Study on the Catalytic Reforming Law of Solid-Phase Carbon and Nitrogen Sources Loaded with MnO_(2)at Low Temperatures in Tahe Heavy Oil

MnO_(2)/Melem composites were synthesized with MnO_(2)nanoparticles loaded onto the Melem using the hydrothermal method.As raw materials for C and N carriers,Melem was prepared from melamine roasted at 354℃,and KMnO_(4)as a raw material for Mn,MnO_(2)nanoparticles were prepared using the hydrothermal synthesis of KMnO_(4).Scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),and a laser particle size analyzer were used for structural characterization,and the catalytic oxidation performance of the heavy oil was investigated at different reaction temperatures(100℃to 180℃)using MnO_(2)/Melem with an oxidant and donor protonic acid.The results showed that the synthesizedβ-MnO_(2)nanoparticles were successfully loaded onto the Melem surface;the oil samples before and after the reaction at different temperatures were subjected to SARA analysis using Fourier transform infrared(FT-IR),elemental analysis,gas chromatography-mass spectrometry(GC-MS)and viscosity tests,respectively.It was determined that the hydrocarbons in the crude oil were converted to heavy mass by oxidation reactions with the oxidant mainly through a low-temperature oxidation process below 140℃in the heavy oil when the temperature exceeds 140℃,in addition to the oxidation reaction with the oxidant,a cleavage reaction in the carbon chain occurs to form hydrocarbon substances with lower molecular weights.

Effects of sol-gel method and lanthanum addition on catalytic performances of nickel-based catalysts for methane reforming with carbon dioxide

The nickel-based catalysts were prepared by the sol-gel method and used for the CH4 reforming with CO2. The effects of the sol-gel method on the specific surface area, catalytic activity, desorption, and reduction performances of catalysts were investigated with BET, TPR, and TPD. Compared with the catalyst prepared by the impregnation method, the results indicated that the catalysts prepared by the sol-gel method had larger specific surface area, showing higher catalytic activities and exhibiting perfect desorption and reduction performances. In addition, the modification effects of adding La were studied, and it was found that the 0.75NLBT catalyst constituted of 5wt.%Ni-0.75wt.%La was optimal.

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

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.

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

由简历油，石油，和 CH 4 改过的催化蒸气的氢生产在新奇做金属的催化剂上被调查(Ca 24 艾尔 28 O 64)4+4O/Mg (C12A7-Mg ) 。改过的催化蒸气从 250 ～ 850 瑡癩?瑳畲瑣牵 e

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.

Preparation and catalytic properties of ZrO_2-Al_2O_3 composite oxide supported nickel catalysts for methane reforming with carbon dioxide

ZrO 2-Al 2O 3 composite oxides and supported Ni catalysts were prepared, and characterized by N 2 adsorption /desorption, X-ray diffraction(XRD) an d X-ray photoelectron spectroscopy(XPS) techniques. The catalytic performance and carbon deposition was also investigated. This mesoporous composite oxide is shown to be a promising catalyst support. An increase in the catalytic activity and stability of methane and carbon dioxide reforming reaction was resulted from the zirconia addition, especially at 5wt% ZrO 2 content. The Ni catalyst supported ZrO 2-Al 2O 3 has a strong resistance to sintering and the carbon deposition in a relatively long-term reaction.

Study and Analysis on Naphtha Catalytic Reforming Reactor Simulation

A naphtha catalytic reforming unit with four reactors connected in series is analyzed. A physicalmodel is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamicsequations are selected to describe the naphtha catalytic reforming reaction characteristics based on idealiz-ing the complex naphtha mixture to represent the paraffin, naphthene, and aromatic groups with individualcompounds. The simulation results based on above models agree very well with actual operating data ofprocess unit.

