Overview of Precious Metal Content Analysis Methods in Automotive Catalytic Converter

With the increasing awareness of environmental protection, people’s concern of pollution issues arising. Vehicles, as the most important means of transportation, its exhaust emission has received considerable attention. The catalytic converter is able to purify harmful substances in exhaust gas. The absolute content of precious metals in the catalytic converter dominates the exhaust gas purification effect. Accurate detection of precious metal content is of great significance for controlling the cost of catalysts, ensuring catalytic performance and recovering precious metals from spent catalysts. We herein summarized several instruments for precious metals content exploration, such as X-ray fluorescence spectrometer (XRF), atomic absorption spectrometer (AAS), inductively coupled plasma emission spectrometer (ICP) and spectrophotometer. In this thesis, the feasibility of using various devices for characterizing precious metal content in catalytic converters is analyzed and their strengths or weaknesses are elaborated.

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.

Revealing the catalytic mechanism of an ionic liquid with an isotope exchange method

The alkylation mechanism catalyzed by an ionic liquid （as a Lewis acid） may be different from the traditional alkylation mechanism catalyzed by Br nsted acid,especially as their initiation steps are still not clear.In this paper,an isotope exchange method is used to investigate the catalytic mechanism of AlCl 3 /butyl-methyl-imidazolium chloride ionic liquid in the alkylation of benzene with 1-dodecene.The proposed catalytic mechanism was confirmed by analysis of ionic liquid before and after reaction and of the alkylation products of deuterated benzene （C 6 D 6） with 1-dodecene.The proposed mechanism consists of the equilibrium reaction between [Al 2 Cl 7 ] ＋H ＋ and [AlHCl 3 ] ＋ ＋[AlCl 4 ],in which the Br nsted acid [AlHCl 3 ] ＋ is supplied by the reaction of 2-H on the imidazolium ring and [Al 2 Cl 7 ].The alkylation reaction is initiated by the Br nsted acid [AlHCl 3 ] ＋ which reacts with 1-dodecene to form a carbonium ion,then the carbonium ion reacts with benzene to form an unstable σ complex,leading to the formation of 2-phenyldodecane.

Solid-phase extraction of trace Au(Ⅲ) with SDG and determination by the catalytic spectrophotometric method

The new catalytic kinetic spectrophotometric method for Au（III） determination was developed and validated. It was based on the catalytic effect of gold on the oxidation of sudan red III by ammonium peroxodisulfate （（NH4）2S2O8） with nitrilo triacetic acid as an activator in microemulsion and H2SO4 medium. Under optimum conditions, there was the linearity of the calibration curve in the concentration range from 0 to 20 μg/L Au（Ⅲ） at 520 nm. The relative standard deviation was 3.0% with a correlation coefficient of 0.9986. The detection limit achieved was 9.75 × 10^-5 μg/mL. A new method using a column packed with sulfhydryl dextrose gel （SDG） as a solid-phase extractant has been developed for the preconcentration and separation of Au（Ⅲ） ions. The method has been applied to the determination of trace gold with satisfactory results.

Mechanistic Study and Kinetic Determination of Cu(Ⅱ) by the Catalytic Kinetic Spectrophotometric Method

A highly sensitive and selective catalytic kinetic spectrophotometric method for the determination of Cu(Ⅱ) is proposed. It is based on the catalytic effect of Cu(Ⅱ) on the oxidation of glutathione(GSH) by potassium hexacyanoferrate(Ⅲ) in acidic medium at 25.0℃. The reaction is monitored spectrophotometrically by measuring the decrease in absorbance of oxidant at 420 nm using the fix-time method. Under the optimum conditions, the proposed method allows the determination of Cu(Ⅱ) in a range of 0-35.0 ng m L^(-1) with good precision and accuracy and the limit of detection is down to 0.04 ng m L^(-1). The relative standard deviation(RSD) is 1.02%. The reaction orders with respect to each reagent are found to be 1, 1/2, and 1/2 for potassium hexacyanoferrate(Ⅲ), glutathione and Cu(Ⅱ) respectively. On the basis of these values, the rate equation is obtained and the possible mechanism is established. Moreover, few anions and cations can interfere with the determination of Cu(Ⅱ). The new proposed method can be successfully used to the determination of Cu(Ⅱ) in fresh water samples and seawater samples. It is found that the proposed method has fairly good selectivity, high sensitivity, good repeatability, simplicity and rapidity.

