Using Aspen HYSYS to Develop a Custom Molecule-based Reformer Model

A new continuous catalytic reforming model was configured by using a molecule-based reactor module. Themodel was based on the Sinopec Research Institute of Petroleum Processing Co., Ltd. continuous catalytic reformer fullmodel, and was reduced to a size of 157 naphtha molecules (C1−C12) that underwent 764 reactions. The new model inheritedthe advantages of the original model, and had better solving performance and flexibility owing to support by the AspenHYSYS environment. Typical commercial plant data were selected for model validation, which showed advantages in theaccuracy of detailed predictions and the range of its application. In addition, the solving time was reduced from minutes toseconds. Therefore, the simplified model proved to be feasible for industrial application.

Aromatic Compounds Production from Sorbitol by Aqueous Catalytic Reforming

The rules on regulating aromatic compounds production was investigated by aqueous cat- alytic reforming of sorbitol. It was found that aromatics, ketones, furans, organic acids were main compounds in organic phase. The obvious effect of metal content showed that the highest carbon selectivity of aromatics was 34.36% when 3wt% Ni content was loaded on HZSM-5 zeolite modified by MCM-41. However, it was decreased only to 4.82% when Ni content was improved to 20wt%. Meanwhile, different reaction parameters also displayed important impacts on carbon selectivity. It was improved with the increase of temperature, while it was decreased as liquid hourly space velocity and hydrogen pressure was increased. The results showed that appropriate higher temperature, longer contact time and lower hy- drogen pressure were in favor of aromatics information, which suggested a feasible process to solve energy crisis.

Hydrogen Production From Crude Bio-oil and Biomass Char by Electrochemical Catalytic Reforming

We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method. The maximal absolute hydrogen yield reached 110.9 g H2/kg dry biomass. The product gas was a mixed gas containing 72%H2, 26%CO2, 1.9%CO, and a trace amount of CH4. It was observed that adding biomass char （a by-product of pyrolysis of biomass） could remarkably increase the absolute H2 yield （about 20%-50%）. The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H20. In addition, the CuZn-Al2O3 catalyst in the water-gas shift bed could also increase the absolute H2 yield via shifting CO to CO2.

Effects of Current upon Electrochemical Catalytic Reforming of Anisole

The reforming of anisole （as model compound of bio-oil） was performed over the NiCuZn-Al2O3 catalyst, using a recently-developed electrochemical catalytic reforming （ECR）. The influence of-the current on the anisole reforming in the ECR process has been investigated. It was observed that anisole reforming was significantly enhanced by the current approached over the catalyst in the electrochemical catalytic process, which was due to the non-uniform temperature distribution in the catalytic bed and the role of the thermal electrons originating from the electrified wire. The maximum hydrogen yield of 88.7% with a carbon conversion of 98.3% was obtained through the ECR reforming of anisole at 700℃ and 4 A. X-ray diffraction was employed to characterize catalyst features and their alterations in the anisole reforming. The apparent activation energy for the anisole reforming is calculated as 99.54 kJ/mol, which is higher than ethanol, acetic acid, and light fraction of bio-oil. It should owe to different physical and chemical properties and reforming mechanism for different hydrocarbons.

Production of Hydrogen from Bio-oil Using Low-temperature Electrochemical Catalytic Reforming Approach over CoZnAI Catalyst

High-efficient production of hydrogen from bio-oil was performed by electrochemical catalytic reforming method over the CoZnAl catalyst. The influence of current on the hydrogen yield, carbon conversion, and products distribution were investigated. Both the hydrogen yield and carbon conversion were remarkably enhanced by the current through the catalyst, reaching hydrogen yield of 70% and carbon conversion of 85% at a lower reforming temperature of 500 ℃. The influence of current on the properties of the CoZnAl catalyst was also characterized by X-ray diffraction, X-ray photoelectron spectroscopy, thermal gravimetric analysis, and Brunauer-Emmett-Teller measurements. The thermal electrons would play an important role in promoting the reforming reactions of the oxygenated-organic compounds in the bio-oil.

