Levent Ballice

Application of infrared spectroscopy to the classification of kerogen types and the thermogravimetrically derived pyrolysis kinetics of oil shales

In this study, the kerogen types of Goynuk, Beypazari oil shale from Turkey and Timahdit oil shale from Morocco were defined by infrared spectroscopy. Aliphatic, carboxyl/carbonyl and aromatic compounds were considered in order to classify the kerogen types. The IR-analysis result shows that the samples can be classified in kerogen evaluation path I for Goynuk, Timahdit oil shales and path II for Beypazari oil shale. The kinetics of thermal decomposition of Goynuk, Beypazari and Timahdit oil shales have been studied by non-isothermal thermogravimetry (TG). The weight loss data have been analyzed by Coats-Redfern and Chen-Nuttall combinations. The kinetic parameters for the decomposition of the samples were determined and discussed.

Classification of volatile products evolved during temperature-programmed co-pyrolysis of Turkish oil shales with low density polyethylene

Temperature programmed co-pyrolysis of Turkish oil shales with LDPE was investigated. The aim of this research was to determine the volatile product distribution and product evolution rate of coprocessing of oil shale with LDPE. A series co-pyrolysis operation was performed with oil shale and LDPE using a 1:3, 1:1, 3:1 total carbon ratio of oil shale to plastic. A fixed bed reactor was used to pyrolyse small sample of oil shale and LDPE mixture under an inert gas flow (Argon). A special sampling technique was used for collecting organic products eluted from the reactor at different temperature and time intervals. The co-pyrolysis products were analyzed by capillary gas chromatography and the total product evolution rate was investigated as a function of temperature and time. n-Paraffins and 1-olefins in aliphatic fraction of pyrolysis products were classified as a carbon number. In addition, the recovery of total organic carbon as a organic volatile products was determined. The assessments were based on incorporating the results on temperature-programmed pyrolysis of oil shale1,2 and LDPE. The effect of coprocessing of oil shale with LDPE was determined by calculating the difference between the experimental and the hypothetical mean value of conversion of total organic carbon into volatile products. The effect of kerogen type of oil shale on co-pyrolysis operation was also investigated. Conversion into volatile hydrocarbons was found lower with increasing LDPE ratio in oil shale-LDPE system while C16+ hydrocarbons and the amount of coke deposit were higher in the presence of LDPE.

Evolution of volatile products from oil shales by temperature-programmed pyrolysis

Temperature-programmed pyrolysis of Beypazari (Turkey) and Timahdit (Morocco) oil shales was investigated. The maximum product evolution temperatures were determined for each sample. n-Paraffins and 1-olefins in the pyrolysis products were classified by carbon number. The effect of kerogen types on the distribution of n-paraffins and 1-olefins was also investigated.

A kinetic approach to the temperature-programmed pyrolysis of low- and high-density polyethylene in a fixed bed reactor: determination of kinetic parameters for the evolution of n-paraffins and 1-olefins

Abstract The thermal degradation of both low-density polyethylene (LDPE) and high-density polyethylene (HDPE) have been investigated under non-isothermal conditions. The weight loss data have been analyzed by Flynn and Wall methods. The activation energies for overall degradation of LDPE and HDPE were determined. In addition, the recovery of carbon as 1-olefins and n -paraffins was determined by temperature-programmed pyrolysis of polyethylene. A fixed bed reactor under argon flow was used to pyrolyze small samples of LDPE and HDPE. A special gas-phase sampling technique was used to determine the composition of products eluted from the reactor as a function of temperature and time. Hydrocarbon evolution data have been analyzed by Coats–Redfern and Chen–Nuttall combinations. It must be emphasized that the evaluation of temperature-programmed pyrolysis data by combined use of Coats–Redfern and Chen–Nuttall methods provide satisfactory mathematical approaches to obtain kinetic parameters for 1-olefin and n -paraffins formation from degradation of polyethylene. Using this method, it is possible to identify every stage of pyrolysis and derive values for kinetic parameters.

Classification of volatile products evolved during temperature-programmed co-pyrolysis of low-density polyethylene (LDPE) with polypropylene (PP) ☆

Temperature programmed co-pyrolysis of low-density polyethylene (LDPE) with polypropylene (PP) was investigated. The aim of this research was to determine the volatile product distribution and product evolution rate of co-processing of LDPE with PP. A series co-pyrolysis operation was performed with LDPE and PP using a 1:3, 1:1, 3:1 total carbon ratio of LDPE to PP. A fixed bed reactor was used to pyrolyse small sample of LDPE and PP mixture under an inert gas flow (argon). A special sampling technique was used for collecting organic products eluted from the reactor at different temperature and time intervals. The co-pyrolysis products were analyzed by capillary gas chromatography and the total product evolution rate was investigated as a function of temperature and time. n-paraffins and 1-olefins in aliphatic fraction of co-pyrolysis products were classified as a carbon number. In addition, the recovery of total organic carbon as an organic volatile product was determined. The assessments were based on incorporating the results on temperature-programmed pyrolysis of LDPE and PP. The effect of co-processing of LDPE with PP was determined by calculating the difference between the experimental and the hypothetical mean value of conversion of total organic carbon into volatile products. Conversion into volatile hydrocarbons was found to be higher, with the increasing PP ratio in the co-pyrolysis operation.