Effect of preparation methods on Pt/alumina catalysts for the hydrogen iodide catalytic decomposition

Three kinds of Pt/alumina catalysts were prepared by impregnation-hydrogen reduction, impregnation-hydrazine reduction and electroless plating methods. Their differences in the structures, specific areas and particle sizes were characterized by XRD, BET and TEM, respectively. Furthermore, their catalytic activities for the hydrogen iodide （HI） decomposition were evaluated in a fixed bed reactor. The results show that the catalyst 5%Pt/Al2O3 prepared by the electroless plating has the optimum catalytic properties for HI decomposition owing to the high dispersion of the platinum nano-particles （〈5 nm） on the alumina supports.

Determination of trace arsenic(V) by catalytic solid substrate-room temperature phosphorescence quenching method

In the H2SO4 medium and in the presence of dodecylbenzene sulfonic acid sodiumsalt (DBS), dimethyl yellow (R) could emit strong and stable solid substrate room temperature phosphorescence (RTP) on filter paper. And NaIO4 could oxidize R to cause the RTP quenching. Arsenic(V) could catalyze the reaction of NaIO4 oxidizing R, which caused the RTP sharply quenching. The reducing value of phosphorescence intensity (ΔIp) for the system with DBS is 3.3 times higher than that without DBS. Moreover, the ΔIp is proportional to the concentration of As(V). Based on the facts above, a new RTP quenching method for the determination of trace As(V) has been established.

Catalytic CVD Growth of Carbon Nanotubes by Electric Heating Method

Carbon nanotubes（CNTs） were synthesized by the electric heating catalytic chemical deposition method（CCVD） using acetylene（C2H2） as the carbon source and nitrogen（N2） as carrier gas,and nickel catalyst was loaded by electroplating.The electric heating method,as a new method,electrifies the carbon fiber directly by using its conductivity.The morphology and structure of CNTs were characterized by SEM and TEM,and the surface properties of carbon fibers before and after the growth of CNT were characterized by Raman spectroscopy.The experimental results show that the electric heating method is a new method to produce CNT,and can grow a large number of CNTs in a short time,the crystallization degree and surface average crystallite size of carbon fiber increased after the growth of CNT on it.In addition,electroplating loading catalyst can also be used as an ideal loading way,which can control the number,shape,and distribution of nickel particles by controlling the plating time.

STUDY OF KINETIC ANALYTICAL METHOD BASED ON CATALYTIC REACTIONS

In this thesis a reviwe is presented for the advances of catalytic spec trophotometric method, three new catalytic reaction systems were presented, and its rela live catalytic spectrophotometric methods have been established by flow injection tech nique. Particulary the relative chemometric methods and theories were used in the field of kinetic - catalytic analysis, in order to solve the problems of multicomponents analysis.

