Fuel Gas Generation from Gasification of Sacha Inchi Shell using a Drop Tube Reactor

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Energy (2017) 000–000 870–876 EnergyProcedia Procedia138 00 (2017) www.elsevier.com/locate/procedia

2017 International Conference on Alternative Energy in Developing Countries and Emerging Economies 2017 International Conference on Alternative in Developing 2017 AEDCEE, 25‐26Energy May 2017, Bangkok,Countries Thailand and Emerging Economies 2017 AEDCEE, 25‐26 May 2017, Bangkok, Thailand

Fuel Gas Generation from Gasification of Sacha Inchi Shell using a Fuel Gas Generation from Gasification of Sacha Shell using a The 15th International Symposium on District HeatingInchi and Cooling Drop Tube Reactor Drop Tube Reactor Assessing the feasibility of using the heat demand-outdoor a Chalatthon Lakkhanaa, Duangduen Atongbb, Viboon Sricharoenchaikula,a,* Chalatthonfunction Lakkhana for , Duangduen Atong district , Viboon Sricharoenchaikul * temperature a long-term heat demand forecast Department of Environmental Engineering, Chulalongkorn University, Bangkok, 10330, Thailand a

a Department of Environmental Engineering, Chulalongkorn University, Bangkok, 10330, Thailand National Metal and Materials Technology Center, Thailand Science Park, Pathumthani, 12120, Thailand a,b,c a a b c b National Metal and Materials Technology Center, Thailand Science Park, Pathumthani, 12120, Thailand b

I. Andrić a

*, A. Pina , P. Ferrão , J. Fournier ., B. Lacarrière , O. Le Correc

IN+ Center for Innovation, Technology and Policy Research - Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal

b Veolia Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, France Abstract c Département Systèmes Énergétiques et Environnement - IMT Atlantique, 4 rue Alfred Kastler, 44300 Nantes, France Abstract The optimal fuel gas production conditions for gasification of sacha inchi shell waste were studied with a drop tube reactor. This The fuel gas production conditions gasification of sacha inchi shell waste were studied with drop tubewere reactor. This wasteoptimal was derived from production of sachafor inchi seed oil. Ultimate, proximate and heating value of rawa material analyzed waste was derived from production of sacha inchi (TGA) seed oil.and Ultimate, proximate and heating value of particle raw material were analyzed by CHNS/O analyzer, thermogravimetric analysis bomb calorimeter, respectively. Waste size was 0.50 - 0.85 Abstract analyzer, thermogravimetric analysis (TGA) and bomb calorimeter, respectively. Waste particle size was 0.50 - 0.85 by mmCHNS/O and the reactor temperature was varied from 700 to 900°C with the equivalent ratio of 0.20 - 0.50. To reduce undesired liquid mm and the reactor temperature was from 700 toSolid 900°C with the ratio of 0.20 -composition 0.50. To reduce undesired liquid product, Ni/dolomite was used asvaried primary catalyst. residue wasequivalent analyzed for elemental while liquid and gas District the heating networks commonly addressed the residue literature as one of the most effective solutions for decreasing the product, Ni/dolomite wasare used as primary catalyst. in Solid was for elemental composition while products were analyzed by gas chromatography-mass spectrometry and analyzed portable gas analyzer, respectively. It wasliquid foundand thatgas at greenhouse gas emissions from the building sector. These systems require high investments which are returned through the heat products were analyzed by gas chromatography-mass spectrometry and portable gas analyzer, respectively. It was found that at optimal operating conditions (ER 0.20, 900°C), conversions of carbon to CO, CO2 and CH4 were approximately 30.63%, 14.50% sales. Due to theconditions changed (ER climate conditions and building renovation policies, heat demand in the future30.63%, could decrease, and CH were approximately 14.50% optimal operating 0.20,the 900°C), conversions of carbon CO 2 4 and CH were approximately 26.94% and 15.40%, and 6.27%, respectively. Similarly, conversion of hydrogen to toHCO, 2 4 prolonging investment return period. approximately and 15.40%, and 6.27%, the respectively. the conversion of 3 hydrogen to H 2 and CH and cold gas efficiency of4 were gasification process is26.94% nearly 40% whereas respectively, with the lowerSimilarly, heating value at 2.27 MJ/m The main scope ofthe thislower paperheating is to assess the feasibility of using thegas heatefficiency demand – outdoor temperature function heatwhereas demand 3 and cold gasification is greater nearlyfor40% respectively, with at 2.27 MJ/m liquid and solid product were 4.55 %value and 34.50%. Apparently, higher temperatureofhad a positive process effect on gas yield and forecast. The district ofwere Alvalade, located in Lisbon (Portugal), wastemperature used as a had casea positive study. The district is consisted of and 665 liquid and solid product 4.55 % and 34.50%. Apparently, higher effect on greater gas yield lower liquid production. Furthermore, catalyst addition reduced liquid proportion and increased potential of CO and H2 production buildings that vary in both construction period and typology. Three weather scenarios (low, medium, high) and three district lower liquid catalystdolomite. addition reduced liquid proportion and increased potential and H2 production especially forproduction. Ni loadingFurthermore, of 5% on calcined The result showed that conversions of carbon to of COCO increased to 37.95% renovationforscenarios were (shallow, intermediate, deep). To estimate the error, obtainedto heat demand values were especially of developed 5% calcined dolomite. result showed of carbon COtoincreased to 14.10%, 37.95% and conversionNiofloading hydrogen to Hon to 34.50%.The In addition, liquidthat and conversions solid production decreased 2.87% and 2 increased compared with results from a dynamic heat demand model, previously developed and validated by the authors. and conversion of hydrogen In addition, andparticular solid production to 2.87% and 14.10%, 2 increased to 34.50%. respectively. The feasibilitytoofHincorporating the catalytic processliquid on this thermaldecreased waste conversion method was The results showed that when only weather change is considered, the margin of error could be acceptable for some applications respectively. discussed. The feasibility of incorporating the catalytic process on this particular thermal waste conversion method was (the error in annual demand was lower than 20% for all weather scenarios considered). However, after introducing renovation discussed. © 2017 The Authors. Published by Elsevier Ltd. error value increased up to 59.5% on the weather and renovation scenarios combination considered). ©scenarios, 2017 Thethe Authors. Published by Ltd. (depending Peer-review under responsibility of Elsevier the Organizing Committee of 2017 AEDCEE. ©The 2017 The of Authors. Published by Elsevier on Ltd.average within the range of 3.8% up to 8% per decade, that corresponds to the value slope coefficient increased Peer-review under responsibility of the Organizing Committee of 2017 AEDCEE. Peer-review responsibility of the scientific committee of the the 2017 International Conference Energy in decrease in under the number of heating hours of 22-139h during heating season (depending on on theAlternative combination of weather and ­Drenovation eveloping Countries EmergingOn Economies. scenarios and considered). the other hand, function intercept increased for 7.8-12.7% per decade (depending on the coupled scenarios). The values suggested could be used to modify the function parameters for the scenarios considered, and improve the accuracy of heat demand estimations.

© 2017 The Authors. Published by Elsevier Ltd. * Corresponding author. Tel.: +66-2-218-6689 ; fax: +66-2-218-6666. Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and * Corresponding author. Tel.: +66-2-218-6689 ; fax: +66-2-218-6666. E-mail address: [email protected] Cooling.

E-mail address: [email protected] 1876-6102 2017demand; The Authors. Published Elsevier Ltd. Keywords:©Heat Forecast; Climatebychange 1876-6102 ©under 2017responsibility The Authors. of Published by Elsevier Ltd. of 2017 AEDCEE. Peer-review the Organizing Committee Peer-review under responsibility of the Organizing Committee of 2017 AEDCEE.

1876-6102 © 2017 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling. 1876-6102 © 2017 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the scientific committee of the 2017 International Conference on Alternative Energy in ­Developing Countries and Emerging Economies. 10.1016/j.egypro.2017.10.109

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Keywords: Biomass, Drop tube reactor, Gasification, Ni/dolomite, Sacha inchi shell.