Modeling, Simulation and Optimization of a Whole Industrial Catalytic Naphtha Reforming Process on Aspen Plus Platform

A new 18-lump kinetic model for naphtha catalytic reforming reactions is discussed. By developing this model as a user module, a whole industrial continuous catalytic reforming process is simulated on Aspen plus plat-form. The technique utilizes the strong databases, complete sets of modules, and flexible simulation tools of the Aspen plus system and retains the characteristics of the proposed kinetic model. The calculated results are in fair agreement with the actual operating data. Based on the model of the whole reforming process, the process is opti-mized and the optimization results are tested in the actual industrial unit for about two months. The test shows that the process profit increases about 1000yuan·h-1 averagely, which is close to the calculated result.

Catalytic Transformation of Oxygenated Organic Compounds into Pure Hydrogen

The continual growth in transportation fuels and more strict environmental legislations have led to immense interest in developing green biomass energy. In this work, a proposed catalytic transformation of oxygenated organic compounds （related to bio-oil） into pure hydrogen was desighed, involving the catalytic reforming of oxygenated organic compounds to hydrogen- rich mixture gas followed by the conversion of CO to CO2 via the water gas reaction and the removal of CO2. The optimization of the different reforming catalyst, the reaction conditions as well as various sources of oxygenated organic compounds were investigated in detail. The production of pure hydrogen, with the H2 content up to 99.96% and the conversion of 97.1%, was achieved by the integrated catalytic transformation. The reaction pathways were addressed based on the investigation of decomposition, catalytic reforming, and the water gas reaction.

Multiobjective Optimization of the Industrial Naphtha Catalytic Re-forming Process

In this article, a multiobjective optimization strategy for an industrial naphtha continuous catalytic reform-ing process that aims to obtain aromatic products is proposed. The process model is based on a 20-lumped kinetics re-action network and has been proved to be quite effective in terms of industrial application. The primary objectives in-clude maximization of yield of the aromatics and minimization of the yield of heavy aromatics. Four reactor inlet tem-peratures, reaction pressure, and hydrogen-to-oil molar ratio are selected as the decision variables. A genetic algorithm, which is proposed by the authors and named as the neighborhood and archived genetic algorithm (NAGA), is applied to solve this multiobjective optimization problem. The relations between each decision variable and the two objectives are also proposed and used for choosing a suitable solution from the obtained Pareto set.

Catalytic performances of Ni/mesoporous SiO_2 catalysts for dry reforming of methane to hydrogen

Several mesoporous silicas with different morphologies were controllably prepared by sol-gel method with adjustable ratio of dual template, and they were further impregnated with aqueous solution of nickel nitrate, followed by calcination in air. The synthesized silica supports and supported nickel samples were characterized using N2-adsorption/desorption, X-ray diffraction (XRD), H2temperature-programmed reduction (H2-TPR), Scanning electron microscope (SEM), Transmission electron microscope (TEM) and thermo-gravimetric analysis (TGA-DTG) techniques. The Ni nanoparticles supported on shell-like silica are highly dispersed and yielded much narrower nickel particle-size than those on other mesoporous silica. The methane reforming with dioxide carbon reaction results showed that Ni nanoparticles supported on shell-like silica carrier exhibited the better catalytic performance and catalytic stability than those of nickel catalyst supported on other silica carrier. The thermo-gravimetric analysis on used nickel catalysts uncovered that catalyst deactivation depends on the type and nature of the coke deposited. The heterogeneous nature of the deposited coke was observed on nickel nanoparticles supported on spherical and peanut-like silica. Much narrower and lower TGA derivative peak was founded on Ni catalyst supported on the shell-like silica. © 2016 Science Press

Hydrogen Production by Catalytic Steam Reforming of Bio-oil, Naphtha and CH4 over C12A7-Mg Catalyst

Hydrogen production by catalytic steam reforming of the bio-oil, naphtha, and CH4 was investigated over a novel metal-doped catalyst of （Ca24Al28O64）^4＋·4O^-/Mg （C12A7-Mg）. The catalytic steam reforming was investigated from 250 to 850℃ in the fixed-bed continuous flow reactor. For the reforming of bio-oil, the yield of hydrogen of 80% was obtained at 750℃, and the maximum carbon conversion is nearly close to 95% under the optimum steam reforming condition. For the reforming of naphtha and CH4, the hydrogen yield and carbon conversion are lower than that of bio-oil at the same temperature. The characteristics of catalyst were also investigated by XPS. The catalyst deactivation was mainly caused by the deposition of carbon in the catalytic steam reforming process.

