Brazilian Journal of Chemical Engineeri…

Brazilian Journal of Chemical Engineering
Print version ISSN 0104-6632

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Braz. J. Chem. Eng. vol. 14 no. 1 São Paulo Mar. 1997
doi: 10.1590/S0104-66321997000100002


L.A.B. CORTEZ1 and L.E. BROSSARD PÉREZ2 1Faculty of Agricultural Engineering - State University of Campinas - CEP 13081-970 - Campinas, SP - Brazil E-mail: cortez@agr.unicamp.br - Phone: 019 2397101 - Fax: 019 2394717 2Faculty of Chemical Engineering - Oriente University, Santiago de Cuba, Cuba

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(Received: July 1, 1996; Accepted:January 4, 1997)

Abstract - Vinasse, a residual substance left after sugarcane alcohol distillation, represents a major environmental problem for the ethanol industry. No one has found a convenient and economical disposal solution for this black-reddish (Vinasse presents a light brown color and a low total solids content, from 2-4%, when it is obtained from straight sugarcane juice and a black-reddish color and total solids ranging from 5-10% when it is obtained from sugarcane molasses, which is the case of the vinasse used in this study.), viscous, high B.O.D. and acid material which is produced in quantities up to 15 times larger than those of the alcohol itself. This research investigated and developed the basic technology of on-site disposal of vinasse by combustion. Besides the clean ecological benefit, this method promotes energy savings and extra benefits when rich potassium vinasse ash is commercialized. Basic research was conducted using the facilities in the Combustion Laboratory (Mechanical Engineering Dept. at the Louisiana State University Campus in Baton Rouge). This research on vinasse combustion consisted of determining heating values, composition, and flame characteristics through combustion tests. Initially only vinasse was used in different solid concentrations and later emulsions were prepared using vinasse and # 6 fuel oil. Keywords: Vinasse disposal, combustion, fuel oil emulsions.

INTRODUCTION The disposal of vinasse, the major effluent from the ethanol industry, represents a major environmental problem. This black liquid that is produced at a rate 10 to 15 times greater than the ethanol itself is a mixture of water and organic and inorganic compounds. These compounds remain after different steps involving the sugar cane production and processing. These hazardous substances cause the vinasse to have a very high B.O.D. (Biological Oxygen Demand), ranging from 30-40,000 and presenting a pH of 4-5 (Polack et al., 1981). Research has demonstrated that vinasse disposal in river basins alone isnt a convenient disposal solution. Due to its high B.O.D., this material can cause damage to aquatic life, especially when dumped in large volumes. In Brazil, most of the vinasse that results from ethanol production is being used as fertilizer due to its high potassium content (Glória, 1975). The problem occurs when some soils don't respond positively to the application of this acid material. The disposal problem is aggravated by an economic drawback, because water must be evaporated



