Selective catalytic reduction of aromatic nitro compounds and hydrocarbons: monograph PDF
Preview Selective catalytic reduction of aromatic nitro compounds and hydrocarbons: monograph
AL-FARABI KAZAKH NATIONAL UNIVERSITY Y. A. Aubakirov, L. R. Sassykova SELECTIVE CATALYTIC REDUCTION OF AROMATIC NITRO COMPOUNDS AND HYDROCARBONS Monograph Almaty «Qazaq university» 2018 UDC 665.6+66.097+541.128:665.658.2+665.654.2+ 665.664.4+661.183.6+66.095.217+66.095.253.7 LBC 24.235, Л61я73, Г23я73-1 A 80 Recommended for publication by the decision of the Academic Council of the al-Farabi KazNU (Protocol № 9 dated 30.04.2018) and RISO of the al-Farabi KazNU (Protocol № 6 dated 04.05.2018) Reviewers: Doctor of Chemistry, Professor B.S. Selenova Doctor of Chemistry, Professor S.M. Tazhibayeva Aubakirov Y.A., Sassykova L.R. A 80 Selective catalytic reduction of aromatic nitro compounds and hydrocarbons: monograph / Y.A. Aubakirov, L.R. Sassykova. – Almaty: Qazaq university, 2018. – P. 338. ISBN 978-601-04-3441-7 In the monograph questions of reduction of aromatic nitro compounds and hydrocarbons for producing valuable intermediate and final products are considered. Catalytic hydrogenation at atmospheric and elevated hydrogen pressures is described in detail. The literature and patent data as well as the results of own studies of the authors are presented. A comparative analysis of the mechanisms of hydrogenation of aromatic nitro compounds and hydrocarbons of various authors is given. For the convenience of the reader the monograph contains a detailed glossary and necessary illustrative material. The monograph is intended for researchers working in the field catalysis, fine organic synthesis, chemical technology of organic substances, oil refining and petrochemistry; bachelors, masters and doctoral students studying in the сhemistry specialties. Publishing in authorial release UDC 665.6+66.097+541.128:665.658.2+665.654.2+ 665.664.4+661.183.6+66.095.217+66.095.253.7 LBC 24.235, Л61я73, Г23я73-1 © Aubakirov Y.A., Sassykova L.R., 2018 ISBN 978-601-04-3441-7 © Al-Farabi KazNU, 2018 TERMS AND ACRONYMS AB – Azobenzene Abs – Absorption ACHOL – Aminocyclohexanol p-ADA – p-Aminodiethylaniline AD – Aromatic Derivatives AEC – Atomic Electric Charge AH – Aromatic Hydrocarbons AHM – Advanced Huckel Method AN – Aniline 4-ANT – 4-Amino-2-Nitrotoluene AO – Atomic Orbitals AOB – Azoxybenzene p-AP – p-Aminophenol APG – Associated Petroleum Gas p-ATSA – p-Aminotoluenesulfonic Acid AVT – Atmospheric-Vacuum Tube BFLH (or WFLH) – Broad (Wide) Fraction of Light Hydrocarbons BMOs – Binding Molecular Orbitals BO – Boundary Orbitals CDA – Color Developing Agent CHA – Cyclohexylamine p-CHNB – p-Chloronitrobenzene CHT – Catalytic Hydrogen Transfer CNM – Carbon Nanomaterials DACH – Diaminocyclohexane DADB – Diaminodibenzyldisulphonic Acid DAS – 4,4’-Diaminostilbene-2,2’-Disulfonic Acid 2,4-DAT – 2,4-Diaminotoluene DA – Diethylenetriamine DDs – Diphenyl Derivatives °С – Degree Celsius Des – Desorption DMF – Dimethylformamide DNDB – Dinitrodibenzyldisulphonic Acid DNS – 4,4’-Dinitrostilbene-2,2’-Disulfonic Acid DNT – Dinitrotoluene 2,4-DNT – 2,4-Dinitrotoluene 2,6-DNT – 2,6-Dinitrotoluene EA – Ethylenediamine EB – Ethyl Benzene EDP – Electrical Desalting Plant GED – Gas Electron Diffraction GHG – Greenhouse Gases GFM – Glass-Fiber Materials GPP – A Gas Processing Plant 3 GTL – Gas-to-Liquid Technology FCC – A Fluid Catalytic Cracking FGO – Functionalized Graphite Oxide FL – Flammable Liquids 4-HA-2-HT – 4-Hydroxylamino-2-Nitrotoluene HAPs – Hazardous Air Pollutants HB – Hydrazobenzene HC – Hydrocarbons HF – Hartree-Fock Method HOAO – Highest Occupied Atomic Orbital HPK – High-Pressure Kinetic Unit IL – Ionic Liquid IR Spectroscopy – Infrared Spectroscopy K – Degree Kelvin KPO – Karachaganak Petroleum Operating LG – Liquefied Gases LMOs – Loosening Molecular Orbitals Molecular Orbitals MAC (MPC) – The Maximum Allowable (Permissible) Concentrations of Substances In – The Method of Molecular Orbitals The Air MMOs MO – Molecular Orbitals MNT – Mononitrotoluene MSC – Metal Supported Catalyst m-NA – meta-Nitroaniline p-NA – para-Nitroaniline NB – Nitrobenzene NBMOs – Non-Binding Molecular Orbitals ND – Nanodiamonds p-NDA – p-Nitrodiethyl Aniline o-NP – ortho-Nitrophenol p-NP – para-Nitrophenol NSB – Nitrosobenzene PAHs – Polynuclear Aromatic Hydrocarbons PES – Potential Energy Surfaces m-PhDA – m-Phenylenediamine PHA – Phenylhydroxylamine PhDA – Phenylenediamine PM – Particulate matter p-NT – p-Nitrotoluene PVA – Polyvinyl Alcohol PVM – Paint and Varnish Material QSPR – Quantitative Structure – Property Relationship REE – Rare Earth Elements RGO – Reduced Graphene Oxide RI – Method of Reactivity Indexes RSPM – Respirable Suspended Particulate Matter SHHRM – Solid and Heavy Hydrocarbon Raw Materials 4 TA – Triethylenetetramine Tamb – Ambient Temperature TDI – Toluene Diisocyanate TLC – Thin Layer Chromatography TNT – Trinitrotoluene, Trotyl TOF – Turnover Frequency TPD – Temperature-Programmed Desorption TPP – Thermal Power Plants TPR – Temperature-Programmed Reduction TPSR – Temperature-Programmed Surface Reaction TTB – Temporary Technological Bundle UNEP – United Nations Environment Program UNFCCC – United Nations Framework Convention on Climate Change VOCs – Volatile Organic Compounds WHO – World Health Organization XAS – X-ray absorption spectroscopy 5 INTRODUCTION The reduction of nitro compounds to amines is a very significant stage in the process, which probably can be considered the most important process in the chemistry of aromatic compounds. Currently, one of the topical areas is the development and investigation of highly efficient and selective catalysts for the hydrogenation of aromatic nitro compounds to the corresponding amines, since amines find wide application in the production of various dyes, drugs, corrosion inhibitors, stabilizers, polyurethanes, antiknock additives for gasolines and motor fuels and others. The processes of hydrogenation of aromatic hydrocarbons are the most important in multitone organic technology. Hydrogenation of aromatic hydrocarbons provides a wide range of different compounds, such as cyclohexane (for example, of the benzene produced in the world, about 20% is used to produce cyclohexane) and its derivatives, cyclohexylamine, tetralin, decalin through the attachment of hydrogen via the double bonds of aromatic rings. The production of cyclohexane is increasing every year since it can be used to produce caprolactam, adipic acid and cyclohexanol. Hydrogenation of naphthalene produces such technically important products as tetralin and decalin. Tetralin is used in the production of β-naphthol, as well as as a solvent for varnishes and paints. Decalin is used in the synthesis of a number of drugs and as a highly effective solvent. Hydrogenation of aromatic hydrocarbons is an important petrochemical process, which aims, in particular, to improve the quality of fuels, due to stricter environmental standards for the content of aromatic compounds. The importance of the processes of hydrogenation of aromatic hydrocarbons is difficult to overestimate these days, as one of the requirements that dictates the transition to high quality motor fuel (Euro-4, Euro-5, Euro-6) is associated with a significant reduction in the content of aromatic hydrocarbons in them. Since at present the demand for quality transport fuels is growing rapidly, the deep hydrogenation of gasoline and diesel fuels to reduce aromatic hydrocarbons is an important role in the world. 6 In many cases, various products of refineries contain aromatic hydrocarbons with significant concentrations. For such fractions, additional processing is required to produce petroleum products with the satisfactory characteristics and properties. It is well known that reducing the content of aromatic hydrocarbons contained in diesel fuel or their complete removal from the composition can increase the cetane number and improve the maximum value of the non-smoking fuel flame. In addition, when removing aromatic hydrocarbons, it is possible to improve the viscosity properties of the solvent and lubricating oils. In the monograph questions of reduction of aromatic nitro compounds and hydrocarbons for producing valuable intermediate and final products are considered. Catalytic hydrogenation at