Microreactor for the Catalytic Partial Oxidation of Methane

Fixed-bed reactors for the partial oxidation of methane to produce synthetic gas still pose hotspot problems. An alternative reactor, which is known as the shell-and-tube-typed microreactor, has been developed to resolve these problems. The microreactor consists of a 1 cm outside-diameter, 0.8 cm insidediameter and 11 cm length tube, and a 1.8 cm inside-diameter shell. The tube is made of dense alumina and the shell is made of quartz. Two different methods dip and spray coating were performed to line the tube side with the LaNixOy catalyst. Combustion and reforming reactions take place simultaneously in this reactor. Methane is oxidized in the tube side to produce flue gases （CO2 and H2O） which flow counter-currently and react with the remaining methane in the shell side to yield synthesis gas. The methane conversion using the higher-loading catalyst spray-coated tube reaches 97% at 700 ℃, whereas that using the lower-loading catalyst dip-coated tube reaches only 7.78% because of poor adhesion between the catalyst film and the alumina support. The turnover frequencies （TOFs） using the catalyst spray-and dip-coated tubes are 5.75×10^-5 and 2.24×10^-5 mol/gcat· s, respectively. The catalyst spray-coated at 900 ℃ provides better performance than that at 1250 ℃ because sintering reduces the surface-area. The hydrogen to carbon monoxide ratio produced by the spray-coated catalyst is greater than the stoichiometric ratio, which is caused by carbon deposition through methane cracking or the Boudouard reaction.

Characterization and CO Catalytic Oxidation of CuO/Ce-Zr-La-O Catalyst

The Ce-Zr-La-O solid solution was prepared by the sol-gel method. Thestructure and the redox behavior of Ce-Zr-La-O solid solution and CuO/Ce-Zr-La-O catalysts wereinvestigated by using XRD, Raman and TPR techniques. The result shows that the reduction capabilityof Ce_(0.7)Zr_(0.3-y)La_yO solid solution is related to content of La. Appropriate content of La canenhance the redox capability of the solid solution. The oxidation activity of the CuO (6 percent)/Ce_(0.7)Zr_(0.15)La_(0.15)O catalyst is the highest. CuO, which finely dispersed and interacted withthe support, is the site of oxidation activity.

Effects of ultrasonic impregnation combined with calcination in N_2 atmosphere on the property of Co_3O_4/CeO_2 composites for catalytic methane combustion

CoO/CeOcomposites with high surface areas and ultrafine crystalline sizes for catalytic combustion of methane were firstly prepared by a new sol-gel method which combined ultrasonic impregnation treatment and calcination in Natmosphere. The samples were characterized by various means such as nitrogen adsorption/desorption, X-ray diffraction(XRD), Htemperature-programmed reduction(H-TPR),X-ray photoelectron spectroscopy(XPS) and transmission electron microscopy(TEM). Results showed that the modified catalyst had the mesoporous structure, comparatively higher amount of surface oxygen and larger oxygen vacancies than others. As a result of the structure and surface composition merits, a high methane combustion conversion(50%) could be obtained at a low temperature of 262 °C for the modified CoO/CeOcomposites catalysts. The experimental results demonstrated that ultrasonic impregnation treatment combined with the Nthermal treatment prior to calcination in air had a promising application for preparation of CoO/CeOcomposites catalysts for low-temperature catalytic combustion of methane.

Response Surface Modeling of Fuel Rich and Fuel Lean Catalytic Combustion of the Stabilized Confined Turbulent Gaseous Diffusion Flames

The Response Surface Methodology (RSM) has been applied to explore the thermal structure of the experimentally studied catalytic combustion of stabilized confined turbulent gaseous diffusion flames. The Pt/γAl2O3 and Pd/γAl2O3 disc burners were situated in the combustion domain and the experiments were performed under both fuel-rich and fuel-lean conditions at a modified equivalence (fuel/air) ratio (ø) of 0.75 and 0.25 respectively. The thermal structure of these catalytic flames developed over the Pt and Pd disc burners were inspected via measuring the mean temperature profiles in the radial direction at different discrete axial locations along the flames. The RSM considers the effect of the two operating parameters explicitly (r), the radial distance from the center line of the flame, and (x), axial distance along the flame over the disc, on the measured temperature of the flames and finds the predicted maximum temperature and the corresponding process variables. Also the RSM has been employed to elucidate such effects in the three and two dimensions and displays the location of the predicted maximum temperature.

