Combination of hydrotreating and delayed coking technologies for conversion of residue

Residue conversion by combining catalytic hydrotreating and delayed coking has been evaluated comparatively with both processes alone.Optimal operating conditions are defined to achieve the greatest economic benefit for upgrading an atmospheric residue from a heavy crude oil.A literature model was adapted to simulate the hydrotreating reactor,and for delayed coking,correlations reported in the literature were used.The results with both approaches were employed to calculate the techno-economic feasibility of the combined process scheme.The combination of hydrotreating and delayed coking presented an increase in light fractions of 29% and a reduction in coke production of 47.8%.Based on the calculated net benefit values,it was demonstrated that the combination of hydrotreating and delayed coking is technically and economically better than using each process alone,with highest benefit of 57.7 USD·m^(-3).

Effect of loading on the Ni_2P/Al_2O_3 catalysts for the hydrotreating reactions

The 80%Ni2P/Al2O3 catalysts were prepared by the phosphidation of corresponding 80%Ni/Al2O3 with triphenylphosphine in liquid phase and compared with the 60%Ni2P/Al2O3 for hydrotreating reactions. Both the60%Ni2P/Al2O3 and 80%Ni2P/Al2O3 in comparison exhibited the small and uniform Ni2 P particles（6.3 and8.4 nm,respectively）,high CO uptakes（305 and 345 μmol/g,respectively） and thus high activities for the hydrotreating reactions. After the hydrotreating reactions,the small and uniform Ni2 P particles were remained,although the CO uptakes on the used 60%Ni2P/Al2O3 and 80%Ni2P/Al2O3 were greatly decreased（to 68 and95 μmol/g,respectively） due to the incorporation of S into the Ni2 P surfaces. The 80%Ni2P/Al2O3 was found to be significantly more active than the 60%Ni2P/Al2O3 due to that the 80%Ni2P/Al2O3 possessed more,and more active Ni2 P sites than the 60%Ni2P/Al2O3,probably due to the less S incorporated in the 80%Ni2P/Al2O3 than in the 60%Ni2P/Al2O3 during the hydrotreating reactions.

Regulating catalyst morphology to boost the stability of Ni–Mo/Al_(2)O_(3) catalyst for ebullated-bed residue hydrotreating

Hydrotreating of vacuum residue by ebullated-bed shows tremendous significance due to more stringent environmental regulations and growing demand for lighter fuels. However, enhancing the catalyst stability still remains as a challenging task. Herein, two Ni–Mo/Al_(2)O_(3) catalysts with distinct morphologies(i.e., spherical and cylindrical) were first designed, and the morphology effect on deactivation was systematically elucidated employing multi-characterizations, such as HRTEM with EDX mapping, electron microprobe analysis, FT-IR, TGA and Raman. It is found that spherical catalyst exhibits superior hydrotreating stability over 1600 h. The carbonaceous deposits on spherical catalyst with less graphite structure are lighter, and the coke weight is also smaller. In addition, the metal deposits uniformly distribute in the spherical catalyst, which is better than the concentrated distribution near the pore mouth for the cylindrical catalyst. Furthermore, the intrinsic reason for the differences was analyzed by the bed expansion experiment. Higher bed expansion rate together with the better mass transfer ability leads to the enhanced performance. This work sheds new light on the design of more efficient industrial hydrotreating catalyst based on morphology effect.

A New Kinetic Model for Residue Hydrotreating Based on Chemical Reaction Sections

New definition of virtual molecular-group components about CH and CH2 is proposed in the paper.The new reaction,hydrogenation of CH to CH2(HDCH),can be used to represent the change of C and H in RHT.By using the lumping approach,the kinetic models about HDCH,HDS,HDN,HDCCR,HDM,HDNi and HDV reactions were established.They are key components of the new kinetic model for RHT based on reaction sections.During the construction of kinetic model,goodness-to-fit(R^2)between test data and model data was set as the target value,and the model parameters were calculated accurately.In verification test,the predicted content of H,S,N,CCR,M,Ni and V can match well with the test data.

