Effect of Residual Cuts on Deactivation of Hierarchical Y Zeolite-Based Catalysts during Co-Processing of Vacuum Gas Oil (VGO) with Atmospheric Residue (ATR).

The influence of residual cuts on the deactivation of hierarchical Y zeolite-based catalysts during the co-processing of vacuum gas oil (VGO) with atmospheric residue (ATR) was investigated. The experiments were conducted in a laboratory-scale MAT-type reactor. The conversion of VGO, ATR, and their 70:30 (mass basis) mixture was examined using two composite catalysts: Cat.Y.0.00 and Cat.Y.0.20. The operating conditions closely resembled those of the commercial catalytic cracking process (550 °C and contact times of 10 to 50 s). When ATR was processed individually, the conversion remained below 50 wt%. However, significant improvements in conversion rates were achieved and catalyst deactivation was mitigated when ATR was co-processed with VGO. Notably, the BET surface area and average mesopore volume were adversely impacted by ATR, which also led to the accumulation of high levels of metals and nitrogen on the spent catalyst, detrimentally affecting its acidic and structural properties. Moreover, substantial coke deposition occurred during ATR cracking. The soluble and insoluble coke analysis revealed H/C ratio values of up to 0.36, indicative of polycondensed coke structures with more than ten aromatic rings. The nature of the coke was confirmed through TPO and FTIR analyses. Interestingly, the CatY.0.20 catalyst exhibited less activity loss, retaining superior acid and structural properties. Co-processing Colombian atmospheric residue with ATR loadings of 30 wt% (higher than the typical 20 wt%) in catalysts formulated with hierarchical zeolites presents a promising alternative for commercial applications. This research opens avenues for optimizing catalytic cracking processes.

Deactivation and regeneration dynamics in hierarchical zeolites: Coke characterization and impact on catalytic cracking of vacuum gas oil.

This study investigated the deactivation and regeneration of hierarchical zeolites in vacuum gas oil conversion, aiming to reach the equilibrium state seen in fluidized bed catalytic cracking (FCC). The research utilized various characterization techniques to analyze the properties of zeolites before and after coking and regeneration. Zeolite Y-0.20-S was found to have the highest gasoline selectivity and quality, mirroring industrial yields, and displayed notable stability across deactivation/regeneration cycles. Higher mesopore concentration in zeolites led to increased coke selectivity and better resistance to deactivation. The study observed a dominance of aromatic coke with a higher degree of condensation in these zeolites. Despite coke deposition affecting acid and textural properties, the regeneration process effectively restored these characteristics, proving its efficiency. The zeolites with greater mesoporosity retained their fundamental properties responsible for activity and selectivity, highlighting the importance of selecting materials that provide high conversions and maintain stability and product selectivity over multiple cycles. The Y-0.20-S zeolite, in particular, was identified as a promising candidate for commercial catalyst development for gasoline production, contributing to the FCC process's energy efficiency.

A comprehensive study of product distributions and coke deposition during catalytic cracking of vacuum gas oil over hierarchical zeolites.

In this study, zeolites (Z) were used as catalysts in the cracking of a Colombian vacuum gas oil (VGO), with a focus on product distribution and coke deposition. The catalytic tests were carried out in a MAT-type reactor under typical conditions. The zeolites were subjected to alkaline treatment with NaOH at concentrations ranging from 0.05 to 0.4 mol/L, resulting in the creation of several samples (Z-0.05, Z-0.10, Z-0.20, Z-0.30 and Z-0.40) that were then hydrothermally stabilized (Z-0.05-M, Z-0.10-M, Z-0.20-M, Z-0.30-M and Z-0.40-M) to increase mesoporosity and reduced crystallinity. The increase in mesoporosity was accompanied by an improvement in acidity. Despite Z-0.30-M having higher acidity, Z-0.00-M and Z-0.10-M exhibited the highest activity due to their high crystallinity and microporosity, yielding the highest gas yields. Gasoline was the main product, with maximum yields exceeding 30%. Z-0.20-M produced more aromatic and olefin compounds than the others, resulting in higher quality gasoline. Coke formation followed the trend: Z-0.00-M < Z-0.10-M < Z-0.20-M < Z-0.30-M. The higher intracrystalline mesoporosity in the zeolites favored the formation of a more condensed coke.

