Miscibility of light oil and flue gas under thermal action

The miscibility of flue gas and different types of light oils is investigated through slender-tube miscible displacement experiment at high temperature and high pressure.Under the conditions of high temperature and high pressure,the miscible displacement of flue gas and light oil is possible.At the same temperature,there is a linear relationship between oil displacement efficiency and pressure.At the same pressure,the oil displacement efficiency increases gently and then rapidly to more than 90% to achieve miscible displacement with the increase of temperature.The rapid increase of oil displacement efficiency is closely related to the process that the light components of oil transit in phase state due to distillation with the rise of temperature.Moreover,at the same pressure,the lighter the oil,the lower the minimum miscibility temperature between flue gas and oil,which allows easier miscibility and ultimately better performance of thermal miscible flooding by air injection.The miscibility between flue gas and light oil at high temperature and high pressure is more typically characterized by phase transition at high temperature in supercritical state,and it is different from the contact extraction miscibility of CO_(2) under conventional high pressure conditions.

A Real-time Prediction System for Molecular-level Information of Heavy Oil Based on Machine Learning

Acquiring accurate molecular-level information about petroleum is crucial for refining and chemical enterprises to implement the“selection of the optimal processing route”strategy.With the development of data prediction systems represented by machine learning,it has become possible for real-time prediction systems of petroleum fraction molecular information to replace analyses such as gas chromatography and mass spectrometry.However,the biggest difficulty lies in acquiring the data required for training the neural network.To address these issues,this work proposes an innovative method that utilizes the Aspen HYSYS and full two-dimensional gas chromatography-time-of-flight mass spectrometry to establish a comprehensive training database.Subsequently,a deep neural network prediction model is developed for heavy distillate oil to predict its composition in terms of molecular structure.After training,the model accurately predicts the molecular composition of catalytically cracked raw oil in a refinery.The validation and test sets exhibit R2 values of 0.99769 and 0.99807,respectively,and the average relative error of molecular composition prediction for raw materials of the catalytic cracking unit is less than 7%.Finally,the SHAP(SHapley Additive ExPlanation)interpretation method is used to disclose the relationship among different variables by performing global and local weight comparisons and correlation analyses.

Adsorption of Naphthenic Acids from Dewaxed Vacuum Gas Oil by Activated Clay: Kinetics, Equilibrium and Thermodynamic Studies

This work was mainly concentrated on the removal of naphthenic acids(NAs) from dewaxed vacuum gas oil(VGO) by adsorption using a commercial grade activated clay(AC) adsorption during lube base oil refining. The NAs in dewaxed VGO cut-4 were identified by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry(ESI FT-ICR MS). The AC sample from a refinery was characterized by XRD, BET, TG/DTA, and SEM. A series of experiments were carried out to investigate the performance of NAs adsorption by AC using a batch adsorption technique, in which some key experimental parameters such as temperature, contact time, initial concentration of NA in oil sample as well as the dosage of adsorbent were investigated. Equilibrium isotherms were analyzed using the Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich(D-R) adsorption models. The pseudo-first order, the pseudo-second order, and intraparticle diffusion models were employed to describe the kinetics data. The results revealed that the D-R isotherm provided a better fit to the experimental data than other isotherms, and the adsorption kinetics followed the pseudo-first order kinetic equation. The thermodynamic data indicated that the adsorption process was feasible and spontaneous as an endothermic process. The results could provide a clear understanding of the NAs adsorption by AC during lube base oil processing at refineries.

A Review of an Expert System Design for Crude Oil Distillation Column Using the Neural Networks Model and Process Optimization and Control Using Genetic Algorithm Framework

This paper presents a comprehensive review of various traditional systems of crude oil distillation column design, modeling, simulation, optimization and control methods. Artificial neural network (ANN), fuzzy logic (FL) and genetic algorithm (GA) framework were chosen as the best methodologies for design, optimization and control of crude oil distillation column. It was discovered that many past researchers used rigorous simulations which led to convergence problems that were time consuming. The use of dynamic mathematical models was also challenging as these models were also time dependent. The proposed methodologies use back-propagation algorithm to replace the convergence problem using error minimal method.

