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CHE2119 - Chemical Process Industries Disadvantages Releases toxic HCl in the...

CHE2119 - Chemical Process Industries Disadvantages Releases toxic HCl in the atmosphere Lecture 1 - Chemical Engineers Behind the CaS waste releases H2S Scenes Definitions of Chemical Engineering Alkali Act - 1st modern air pollution legislation AIChE Constitution, Art. III: Definition of the Profession Solvay Process - a new method formulated by “Profession in which knowledge of mathematics, Ernest Solvay in 1863 chemistry, and other natural sciences gained by study, experience, and practice is applied with judgment to Chemical Engineers that Shaped the World develop economic ways of using materials and energy for George Davis - alkali inspector the benefit of mankind” ○ “Father of Chemical Engineering” ○ Organized 12 lectures at the Manchester American Heritage Dictionary of the English Language, 5th Technical School in 1887 Edition ○ Founded the “Society of Chemical “Branch of engineering that deals with the technology of Engineers” in 1880 but was denied large-scale chemical production and the manufacture of Arthur D. Little products through chemical processes” ○ Coined the term “unit operations” to distinguish ChemEng from others Columbia Encyclopedia, 6th Edition ○ “American Father of Chemical “Deals with the design, construction, and operation of Engineering” plants and machinery for making such products as acids, Lewis Mills Norton dyes, drugs, plastics, and synthetic rubber by adapting the ○ Chemistry Prof. at the Massachusetts chemical reactions discovered by the laboratory chemist Institute of Technology (MIT) made the to large-scale production. The chemical engineer must be 1st 4-year bachelor program in chemical familiar with both chemistry and mechanical engineering” engineering called “Course X” ○ Course X - combination of mechanical History of Chemical Engineering engineering and industrial chemistry Before 1880’s William Page Bryant - first of the 7 students to ○ MechEng with some knowledge of graduate from “Course X” chemical process equipment ○ First formal chemical engineer ○ Applied Chemist with knowledge of Carl Bosch - “Haber-Bosch Process” large-scale industrial chemical reactions ○ Haber-Bosch Process - allows the ○ Chemical Plant Foreman with a lifetime economical mass synthesis of ammonia, of experience but little education NH3, from nitrogen, N2, and hydrogen, H2 The first industrial chemical Industrial Revolution (18th to 19th Century) process to make use of ○ First Industrial Chemicals extremely high pressures (200- Sodium carbonate 400 atm) and high temperatures Sulfuric acid (oil of vitriol) (400-650 oC) Provided a solution to the Sodium Carbonate (Soda Ash) - a vital chemical shortage of fixed nitrogen in the glass, soap, textile, and paper industries Replaced Chilean saltpeter as a ○ Traditionally sourced from wood ashes, source of nitrates causing massive deforestation Margaret Hutchinson Rousseau - designed the ○ Nicholas Leblanc - patented a method 1st commercial penicillin plant for the production of Na2CO3 from sea ○ First woman with, a doctorate degree in brine, NaCl (Leblanc Process) ChemEng from MIT 1  Dermot Manning - full-scale production of b. Fine Chemicals - completely purified polyethylene using a high-pressure reactor substances and produced in limited John H. Perry - author of the Perry’s Chemical quantity (e.g. specialty solvents, Engineers’ Handbook perfumes, medicines) ○ He edited the first edition in 1934 2. Chemical Composition Fundamental Areas of Chemical Engineering a. Organic Compounds - nucleic acids, fats, 1. Material and energy balances sugars, proteins, enzymes, and 2. Chemical reaction and kinetics hydrocarbon fuels (e.g. hydrocarbons, 3. Phase equilibria phenols, carboxylic acid) 4. Transport phenomena and processes b. Inorganic Compounds - salts, metals, Roles of Chemical Engineers and other elemental compounds (e.g. 1. Process design Na2CO3, K2Cr2O7, MgCl2) 2. Plant design 3. Availability 3. Pilot plant operation a. Natural Compounds - available in nature 4. Process engineering/plant operation or produced or extracted from plants and 5. R & D / product development animals (e.g, coal, petroleum) 6. Academe b. Synthetic Products - synthesized using 7. Technical sales/services natural products, or they are synthesized 8. Management/administration completely using other types of synthetic Interdisciplinary Fields materials (e.g., polystyrene, polyvinyl 1. Energy Engineering chloride) 2. Biological-related Fields 4. Application a. Biochemical Engineering a. Catalyst - increases or decreases the b. Biotechnology rate of a reaction without being c. Biomedical Applications consumed in the process (e.g., AlCl3, d. Bioremediation MnO2, Pt) 3. Environmental Engineering b. Bulk Drug - becomes an active ingredient 4. Polymer Chemistry/Engineering of the finished dosage form of the drug, 5. Food Processing/Engineering but the term does not include 6. Materials Engineering intermediates used in the synthesis of such substances (e.g., pantoprazole, Lecture 2 - Chemical Process Industries: An bisacodyl) Overview c. Resin - a natural or synthetic compound that begins in a highly viscous state and hardens with treatment (e.g. urea Chemical Process Industry - includes those formaldehyde, epoxy, polyester) manufacturing facilities whose products result from: d. Dyes and Pigments a. Chemical reactions between organic materials, i. Pigments - DOES NOT dissolve or inorganic materials, or both ii. Dyes - Soluble b. Extraction, separation, or purification of a natural e. Solvent - liquid that dissolves solute (e.g. product, with or without the aid of chemical benzene, THF, DMF, DMSO) reactions f. Miscellaneous - all other compounds c. The preparation of specifically formulated which do not cover in the above class are mixtures of materials, either natural or synthetic called miscellaneous (e.g., fertilizer, glass) Classification of Chemical Process Industries 1. Quantity of Production and Consumption Chemical Process Industries in the Philippines a. Heavy Chemicals - large quantities, Chemical Industries Association of the crude (e.g. mineral acid, NaOH, Na2CO3) Philippines (Samahan sa Pilipinas ng mga Industriyang Kimika) 2  Chemical Reaction - a process that always results in the Sectors interconversion of chemical substances Process Engineering - often the synonym for chemical engineering and focuses on the design, operation, and maintenance of chemical and material manufacturing processes Product Engineering - refers to the process of designing and developing a device, assembly, or system such that it can be produced as an item for sale through some production manufacturing process Usually entails activities dealing with issues of cost, producibility, quality, performance, reliability, serviceability, and user features Basic Modes of Manufacturing Operation Batch Processing - involves the processing of bulk material in batches through each step of the Sources of Natural Environment desired process. 