atmospheric and elevated hydrogen pressures is described in detail. The subject of the monograph offered to the reader is relevant from the scientific and applied point of view. The monograph is prepared on the problem of synthesis of valuable products and intermediates for the preparation of various dyes, drugs, corrosion inhibitors, stabilizers, polyurethanes, antiknock additives for gasoline and motor fuels, etc. The data described by the authors on theoretical issues (adsorption, quantum chemical description of reactivity molecules, the mechanisms of reduction, the electronic state of metals, the chemistry of the processes of conversion of aromatic nitrocompounds and hydrocarbons) and practical (hydrogenation technology, special equipment) are very relevant. A comparative analysis of the mechanisms of hydrogenation of aromatic nitro compounds and hydrocarbons of various authors is given. The monograph is compiled on the basis of an analysis of domestic and foreign literature with a depth of 50 years. The manuscript also describes the results of the authors's own experimental data, summarized for many years of experience in conducting catalytic reduction of aromatic nitrocompounds and hydrocarbons. In the monograph references for convenience are given to each part of the monograph. The monograph contains a detailed glossary and necessary illustrative material. The monograph is intended for researchers working in the field of catalysis, fine organic synthesis, chemical technology of organic substances, oil refining and petrochemistry; bachelors, masters and 7 doctoral students studying in the specialties “Chemistry”, “Petrochemistry”, “Chemical Technology of Organic Substances”, students, undergraduates and doctoral students, when studying disciplines “Technology of processing natural and oil associated gas”, “Technology of oil, gas and coal”, “Modern aspects of petrochemistry”, “Technologies for processing natural, oil associated and technological gases”, “Modern technologies of oil, gas and coal”, “Syntheses based on liquid and solid hydrocarbons of oil origin”, “Chemistry and physics of oil, gas and coal” “Structure of matter”, “Theory and technology of catalytic petrochemical productions”. The majority of points of the monograph is written taking into account curricula of above-mentioned disciplines. 8 Part I. THE CATALYTIC REDUCTION OF AROMATIC NITRO COMPOUNDS Chapter 1. Aromatic nitrocompounds 1.1. Typical representatives of aromatic nitro compounds, properties Nitro compounds are derivatives of hydrocarbons of the general formula R-NO having in their composition a nitro group directly 2 linked to an aliphatic or aromatic radical [1]. Depending on the nature of the hydrocarbon radical “R”, nitro compounds are divided into aliphatic and aromatic. The simplest representative of nitrocompounds of the aliphatic series is nitromethane, chemical compound with the formula CH -NO 3 2 (fig.1). a b Figure 1 – Molecule of nitromethane Aliphatic nitro compounds are divided into primary, secondary and tertiary (fig. 2). Figure 2 – Aliphatic nitro compounds: a – primary, 1-nitropropane; b – secondary, 2-nitropropane; c – tertiary, 2-methyl-2-nitropropane 9 Aromatic nitrocompounds (fig.3) are a group of organic substances, headed by nitrobenzene (fig.3a, fig.4) and formed from benzene and its homologues (toluene and xylene), naphthalene and anthracene by replacing one or more atoms with a nitro group. In aromatic nitrocompounds, the nitro group is bound to the aromatic ring. The nitro group can be replaced, along with halogen and some alkyl radicals, in almost any place of the ring [2]. Figure 3 – Aromatic nitro compounds of different structure: a – nitrobenzene, b – 2,4,6-trinitrophenol (picric acid), c-1-nitronaphthalene. Figure 4 – Nitrobenzene Compounds containing a nitro group are very rare in nature, almost the only natural representative of this class is the antibiotic levomycetin (fig.5): Figure 5 – The antibiotic levomycetin In the nitro group there is a π-conjugation (p-π-conjugation), as a result of which both bonds become equivalent. The structure of the 10
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