Because Polack had not been successful in the combustion of vinasse.br/scielo. and by-products. lack of information prevents this technology from being applied to solve the stillage problem. The Swedish Alpha-Laval (Nilsson. the flue gas was used as the heat source and the ash as a fertilizer. India by Chakrabarty (1964) in the distillery of the Dyer Meaking Breweries Ltd. reported (H. Yamauchi and collaborators in 1977 also conducted experiments on the combustion of vinasse at a 21% solids concentration with heavy oil. 1979) and # 6 fuel oil with an average heating value of 43.S. (1968) was perhaps the first to conduct experiments using a fluidized bed combustion unit. (1981) showed that Louisiana's vinasse is a very difficult effluent to be disposed via incineration. reporting no flame and no sustainable combustion. the present research was initiated using vinasse-oil fuel emulsions as a possible alternative fuel.A. Table 3 presents a comparison between vinasse.3/12/2010 Brazilian Journal of Chemical Engineeri… for easy transportation at low costs. Both reports mention the use of "swirl" combustion technology to burn 60% solids vinasse. The heating values of vinasse-oil fuel emulsions are given by equation 1.php?pid=S… 2/9 . Polack et al. Some other applications.390 kJ/kg) dry basis for vinasse only and http://www. Two incineration plants were installed in Brazil in the state of Pernambuco around 50 years ago but both were closed after a short time for economic reasons (D'Andrada cited in Monteiro. due to the absence of information about vinasse. According to Kujala et al. none of the above mentioned papers report detailed technical information regarding the combustion of vinasse itself. when the Porion Furnace was developed by Whitaker and U.G.). 1993). The results verify what was reported by Polack et al. Table 1 presents vinasse composition evaluated in different countries and sources. a series of combustion tests demonstrated that vinasse mixed with # 6 fuel oil would be an appropriate way to dispose of the waste material by combustion. such as alcohol.4 MPa). The furnace firebox was maintained at from 760 to 927 C by firing with natural gas and the pre-heated (50 C) vinasse was atomized in concentrations varying from 63. and determinations of composition encouraged the investigation of its potential to sustain combustion. It can be noted that the results vary considerably.4 kgf/cm2 (1. Preliminary evaluations of heating values.V. Industrial Chemicals Inc.350 kJ/kg (ASHRAE Fundamentals Handbook. when a pilot plant was built for the recovery of potassium salts from molasses alcohol stillage (M. These property differences are caused by sugarcane production and the industrial processing of the ethanol itself. 1979) of 6. However. According to Sheehan and Greenfield (1980). The same principle was used in Lucknow. Gupta et al. a good correlation was obtained with the previously reported heating values (Kujala. which was developed using 45 BRIX molasses vinasse with a heating value of 7. BASIC COMBUSTION STUDIES Initially. a significant amount of laboratory work had to be conducted to determine Sherpherd Oil Distillery's molasses vinasse composition. (1981). economic.C. followed by subsequent combustion (343 C) using the resulting carbon to produce potash and ash char.187 BTU/lb (14. Finally. Also. Reich (1945) proposed a concentration of vinasse in a quadruple effect evaporator up to 70-80% solids. This paper investigates the technical feasibility of on-site vinasse disposal via combustion. the concept of vinasse evaporation followed by combustion dates back to World War I. Although most of the existing literature reports success when incineration is used as a disposal method. In addition. a Dutch company named Hollandse Constructive Group B. sugarcane bagasse.800 kJ/kg (Kujala. 1975). Spruytenburg. 1981) also reports the technical.scielo. 1980. have been investigated but the economics associated with technical problems acts as a limiting factor. and research conducted did not lead to any technical development in this area. More recently. Table 2 presents the vinasse composition in the perspective of its use as a fuel (as received and dry basis). These values indicate that vinasse has a substantial potential application as a boiler fuel.. and commercial feasibility of burning vinasse. A BRIEF HISTORY OF VINASSE COMBUSTION The combustion of vinasse has been investigated by several researchers. such as bagasse and vinasse. 1982) the complete combustion of vinasse with a concentration up to 60% solids in its specially designed steam generator. (1976). Here.9 to 73 BRIX. and coal as far as ultimate analysis is concerned and Table 4 shows some typical heating values for sugarcane products. A similar scheme was described by Dubey (1974) who used a dual fuel furnace (vinasse at 60% solids and bagasse). The vinasse was prepared at 3040 BRIX and then spray dried and combusted at 700 C. because vinasse composition can be affected by several parameters. like methane gas production by anaerobic fermentation. who achieved varying results. Particular attention should be given to the material's proximate analysis which gives the percent of volatile matter and fixed carbon used as fuel. even after experimenting different alternatives such as the use of pre-heated air and different air/fuel ratios. The authors used a modified bagasse furnace previously developed by Harper (1980) which was adapted and equipped with an air atomizing burner (Eclipse Convecto-Flame oil burner Model 168 HCF-CGO) and fed at pressures of 51 cm of H2O to 1.S.