1. The earth’s crust (lithosphere) ○ Generally used for small-scale a. Elements production; easier to operate, maintain, i. Earth’s crust: mineral ores, and repair carbon, hydrocarbons Continuous Processing - involves moving one b. Coal, natural gas, and petroleum work unit at a time between each step of the i. Energy sources process with no breaks in time, sequence, ii. Converted to thousands of substance, or extent chemicals ○ Volume remains constant 2. The marine and oceanic environment (hydrosphere) a. Ocean water i. 1.5 x 1021L contains about 3.5% mass-dissolved material b. Sea water i. Good source of sodium chloride, magnesium, and bromine Unit Processes 3. The air (atmosphere) Chemical Changes - commercialization of a a. Air chemical reaction under such conditions as to be i. N2, O2, Ne, Ar, Kr, and Xe economically profitable b. Earth’s atmosphere ○ Are chemical transformations or i. 5 x 1015 tons; unlimited conversions that are performed in a 4. The plants (biosphere) process a. Vegetation and animals Physical Changes - based on the fundamental i. Agro-based industries laws and physicochemical principles b. Natural products ○ Are the physical treatment steps which i. Oils, fats, waxes, resins, sugar, are required to: natural fibers, and leathers Put the raw materials in a form in Chemical Process - consists of a combination of which they can be reacted chemical reactions and operations based on physical chemically phenomena Put the product in a form that is suitable for the market 3 Flow Diagrams Block Diagram Process Flow Diagram (PFD) Balloon Symbols/Instrument Tags 1st letter - parameter measured 2nd letter - type of control device being used Numbers (logical numerator) - loop it represents Piping and Instrumentation Diagram (P&ID) Symbols for P&ID 4  Lecture 3 - Chemical Engineering: Molecular Transport Processes - concerned with the Fundamental Concepts transfer or movement of a certain property by molecular movement through a medium, which can be a fluid (gas or liquid) or a solid Mass and Energy Balances Properties that can be transferred Mass transport –mass Heat transport –thermal energy (heat) Momentum transport –momentum General Molecular Transport Equation Mechanical Equilibrium - no physical changes occur (no change in motion) Net force is zero Momentum Transfer Thermal Equilibrium - same temperature Chemical Equilibrium - both the forward and reverse reactions are occurring at the same rate Phase Equilibria - At equilibrium, temperature, pressure and chemical potential of constituent component molecules in the system must be the same throughout all the phases Occurs when there is no net transfer of matter or heat energy from one phase to another phase Applications Newtonian Fluid - constant dynamic viscosity under any Production of different allotropes of carbon shear rate Lowering of freezing point of water by dissolving Linear relationship between shear stress and salt (brine) shear rate Purification of components by distillation Non-Newtonian Fluid Usage of emulsions in food production, Pseudoplastic Fluid - ↓ dynamic viscosity pharmaceutical industry at ↑ shear rate Used in metallurgy to make alloys of different Dilatant Fluid - ↑ dynamic viscosity at ↑ physical and chemical properties Two Assumptions in Mass Balances shear rate There is no transfer of mass to energy Bingham Plastic - linear shear-stress, shear-rate Mass is conserved for each element or behavior after an initial shear-stress threshold compound on either molar or weight basis has been reached Notes Mass and atoms are conserved Moles are conserved only when there is NO REACTION Volume is NOT conserved Transport Phenomena Time-dependent Non-Newtonian Fluids 5  Rheopectic Fluid - viscosity increases Thixotropic Fluid - viscosity decreases Dimensionless Groups Heat Transfer Unit Processes - can be summarized as follows: 1. Each unit process points out the unitary or like aspects in a group of numerous individual reactions. 2. Frequently there is a factory segregation by unit processes wherein a building or section of a building may be devoted to the making of many chemicals under a given unit process. 3. There frequently is a close relationship in the equipment used for making many examples under a unit process. 4. Equipment may be conveniently transferred from the making of one chemical to that of another within the same unit process 5. Needs chiefly to remember principles rather than specific performances. Mass Transfer 6. This places stress upon the chemical reaction. Hence the unit process emphasis - exhaustive study of the basic chemical change. 7. The inorganic and the organic procedures do not need to be set apart industrially. Comparison between Momentum, Heat, and Mass 8. The design of equipment is greatly aided by the Transfer generalizations arising from the unit process arrangement rather than by considering each reaction separately. Types of Unit Processes 1. Combustion a. Burning of fuels b. Oxygen source can either free-form as in O2 or in combination with other elements or compounds like HNO3, H2O2 c. The heat of reaction is a common source of energy i. Industries - fuel and power ii. Equipment - boilers (steel, firebrick) 6 2. Neutralization i. Industries - industrial gases (H2, a. Reaction of acids and bases O2), caustic soda and chlorine, i. Industries - water treatment, aluminum, magnesium, sodium sodium salts, ammonium ii. Equipment - electrolytic cells sulfates, ammonium nitrates, urea, arsenites, arsenates, soap 6. Double Decomposition from fatty acids a. Also known as exchange reaction ii. Equipment - reactors, treaters, i. Industries - water softening, Ca adsorbers, tanks, kettles and Mg salts, potassium salts, sodium salts, soda ash, 3. Oxidation (controlled) phosphoric acid, a. Uses oxygen as the oxidizing agent superphosphate, hydrochloric, b. In liquid-phase reactions: hydrofluoric, pigments permanganates, dichromates, chloric