Pyrolytic behavior of cellulose in presence of montmorillonite K10 as catalyst

Cellulose and cellulose/montmorillonite K10 mixtures of different ratio (9:1, 3:1, 1:1) were subjected to pyrolysis at temperatures from 350 to 500 °C with different heating rate (10 °C/min, 100 °C/s) to produce bio-oil and selected chemicals with high yield. The pyrolytic oil yield was in the range of 46–73.5 wt% depending on the temperature, the heating rate and the amount of catalyst. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil (84 wt%). The blending cellulose with increasing amount of montmorillonite K10 results in significant, linear decrease in bio-oil yield. The great influence of montmorillonite K10 amount on the distribution of bio-oil components was observed at 450 °C with a heating rate of 100 °C/s. The addition of catalyst to cellulose promotes the formation of 2-furfural (FF), various furan derivatives, levoglucosenone (LGO) and (1R,5S)-1-hydroxy-3,6-dioxabicyclo-[3.2.1]octan-2-one (LAC). Simultaneously, the share of levoglucosan (LG) in bio-oil decreases from 6.92 wt% and is less than 1 wt% when cellulose:MK10 (1:1, w/w) mixture at 450 °C is rapidly pyrolyzed. Additionally, several other compounds have been identified but in minor quantities. Their contributions in bio-oil also depend on the amount of catalyst.     

Catalytic effects of copper(II) chloride and aluminum chloride on the pyrolytic behavior of cellulose

The cellulose without and with catalyst (CuCl₂, AlCl₃) was subjected to pyrolysis at temperatures from 350 to 500 °C with different heating rate (10 °C/min, 100 °C/s) to produce bio-oil and selected chemicals with high yield. The pyrolytic oil yield was in the range of 37–84 wt% depending on the temperature, the heating rate and the amount of metal chloride. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil. The mixing cellulose with both metal chlorides results with a significant decrease of the liquid product. The non-catalytic pyrolysis of cellulose gives the highest mass yield of levoglucosan (up to 11.69 wt%). The great influence of metal chloride amount on the distribution of bio-oil components was observed. The copper(II) chloride and aluminum chloride addition to cellulose clearly promotes the formation of levoglucosenone (up to 3.61 wt%), 1,4:3,6-dianhydro-α-d-glucopyranose (up to 3.37 wt%) and unidentified dianhydrosugar (MW = 144; up to 1.64 wt%). Additionally, several other compounds have been identified but in minor quantities. Based on the results of the GC–MS, the effect of pyrolysis process conditions on the productivity of selected chemicals was discussed. These results allowed to create a general model of reactions during the catalytic pyrolysis of cellulose in the presence of copper(II) chloride and aluminum chloride.     

Pyrolysis of cohesive meat and bone meal in a bubbling fluidized bed with an intermittent solid slug feeder

Meat and bone meal (MBM) is a mass-produced by-product of the meat rendering industry. It has great potential as a feedstock for the production of bio-fuels. Meat and bone meal, however, is a highly cohesive and temperature sensitive material and has traditionally been found to be very difficult, if not impossible, to feed properly into pyrolysis reactors or bubbling fluidized beds. This study showcases an application of the ICFAR intermittent solid slug feeder technology and its capability of successfully feeding the MBM regularly at an average feeding rate of 0.34 g/s into the reactor.A highly automated and instrumented fast pyrolysis pilot plant has been used to process meat and bone meal residues and to operate within a wide range of temperatures (450–600 °C). This is the first study dealing with the pyrolysis of pure meat and bone meal at various operating conditions continuously fed into a laboratory-scale fluidized bed reactor. All liquid and solid products have been analyzed (yields, HHV, GC–MS, elemental analysis, and ash mineral analysis). The homogenous bio-oil produced is an attractive fuel with a significant high heating value (HHV) of 31.5 MJ/kg and an average liquid yield of 43 wt% at 550 °C. The highest water-free HHV (36.7 MJ/kg) was found at 500 °C, with a liquid yield of 35 wt% at this temperature. The optimized pyrolysis temperature, at which the heat from the gas combustion can provide the heat required for processing MBM, while maximizing the bio-oil liquid yield and process energy yield, is 550 °C. Under these conditions, the pyrolysis process energy yield is 91%.The study also demonstrates a new technique to accurately determine the heat of pyrolysis reaction energy required by the process, using a non-invasive water calibration method.     

