Bioleaching of Metals Contained in Spent Catalysts by Acidithiobacillus thiooxidans DSM 26636

Spent catalysts are considered as hazardous residues of major concern, mainly due to the simultaneous presence of several metals in elevated concentrations. Although hydrometallurgical, pyrometallurgical and chelating agent methods are available to remove and recover some metals contained in spent catalysts; these procedures generate potentially hazardous wastes and the emission of harmful gases. Thus, biotechnological treatments are currently gaining importance to avoid the negative impacts of chemical technologies. To this end, diverse microorganisms have been used to assess the removal of metals from spent catalysts, comprising bacteria, archaea and fungi, whose resistance and metal uptake capabilities differ depending on the microorganism tested. Acidophilic sulfur oxidizing bacteria have been used to investigate the biotreatment and extraction of valuable metals from spent catalysts, namely Acidithiobacillus thiooxidans and Acidithiobacillus ferroxidans, as they present the ability to produce leaching agents such as sulfuric acid and sulfur oxidation intermediates. In the present work, the ability of A. thiooxidans DSM 26636 for the bioleaching of metals contained in five different spent catalysts was assessed by growing the culture in modified Starkey mineral medium (with elemental sulfur at 1%, w/v), and 1% (w/v) pulp density of each residue for up to 21 days at 30 °C and 150 rpm. Sulfur-oxidizing activity was periodically evaluated by determining sulfate concentration in the supernatants according to the NMX-k-436-1977 method. The production of sulfuric acid was assessed in the supernatants as well, by a titration procedure using NaOH 0.5 M with bromothymol blue as acid-base indicator, and by measuring pH using a digital potentiometer. On the other hand, Inductively Coupled Plasma - Optical Emission Spectrometry was used to analyze metal removal from the five different spent catalysts by A. thiooxidans DSM 26636. Results obtained show that, as could be expected, sulfuric acid production is directly related to the diminish of pH, and also to highest metal removal efficiencies. It was observed that Al and Fe are recurrently removed from refinery spent catalysts regardless of their origin and previous usage, although these removals may vary from 9.5 ± 2.2 to 439 ± 3.9 mg/kg for Al, and from 7.13 ± 0.31 to 368.4 ± 47.8 mg/kg for Fe, depending on the spent catalyst proven. Besides, bioleaching of metals like Mg, Ni, and Si was also obtained from automotive spent catalysts, which removals were of up to 66 ± 2.2, 6.2±0.07, and 100±2.4, respectively. Hence, the data presented here exhibit the potential of A. thiooxidans DSM 26636 for the simultaneous bioleaching of metals contained in spent catalysts from diverse provenance.

Comparison between Post- and Oxy-Combustion Systems in a Petroleum Refinery Unit Using Modeling and Optimization

A fluidized catalytic cracking unit (FCCU) is one of the effective units in many refineries. Modeling and optimization of FCCU were done by many researchers in past decades, but in this research, comparison between post- and oxy-combustion was studied in the regenerator-FCCU. Therefore, a simplified mathematical model was derived by doing mass/heat balances around both reactor and regenerator. A state space analysis was employed to show effects of the flow rates variables such as air, feed, spent catalyst, regenerated catalyst and flue gas on the output variables. The main aim of studying dynamic responses is to figure out the most influencing variables that affect both reactor/regenerator temperatures; also, finding the upper/lower limits of the influencing variables to ensure that temperatures of the reactors and regenerator work within normal operating conditions. Therefore, those values will be used as side constraints in the optimization technique to find appropriate operating regimes. The objective functions were modeled to be maximizing the energy in the reactor while minimizing the energy consumption in the regenerator. In conclusion, an oxy-combustion process can be used instead of a post-combustion one.