ii. Equipment - reactors, brine anhydrides, hypochlorites, chlorates, treaters, stills, kilns lead peroxide, and hydrogen peroxides c. The reaction is basically exothermic 7. Causticization d. Heat transfer systems are carefully a. Alkaline carbonate → lime designed to prevent controlled oxidation i. Industries - caustic soda from turning to combustion ii. Equipment - causticizers, lime i. Industries - water and wastes, kiln water gas, industrial gasses (CO2, H2), phosphoric acid (from 8. Calcination P), sulfuric acid, nitric acid (from a. Heating below melting point to remove NH3), paints and pigments, moisture and other volatile compounds linoleum, perfumes, b. Materials undergoing such process will formaldehyde be oxidized or reduced ii. Equipment - tanks, generators, i. Industries - lime, gypsum, soda boilers, oxidizers, burners, ash reactors ii. Equipment - kilns, calciners 4. Reduction 9. Esterification a. The reaction is basically endothermic a. A chemical process in which an ester and b. Reducing agents: lithium, sodium, water are formed when an organic magnesium, iron, zinc, aluminum, NaBH4 radical is substituted for in a molecule by and LiAlH4, and hydrogen gas (H2) with a an ionizable hydrogen of an acid. palladium, platinum, or nickel catalyst i. Industries - rayon: xanthate, i. Industries - phosphorus, sulfur acetate, ethyl and vinyl acetate from SO2, aniline from nitro- ii. Equipment - acetylators, benzene reactors, agers ii. Equipment - furnaces, reactors, reducers 10. Nitration a. Treatment with nitric acid to produce 5. Electrolysis either nitrates or nitro compounds a. Reactions are carried out in solutions of b. Hastened with sulfuric acid electrolytes or molten salts by passage i. Industries - explosives, of electricity intermediates for dyes, nitro- b. Electrodes are dipped in the solution and benzene, etc direct current is passed through it ii. Equipment - nitrators, reactors c. Oxidation: positive electrode or anode d. Reduction: negative electrode or cathode 7 11. Sulfonation i. Industries - photography, a. Involves the introduction of sulfonic acid styrene, petroleum, group (SO2OH) or its corresponding salt intermediates, medicines or sulfonyl halide (=SO2Cl) into an ii. Equipment - autoclaves, organic molecule reactors, alkylators b. Sulphonatic agents: sulphuric acid, SO3 in H2O (oleum) and fuming sulphuric acid 16. Hydrogenation and Hydrogenolysis i. Industries - explosives, sulfite a. A chemical reaction of molecular paper, intermediates for dyes, hydrogen with another substance in the benzene-sulfonate for phenols presence of a catalyst ii. Equipment - sulfonators, burners i. Industries - ammonia from nitrogen, hydrochloric acid from 12. Hydration and Hydrolysis chlorine, hydrogenated oils and a. Reaction with water done in the presence fats, detergents, petroleum, of a catalyst methanol from CO b. If reactants are not miscible, emulsifying ii. Equipment - catalyst chambers, agents are added. reactors hydrogenator, i. Industries - slaked lime, hydrogenating autoclaves phosphoric acid from phosphorus pentoxide, 17. Condensation glycerine, soap, corn sugar, a. Combination reaction of two smaller dextrin, sucrose to glucose and molecules to form a larger molecule, fructose, phenol producing a small molecule such as H2O ii. Equipment - hydrators, soap as a by-product kettles, autoclaves, fermenters, i. Industries - resinification, fusion pots, hydrolyzers benzoyl-benzoic acid for anthraquinone phenolphthalein 13. Halogenation ii. Equipment – reactors a. Introduction of halogens b. Most widely used: chlorination 18. Polymerization c. Seldom used: iodination a. Simple molecules (monomer) react to i. Industries - chemical for form large molecules warfare, insecticides, b. Classified as intermediate for dyes, i. Condensation reactions occur chlorobenzene, benzyl chloride, between two groups to form a carbon tetrachloride new group not present in the ii. Equipment - reactors, reactant with a small compound halogenators, chlorinators split out like water; usually, the elimination of water or alcohol 14. Amination by Ammonolysis from bi-functional molecules a. Introduction of amine group ii. Addition by reopening of a i. Industries - aniline from chloro- multiple bond without benzene, B-naphthylamine, elimination of any part of a ethanolamines molecule ii. Equipment – autoclaves c. Can be carried out in bulk, solution, emulsion or suspension 15. Alkylation i. Industries - rubber, petroleum a. Introduction of alkyl group industry b. In petroleum industries, low-molecular- ii. Equipment - polymerizers, weight are converted to higher polymerization reactors molecular-weight compounds 8 19. Pyrolysis or Cracking calcium and magnesium ions a. Process where heat is employed to are exchanged for sodium decompose compounds ii. Removal of ionic constituents b. Some reactions take place at low like deionization of water temperature in the presence of solvents iii. Separation of ionic substances i. Industries - distillation of coal, like amino acids fuel (coal) gasses, oil gas for iv. Concentration of ionic solutions carbureted water gas, carbon v. Industries - wastewater, acids, black, lampblack, distillation of bases, salts wood, petroleum industry vi. Equipment - ion exchange ii. Equipment - retorts, carburetors, column, ion exchangers distillation chambers, reaction chambers Types of Unit Operations 1. Fluid Flow or Fluid Dynamics 20. Fermentation a. Deals with the transportation of fluid a. Substance conversion using i. Industries - water and wastes, microorganisms like yeasts and bacteria oils and fats, petroleum b. Involves complex processes like ii. Equipment - pumps, tanks oxidation, reduction, hydrolysis, 2. Heat Transfers esterification, etc. a. Fundamental modes of heat transfer: c. Parameters being monitored are conduction, convection, and radiation temperature, concentration, pH, and, to a i. Industries - fuels and power, certain extent, pressure distillation of coal, fuel gasses, i. Industries - industrial gasses industrial gasses, phosphorus, (CO2), alcohol and CO2 from sulfuric acid, ammonia, monosaccharides, alcohol, petroleum industry acetone, and butanol from ii. Equipment - boilers, heat carbohydrates, wines, beers, exchangers, generators, coolers liquors, lactic acid, penicillin ii. Equipment – fermenters 3. Evaporation a. Removal of valueless component from a 21. Isomerization mixture through vaporization a. Transformation of a compound into any b. The mixture is usually a non-volatile