Solubility and mass transfer of H2, CH4, and their mixtures in vacuum gas oil: An experimental and modeling study

In this work,the solubility data and liquid-phase mass transfer coefficients of hydrogen(H2),methane(CH4)and their mixtures in vacuum gas oil(VGO)at temperatures(353.15-453.15 K)and pressures(1-7 MPa)were measured,which are necessary for catalytic cracking process simulation and design.The solubility of H2 and CH4 in VGO increases with the increase of pressure,but decreases with the increase of temperature.Henry’s constants of H2 and CH4 follow the relation of In H=-413.05/T+5.27 and In H=-990.67/T+5.87,respectively.The molar fractions of H2 and system pressures at different equilibrium time were measured to estimate the liquid-phase mass transfer coefficients.The results showed that with the increase of pressure,the liquid-phase mass transfer coefficients increase.Furthermore,the solubility of H2 and CH4 in VGO was predicted by the predictive COSMO-RS model,and the predicted values agree well with experimental data.In addition,the gas-liquid equilibrium(GLE)for H2+CH4+VGO system at different feeding gas ratios in volume fraction(i.e.,H285%+CH415%and H290%+CH410%)was measured.The selectivity of H2 to CH4 predicted by the COSMO-RS model agrees well with experimental data.This work provides the basic thermodynamic and dynamic data for fuel oil catalytic cracking processes.

Development of Dispersion Models for the Simulation of Fluid Catalytic Cracking of Vacuum Gas Oil in Riser Reactor

Dispersion models for the simulation of an industrial Fluid Catalytic Cracking Riser Reactor have been developed. The models were developed based on the principle of conservation of mass and energy on the reacting species due to bulk flow and axial dispersion. The four-lump kinetic scheme was used to describe the cracking reactions occurring in the reactor. The model equations were a set of parabolic Ordinary Differential Equations which were reduced to first order differential equations by appropriate substitutions and integrated numerically using 4th order Runge Kutta algorithm using Visual Basic 6.0. Results obtained showed a maximum percentage deviation ranging from 0.31% to 5.7% between model predictions and industrial plant data indicating reasonable agreement. Simulation of model at various operating parameters gave optimum gasoline yield of 45.6% of the most significant variable of temperature (658 K), superficial velocity (0.1 m/s), catalyst to gas oil ratio (7.0) and diffusion coefficient of 0.23 m2/s.

Application of Artificial Neural Networks Based Monte Carlo Simulation in the Expert System Design and Control of Crude Oil Distillation Column of a Nigerian Refinery

This research work investigated comparative studies of expert system design and control of crude oil distillation column (CODC) using artificial neural networks based Monte Carlo (ANNBMC) simulation of random processes and artificial neural networks (ANN) model which were validated using experimental data obtained from functioning crude oil distillation column of Port-Harcourt Refinery, Nigeria by MATLAB computer program. Ninety percent (90%) of the experimental data sets were used for training while ten percent (10%) were used for testing the networks. The maximum relative errors between the experimental and calculated data obtained from the output variables of the neural network for CODC design were 1.98 error % and 0.57 error % when ANN only and ANNBMC were used respectively while their respective values for the maximum relative error were 0.346 error % and 0.124 error % when they were used for the controller prediction. Larger number of iteration steps of below 2500 and 5000 were required to achieve convergence of less than 10-7?for the training error using ANNBMC for both the design of the CODC and controller respectively while less than 400 and 700 iteration steps were needed to achieve convergence of 10-4?using ANN only. The linear regression analysis performed revealed the minimum and maximum prediction accuracies to be 80.65% and 98.79%;and 98.38% and 99.98% when ANN and ANNBMC were used for the CODC design respectively. Also, the minimum and maximum prediction accuracies were 92.83% and 99.34%;and 98.89% and 99.71% when ANN and ANNBMC were used for the CODC controller respectively as both methodologies have excellent predictions. Hence, artificial neural networks based Monte Carlo simulation is an effective and better tool for the design and control of crude oil distillation column.

Thermodynamics of removing impurities from crude lead by vacuum distillation refining

A novel technique was developed to remove impurities from crude lead by vacuum distillation.The thermodynamics on vacuum distillation refining process of crude lead was studied by means of saturated vapor pressure of main components of crude lead,separation coefficients and vapor-liquid equilibrium composition of Pb-i（i stands for an impurity） system at different temperatures.The behaviors of impurities in the vacuum distillation refining process were investigated.The results show that the vacuum distillation should be taken to obtain lead from crude lead,in which Zn,As and partial Sb are volatilized at lower temperature of 923-1023 K.Lead is distilled from the residue containing Cu,Sn,Ag and Bi at higher temperature of 1323-1423 K,but the impurity Bi is also volatilized along with lead and cannot be separated from lead.