Pyrolysis of sweet orange (Citrus sinensis) dry peel

Three different products were obtained from the pyrolysis of dry peel sweet orange: bio-oil, char and non-condensable gases. The yield of each product was determined. The bio-oil was characterized by GC–MS to determine that can be used as a renewable source of valuable industrial chemicals or as a source of energy, high heating value was calculated by Channiwala and Parikh correlation based on Dulong's Formula.Thermogravimetric analysis at 1, 5, 10, 20, and 40 °C/min, shows three different overlapped steps resulting in an average mass loss of ∼80% within the temperature range of 114–569 °C. The bench scale pyrolysis experiments, produces average yields of 53.1, 21.1 and 25.8 wt.% for bio-oil, char and gases, respectively. Bio-oil characterization by GC–MS and FTIR identified limonene as its main component while other identified compounds included δ-limonene, alcohols, phenols, benzene, toluene, xylene and carboxylic acids.     

The effects of temperature on product yields and composition of bio-oils in hydropyrolysis of rice husk using nickel-loaded brown coal char catalyst

Hydropyrolysis of rice husk was performed using nickel-loaded Loy Yang brown coal char (Ni/LY) catalyst in a fluidized bed reactor at 500, 550, 600 and 650 °C with an aim to study the influence of catalyst and catalytic hydropyrolysis temperature on product yields and the composition of bio-oil. An inexpensive Ni/LY char was prepared by the ion-exchange method with nickel loading rate of 9 ± 1 wt.%. Nickel particles which dispersed well in Loy Yang brown coal char showed a large specific surface area of Ni/LY char of 350 m²/g. The effects of catalytic activity and hydropyrolysis temperature of rice husk using Ni/LY char were examined at the optimal condition for bio-oil yield (i.e., pyrolysis temperature 500 °C, static bed height 5 cm, and gas flow rate 2 L/min without catalyst). In the presence of catalyst, the oxygen content of bio-oil decreased by about 16% compared with that of non-catalyst. Raising the temperature from 500 to 650 °C reduced the oxygen content of bio-oil from 27.50% to 21.50%. Bio-oil yields decreased while gas yields and water content increased with increasing temperature due to more oxygen being converted into H₂O, CO₂, and CO. The decreasing of the oxygen content contributed to a remarkable increase in the heating value of bio-oil. The characteristics of bio-oil were analyzed by Karl Fischer, GC/MS, GPC, FT-IR, and CHN elemental analysis. The result indicated that the hydropyrolysis of rice husk using Ni/LY char at high temperature can be used to improved the quality of bio-oil to level suitable for a potential liquid fuel and chemical feedstock.     

Syngas Production from Lignite Coal Using K2CO3 Catalytic Steam Gasification with Controlled Heating Rate in Pyrolysis Step

