Ind. Eng. Chem. Prod. Res. Dev. 1981, 20, 719-721
conceptual schemes indicate that it may be possible to get surplus gas suitable for use in industrial heating. In a similar way, cracking over semicoke and charcoal gives more gas of similar quality. In these cases, however, 14.08 kg of semicoke and 9.6 kg of charcoal, respectively, are to be used for every 100 kg of sawdust carbonized. Conclusions Experiments on carbonization of sawdust showed that charcoal suitable for smokeless domestic fuel can be obtained at 538 OC. Cracking of the vapor and gaseous products of carbonization over firebrick, semicoke, and charcoal showed that the yield and calorific value of the gas can be increased. When semicoke or charcoal is used as packing material, tar and pyroligneous liquor are completely decomposed and the yield and calorific value of the gaseous products obtained are higher than those obtained by cracking over firebrick. Some carbon in semicoke and charcoal was used up. Acknowledgment The authors wish to express their thanks to the Director, Regional Research Laboratory, Hyderabad, for permission to publish the paper.
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Literature Cited Campbell, J. R. “Methods of Analysis of Fuels and Oils”, Constable and Com pany Ltd.: London, 1951. Framer, R. H. ”Chemistry in the Utilization of Wood”, Pergamon Press: Oxford, 1967. Haeaaiund, E. “Holzchemie”, Akadamlsche Veriaa Geselschaft, M.b.H.: L a i6sg, 1944. Hassler, W. J. “Active Carbon”. Chemical Publishing Co.: Brooklyn, NY, 1951.
Hesp,-W. R.; Waters, P. L. Ind. Eng. Chem. Prod. Res. Dev. 1970, 9 , 195. Himus, G. W. ”Fuel Testing”, Leonard Hili Ltd.: London, 1954. Kiar, M. “The Technology of Wood Distillation”, Chapmann and Hall Ltd.: London, 1925. Kollman, F. “Technoiogle des Hoizes”, Verlag Julius Springer: Berlin. 1936. Kroeger, C. ”Grundrls der technische Chemie”, Part IV, Vanden Hoeck and Ruprecht: Gottingen, 1952. Methods of Test for Coal and Coke, I.S.1350;Indian Standards Institution, New Delhi, 1965. Plret de Bihaln, A.; Padakl, P. B. Chem. Age Indk, 1978, 29, 951. Processed Solid Smokeless Domestic Fuel, I.S. 4286,Indian Standards Institution, New Delhi, 1967. Sadakichl, K. 11th Biennial Conference of the Institute for Brlquetting and Agglomeration Proceedings, Aug 27-29, 1969. Stamm, A.; Harris, E. E. “Chemical Processing of Wood”, Chemical Publishing Co. Inc., 1954. Van Chzhao-Syum; Makavan, G. N. Coke-Si-Chimia, Apr 14, 1960. Wlnnacker, K.; Welngartner, E. “Chemlsche Technologie”, Organlsche Technoiogle, Carl Hamsa Verlag: Munich, 1952.
Receiued for review October 14, 1980 Accepted February 23,1981
Selective Conversion of D-Fructose to 5-Hydroxymethyl-2-furancarboxaldehyde Using a W at er-Solvent-Ion-Exchange Resin Triphasic System Luc Rigal, Antoine Gaset, and Jean-Pierre Gorrichon’ Laborafolre de Chimie Organlque et d‘Agrochimle, €cole Nationale Sup6rleure de Chimie, 118, route de Narbonne 31007 Toulouse Cedex, France
The propounded way of synthesis allows the dehydration of pfructose into 5-hydroxymethyl-2-furancarboxaklehyde (HMF). It implies the use of an ion-exchange resin as catalyst together with an extracting solvent. This system gives satisfactory yields when a macroporous strong acidic resin is used. Therefore, the development of such a system on a larger scale, in a dynamic state, could be considered.
Among biomass resources, carbohydrates are a plant raw material that is liable to be used for various chemical syntheses. 5-Hydroxymethyl-2-furancarboxaldehyde,2, a degradation product of hexoses in acidic media, is commonly occurring at low concentrations in various foods and could be an interesting starting material for the chemical industry. The search for new ways of synthesis of 2 is therefore of major interest, owing to the possible economical value of new processes (Nakamura, 1980;Nakamura and Morikawa, 1979). Previous work generally involved the use of an acid as a catalyst dissolved in the reaction medium. Drastic experimental conditions [temperature above 150 “C,high pressure (Kuster and Van der Steen, 1977;Kuster and Laurens, 1977;Morikawa, 1978; Garber and Jones, 1966)] are required so as to obtain satisfactory yields. The main difficulty lies in the control of the selectivity of the reaction leading to 2. The data reported here concern the dehydration reaction of D-fructose 1 (Scheme I). The procedure considered involves H+ ion-exchange resins as catalysts, together with a water-solvent biphasic 0196-4321/81/1220-0719$01.25/0
Scheme I. Dehydration Reaction of D-Fructose !H,OH
.
