Xiangxin Han

Pyrolysis treatment of oil sludge and model-free kinetics analysis

Pyrolysis of tank bottom oil sludge was investigated to summarize the pyrolysis characteristics through analyzing the change of mass loss, pyrolysis gas compositions in heating process. For this propose, various approaches including thermogravimetric analysis (TGA), CNHS/O elemental analysis, electrically heated fixed bed quartz reactor coupled with Vario Plus emission monitoring system, and oil-gas evaluation workstation (OGE-II) equipped with a flame ionization detector (FID) were used. The pyrolysis reaction is significant in the range of 473-773 K where multi-peak DTG curves can be gained. Higher heating rate increases the carbon (C) and sulfur (S) contents but decreases hydrogen (H) content in solid residues. The major gaseous products excluding N(2) are CHs (Hydrocarbons), CO(2), H(2), CO. The yield of CHs is significant in the range of 600-723 K. Higher heating rate causes the peak intensity of CHs evolution to increase and the CHs evolution to move towards a high-temperature region. Around 80% of total organic carbon content (TOC) in oil sludge can be converted into CHs in pyrolysis process. The CHs data were used for kinetic analysis by Vyazovkin model-free iso-conversion approach. Dependences of the activation energy on the degree of conversion obtained from different methods were compared.

Co-firing of oil sludge with coal-water slurry in an industrial internal circulating fluidized bed boiler.

Incineration has been proven to be an alternative for disposal of sludge with its unique characteristics to minimize the volume and recover energy. In this paper, a new fluidized bed (FB) incineration system for treating oil sludge is presented. Co-firing of oil sludge with coal-water slurry (CWS) was investigated in the new incineration system to study combustion characteristics, gaseous pollutant emissions and ash management. The study results show the co-firing of oil sludge with CWS in FB has good operating characteristic. CWS as an auxiliary fuel can flexibly control the dense bed temperatures by adjusting its feeding rate. All emissions met the local environmental requirements. The CO emission was less than 1 ppm or essentially zero; the emissions of SO(2) and NO(x) were 120-220 and 120-160 mg/Nm(3), respectively. The heavy metal analyses of the bottom ash and the fly ash by ICP/AES show that the combustion ashes could be recycled as soil for farming.

Devolatilization of oil sludge in a lab-scale bubbling fluidized bed.

Devolatilization of oil sludge pellets was investigated in nitrogen and air atmosphere in a lab-scale bubbling fluidized bed (BFB). Devolatilization times were measured by the degree of completion of the evolution of the volatiles for individual oil sludge pellets in the 5-15 mm diameter range. The influences of pellet size, bed temperature and superficial fluidization velocity on devolatilization time were evaluated. The variation of devolatilization time with particle diameter was expressed by the correlation, τ(d) = Ad(p)(N). The devolatilization time to pellet diameter curve shows nearly a linear increase in nitrogen, whereas an exponential increase in air. No noticeable effect of superficial fluidization velocity on devolatilization time in air atmosphere was observed. The behavior of the sludge pellets in the BFB was also focused during combustion experiments, primary fragmentation (a micro-explosive combustion phenomenon) was observed for bigger pellets (>10mm) at high bed temperatures (>700 °C), which occurred towards the end of combustion and remarkably reduce the devolatilization time of the oil sludge pellet. The size analysis of bed materials and fly ash showed that entire ash particle was entrained or elutriated out of the BFB furnace due to the fragile structure of oil sludge ash particles.

Effects of retorting factors on combustion properties of shale char. 3. Distribution of residual organic matters

Shale char, formed in retort furnaces of oil shale, is classified as a dangerous waste containing several toxic compounds. In order to retort oil shale to produce shale oil as well as treat shale char efficiently and in an environmentally friendly way, a novel kind of comprehensive utilization system was developed to use oil shale for shale oil production, electricity generation (shale char fired) and the extensive application of oil shale ash. For exploring the combustion properties of shale char further, in this paper organic matters within shale chars obtained under different retorting conditions were extracted and identified using a gas chromatography-mass spectrometry (GC-MS) method. Subsequently, the effects of retorting factors, including retorting temperature, residence time, particle size and heating rate, were analyzed in detail. As a result, a retorting condition with a retorting temperature of 460-490 degrees C, residence time of <40 min and a middle particle size was recommended for both keeping nitrogenous organic matters and aromatic hydrocarbons in shale char and improving the yield and quality of shale oil. In addition, shale char obtained under such retorting condition can also be treated efficiently using a circulating fluidized bed technology with fractional combustion.

Mathematical model of oil shale particle combustion

At first this paper simply introduces the ignition mechanism and combustion characteristics of Huadian oil shale. Combustion behaviour was found to be homogeneous at the beginning of combustion, shifting to heterogeneous combustion in the high-temperature stage; combustible matter was noted to be volatile in the low-temperature stage, but in the high-temperature stage combustible matter included fixed carbon and residual volatile. On the basis of the combustion characteristics of Huadian oil shale, homogeneous and heterogeneous combustion processes of Huadian oil shale are modelled. In the mathematical models, conductive, convective and radiative heat transfer between particles and the surrounding atmosphere, pyrolytic heat and also the heat value of the volatiles are all included in the energy equations; inference of volatile release to particle density is also considered in the models. Thermogravimetric experimental data are used to validate the described models.

A TGA-MS INVESTIGATION OF THE EFFECT OF HEATING RATE AND MINERAL MATRIX ON THE PYROLYSIS OF KEROGEN IN OIL SHALE

A demineralized Dachengzi oil shale sample, p-kerogen, is obtained through hydrochloric & hydrofluoric (HCl&HF) treatment. Themogravimetric analysis combined with on-line mass spectrometry (TGAMS) tests on original oil shale and p-kerogen were carried out at two heating rates, 5 °C/min and 15 °C/min, to study the effect of heating rate and mineral matrix on the pyrolysis of kerogen in oil shale. In the pyrolysis products, the amounts of both the organic and inorganic gases generated are significant with the evolution of oil in the temperature range of 370–570 °C. Increasing the heating rate from 5 °C/min to 15 °C/min leads to the decrease of most of the small molecule products of interest in this research, which indicates that in the oil shale pyrolysis the secondary cracking reactions may be inhibited by such increase. With increasing heating rate the thermogravimetric (TG) curves shift to a higher temperature region with an increase of about 10 °C due to the temperature difference between the surface and the center of the sample particles. The amount of alkenes generated is higher than that of alkanes and the alkene/alkane ratio increases with heating rate. At the same heating rate, the amounts of both the inorganic and organic compounds generated in the oil shale pyrolysis are higher than those produced in the pkerogen pyrolysis, suggesting that mineral matrix has an obvious catalytic effect on the pyrolysis of kerogen. Hydrogen release is markedly strengthened in the oil evolution process because of the resultant effect of mineral matter which promotes the cracking reactions in the pyrolysis of kerogen. Compared with oil shale, the TG curves of p-kerogen shift to a lower temperature zone with a decrease of about 10 °C because the pore channels formed in the demineralization treatment intensify the heat and mass transfer in the sample particles.