1. Introduction Major cause of air pollution, global warming and acid rain came from using fossil fuel [1]. Many researchers found that biomass was environmental friendly which can be used for renewable energy. Since agricultural is one of the largest economical sector in Thailand, there are a lot of related byproducts and wastes. To manage and reduce the amount of these biomass, one of the optimal choice that can be applied is to convert them to energy by thermochemical processes such as direct combustion, pyrolysis and gasification. Sacha inchi is a new economic plant that contains very high omega-3 which resulted in relatively popular industrial production of its seed oil. However, a large amount of sacha inchi shell residues are discarded after the production process. Gasification process is proposed as a potential method to convert this biomass to fuel gas, mainly carbon monoxide, carbon dioxide, hydrogen and methane. This process has an advantage over the others because gas product can be readily utilized in combustion engines. On the contrary, bio-oil, a product from pyrolysis, must be upgraded by many processes prior to usage. In addition, the product from gasification process can be conditioned to high quality by using catalyst. Ni –based catalysts are of interested due to their selective activities for tar cracking in primary reactor [2]. Ni catalysts may be supported by nature minerals such as dolomite and olivine. Dolomites, inexpensive and abundant materials, can provide relatively high tar conversion [3]. Elbaba et al. [4] studied an effect of Ni loading on dolomite support; though, the results indicated that Ni loadings promote higher reaction rate and H2 production. The purpose of this work was to study the optimal fuel gas production operating conditions for gasification of sacha inchi shell by using a drop tube reactor. Significant parameters that effect composition of the producer gas such as temperature, residence time and equivalence ratio were investigated. Moreover, the effect of Ni/dolomite on liquid reduction and increase the syngas production (CO and H2) were explored. 2. Experimental methods 2.1. Raw materials Sacha inchi shell used in this work was derived from production of seed oil in Ratchaburi province of Thailand. The sample was first crushed and sieved into 0.50-0.85 mm. Then, it was dried in an oven at 105oC for 24 hrs. The resulting dried sample was characterized for proximate analysis (ASTM-D5142-02), ultimate analysis (ASTMD5373), heating value and component analysis (cellulose, hemicellulose and lignin) according to TAPPI T264, T-203 and T-222 standard methods, respectively. The results of the analysis are shown in Table 1. Proximate analysis

Wt.%

Ultimate analysis

Wt.%

Component analysis

Wt.%

Volatile matter

68.93

Carbon

41.24

Cellulose

35.20

Fixed carbon

13.78

Hydrogen

6.78

Hemicellulose

11.96

Moisture

4.695

Nitrogen

1.51

Lignin

0.71

Ash

11.70

Oxygena

50.47

Extractives

LHV (MJ/kg)

18.55

a

52.13

By difference

Table 1 Characteristics of sacha inchi shell

2.2. Catalyst preparation Dolomite support was prepared by the combination of dolomite powder with kaolin, organic binder and distilled water. Then the mixture was extruded into cylindrical shape and calcined at 1200oC for 4 hrs. After this process was completed, it was crushed and sieved to 0.50-0.85 mm. Then the dolomite support was put into Ni(NO3)2∙6H2O solution and stirred in water bath at 80oC for 3 hrs via impregnation method. The resulting catalyst was Ni loading of 5% on calcined dolomite using in this work. After impregnation process, Ni/dolomite was dried overnight in the oven

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at 105oC. At the final point, it was calcined at 700oC for 2 hrs. Once, everything is completed, Ni/dolomite is ready to be tested in Gasification process. 2.3. Catalyst characterization The specific surface area and pore volume of catalysts were analyzed by the BET (Brunauer, Emmett and Teller) method. The structure of catalysts and active phase were characterized by X-Ray diffraction. Scanning electron microscopy (SEM) was used to investigate morphology and elemental dispersion of catalysts. 2.4. Experimental system In this study, drop tube reactor was used to investigate the optimal fuel gas production conditions. The reactor system consisted of biomass feeder at the top of reactor vessel, electrical furnace, condenser, washers system, flow meter and portable gas analyzer. The bottom end of the reactor tube contained alumina balls (diameter 8 mm) of 200 g that acted as heating bed supporter. Carrier gas (N2) and gasifying agent (O2) was fed into bottom of reactor that the ratio of N2 and O2 can be adjusted to requiring equivalence ratio (ER) for gasification system. Temperature controllers and K-type thermocouples were used to measure reaction temperature of reactor. In this experiment, biomass feed rate was 1.0 g/min for the duration of 30 min. Gas products from gasification process first passed through condenser to collect liquid products. Then, the gas stream went through washer system, flow meter and portable gas analyzer, respectively. Portable gas analyzer (Gasboard-3100p) reported the composition of gas products into CO2, CO, H2, CH4 and CxHy. Finally, solid products of gasification process were settled at the bottom of reactor and later collected for further analysis. 3. Results and discussion 3.1. Characterization of catalysts X-ray diffraction (XRD) analysis of dolomite, calcined dolomite, 5% Ni/dolomite and calcined 5% Ni/dolomite are shown in Figure 1. Calcined dolomite showed intensity peaks of MgO at 2θ = 43o, 62o and CaO at 2θ = 34o, 37o. The presence of CaO, MgO, NiO and MgNiO2 in 5% Ni/dolomite can be noticed at 2θ = 37o, 43o, 62o. MgNiO2 is a form of stable Ni species that demonstrated the interaction between Ni and dolomite support. The surface area of 5% Ni/dolomite which characterized by the BET method is 78.55 m2/g. After calcination, surface area of calcined 5% Ni/dolomite reduced to 35.96 m2/g. This is due to the fact that during calcination process, Ni loading on dolomite support is sintering and covering on pore space of the dolomite. Therefore, surface area of 5% Ni/dolomite after calcination decreased. The morphology and porosity of catalysts were investigated by SEM analysis and the results are shown in Figure 2.