Bimetallic Ni-Ru and Ni-Re Catalysts for Dry Reforming of Methane: Understanding the Synergies of the Selected Promoters.

Designing an economically viable catalyst that maintains high catalytic activity and stability is the key to unlock dry reforming of methane (DRM) as a primary strategy for biogas valorization. Ni/Al2O3 catalysts have been widely used for this purpose; however, several modifications have been reported in the last years in order to prevent coke deposition and deactivation of the samples. Modification of the acidity of the support and the addition of noble metal promoters are between the most reported strategies. Nevertheless, in the task of designing an active and stable catalyst for DRM, the selection of an appropriate noble metal promoter is turning more challenging owing to the lack of homogeneity of the different studies. Therefore, this research aims to compare Ru (0.50 and 2.0%) and Re (0.50 and 2.0%) as noble metal promoters for a Ni/MgAl2O4 catalyst under the same synthesis and reaction conditions. Catalysts were characterized by XRF, BET, XRD, TPR, hydrogen chemisorption (H2-TPD), and dry reforming reaction tests. Results show that both promoters increase Ni reducibility and dispersion. However, Ru seems a better promoter for DRM since 0.50% of Ru increases the catalytic activity in 10% and leads to less coke deposition.

The effect of recycled plastics and cooking oil on coke quality.

This study assessed the effects of adding plastics and waste vegetable oil on the quality of coke in the coking process, on a pilot scale. A typical composition of the main plastics found in municipal solid waste was prepared using 33% HDPE, 5% LDPE, 10% PP, 21% PET, 24.8% PS, 5.2% PVC, 1% cellulose and also a 0.5% waste vegetable oil was added. The wastes were added to the coal blends in the proportions of 1%, 2% and 3% for plastics and 0.5% for vegetable oil. Two types of experiments were performed. The first was carried out in a hearth heating furnace (HHF) at temperatures of up to 900°C for a 7 h period. The second was a box test, which consists of heating coal blends in 18L cans using a pilot coking oven, for approximately 20 h at temperatures between 1050 and 1100°C. The quality parameters used for the assessment were the CSR (coke strength after reaction), CRI (coke reactivity index), ash, volatile matter and sulfur in order to identify the effect of plastic and vegetable oil on coke quality. Results for CSR in the HHF averaged 52.3%, and 56.63% in box test trials. The CRI results ranged from 26.6% to 35.7%. Among the different percentages of plastics used, 3% plastic blends provided the most stable CSR results. The industrial furnaces work at temperatures between 1100 and 1350°C and time coking 21-24h, compared to the test conditions achieved in the HHF and pilot furnace with box test. It was concluded that the results of CSR and CRI are consistent with the tests confirming the feasibility of using plastic in the steelmaking process.

Human health risk characterization of petroleum coke calcining facility emissions.

Calcining processes including handling and storage of raw petroleum coke may result in Particulate Matter (PM) and gaseous emissions. Concerns have been raised over the potential association between particulate and aerosol pollution and adverse respiratory health effects including decrements in lung function. This risk characterization evaluated the exposure concentrations of ambient air pollutants including PM10 and gaseous pollutants from a petroleum coke calciner facility. The ambient air pollutant levels were collected through monitors installed at multiple locations in the vicinity of the facility. The measured and modeled particulate levels in ambient air from the calciner facility were compared to standards protective of public health. The results indicated that exposure levels were, on occasions at sites farther from the facility, higher than the public health limit of 150 µg/m(3) 24-h average for PM10. However, the carbon fraction demonstrated that the contribution from the calciner facility was de minimis. Exposure levels of the modeled SO2, CO, NOx and PM10 concentrations were also below public health air quality standards. These results demonstrate that emissions from calcining processes involving petroleum coke, at facilities that are well controlled, are below regulatory standards and are not expected to produce a public health risk.

Microwave-assisted ultraviolet digestion of petroleum coke for the simultaneous determination of nickel, vanadium and sulfur by ICP-OES.

