Abstract: Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contain four obvious stages and the main decomposition reaction occurred in the range of 200-600 °C. Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2 and 3 were in the range of 6.67-20.37 kJ/mol for SS; 1.51-6.87 kJ/mol for HZSM5; and 2.29-9.17 kJ/mol for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1 and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with HZSM5 and AC were in the total range of C4-C17 with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds while the presence of HZSM5 and AC dropped to 7.3% and 13.02%, respectively. Meanwhile, generation of value-added chemicals such as light aromatic compounds were significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR and TGA techniques. Overall, this research demonstrated that AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.
Abstract: Pyrolysis of waste oil is an effective process to produce high quality liquid fuels. In this work, pyrolysis experiments of waste oil over Y zeolite were carried out in a semi-batch reactor under a flow of nitrogen at atmospheric pressure and at different reaction temperatures (350-450 oC). The products were gas, liquid fuel, and residue. Only liquid fuel was further characterized for its composition and properties by using gas chromatography, thermogravimetric analyzer, and bomb calorimeter. Experimental results indicated that the pyrolysis reaction temperature significantly affected both yield and composition distribution of pyrolysis oil. An increase in reaction temperature resulted in increased fuel yield, especially gasoline fraction. To obtain high amount of fuel, the optimal reaction temperature should be higher than 350 oC. A presence of Y zeolite in the system enhanced the cracking activity. In addition, the pyrolysis oil yield is proportional to the catalyst quantity.
Abstract: Nanostructured catalysts were successfully prepared
by acidification of diatomite and regeneration of FCC spent catalysts.
The obtained samples were characterized by IR, XRD, SEM, EDX,
MAS-NMR (27Al and 29Si), NH3-TPD and tested in catalytic
pyrolysis of biomass (rice straw). The results showed that the similar
bio-oil yield of 41.4% can be obtained by pyrolysis with catalysts at
450oC as compared to that of the pyrolysis without catalyst at 550oC.
The bio-oil yield reached a maximum of 42.55% at the pyrolysis
temperature of 500oC with catalytic content of 20%. Moreover, by
catalytic pyrolysis, bio-oil quality was better as reflected in higher
ratio of H/C, lower ratio of O/C. This clearly indicated high
application potential of these new nanostructured catalysts in the
production of bio-oil with low oxygenated compounds.
Abstract: Pyrolysis of waste tire is one of alternative technique
to produce petrochemicals, such as light olefins, mixed C4, and monoaromatics.
Noble metals supported on acid zeolite catalysts were
reported as potential catalysts to produce the high valuable products
from waste tire pyrolysis. Especially, Pd supported on HBeta gave a
high yield of olefins, mixed C4, and mono-aromatics. Due to the high
prices of noble metals, the objective of this work was to investigate
whether or not a non-noble Ni metal can be used as a substitute of a
noble metal, Pd, supported on HBeta as a catalyst for waste tire pyrolysis.
Ni metal was selected in this work because Ni has high activity
in cracking, isomerization, hydrogenation and the ring opening of
hydrocarbons Moreover, Ni is an element in the same group as Pd
noble metal, which is VIIIB group, aiming to produce high valuable
products similarly obtained from Pd. The amount of Ni was varied as
5, 10, and 20% by weight, for comparison with a fixed 1 wt% Pd,
using incipient wetness impregnation. The results showed that as a
petrochemical-producing catalyst, 10%Ni/HBeta performed better
than 1%Pd/HBeta because it did not only produce the highest yield of
olefins and cooking gases, but the yields were also higher than
1%Pd/HBeta. 5%Ni/HBeta can be used as a substitute of
1%Pd/HBeta for similar crude production because its crude contains
the similar amounts of naphtha and saturated HCs, although it gave
no concentration of light mono-aromatics (C6-C11) in the oil. Additionally,
10%Ni/HBeta that gave high olefins and cooking gases was
found to give a fairly high concentration of the light mono-aromatics
in the oil.
Abstract: This work presents the experimental results obtained
at a pilot plant which works with a slow, wet and catalytic pyrolysis
process of dry fowl manure. This kind of process mainly consists in
the cracking of the organic matrix and in the following reaction of
carbon with water, which is either already contained in the organic
feed or added, to produce carbon monoxide and hydrogen. Reactions
are conducted in a rotating reactor maintained at a temperature of
500°C; the required amount of water is about 30% of the dry organic
feed. This operation yields a gas containing about 59% (on a volume
basis) of hydrogen, 17% of carbon monoxide and other products such
as light hydrocarbons (methane, ethane, propane) and carbon
monoxide in lesser amounts. The gas coming from the reactor can be
used to produce not only electricity, through internal combustion
engines, but also heat, through direct combustion in industrial
boilers. Furthermore, as the produced gas is devoid of both solid
particles and pollutant species (such as dioxins and furans), the
process (in this case applied to fowl manure) can be considered as an
optimal way for the disposal and the contemporary energetic
valorization of organic materials, in such a way that is not damaging
to the environment.