Synthesis of Co Nanoparticles and Their Catalytic Effect on the Decomposition of Ammonium Perchlorate

单音的驱散的公司 nanoparticles 成功地在惰性气氛借助于氢血浆方法被准备。样品的粒子大小，比表面积，晶体结构和形态学被传播描绘电子显微检查法(TEM ) ，赌注方程， X 射线衍射(XRD ) ，和相应选择区域电子衍射(SAED ) 。铵高氯酸盐(AP ) 的分解上的公司 nanoparticles 的催化效果被差热分析仪(DTA ) 调查。与纯 AP 的热解相比，公司 nanoparticles 的增加(2%-10% ，由质量) 减少由 145.01-155.72 ° C 的 AP 的分解温度。与 Co3O4 nanoparticles 和微大小的公司粒子相比，为 AP 的公司 nanoparticles 的催化效果更强壮。如此的效果被归因于大比表面积和它和分解中介气体的公司的相互作用。现在的工作在基于 AP 的燃料为公司 nanoparticles 的申请提供有用信息。

Transition Metal Doped MnO_x-CeO₂Catalysts by Ultrasonic Immersing for Selective Catalytic Reduction of NO with NH₃at Low Temperature

Transition metals doped Mn-based catalysts were prepared via ultrasonic immersing method for the selective catalytic reduction (SCR) of NOx from fuel gas. The Catalysts’ DeNOx efficiency and tolerance to sulfur were investigated in the paper. XRD results demonstrate high dispersion of Mn, Ce and M (Pr, Y, Zr, W) elements on TiO2 carrier, which is favor for reduction of active materials content. Mn-Ce-W catalyst presents uniform particle size about 500 nm to 800 nm from SEM pictures and shows the best NOx conversion of 93.2% at 200°C and 98.4% at 250°C, respectively. Sulfur tolerance analysis indicated that transition metals M can improve the catalysts’ performance when 0.01% SO2 exists in the fuel gas, because metal doping into the Mn-Ce catalyst can inhibit the sulfate deposition, especially metal sulfate, on the catalyst, which can be seen from the Fourier infrared spectrum.

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.

Catalytic effects of Cu-Co~* on the thermal decomposition of AN and AN/KDN based green oxidizer and propellant samples

This paper presents the catalytic effects of Cu-Co~* catalyst on the decomposition of AN and AN/KDN based oxidizer and propellant samples. Ozawa-Flynn-Wall(OFW) iso-conversional method was used for the kinetic studies and to compute the activation energy(Ea) values for various decomposition steps of the prepared oxidizer and propellant samples in the temperature range of 50 e500C. TG-DTG experiments were carried out for both oxidizer and propellant samples at the heating rates of 3, 5, and 10C/min. AN/KDN based oxidizer samples were prepared by an evaporative co-crystallization method. Citric acid sol-gel method was used for the synthesis of Cu-Co~* catalyst. The propellant sample contains HTPB as the fuel binder along with other ingredients such as TDI, DOA, and Glycerol. The Cu-Co~* catalyst was used as 2% by weight to the total weight of catalyzed oxidizer and propellant samples. It was observed from the present study that, Cu-Co~* catalyst helps in reducing the Ea values for AN and AN based propellant samples. However, with the percentage increment of KDN in the AN crystals, Ea value increases.Further, it was observed that Cu-Co~* catalyst stabilizes the initial partial decomposition of KDN.

ESTIMATION OF OVERALL EFFECTIVENESS FACTORS FOR PARALLEL CATALYTIC REACTIONS

Approximate analytical expressions of overall effectiveness factors for parallel catalytic reac-tions occurring in a spherical catalyst pellet with both internal and external mass transfer resistancesare obtained after taking the information given by asymptotic solutions valid for small and largevalues of Thiele moduli.This approximate procedure is feasible for power law as well asLangmuir-Hinshelwood kinetics and the agreement between the approximation and the numerical re-sults is good enough for practical purposes.Moreover,the method does not require any iterative ortrial-and-error computation,and can be conveniently applied in most practical calculations for reac-tors giving reliable results.