Problems Recorded on the Appropriateness of a Pilot Plant for Production of Second Generation Biofuels by Fast Pyrolysis

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Problems Recorded on the Appropriateness of a Pilot Plant for Production of Second Generation Biofuels by Fast Pyrolysis Fabio Mendes 1, Marco Figueiredo 2 * 1 Centro de Pesquisas Leopoldo Miguez de Melo, Petrobras, Brazil 2 Universidade do Estado do Rio de Janeiro. Centro de Tecnologia e Ciências Instituto de Química. Laboratório de Engenharia e Tecnologia de Petróleo e Petroquímica. PHLC - Sala 43, Brazil The use of biomass as an energy source has proven to be a promising option as a means of reducing dependence on oil and mitigate climate change. The fuels produced from biomass are classified as first and second generation. The first-generation biofuels are produced mainly from sugar, starch and vegetable oil using conventional technologies, and in this segment, the most important ethanol and biodiesel. Ethanol is produced from biomass such as sugarcane, beet sugar and starch crops (maize and wheat). The secondgeneration biofuels are produced from lignocellulosic biomass mainly consisting of agricultural waste, forestry and industrial. In order to study routes for the processing of lignocellulosic biomass was performed a survey of the main technological routes, opting for tailor a pilot unit, already available for evaluation of reaction conditions via fast pyrolysis. The aim of this paper is to present the main problems identified in the operational suitability of a pilot unit of Fluid Catalytic Cracking (FCC), from the Research Center of Petrobras and its alternatives taken to resolve them. The test conditions were based on data identified in literature, namely, temperature: 45-55 C, residence time:.5 to 5 heating rate is high. The tests show the viability of adapting an FCC unit to accomplish the fast pyrolysis process. Currently, the unit is being used to test new catalysts to obtain second-generation biofuels. 1 Introduction According to the report "International Energy Outlook" of the 29 Energy Information Administration (EIA), among the available energy resources, consumption of renewable energy is the fastest growing in the world at a rate of 3% per annum (Aperger and Payne, 21 ) representing 14% of all energy consumed in the world (Zhang et al., 21). The biomass used in biofuel generation allows the CO 2 generated by burning is recycled through its absorption by the photosynthesis process to grow a new plant biomass (Mohan et al., 26 and Zhang et al., 21; Aperger and Payne, 21). The fuels produced from biomass are classified as first and second generation. Most important, the first generation, are ethanol and biodiesel. Ethanol is produced from

biomass such as sugarcane, beet sugar and starch crops (maize and wheat). Biodiesel is produced from vegetable oils through transesterification process (Cherubini, 21). According to balance the International Energy Agency, 21, world production of first generation biofuels to 82 billion liters in 28, with 28 billion liters (34%) were produced by Brazil, the second largest producer in the world, behind only the United States. Brazil has pioneered the use of ethanol as a fuel on a large scale between 1975 and 1986. Currently, all gasoline sold in the country is blended with ethanol in proportions ranging from 2 to 25%. The second-generation biofuels are produced from lignocellulosic biomass mainly consisting of agricultural waste, forestry and industrial. Investments in the development of processes for production of second generation biofuels, have grown considerably in recent years, mainly because of the raw material is cheap and plentiful and not compete with food production, so these factors are advantageous in relation to first generation fuels. The potential energy derived from biomass waste worldwide is estimated at 3 million GJ / year, while energy demand is around 4 million GJ / year (Mckendry, 22). The fast pyrolysis seems more promising, among the processes of developing biomass conversion. Among the technologies identified the fast pyrolysis reactor, circulating fluidized bed has proved very attractive in terms of process. The continuously burning coal and coke produced in this reaction, a characteristic of this type of reactor, has a significant advantage over other technologies. Commercially, a similar technology is used for production of LPG and gasoline at oil refineries, called the Fluidized Catalytic Cracking (FCC). 2 Experimental Method 2.1 The pilot plant to study the fast pyrolysis process 2.1.1 General considerations The process that uses circulating fluidized bed reactor is most recommended by the literature search was undertaken. Buoyed this survey we chose to adapt a fluid catalytic cracking pilot unit exists (Figure 1) to study the processability of sugar cane bagasse as filler and silica as bed stock. The selected drive has a processing capacity of 1 g / h of liquid fed. In this unit, the catalyst is all loaded in the regenerator. The load is fed to crack at the base of the riser. The flow of catalyst is controlled by screw conveyors and flow between the vessels is done by injecting nitrogen in transfer lines. The regenerator and rectifier operate under fluidized by injecting nitrogen or steam. The cracking reactions occurring in the riser at a temperature of 7 C. The vaporized reaction mixture and the catalyst are separated in the stripper. The catalyst is rectified in the bottom of the vessel by injection of water vapor or nitrogen returned to the regenerator. The regenerator has the function of burning coke that has been generated on the catalyst surface, restoring its catalytic activity. The released product is directed to the cooling tower for condensing.

