ADMET

The use of acyclic diene metathesis (ADMET) in the synthesis of functionalized polyolefins is discussed. The nature of polymerizations, catalysts, and techniques are briefly covered. An overview of recent functionalized ADMET polymers and major contributions to its methodology is given. This chapter will place special emphasis on the use of ADMET to synthesize increasingly complex and new morphologies, resulting in well-defined polyolefin structures and functionalized materials unlocked as a result of this powerful polymerization method. Presented are polyolefins, materials, and architectures not possible through conventional polymerization techniques.

Dual Role of Perovskite Hollow Fiber Membrane in the Methane Oxidation Reactions

The Mixed Ionic and Electronic Conducting (MIEC) membrane reactors are of interest because they have the potential to produce high purity oxygen from air at lower costs and provide a continuous oxygen supply to reactions or/and industrial processes. The study of the dual role oxygen flux and catalytic performance of the unmodified and Ni-coated La0.6Sr0.4Co0.2Fe0.8O3-d hollow fibre membranes (LSCF6428 HFM) in the methane oxidation reactions (i.e., partial oxidation of methane and methane combustion) by using air on lumen side and methane on shell side are shown in this chapter. The LSCF6428 HFM participates not only in the oxygen flux but also in the methane conversion to C2. A Ni-coated LSCF6428 HFM under lean O2/CH4 gradient (i.e., 0.5) showed the production of syngas, carbon dioxide and C2 products in agreement with the thermodynamic calculation. At rich O2/CH4 gradient (i.e., 1.0), the formation of carbon dioxide was facilitated. The main catalytic pathway at lean O2/CH4 gradient and H2 reduction treatment was partial oxidation of methane to C2 and syngas.

Palladium in Heterogeneous Oxidation Catalysis

Palladium is one of the precious group metals mainly used in automobile catalytic converters. Besides, it has an importance in various catalytic processes. Although it is well known for hydrogenation reactions, various oxidations can also be catalyzed by palladium. This chapter gives an overview on the most common application of palladium catalysts in heterogeneously catalyzed acetoxylation, i.e. the acetoxylation of ethylene to vinyl acetate. Derived from this knowledge, the authors summarize in detail recently accumulated research results in acetoxylation of toluene to benzyl acetate that can be easily converted to benzyl alcohol. The chapter includes a detailed description of catalyst syntheses, gas phase oxidation runs, comprehensive characterizations and a deep understanding in catalyst-feed interaction. This development can turn away the manufacture of important petrochemicals from chlorine chemistry to oxidations using molecular oxygen.

Kinetic Models for Complex Parallel–Consecutive Reactions Assessment of Reaction Network and Product Selectivity

Kinetic models were developed to account for the partial contributions of intermediates in complex parallel–consecutive reactions. The models allow precise estimation of the apparent rate constants of all steps in such a reaction network. The hydrodesulfurization (HDS) of dibenzothiophene (DBT) over CoMo-based alumina and carbon catalysts, and over an unsupported molybdenum sulfide catalyst, were investigated in a batch reactor and used to represent this type of reaction. The HDS reactions proceeded through two parallel–consecutive reaction pathways, i.e., direct desulfurization (DDS) and hydrogenation (HYD), in which two main intermediates, namely biphenyl and partially hydrogenated DBT, were involved. Different selectivities in terms of yield fraction (percentage ratio of HYD/DDS) were observed for these catalysts. The results are discussed in the context of proposed HDS reaction networks. Use of these models enables more accurate assessment of differences among the performances of different catalysts.

Catalysis with Room Temperature Ionic Liquids Mediated Metal Nanoparticles

There has been still a growing interest in ionic liquids (ILs) for catalysis, in particular considering their tremendous success made over the past decades. Indeed, ILs for catalysis has been a main subject in chemistry and technology, and a rough estimate is that more than 6000 publications involving IL catalysis have been reported in the past fifteen years. Since there have been a large number of excellent reviews and books concerning the catalysis in ILs, in this chapter the authors mainly focus on the IL immobilized nano- or super-fine metal particles for catalysis, which could bridge or fill the gap between homogeneous and heterogeneous catalysis. Detailed IL-immobilized catalyst preparation, characterization and their application in hydrogenation, C-C coupling, oxidation, etc. will be discussed.