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Fig. 1 XRD results of fresh catalyst: (a) dolomite (b) calcined dolomite (c) 5% Ni/dolomite (d) calcined 5%Ni/dolomite. (a)

(b)

(c)

(d)

(e)

(f)

Fig. 2 Scanning electron microscopy (SEM) of (a) dolomite (b) calcined dolomite (c) spent dolomite (d) 5% Ni/dolomite (e) calcined 5% Ni/dolomite (f) spent 5% Ni/dolomite

3.2. Effect of temperature The effect of temperature on conversion of carbon and hydrogen components are shown in Figure 3 for reaction at ER 0.2. In this experiment, sacha inchi shell size 0.50-.085 mm were gasified at 700-900oC. Each typical run take approximately 30 min and at a feed rate of 1.0 g per min. The reaction temperature is an important factor for biomass gasification especially on gas product distribution. When the reaction temperature increased from 700 to 900oC, liquid product decreased from 10.79% to 4.55% because more liquid product was cracked into gaseous species. For the conversion of carbon in sacha inchi shell to fuel gas, CO and CH4 incrased from 10.97% to 30.63% and 5.21% to 6.27%, respectively. However, conversion of carbon to CO2 decreased from 24.26% to 14.50% due to the dominant of Boudouard’s reaction in which the endothermic reaction favors high temperature. Higher temperature contributes to forward reaction in this case. As a result, CO2 was expense in this reaction in order to produce more CO. The conversion of hydrogen to H2 and CH4 increased from 17.32% to 26.94% and 12.81% to 15.40%, respectively. The increased amount of H2 came from water-gas reaction that enhances production of H2 and CO in relative with high temperature while methane might have been increased from methanation reaction. Moreover, the increment of temperature also affects the lower heating value and cold gas efficiency of gas product that increased to 2.27 MJ/m3 and 40%, respectively.

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Fig. 3 Effect of temperature on conversion of carbon and hydrogen at ER 0.2

3.3. Effect of equivalence ratio In biomass gasification, equivalence ratio (ER) is an important parameter that regulate the composition of gas. For each run, gas products from gasification are mainly composed of CO, CO2, H2 and CH4. In this experiment, the ER was varied from 0.2 to 0.5. The carbon and hydrogen conversion results are shown in Figure 4. When ER increased from 0.2 to 0.5, the amount of total gas product increased from 60.90% to 76.23% then declined to 65.11% at ER 0.5. Moreover, conversion of carbon to CO and CH4 was slightly increased then tapered off. However, conversion of carbon to CO2 increased from 14.50% to 34.07%. Conversions of hydrogen to H2 and CH4 displayed the similar trend as conversion of carbon because higher ER means more oxygen supplied. Thus, CO, H2 and CH4 were oxidized to CO2 and H2O [5]. As a result, too high ER would adversely support CO2 formation. Particular dominant reactions exhibit greater role at higher ER such as oxidation reaction and water-gas shift reaction. For gasification process, ER must be properly controlled in order to achieve optimal syngas (CO and H2) generation.