A method for the simultaneous determination of Ni, V and S in petroleum coke by inductively coupled plasma optical emission spectrometry (ICP-OES) after microwave-assisted ultraviolet digestion (MW-UV) in closed vessels was proposed. Digestion was performed using electrodeless discharge lamps positioned inside quartz vessels and turned on by microwave radiation. The following parameters were evaluated: HNO3 concentration (15 mL of 1, 4, 7, 10 or 14.4 mol L(-1)), volume of H2O2 (30%, 1 or 3 mL), sample mass (100, 250 or 500 mg) and heating time (40 or 60 min) with or without the use of UV lamps. Digestion efficiency was evaluated by the determination of the residual carbon content (RCC) in digests. Using UV lamps lower RCC was obtained and the combination of 4 mol L(-1) HNO3 with 3 mL of H2O2 and 60 min of heating allowed a suitable digestion of up to 500 mg of petroleum coke (RCC< 21%). The agreement with the reference values for Ni, V and S (obtained by digestion of petroleum coke by microwave-induced combustion) and with a certified reference material of petroleum coke was between 96 and 101%. The proposed method was considered as advantageous when compared to American Society for Testing and Materials method because it allowed the simultaneous determination of Ni, V and S with lower limit of detection (0.22, 0.12 and 8.7 µg g(-1) for Ni, V and S, respectively) avoiding the use of concentrated nitric acid and providing digests suitable for routine analysis by ICP-OES.

CO2 carbonation under aqueous conditions using petroleum coke combustion fly ash.

Fly ash from petroleum coke combustion was evaluated for CO2 capture in aqueous medium. Moreover the carbonation efficiency based on different methodologies and the kinetic parameters of the process were determined. The results show that petroleum coke fly ash achieved a CO2 capture yield of 21% at the experimental conditions of 12 g L(-1), 363°K without stirring. The carbonation efficiency by petroleum coke fly ash based on reactive calcium species was within carbonation efficiencies reported by several authors. In addition, carbonation by petroleum coke fly ash follows a pseudo-second order kinetic model.

Análisis termogaavimétrico en la caracterizació de carbones Colombianos empleaados en la producción de coque / Themogravimetricc analysis in the characterization f Colombian coaals used in the production of coke / Análise termogrvvimétrica na caracterização de carvões Colombiaos utilizados nna produção de coque

Cinco carbones de los departamentos de Cundinamarca, Boyacá y Norte de Santander (Colombia) se caracterizaron mediante análisis próximo, último, reológico, petrográfico, calorífico y termogravimétrico. Los parámetros analizados, especialmente aquellos que determinan las propiedades reológicas, muestran que los carbones estudiados y sus mezclas podrían producir un coque de buena calidad. Se observó la relación inversa entre el contenido de materia volátil y la reflectancia media aleatoria de la vitrinita, que se atribuye al aumento de la aromaticidad en la estructura molecular del carbón como una consecuencia del incremento en el rango. Los parámetros derivados del análisis termogravimétrico -máxima velocidad de desvolatilización y temperatura de máxima velocidad de desvolatilización- mostraron buenas correlaciones con la reflectancia media aleatoria de la vitrinita, igual que la máxima velocidad de desvolatilización con la fluidez máxima. Lo anterior indica que el análisis termogravimétrico podría ser una herramienta útil para caracterizar de manera rápida carbones usados en procesos de fabricación de coque metalúrgico.

Five types of coal from the states of Cundinamarca, Boyaca and Norte de Santander (Colombia) were characterized by proximate, ultimate, rheological, petrographic, calorific and thermogravimetric analysis. The parameters used, especially the ones which determine the rheological properties show that the studied coals and its blends could produce good quality coke. It was observed the inverse relationship between the volatile matter content and the mean vitrinite reflectance, relationship which is attributed to the increase of the aromaticity in the molecular structure of the coal as a consequence of the rank increase. The parameters derived from the thermogravimetric analysis, maximum velocity of de-volatilization and the temperature of maximum velocity of de-volatilization and the media reflectance of the vitrinite showed good correlations. Also was observed an interesting correlation between the velocity ofde-volatilization and maximum fluidity. This shows that the thermogravimetric analysis can be a useful tool to characterize in a quick way coals used for metallurgical coke production.