Gasification uses steam increases H2 content in the syngas. Kinetics of gasification process can be improved by using K₂CO₃ catalyst. Controlled heating rate in pyrolysis step determines the pore size of charcoal that affects yield gas and H₂ and CO content in the syngas. In previous research, pyrolisis step was performed without considering heating rate in pyrolysis step. This experiment was performed by catalytic steam gasification using lignite char from pyrolysis with controlled heating rate intended to produce maximum yield of syngas with mole ratio of H₂/CO ≈ 2. Slow heating rate (3 °C/min) until 850 °C in the pyrolysis step has resulted in largest surface area of char. This study was performed by feeding Indonesian lignite char particles and K₂CO₃ catalyst into a fixed bed reactor with variation of steam/char mole ratio (2.2; 2.9; 4.0) and gasification temperature (750 °C, 825 °C, and 900 °C). Highest ratio of H₂/CO (1.682) was obtained at 750 °C and steam/char ratio 2.2. Largest gas yield obtained from this study was 0.504 mol/g of char at 900 °C and steam/char ratio 2.9. Optimum condition for syngas production was at 750 °C and steam/char mole ratio 2.2 with gas yield 0.353 mol/g of char and H₂/CO ratio 1.682.     

Pyrolysis of textile wastes: I. Kinetics and yields

Thermal behavior of textile waste was studied by thermogravimetry at different heating rates and also by semi-batch pyrolysis. It was shown that the onset temperature of mass loss is within 104–156 °C and the final reaction temperature is within 423–500 °C. The average mass loss is 89.5%. There are three DTG peaks located at the temperature ranges of 135–309, 276–394 and 374–500 °C, respectively. The first two might be associated with either with decomposition of the hemicellulose and cellulose or with different processes of cellulose decomposition. The third peak is possibly associated to a synthetic polymer. At a temperature of 460 °C, the expected amount of volatiles of this waste is within 85–89%. The kinetic parameters of the individual degradation processes were determined by using a parallel model. Their dependence on the heating rate was also established. The pyrolysis rate is considered as the sum of the three reaction rates. The pyrolysis in a batch reactor at 700 °C and nitrogen flow of 60 ml/min produces 72 wt.% of oil, 13.5 wt.% of gas and 12.5 wt.% of char. The kinetic parameters of the first peak do not vary with heating rate, while those of the second and the third peak increase and decrease, respectively, with an increasing heating rate, proving the existence of complex reaction mechanisms for both cases.     

Scale-up of microwave heating process for the production of bio-oil from sewage sludge

A pilot-scale microwave heating apparatus was constructed for the production of bio-oil from sewage sludge, and the effects of important microwave processing parameters and chemical additives on the quality and yield of bio-oils were investigated. It was found that bio-oil was mainly formed at the pyrolysis temperature range of 200–400 °C. A higher heating rate (faster pyrolysis) not only increased the yield of bio-oil, but also improved the quality of bio-oil according to the elemental composition and calorific values. The maximum bio-oil yield was 30.4% of organic fraction, obtained from the pyrolysis of original sewage sludge at microwave radiation power of 8.8 kW and final pyrolysis temperature of 500 °C. All of five simple additives (KOH, H₂SO₄, H₃BO₃, ZnCl₂, and FeSO₄) reduced the bio-oil yield, but the composition and property of bio-oil varied with the additive types greatly. KOH, H₂SO₄, H₃BO₃ and FeSO₄ were found to improve the quality of bio-oils remarkably according to the calorific value, density, viscosity and carbon content of bio-oils, but ZnCl₂ treatment went against that. GC–MS analysis of the bio-oils showed that, alkali treatment promoted the formation of alkanes and monoaromatics, while acid treatment favored the formation of heterocyclics, ketones, alcohols and nitriles. Compared with sulfate slat FeSO₄, chloride salt ZnCl₂ was a better catalyst for selective catalytic pyrolysis of sewage sludge. The addition of ZnCl₂ only promoted the formation reactions of a few kinds of nitriles and ketones remarkably. It is technologically feasible to produce bio-oil form microwave-induced pyrolysis of sewage sludge by optimizing pyrolysis conditions and selecting appropriate additives.     