Dynamic Modeling and Simulation of a Commercial Naphtha Catalytic Reforming Process

A first principles-based dynamic model for a continuous catalyst regeneration (CCR) platforming process, the UOP commercial naphtha catalytic reforming process, is developed in this paper. The lumping details of the naphtha feed and reaction scheme of the reaction model are given. The process model is composed of the reforming reaction model with catalyst deactivation, the furnace model and the separator model, which is capable of capturing the major dynamics that occurs in this process system. Dynamic simulations are performed based on Gear numerical algorithm and method of lines (MOL), a numerical technique dealing with partial differential equations (PDEs). The results of simulation are also presented. Dynamic responses caused by disturbances in the process system can be correctly predicted through simulations.

Modelling of a tubular solid oxide fuel cell with different designs of indirect internal reformer

The cell performance and temperature gradient of a tubular solid oxide fuel cell with indirect internal reformer （IIR-SOFC） fuelled by natural gas, containing a typical catalytic packed-bed reformer, a catalytic coated wall reformer, a catalytic annular reformer, and a novel catalytic annular-coated wall reformer were investigated with an aim to determine the most efficient internal reformer system. Among the four reformer designs, IIR-SOFC containing an annular-coated wall reformer exhibited the highest performance in terms of cell power density （0.67 W.cm 2） and electrical efficiency （68%） with an acceptable temperature gradient and a moderate pressure drop across the reformer （3.53 × 10 5 kPa）. IIR-SOFC with an annular-coated wall reformer was then studied over a range of operating conditions： inlet fuel temperature, operating pressure, steam to carbon （S ： C） ratio, gas flow pattern （co-flow and counter-flow pattern）, and natural gas compositions. The simulation results showed that the temperature gradient across the reformer could not be decreased using a lower fuel inlet temperature （1223 K-1173 K） and both the power density and electrical efficiency of the cell also decreased by lowering fuel inlet temperature. Operating in higher pressure mode （1-10 bar） improved the temperature gradient and cell performance. Increasing the S ： C ratio from 2 ： 1 to 4：1 could decrease the temperature drop across the reformer but also decrease the cell performance. The average temperature gradient was higher and smoother in IIR-SOFC under a co-flow pattern than that under a counter-flow pattern, leading to lower overpotential and higher cell performance. Natural gas compositions significantly affected the cell performance and temperature gradient. Natural gas containing lower methane content provided smoother temperature gradient in the system but showed lower power density and electrical efficiency.

Investigation of the role of Ca(OH)2 in the catalytic Alkaline Thermal Treatment of cellulose to produce H2 with integrated carbon capture

The Alkaline Thermal Treatment(ATT)of biomass is one of the few biomass conversion processes that has a potential for BECCS(bio-energy with carbon capture and storage).Combining in-situ carbon capture withcreates a carbon-neutral process that has the potential to be carbon-negative.This study has shown that the conversion of cellulose tosuppressedcan be achieved through the reforming of gaseous intermediates in a fixed bed of 10%Ni/ZrO2.Reforming occurs at low temperatures≤773 K,which could allow for improved sustainability.

A study on naphtha catalytic reforming reactor simulation and analysis

A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data.

Development Forecast of Catalytic Reforming in China

The current status of catalytic reforming in China is reviewed and a forecastof the development in a couple of years or a decade is given. Distinguished from the past decade,the future trend will be focused on revamps, expansions, higher severity, diversified feeds,combination with other processes for higher product quality, and novel catalysts and equipment.

Commercial Application of the PS-VI Catalyst in the Revamped 0.8 Mt/a Catalytic Reforming Unit

This article makes an analysis on the major technical difficulties encountered in the process of revamping and expanding the capacity of the continuous catalytic reforming （CCR） unit from 600 kt/a to 800 kt/a at Tianjin Petrochemical Company. The requirements for expanding the CCR unit capacity to 800 kt/a have been met through adopting the low carbon-make PS-Ⅵ catalyst, properly lowering the RONC of the reformate, and appropriately retrofitting the towers and furnaces while keeping the reaction system, the catalyst regeneration system and the recycle hydrogen compressor intact. The calibration results have revealed that the liquid yield of reformate products, the octane rating of reformate, the pure hydrogen yield, the aromatics yield and the overall conversion rate all have met the revamp design targets.

