Insight into the oxidative desulfurization of high-sulfur petroleum coke under mild conditions:a journey of vanadium-substituted Dawson-type phosphotungstic acid

High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.

Orientational Separation of Sulfur in Petroleum Coke by Alkali Calcining and Reflux Washing

The application of high-sulfur petroleum coke after desulfurization in aluminum electrolysis anodes is an important development trend. However, removing sulfur from high-sulfur petroleum coke is still a significant challenge.This study proposes alkali calcining and reflux washing to examine the impacts of temperature, particle size, the mass ratio of Na_(2)CO_(3) to NaOH, and total sodium addition on the desulfurization efficiency and mechanism. The results show that the desulfurization rate increases with increasing temperature, increasing total sodium content, and decreasing particle size. The addition of alkali can significantly reduce the opening-ring reaction temperature of thiophene and convert organic sulfur into inorganic sulfur(Na_(2)S). Three washing methods were compared, and reflux washing was selected to separate inorganic sulfur(Na_(2)S) from calcined petroleum coke. The sulfur content in petroleum coke decreased from 7.29% to 1.90%, with a desulfurization rate of 80.13% under optimal conditions. The petroleum coke was analyzed before and after desulfurization using X-Ray diffraction(XRD), Scanning Electron Microscopy(SEM), Infrared Spectroscopy(IR), Thermogravimetric Analysis and Differential Scanning Calorimetry(TG-DSC), Gaschromatography-mass Spectrometry(GC-MS). The results show that thiophene and benzothiophene in petroleum coke are decomposed and converted into octane and ethyl cyclohexane. These new observations are expected to provide further understanding and guidance for the utilization of highsulfur petroleum coke.

SO_2 emission characteristics from co-firing of petroleum coke and coal in circulating fluidized bed

Combustion and sulfur retention experiments of mixed fuel of petroleum cokeand coal were conducted on a pilot-scale circulating fluidized bed (CFB) combustor with the thermalinput of 0. 6 MW. The effects of several parameters, such as the primary air percentage, excess aircoefficient, bed temperature, Ca/S molar ratio and mass ratio of petroleum coke to coal on SO_2emission were verified. Experimental results show that when the ratio of petroleum coke to coal inthe mixed fuel increases, the SO_2emission increases. The maximum SO_2 emission appears when purecoke burns. The SO_2 concentration in flue gas reduces with the increase in the primary airpercentage, excess air coefficient and Ca/S molar ratio for all kinds of fuel mixtures. Therangebetween 830 t and 850 t is the optimal temperature for sulfur retention during co-firing ofpetroleum coke and coal with the mass ratio R of 1 and 3 in CFB.

Effect of heat treatment on structure and gasification reactivity of petroleum coke

Petroleum coke was thermally treated on a fixed bed reactor in a temperature range of 1173-1673 K. The changes of the elemental composition and crystalline structure of petroleum coke, with heat treatments as well as the gasification reactivity of the heat-treated petroleum cokes were investigated. The results showed that the petroleum coke was carbonized and grapbitized to a higher degree with increasing heating temperature, while the gasification reactivity decreased. The treatment at temperatures of 1173 and 1473 K significantly enlarged the specific surface area and the pore volume of petroleum coke. Both the specific surface area and the pore volume decreased at 1673 K. An empirical normal distribution function model （NDFM） was found to fit the gasification rates of petroleum coke well. The correlation coefficient of petroleum coke by normal distribution function model at different heat treatment temperatures is between 0.93 and 0.95.

