MINISTRY OF EDUCATION AND SCIENCE OF UKRAINE NATIONAL TECHNICAL UNIVERSITY OF UKRAINE «IGOR SIKORSKY KYIV POLYTECHNIC INSTITUTE» I. M. Ivanenko, T. A. Dontsova, Yu. M. Fedenko ADSORPTION, ADSORBENTS AND CATALYSTS BASED ON THEM Approved by the Academic Council of National Technical University of Ukraine «Igor Sikorsky Kyiv Polytechnic Institute» as Manual for Master students of the specialty 161 «Chemical technologies and engineering» specialization «Chemical technologies of inorganic substances and water purification» Kyiv Igor Sikorsky Kyiv Polytechnic Institute 2019 2 Reviewers: Chygyrynets O.E., Dr. Sci., Prof. Sabliy L.A., Dr. Sci., Prof. Responsible editor Kontsevoy A.L., PhD, Assoc. Prof. The Grief is provided by the Academic Council of National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute" (protocol № 11 from 09.12.2019) Electronic educational edition Ivanenko Iryna Mykolaivna, PhD, Assoc. Prof. Dontsova Tetiana Anatoliivna, PhD, Assoc. Prof. Fedenko Yurii Mykolayovich, PhD ADSORPTION, ADSORBENTS AND CATALYSTS BASED ON THEM Adsorption, Adsorbents and Catalysts Based on Them [Electronic resource]: Manual for Master students of the specialty 161 Chemical technologies and engineering specialization «Chemical technologies of inorganic substances and water purification» / Igor Sikorsky Kyiv Polytechnic Institute; redactors: І.M. Ivanenko, Т.А. Dontsova, Yu.M. Fedenko. – Electronic text data (1 file: 3,43 Mbyte). – Кyiv : Igor Sikorsky Kyiv Polytechnic Institute, Faculty of Chemical Technology, 2019. – 256 p. The material of this manual is set out in accordance with The Program of the discipline «Adsorption, Adsorbents and Catalysts Based on Them», covers and reveals most of the lecture material. It can have used by students at preparation to practical and laboratory classes, at performance individual and independent kinds of works, and also at preparation to control works and examination. The tutorial contains three sections. The first section extended the technology of carbon sorbents. The second section contains the technologies of main mineral pigments, the classification and appointment of mineral pigments. The third section contains laboratory work, the purpose of which is the practical mastering of the material described in the two preceding sections. © I. M. Ivanenko, T. A. Dontsova, Yu. M. Fedenko, 2019 © Igor Sikorsky Kyiv Polytechnic Institute, 2019 3 CONTENT INTRODUCTION .......................................................................................... 5 CHAPTER 1 TECHNOLOGY OF CARBON SORBENTS ...................... 7 1.1 PHYSICOCHEMICAL BASES ........................................................................ 7 1.1.1 Sorption of gases.......................................................................................... 7 1.1.2 Sorption from water solutions ................................................................... 29 1.2 Structural chemistry of activated carbon ......................................................... 38 1.3 TECHNOLOGIES OF OBTAINING CARBON ADSORBENTS ................ 48 1.3.1 Method of vapor-gas activation ................................................................. 49 1.3.2 Production of granular activated carbon by steam activation ................... 56 1.3.3 Production of crushed activated carbon by steam activation .................... 66 1.3.4 The technology of carbon molecular sieves .............................................. 72 3.5 Production of activated carbon from fossil raw materials ............................... 77 1.3.6 Getting active carbon by chemical activation ........................................... 80 1.3.7 Production technology of peat adsorbent by sulfur-potassium activation 88 1.3.8 The technology of carbon adsorbents with lignite, modified potassium hydroxide ............................................................................................................ 94 1.3.9 The technology of carbon adsorbents from waste wood, modified phosphoric acid ................................................................................................. 100 QUESTIONS FOR SELF-CONTROL ................................................................ 102 CHAPTER 2 TECHNOLOGY OF MINERAL PIGMENTS ................ 104 2.1 MINERAL PIGMENTS AND THEIR BASIC PROPERTIES .................... 104 2.1.1 Classification and designation of mineral pigments ................................ 104 2.1.2 Application of mineral pigments ............................................................. 105 2.1.3 Main pigment properties .......................................................................... 107 2.2 SOURCE OF RAW MATERIALS ............................................................... 