FILTER MGU KNOCKOUT POT STRIPPER RISER REGENERATOR COOLER TOWER N2 FEED Ar/O2 TEST PRETEST PRODUCT VESSELS N2 STTRPPER N2 REGENERATOR Figure 1. Schematic flowchart of the pilot plant FCC 2.1.2 Problems identified in the adequacy 2.1.2.1 Biomass Power System In the FCC pilot unit, the catalyst was loaded at once and the reaction happening for a specified time. In the process of fast pyrolysis, biomass is loaded in a controlled and continuous. In all, four types of charging systems based on the use of biomass screw conveyors. The first three systems to control flow, were associated with the pneumatic transport of biomass to the reactor system and the latter engaged the screw directly into the reactor, which showed the best results in terms of flow control. 2.1.2.2 Physico chemical Biomass Clogging problems in the screw insertion were observed due to the format of the fibrous particles of straw biomass from sugar cane. To solve this problem an agitator has been adapted in a silo loading. 2.1.2.3 Suitability of equipment The regenerator, by having a larger volume, is now used as a fluidized bed reactor being the stripper with the task of regenerating. The reactor of the FCC process, now used only as a catalyst transfer line between the reactor and regenerator, as shown in the flowchart of the unit of production of biofuel from second generation (Figure 2).

REGENERATOR MGU FEEDER HOOPER MGU KNOCK-OUT POT COOLER TOWER RISER FEEDER REACTOR REGENERATOR REACTOR PRODUCT VESSELS Figure 2. Schematic flowchart of the reaction unit in fluidized bed. 2.1.3 Tests of conditioning Unit Tests of conditioning, aimed to evaluate the system load of biomass in the reactor and the effects of high temperatures, the flow of biomass and type of catalyst. The test conditions were based on data identified in literature, namely, temperature: 45-55 C. The parameters were monitoring the process, the gas flow generated, the feed rate of biomass and the overall efficiency of the process.. 2.1.3.1 Gas flow generated in the process In tests of conditioning were observed instabilities in some variables in the process, among them the flow of product gas unit, indicating a possible discontinuous feeding of biomass in the reactor, as shown in Table 1. Table 1: Variation of the gas flow generated in fitness race Run Gas flow reactor (l/h) Standard deviation RSD (%) 1 666,91 69,11 1,36 3 655,54 188,96 28,83 3 5,7 92,6 18,41 4 441,96 59,65 13,5 5 957,59 133,67 13,96 Peak flows of biomass resulted in excessive formation of coke and coal in the reactor, and consequently the overhead of the regenerator. Due to the inefficient burning of the catalyst, clogging lines occurred and tests were stopped prematurely. 2.1.3.2 Overall yield In the case of a pyrolysis unit, three chains make up the mass balance: liquid (bio-oil), gas and solid (coke and coal). The mass of liquid is obtained by weighing the effluent. The amount of gas generated is measured using a wet gas meter (MGU). The current

sound is measured by counting the mass of carbon gas regeneration. As shown in Figure 3, it was observed that increasing the flow of cargo generated losses in overall yield, indicating the need to limit the flow to values between 5 and 7 g / h, obtaining thus income in the range between 8 and 9%. g/h 25 2 15 1 5 12 1 14 13 9 8 5 1 11 2 7 run mass flow global yield 1 9 8 7 6 5 4 3 2 1 % Figure 3. Behavior of total income due to the variation of the flow of biomass 2.1.3.3 Biomass Power System As shown in Figure 4, during the conditioning tests, it was found that even by fixing the feed screw rotation, the system indicated a wide variation in the mass loaded flow. 18 15 mass flow (screw rotation 3%) 1378,97 1599,86 12 g/h 9 6 423,92 668,45 521,92 3 2 3 9 1 11 run Figure 4. Behavior of the feed flow in the process of biomass 3 Results and Discussion With the data obtained in tests of conditioning, adjustments were made in the plant that made possible the races varying load flow, reaction temperature and type of catalyst. In Figures 5 and 6, we observe that the plant operated stably indicating only small variations in gas flow, a product generated in the process.

Reactor gas flow (run 6) L/h 14 12 1 8 6 4 2 2 4 6 8 min Figure 5. Gas flow in the reactor g/h 16, 14, 12, 1, 8, 6, 4, 2,, conditioning runs (screw rotation 3%) Average mass flow studying runs (screw rotation 15%) Figure 6. Flow behavior of biomass in the reactor Currently, the plant has been used for the study of new catalysts to improve both the yield on the amount of bio-oil obtained as its quality. References Aperger A., J. Payne E., 21. Renewable Energy Consumption and Economic Growth: Evidence from a panel of OECD countries. Energy Policy, 38, 656-66. Cherubini F., 21. The Biorefinery Concept: Instead of Using Biomass for Oil Producing Energy and Chemicals. Energy Conversion and Management, 29. Energy Information Administration. International Energy Outlook. Available in: http://www.eia.doe.gov/oiaf/ieo/world.html. [Access: mar. 21] International Energy Agency, 21. Sustainable Production of Second Generation Biofuels: Potential and prospects in Major Economies and developing countries. Paris, Mckendry, P. 22. Energy production from biomass (part 1): overview of biomass. Bioresource Technology, 83, 37-46. Mohan, D., Pittman, C. U. Steele, P. H., 26, Pyrolysis of Wood / Biomass for Bio-oil: A Critical Review. Energy & Fuels, 2, 848-889. Zhang L., C. Xu, P. Champagne, 21, Overview of recent Advances in thermochemical conversion of biomass. Energy Conversion and Management.