Cinco carvões dos departamentos de Cundinamarca, Boyacá e Norte de Santander (Colômbia) foram caracterizados por análise próxima, última, reológica, petrográfica e termogravimétrica. Os parâmetros analisados, em especial aqueles que determinam as propriedades reológicas mostram que os carvões estudados e suas misturas podem produzir coque de boa qualidade. Foi observada relação inversa entre o teor de matéria volátil e refletância média vitrinite, que é atribuído ao aumento da aromaticidade da estrutura molecular do carvão como um resultado do aumento no rango. Os parâmetros derivados da análise termogravimétrica, velocidade máxima de pirólise e temperatura de máxima velocidade de pirólise mostraram boas correlações com a refletância média vitrinite, tal como a velocidade máxima de pirólise e a fluidez máxima. Isto mostra que a análise termogravimétrica pode ser uma ferramenta útil para caracterizar rapidamente carvões utilizados nos processos de fabricação de coque metalúrgico.

Nivel de níquel urinario en niños residentes en ciudades cercanas a megafuentes / Urinary nickel in children exposed to petcoke pollution

Background: Petcoke is a remmant of the oil refiningprocess that contains Ni and other heavy metáis. Undesired human exposure to these compounds may result from petcoke combustión in plants located in the vicinity ofthe cities. Aim: To compare levéis of urinary Ni in schoolchildren residing in cities exposed and not exposed to petcoke pollution. Material and methods: A cross sectional study was done in schoolchildren aged 7 to 8 years oíd in two cities in northern Chile: Mejillones (n = 59), near to a petcoke plant and Tocopilla (n = 56) as the reference city. First, morning urinary samples were collected and urinary Ni was determined by Atomic Absorption Spectrometry. Socioeconomic and environmental exposure information of families was obtained applying a questionnaire to parents. Múltiple linear regression was performed to identify other variables that may explain urinary Ni differences among the cities. Results: Median level of Ni was higher in Mejillones (4.9 fig/L) than in Tocopilla (3.9 fig/L). Residing in the exposed city was the most important explaining factor (B = 0.26; IC 0.107 - 0.428). Additionally years of residency was associated with urinary Ni (B = 0.03; IC 0.004 - 0.060). Conclusions: Urinary Ni in schoolchildren is higher in the city exposed to petcoke emissions. The difference does not imply that there are concrete hazards for the population s health. However, it warns about the existence of a higher exposure in places where petcoke is used.

Cytochrome P450 (CYP) and glutathione S-transferases (GST) polymorphisms (CYP1A1, CYP1B1, GSTM1, GSTP1 and GSTT1) and urinary levels of 1-hydroxypyrene in Turkish coke oven workers

Genetic polymorphisms of xenobiotic metabolizing enzymes have been associated with cancer risk. We evaluated the influences of genetic polymorphisms of polycyclic aromatic hydrocarbon (PAH) metabolizing enzymes on urinary 1-hydroxypyrene (1-OHP) excretion in Turkish coke oven workers. Urinary 1-OHP was analyzed by HPLC after enzymatic hydrolysis. Lymphocyte DNA was used for PCR-based genotyping of cytochrome P450 (CYP) polymorphisms (CYP1A1 and CYP1B1) and glutathione S-transferases (GST) polymorphisms (GSTM1, GSTT1 and GSTP1). The mean urinary 1-OHP levels of coke oven workers were significantly higher than that of controls. No significant difference was detected in the mean urinary 1-OHP levels of smokers and non-smokers either for coke oven workers or controls. Genetic polymorphisms of the CYPs and GSTs studied had no significant influence on 1-OHP excretion in coke oven workers, but in the control group the urinary 1-OHP levels of individuals carrying the GSTT1- genotype were significantly higher than those of individuals carrying GSTT1+ genotype. The duration of occupational exposure and metabolic genotype for GSTT1 were the significant predictors of urinary 1-OHP levels. The control individuals carrying combined GSTM1-/GSTT1- genotypes also had significantly higher levels of urinary 1-OHP than those of individuals carrying GSTM1+/GSTTI+, GSTM1-/GSTT1+, and GSTM1+/GSTT1- genotypes. These results indicate that urinary 1-OHP is a sensitive indicator of recent human exposure to PAHs and that genetic polymorphism of GSTT1 may also to some extent reflect the interindividual variation in susceptibility to PAHs only at low PAH exposure.