Heavy Residues Research Articles

Creating graphene from asphaltenes

Asphaltenes, a carbon-rich by-product of crude oil production, can be used to make graphene, according to a new study ( Sci. Adv. 2022, DOI: 10.1126/sciadv.add3555 ). Asphaltenes are used for roofing and paving, and some refineries make synthetic fuel from the heavy residue. But unused asphaltenes can be a massive environmental headache. They emit carbon when burned, and if they’re discarded into landfills and tailing ponds—storage facilities for by-products of oil sands mining—they can pollute land, water, and air. Md Golam Kibria of the University of Calgary and colleagues zeroed in on a way to create a higher-value material from asphaltenes using a technique called flash joule heating . Passing a short pulse of current through powdered asphaltenes turns them into a carbon allotrope called asphaltene-derived flash graphene (AFG) in a matter of seconds. No furnaces, solvents, or reactive gases are needed, making the process relatively inexpensive. Because asphaltenes are

Исследование термического превращения мазута в присутствии регенерированного отработанного катализатора гидроочистки

An urgent task of the oil refining industry is the development of a thermodestructive process for the processing of heavy oil residues. This paper presents the results of a study of thermal cracking of fuel oil in the presence of aluminocobaltmolybdenum regenerated spent hydrotreating catalyst. The experiments were carried out using an autoclave, as well as using a number of instrumental methods of analysis. The effect of the degree of dispersity and catalyst content on the results of the process under study was studied. The material balance of the thermal cracking process in the presence of catalyst samples of different fractional composition is compared with the material balance of thermal cracking in the temperature range of 450-470 °C. The physical and chemical properties of the samples of catalysts, raw materials and products of the process were determined. The analysis of the obtained experimental data was carried out, the conditions for the most efficient processing of raw materials in the process of thermal cracking in the presence of a catalyst were determined, and conclusions were drawn about the prospects for its use for processing heavy oil residues.

Carbon Additives of Petroleum Origin in Coal Mines and Prospects for Their Industrial Production

The possibility of qualified use of heavy oil residues and oil refining waste as carbon additives in coal charges in the production of metallurgical coke is considered. The involvement of petroleum coke fines and coking additives in coal charges can significantlyimprove the operational properties of blast furnace coke. The available and promising technologies for obtaining sintering additives using heavy oil residues are considered and compared.

Получение бензиновой фракции в процессе гидрокрекинга мазута

In the article, a new processing technology is presented in the «Hydrocracking of heavy oil residues» (SPR-1) unit with the presence of highly dispersed aluminosilicate catalysts suspended in fuel oil. The hydrocracking process of fuel oil obtained from Baku oils was studied with the participation of catalysts modified by means of ion exchange and impregnation methods of Az-4 mineral. The main results of the study on the production of gasoline fraction by hydrogenation of heavy oil residues under low pressure with the presence of purchased catalysts are presented.It was determined that under optimal conditions 6% of fuel oil hydrocracking without catalyst; 26% with 2.5% Az-4 addition. When Az-4 catalyst modified with Ni and Mo by impregnation and ion exchange methods is used, the yield of gasoline fraction is 32 and 34.45% by mass, respectively. It was shown that the amount of sulfur, unsaturated hydrocarbons and iodine in the gasoline fraction decreased. The octane number increases from 64 to 71.The composition and properties of the obtained gasoline fraction were studied by NMR and IR spectroscopy methods.

Влияние гидрокрекинга тяжелых остатков перегонки нефти на производственную эффективность АО «ТАИФ-НК»

The article is devoted to the experience of the TAIF-NK JSC in the application of the process of combined thermal and hydrocracking for deep processing of heavy residues of oil distillation - vacuum residue and vacuum gasoil. The Veba Combi Cracker (VCC) process was taken as a basis and during the commissioning and pilot tests it was significantly improvedby the specialists of TAIF Group, as a result of which the Heavy Residue Conversion Complex of TAIF-NK JSC is the only one in the world, which allows heavy residues conversion with maximum recovery of high-quality light oil products. The implementationof the technology of combined thermal and hydrocracking at TAIF-NK JSC ensured 85.1% achievement of the refining depth and 80.7% yield of light oil products in 2021. A retrospective of the dynamics of indicators of the depth of oil refining and the yield of light oil products from the implementation of the project is showny.