and from 40 to 100% solids for the combustion experiments.a. % Volatile Matter. 4.0012 O0.04 0.a.1-0..0194) and based on that vinasses moleculecular weight (13.15 3.6 n.86 0.24 n.8 4.14 n.5 6. % Fixed Carbon.01 0.01 0.350 kJ/kg is the average heating value of # 6 fuel oil Y is the # 6 fuel oil fraction in the vinasse-# 6 fuel oil emulsion Because previous research has revealed that # 6 fuel oil should be added to the vinasse for combustion. the vinasse approximative formula can be calculated (C0. PARR Adiabatic Calorimeter Model 1241 was used.U. 4.73 http://www. (1) where: is the low heating value for the vinasse-# 6 fuel oil emulsions in kJ/kg 7.015 0. wt % Source K P N Ca Mg Ash Vinasse Origin Total Organic Solids Solids % % pH Brazil (1) Molasses 0.31 0.3 4.0331 H0. % Sulphur.a.13 n. a number of tests were performed to evaluate the heating values of # 6 fuel oil-vinasse emulsions.0 n.04 0.0001 0.2 n. In the bomb calorimeter experiments.63 5.a n.12 n.a.05 0.3/12/2010 Brazilian Journal of Chemical Engineeri… heating values experimentally determined using Shepherd Oil Distillery's molasses vinasse (equation 1).11 0. In this determination. combustion was observed only in vinasse concentrations above 70%.5 (*) this analysis was conducted at the Feed and Fertilizer Laboratory at L.95 46.a.a.47 Brazil (2) Juice 0.12 69. The vinasse was evaporated and samples with solids concentrations varying from 10 to 73% were submitted for the rheological studies (see Experiences on Vinasse Disposal. 4.01 1. % 29.621 kg of air/kg of fuel (on dry-ash free basis). Than. 6-8 Louisiana (*) Molasses 0.31 11.89 0.br/scielo.a.79 13. for the air/fuel ratio is 7. The goal of this study was to determine the properties that would allow atomization which is required for successful combustion to be accomplished.3-5.a. Source: remaining data extracted from Polack et al.0 India Molasses 0. n.800 kJ/kg is the heating value of 45 BRIX molasses vinasse X is the vinasse fraction in the vinasse-# 6 fuel oil emulsion 43. This composition dependent parameter was calculated using the same Shepherd Oil Distillery vinasse which had its composition analyzed by the Guardian laboratories.S.2 0.006 5.014 0. 9.a.a. Table 1: Comparative vinasse composition from different countries and sources* Composition.69 Australia (1) Molasses 0.08 48.18 0. n.012 0. Another important combustion parameter is the adiabatic or theoretical flame temperature.5-1.php?pid=S… 3/9 . Part II). n. Based on dried composition and different water contents (Table 2) and the heating value (Table 4). 18.a.002 0. the main results for the adiabatic flame temperatures are 1290 F (700 C) for 50% solids and 1460 F (793 C) for 60% solids vinasse.67 8.0860 N0. using Shepherd Oil Distillery vinasse.5 0.07 0.scielo.31 0.48 0.17 0.007 0. n.2 0.95 0.02 1. n.a. 1981 Table 2: Shepherd Oil Distillery vinasse "as received" and "dry basis" composition As Received Dry Basis Solids.4-1. % Ash. Australia (2) Molasses 1.431 kg).

7 52. The furnace temperature is measured by the thermocouples installed inside the furnace (Figure 2 gives location).a. 39.65 Table 3: Comparison of ultimate and proximate analyses between vinasse.0 16-93 3-50 50-95 2-5.070 7.935 10.a. The furnace is equipped with a complete cooling system to provide safe operation.75 ft (3.410 12.837 18.52 m) wide x 5 ft (1.2 23. (1981) COMBUSTION TESTS The core of this research was conducted in the Combustion Laboratory located in the Mechanical Engineering Department at Louisiana State University. as shown in Figure 1.44 m) wide x 7 ft (2.5-7 0.28 m) long. % Hydrogen. It has inner dimensions of 5 ft (1. % Vinasse*1 Bagasse*2 Coal*3 39. http://www.13 m) high x 12 ft (3. sugarcane bagasse.60 n. The fuel feeding system is shown in Figure 3. % Volatile Matter.31 39.8 20.52 m) high x 10.5 2-40 0.66 m) long. The barrels are equipped with independent heating systems that control fuel temperature.php?pid=S… 4/9 . n. % n. The barrels are equipped with an independent heating system to supply the fuel to the furnace. and coal Analysis Proximate Ultimate Fixed Carbon. % Moisture. % H. Overall outer dimensions are 8 ft (2.72 69.a.95 0 6.62 m3). % S.72 8.600 Sources: * 1 MME (1994).5-3 2-30 0 Sources: *1 analysis made using Shepherd Oil Distillery vinasse. n. 0.scielo.1 40.br/scielo. *2 Harper (1980). It consists of two storage barrels. % Ash.65 18. kJ/kg 27. % O. giving an inner volume of 269 cubic feet (7. It also has a view port in the rear wall that provides visual observation of the flame and also allows photographs to be taken of the flame. The combustion chamber is a refractory lined surface with no boiler-type heat transfer surfaces present. * 2 Harper (1981) * 3 Polack et al.a. % C.560-15. This laboratory is a complete combustion facility that allows conduction of combustion experiments of this nature. % Nitrogen. These thermocouples are recorded by a Datalogger System allowing data recording. The fuel is atomized in the hot furnace (more than 1500 F and heated with natural gas) by the burner shown in Figure 4.3/12/2010 Brazilian Journal of Chemical Engineeri… Carbon.12 1. and a piping system to supply the fuel to the furnace.1 trace trace 1. % N.72 8.600-20. a pump.8 2. *3 Haalam and Russel (1926) Table 4: Typical heating values of sugarcane products and by-products Product/By-Product Ethanol (96%)* 1 Bagasse dry* 2 Bagasse 60% dry solids* 2 Vinasse dry* 3 Vinasse 60% dry solids* 3 Heating Value.60 1.