solid of its isomeric forms or liquid and a volatile liquid i. Industries - petroleum i. Industries - potassium salts, salt ii. Equipment – isomerizers caustic soda, phosphoric acid, glycerine, sugar, oils and fats, 22. Aromatization petroleum a. Conversion of aliphatic or alicyclic ii. Equipment – evaporators compounds to aromatic hydrocarbons i. Industries - petroleum 4. Humidification ii. Equipment - reaction chambers a. Process in which the moisture or water vapor or humidity is added to air without 23. Ion Exchange changing its dry bulb (DB) temperature a. Refers to the interchange of ions that b. Usually accompanied by cooling or takes place when an ionic solid is heating of the air contracted with electrolytic solutions i. Industries – textile fibers b. Can be used for ii. Equipment – humidifiers i. Transformation of electrolytes like in water softening where 9 5. Gas Absorption/Stripping ii. Equipment - spray drier, tray a. Gas Absorption - transfer of a soluble drier, rotary drier, pan drier, component of a gas mixture to a liquid steam-heated cylinder b. Desorption/Stripping - transfer of a 10. Mixing volatile component from a liquid to a gas a. Make it more homogeneous i. Industry - distillation of coal, fuel i. Industries - fertilizers, dynamite, gasses, industrial gasses, paints, lacquers, dyes bleach, nitric acid, hydrochloric ii. Equipment - mixers, mixing vats acid, leather ii. Equipment - absorbing tower 11. Classification or Sedimentation a. A physical water treatment process 6. Solvent Extraction using gravity to remove suspended a. Separation of compounds based on solids from water relative solubilities in two different i. Industry - cement rock, immiscible liquids phosphate rock, potassium i. Industry - coal gas, insecticides, salts, caustic soda, wastewater perfumes, oils, acetic acid, treatment lubricating oils ii. Equipment - beneficiation, ii. Equipment - percolator, tower, thickeners, clarifiers, extractor sedimentation tank 7. Adsorption 12. Filtration a. Adhesion of atoms, ions, or molecules to a. Removal of solid from a liquid/solid or a surface of a liquid or solid gas/solid mixture b. Due to residual forces at the surface of b. Use this if there is SEDIMENT liquid or solid phase i. Industry - ceramics, Ca and Mg i. Industry - water and wastes salts, potassium salts, sodium purification, artificial leather salts, sugar, rayon, paraffin, solvent recovery intermediates and dyes, organic ii. Equipment – tanks chemicals, wastewater ii. Equipment - plate and frame 8. Distillation filter press, rotary drum filter a. Extraction by vaporization and condensation 13. Screening b. Depends on different boiling points of a. Separation of materials based on particle components size i. Industries - distillation of coal, b. Screens are classified based on Mesh industrial gasses (O2, N2), number, the number of openings across perfumes, glycerine, alcohol, one linear inch of screen acetone, petroleum, i. Industries – cement, soda ash, intermediates silicon carbide, sugar, minerals ii. Equipment - still, distilling ii. Equipment – screen column, rectifier 14. Crystallization 9. Drying a. Separation of solid particles from their a. Removal of water or volatile solvent saturated solutions i. Industries - ceramics, sodium i. Industries - Ca and Mg salts, salts, pigments, soap, sugar, potassium salts, sodium salts, pulp and paper, rubber sugar, pharmaceuticals ii. Equipment – crystallizer 10  15. Centrifugation ○ Ocean water: 10,500 g/ton Na, 1270 a. Uses the action of centrifugal force to g/ton Mg, 400 g/ton Ca, 380 g/ton K; promote accelerated settling of particles ocean nodules: 23.86% Mn, 1.166% Mg, in a solid-liquid mixture 2.86% Al, 13.80% Fe i. Industries - NH4 sulfate, Ca and ○ Recycled scrap: at the end of metals’ life Mg salts, potassium salts Types of Metallurgy ii. Equipment - centrifuge ○ Pyrometallurgy ○ Hydrometallurgy 16. Size Reduction ○ Electrometallurgy a. An operation carried out for reducing the size of bigger particles into smaller ones Mineral Ores – mineral deposit; profitably exploited. of the desired size and shape with the May contain three groups of minerals help of external forces ○ Valuable minerals of the metal which is i. Industries - ceramics, cement, being sought glass raw materials, rock wool, ○ Compounds of associated metals which paints, resins, minerals may be of secondary value ii. Equipment - ball/cylinder/disk ○ Gangue minerals of minimum value mills, gyratory crushers Ore Dressing - physical pre-treatment before ores are 17. Leaching subjected to the main chemical treatment a. Extraction of a soluble solid from its Meant to affect the concentration of the valuable mixture with an inert solid by use of a minerals and to render the enriched material into liquid solvent in which it is soluble the most suitable physical condition for i. Industries - sugar, fats and oils, subsequent operations minerals Comminution - reduction of the size of the ore by ii. Equipment – extractors crushing, grinding, cutting, and vibrating to such a size that will release or expose all valuable 18. Materials Handling minerals a. Includes consideration of the protection, ○ Followed by screening storage, transportation, and control of materials throughout their manufacturing, warehousing, distribution, consumption, and disposal i. Industries - fuels, fuel gasses, ceramics, cement, glass, soda ash, wood, rubber ii. Equipment - belt conveyor, screw conveyor, pumps and pipes, trucks Lecture 4 - Extractive Metallurgy Extractive Metallurgy - deals with the extraction and refining of metals from its naturally existing ore or minerals Source of Minerals ○ Earth’s crust: 8.1% aluminum, 5.1% iron, 3.6% calcium, 2.8%, sodium, 2.6% potassium, 2.1% magnesium, 2.1% titanium, 0.10% manganese 11  Sorting - performed to separate particles of ore ○ Done by any of the following methods minerals from gangue (non-valuable) minerals or Pelletizing different ores from one another Briquetting ○ Classification Process - based on the Sintering following factors Smaller = fall slower in fluids Extraction Processes than larger ones 1. Calcination Larger = more centrifugal force a. Thermal treatment of an ore to affect its Small particles having less decomposition and the elimination of a inertia tend to behave like the volatile product, usually CO2 or H2O suspending medium or fluid 2. Roasting Larger needs higher velocity for a. Process of heating of concentrated ore separation to a high temperature in excess air ○ Froth Flotation - uses differences in b. Involves chemical changes other than surface properties of the individual decomposition, usually with furnace minerals to selectively adsorb material atmosphere on the air bubbles ○ Magnetic Separation - uses differences 3. Smelting in magnetic properties of materials a. Ore (usually mixed with purifying and/or Ferromagnetic - magnetic heat-generating substances such as materials limestone and coke) is heated at high Paramagnetic - weakly attracted temperatures in an enclosed furnace into a magnetic field b. It is opposite to roasting (oxidizing Diamagnetic - weakly repelled by reaction) as it has reducing reactions a magnetic field c. The components of the charge in the ○ Electrostatic Separation - selective molten state separate into two or more sorting of solid species by means of layers which may be: utilizing forces acting on charged and i. Matte polarized bodies in an electric field ii. Slag iii. Speiss Agglomeration - formation of lumps of appropriate size and strength when ore or concentrate is too small for use in a later stage of treatment 12 Extractive Metallurgy of Iron Digestion - extraction of the alumina through Iron Ores digestion with hot NaOH solution which dissolves ○ haematite (Fe2O3) the aluminum hydroxide, forming a solution of ○ limonite (FeO(OH).nH2O) sodium aluminate ○ magnetite (FeO.Fe2O3) ○ Pyrite, (FeS2) Iron Forms Clarification - removal of undissolved solid ○ White cast iron impurities (calcium oxide, iron oxide, titanium ○ Grey pig iron oxide) that form the “red mud”, which settles ○ Steel down at the bottom of mud thickeners ○ Alloy Precipitation - recovery of crystals of aluminum Raw Materials hydroxide (Al(OH)3) ○ Iron Ore ○ Precipitation is promoted by seeding the Abundant, makes up 5% of liquor with pure alumina crystals acting earth’s crust as nuclei for the precipitation process. Main impurities: silica and ○ Crystals of aluminum hydroxide/ alumina alumina trihydrate (Al2O3.3H2O) grow ○ Limestone or Dolomite and aggregate Calcium carbonate Used to remove impurities Calcination - the aluminum hydroxide, after ○ Coke separation from the sodium hydroxide, is Produced at the bottom of the converted to pure aluminum oxide by heating to blast furnace by carbonization of 1800oF (1000oC) in rotary kilns or fluidized bed coal calciners Used to heat the furnace and produce CO which acts as the Hall-Heroult Process - production of aluminum by reducing agent the electrolytic reduction of the aluminum oxide It involves the dissolution of aluminum oxide in Extractive Metallurgy of Aluminum molten cryolite (a mineral containing sodium Most abundant metallic element aluminum fluoride, Na3AlF6) and electrolysis of Bauxite ores - a mixture of hydrous aluminum the molten salt bath oxides, aluminum hydroxides, clay minerals, and insoluble materials Three Stages of Aluminum Extraction from Bauxite Extractive Metallurgy of Copper 1. Ore Dressing - cleaning ore by means of Concentration - separation of the copper mineral separation of the metal-containing mineral from from the gangue the waste (gangue) ○ In froth flotation cell, the ore particles are 2. Chemical Treatment of Bauxite - conversion of lifted by air bubble while the gangue hydrated to pure aluminum oxide remain in the cell 3. Reduction of Aluminum from Aluminum Oxide - Roasting - removal of excess sulfur by the electrolytic process ○ The dry pulp is fed into the roaster at 600 to 700oC Bayer Process - the process of refining alumina from ○ The burning of the sulfide ores supplies bauxite by selective extraction of pure aluminum oxide the heat to maintain the temperature at dissolved in sodium hydroxide which roasting takes place 13  Matte Smelting - concentrate is smelted in a Uses and Economics furnace to produce a mixture of copper Blister Copper Production - conversion of matte into molten blister copper containing 96 to 98% copper and remove the iron-rich slag Soda Ash - a lightweight solid, readily soluble in water, contains 99.2% Na2CO3 Application: used in the manufacture of caustic Electrolytic Refining - cathodes produced as a soda, sodium bicarbonate, sal soda, glass, result of the electrolytic refining process contain detergents, soaps, pulp and paper, textiles, water 99.9% copper softeners, and a desulfurizing agent in ferrous metallurgy Lecture 5 - Alkali Industry Caustic Soda - brittle white solid which readily absorbs moisture and carbon dioxide from the air, 98% NaOH Application: manufacture of rayon, explosives, soap, paper, and in many others Chlorine - used for the direct treatment of a given product (i.e. pulp, paper, textile bleaching, water treatment, and sewage purification) Used in insecticides, fungicides, bactericides, and herbicides Manufacture of Soda Ash (Solvay Process) Raw Materials ○ Sodium Chloride or Salt (NaCl) History of the Alkali Industry ○ Limestone (CaCO3) - burned in kilns to Leblanc Process (1773) - Nicholas Leblanc furnish both the CO2 for the soda ash and the lime for the recovery of NH3 ○ Ammonia Gas (NH3) - recovered from ammonium bicarbonate and ammonium chloride produced in the process Process Flow Diagram of the Solvay Process Solvay Process (1869) - Ernest Solvay ○ Ammonia-soda process ○ Reduced the price of soda ash to 1/3 Chlor-Alkali Process (1890) ○ Caustic soda and chlorine Ammonia Absorber - NH3 gas mixed with CO2 gas ○ Cheap electricity, a ready source of salt, is bubbled through a 20% sodium chloride and proximity to markets solution (brine) ○ Impurities of calcium and magnesium salts in the brine precipitate as carbonates and hydroxides 14  Filter – after saturation, the ammoniacal brine is Ammonia Recovery Tower pumped through the filter to remove the precipitated carbonates and hydroxides. Carbonating Tower - site for the carbonation of ammoniacal brine ○ Operates with a counter-current flow ○ Ammonium chloride and sodium bicarbonate crystals are formed Unit Processes and Operations in detail Preparation and Purification of the Salt Brine ○ Mining and solution of salt, or pumping of water to salt beds and of brine from these deposits (op.) ○ Purification of brine (pr. and op.) The NH3 helps to buffer the solution to stop the absorption of CO2 making the solution acidic, thus arresting the precipitation of NaHCO3 Rotary Suction Filter - Thick milky liquid from the base of the carbonating tower is filtered Ammoniation of Brine ○ Solution of NH3 in the purified brine (op. ○ Calcination of NaHCO3 and Production and pr.) of Na2CO3 - the most