Improving slurryability, rheology,and stability of slurry fuel from blending petroleum coke with lignite

Petroleum coke and lignite are two important fossil fuels that have not been widely used in China. Petroleum coke-lignite slurry （PCLS）, a mixture of petro- leum coke, lignite, water, and additives, efficiently utilizes the two materials. In this study, we investigate the effects of the proportion （7） of petroleum coke on slurryability, rheo- logical behavior, stability, and increasing temperature characteristics of PCLSs. The results show that the fixed- viscosity solid concentration （COo） increases with increasing 7. The ~Oo of lignite-water slurry （LWS, ~ = 0） is 46.7 %, compared to 71.3 % for the petroleum coke-water slurry （PCWS, c~ --- i00 %）, while that of PCLS is in between the two values. The rheological behavior of PCLS perfectly fits the power-law model. The PCWS acts as a dilatant fluid. As decreases, the slurry behaves first as an approximate Newtonian fluid, and then turns into a pseudo-plastic fluid that exhibits shear-thinning behavior. With increasing ct, the rigid sedimentation and water separation ratio （WSR） increase, indicating a decrease in the stability of PCLS. When α is 60-70 %, the result is a high-quality slurry fuel for industrial applications, which has high slurryability （ω0 = 57-60 %）, good stability （WSR 〈 2 %）, and superior pseudo-plastic behavior （n = 0.9）.

Effects of the physical and chemical properties of petroleum coke on its slurryability

In this study, the effects of particle size distribution （PSD）, chemical composition and pore structure of petroleum coke on the slurryability of petroleum coke water slurry （PCWS） were investigated. Four petroleum cokes were studied, and they showed completely different slurryability. The solid concentration at fixed viscosity （i.e. apparent viscosity of 1000 mPa） （SCFV） of four PCWSs is different from each other, with the highest value of 70.9%, and lowest of 62.1%. The apparent viscosity of the four PCWSs all increased with an increase of the solid concentration. The results showed that the PSD, inherent moisture content, specific surface area and pore volume of petroleum coke were key factors to affect the slurryability. The slurryability was enhanced with increasing PSD range and particle packing fraction, and with decreasing inherent moisture content, specific surface area and pore volume.

Effects of pH on rheological characteristics and stability of petroleum coke water slurry

In this study, the effects of pH on slurrying properties of petroleum coke water slurry（PCWS） were investigated. The slurrying concentration, rheological characteristics and stability of PCWS were studied with four different types of additives at pH varying from 5 to 11.The results showed that the slurrying concentration, rheological characteristics and stability of PCWS all increased at first and then decreased with increasing pH from 5 to 11,and a pH of around 9 was found to be the most favorable acid–alkali environment to all these three slurrying properties. It was also indicated that only in a moderate alkaline environment can the additives be active enough to react with particle surfaces sufficiently to obtain good slurrying concentration and form a stable three-dimensional network structure, which can support strong pseudoplastic characteristics and good stability. An acid environment was a very unfavorable factor to the slurrying properties of PCWS.

Comparative evaluation for catalytic gasification of petroleum coke and asphaltene in subcritical and supercritical water

Subcritical and supercritical water gasification of petroleum coke and asphaltene was performed at variable temperatures(350–650°C),feed concentrations(15–30 wt%)and reaction times(15–60 min).Nickel-impregnated activated carbon(Ni/AC)was synthesized as a catalyst for enhancing syngas yields at optimal gasification conditions(650°C,15 wt%and 60 min).Structural chemistry of precursors and chars developed at different gasification temperatures was studied using physicochemical and synchrotronbased approaches such as carbon–hydrogen–nitrogen–sulfur(CHNS)analysis,thermogravimetric and differential thermogravimetric analysis(TGA/DTA),scanning electron microscopy(SEM),Fourier-Transform Infrared spectroscopy(FTIR),Raman spectroscopy,X-ray diffraction(XRD)and X-ray absorption spectroscopy(XAS).Asphaltene testified to be a better precursor for catalytic hydrothermal gasification leading to 11.97 mmol/g of total gas yield compared to petroleum coke(8.04 mmol/g).In particular,supercritical water gasification using 5 wt%Ni/AC at 650°C with 15 wt%feed concentration for 60 min resulted in 4.17 and 2.98 mmol/g of H_2from asphaltene and petroleum coke,respectively.Under the same conditions,the respective CH_4yields from catalytic gasification of asphaltene and petroleum coke were 2.54and 1.07 mmol/g.Nonetheless,asphaltene also seemed to an attractive feedstock for the production of highly aromatic chars through hydrothermal gasification.

