioneer. In

1566-7367/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.catcom.2008.02.014

1834

J. ojewska et al. / Catalysis Communications 9 (2008) 18331837

this paper, we have focused most of all on nding the reaction prole at various conditions using FeMo (FeMo _ le) CoBi) catalyst (ICSO Blachownia, Kedzierzyn-Koz and the commercial FeMo catalyst. 2. Experimental 2.1. Materials The catalyst used for the study was mixed oxide catalyst of an empirical formulae: Mo12Fe3Co4,5Bi1P0,5K0,07Ox (assigned as FeMo). The catalyst was obtained by coprecipitation in the water suspension of SiO2 (Arsil, Rudniki) at temperature 95 C. After drying and forming (pellets 5 5 mm), the catalyst was calcined at 600 C. The nal concentration of catalyst on the SiO2 support was 70% [7]. As a reference catalyst FeMo commercial catalyst supported on Rashig rings (OD = 5 mm) was used (assigned as ind-FeMo). 2.2. Apparatus and procedures The reaction kinetics was studied in a gradientless internal recycle reactor (MicroBerty, Autoclave Engineers) equipped with a gas/vapour supplying system and analyzing system. The ow of gases (air, nitrogen) was controlled with thermocouple owmeters (Brooks). The vapours (methylal, water) were fed from saturators thermostated at a desired temperature. For reactants separation and analysis GC (SRI) with packed column (Hyesep) and FID and TCD detectors was used. The reaction was carried out under atmospheric pressure in a gas mixture containing air, methylal, water vapour and nitrogen/helium as dilutants, in a fairly broad range of parameters: in temperature range 100500 C at various space-time values between 0.2 and 2 s and reactant concentrations. Calibration of vapours ows was performed by determination of the loss of mass of liquids at a given ow of a carrier gas washing the saturator. The reaction conditions are given in Table 1. The catalytic tests examining the inuence of reactants concentration were performed under constant total ow of reaction mixture. While the ow of one of the reactants was varied the ow of the carrier gas (He or N2) was adjusted to balance the total ow. In such a way, the molar fractions of other components were kept constant.

The relative rate of formaldehyde formation, rHCHO, was dened as follows and referred to the catalyst volume, V cat , cm3: rHCHO 1 dcHCHO V cat dt nmol s1 cm3

where cHCHO is the formaldehyde concentration in the outgoing reactants stream, nmol and t is the reaction time, s. The rate of formaldehyde formation, rHCHO, was calculated for the approximation of a gradientless reactor using chromatographic data from the following expression: rHCHO f S HCHO X F tot V cat RT p nmol s1 cm3

where f unit transfer factor is equal to 0.016, SHCHO is selectivity towards formaldehyde, X DMM conversion, Ftot total ow, cm3/s, p pressure, Pa, T temperature, K, R gas constant, J/mol K. 3. Results and discussion The yield towards formaldehyde and product distribution depends on various parameters such as temperature, contact time, reaction mixture composition, and in particular water vapour partial pressure. A typical temperature prole of selective oxidation of methylal obtained for FeMo and ind-FeMo catalysts is shown in Fig. 1A and B. The conversion of methylal, adjusted to around 40%, is almost constant or slightly increases with temperature. In the range 120260 C formaldehyde yield signicantly increases upon increasing temperature whereas methanol yield decreases. Above 260 C this tendency collapses. Most evidently, at lower temperature (<180 C), methylal decomposition to formaldehyde and methanol, and to a much lesser degree, to formaldehyde and dimethyl ether, is favoured (results of chromatographic analyses), while at higher temperature (>300 C) the number of possible recombinations grows, giving methane, carbon oxides, formic acid and other unrecognized products, except formaldehyde and methanol. An optimal formaldehyde yield (conversion multiplied by selectivity, X S) is achieved at temperature around 230 C. This corresponds to 90% selectivity towards formaldehyde. The results suggest that below 260 C the mechanism of methylal selective oxidation runs through methylal decomposi-

Table 1 Reaction conditions used for various catalytic tests during oxidation of DMM Test type Catalyst Temperature (C) Contact time (s) Molar fraction O2 Temperature dependence Temperature dependence Contact time dependence xO2 inuence xDMM inuence x H2O inuence FeMo ind-FeMo FeMo FeMo FeMo FeMo Varied Varied 230 230 230 230 1.82 1.82 Varied 1.21 1.21 1.21 0.08 0.08 0.08 Varied 0.08 0.08 DMM 0.11 0.11 0.11 0.11 Varied 0.11 H2O 0.05 0.05 0.05 0.05 0.05 Varied He + N2 0.76 0.76 0.76 Varied Varied Varied Figs. 1A and 2 Figs. 1B and 2 Fig. 3 Fig. 4A Fig. 4B Fig. 5 Figure number

J. ojewska et al. / Catalysis Communications 9 (2008) 18331837

1835

Fig. 2. Arrhenius plots derived from Fig. 1.

Fig. 1. Temperature dependence of the methylal conversion (X METH) and selectivity towards formaldehyde and methanol (S) during methylal selective oxidation (see Table 1 for conditions). (A) FeMo catalyst, (B) ind-FeMo catalyst.

Fig. 3. Dependence of the methylal conversion (X DMM) and selectivity towards formaldehyde (S) on contact time (conditions in Table 1).

tion to methanol and formaldehyde, the rst of which undergoing consecutive oxidation to formaldehyde. Fitting Arrhenius equation is not fully justied for the results presented above because the conversion was too high to make assumption of constant concentration of reactants in the rate law. The parameters derived from the equation are thus apparent and should be treated more comparatively. Overall, the apparent activation energy derived in the temperature range from 160 to 230 C (Fig. 2) is slightly lower for the FeMo catalyst (62 kJ/ mol) than for the ind-FeMo catalyst (64 kJ/mol). The inuence of contact time on the conversion and selectivity towards formaldehyde is presented in Fig. 3. The contact time is dened here as a ratio between catalyst volume and total ow. According to the results the optimum yield is achieved at contact time around 1 s and then decreases with its prolonging.

