1. WWW.GBHENTERPRISES.COM

2. AMINES Contents Historical perspective Background (MMA, DMA and TMA) Stereochemistry and Structure Reaction Mechanisms and Thermodynamics CATALYSTS FOR AMINATION Non-Zeolitic Catalysts for Amination Mordinite (MOR) Catalysts for Amination Zeolite Catalysts for Amination WWW.GBHENTERPRISES.COM 3. AMINES Contents Amines Production Amines: Markets and Applications Gas Separation Conventional Amines Treating System Amine System for Gas Sweetening APPENDIX Structures Ethyleneamines Production WWW.GBHENTERPRISES.COM 4. AMINES Historical Perspective Industrially the synthesis of methylamines in batch mode from methanol and ammonia, using zinc chloride, was first reported in 1884. The first report of amination of alcohols in the gas phase was in 1909 Methylamines were first made commercially in the 1920s for use in the tanning industry for the dehairing of animal skins by Commercial Solvents Corporation in Terra Haute, Indiana. 5. AMINES Historical Perspective The process used at that time and the current processes [are essentially the contact of gaseous methanol and ammonia over dehydrating catalysts (e.g. silica-alumina), followed by collection and separation of the products. For higher aliphatic amines, catalysts having hydrogenating and dehydrogenating properties have also become important 6. Amines Background (MMA, DMA and TMA) 7. Mono-methyamine (MMA) Mono-methylamine is the organic compound with the chemical formula CH3NH2. This colorless gas is a derivative of ammonia, but with one H atom replaced by a methyl group. It is the simplest primary amine. It is sold as a solution in methanol, ethanol, and water or as the anhydrous gas in pressurized metal containers. 8. Di-methylamine (DMA) Dimethylamine is an organic compound with the chemical formula (CH3)2NH. This secondary amine is a colorless, flammable liquefied gas with an ammonia-like odor. Dimethylamine is generally encountered as a solution in water at concentrations up to around 40%. Dimethylamine is a precursor to several industrially significant compounds. It reacts with carbon disulfide to give dimethyldithiocarbamate, a precursor to a family of chemicals widely used in the vulcanization of rubber. 9. Tri-methylamine (TMA) Trimethylamine is an organic compound with the chemical formula N(CH3)3. This colorless, hygroscopic, and flammable tertiary amine has a strong "fishy" odor in low concentrations and an ammonia-like odor at higher concentrations. It is a gas at room temperature but is usually sold in pressurized gas cylinders or as a 40% solution in water. Tri-methylamine is used in the synthesis of choline, tetramethylammonium hydroxide, plant growth regulators, strongly basic anion exchange resins, dye leveling agents and a number of basic dyes [1]. Gas sensors to test for fish freshness detect trimethylamine. 10. Physical Properties of MMA, DMA and TMA 11. Stereochemistry and Structure 12. The electron structure of amines 13. Reaction Mechanisms and Thermodynamics WWW.GBHENTERPRISES.COM 14. Chemical reactions and catalysts The reaction of ammonia and methanol in the presence of a solid acid catalyst forms a mixture of mono-, di- and trimethylamine (MMA, DMA and TMA, respectively). 15. Reactions and Thermodynamics Table I shows the different classes of reactions that play a role in the amination of alcohols over solid acid catalysts. Alkylation of Ammonia with Alcohols 16. Reactions and Thermodynamics The alkylation reactions are exothermic and are regarded as Irreversible due to their high equilibrium constant. They proceed in sequential order to yield the mono-, di- and tri-substituted amines. The transalkylation reactions are regarded as being reversible and are held responsible for the amine product distribution at higher alcohol conversion. Alkylation of Ammonia with Alcohols 17. Reactions and Thermodynamics Dependence of the equilibrium amine distribution on (a) the NH /MeOH ratio and Reaction temperature () MMA, () DMA, () TMA Alkylation of Ammonia with Alcohols 18. Reactions and Thermodynamics The equilibrium distribution of the reactants and products in methanol and ethanol amination: Dependence of the equilibrium product distribution on: (a) and (b) NH3/EtOH ratio at 573 K and p=1 bar () MEA, ()DEA, () TEA, () ethene 19. Reactions and Thermodynamics The equilibrium distribution of the reactants and products in methanol and ethanol amination: Dependence of the equilibrium product distribution on reaction temperature at NH /EtOH=4 and p=1 bar Bar. () MEA, ()DEA, () TEA, () ethene 20. Reactions and Thermodynamics OBSERVATIONS The equilibrium distribution of the reactants and products in methanol and ethanol amination given in the previous three slides suggest the following: The necessity to shift the reactions away from equilibrium In ethylamine synthesis this need arises from the necessity to avoid the formation of ethene and its oligomerization