Kinetics of petroleum coke/biomass blends during co-gasification

The co-gasification behavior and synergistic effect of petroleum coke, biomass, and their blends were studied by thermogravimetric analysis under CO2 atmosphere at different heating rates. The isoconversional method was used to calculate the activation energy. The results showed that the gasification process occurred in two stages： pyrolysis and char gasification. A synergistic effect was observed in the char gasification stage. This effect was caused by alkali and alkaline earth metals in the biomass ash. Kinetics analysis showed that the activation energy in the pyrolysis stage was less than that in the char gasification stage. In the char gasification stage, the activation energy was 129.1–177.8 k J/mol for petroleum coke, whereas it was 120.3–150.5 k J/mol for biomass. We also observed that the activation energy calculated by the Flynn–Wall–Ozawa（FWO） method were larger than those calculated by the Kissinger–Akahira–Sunosen（KAS） method. When the conversion was 1.0, the activation energy was 106.2 k J/mol when calculated by the KAS method, whereas it was 120.3 k J/mol when calculated by the FWO method.

Inherent relations between yield stress and stability of bubble petroleum coke water slurry

The stability of petroleum coke water slurry（PCWS） is currently a hot topic. The inherent relationship between yield stress and stability of bubble-PCWS was studied through orthogonal experiments and range analysis in this work. The results showed that the stability of bubble-PCWS was positively related to the yield stress and that the yield stress could be greatly impacted by the operation conditions during preparation of bubble-PCWS. The main factors affecting the yield stress of bubble-PCWS were solid concentration, aeration time and dosage of frother. However, the effects of aperture size of air distribution plates and type of frother on the yield stress were slight within the experimental range. The optimal conditions for the greatest yield stress were as follows： aeration time of 30 min, solid concentration of 65 wt%, frother dosage of0.030 wt% of the air-dried pulverized petroleum coke, aperture size of air distribution plate of 2-5 lm and AOS frother.The yield stress and the pour rate of bubble-PCWS under this optimum operation condition could reach maxima of more than 0.4 Pa and 96%, respectively.

Petroleum coke as reductant in co-reduction of low-grade laterite ore and red mud to prepare ferronickel: Reductant and reduction effects

Petroleum coke is industrial solid wastes and its disposal and storage has been a great challenge to the environment. In this study, petroleum coke was utilized as a novel co-reduction reductant of low-grade laterite ore and red mud. A ferronickel product of 1.98wt% nickel and 87.98wt% iron was obtained with 20wt% petroleum coke, when the roasting temperature and time was 1250°C and 60 min, respectively. The corresponding recoveries of nickel and total iron were 99.54wt% and 95.59wt%, respectively. Scanning electron microscopy-energy dis- persive spectrometry (SEM-EDS) analysis showed metallic nickel and iron mainly existed in the form of ferronickel particles which distrib- uted uniformly at a size of approximately 30 μm with high purity. This study demonstrated that petroleum coke is a promising reductant in the co-reduction of laterite ore and red mud. Compared to other alternatives, petroleum coke is advantageous with reduced production cost and high applicability in anthracite-deficient areas.

Optimizing Utilization of Petroleum Coke in Nigerian Metallurgical Industry

Utilization of petroleum coke in the rejuvenating Nigerian metallurgical industry is currently satisfied by importation from more industrialized nations of the world such as the USA, Brazil and Venezuela where delayed coking plants operate and grow in number. The sad years of poor planning have revealed lapses in integration and synergic planning of our industrial complex. The sources of petroleum coke feedstock have been identified and confirmed as atmospheric and vacuum residues of Nigerian refineries. Analysis has portrayed a symbiotic relationship between the metallurgical industry as one of the major end users of various petroleum coke grades, the shot coke, the sponge coke and the needle coke, and the petroleum industry on its part benefiting while providing ready market for steel sheet metals for even coke drum manufacture. This effort shall greatly increase the Nigerian content in these key industrial sectors, with the resultant reduction in capital flight through importation, if rethinking, and re-strategizing are injected into our industrial planning, and revamps models. Redesign options of existing refineries and reengineering of newly proposed refineries should contain resid processing units such as Delayed Coking Plant which will deepen conversion of residual petroleum feed stocks and produce various petroleum coke grades for utilization in power generation sector and our growing metallurgical and electrode industries.