As regards the composition eect of methylal concentration on the products formation the general trend is that both conversion and formaldehyde selectivity declines while methanol selectivity grows for both catalyst used. The results obtained for FeMo are shown as an example in Fig. 4A. This supports the hypothesis of the reaction mechanism presented above. In light of the observed trends, methylal competes with oxygen for the active centres on the catalyst surface. If concentration of methylal is too high, decomposition to methanol and formaldehyde prevails and selective oxidation is much inhabited due to low concentration of oxygen on the surface. From this standpoint, Marsvan-Krevelen mechanism of oxidation, considered usually for selective oxidation [8], in which oxygen included in metal oxide lattice provides oxygen for the reaction, does not seem to be a prevailing reaction route for the methylal oxidation. Thus also, possible mechanism should be more of LangmuirHinshelwood type rather

1836

J. ojewska et al. / Catalysis Communications 9 (2008) 18331837

Fig. 5. The inuence of water vapour molar fraction on the methylal conversion (X DMM) and selectivity towards formaldehyde and methanol (S) during methylal selective oxidation (conditions in Table 1).

concentration can be accounted for by the same competitive eect for active centres. 4. Conclusions Surprisingly enough methylal selective oxidation has proved to be a promising route towards formaldehyde of high concentration which is secured by the advantageous reaction stoichiometry (HCHO:H2O = 3). According to catalytic test performed in the stirred-jet reactor on Fe Mo oxide catalysts, the reaction runs through decomposition of methylal towards formaldehyde and methanol (also dimethyl ether) being further oxidized to formaldehyde. The decomposition is a dominating reaction path at temperatures below 230 C. At a narrow parameter window: 230260 C, contact time around 1 s, and reaction mixture containing O2:N2:(CH3)2CH2O2:H2O = 0.08:0.76:0.11:0.05 the highest selectivity towards formaldehyde (90%) was observed. The FeMo catalyst prepared in our laboratory has been shown to have comparable activity and selectivity to the industrial one. Acknowledgements The study was supported by Polish State Committee for Scientic Research which funded the Project 3T09B01927. The nancial support is gratefully acknowledged. References
[1] K. Terelak, S. Trybula, M. Majchrzak, M. Ott, H. Hasse, Pilot plant formaldehyde distillation: experiments and modeling, Chemical Engineering and Processing 44 (2005) 671676. [2] Youzhu Yuan, Haichao Liu, Hideo Imoto, Takafumi Shido, Yasuhiro Iwasawa, Performance and characterization of a new crystalline SbRe2O6 catalyst for selective oxidation of methanol to methylal, Journal of Catalysis 195 (2000) 5161.

Fig. 4. The inuence of reactants mixture composition on the methylal conversion (X DMM) and selectivity towards formaldehyde and methanol (S) during methylal selective oxidation (conditions in Table 1) (A) dependence of methylal molar fraction (xDMM), (B) oxygen molar fraction xO2 .

than of RidealEley. The trend with oxygen molar fraction is slightly dierent but consistent with previous observations and also supports postulated mechanism. Upon increase in oxygen concentration (Fig. 4B), methylal conversion decreases slightly and formaldehyde selectivity goes through maximum at around 0.09 O2 molar fraction, unlike methanol selectivity which shows a minimum at the same point. These ndings were used to optimise the reaction conditions. It has been found that formaldehyde selectivity is also aected by the presence of water vapour in the reaction mixture. Indeed, water is a necessary substrate for the decomposition of methylal towards methanol and formaldehyde. Maximum selectivity of formaldehyde was observed at water vapour molar fractions around 0.04 as shown in Fig. 5. The decrease in the conversion upon water

J. ojewska et al. / Catalysis Communications 9 (2008) 18331837 [3] Corey R. Anthony, Lisa McElwee-White, Selective electrochemical oxidation of methanol to dimethoxymethane using Ru/Sn catalysts, Journal of Molecular Catalysis A: Chemical 227 (2005) 113117. [4] Examples Japanese patens: Pat no. JP 60 251 932 (1985), JP 63 201 142 (1988), JP 63 188 640 (1988), JP 05 09 145 (1991), in Chinese journal Nanjing Huagong Xueyuan Xuebao, 16 (1994) 1115, 15 (1993) 1319, 17 (1995) 1824 10 (1996) 287293 23 (1997) 170175. [5] J. Masamoto, T. Iwaisako, M. Chohno, M. Kawamura, J. Ohtake, K. Matsuzaki, Development of a new advanced process for manufactur-

1837

ing polyacetal resins. Part I. Development of a new process for manufacturing highly concentrated aqueous formaldehyde solution by methylal oxidation, Journal of Applied Polymer Science 50 (1993) 12991305. [6] C.A. Daly, J.M. Simmie, P. Dagaut, M. Cathonnet, Oxidation of dimethoxymethane in a jet-stirred reactor, Combustion and Flame 125 (2001) 11061117. [7] Pat no. PL 116 086 (1983), PL 122 963 (1984). [8] G. Ertl, H. Kno zinger, J. Weitkamp (Eds.), Handbook of Heterogeneous Catalysis, Wiley-VCH, 1997, p. 2307.

Anda mungkin juga menyukai