Experimental Study on the Effects of Water-in-Oil Emulsions to the Pressure Drop in Pipeline Flow

Emulsion formation is unavoidable and can be detrimental to an oil field production. The presence of stable emulsions also reduces the quality of crude oil and causes more problems in the downstream refinery operations, such as corrosion and pipeline pressure drop. Hence, it is important to know the effects of emulsions in the pipeline. Light crude oil was used for the continuous phase in the W/O emulsions where the emulsions pass through a flow loop to test the pressure drop across the pipeline. The results obtained shows that pressure drop increases as water cut is increased until it peaks at the phase inversion of the W/O emulsion between 30% to 40% water cut. Emulsions produced by gradual constrictions show a lower stability as compared to sudden constrictions. Lower stability of emulsions in gradual constriction has the higher influence of pressure drop compared to a sudden sharp decrease in diameter in sudden constriction. Generally, sudden constriction experiences pressure drop of 0.013% to 0.067% higher than gradual constriction of the same ratio. Lower constriction ratio cases cause larger pressure drop ranging from 0.061% to 0.241%. Considering the higher profitability in lower emulsion stability and lower pressure drop at the developed flow region of different constrictions, an optimum design of constriction is found to be gradual constriction with a ratio of 0.5.

Treatment of Leaden Sludge of Algiers Refinery by Electrooxidation

Oil industries are responsible for most cases of contamination of our ecosystem by oil and heavy metals. They are toxic and considered carcinogenic and dangerous even when they exist in trace amounts. At Algiers refinery, production, transportation, and refining of crude oil generate considerable waste in storage tanks; these residues result from the gravitational settling. The composition of these residues is essentially a mixture of hydrocarbon and lead. We propose in this work the application of electrooxidation treatment for the leachate of the leaden sludge. The effect of pH, current density and the electrolysis time were studied, the effectiveness of the processes is evaluated by measuring the chemical oxygen demand (COD). The dissolution is the best way to mobilize pollutants from leaden mud, so we conducted leaching before starting the electrochemical treatment. The process was carried out in batch mode using graphite anode and a stainless steel cathode. The results clearly demonstrate the compatibility of the technique used with the type of pollution studied. In fact, it allowed COD removal about 80%.

Rheological and Computational Analysis of Crude Oil Transportation

Transportation of unrefined crude oil from the production unit to a refinery or large storage area by a pipeline is difficult due to the different properties of crude in various areas. Thus, the design of a crude oil pipeline is a very complex and time consuming process, when considering all the various parameters. There were three very important parameters that play a significant role in the transportation and processing pipeline design; these are: viscosity profile, temperature profile and the velocity profile of waxy crude oil through the crude oil pipeline. Knowledge of the Rheological computational technique is required for better understanding the flow behavior and predicting the flow profile in a crude oil pipeline. From these profile parameters, the material and the emulsion that is best suited for crude oil transportation can be predicted. Rheological computational fluid dynamic technique is a fast method used for designing flow profile in a crude oil pipeline with the help of computational fluid dynamics and rheological modeling. With this technique, the effect of fluid properties including shear rate range with temperature variation, degree of viscosity, elastic modulus and viscous modulus was evaluated under different conditions in a transport pipeline. In this paper, two crude oil samples was used, as well as a prepared emulsion with natural and synthetic additives, at different concentrations ranging from 1,000 ppm to 3,000 ppm. The rheological properties was then evaluated at a temperature range of 25 to 60 °C and which additive was best suited for transportation of crude oil is determined. Commercial computational fluid dynamics (CFD) has been used to generate the flow, velocity and viscosity profile of the emulsions for flow behavior analysis in crude oil transportation pipeline. This rheological CFD design can be further applied in developing designs of pipeline in the future.

Analysis of Heat Exchanger Network of Distillation Unit of Shiraz Oil Refinery

The reduction of energy consumption through improvements in energy efficiency has become an important goal for all industries, in order to improve the efficiency of the economy, and to reduce the emissions of Co2 caused by power generation. The objective of this paper is to investigate opportunities to increase process energy efficiency at the distillation unit of Shiraz oil refinery in south of Iran. The main aim of the project is to locate energy savings by use of pinch technology and to assess them. At first all the required data of hot and cold streams in preheating section of distillation unit has been extracted from the available flow sheets and then pinch analysis has been conducted. The present case study is a threshold one which does not need any utilities. After running range, targeting several heat exchanger networks were designed with respect to operating conditions and different ΔTmin. The optimal value of ΔTmin was calculated to be 22.3 °C. Based on this optimal value, there will be 5% reduction in annual total cost of heat exchanger network.