Study of products yield of bagasse and sawdust via slow pyrolysis and iron-catalyze

In this paper, the via slow pyrolysis behavior of the bagasse and sawdust were studied at the different heating rates, the different iron-containing blend pyrolysis and the treatment temperature, the further understood for the pyrolysis of agricultural residues. The distribution of the products yield of the slow pyrolysis process, it is typically performed at temperature between 200 and 600 °C, the pyrolysis temperature increased, the bio-liquids and gas yields tended to increase, which at 400 °C was able to achieve maximum bio-liquids yields, the biochar yields tended to downward. For different heating rate, in the heating rate ranges for 80–100 W, the bio-liquids products yield curve increased from 44.5 wt% to 46.5 wt% for bagasse; the sawdust products yield increased from 41 wt% to 42.75 wt%. Iron-catalysts blend pyrolysis (0, 10, 25, 40 and 50 wt%), the bagasse bio-liquid yields respectively 56.25 wt% in the presence 50% iron-catalysts blend pyrolysis; the sawdust bio-liquid yields respectively 52.5 wt% in the presence 40% iron-catalysts blend. The pyrolysis process were calculated according to the kinetic mechanism were examined, the pyrolysis activation energy was between 6.55 and 7.49 kcal/mol for bagasse. Sawdust the pyrolysis activation energy was between 11.52 and 11.76 kcal/mol. Therefore, in this study a pyrolysis model of bagasse and sawdust thermal treatment may provide both agricultural and forestry transformation importance of resources.     

Bio-oil from fast pyrolysis of rice husk: Yields and related properties and improvement of the pyrolysis system

Rice husk was fast pyrolysed at temperatures between 420 °C and 540 °C in a fluidized bed, and the main product of bio-oil is obtained. The experimental result shows that the highest bio-oil yield of 56 wt% was obtained at 465 °C for rice husk. Chemical composition of bio-oil acquired was analyzed by GC–MS and its heat value, stability, miscibility and corrosion characteristics were determined. These results showed that bio-oil obtained can be directly used as a fuel oil for combustion in a boiler or a furnace without any upgrading. Alternatively, the fuel can be refined to be used by vehicles. Furthermore, the energy performance of the pyrolysis process was analyzed.     

Evaluation of the porous structure development of chars from pyrolysis of rice straw: Effects of pyrolysis temperature and heating rate

The effects of pyrolysis temperature and heating rate on the porous structure characteristics of rice straw chars were investigated. The pyrolysis was done at atmospheric pressure and at temperatures ranging from 600 to 1000 °C under low heating rate (LHR) and high heating rates (HHR) conditions. The chars were characterized by ultimate analysis, field emission scanning electron microscope (FESEM), helium density measurement and N₂ physisorption method. The results showed that temperature had obvious influence on the char porous characteristics. The char yield decreased by approximately 16% with increasing temperature from 600 to 1000 °C. The carbon structure shrinkage and pore narrowing occurred above 600 °C. The shrinkage of carbon skeleton increased by more than 22% with temperatures rising from 600 to 1000 °C. At HHR condition, progressive increases in porosity development with increasing pyrolysis temperature occurred, whereas a maximum porosity development appeared at 900 °C. The total surface area (S_total) and micropore surface area (S_micro) reached maximum values of 30.94 and 21.81 m²/g at 900 °C and decreased slightly at higher temperatures. The influence of heating rate on S_total and S_micro was less significant than that of pyrolysis temperature. The pore surface fractal dimension and average pore diameter showed a good linear relationship.     

Production of bio-oil via fast pyrolysis of agricultural residues from cassava plantations in a fluidised-bed reactor with a hot vapour filtration unit

This article reports experimental results on fast pyrolysis of agricultural residues from cassava plantations, namely cassava rhizome (CR) and cassava stalk (CS), in a fluidised-bed fast pyrolysis reactor unit incorporated with a hot vapour filter. The objective of this research was to investigate the effects of reaction temperatures, biomass particle size and the use of simple hot vapour filtration on pyrolysis product yields and properties. Results showed that the optimum pyrolysis temperatures for CR and CS were 475 °C and 469 °C, which gave maximum bio-oil yields of 69.1 wt% and 61.4 wt% on dry biomass basis, respectively. The optimum particle size for bio-oil production in this study was 250–425 μm. The use of the hot filter led to a reduction of 6–7 wt% of bio-oil yield. Nevertheless, the filtered bio-oils appeared to have a better quality in terms of initial viscosity, solids content, ash content and stability.     