Formulating Highway Paving Asphalts from the Vacuum Residue of a Paraffinic Crude

Many specifications of paving asphalts are closely related to their colloidal stability, which is, however, determined by their exact chemical compositions. The Yumen vacuum residue (YVR), the bottoms of a paraffinic crude oil is unfit for the production of highway paving asphalts directly, Neither are the de-oiled asphalts of the YVR. In this research a blending method and an optimal process of solvent de-asphalts are adopted to investigate the feasibility of formulating highway-paving asphalts from YVR. Results show that highway paving asphalts are formulated by blending solvent de-oiled asphalts with one or more of the materials including YVR, decanted oil from FCC process, and furfural extracts from lubricating base stocks. Further investigations indicate that adding oil decanted from FCC process to the solvent de-asphalting process can increase the de-asphalted oil production, improve the de-oiled asphalts quality, and thus optimize the refinery processes. The methodology of this research can be extended even to refineries processing non-paraffinic crude oils.

Design of artificial neural networks using a genetic algorithm to predict saturates of vacuum gas oil

Accurate prediction of chemical composition of vacuum gas oil （VGO） is essential for the routine operation of refineries. In this work, a new approach for auto-design of artificial neural networks （ANN） based on a genetic algorithm （GA） is developed for predicting VGO saturates. The number of neurons in the hidden layer, the momentum and the learning rates are determined by using the genetic algorithm. The inputs for the artificial neural networks model are five physical properties, namely, average boiling point, density, molecular weight, viscosity and refractive index. It is verified that the genetic algorithm could find the optimal structural parameters and training parameters of ANN. In addition, an artificial neural networks model based on a genetic algorithm was tested and the results indicated that the VGO saturates can be efficiently predicted. Compared with conventional artificial neural networks models, this approach can improve the prediction accuracy.

Study on the Removal of MIBK from Aqueous Solution by Vacuum Membrane Distillation

Methyl isobutyl ketone(MIBK) is widely used as extraction agent in hydrometallurgy. As it has a definite solubility in water, so when using MIBK as extraction agent, there will be MIBK in stripping solutions inevitably, which not only pollutes working conditions, but also affects the quality of ultimate product. In order to remove MIBK from aqueous solutions, the means of flat vacuum membrane distillation(VMD) is studied in the paper. The area of the membrane used in the study is 0.02 m 2, the initial volume of feed is 2 L, each experiment was conducted over a time period of 60 120 min. The influences of the factors such as temperature(34.8 55.0 ℃); pressure in the permeate side(10.67 14.67 kPa) and feed flow rate(27.8 69.4 mL/s) were experimentally studied. Increasing the temperature or reducing the pressure in the permeate side results in a faster removal of MIBK; however there is a decrease in removal factor β , increasing the feed flow rate results in a faster removal of MIBK and an increase of removal factor β , especially in the range of lower flow rate. The study indicates that the aim of MIBK removal and recycle from dilute aqueous solutions can be achieved by VMD.

Efficacy and safety of active silicone oil removal through a 23-gauge transconjunctival cannula using an external vacuum pump

AIM: To evaluate the efficacy and safety of active removal of silicone oil with low and high viscosity through a 23-gauge transconjunctival cannula using an external vacuum pump.METHODS: This study was conducted as a prospective, interventional case series. A total of 22 eyes of 21 patients [1000 centistokes(c St): 17 eyes, 5700 c St:5 eyes] were included in this study. All patients underwent active silicone oil removal via the entire lumen of a 23-gauge microcannula with suction pressure of a650-700 mm Hg vacuum using an external vacuum pump. A tubing adaptor from the Total Plus Pak誖(Alcon,Fort Worth, USA) was used to join the microcannula and silicone vacuum tube connected to an external vacuum pump. Main outcome measures were mean removal time,changes of intraocular pressure(IOP) and visual acuity,and intraoperative and postoperative complications.RESULTS: Mean removal time(min) was 1.49±0.43 for1000 c St and 7. 12 ± 1. 27 for 5700 c St. The IOP was18.57±7.48 mm Hg at baseline, 11.68 ±4.55 mm Hg at day1 postoperatively(P <0.001), and 15.95±4.92, 16.82±3.81,17.41 ±3.50, and 17.09 ±3.01 mm Hg after one week, one month, three months, and six months, respectively. All patients showed improved or stabilized visual acuity.There was no occurrence of intraoperative or postoperative complications during the follow up period.CONCLUSION: This technique for active removal of silicone oil through a 23-gauge cannula using an external vacuum pump is fast, effective, and safe as well as economical for silicone oil with both low and high viscosity in all eyes with pseudophakia, aphakia, or phakia.