Effect of Crude Oil on Soil-Water Characteristic Curve of Clayey Soil

The measured soil suction values when related to water content is called suction-water content relationship (SWR) or soil-water characteristic curve (SWCC) and forms the basis of unsaturated soil behavior assessment. The SWCC can be measured or predicted based on soil index properties such as grain-size distribution and plasticity index. In this paper, the SWCC of clean and contaminated clayey soil classified as clay with low plasticity (CL) are presented. Laboratory studies were conducted on virgin (disturbed-uncontaminated soil collected from vicinity of Tehran oil refinery) soil and soil samples simulated to varying degrees of contamination with crude oil (i.e., 3, 6, and 9% by dry weight of soil) to compare the results before and after contamination. Laboratory tests were conducted using a device which is capable of measuring volume change and pore pressures. The soil matric suction at the ends of samples controlled by using the axis translation technique. The results show that contamination with crude oil facilitates the movement of water and reduces the soil suction.

Bioremediation of Hydrocarbon and Some Heavy Metal Polluted Wastewater Effluent of a Typical Refinery

Environment free of pollutants should be the concern of every individual but with industrialization and urbanization it is difficult to achieve. In view of achieving a pollution limited environment at low cost, a study was conducted on the use of bioremediation technology to remediate hydrocarbons and three heavy metals namely; copper (Cu), zinc (Zn) and iron (Fe) from a typical petroleum refinery wastewater in a closed system. Physicochemical and microbiological characteristics on the wastewater sample revealed that it was polluted with the aforementioned pollutants. Isolation and identification of microorganisms present in the wastewater sample revealed the presence of Bacillus subtilis, Micrococcus luteus, Staphylococcus aureus and Staphylococcus epidermidis. Bioremediation experiments carried out on five batch reactors with different compositions but at same environmental conditions revealed that treatment T5 (boosted with the association of Bacillus subtilis, Micrococcus luteus) gave the best result in terms of oil and grease content removal (i.e. 67% in 63 days). In addition, these microorganisms were able of reducing the concentrations of heavy metals in the sample. Treatments T5, T3 (boosted with Bacillus subtilis only) and T4 (boosted with Micrococcus luteus only) gave optimum percentage uptakes of 65, 75 and 25 for Cu, Zn and Fe respectively.

A Novel Solution to Restricted Earth Fault Low Impedance Relay Maloperation

In this paper, various methods of providing restricted earth fault protection are discussed. The proper operation of high and low impedance Restricted Earth Fault (REF) protection for various applications has been discussed. The maloperation of a relay due to improper placement of CTs has been identified and a simple/unique solution has been proposed in this work with a case study. Moreover, it is found that the proper placement of CT in high impedance method will provide the same result with reduced CT. This methodology has been successfully implemented in Al Takreer refinery for a 2000 KVA transformer. The outcome of the paper may be included in IEEEC37.91 standard to give the proper guidance for protection engineers to sort out the issues related to mal functioning of REF relays.

Microfiltration of the Sugar Refinery Wastewater Using Ceramic Membrane with Kenics Static Mixer

New environmental regulations and the increasing market preference for companies that respect the ecosystem had encouraged the industry to look after new treatments for its effluents. The sugar industry, one of the largest emitter of environmental pollutants, follows this tendency. Membrane technology is convenient for separation of suspended solids, colloids and high molecular weight materials that are present in a wastewater from sugar industry. The idea is to microfilter the wastewater, where the permeate passes through the membrane and becomes available for recycle and re-use in the sugar manufacturing process. For microfiltration of this effluent a tubular ceramic membrane was used with a pore size of 200 nm at transmembrane pressure in range of 1–3 bars and in range of flow rate of 50–150 l/h. Kenics static mixer was used for permeate flux enhancement. Turbidity and suspended solids were removed and the permeate flux was continuously monitored during the microfiltration process. The flux achieved after 90 minutes of microfiltration was in a range of 50–70 l/m2h. The obtained turbidity decrease was in the range of 50-99 % and total amount of suspended solids was removed.