Fig. 4 Effect of equivalence ratio on conversion of carbon and hydrogen at 900 OC

3.4. Effect of catalyst To study effect of catalyst in gasification process on composition of products, the sacha in shell size 0.50-0.85 mm was mixed with catalysts at ratio of 1:1 and gasify at reaction temperature of 900oC and ER of 0.2 for 30 min. The comparison between non-catalytic and catalytic trials was demonstrated in Figure 5. When calcined dolomite size 0.50-0.85 mm was being utilized, gas product increased from 60.90% to 76.61%. In contrast, liquid and solid product declined from 34.55% to 19.39% and 4.55% to 4.00%, respectively. This confirm the capability of calcined dolomite on tar cracking. Conversion of carbon to CO2, CO, CH4 increased as similar trend as conversion of hydrogen to H2 and CH4. Although using calcined dolomite did not decrease the amount of CO2 because of the limitation of this drop tube reactor which has relatively short residence time. In the presence of 5% Ni/dolomite catalyst, the reaction activity results are greater than that of calcined dolomite. Here, the amount of gas product increased from 76.71% to 83.03%. However, liquid and solid product declined obviously from 19.39% to 14.10% and 4.00% to 2.87%, respectively. In

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addition, conversion of carbon to CO was also increased to 37.95% as well as conversion of hydrogen to H2 which increased to 34.50%. Lower heating value of gas product increased to 2.77 MJ/m3 with cold gas efficiency was nearly 46%. From the results, it was clear that the catalysts can significantly reduce liquid production while increasing the quality of gas product especially CO and H2. Calcined dolomite and 5 % Ni/dolomite enhanced the Boudouard’s, water-gas shift and steam reforming reactions. The morphology of spent catalysts are also shown in Figure 2.

Fig. 5 Effect of catalyst on conversion of carbon and hydrogen at 900 OC, ER 0.2

4. Conclusion Sacha inchi shell was a new potential feedstock for gasification process. In this experiment, optimal conditions for gas production was performed with drop tube reactor producing fuel gas (CO, H2, CH4), CO2, solid and liquid products. Temperature and ER are significant parameters that affect composition of gas and other products. Increasing temperature enhanced syngas (CO and H2) generation while decreased liquid production. When temperature changed from 700 to 900oC, liquid concentration also decreased to 4.55%. Lower heating value was 2.27 MJ/m3 and cold gas efficiency was nearly 40%. Too high ER adversely supported CO2 formation from extra oxygen supply. Thus, optimal condition in this experiment was ER 0.2 at reaction temperature of 900oC. In catalytic cases, calcined dolomite and 5% Ni/dolomite reduced solid production and increased gas production, especially on syngas formation. The results showed that CO and H2 increased to 33.99% and 33.44%, respectively and liquid product decreased to 4% when using calcined dolomite. Moreover, CO and H2 production increased to 37.95% and 35.40%, respectively with lower liquid production (2.87%) when using 5% Ni/dolomite. The results indicated that Ni/dolomite catalyst is an excellent candidate which can be applied for selectively improved the quality and quantity of gas product. Finally, optimal condition data from gasification process of sacha inchi shell with a drop tube reactor can be further applied in industrial scale as a way to manage agricultural wastes while producing quality gas that can be used as renewable energy source for many heat and power applications such as boiler, engine, and gas turbine. Acknowledgements This work was supported by a Grant for International Research Integration: Chula Research Scholar, Ratchadaphiseksomphot Endowment Fund. Authors also thank National Metal and Materials Technology Center (MTEC) for assistance on equipment and facility. References [1] Goyal HB, Seal D, Saxena RC. Bio-fuels from thermochemical conversion of renewable resources: A review. Renewable and Sustainable Energy Reviews 2008;12:504-517. [2] Miguel CA, Jose´ C, Marı´a-Pilar A, Javier G. Biomass Gasification with Air in Fluidized Bed. Hot Gas Cleanup with Selected Commercial and Full-Size Nickel-Based Catalysts. Ind. Eng. Chem. Res 2000;39:1143-1154. [3] EI-Rub ZA, Bramer EA, Brem G. Review of Catalysts for Tar Elimination in Biomass Gasification Processes. Industrial and Engineering Chemistry Research 2004;43:6911-6919.

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