Pyrolysis of wood impregnated with phosphoric acid for the production of activated carbon: Kinetics and porosity development studies

The pyrolysis of impregnated wood for the production of activated carbon is investigated. Laboratory experiments are performed in a TG for heating rates of 10 °C/min and 20 °C/min and a mathematical model for the kinetics of the pyrolysis process is developed and validated. The effect of the temperature and of the time duration of the pyrolysis process on the specific surface of the activated carbon is examined on the basis of experiments conducted in a crossed bed reactor. Results indicate that the temperature and the residence time in the pyrolysis reactor may be optimised. Indeed, it is found that the maximum specific surface of the end product is obtained for pyrolysis processes conducted at a temperature of 400 °C for a time period of 1 h.     

Pyrolysis of biocollagenic wastes of vegetable tanning. Optimization and kinetic study

Three solid wastes generated from the vegetable tanning of bovine skin in the Leather Industry (shavings, trimmings and buffing dust) were mixed together in the same proportions in which they were produced and the mixture was then used as a pyrolysis precursor for this research study. The optimal pyrolysis conditions for obtaining energy from the generated fractions (char, tar and gas fraction), and the preparation of activated carbons from the carbonaceous material (char), were established. The final conditions were chosen from two different points of view, the thermogravimetric results (TG/DTG) obtained at different heating rates (2–20 °C/min) and an optimization of the pyrolysis parameters by means of experiments carried out in a conventional furnace. The pyrolysis conditions finally selected were: heating rate (5 °C/min), final temperature (750 °C), and time at final temperature (60 min) and inert gas flow (N₂ 150 ml/min). The carbonaceous material (char) obtained exhibits good properties as a solid fuel due to its high calorific value and relatively low ash content. It also shows suitable characteristics as a precursor for the preparation of activated carbons. The condensable fraction has a predominantly phenolic nature and contains significant amounts of nitrogen compounds (nitriles, diketopiperazines, etc.), alkanes, alkenes, acids and esters, derived from the decomposition of tannins and collagen, with possible industrial applications in the preparation of chemical products. The gaseous phase is rich in carbon monoxide and carbon dioxide, and also contains a certain amount of methane and hydrogen. The syngas content increases with the pyrolysis temperature. A kinetic study of the pyrolysis was carried out using a model of independent reactions. The variation in the heating rate produced a slight shift to higher temperatures of the decomposition peaks, although this did not significantly affect either the kinetic parameters of the degradation processes or the percentage weight losses.     

Micro-pyrolysis of technical lignins in a new modular rig and product analysis by GC–MS/FID and GC × GC–TOFMS/FID

A new offline-pyrolysis rig has been designed to allow multifunctional experiments for preparative and analytical purposes. The system conditions can be set and monitored, e.g. temperature, its gradients and heat flux. Some special features include (1) high heating rates up to 120 °C/s with pyrolysis temperatures up to 850 °C at variable pyrolysis times and (2) the selection of different atmospheres during pyrolysis. A complete mass balance of products and reactants (gas, liquids and solids) by gravimetric methods and sequential chromatographic analyses was obtained.The pyrolytic behaviour and the decomposition products of lignin-related compounds were studied under different conditions: heating rates (from 2.6 °C/s up to 120 °C/s), pyrolysis temperatures at 500 °C and 800 °C in different atmospheres (N₂, H₂, and mixtures of N₂ and acetylene). Kraft lignin, soda lignin, organosolv lignin, pyrolytic lignin from pine bio-oil, residues from biomass hydrolysis and fermentation were studied.The obtained pyrolysis products were classified into three general groups: coke, liquid phase and gas phase (volatile organic compounds (VOC) and permanent gases). The liquid fraction was analysed by GC–MS/FID. In addition, comprehensive two-dimensional GC was applied to further characterise the liquid fraction. VOCs were semi-quantified by a modified headspace technique using GC–MS/FID analysis. The micro-pyrolysis rig proved to be an efficient and useful device for complex pyrolysis applications.     