Optimization of Diluted Organic Acid Pretreatment on Rice Straw Using Response Surface Methodology

Lignocellolusic material is a substance that is resistant to be degraded by microorganisms or hydrolysis enzymes. To be used as materials for biofuel production, it needs pretreatment process to improve efficiency of hydrolysis. In this work, chemical pretreatments on rice straw using three diluted organic acids, including acetic acid, citric acid, oxalic acid, were optimized. Using Response Surface Methodology (RSM), the effect of three pretreatment parameters, acid concentration, treatment time, and reaction temperature, on pretreatment efficiency were statistically evaluated. The results indicated that dilute oxalic acid pretreatment led to the highest enhancement of enzymatic saccharification by commercial cellulase and yielded sugar up to 10.67 mg/ml when using 5.04% oxalic acid at 137.11 oC for 30.01 min. Compared to other acid pretreatment by acetic acid, citric acid, and hydrochloric acid, the maximum sugar yields are 7.07, 6.30, and 8.53 mg/ml, respectively. Here, it was demonstrated that organic acids can be used for pretreatment of lignocellulosic materials to enhance of hydrolysis process, which could be integrated to other applications for various biorefinery processes. 

Reduction of Energy Consumption of Distillation Process by Recovering the Heat from Exit Streams

Distillation consumes enormous quantity of energy. This work proposed a process to recover the energy from exit streams during the distillation process of three consecutive columns. There are several novel techniques to recover the heat with the distillation system; however, a complex control system is required. This work proposed a simpler technique by exchanging the heat between streams without interrupting the internal distillation process that might cause a serious control problem. The proposed process is executed by using heat exchanger network with pinch analysis to maximize the process heat recovery. The test model is the distillation of butane, pentane, hexane, and heptanes, which is a common mixture in the petroleum refinery. This proposed process saved the energy consumption for hot and cold utilities of 29 and 27%, which is considered significant. Therefore, the recovery of heat from exit streams from distillation process is proved to be effective for energy saving.

Development of Efficient Fungal Biomass-Degrading Enzyme Mixtures for Saccharification of Local Lignocellulosic Feedstock

Conversion of lignocellulosic biomass is the basis process for production of fuels, chemicals and materials in the sustainable biorefinery industry. Saccharification of lignocellulosic biomass is an essential step which produces sugars for further conversion to target value-added products e.g. bio-ethanol, bio-plastic, g-valerolactone (GVL), 5-hydroxymethylfuroic acid (HMF), levulinic acid, etc. The goal of this work was to develop an efficient enzyme for conversion of biomass to reducing sugar based on crude fungal enzyme from Chaetomium globosum BCC5776 produced by submerged fermentation and evaluate its activity comparing to a commercial Acremonium cellulase. Five local biomasses in Thailand: rice straw, sugarcane bagasse, corncobs, corn stovers, and palm empty fruit bunches were pretreated and hydrolyzed with varying enzyme loadings. Saccharification of the biomass led to different reducing sugar levels from 115 mg/g to 720 mg/g from different types of biomass using cellulase dosage of 9 FPU/g. The reducing sugar will be further employed as sugar feedstock for production of ethanol or commodity chemicals. This work demonstrated the use of promising enzyme candidate for conversion of local lignocellulosic biomass in biorefinery industry.

An Approach to Manage and Evaluate Asset Performance

Modern engineering assets are complex and very high in value. They are expected to function for years to come, with ability to handle the change in technology and ageing modification. The aging of an engineering asset and continues increase of vendors and contractors numbers forces the asset operation management (or Owner) to design an asset system which can capture these changes. Furthermore, an accurate performance measurement and risk evaluation processes are highly needed. Therefore, this paper explores the nature of the asset management system performance evaluation for an engineering asset based on the System Support Engineering (SSE) principles. The research work explores the asset support system from a range of perspectives, interviewing managers from across a refinery organization. The factors contributing to complexity of an asset management system are described in context which clusters them into several key areas. It is proposed that SSE framework may then be used as a tool for analysis and management of asset. The paper will conclude with discussion of potential application of the framework and opportunities for future research.

The Influence of Zeolitic Spent Refinery Admixture on the Rheological and Technological Properties of Steel Fiber Reinforced Self-Compacting Concrete

By planning this experimental work to investigate the effect of zeolitic waste on rheological and technological properties of self-compacting fiber reinforced concrete, we had an intention to draw attention to the environmental factor. Large amount of zeolitic waste, as secondary raw materials are not in use properly and large amount of it is collected without a clear view of its usage in future. The principal aim of this work is to assure, that zeolitic waste admixture takes positive effect to the self-compacting fiber reinforced concrete mixes stability, flowability and other properties by using the experimental research methods. In addition to that a research on cement and zeolitic waste mortars were implemented to clarify the effect of zeolitic waste on properties of cement paste and stone. Primary studies indicates that zeolitic waste characterizes clear pozzolanic behavior, do not deteriorate and in some cases ensure positive rheological and mechanical characteristics of self-compacting concrete mixes.