Heavy Metal Residues in Some Marketed Fish with a Trial of Decontamination using Lactobacillus rhamnosus

Heavy Metal Residues in Some Marketed Fish with a Trial of Decontamination using Lactobacillus rhamnosus

Синтез и исследование никель-алюминиевого катализатора для переработки тяжелого нефтяного остатка

Structural characteristics of catalytic systems obtained by modification of activated carbon with Al and Ni metal oxides have been studied. Modification of activated carbon was carried out by impregnating them with metal hydroxides from salt solutions with a Ni+2/Al+3 ratio of 2:1 and 3:1, followed by calcination in a stream of nitrogen and hydrogen until oxide phaseswere formed. With an increase in the ratio of metal cations in the impregnating solution in activated carbon, the specific surface area and the number of micropores increase, and the total volume and average pore diameter. Ignition in a hydrogen flowat the final stage of activated carbon modification leads to a decrease in the pore space and a decrease in the specific surface area of the catalytic system. The optimal combination of specific surface values and maximum average pore diameters for the processing of heavy oil residue have Ni/Al (2:1) catalytic systems obtained in nitrogen and hydrogen.

Инновационные достижения и разработки АО «СвНИИНП», реализуемые и планируемые к внедрению

JSC "MidVolgaNIINP" (Middle Volga Research Institute for Oil Refining) carries out its innovative activities in the direction of "Science in oil refining and petrochemistry" as part of a complex of research and design institutes of Rosneft. Institute specialists conduct scientific research in the field of development of lubricants, additive packages for oils and fuels, production of oil bitumen and processing of heavy oil residues. The priority direction of scientific and technical activity of the Institute is the import substitution of lubricants and additives to them. This article presents the results of the scientific activities of the Institute in connection with the 65th anniversary of its foundation. The main long-term tasks requiring solutions and the state of the scientific potential of the institute are considered.

Assessment of Heavy Metal Residues in Hides of animals Singed with Tyres, and Public Health Implications Associated with such Practice in Lokoja Metropolis

The safety of food has been an issue of concern in developing countries like Nigeria where the processing method can pose some environmental health challenge. The use of scrap automobile tires to singe meat has been reported to possess some toxic materials that can pose health challenge to humans. Hence, this study was conducted to determine the concentration of heavy metals in meat singed with fire wood and scrap tires in Lokoja, Nigeria. Samples of cattle hides singed with firewood and scrap tires were collected from four (4) different abattoirs and analyzed for the concentration of Cu, Pb, Fe and Zn using Atomic Absorption Spectrophotometry. There was significant increase in the concentration of Cu, Zn and Pb of the cattle hides singed with firewood and scrap tires when compared to the unsinged. The concentration of heavy metals for firewood singed cattle hide is within recommended Maximum Permissible Levels (MPLs) of the European Commission Regulations while the concentration of scrap tires is above the recommended Maximum Permissible Levels (MPLs) of the European Commission Regulations for Cu, Zn and Fe. Though there was increase in the concentration of Fe it is within the recommended Maximum Permissible Levels. The presence of heavy metals concentration above the permissible levels in cattle hides singed with scrap tires makes it unsafe for human consumption hence safer method should be adopted by the abattoirs.

Paraffinic oil residues after heating as a basis for fuel

The possibility of reuse of heavy residues (oily sludge) of low-sulfur, highly paraffinic Mangyshlak oils as a basis for fuel with improved environmental characteristics for engines to marine, river and railway transport, gas turbine and boiler plants, steam boilers and industrial furnaces was shown. A variant of the joint application of the methods of nuclear magnetic resonance, laser confocal microscopy and rheology for study of micro- and mesoscopic structure and some physicochemical properties of crude oil products has been developed. It has been shown that preliminary heating to 90 ° C leads to disruption of the structure and hydrogen bonds between oil associates and complexes, increasing sample homogeneity due to precipitation of solid impurities, partial removal of water content, air bubbles and dissolved gases. The addition of medium distillate diesel fractions to preliminary heated oil residues will make it possible to obtain a higher quality version of the fuel with a reduced resinous and asphaltene substances, lower pour point, good energy content and low sulfur content. Thus, valuable energy-containing raw materials can be reused. It should also be noted that the reuse of accumulated oil waste will reduce the harmful effects of landfills, will preserve the natural landscape, and will cut the cost of extracting natural resources.

Математическая модель процесса сжигания сероводородных и аммиачных газов в реакционной печи Клауса с использованием вычислительной гидродинамики

Based on the method of computational fluid dynamics using the ANSYS Fluent software package, the combustion process in the Claus furnace of sour gas containing ammonia was simulated. The vortex dissipation model was used to describe the chemical kinetics of combustion (Eddy-dissipation model). The object of study was the sulfur recovery unit of the Heavy Residue Processing Complex. Options for increasing the efficiency of the process of burning ammonia-containing sour gases, depending on the scheme for supplying acid to the furnace, its moisture content, as well as the temperature of air and sour gases at the furnace inlet were considered.