Optimization of MgO/Al_2O_3 ratio for the maximization of active site densities in the Ni_2P/MgAlO catalysts for the hydrotreating reactions

The Ni2P/MgAlO catalysts with different MgO/Al2O3 ratios were prepared by the phosphidation of corresponding Ni/MgAlO catalysts with triphenylphosphine in liquid phase. It was found that the MgO/Al2O3 ratio affected the Ni2P/MgAlO catalysts significantly. The Ni2P/MgAlO catalyst with the MgO/Al2O3 ratio of 3 (w/w) exhibited the highly dispersed Ni2P particles (similar to 9 nm) with the highest CO uptake (344 mu mol/g) and thus the highest activities for the hydrotreating reactions. However, based on the CO uptakes on the used catalysts, the TOF values for the hydrodesulphurization of dibenzothiophene as well as those for the hydrogenation of tetralin on all the Ni2P/MgAlO catalysts were respectively similar, indicating that the MgO/Al2O3 ratio did not affect the intrinsic activities of Ni2P supported on the MgAlO support for the hydrotreating reactions. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Preparation of Fe_2P/Al_2O_3 and FeP/Al_2O_3 catalysts for the hydrotreating reactions

A 60%Fe/Al_2O_3 catalyst was prepared by the co-precipitation method.It was reduced by H_2 to produce metallic Fe,which was then sulfided by CS_2 to Fe_(0.96) S and Fe_3S_4 or phosphided by triphenylphosphine(PPh3) in liquid phases to Fe2 P and Fe P.It was found that the iron sulfides(Fe0.96 S and Fe_3S_4) exhibited the low activity for the hydrodesulfurization(HDS) reactions.The HDS activity was also low on the Fe(metal)/Al_2O_3 and Fe_2 P/Al_2O_3 catalysts since they were converted into Fe0.96 S and Fe_3S_4 during the HDS reactions.In contrast,the FeP/Al_2O_3 was found to be stable and active for the HDS reactions.In particular,Fe P/Al_2O_3 possessed significantly smaller Fe P particles than Fe P/C,leading to the significant higher HDS activity of FeP/Al_2O_3 than Fe P/C.

Experimental Study of Integrated Ebullated-bed and Fixed-bed for Hydrotreating Mid-Low Temperature Coal Tar to Clean Fuel

A new hydrotreating technology integrating the ebullated-bed(EB) and the fixed-bed(FB) hydrogenation was proposed to investigate the efficiency for hydrotreating mid- low-temperature coal tar to clean fuel, and multiple tests at the bench scale were carried out. The results showed that the distillates obtained from EB reactors were greatly upgraded and could meet the requirements of FB unit without discarding any tail oil. The naphtha produced from FB reactors could be fed to the catalytic reforming unit, while a high quality diesel was also obtained. The unconverted oil(UCO) could be further hydrocracked to clean fuel. It is found that the removal of impurities from the coal tar oil is related with the molecular aggregation structure and composition of the coal tar. Application of the integrated hydrotreating technology to the hightemperature coal tar processing demonstrated that more than half of heavy components could be effectively upgraded.

Application of a New Catalyst Deactivation Model for Residue Hydrotreating

This article reports a new catalyst deactivation model for residue hydrotreating technology(RHT)with three adjustable parameters,named as“active-region-migration model”.The active-region-migration model is proposed to describe the catalyst deactivation of RHT where the catalysts are deactivated due to metal loading.Along with the lumped reaction kinetics,the deactivation model can be applied to simulate the hydrogenation reaction performance in RHT.Industrial data from a commercial RHT unit show reasonably good agreements with the model calculations.Essentially,the active-region-migration model can separately simulate the catalytic-activity change of each hydrogenation reaction during the whole run of RHT,with a single curve.

Heat Exchanger Network Retrofit of Diesel Hydrotreating Unit Using Pinch Analysis

Diesel hydrotreating unit(DHT)is an integral part of the refinery,and its energy-saving optimization is of great significance to the enterprise.In this paper,process simulation software and energy management software are used to simulate the flowsheet and analyze the energy consumption,respectively.Stream data obtained from an existing DHT are applied in the pinch analysis for retrofitting the heat exchanger network(HEN)to achieve maximum energy utilization by using pinch analysis.Since DHT is constrained by pressure,the pressure factor is considered in the process of retrofitting.The results show that the amount of cross-pinch heat transfer is reduced,the inlet temperature of the furnace is increased by 55℃,and the amount of hot and cold utilities can be reduced by 70.25%and 50.16%,respectively.The economic evaluation indicates that the operating cost is saved by 4.39×10^(6)$/a,and the payback period is about 2 months.