Hydrochloric Acid Recovery from Rare Earth Chloride Solutions by Vacuum Membrane Distillation (1) Study on the Possibility

The equilibrium between the gas-liquid phases of the system of HCl-RECl_3-H_2O was analyzed,and the possibility of hydrochloric acid recovery from rare earth chloride solutions by vacuum membrane distillation (VMD) was experimentally studied in the laboratory scale. The results indicate that increasing initial concentrations of both hydrochloric acid and rare earth increase recovery ratio of hydrochloric acid,and recovery ratio of 80% can be achieved. Concentrated multiple of rare earth shows great influence on recovery ratio,leakage ratio of rare earth is less than 2% generally,and pure acid can be acquired in the permeate side. The two factors,namely flux and leakage ratio,which may determine the future use of VMD were also discussed.

Impurity distribution in distillate of terbium metal during vacuum distillation purification

The distribution rules of impurities in distilled terbium metal were investigated by vacuum distillation purificationexperiment and theoretical analysis.It is found that Ti impurity in distilled terbium is220mg/kg in the initial stage of the distillationpurification,increases slowly in the middle stage,and increases rapidly in the last stage,reaching2260mg/kg,and the modifiedseparation coefficient of Ti is1/19.02.The diffusion of the impurity Ti in liquid metal can reach a quasi-equilibrium state in theinitial stage of distillation purification and the calculated results agree well with experimental results;the distribution profile ofimpurity Cu is opposite to Ti,being380mg/kg in the initial stage,decreasing linearly to290mg/kg in the last stage,and themodified separation coefficient is17.99,and the theoretical calculated results are inconsistent with the experimental result.

Application of Discrete Lumped Kinetic Modeling on Vacuum Gas Oil Hydrocracking

The kinetic model of vacuum gas oil （VGO） hydrocracking based on discrete lumped approach was investigated, and some improvement was put forward at the same time in this article. A parallel reaction scheme to describe the conver- sion of VGO into products （gases, gasoline, and diesel） proposed by Orochko was used. The different experimental data were analyzed statistically and then the product distribution and kinetic parameters were simulated by available data. Fur- thermore, the kinetic parameters were correlated based on the feed property, reaction temperature, and catalyst activity. An optimization code in Matlab 2011b was written to fine-me these parameters. The model had a favorable ability to predict the product distribution and there was a good agreement between the model predictions and experiment data. Hence, the ki- netic parameters indeed had something to do with feed properties, reaction temperature and catalyst activity.

Egyptian heavy vacuum gas oil hydrotreating over Co-Mo/CNT and Co-Mo/γ-Al2O3 catalysts

The catalytic activity of CoMoS /CNT towards the Egyptian heavy vacuum gas oil hydrotreating was studied. The delivered CNT was functionalized with 6 mol /L HNO_3. The CNT were loaded with 12% MoO_3( by weight) and 0.7 Co /Mo atomic ratio with impregnation methods. The γ-Al_2O_3 catalyst was also prepared by impregnation method to compare both catalysts activities.The analysis tools such XRD,Raman spectroscopy,TEM,and BET were used to characterize the catalysts. The autoclave reactor was used to operate the hydrotreating experiments. The hydrotreating reactions were tested at various operating conditions of temperature 325-375 ℃,pressure 2-6 MPa,time 2-6 h,and catalyst /oil ratio( by weight) of 1 ∶75,1 ∶33 and 1 ∶10. The results revealed that the CoMoS /CNT was highly efficient for the hydrotreating more than the CoMoS /γ-Al_2O_3. Also, the hydrodesulfurization( HDS) increased with increasing catalyst /oil ratio. Additionally,results showed that the optimum condition was temperature 350℃,pressure 4 MPa,catalyst /oil ratio of 1 ∶75 for 2 h. Furthermore,even at low CoMoS /CNT catalyst /oil ratio of 1 ∶75,an acceptable HDS of 77.1% was achieved.