difficult step due to ○ Solution of weak CO2 in the purified brine the formation of lumps and non- (op. and pr.) conducting scales on the steel shell of the calciner Lime Kiln - limestone is burnt to produce CO2 and lime. ○ CO2 → carbonating tower ○ Lime → lime slaker Carbonation of Ammoniated Brine ○ Formation of ammonium carbonate (pr.) ○ Formation of ammonium bicarbonate Lime Slaker - lime is slaked in a large quantity of (pr.) water to form milk of lime pumped to the middle ○ Formation and controlled precipitation of of the ammonia recovery tower sodium bicarbonate (pr.) ○ Filtration and washing of the sodium bicarbonate (op.) ○ Burning of limestone with coke to form CO2 and CaO (pr.) 15  ○ Compressing and cooling of lime kiln or Recovery of Ammonia lean CO2 ○ Slaking of quicklime (pr.) ○ Piping to carbonator (op.) ○ Treatment of sodium bicarbonate mother liquors with steam and Ca(OH)2 in strong NH3 liquor still to recover NH3 (pr.) Manufacture of Sodium Bicarbonate Why Solvay Process is not Employed in Sodium Bicarbonate Difficulty in complete drying The value of the ammonia would be lost Even a small amount of ammonia gives the bicarbonate an odor It contains many other impurities Calcination of Sodium Bicarbonate ○ Conveying and charging of moist sodium bicarbonate to the calciner (op.) ○ Calcination of sodium bicarbonate (pr. and op.) ○ Cooling, screening, and bagging of soda ash (for sale) (op.) ○ Cooling, purifying, and compressing; Manufacture of Caustic Soda: Lime-Soda Process piping of rich CO2 gas to carbonator (op.) Lime Slaking 16  Dorr Agitators ○ Causticization of Soda Ash Dorr Central Drive Thickener ○ Feed ○ Discharge ○ Overflow Unit Processes and Operations Brine Purification - purification of NaCl solution from Ca, Fe, and Mg impurities using soda ash with some caustic soda ○ Performed to lessen clogging of cell diaphragm with consequent voltage increase ○ Brine Filters - removes the suspended solids overflowing with the brine from Manufacture of Electrolytic Caustic Soda and Chlorine the settler Raw Materials Brine Electrolysis (via Diaphragm cells) - the ○ Salt - brine from rock salt, natural or cathode is surrounded by a porous diagram of artificial brine, or sea salt asbestos since H2(g) and Cl2(g) are explosive Reactions and Energy Changes upon contact ○ Theoretical/Minimum Voltage: Gibbs- Evaporation and Salt Separation - about 10 – Helmholtz equation 15% NaOH solution is evaporated to 50% NaOH in a double or triple-effect evaporator with salt separators, followed by a washing filter Final Evaporation - concentration of 50% NaOH to 70-75% NaOH in a single-effect final or high evaporator ○ Alternative method: precipitation of ○ Voltage Efficiency - ratio of theoretical sodium hydroxide monohydrate by the voltage to the actual voltage used addition of ammonia to the 50% NaOH (usually 45 – 65%) solution ○ Recall Faraday’s Law - 96,500 C of Special purification of caustic soda electricity = 1 gram-equivalent of ○ Chlorine drying - treatment with CaCO3 chemical reaction at each electrode and filtering the resulting mixture ○ Current Efficiency - ratio of the ○ Removal of Chloride and Chlorate - theoretical to the actual current dropping of 50% NaOH through a column consumed (cathode current efficiencies: of 50% NH3 (aq) solution usually 95 – 97%) ○ Salt Content Reduction - cooling to 20oC ○ Energy Efficiency of the Cell - voltage Chlorine Drying - hot chlorine from the anode is efficiency X current efficiency cooled to condense most of its vapor ○ Decomposition Efficiency - ratio of ○ Chlorine temperature should be kept in a equivalents produced in the cell to range of 15-20oC. equivalents charges (usually 50 %) ○ After cooling, chlorine gas is dried in a sulfuric acid scrubber 17  Chlorine Compression and Liquefaction - compression to 35-80 lb gage ○ Liquefaction by refrigeration to – 20oF ○ Cooling to – 50oF once all chlorine has liquefied Purification of Caustic via Mercury cells ○ Cathode: a thin layer of mercury ○ Anode: graphite or titanium Hydrogen Disposal - conversion to hydrochloric acid or ammonia or use for hydrogenation of organic compounds Sources of Elemental Sulfur Electrolytic Cells Pyrite Diaphragm cells - asbestos allows ions to pass Sulfur mining (Frasch) by electrical migration but limit the diffusion of Hydrogen sulfide (from natural gasses and products refineries) ○ Cathode: cast iron Smelter gasses ○ Anode: graphite Calcium sulfate ○ Chlorine gas report to the anode Coal ○ Hydrogen ions report to the Low-grade sulfur deposits cathode → NaOH Mercury cells Mining and Extraction of Sulfur ○ Cathode: moving pool of mercury Frasch Process (1890) - by Herman Frasch ○ Anode: graphite / modified titanium Sulfur-bearing limestones (90% elemental sulfur) ○ Chlorine reports to the anode as a source of elemental sulfur ○ Sodium reports to the cathode: Involves the burrowing of three concentric pipes ○ Amalgam (mercury + sodium alloy) to a depth of 150 to 750 m to reach the bottom of Membrane cells - plastic sheets porous and the sulfur-bearing strata chemically active to allow sodium ions to pass through but reject hydroxyl ions ○ Uses more concentrated brine solutions and produce purer and more concentrated sodium hydroxide ○ Cathode: steel ○ Anode: graphite Lecture 6 - Sulfur and Sulfuric Acid Properties of Sulfur Commonly appears as yellow crystals or powder at room temperature Steps in the Frasch Process Essential to all living things (taken up as sulfates 1. Superheated water is forced down the outermost by plants and animals; makes up essential amino of 3 concentric pipes to the underground deposit. acids) 2. The hot water melts the sulfur. Widely found in many minerals like iron pyrites, 3. The innermost pipe conducts compressed air galena, gypsum, and Epsom salts into the liquid sulfur. Abundant and occurs throughout the universe, 4. The air forces the liquid sulfur, mixed with air, to but is rarely found in pure, uncombined form at flow up through the outlet pipe. the Earth’s surface 18 Sulfur from Smelter Gases - sulfur recovery from SO2 and 1746 - Lead Chamber Process (Dr. Roebuck of H2S (controlled by air pollution regulations) Birmingham) Sources ○ Ignition of brimstone and saltpeter in a ○ Roasting of sulfide ores room lined with lead foil ○ Coal combustion ○ Burning of acid sludge from petroleum ○ Sulfur trioxide reacts with water to refining produce sulfuric acid Products ○ Elemental sulfur ○ Sulfuric acid 1835 - Joseph Gay-Lussac invented a process to ○ Liquid