Upgrading the atmospheric distillation residue of Al- Samawah refinery utilizing thermal cracking process

Thermal cracking of heavy oil residues has gained the attention of oil refineries due to the increasing need for light oil fractions, as well as its lower value compared to light oil fractions. In this paper, the thermal cracking process of the residual crude oil that product from atmospheric distillation towers in the Samawah Refinery was studied in order to convert the heavy oil into a lighter oil. API gravity and conversion ratio for the result from the cracking process has been adopted as indicators of the accuracy and efficiency of the thermal cracking process for AR (atmospheric residue), where the API gravity for AR is equal to 15.5 .The response surface methodology (RSM) was adopted in the design of experiments to reach the best variables of operational conditions , which were in a range of temperatures (350-450 degrees Celsius) and time (30-60 minutes), through which we obtain the best results for the conversion ratio and API gravity for the liquid resulting from the thermal cracking process of AR, where the conversion ratio was 53.4% and API gravity equals 34.4 with a time of 45 minutes and temperature 386 0C.

The Occurrence of Arsenic, Cadmium, and Lead Residues in Cattle Feed Collected in Kırıkkale, Türkiye: A Preliminary Study

The aim of this study is to investigate the occurrence of arsenic (As), cadmium (Cd), and lead (Pb) residues in 15 cattle feed collected from dairy and beef cattle breeding farms located in 6 different districts (Kırıkkale Province, Yahşihan, Karakeçili, Balışeyh, Delice and Keskin) of Kırıkkale. The quantitative analysis of the As, Cd and Pb levels of the samples was analyzed by ICP-MS. Arsenic and Pb residues were found in all of the collected samples, while Cd residues were found in 13 (86. 67%) of the collected samples. In the samples with heavy metal residues; the mean value ± standard deviation for As, Cd, and Pb were found as 0.1475±0.1060 mg/kg, 0.0382±0.0079 mg/kg and 0.1944±0.1074 mg/kg respectively. The maximum tolerable limit in cattle feed is 2 mg/kg for As, 5 mg/kg for Pb, and for Cd in cattle feed is 1 mg/kg for Cd according to an official announcement (2014/11) of the Ministry of Agriculture and Forestry Turkey. The results of this study showed that detected As, Cd and Pb levels in cattle feeds were below the tolerable limit. Therefore, it is suggested that the heavy metal pollution in terms of As, Cd, and Pb in feed does not pose a risk for cattle farming in Kırıkkale province.

Impact of processing pre-treatments on color and the level of heavy metal reduction of the green alga Ulva sp.: A preliminary study

Ulva sp. is an abundant green alga in Gunungkidul waters, Indonesia, considered a source of nourishing food, sought after by food industries. This green alga could be served as a dish, a seasoning, or an ingredient; hence, the assessment of its safety is important. The present study was conducted to reduce heavy metal residues in Ulva sp. collected from Sepanjang beach, Gunungkidul, Indonesia by using two different processing treatments, i.e., washing with citric acid and blanching at various times and seaweed-to-solution ratios. The number of heavy metal residues (As, Cd, Pb, and Hg) was determined by Inductive Coupled Plasma Mass Spectrometry (ICP-MS) and visual green color loss was measured by a color spectrophotometer. The result showed that the concentration of As and Cd in the unprocessed sample was higher than SNI 2690:2015 specification for raw seaweed as well as the National Food and Drug Agency of the Government of Indonesia (BPOM Indonesia) permissible limits in food. Washing Ulva sp. with citric acid 0.5% for 10 min in a seaweed-to-solution ratio of 1:20 could reduce the level of as up to 42.53%, whereas washing Ulva sp. with citric acid 0.5% for 15 min in a seaweed-to-solution of 1:10 could reduce the level of Cd up to 96.12%. All processing treatments affected the appearance of Ulva sp. which is indicated by the increase in color differences (ΔE) > 2.