Minimizing Fresh and Wastewater Using Water Pinch Technique in Petrochemical Industries

This research involves the design and analysis of pinch-based water/wastewater networks to minimize water utility in the petrochemical and petroleum industries. A study has been done on Tehran Oil Refinery to analyze feasibilities of regeneration, reuse and recycling of water network. COD is considered as a single key contaminant. Amount of freshwater was reduced about 149m3/h (43.8%) regarding COD. Re-design (or retrofitting) of water allocation in the networks was undertaken. The results were analyzed through graphical method and mathematical programming technique which clearly demonstrated that amount of required water would be determined by mass transfer of COD.

Groundwater Quality and the Sources of Pollution in Baghan Watershed, Iran

The protection of groundwater resources is the great important many semiarid and arid environments. Baghan watershed is located in the north of Kangan in the Boshehr province in Iran. The groundwater resources have a vital role in supplying agricultural, drinking, domestic and industrial water demand in Baghan watershed. For our investigation into the water quality we collected 30 samples to chemical and physical analysis. The result showed the marl and evaporation deposits that contain anhydrite and gypsum is the main source of groundwater pollution, and one part of the groundwater was polluted by oil and gas industrial. Another part of the groundwater was contaminated by urban waste water. The electrical conductivity and captions and anions increased around of towns and gas refinery. Although the negative impact of untreated domestic wastewater is relatively low but the results showed strongly the negative impact of wastewater refinery is very considerable. This negative impact increased in downstream due to shallow aquifer. Additionally, the agents that adversely affect the quality of groundwater come from a variety of sources, including geology, domestic wastewater and the Jam refinery in Baghan watershed.

Oil Refineries Emissions: Source and Impact: A Study using AERMOD

The main objectives of this paper are to measure pollutants concentrations in the oil refinery area in Kuwait over three periods during one year, obtain recent emission inventory for the three refineries of Kuwait, use AERMOD and the emission inventory to predict pollutants concentrations and distribution, compare model predictions against measured data, and perform numerical experiments to determine conditions at which emission rates and the resulting pollutant dispersion is below maximum allowable limits.

Reducing Energy Consumption and GHG Emission by Integration of Flare Gas with Fuel Gas Network in Refinery

Gas flaring is one of the most GHG emitting sources in the oil and gas industries. It is also a major way for wasting such an energy that could be better utilized and even generates revenue. Minimize flaring is an effective approach for reducing GHG emissions and also conserving energy in flaring systems. Integrating waste and flared gases into the fuel gas networks (FGN) of refineries is an efficient tool. A fuel gas network collects fuel gases from various source streams and mixes them in an optimal manner, and supplies them to different fuel sinks such as furnaces, boilers, turbines, etc. In this article we use fuel gas network model proposed by Hasan et al. as a base model and modify some of its features and add constraints on emission pollution by gas flaring to reduce GHG emissions as possible. Results for a refinery case study showed that integration of flare gas stream with waste and natural gas streams to construct an optimal FGN can significantly reduce total annualized cost and flaring emissions.

Steady State Simulation and Experimental Study of an Ethane Recovery Unit in an Iranian Natural Gas Refinery

The production and consumption of natural gas is on the rise throughout the world as a result of its wide availability, ease of transportation, use and clean-burning characteristics. The chief use of ethane is in the chemical industry in the production of Ethene (ethylene) by steam cracking. In this simulation, obtained ethane recovery percent based on Gas sub-cooled process (GSP) is 99.9 by mole that is included 32.1% by using de-methanizer column and 67.8% by de-ethanizer tower. The outstanding feature of this process is the novel split-vapor concept that employs to generate reflux for de-methanizer column. Remain amount of ethane in export gas cause rise in gross heating value up to 36.66 MJ/Nm3 in order to use in industrial and household consumptions.