sulfur dioxide recover nitrogen ○ Replaced expensive saltpeter as a Sulfur from Industrial Gases source of nitrogen Removal of Hydrogen Sulfide, H2S ○ Sharply reduced NO emissions ○ Purification of natural and manufactured gas Lead Chamber Process ○ Petroleum refining Sulfur from Pyrites ○ Flash roasting of sulfide ores Sulfur Dioxide from By-products ○ Liquid Waste from Steel Industry (Pickling of Metals) 2-15% sulfuric acid and 10-15% ferrous sulfate ○ Sludge and Alkylation Acids Recovered by decomposing to Manufacturing Procedure SO2 (processed to H2SO4) Combustion Chamber - either sulfur or pyrite is burned Properties of Sulfuric Acid Colorless to yellowish in color Highly corrosive Highly oxidizing Nitre Pots - oxide of nitrogen is obtained by Miscible in water heating NaNO3 and concentrated H2SO4 Dehydrating agent ○ Important in nitrification, esterification, and sulfonation Forms ○ Sulfuric Acid - H2SO4 in water ○ Oleum - SO3 in H2SO4 Common Sulfuric Acid Concentrations Glover Tower - made of acid-resistant bricks History of Sulfuric Acid Manufacturing packed with stone pieces 15th century - burning of saltpeter with sulfur ○ Liquid Phase - H2SO4 is concentrated to (Valentinus) 62-68% due to H2O evaporation 19  Some SO2 is oxidized to H2SO4 (further concentrates H2SO4) Reactions and Thermodynamics Generation of Sulfur Dioxide from Elemental Sulfur NO∙HSO4 is hydrolyzed to H2SO4 Catalytic Oxidation of Sulfur Dioxide ○ Gaseous Phase (SO2 + air + NOX) - gas is cooled Absorption of Sulfur Trioxide in Water NOX from the liquid phase reports to the gaseous phase Ideal Conditions As temperature increases, the conversion of SO2 to SO3 decreases. At 600 K, the rate of reaction is slow 680-751 K (shaded area) is the range of practical operating temperature The successive lowering of temperature between the beds ensures an overall conversion of 98-99% Platinum Catalysts Carriers: silica gel, calcined magnesium sulfate, and asbestos Advantages ○ 90% recovery of metal ○ Lower operating cost ○ Lower initial capital cost; higher proportions of SO2 may be used Disadvantages ○ Suffers a decline of activity with use Gay-Lussac’s Tower - unreacted gasses from the ○ Shorter life; subject to poisoning under lead chamber are passed upwards into Gay- some conditions Lussac’s tower. ○ Difficulty to handle; fragile ○ H2SO4 is sprayed from the top. Vanadium Catalysts Carriers: zeolite or another base Advantages: ○ higher conversion efficiency maintained for a longer period ○ immunity to poisoning ○ mass is less troublesome during operation; easier to handle ○ lower initial cost Disadvantages: ○ handle lower SO2 content gas ○ no salvage value when worn out Contact Process Contact Process (1831, Phillips) - yields strong acid: 98 – Combustion Chamber - brick-lined 100% H2SO4 ○ Dried air and atomized molten sulfur are Decomposition of chamber acid introduced to the chamber. Passing a mixture of sulfur dioxide over a ○ Atomizing and good mixing are key catalyst factors in producing efficient Absorption of sulfur trioxide in water combustion. 20  ○ Conversion of atmospheric nitrogen into Waste Heat Boiler - reduces gas temperature ammonia ○ Produces high-pressure steam ○ Carried out by leguminous plants and some bacteria (e.g. azotobacter, clostridium, rhizobium) Catalytic Reactor - successive cooling through Nitrification the heat exchangers ○ Carried out by nitrifying bacteria (e.g. ○ Most of the SO3 produced is absorbed in nitrococcus, nitrosomonas) a circulating stream of sulfuric acid. ○ Ammonia is first converted to nitrites ○ Overall conversion of > 99.7% is achieved then nitrites are converted to nitrates (by after the fourth catalyst bed. nitrobacter) Nitrogen Assimilation Absorption Towers - removes SO3 from the gas ○ The process of absorbing nitrates and stream before release to the atmosphere ammonia into organic nitrogen ○ SO3 is absorbed in water to produce ○ Organic nitrogen is transferred into H2SO4 animals when they consume plants. ○ Have demisters installed to prevent Ammonification corrosion and process stack emission ○ The process of converting organic due to sulfuric acid mist nitrogen into ammonia when plants and animals die ○ Carried out by saprophytes like fungi and bacteria Lecture 7 - Nitrogen Industry ○ Ammonia is also produced from volcanic eruptions and the excretory products of Nitrogen - comprises 78% of the atmosphere animals. Cannot be utilized by plants in atmospheric form Denitrification Essential for the synthesis of amino acids, ○ Nitrates are converted into molecular proteins, enzymes nitrogen through nitric oxide. A limiting nutrient ○ Carried out by denitrifying bacteria (e.g. thiobacillus denitrificans) Nitrogen Cycle - the circulation or cyclic movement of nitrogen from the atmosphere to soil back into the Synthetic Ammonia: History atmosphere Sources of Fixed Nitrogen Manures Ammonium sulfates (by-product from coking of coal) Ammonia (recovered from coke) Chile Saltpeter (sodium nitrate) Dry distillation of nitrogenous biomaterial waste Decomposition of ammonium salts Haber (Haber-Bosch) process - Fritz Haber and Carl Bosch, 20th century Practical and large-scale synthetic ammonia process Use of abundant and inexpensive elemental H2 Nitrogen falls from the atmosphere to the earth by and N2 gas precipitation (e.g. rain or snow). Nitrogen Fixation 21 Synthetic Ammonia: Haber-Bosch Process Feedstock Desulfurization Raw Materials Removal of sulfur oxide and hydrogen sulfide ○ Air R-SH + H2 → H2S + RH ○ Water H2S + ZnO → ZnS + H2 ○ Hydrocarbons The sulfur is removed to < 0.1 ppm S in the gas Reactions and Equilibrium feed Zinc sulfide remains in the adsorption bed. 1. Manufacture of Hydrogen Steam-water gas process Steam-hydrogen (natural gas) process Coke-oven gas process Electrolysis of water Return to equilibrium with increase in [N2] Primary (Steam) Reforming Return to pressure upon compression Rate and Catalysis of the Reaction Hydrogen and nitrogen react very slowly Reformer consists of nickel-based catalysts Catalyst: iron → promoted by the addition Secondary Reforming of small amounts of oxides of Al and K Space velocity → cu. ft. of exit gasses in STP (0oC and 760 mmHg) that pass over 1 cu. ft. Only 30-40% of the hydrocarbon react of catalyst space per hour (usually 20,000 – Addition of air to convert the unreacted methane 40,000) molecules 5,000 space velocity, 450oC, 100 atm, pure 3:1 Shift Conversion hydrogen-nitrogen mixture: ○ doubly promoted: 13 – 14% ammonia The process gas from the