Comparative analysis of the effects of hydrogen and formic acid on the vacuum residue hydrocracking

The improvement of the existing technologies aimed at deeper processing of heavy oils and oil residues and development of new ones is an urgent task of modern oil refining. Experiments in a flow installation using a quartz reactor were performed to determine the formic acid decomposition pathway. The experiments showed that the formic acid decomposition over the Ni-Mo/Al2O3 catalyst predominantly yielded hydrogen and CO2. Therefore, in this study comparative experiments on the effects of hydrogen and formic acid on the vacuum residue hydrocracking in the presence of the Ni-Mo/Y-Al2O3 and Ni-Mo/Al2O3 catalysts were performed at 375–400 °C and 0.45 MPa pressure. The concentration of hydrogen or formic acid in argon was 10 vol%. The catalysts were prepared by impregnation of the corresponding supports with the aqueous solution obtained using nickel hydroxide, ammonium heptamolybdate and citric acid. Electron microscopy and XRD studies of the Ni-Mo/Y-Al2O3 and Ni-Mo/Al2O3 catalysts demonstrated that the active component in the studied catalysts was in a finely dispersed state. The size of Ni-Mo particles was 0.4–0.6 nm in the Ni-Mo/Y-Al2O3 catalyst and 0.3–0.6 nm in Ni-Mo/Al2O3. For both catalysts Ni-Mo/Y-Al2O3 and Ni-Mo/Al2O3 higher vacuum residue conversion to liquid products was observed in the presence of formic acid than in the presence of hydrogen. Hydrogen substitution for formic acid vapor during the vacuum residue hydrocracking also results in the lower sulfur content in the liquid reaction products. The use of formic acid as a hydrogen donor significantly simplifies the process hydrocracking.

Investigation of the process and products of plasma treatment of asphaltenes

The results of experiments on plasma processing of the samples of high-molecular fraction of the asphaltenes emitted from the asphaltite representing natural bitumen are reported. The asphaltite, according to its structure and properties, can serve as an analog of heavy oil residues of oil refining. The asphaltenes are treated with the plasma of an arc discharge in a laboratory reactor in ambient air. The structure and properties of the resulting carbon materials are determined by the methods of X-ray diffractometry, thermogravimetric analysis, differential scanning calorimetry, IR-spectroscopy, X-ray fluorescent analysis and laser diffraction. It is found out that during plasma processing of asphaltenes a mixture of gases consisting mainly of H 2 and CH 4 with CO 2 , CO, NO, SO 2 , H 2 S impurities is formed, and an polydisperse carbon material is formed with the structure of graphite, containing the elements present in the initial asphaltite forms: vanadium, nickel, iron, calcium, aluminum, sulfur, silicon and chlorine. The optimum modes of the arc reactor performing the plasma processing of asphaltenes (30 s and current 100 A), allowing to achieve the maximum yield of hydrogen and graphite-like material, are defined.

Quantification and Reduction in Heavy Metal Residues in Some Fruits and Vegetables: A Case Study Galați County, Romania

One of the main issues for sustainable global development with high priority is food security. The negative effects of contaminants on crop quality have threatened both food security and human health. Long-term heavy metal exposure from food, drinking water, or other occupational sources causes serious problems, such as kidney failure, hepatotoxicity, and neurotoxicity. This study was conducted to determine the concentrations of three toxic trace elements (As, Cd, Pb) and one microelement (Zn) in fruits and vegetables using ICP-MS, and it also sought to reduce the concentrations of metals by washing with vinegar (5% and 10% acetic acid). The potential of vinegar to influence heavy metal contents may be due to its effect on pH values that influence the solution chemistry of the heavy metals, such as hydrolysis, redox reactions, precipitation, and availability of heavy metals. Sample origin has a significant influence in terms of metal accumulation; values up to 35%, 68%, 67%, and 3% lower were recorded in the case samples originating from amateur farmers (for As, Cd, Pb, and Zn, respectively). Regarding the efficiency of the vinegar, As and Zn recorded levels up to 8% lower for samples washed with 10% vinegar, and Cd showed levels up to 20% lower for samples washed with 10% vinegar, while Pb did not register any differences.

Na2O induced stable heavy metal silicates phase transformation and glass network depolymerization

The pollution of heavy metals and chlorine salts widely exists in solid/hazardous waste, while the stable heavy metal silicates limit the heavy metals removal. This work proposed mechanism of Na2O induced stable heavy metal silicates phase transformation and glass network depolymerization to promote heavy metals chlorination volatilization. Medical waste incineration slag (MWI S) containing heavy metal silicates was used as typical sample. Compared with the control, Cu and Zn volatilization efficiencies sharply increased from 77.54% to 92.22% and 18.70% to 93.82% at 3% Na2CO3, 1200 °C, 40 min. It showed that Na2O successfully induced phase transformation from stable Zn2SiO4 and CuSiO3 to ZnO and CuO easy to react with chloride by destroying the Si–O of Zn–O–Si and Cu–O–Si, respectively. Meanwhile, Na2O effectively destructed Si–O bond to depolymerize the glass network, resulting in the percentage of Q0 and Q1 increase from 25.14% to 38.29%, reducing melt viscosity and improvement of volatilization environment to form bigger bubbles. Medical waste incineration fly ash (MWI FA) was applied as Na source to further verify that the mechanism was significantly enhance Cu and Zn volatilization efficiencies. This study provided new method to reduce heavy metal residues in glass products prepared by melting treatment of solid/hazardous wastes.