Upgrading of woody biomass by torrefaction under pressure

In this study, the upgrading by torrefaction of leucaena, woody biomass, at 200–250 °C under volumetric pressure up to 4 MPa was examined. It was found that the yield of torrefied leucaena decreased with the increase in torrefaction temperature, whereas at the same temperature the yield of torrefied leucaena increased with the increase in torrefaction pressure. From the elemental analyses, the higher carbon content in torrefied leucaena can be achieved by the rising of torrefaction pressure. As large as 92.6% of carbon was recovered in the torrefied leucaena prepared at 250 °C and 4 MPa. On the other hand, the oxygen content decreased to 31.1% for the leucaena torrefied at 250 °C and 4 MPa. The higher heating value (HHV) of leucaena torrefied at high pressure increased significantly when compared to that of leucaena torrefied at atmospheric pressure. As large as 94.3% of energy yield was achieved with the mass yield of 74.4% for the torrefaction at 250 °C and 4 MPa. From the subsequent pyrolysis and combustion in TGA, leucaena torrefied under pressure showed the difference of weight decreasing curves comparing to that of leucaena torrefied at atmospheric pressure. It was found that the weight of leucaena torrefied at high pressure started to decrease at temperature lower than 200 °C. The char yield at 800 °C for the leucaena torrefied at high pressure increased with the increase in torrefaction pressure. These results suggested that the structure of leucaena was changed by the torrefaction under pressure and the cross-linking reactions during the pyrolysis were enhanced by the pressure during the torrefaction resulting in increase in char yields. The substantial increase in char combustion rate was also found for leucaena torrefied under pressure.     

Study of cellulose pyrolysis using an in situ visualization technique and thermogravimetric analyzer

A technique has been developed to study cellulose pyrolysis by in situ visualization of cellulose transformation in a quartz capillary under a microscope using a CCD camera monitoring system and Raman spectroscopy. The processes and temperature of cellulose transformation during pyrolysis reaction can be observed directly. In situ visualization of reaction revealed that how oil is generated and expulsed concurrently from cellulose during pyrolysis. The in situ visualization result is the first direct evidence to show cellulose pyrolysis transformation. Pyrolysis characteristics were investigated under a highly purified N₂ atmosphere using a thermogravimetric analyzer from room temperature to 500 °C at the heating rate of 5 °C/min. The results showed that three stages appeared in this thermal degradation process. Kinetic parameters in terms of apparent activation energy and pre-exponential factor were determined.     

Thermal degradation of heavy pyrolytic oil in a batch and continuous reaction system

Degradation of heavy pyrolytic oil obtained from a commercial rotary kiln pyrolysis plant for municipal plastic waste was conducted in batch and continuous reaction systems. The experiment was conducted by temperature programming with a 10 °C/min heating rate up to 450 °C and then maintained for a specific time at 450 °C. The product oil was sampled at different degradation temperatures with a specific interval of elapsed time of reaction. In this study, the characteristics of product oil obtained in both batch and continuous reaction systems were compared, according to degradation temperature and elapsed time at 450 °C. Raw pyrolytic oil showed a wide boiling point distribution from around 10 carbon number to about 35 and a high heating value, relative to of those of commercial oils (gasoline, kerosene, and diesel). In the two reaction systems, the characteristics of product oils were influenced by degradation temperature and elapsed time. Moreover, heavy hydrocarbons showed greater cracking at high degradation temperature and long elapsed time into light hydrocarbons as gasoline components range. Also, the continuous reaction system showed different characteristics of product oil, compared with those of the batch reaction system, such as the cumulative amount distribution, production rate, and carbon number distribution of the product oil, as a function of degradation temperature and elapsed time.     