ti -C - O H
-
/‘
I
CH,OH
Byproducts
1
H C O O H + C H 3 C 0 CH,CH,COOH 4
-
3
liquid reaction medium: 2 is thus extracted as soon as it is formed; its possible breakdown to byproducts, particularly levulinic acid 3 and formic acid 4, within the aqueous phase, is thus kept to a minimum. The reaction selectivity is markedly improved by the presence of an organic solvent in the reaction medium, as shown by a comparison with the data of Schraufnagel and Rase (1975),who had investigated this reaction in aqueous media, favoring thus the formation of 3. Methyl isobutyl ketone is the extraction solvent; the water-solvent ratio is 1:9 (v/v). The 0 1981 American Chemical Society
720
Ind. Eng. Chem. Prod. Res. Dev., Vol. 20, No. 4, 1981
Table I. Catalytic Effect of the Ion-Exchange Resins on the Synthesis of 5-Hydroxymethyl-2-furancarboxaldehyde2 ion-exchange resin
reaction temp, "C
reaction time, h
88 88 88 88 88 88 88 88 88 88 88 84 84 84 84 88 88 88 88 88
4 4 4 4 4 4 5 3 5 15 24 3 5 15 24 5 15 24 4 15
Ra
2 c conv rates, %
0.61 0.61 0.61 0.61 0.61 0.61 0.61 0.61 0.61 0.61 0.61 0.61 0.61 0.61 0.61 0.125 0.125 0.125b 0.61 0.61
34 35 25 13 14
2*
yield, %
3 c conv rates, %
47 58 54 42 30 38 49 61 63 66 51 50 55 66 62 32 49 53 51 50
11
19 22 28 56 46 11
16
36 45 25 49 47 24 46
1 0 0 0 0 0 0 0 0 17 28 0 6 7 16 0 11 13 0 6
Owing to a R is the ratio of the number of H+ mequiv of the resin to the number of D-fructose millimoles introduced. the particle size and the exchange capacity of Spherosil S, the ratio R used for the other ion-exchange resins could not be Conversion rate is the ratio of the number of moles of obtained product to the taken into account in the present case, Yield is the ratio of the number of moles of produced HMF to the number number of moles of introduced D-fructose. of moles of consumated D-fructose. Table 11. Main Physical Properties of Ion-Exchange Resins
designation A
B C
D
E F G
H I
trade name (manufacturers) Lewatit SC 102 (Bayer) Amberlite IR 118 (Rohm and Haas) Duolite C 26 (Diaprosim) Amberlite A200C (Rohm and Haas) Amberlyst A 15 (Rohm and Haas) Lewatitt SPC 118 (Bayer) Lewatitt SPC 108 (Bawl Spherosil S (Rh8ne-Poulenc) Nafion-501 H (Dupont de Nemours)
type
exchange capacity of dry int surresina H+ face area, mequiv g-' mz g-l
porosity, vol %
gel-like
4.3
7.5 (in water) b
gel-like
3
macroporous
2.9
40-80
30-50
macroporous
1.8
50
macroporous
4.1
macroporous
max av pore recomdiameter, mended a temp, "C 15
120
b
250
400
140
36
80
300
40-50
30-35
400
150
4.2
39-40
46-47
64 5
120
macro porous
4.2
18-23
23-25
44 5
120
macroporous on silica support on carbofluorinated support
0.4
25
40
1000
b
b
0.81
a Exchange capacities given here, have been measured in our laboratory. (Mercadier, 1980). facturer.
temperature of the reaction medium (88 O C ) is the boiling point of the water-methyl isobutyl ketone azeotrope. The initial concentration of 1 in water is 222 g/L (1.2 M). The amount of catalyst is determined from the ratio R of the number of H+ milliequivalents of the ion-exchange resin to the number of D-fructose millimoles introduced. The selection of the values of these parameters resulted from the previous investigations of Mercadier (1980). The experiments carried out in the presence of weakly acidic ion-exchange resins (CC3, IRC 50) did not lead to the formation of 2, whereas highly acidic ion-exchange resins enhanced the reaction. The data are listed in the Table I and the main characteristics of the ion-exchange resins used, in Table 11. The solvent-water-resin association is the main factor involved. The gel-like resins that were used led to satisfactory conversion rates and yields of 2, without inducing
b
b
N o t given by the manu-
the formation of 3. The use of Ndion-H, which possesses the properties of a super-acid, was characterized, in spite of suitable conversion rates, by a poor selectivity, mainly as a result of the formation of byproduck as well as of 3. In the case of Spherosil S, the reaction selectivity was impaired as the conversion rate increased. The macroporous ion-exchange resins were characterized by the highest rate of conversion to 2 as well as by the best reaction selectivity. In the presence of such catalysts, the reaction medium remained clean, free of any suspended product, and nearly devoid of 3 during the first 8 h of the reaction. The processing of such reaction media is obviously easy. The quality of the results obtained with macroporous resins as well as with gel-like resins underlines the effect of the diffusion of 1 within the resin, the availability of the catalytic sites of that reaction micromedium, and the efficiency of the extraction solvent.