Evolution of volatile products from Göynük (Turkey) oil shales by temperature-programmed pyrolysis

A fixed-bed reactor was used to pyrolyse small samples of oil shale particles under an inert gas flow (argon). A special sampling technique was used for collecting organic products eluted from the reactor at different temperatures and time intervals. The pyrolysis products were analysed by capillary gas chromatography and the total product evolution rate was investigated as a function of temperature and time. The maximum volatile product evolution temperature was ∼440°C. The aliphatic hydrocarbon content of the pyrolysis products was characterized and classified by carbon number. In addition, the performance of the experimental system was assessed by a carbon balance. The recovery of total organic carbon as organic volatile products, CO2 and coke was determined.

Solvent swelling studies of Göynük (Kerogen Type-I) and Beypazarı oil shales (Kerogen Type-II)☆☆

Abstract The volumetric swelling procedure was applied to Goynuk and Beypazari oil shales from Turkey by using 10 solvents and the cross-linking in the macromolecular network of oil shales were investigated using this technique. Results from solvent swelling measurements show that the volumetric solvent swelling of oil shales samples roughly follows the regular solution theory. The theory of solvent swelling of cross-linked polymers developed Flory–Rehner and extension of this theory by Kovac–Peppas was used to calculate number average molecular weight per cross-link of kerogen structure ( M c ) in oil shale samples. Results indicate no remarkable difference between M c values for Goynuk oil shale (Kerogen Type I) and Beypazari oil shale (Kerogen Type II).

Temperature-programmed co-pyrolysis of Turkish lignite with polypropylene

Abstract Temperature-programmed co-pyrolysis of Soma-lignites form Turkey with polypropylene (PP) was investigated. The aim of this research was to determine the volatile product distribution and product evolution rate of co-processing of Soma-lignites with PP. A series co-pyrolysis operation was performed with lignites and PP using a 1:3, 1:1, 3:1 total carbon ratio of lignites to plastic. A fixed bed reactor was used to pyrolyse small sample of lignites and PP mixture under an inert gas flow (argon). A special sampling technique was used for collecting organic products released from the reactor at different temperature and time intervals. The co-pyrolysis products were analyzed by capillary gas chromatography and the total product evolution rate was investigated as a function of temperature and time. n -Paraffins and 1-olefins in aliphatic fraction of co-pyrolysis products were classified by a carbon number. In addition, the performance of the experimental apparatus was investigated by establishing a carbon balance, and the degree of recovery of total organic carbon of the samples as aliphatic hydrocarbons and in solid residue was determined. The assessments were based on incorporating the results on temperature-programmed pyrolysis of lignites and PP. The effect of co-processing of lignites with PP was determined by calculating the difference between the experimental and the hypothetical mean value of conversion of total organic carbon into volatile products. Conversion into volatile hydrocarbons was found higher with increasing PP ratio in lignites–PP system while C 16+ hydrocarbons and the amount of coke deposit were lower in the presence of PP.

Co-pyrolysis of Göynük-oil shale and Şırnak-asphaltite from Turkey and analysis of co-pyrolysis products by capillary GC total stream sampling technique☆ ☆

Temperature-programmed co-pyrolysis of Goynuk-oil shale (GOS) with Şirnak-asphaltite (ASP) from Turkey was investigated. The aim of this research was to determine the volatile product distribution and product evolution rate of co-processing of GOS with ASP. A series co-pyrolysis operation was performed with GOS and ASP using a 1/2, 1/1, 2/1 total carbon ratio of GOS to ASP. A fixed-bed reactor was used to pyrolyse small sample of GOS and ASP mixture under an inert gas flow (Argon). A special sampling technique was used for collecting organic products eluted from the reactor at different temperature and time intervals. The co-pyrolysis products were analyzed by capillary gas chromatography and the total product evolution rate was investigated as a function of temperature and time. n-Paraffins and 1-olefins in aliphatic fraction of pyrolysis products were classified as a carbon number. In addition, the recovery of total organic carbon as an organic volatile product was determined. The assessments were based on incorporating the results on temperature-programmed pyrolysis of GOS and ASP. The effect of co-processing of GOS with ASP was determined by calculating the difference between the experimental and the hypothetical mean value of conversion of total organic carbon into volatile products.

Changes in the cross-link density of Goynuk oil shale (Turkey) on pyrolysis

Abstract The effect of temperature and heating rate on the cross-link density of char samples obtained by pyrolysing Goynuk oil shale was investigated using the volumetric solvent swelling technique. The cross-link density decreases slightly with increasing pyrolysis temperature. The heating rate and thus the pyrolysis time had at most a small effect on the cross-link density. Char–solvent interactions do not follow regular solution theory. The demineralized kerogen swells more than does the native kerogen (16% ash).