Effects of Hydrotreating Severity on Hydrocarbon Compositions and Deep Catalytic Cracking Product Yields

Residue deep hydrotreating(RDHT)process was developed by the Research Institute of Petroleum Processing(RIPP)to provide high quality feedstock for deep catalytic cracking(DCC)process.In this research work,the effects of RDHT process and reaction severity on heteroatom removal,hydrogen content increase,hydrocarbon composition improvement,and DCC product yields were studied.It was showed that the RDHT process can effectively reduce heteroatoms,increase hydrogen content and improve the hydrocarbon compositions,which can contribute to an increase of light olefins yield in DCC unit.

Effect of vacuum gas oil hydrotreating reactor on multiple reactors and hydrogen network

The inlet temperature of the Vacuum Gas Oil(VGO)hydrotreating reactor of a refinery is analyzed with the integration of multiple series reactors and hydrogen network considered.The effect of the inlet temperature(T1)on hydrogen sinks/sources and the product output is analyzed systematically based on the simulation of the series reactors,including VGO hydrotreating reactor,hydrocracking reactor,fluid catalytic cracking reactor and visbreaking reactor.The general relation between the Hydrogen Utility Adjustment(HUA)and multiple pairs of varying sinks and sources is deduced,and correlations between varying streams and T1 are linearly fitted.Based on this,the quantitative equation between HUA and T1 is derived,and corresponding diagram is constructed.The T1 corresponding the minimum hydrogen consumption is identified to be 345°C.

Study on the Active Phases of Ni-W System Hydrotreating Catalysts

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X-Ray Absorption Spectroscopy of Mo and Ni K-edge of Supported Hydrotreating Catalysts

X-ray absorption fine structure (XAFS) and other techniques have been used to characterize Ni-Mo/Al2O3 supported catalysts. The analysis of Mo K-edge spetrum shows that the active species over sulfide catalysts are MoS2-alike and the dispersion of Mo is high at the level of nanometer particles. There may exist some distortion of the local environment of MoS2, which has an influence on the hydrotreating activities of catalysts. Ni K-edge analysis shows that the coordination effects of Ni-Mo favor the dispersion state of active phase and imply a close relationship with catalyst activities.

The S-RHT(R) Technology for Residue Hydrotreating

The S-RHT technology is developed by FRIPP for residue hydrotreating in the fixed bed in order to process the high sulfur crude and increase the yield of light distillates. The technology can be used for treating various kinds of atmospheric residues (AR) or vacuum residues (VR) with a total metal content less than 150 ppm under the operating conditions of a temperature ranging from 360-410℃, a hydrogen partial pressure of 14-15 MPa, a LHSV of 0.20-0.30h-1 and a hydrogen to oil ratio of 700-1000. A certain amount of light products can be obtained and the hydrotreated atmospheric residue can fully meet the needs for the feedstock to RFCC or a blending feedstock to FCC. Based on the S-RHT technology, a 2 Mt/a residue hydrotreating unit has been constructed and successfully started up at Maoming Petrochemical Company by the end of 1999.

Effect of Dodecylbenzene Sulfonic Acid Used as Additive on Residue Hydrotreating

The effect of additive—dodecylbenzene sulfonic acid(DBSA)—on residue hydrotreating was studied in the au toclave. The results showed that the additive improved stabilization of the colloid system of residue, which could delay th aggregation and coke formation from asphaltenes on the catalyst, and make heavy components transformed into light oi The residue conversion in the presence of this additive increased by 1.94%, and the yield of light oil increased by 1.53%when the reaction time was 90 min. The surface properties of the catalyst in the presence of this additive were better tha that of the blank test within a very short time(30 min) and deteriorated rapidly after a longer reaction time due to highe conversion and coke deposition. Compared with the blank test, the case using the said additive had shown that the structur of hydrotreated asphaltene units was smaller and the condensation degrees were higher. The test results indicated that th additive could improve the hydrotreating reactivity of residue via permeation and depolymerization, the heavier componen could be transformed into light oil more easily, and the light oil yield and residue conversion were higher for the case usin the said additive in residue hydrotreating process.