5. When the water content is high enough (i. The combustion experiments were performed. 20%) a constant CO content in the flue gas is reached as O2 . should be an obstacle for O2 access resulting in poorer combustion. http://www. Excess air in the stack was varied and Carbon Monoxide (CO) and Oxygen (O2) were measured. First.scielo.3/12/2010 Brazilian Journal of Chemical Engineeri… The fuel is surrounded by an air jet that breaks the fuel into small particles. The results presented show that there is a clear tendency to stabilize the CO content in the flue gas when the proportion of vinasse in the mixture is raised. 15. combustion tests were conducted increasing vinasse proportions in the emulsions: 10. In this way an increase in O2 in the burning emulsions works well up to a certain limit that depends on the proportion of water in the particular emulsion. probably because of the oil-in-water type of emulsion that is formed when both components are thoroughly mixed. They suggest that the effect of O2 in diminishing CO concentration in the flue gas works well with 100% # 6 fuel oil but does not operate in the same way when # 6 fuel oil-vinasse emulsions are burned instead. 25. The presence of an increasing proportion of a non-combustible continuous phase (mainly water) that surrounds the oil droplets in the emulsion. Then. Tests with diesel-vinasse emulsions were not conducted because of difficulties to sustain stable emulsion once they were heated. Results from combustion tests are presented in Figure 5. allowing contact between the combustion air and the droplets. 12. This means that the introduction of vinasse makes the complete combustion of # 6 fuel oil more difficult. Pictures of the flame were taken for each test conducted.34 MPa) and combustion parameters were set for further comparison. varying the emulsion vinasse and # 6 fuel oil proportions and always using 45 BRIX.br/scielo. and 50%.php?pid=S… 5/9 . In the last case. pure # 6 fuel oil was burned at 50 lbf/in2 (0. 40. emulsions with 20% vinasse and higher reach an almost constant CO content in the flue gas of 105 to 110 ppm independent of the presence of O2.# 6 fuel oil contact in the emulsion is not further improved.e. Figure 1: The Combustion Chamber Dimensions and Main Components..

br/scielo. Figure 3: The Fuel Feeding System Used During the Combustion Experiments. http://www.3/12/2010 Brazilian Journal of Chemical Engineeri… Figure 2: Thermocouple Location Inside the Combustion Chamber.php?pid=S… 6/9 .scielo.

br/scielo.php?pid=S… 7/9 . CONCLUSIONS http://www.scielo.3/12/2010 Brazilian Journal of Chemical Engineeri… Figure 4: Front and Cross-Section View of the Burner Used During the Combustion Experiments. Figure 5: Flue Gas Composition for Different # 6 Fuel Oil-Vinasse Mixtures.