Ind. Eng. Chem. Prod. Res. Dev. 1981, 20, 721-726
5-Hydroxymethyl-2-furancarboxaldehyde (2), is collected in the organic phase and is thus obtained readily under soft operating conditions. The development of such a reaction system on a larger scale can therefore be considered. The resin can be recycled as its capacity is maintained after the reaction (Flsche et al., 1979). Since the dehydration of D-fructose, which is in the aqueous phase, into HMF,takes place when a nonwater-miscible solvent is used, it can be underlined that this triphasic system compares favorably with a phase transfer catalysis promoted by cation-exchangers (Delmas and Gaset, 1981). 5-Hydroxymethyl-2-furancarboxaldehyde: General Procedure
a 250-mL reactor was fitted with a mechanical stirrer, a thermometer, and a reflux condenser. The suitable amount of resin (see Table I, ratio R), the solution of D-fructose (222 g/L; 10 mL), and the solvent (90 mL; water-solvent ratio, 1:9 v/v) were then introduced. The reaction mixture was kept at 88 "C for the time mentioned in the Table I. At the end of reaction, the reactor was cooled in an ice bath; the resin was filtered off and then washed with water and with the solvent. The determinations were carried out on the organic phase and on the aqueous phase; 2 was determined, after silylation,by GLC,
721
directly on the organic phase of the reaction medium, and after a further extraction of the aqueous phase. D-Fructose (l),which occurred only in the aqueous phase, was determined according to the method of Bertrand described by Ribereau-Gayon et al. 1972). Acknowledgment
The authors are grateful to Roquette Frgres and Co. for financial support and wish to thank more especially G. Flsche, M. Huchette, and P. Sicard for fruitful discussions. Literature Cited Delmas, M.; Gaset, A. TetrahedronLett. 1981, 22, 723. FIBche, G.; Gaset, A.; Gorrichon, J. P.; Sicard, P.; Truchot, E. f r . hmande, 1979, 79, 22251. Garber, J. D.; Jones, R. E. US. Patent 3483228, 1966. Kuster, B. F. M.; Van der Steen, H. J. C. Staerke 1977, 29, 99. Kuster, B. F. M.; Laurens, J. Staerke, 1977, 29, 172. Mercadier, D. Thesis No. 94, Touiouse, France, 1980. Morikawa, S. Nogushi Kenkyusho J i b , 1978, 21, 25. Nakamura, Y.; Morikawa, S. Jpn. Kokal Tokkyo Koho. 1979, 79, 154, 757. Nakamura, Y. Jpn. Kokai Tokkyo Koho, 1980, 80, 13, 243. Ribereau-Gayon, J.; Peynaud, E.; Sudreau, P; Ribereau-Gayon, P. "Sciences et Techniques du vin"; Dunod Ed.; Paris, 1972; Chapter 8, pp 299-304. Schraufnagel, R. A.; Rase, H. F. I&. Eng. Chem. prod. Res. h v . , 1975, 14. 40.
Received for review December 29,1980 Revised manuscript received April 20, 1981 Accepted May 26, 1981
Synthesis of Mordenite Type Zeolite Using Silica from Rice Husk Ash Pramod K. Bajpai and Musti S. Rao" Department of Chemical Engineering, Indian Institute of Technology, Kanpur-208016 (UP.), India
K. V. G. K. Gokhale Department of Civil Englneerlng, Indian Institute of Technology, Kanpur-208016 (UP.), India
Mordenite has been synthesized, using silica from rice husk ash for the first time, at temperatures ranging between 135 and 165 'C, using several compositions for the starting mixture and varied periods of time. The roles of different parameters such as the composition of the starting mixture, the temperature, and the duration of synthesis on the formation of sodium mordenite and its stability were investigated. The progress of the reaction under different conditions was tracked using the X-ray diffraction technique. The crystallization kinetics for mordenite formation also was studied. The results were compared to those obtained previously using a chemical source of silica.
Introduction
Mordenite, a high silica zeolite,is increasingly being used as a molecular sieve in the adsorptive separation of gasliquid mixtures involving acidic components. It also finds extensive application as a catalyst for various industrially important reactions such as hydrocracking, hydroisomerization, alkylation, reforming, and cracking (Breck, *Address correspondence to this author at the Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA 70803.
1974a; Kladnig, 1975). The unit cell dimensions of the sodium form of mordenite were determined by Meier (1961) as a = 18.13 A, b = 20.49 A, and c = 7.52 A. Its idealized chemical constitution is represented by (Naz0)4.(A1203)4.(Si02)40.24H20. Although mordenite occurs as a mineral, synthetic mordenites, owing to their chemical purity, are better suited to meet the stringent requirements imposed on molecular sieve adsorbents in adsorption and catalytic processes. Of the currently available commercial molecular sieve adsorbents, mordenite molecular sieves, being high in their silica/alumina ratio, are preferred for use in which acidic components are involved. 0 1981 American Chemical Society