secondary reformer ○ singly promoted: 8 – 9% ammonia contains 12 – 15% CO. ○ pure iron: 3 – 5% ammonia The gas is passed through a bed of iron Catalyst promotion - oxide/chromium catalyst around 400 – 500 ○ Melting iron oxide + promoter (protecting degrees Celsius bed) 2. Purification ○ Rapid cooling CO2 Removal ○ Crushing Scrubbing with water, amine solutions, or hot ○ Poisoning of catalyst potassium carbonate solutions CO and Further CO2 Removal (Methanation) Manufacturing Procedure feed stock desulfurization manufacture of reactant gasses purification compression catalytic reaction Small amounts of CO and CO2 are removed by recovery of formed ammonia conversion to CH4 using Ni catalyst recirculation and ammonia removal 3. Ammonia Conversion Modern NH3 plants use centrifugal compressors for synthesis gas compression. The synthesis of ammonia takes place on iron catalysts. Reaction is highly exothermic 22  Only 20 – 30% is reacted per pass in the converter due to unfavorable equilibrium conditions 4. Ammonia Separation By mechanical refrigeration or adsorption/distillation 5. Ammonia Storage Urea (46% nitrogen) Ammonium nitrate (34% nitrogen) 1. Evaporation of Anhydrous Ammonia anhydrous ammonia is evaporated using steam Air required for all reactions are compressed and mixed with ammonia gas 2. Oxidation of Ammonia Gas with Air NH3 gas is oxidized with air to nitric oxide by passing through a platinum gauze at 920oC Nitric Acid: Uses and Economics 3. Cooling of Nitric Oxide Used for the manufacture of ammonium nitrates Nitric oxide with excess air is cooled in two heat (fertilizers) exchangers and a water cooler Intermediate in polymer industry (polyamides 4. Oxidation and Hydration of Nitric Oxide and polyurethanes) Successive oxidations and hydrations of the Oxidizing acid for the parting of gold and silver, nitric oxide are carried out with continuous water pickling of brass, and photoengraving cooling in a stainless-steel absorption tower. Nitric Acid: Production Raw Materials ○ Anhydrous ammonia 5. Collection of Nitric Acid using Acid Trap ○ Air 61 – 65% nitric acid ○ Water water and nitric acid form an azeotrope Reactions and Energy Changes 6. Waste Gas Treatment The waste gas from the top of the absorption tower is heated and expanded before being exhausted to the atmosphere Manufacturing Procedure Evaporation of anhydrous ammonia Oxidation of ammonia gas with air (platinum gauze at 920oC) Cooling of nitric oxide Oxidation and hydration of nitric oxide Collection of 61 – 65% nitric acid using acid trap Waste gas treatment 23  Ten Lasting Achievements First commercial plant built to convert natural 1 - Power Expanding Economies gas to methanol and then to a premium unleaded gasoline. 1912 - Standard Oil Co. of Indiana Thermal cracking at 850° F and 75 psig doubles 2 - Broadening Energy Options the yield of gasoline from crude oil, compared with 650° F atmospheric distillation. 1945 - Oak Ridge National Laboratory Enriched uranium is produced at the Clinton 1921 - Standard Oil Co. of New Jersey Engineer works — the 2,142- column thermal Continuous thermal cracking to convert heavy oil diffusion plant at Oak Ridge, TN. into gasoline is achieved using double coils and The Oak Ridge K-25 gaseous diffusion plant. Built tubes. in 1943 as part of the Manhattan Project, the plant was designed to separate U-235 from U- 1930 - Standard Oil Development 238. Low-temperature lube oils are produced using an additive to prevent paraffin crystallization. 1957 - Duquesne Light Co. Shippingport, the world’s first largescale nuclear 1937 - Houdry, Socony Vacuum, Sun Oil power plant, goes into service 15 years after High-octane gasoline is achieved by catalytic sustained nuclear reaction was demonstrated by cracking using rapidly deactivating silica catalyst Enrico Fermi. regenerated in cyclic operations. This The Shippingport reactor pressure vessel during development paved the way for fixed-bed construction, 1956. The plant — built on the Ohio catalytic cracking using reactors packed with River about 25 miles from Pittsburgh, PA — catalyst pellets. operated from 1957–1982, and had a capacity of 60 MWe 1942 - Standard Oil Co. of New Jersey Continuous catalytic cracking is achieved by 1959 - Conch Methane Services, Ltd. fluidizing fine silica alumina catalyst so that it Mass-scale storage and marine transport of flows between reactor and regenerator. liquefied natural gas is proven feasible using a converted World War II liberty freighter. 1944 - Socony Vacuum High-powered Ni-MH battery of the Toyota First jet fuel, called JP-e, is manufactured to fuel NHW20 Prius. early U.S. jet planes. 1937 - Houdry, Socony Vacuum, Sun Oil 1950 - Standard Oil Development High-octane gasoline is achieved by catalytic First synthetic jet and turbo-prop aircraft engine cracking using rapidly deactivating silica catalyst lubricants are developed, providing superior regenerated in cyclic operations. This lubrication and greater thermal stability. development paved the way for fixed-bed catalytic cracking using reactors packed with 1952 - Standard Oil Development catalyst pellets. Multi-grade all-season motor oil is developed; additives are used to reduce viscosity, circa 1964 - Lawrence Berkeley National Laboratory temperature dependency, and pour point. High-energy lithium batteries using reactive metals in polar (hydrophilic) aprotic (no O-H or N- 1970 - Mobil Oil H bonds) solvents are developed. BF3-catalyzed 1-decene polymerization leads to energy efficient syn - thetic motor oil (Mobil1— first introduced in 1974; improved polymer added in 2000). 1985 - Mobil Oil 24 late 1970s - Philips; Centre National de la Recherche Membrane-based chemisorption process Scientifique Laboratories permits ammonia recovery from anaerobic Environmentally-friendly, high-energy NiMH digested wastes; allowed for a 99.9+% recovery battery is developed; later used in the Toyota of waste stream ammonia at Staten Island, NY, Prius. location. Individual fibers of Polybenzimidazole 3 - Dealing With an Ever-More-Crowded (trademarked as Celazole PBI) — a high Environment performance imidized thermoplastic that replaces asbestos 1918 - Standard Oil of New Jersey 2002 - Teijin Limited FLIT, the first petroleum-based household Dimethyl terephthalate (DMT) equal in purity to insecticide, is marketed. Its advertising art was that made from petroleum is made from recycled created by Theodor Seuss Geisel (later known as polyethylene terephtalate (PET) bottles and Dr. Seuss).