Feasibility of Combustion of Petroleum Coke in 230t/h Circulating Fluidized Bed Boiler

In order to reuse the high sulfur petroleum coke, the waste in chemical industry, as fuel of power plant for energy recovery, the combustion property of petroleum coke was researched experimentally in circulating fluidized bed (CFB) boiler. The performance of the boiler in burning mixed fuel with different ratios of coal to petroleum coke is obtained. Based on the experimental data, Factors influencing the stability of combustion,thermal efficiency of boiler, and emissions and desulphurisation are discussed. This study demonstrates that the combustion of petroleum coke in CFB boiler is applicable, and has great significance on the design and operation of CFB boiler to burn petroleum coke.

Desulfurization of Petroleum Coke by Calcination in Ammonia Atmosphere below 1000℃

The desulfurization efficiency and mechanism of the calcination of petroleum coke in ammonia atmosphere at lower than 1000 ℃ were investigated through a series of conditional experiments and comparison with other gases such as H_2. The topics of efficiency and reaction mechanism are usually discussed through investigation by means of the Fourier transform infrared spectroscopy(FT-IR), the Brunauer-Emmett-Teller(BET) technique, and the thermogravimetry coupled with the mass spectrometry(TG-MS). Results showed that in addition to H_2, ammonia not only could retain a high desulfurization rate but could also reduce coke loss during the desulfurization process of petroleum coke. The best desulfurization conditions covered a petroleum coke particle size of less than 0.1 mm, a calcination temperature of 800 ℃ in ammonia atmosphere with a flow rate of 10 L/h, and a heating duration of more than 120 min. Ammonia decomposition, H_2 generation, decline in the activation energy of the carbon–sulfur bonds, and petroleum coke with a largest specific surface area at 800 ℃ are the key goals of desulfurization studied thereby. As proved by TG-MS analysis, given a large quantity of H_2, ammonia can be decomposed at the same temperature to completely come into contact with the sulfur species in petroleum coke to generate H_2S.

Synthesis of ZnS from organic sulfur in petroleum coke and its photocatalysis properties

Organic sulfur in high sulfur petroleum coke was treated as the S source for synthesis of ZnS photocatalyst. Experimental results showed that with ball milling and subsequent heating treatment, ZnS compound could be successfully synthesized and showed considerable photocatalysis activity for decomposing industrial pollutants. The concentration of methyl orange or ethylene blue may be lowered to less than 5% after being decomposed by the synthesized-ZnS photocatalysis. Results of this study suggested a potential technique of turning high sulfur petroleum cokes from industrial wastes into useful products for environment improvement.

Performances and emissions of a petroleum coke oil slurry engine

In order to solve the failure of fuel system when using petroleum coke oil slurry (PCOS) in a R180 diesel engine directly,a petroleum coke oil slurry fuel system (PCOSFS) was developed and installed in R180 engine,which was called PCOS engine.In order to analyze performances and emissions of the PCOS engine,a comparative experiment between PCOS engine fueled with PCOS and R180 engine fueled with diesel oil was carried out.The results show that the PCOS engine can run smoothly,the maximum output power decreases by about 6.2% and 19.0% and the maximum brake thermal efficiency reduces by around 5.85% and 4.13% as compared to R180 engine under the conditions of 1 200 and 1 600 r/min.The HC emissions of PCOS engine are lower than those of R180 engine at 1 200 r/min,and are close to those of R180 engine at 1 600 r/min.The CO emissions are similar to R180 engine at 1 200 and 1 600 r/min.The smoke intensity is close to R180 engine at 1 200 r/min,and is higher than R180 engine at 1 600 r/min.The particles emitted from PCOS engine array sparsely,but particles emitted from R180 engine array closely,cohering together.