Impact of substrate depth and fertilizer type on growth, production, quality characteristics and heavy metal contamination of tomato and lettuce grown on urban green roofs

Urban farming on rooftops is a contemporary approach that combines the benefits of green roofing with food production within the city sprawl. The present study aims at assessing plant growth, nutritional value, and consumer safety of two vegetables, lettuce (Lactuca sativa L.) and tomato (Solanum lycopersicum L.) grown on urban green roof. Treatments included: (a) two substrate depths (7.5 and 15 cm) and (b) three types of fertilization (granulated complex fertilizer [GF], slow nitrogen release complex fertilizer [SR], and liquid fertigation [LF]). Measurements included plant growth, total fresh yield, dry weight, and quality characteristics such as nutrient content, nitrate accumulation in lettuce and firmness, and total soluble solids [TSS] in tomatoes. Production safety was evaluated through tissue analyses of the edible parts for heavy metal residues. Results showed that 15 cm substrate depth improved the total yield for both vegetables, and the firmness of tomato fruit, compared to 7.5 cm depth. Fertilization type had no impact on tomato productivity but GF increased TSS in tomato fruits while LF enhanced lettuce yield. The deeper substrate increased N, P, K, Ca, Mg in lettuce leaves but only P and Mn in tomato fruits. In contrast, fertilization type affected leaf nutrient levels in lettuce, where N, P, and Mg were increased using LF. In tomato, the LF increased the fruit P, K, Ca, Mg, and Fe concentration. LF increased the concentration of nitrates in lettuce to levels exceeding the maximum safety limits according to the European Food Safety Authority (EFSA) but not according to EU regulation No 1258/2011. The leaf Mn concentrations in lettuce were higher than the health limits for young children in all measured samples irrespective of the experimental treatments. Selenium (Se) exceeded the health limits in tomato fruits for adults and toddlers using SR but only for toddlers using LF, while GF maintained the Se content below the safety levels. Lead (Pb) and aluminium (Al) were high for both vegetables but did not exceed the EFSA safety limits for adults. However, Pb exceeded the EU Commission Regulation No 420/2011 limit, for both vegetables and fertilization treatments. Washing the leaves of lettuce reduced only Fe and Al concentration but the remaining elements were unaffected. In conclusion, our results suggest that lettuce and tomato of adequately high quality for human consumption can be produced on urban green roofs with shallow substrate depths ranging from 7.5 to 15 cm but, further research is needed to ensure production safety.

Determination of Heavy Metal Residues in Tropical Fruits near Industrial Estates in Rayong Province, Thailand: A Risk Assessment Study

This study determined the extent of heavy metal contamination of local fruit in Rayong, Thailand, an area where an industrial base is adjacent to agricultural areas. Dietary exposure to agricultural products grown in contaminated areas can cause multiple adverse effects to the human body. In order to avoid such undesirable effects, concentrations of heavy metals [arsenic (As), cadmium (Cd), copper (Cu), mercury (Hg), lead (Pb), and zinc (Zn)] were investigated in popular tropical fruits from three districts of Rayong, namely Wang Chan, Klang and Mueang. The levels of heavy metals were determined by inductively coupled plasma-mass spectrometry (ICP-MS) and cold vapor-atomic absorption spectrometry (CV-AAS). Levels of the six heavy metals in sampled fruits (durian, jackfruit, pineapple, rambutan, long kong, and mangosteen) were in the range of 0.0004-6.7095 mg/kg; 16.7% of fruit samples exceeded maximum permissible limits of Pb. Based on health risk assessments, values of estimated daily intake (EDI) were less than those of maximum tolerable daily intake. However, for non-carcinogenic risks, high hazard index (HI) values were found in some markets while for carcinogenic risks (CRs), CR values of three fruits (durian, jackfruit, and mangosteen) exceeded acceptable levels. Therefore, long-term fruit consumption could impact health of local consumers. These results provided insight into the need for regular monitoring of heavy metal concentrations in potentially contaminated fruits and for prevention of its potential effects.