113 2.2.1 White pigments based on titanium oxide compounds ............................. 113 2.2.2 Colored pigments containing iron ........................................................... 121 4 2.3 GENERAL CHARACTERISTICS OF MINERAL PIGMENTS ................. 122 2.3.1 Characterization and chemical properties of titanium (IV) oxide ........... 122 2.3.2 Characteristics, structure and chemical properties of iron– containing pigments ............................................................................................................ 127 Akageneite ................................................................................................... 130 2.4 TECHNOLOGY FOR PRODUCING OF MINERAL PIGMENTS ............ 134 2.4.1 Production technology of pigmentary titanium (IV) oxide by sulfate method .............................................................................................. 136 2.4.2 Technology for pigmentary titanium (IV) oxide chloride process .......... 159 2.4.3 Production of iron– containing pigments ................................................ 163 2.4.4 Production of natural iron-containing pigments ...................................... 181 QUESTIONS AND TASKS FOR SELF-CONTROL ........................................ 184 CHAPTER 3 LABORATORY WORKSHOPS ....................................... 187 3.1 DETERMINATION OF SORPTIVE PROPERTIES OF TITANIUM (IV) OXIDE ................................................................................................................. 187 3.2 SYNTHESIS OF ACTIVATED CARBON .................................................. 192 3.3 DETERMINATION OF TOTAL PORE VOLUME AND BOUNDARY VOLUME OF ADSORPTION SPACE OF ACTIVATED CARBON .............. 199 3.4 RESEARCH PORE VOLUME AND SPECIFIC SURFACE AREA OF ACTIVATED CARBON ..................................................................................... 207 3.5 STUDYING SURFACE PROPERTIES OF ACTIVATED CARBON ....... 216 3.6 TEST METHOD ACTIVATED CARBON .................................................. 225 3.7 DESIGNING THE SORPTION ISOTHERM OF CARBOXYLIC ACID .. 232 3.8 SYNTHESIS OF FINE SORBENT – NICKEL (II) FERROCYANIDES ... 237 3.9 BIOSORPTION OF HEAVY METALS FROM WATER SOLUTIONS .... 243 3.10 PREPARATION OF SILICA GEL BY SOL-GEL METHOD .................. 248 REFERENCES ............................................................................................ 254 5 INTRODUCTION The discipline «Adsorption, Adsorbents and Catalysts Based on Them» taught in the first year of master’s studies of the specialty 161 «Chemical technologies and engineering», attends to selective academic disciplines, i.e. disciplines of a free choice of students, and are profiling in the relevant curriculum. The discipline «Adsorption, Adsorbents and Catalysts Based on Them» takes important role in formation outlook of modern specialist in specialization "Chemical technologies of inorganic substances and water purification" and is final in preparation of specialists of inorganic substances chemical technologies. Educational material of discipline «Adsorption, Adsorbents and Catalysts Based on Them» based on knowledge of normative disciplines «Applied chemistry», «Physics», «General and inorganic chemistry», «Physical chemistry», «General chemical technology», «Processes and apparatuses of chemical manufactures», «Chemical technology of inorganic substances». The material of this manual is set out in accordance with The Program of the discipline «Adsorption, Adsorbents and Catalysts Based on Them», covers and reveals most of the lecture material. It can have used by students at preparation to practical and laboratory classes, at performance individual and independent kinds of works, and also at preparation to control works and examination. The tutorial contains two sections. The first section extended the technology of carbon sorbents, including physical and chemical bases of adsorption, structural chemistry of activated carbon and main technologies of synthesis of carbon adsorbents. The second section contains the technologies of main mineral pigments, the classification and appointment of mineral pigments, branches of its applications, the main properties of pigments and review of raw base has been presented. The material contributes to assimilation of material of such branches in chemical technology, as adsorbents and its producing, and also sorption processes 6 and its application in different branches: pigments and technologies of its obtaining (can have used for getting of metal oxides with other purpose). 7 CHAPTER 1 TECHNOLOGY OF CARBON SORBENTS 1.1 PHYSICOCHEMICAL BASES 1.1.1 Sorption of gases Any technological adsorption process, no matter at what sequence it is carried – periodically or continuously, includes a row of mandatory stages,