Development and Commercial Application of High-Platinum CCR Catalyst with Low Coke Deposition Rate

By means of selecting proper additives and optimizing catalyst composition and preparation procedures, a high-platinum and low coke deposition catalyst PS-Ⅶ for continuous catalytic reforming （CCR） without reducing its specific surface area has been successfully developed. This catalyst PS-Ⅶ was evaluated in a 100-mL pilot test unit. Study results showed that under the same reaction conditions the newly developed catalyst PS-Ⅶ achieved a 26% reduction in coke deposition as compared to the existing high-platinum CCR catalyst. This catalyst upon its first commercial application in a 1.39 Mt/a CCR unit had exhibited good anti-attrition performance and good stability in terms of its specific surface area. Compared to the original CCR catalyst this PS-Ⅶ type catalyst could reduce the coke deposition by 27.32% when operating on feedstock with low potential aromatic content, along with apparent increase in C6^＋ liquid yield, hydrogen yield and aromatics yield, which could grapple with the problem associated with the catalyst regeneration constraints after CCR capacity expansion to ensure the longcycle high-load operation of the CCR unit.

Development and Commercial Application of Ultra-Low Pressure Naphtha Reforming Technology with Continuous Catalyst Regeneration

The development history and major technological innovations of the ultra-low pressure naphtha reforming technology with continuous catalyst regeneration in China were introduced.This technology had been adopted by the 1.0 Mt/a CCR unit at the Guangzhou Company.The appropriate catalyst was selected to meet the demand of the unit capacity,the feedstock,and the product slate.The design parameters,including the reaction pressure,the octane number of C5+liquid product,the reaction temperature,the space velocity,the hydrogen/oil molar ratio,and the catalyst circulating rate,were chosen based on the study of process conditions and parameters.The commercial test results showed that the research octane number of C5+product reached 104 when the capacity of the CCR unit was 100%and 115%of the design value.The other technical targets attained or exceeded the expected value.

Ni nanoparticles supported on carbon as efficient catalysts for steam reforming of toluene(model tar)

This paper investigated the influences of surface properties of carbon support and nickel precursors(nickel nitrate, nickel chloride and nickel acetate) on Ni nanoparticle sizes and catalytic performances for steam reforming of toluene. Treatment with nitric acid helped to increase the amount of functional groups on the surface and hydrophilic nature of carbon support, leading to a homogeneous distribution of Ni nanoparticles. The thermal decomposition products of nickel precursor also played an important role, Ni nanoparticles supported on carbon treated with acid using nickel nitrate as the precursor exhibited the smallest mean diameter of 4.5 nm. With the loading amount increased from 6 wt% to 18 wt%, the mean particle size of Ni nanoparticles varied from4.5 nm to 9.1 nm. The as-prepared catalyst showed a high catalytic activity and a good stability for toluene steam reforming: 98.1% conversion of toluene was obtained with the Ni content of 12 wt% and the S/C ratio of3, and the conversion only decreased to 92.0% after 700 min. Because of the high activity, good stability, and low cost, the as-prepared catalyst opens up new opportunities for tar removing.

Advanced characterization for industrial catalysis applications

The interplay between analytical technique and industrial practice has been central in the development of catalytic materials for processing petroleum. This article presents reviews of key aspects of two of the most important classes of catalytic materials: noble-metal Pt nanoparticles (NPs) on alumina, which are the basis of catalytic reforming;and layered sulfides of Mo and W, which catalyze hydrogenation and hetero-atom removal in hydroprocessing. The state of understanding of Pt cluster growth and resulting structures, as developed using X-ray absorption spectroscopy and STEM, is reviewed. Influences of both Pt reduction temperature in hydrogen gas, and oxidizing pretreatment conditions prior to Pt reduction, are considered. Recent work by the present authors on Pt NP structure evolution is presented in the context of the previous work. A review is subsequently presented of layered sulfide based NPs, summarizing contributions from a range of analytical techniques. Work on active site structures of sulfide NPs is reviewed, focusing particularly on the critical interactions of active edge sites with sulfur and hydrogen in chemisorption, physisorption, and spillover interactions. New temperature programmed reduction (TPR) results are presented for supported and unsupported sulfide NPs. Structural changes in TPR of alumina-supported MoS2 are investigated using extended X-ray absorption fine structure and density functional theory modeling, and are determined to arise from removal of identifiable edge-site sulfur species.