Characterization of Hydrotreating Catalysts in Fundamental Research and Development

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PetroChina's Aldehyde Hydrotreating Catalyst Has Been for the First Time Applied at SINOPEC's Qilu Petrochemical Company

The VAH type catalyst for gas-phase hydrotreating of aldehyde developed by PetroChina’s Petrochemical Research Institute has been applied in commercial scale at the 85 kt/a octanol unit of SINOPEC’s Qilu Petrochemical Company. This unit was successfully put on stream at the first attempt with all quality indicators of products meeting the requirements of the technical agreement to display the advantages of the catalyst in terms of its high activity, high selectivity and high liquid-resistant ability.

Morphology effect on catalytic performance of ebullated-bed residue hydrotreating over Ni-Mo/Al_(2)O_(3)catalyst:a kinetic modeling study

Upgrading of vacuum residue is of prime industrial significance due to the increasing demand for light oils.Elucidating the effect of catalyst morphology on vacuum residue hydrotreating performance by kinetic modeling is therefore of great importance.Herein,kinetic analysis of hydrodemetallization(HDM)and hydrodeconradsoncarbon-residue(HDCCR)performances on industrial Ni-Mo/Al_(2)O_(3)catalysts with spherical and cylindrical morphologies in ebullated-bed were evaluated for more than 1600 h.It was found that the percentage of light impurities easier to be removed on spherical catalysts were 78.20%and 39.43%in HDM and HDCCR reactions,respectively,higher than 65.20%and 17.50%on cylindrical catalysts.This suggests that catalyst morphology affects the impurity removal ability and the impurity properties,resulting in better hydrotreating performance of spherical catalysts.This work not only combines catalyst morphology with impurity removal capability through kinetic modeling,but also provides new insights into the design of efficient hydrotreating catalysts.

Development and application of ex-situ presulfurization technology for hydrotreating catalysts in China

The development and application of ex-situ presulfurization(EPRES)technology for hydrotreating catalysts has been reviewed in the present article.The studies in laboratory scale and commercial practice indicated that the adoption of the EPRES catalyst in industrial application can significantly enhance the degree of presulfurization of metal oxide components,shorten the start-up period,and effectively reduce the environmental impact as well as the danger of start-up procedure in industrial hydrotreating unit.This catalyst has been proved to be versatile for different types of hydrogenation reactions.Different types of active site models are also discussed for better understanding the nature of presulfur-ized catalysts.

Hydrotreating of light gas oil using a NiMo catalyst supported on activated carbon produced from fluid petroleum coke

Nitric acid functionalized steam activated carbon （NAFSAC） was prepared from waste fluid petroleum coke （FPC） and used as a support material for the synthesis ofa NiMo catalyst （2.5 wt-% Ni and 13 wt-% Mo）. The catalyst was then used for the hydrotreatment of light gas oil. The support and catalysts were characterized by Brunauer-Emmett-Teller （BET） gas adsorption method, X-ray diffraction, H2-temperature programmed reduction, NH3-temperature programmed desorption, CO-chemisorption, mass spetrography, scanning electron microscopy （SEM）, Boehm titration, and Fourier transform infrared spectroscopy （FTIR）. The SEM results showed that the carbon material retained a needle like structure after functionalization with HNO3. The Boehm titration, FTIR, and BET results confirmed that the HNO3 functionalized material had moderate acidity, surface functional groups, and mesoporosity respectively. The produced NAFSAC had an inert nature, exhibited the sink effect and few metal support interactions, and contained functional groups. All of which make it a suitable support material for the preparation of a NiMo hydrotreating catalyst. Hydrotreating activity studies of the NiMo/NAFSAC catalyst were carried out under industrial operating conditions in a laboratory trickle bed reactor using coker light gas oil as the feedstock. A parallel study was performed on the hydrotreating activity of NiMo/7-A1203 as a reference catalyst. The hydrodesulfurization and hydrodenitrogena- tion activities of the NiMo/NAFSAC catalyst were 62% and 30%, respectively.