br/scielo.6.Y. The atomization is. Sugar y Azucar.Sc. 86.C.P. N. 978. India. N. R.P. the conclusions can be derived from two different perspectives: a) Rheological. Although the vinasse concentration was tested over the wide range given above. Combustion System Development for Firing of Pulverized Bagasse. McGraw Hill Co. Shula. LXXXII... Refrigerating and Air-Conditioning Engineers. [ Links ] Chakrabarty. nozzle type. 9-26 (1974).. d) The ash fusion occuring at 700 C. G.. Although emulsions with more than 50% vinasse have a satisfactory heating value. Sugar News Ann.S. New Delhi.S. N. vinasse and air pressures and temperatures. [ Links ] Hollandse Constructie Groep B. atomization and combustion problems did not occur during any of the tests. and b) Combustion. P. Vinasse solids concentration below 50% was used for the combustion tests conducted.A. Distillery Fuel Savings by Efficient Molasses Processing and Stillage Utilization. ACKNOWLEDGMENTS The authors thank the Brazilian National Council for Scientific and Technological Development-CNPq and the State of São Paulo Research Foundation-FAPESP for the financial support which made this research possible.scielo. e) The difficult task of recovering salts and technology still under development. pp. [ Links ] http://www.N. XXXXIII-1 to XXXXIII-7 (1968). 1968-Proceedings of the 36th Annual Conv. vol. naturally. [ Links ] Dubey. S. [ Links ] Glória. Once the correct temperature and shear rate were obtained. Utilização Agrícola da Vinhaça (in Portuguese). Mechanical Eng. J.. pp. Baton Rouge. International Sugar Journal. Dept.. the following can be pointed out: a) The considerable amount of energy used during vinasse pre-evaporation. causing pumping difficulties.T. b) Combustion: The combustion of # 6 fuel oil-vinasse emulsions is feasible in the range of 95% # 6 fuel oil-5% vinasse to 50% # 6 fuel oil-50% vinasse emulsions.A.php?pid=S… 8/9 . New York. Noyes Development Corp. 809 (1926). [ Links ] Haalam.P. temperature.3/12/2010 Brazilian Journal of Chemical Engineeri… Because the purpose of this research was to generate enough data to evaluate the technical feasibility of vinasse combustion via atomization. October.V. REFERENCES ASHRAE. La.Y. 93-97. Recovery of Crude Potassium Salts from Spent Wash of Molasses Distilleries by Fluidized Incineration.. a) Rheological: Both the vinasse alone and the # 6 fuel oil-vinasse emulsions have rheological behavior close to the # 6 fuel oil alone when they are submitted to about 200 F (90 C) in the Brookfield Rotary Viscometer. November. December (1980). Number 6. among other important factors. Melted ash creating insoluble solids with no commercial value. Inc. Fuels and Their Combustion. and Russel.A Method of Disposal of Distillery Wastes and Saving Foreign Exchange.15. and Shukla. M. the resulting flame was unstable and not compact. Among the existing drawbacks of vinasse combustion. f) Additional studies on the vinasse atomization patterns are necessary because of this parameter affecting the combustion efficiency.. pp. 1993 ASHRAE handbook Fundamentals. b) The foaming in the evaporators when concentrating up to 75% solids. Energy Saver-NEM Vinasse Fired Boiler. Distillery Effluents-Treatment and Disposal. N. R. USA. Potash Recovery . U. (Advertisement). R. June (1980). a function of vinasse solids concentration. c) The salt crystallization in the syrup. pp. [ Links ] Gupta. chapter 15.. 11-17 (1975). Symposium on Ethyl Alcohol Production Technique. which is a process required for combustion.. the best results were obtained with 95 to 75% # 6 fuel oil-5 to 25% vinasse. [ Links ] Kujala. pp. Thesis. da. Louisiana State University. pp.L. (1964). 13-16 (1979).. India. (1993). Sugar Technology Ass. thus limiting the incineration operation. [ Links ] Harper. Brasil Açucareiro. Publ. Atlanta: American Society of Heating.. R...

March. Great Britain (1980). Balanço Energético Nacional-1994..br/scielo.B. pp. p. is licensed under a C reative C ommons License Associação Brasileira de Engenharia Quím ica Rua Líbero Badaró. M. from Alfa-Laval A. J. from Hollandse Constructie Groep B. G. vol. Engstrom.A. Utilisation. [ Links ] Reich.F. International Sugar Journal. and.73-74 (1982).F. November. 01008-903 São Paulo SP Brazil Tel. Engrs.. G.F.3/12/2010 Brazilian Journal of Chemical Engineeri… Kujala. Process Biochemistry. [ Links ] Nilsson. pp. September.. Vol.. All the content of the journal. C.. 11. 28-39 (1976).J. Energy Recovery from Distillery Wastes.. Vinasse Pollution Elimination and Energy Recovery. Inst. Brazil. Brazilian Gouvernment Publication. March. 233-251 (1945). 83.. R. September. issue 993... Ministério das Minas e Energia. 259-261 (1981). except where otherwise noted. [ Links ] MME. Treatment and Disposal of Distillery Wastewater. pp. Hull.scielo. Y. 41. P. E. [ Links ] Spruytenburg. F. Alcohol from Molasses as a Possible Fuel and Economics of Distillery Effluent Treatment. p. 140 (1994).E. 152 . Production of Carbon and Potash from Molasses Distillers' Stillage. International Sugar Journal. Day.. Louisiana State University.. D. D. Amer. and Cho.br http://www.V. 33-41 (1975). and Jackman. Audubon Sugar Institute. Water Research. pp. Greenfield. 71. pp..: +55 11 3104-4649 Fax: +55 11 3104-4649 rgiudici@usp. vol.php?pid=S… 9/9 . Gasohol from Sugarcane-Stillage Disposition. Chem. Brasília.T. G. pp.. 257-277. [ Links ] Polack. Sugar y Azucar. 14.P. Trans.: +55 11 3107-8747 Fax. Brazilian Experience with the Disposal of Waste Water from the Cane Sugar and Alcohol Industry. and P. [ Links ] Sheehan. (1981). [ Links ] Monteiro.K. 47.

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