Novel design of lubricant-type vacuum distillation process for lube base oils production from hydrocracking tail oil

Dividing-wall columns(DWCs)are widely used in the separation of ternary mixtures,but rarely seen in the separation of petroleum fractions.This work develops two novel and energy-efficient designs of lubricant-type vacuum distillation process(LVDP)for the separation of hydroisomerization fractions(HIF)of a hydrocracking tail oil(HTO).First,the HTO hydroisomerization reaction is investigated in an experimental fixed-bed reactor to achieve the optimum liquid HIF by analyzing the impact of the operating conditions.A LVDP used for HIF separation is proposed and optimized.Subsequently,two thermal coupling intensified technologies,including side-stream(SC)and dividing-wall column(DWC),are combined with the LVDP to develop side-stream vacuum distillation process(SC-LVDP)and dividing-wall column vacuum distillation process(DWC-LVDP).The performance of LVDP,SC-LVDP,and DWC-LVDP are evaluated in terms of energy consumption,capital cost,total annual cost,product yields,and stripping steam consumption.The results demonstrates that the intensified processes,SC-LVDP and DWC-LVDP significantly decreases the energy consumption and capital cost compared with LVDP.DWC-LVDP further decreases in capital cost due to the removal of the side stripper and narrows the overlap between the third lube oils and fourth lube oils.This study attempts to combine DWC structure into the separation of petroleum fractions,and the proposed approach and the results presented provide an incentive for the industrial implementation of high-quality utilization of HTO through intensified LVDP.

THE SEPARATION OF Pb-Sb ALLOYS BY VACUUM DISTILLATION

This paper summarizes the research results of vacuum distillation of Pb-Sb alloy and crude antimony.In our study,we have found the basic law which states that in Pb-Sb phase diagrams,the part which is rich in lead can be used to guide the purification of lead by distillation,while the part rich in antimony can be used to guide the purification of Sb.where the compositional point C is the azeotropic mixture.The technical experi-mental results at temperatures between 7OO-85OC are coincident with those of theorical study.The expanding experiment at the 100kg scale produced satisfactory results.

Study of Oil/Water Interfacial Tension of Vacuum Residual Fractions from Iranian Light Crude Oil

The vacuum residual from Iranian Light crude oil are separated into a series of 16 narrow fractions according to the molecular weight by the supercritical fluid extraction and fractional (SFEF) technology. The chemical element and the UV spectrum of each fraction are analyzed. The effects of several factors on the interfacial tension are investigated, which are the fraction concentration in oil phase, the ratio of oil component, the salts dissolved in the water phase and the pH value. The interfacial tension decreases rapidly as the concentration of the residual fraction in the oil increases, showing a higher interfacial activity of the fraction. The interfacial tension changes, as the amount of absorption or the state of the fractions in the interface changes resulting from different ratios of oil, different kinds or concentrations of salts in water, and different pH values. It is concluded that the interfacial tension changes regularly, corresponding to the regular molecular parameters of the vacuum residual fractions.

Innovative hydrophobic/hydrophilic perfluoropolyether(PFPE)/polyvinylidene fluoride(PVDF)composite membrane for vacuum membrane distillation

Though membrane distillation(MD)has gained more and more attention in the field of desalination,the wetting phenomenon was still a non-negligible problem.In this work,a method combined dip-coating and UV in situ polymerization for preparing hydrophobic/hydrophilic perfluoropolyether(PFPE)/polyvinylidene fluoride composite membranes.This composite membrane consisted of a top thin hydrophobic coating layer and hydrophilic substrate membrane.In terms of anti-wetting properties,contact angle and liquid entry pressure of all composite membranes(except for those based on 0.45μm)exceeded 160°and 0.3 MPa,respectively.In particular,the desalination performance was tested in vacuum membrane distillation tests by feeding 3.5%(mass)saline solution(NaCl)at 60℃.The composite membranes with larger support pore size and lower PFPE content had higher membrane distillation flux.And for stability tests(testing the 0.22μm membrane coated by 5%(mass)PFPE),the highest MD flux29.08 kg·m^(-2)·h^(-1) and stable salt rejection(over 99.99%)during the period.Except that,the effects of coating material concentration and pore sizes of substrate membrane were also investigated for surface morphology and topography,porosity,mechanical strength and pore size characteristics.This work provided a simple and effective alternative to prepare excellent hydrophobic composite membranes for MD applications.