A Lumping Kinetic Model for Catalytic Reforming

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Fuel Oil Production from Two-Stage Pyrolysis-Catalytic Reforming of Brominated High Impact Polystyrene Using Zeolite and Iron Oxide Loaded Zeolite Catalysts

The experiments of two-stage pyrolysis and catalytic reforming of high impact polystyrene (HIPS) containing brominated flame retardants and antimony trioxide (Sb2O3) were conducted in the presence of four zeolite catalysts in order to remove the bromine content from the derived oil products. The four catalysts used were natural zeolite (NZ), iron oxide loaded natural zeolite (Fe-NZ), HY zeolite (YZ) and iron oxide loaded HY zeolite (Fe-NZ). The effect of catalyst types on the product yield, the gas and oil product composition and the debromination efficiency of the oil products was evaluated in details. The results showed that the loading of iron oxides reduced the pore size and surface areas of natural zeolite and HY zeolite. Regardless of the presence of catalysts, the single-ring aromatic compounds were the main components of the oil products, such as ethylbenzene, toluene, styrene and cumene. Meanwhile, when YZ and Fe-YZ were used, the two-ring and multi-ring aromatic compounds in the oils, as well as the yield of gas products, significantly increased at the expense of valuable single-ring aromatic compounds. Furthermore, in terms of the debromination performance of the oil products, Fe-NZ and Fe-YZ were better than NZ and YZ, duo to the loading of iron oxide, which could react with derived HBr and then remove more bromine from the oil products.

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.

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 Forecast of Catalytic Reforming in China

The current status of catalytic reforming in China is reviewed and a forecast of 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

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.

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.

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.

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.

Methane Dry Reforming over Alumina Supported Co Catalysts

A series of Co/γ-Al_2O_3 catalysts were prepared with the impregnation method and characterized by means of the BET specific surface area, X-ray diffraction(XRD), thermogravimetric analysis(TGA) and Laser Raman spectroscopy. The Co/γ-Al_2O_3 catalysts were activated by using H_2, 20%CH_4/H_2 or CH_4, respectively. There was no obvious difference between the activities of the Co/γ-Al_2O_3 catalyst activated by using the different activation methods for methane dry reforming. The catalytic properties of the Co/γ-Al_2O_3 catalysts with different Co loadings were also investigated. The optimized Co loading for the Co/γ-Al_2O_3 catalyst pretreated with 20% CH_4/H_2 is around 12%(mass fraction).

Real-Time Optimization Model for Continuous Reforming Regenerator

An approach for the simulation and optimization of continuous catalyst-regenerative process of reforming is proposed in this paper.Compared to traditional method such as finite difference method,the orthogonal collocation method is less time-consuming and more accurate,which can meet the requirement of real-time optimization(RTO).In this paper,the equation-oriented method combined with the orthogonal collocation method and the finite difference method is adopted to build the RTO model for catalytic reforming regenerator.The orthogonal collocation method was adopted to discretize the differential equations and sequential quadratic programming(SQP)algorithm was used to solve the algebraic equations.The rate constants,active energy and reaction order were estimated,with the sum of relative errors between actual value and simulated value serving as optimization objective function.The model can quickly predict the fields of component concentration,temperature and pressure inside the regenerator under different conditions,as well as the real-time optimized conditions for industrial reforming regenerator.

Effects of Current on Microcosmic Properties of Catalyst and Reforming of Bio-oil

从简历油的氢的高度有效的生产被在常规基于 Ni 的改过催化剂上使用一条低温度的电气化学的催化改过途径完成(NiO-Al 2 交流电子水流通过了催化剂床的 O 3), 。改过的简历油上的电流的支持的效果被学习。改过的简历油的表演被通过了催化剂的水流显著地提高，这被发现。包括 Brunauer Emmett 出纳(赌注)表面区域，毛孔直径，毛孔体积，雏晶的尺寸和进 Ni 的 NiO 的减小水平，催化剂的小宇宙的性质上的水流的效果被赌注小心地描绘，X光检查衍射，X光检查光电子光谱学，并且扫描电子显微镜。从触电的催化剂的热电子的解吸附作用被 TOF (飞行的时间) 直接观察大小。机制简历油的电气化学的催化改过基于上述调查被讨论。