Hydrogen production by catalytic steam reforming of acetic acid,a model compound of biomass pyrolysis liquids

An environmentally friendly and cost-competitive way of producing hydrogen is the catalytic steam reforming of biomass pyrolysis liquids, known as bio-oil, which can be separated into two fractions: ligninic and aqueous. Acetic acid has been identified as one of the major organic acids present in the latter, and catalytic steam reforming has been studied for this model compound. Three different Ni coprecipitated catalysts have been prepared with varying nickel content (23, 28 and 33% expressed as a Ni/(Ni + Al) relative at.% of nickel). Several parameters have been analysed using a microscale fixed-bed facility: the effect of the catalyst reduction time, the reaction temperature, the catalyst weight/acetic acid flow rate (W/m_HAc) ratio, and the effect of the nickel content. The catalyst with 33% Ni content at 650 °C showed no significant enhancement of the hydrogen yield after 2 h of reduction compared to 1 h under the same experimental conditions. Its performance was poorer when reduced for just 0.5 h. For W/m_HAc ratios greater than 2.29 g catalyst min/g acetic acid (650 °C, 33% Ni content) no improvement was observed, whereas for values lower than 2.18 g catalyst min/g acetic acid a decrease in product gas yields occurred rapidly. The temperatures studied were 550, 650 and 750 °C. No decrease in product gas yields was observed at 750 °C under the established experimental conditions. Below this temperature, the aforementioned decrease became more important with decreasing temperatures. The catalyst with 28% Ni content performed better than the other two.     

The Characteristics of Green Calcium Oxide Derived from Aquatic Materials

Thermogravimetric Analysis of three aquatic materials, i.e. cuttlebone, mussel shell and oyster shell, and other physicochemical characteristics were investigated. The highest decomposition rates of aquatic materials under two surrounding gases, i.e. oxygen and nitrogen, exhibited no significant difference for cuttlebone (3.6×10^-5-4.8×10^-5 mg s^-1 mg_initial^-1 at heating rate 5 °C/min and 11.8 ×10^-5 -12.5×10^-5 mg s^-1 mg_initial^-1 at heating rate 15 °C/min) and mussel shell (3.4×10^-5- 5.2×10^-5 mg s^-1 mg_initial^-1 at heating rate 5 °C/min and 11.9×10^-5 – 12.4×10^-5 mg s^-1 mg_initial^-1 at heating rate 15 °C/min), while oyster shell provided the higher decomposition rate under nitrogen surrounding gas (7.6×10^-4 mg s^-1 mg_initial^-1 at heat rate 5 °C/min and 21.53×10^-4 mg s^-1 mg_initial^-1 at heating rate 15 °C/min). This is probably because of the difference in their starting crystalline structures, i.e. aragonite (cuttlebone and mussel shell) and calcite (oyster shell). The cubic calcium oxides were prepared by calcination of three aquatic materials under oxygen and nitrogen surrounding gases at 5 °C/min ramping to 850 °C for 2 hours. All resulting calcium oxides obtained from oxygen atmosphere provided only cubic crystalline phases and the adsorption-desorption isotherms (IUPAC Type III), whereas the calcinations under nitrogen surrounding gas gave a presence of calcium hydroxide crystalline or hydroxyl- contaminate existing with cubic calcium oxide that influences on the strength and the number of carbon dioxide adsorption sites. The specific surface area of all resulting calcium oxides ranged from 0.1 – 1.5 m²/g and the average pore diameter was found in the range of 40-60 nm. The the number of basic sites belonging to CaO derived from Oyster shell or Cuttlebone were improved while firing under oxygen atmosphere. The suitable firing condition is at the low heating rate to develop porous materials.