Preparation of Deep Hydrodesulfurzation Catalysts for Diesel Fuel using Organic Matrix Decomposition Method

In this work, a series of supported CoMo or NiMo HDS catalysts have been prepared based on the organic-metal matrix decomposition method and tested for diesel deep HDS with minimum hydrogen consumption under relatively low hydrogen partial pressure conditions. The aim is to develop a HDS catalyst which can reduce sulphur in diesel fuel from 5000ppm down to 50 ppm in a single pass with minimum hydrogen consumption under the conditions of 340oC, 35 bar, LHSV 1.2 h-1 with low H2/oil ratio. The catalysts preparation process was monitored and the resultant catalyst samples before and after the HDS performance test have been characterised, some interesting results have been obtained. The presence of citric acid as organic additive/dispersing agent/chelating agent in the impregnation solution improved HDS activity compared to the equivalent CoMo catalyst prepared without citric acid, The order of activity of the cobalt precursors is Co citrate > Co acetate > Co nitrate.

Production of Ethylene and its Commercial Importance in the Global Market

Ethylene is the largest of the olefin markets and is also one of the most important petrochemically derived monomers that are used as a feedstock for the production of various commercially useful chemical products (e.g. polyethylene, polymers, fibers etc.). The primary objective of this chapter is to provide a comprehensive overview about olefins particularly ethylene production technologies and its commercial significance in the world market. The content of this chapter is presented as follows: a general overview about olefins production is given. This is followed by introducing the reader to ethylene including its properties importance/applications. The next section describes the production technologies of ethylene and some of its selected derivatives, followed by an overview of the technology, market, costs, capacity, global demand and supply of ethylene technology. Finally, main points and outlook of this highly industrially important commodity chemical are summarized.

Advances in Catalytic Technologies for Selective Oxidation of Lower Alkanes

The main challenge for selective oxidation catalysis has always been achieving an economically viable selectivity. In this chapter, the advances made around the last decade in catalyst development for the selective oxidation of C2-C4 alkanes to carboxylic acids and olefins are discussed. To assess the progress made and to study the trends, particular attention has been given to the results reported in patents. A review of the developments reported in the research literature and new knowledge about the catalysts and their functioning have also been summarized. A comparison with existing processes is provided to obtain an idea of which selective oxidation routes are approaching closer to commercial implementation. Finally, some of the challenges that the selective oxidation routes must overcome for widespread commercial adoption are discussed and suggestions for future research are provided.

Desulphurization of Fuel Oils Using Ionic Liquids

Hydrodesulphurization (HDS) is a standard process for removing sulphur compounds in fuel oils in industry. HDS is effective to remove simple aliphatic sulphur compounds while less effective to remove thiophenes, dibenzothiophenes, and their derivatives because of sterically hindered adsorption on catalyst surface. Application of ionic liquids (ILs, a new class of compounds) substituting for traditional volatile organic solvents in extractive desulphurization (EDS) or oxidative desulphurization (ODS), have been being studied intensively in the latest decades, and many very promising results have been obtained, showing a good prospect as complement method to HDS. In this chapter, these fresh research results of EDS and ODS using ILs are summarized along with comprehensive discussions on diversified desulphurization factors along with some potential problems. It can be inferred that ILs are a class of potential ideal solvents to realize clean fuel oil in future although some problems come too.

Sustainable Process Integration in the Petrochemical Industries

The petrochemical industry has a substantial impact on the environment through the use of large quantities of natural resources (mass and energy) and discharge of wastes into the environment. Process integration offers a powerful framework for the sustainable development of the petrochemical through conservation of mass and energy and synergism among the different building blocks in the supply chain. The chapter provides an overview of process integration basics and tools that can be used to enhance the performance of the petrochemical industry. The chapter also describes the key building blocks of the petrochemical supply chain and how they may be integrated. Finally, the chapter describes key drivers and opportunities of process integration within individual petrochemical plants, among various petrochemical facilities, and the relationship to the existing refining infrastructure.