The Economic Impacts of Restrictions on the Transportation of Petroleum Coke

Petroleum coke is the?third?leading refined petroleum product export from the US behind distillate fuel oil. Legal challenges and proposals could either increase the cost or restrict the transportation of petroleum coke. This paper develops an econometric model of world markets for refined petroleum markets to estimate the effects of such restrictions. The model is used to estimate how supply, demand, trade flows, and prices would adjust under a shutdown of US petroleum coke production. The market impacts are significant, withsubstantially higher prices for jet fuel and petroleum coke, significantly higher prices for gasoline and other products, and sharply lower prices for residual fuel oil. Over a four-year simulation of the model, the US petroleum trade balance deteriorates by $85 billion and consumers pay over $187 and $376 billion more for refined petroleum products in the US and the rest of the world respectively.

Evaluation of the Impact of the Handling and Storage System of Petroleum Coke on PM10 Emissions in an Oil Refinery

The objective of this study was to identify the impact of the coke handling and storage system on the emission of PM10 particulate material.The methodology was based on AP-42 emission factors from U.S.EPA(United States Environmental Protection Agency)for the calculation of PM10 emissions from operations in the handling and storage of petroleum coke in an oil refinery in the northeastern of Brazil.The knowledge of the emission potential of each operation of the coke handling and storage system allows the adoption of more effective control measures,contributing to the effective reduction of PM10 emissions in this system.To complement the environmental impact assessment of each configuration,an air quality modelling was performed using the atmospheric dispersion software.The comparison performed in this study enables authors to conclude,even for a totally mechanic system,that adopts control measures,PM10 emissions are low when confronted with the remaining sources of an oil refinery.By analyzing emissions from automated systems operation(scenario 1),it can be observed that the source with higher emission potential is the stockpile,which represents 60%of the system’s emission.Transfer and transport operations by conveyor belts together correspond to 40%of emissions.Even though transfer operations also represent a significant part(27%),they are not clustered in a unique point,making these emissions abatement difficult.The same is valid for transport using conveyor belts.Emissions from the piles are really the most significant.For this reason,this work concentrated efforts in the storage area,the ones that motivate the majority of studies relating to abatement technologies.

Basic Engineering of a Two-Stage Process for Co-Upgrading Natural Gas and Petroleum Coke

This communication highlights the possibility of using a novel two-stage process for the co-upgrading of natural gas and petroleum coke into liquid hydrocarbons. The first stage consists of the catalytic dehydroaromatization of methane characterized by producing hydrogen and aromatics: benzene, naphtalene, toluene, etc. The non-reacted methane plus hydrogen and aromatics produced in the first stage are directed to the second stage to react with the petroleum coke. Basic engineering analysis of proposed two-stage process suggests light petroleum production of 160,000 bbl/day from 20,000 ton/day of petroleum coke actually by-produced from Venezuelan Orinoco’s heavy oil belt. Residual coke should be volatiles free therefore useful as a calcined coke.

Comparative Study on Combustion Performance of Petroleum Coke, Hejin Coal and Shenmu Coal

The effects of three factors on combustion performance of petroleum coke, Herin Coal and Shenmu Coal have been studied, including the ratio of primary air, excess air factor, and the swirling intensity of outer secondary air. The experiments were carried out on a one-dimensional furnace with dual channel swirling burner, in which temperature of center furnace, emission of air pollutants, and burn-out rate of fuel were measured. The results provide the optimal ratio of primary air, excess air factor and swirling intensity of outer secondary air for the fuels. The combustion performance of petroleum coke B is much better than petroleum coke A, but worse than Hejin coal and Shenmu coal. In addition, the burn-out rate of petroleum coke depends much more on the temperature in terminal stage of combustion than in the early stage of combustion.