products and thus to increase catalyst and equipment lifetime 21. Synthesis of Secondary Amines 22. Synthesis of Tertiary Aliphatic Amines 23. Psychoactive Compounds I 24. Psychoactive Compounds II 25. CATALYSTS FOR AMINATION WWW.GBHENTERPRISES.COM 26. Non-Zeolitic Catalysts for Amination WWW.GBHENTERPRISES.COM 27. Non-Zeolitic Catalysts for Amination Variety of catalysts for the vapor phase methanol-ammonia reaction has been reported: Aluminas, Silicas, Zirconia, Thoria Phosphates. *other materials that perform dehydration chemistry have been used for methylamines synthesis 28. Non-Zeolitic Catalysts for Amination Among the more exotic candidates are a photocatalytic Pt/titania system where at MeOH conversion of < 0.1% only TMA is produced and a heteropoly acid catalyst that suppresses TMA completely at 477C and N/C=2. It was recognized early on that a high N/C ratio favored MMA formation. The temperature range employed was, as expected, large 250-500C. Photocatalytic Pt/titania 29. Non-Zeolitic Catalysts for Amination Silica-alumina (SA) is currently the most widely used catalyst for methylamines synthesis. Silica-alumina (SA) It is usually made by coprecipitation. 30. Non-Zeolitic Catalysts for Amination A SA (46.9 wt% SiOa) was compared to a boron phosphate and an SA-boron phosphate hybrid, SA was found to be the preferred catalyst; it had a higher selectivity to amines. Reduced coking and improved rates are obtained by using a high alumina (94 wt%) content SA catalyst. Silica-alumina (SA) *at the same conditions, conversion and selectivity to amines increased with increasing surface area and acidity. 31. MORDENITE (MOR) CATALYSTS FOR AMINATION WWW.GBHENTERPRISES.COM 32. Mordenite (MOR) CATALYSTS FOR AMINATION Among the zeolites seen suitable for shape selective alkylamine synthesis, mordenite is industrially the most widespread applied. Mordenite consists of a one dimensional system of large channels (12-ring, 6.5 x 7.0 ) lined with so-called side pockets, which have an aperture of approx. 4.8 x 3.7 [14,15], these side pockets are separated by a restriction of 2.6 x 5.7 , as shown in the Figure to the Right, in which the accessibility of the MOR structure to ammonia is represented (obtained using the Insight II program from Biosym/MSI). 33. Mordenite (MOR) CATALYSTS FOR AMINATION 34. Mordenite (MOR) CATALYSTS FOR AMINATION 35. Mordenite (MOR) CATALYSTS FOR AMINATION 36. ZEOLITE CATALYSTS FOR AMINATION 37. ZEOLITE CATALYSTS FOR AMINATION The primary building blocks of zeolites are {SiO4}4- and {AlO4}5- tetrahedra. As a result of the difference in charge between these tetrahedra, the total framework charge is negative and hence must be balanced by cations, typically protons, alkali, or alkaline earth metal ions. 38. ZEOLITE CATALYSTS FOR AMINATION Generally in the protonic or acid form, these materials behave as solid acids and as such are excellent candidates as catalysts for methylamines synthesis. 39. ZEOLITE CATALYSTS FOR AMINATION Zeolite Properties 1 Zeolites have uniform pore systems of a size that is comparable to a number of organic molecules. Zeolites are crystalline materials that are composed of a three dimensional network of metal oxygen tetrahedral with: - a one-dimensional channel system - a two-dimensional channel system - a three-dimensional channel system * Depending on the way these tetrahedral are linked together. 40. ZEOLITE CATALYSTS FOR AMINATION Zeolite Properties 1 Zeolites can be classified according to their largest pore size. 'Small pore' zeolites are those containing 8-membered ring openings, 'medium' containing 10-membered rings and 'large' containing 12-membered rings Zeolites of all three classes have been tested for amine synthesis. The pore openings of these zeolites range from 3 to 7.5 and allow for exclusion of molecules based on their minimum kinetic diameter and shape. 41. ZEOLITE CATALYSTS FOR AMINATION Zeolite Properties 1 Mechanistically, different reasons for the occurrence of shape selectivity are distinguished: (i) Reactant shape selectivity (a consequence of one reactant being too large to pass through the zeolite channel) and (ii)Product selectivity (when only certain products are of the proper size and shape are able to diffuse out of the channels. (iii)Transition state selectivity occurs when the corresponding transition state of a certain reaction requires more space than available in the framework of the zeolite. 42. ZEOLITE CATALYSTS FOR AMINATION Zeolite Properties 2 Zeolites can contain high concentrations of localized acid sites. The acid sites of zeolites are an integral part of the microporous structure resulting from an imbalance between the metal oxygen stoichiometry and the formal charges of the cations. In zeolites the tetrahedral are based on silicon and oxygen. In this network of tetrahedral a Si atom has a charge of +4, an O atom of -2. As every O atom belongs to two tetrahedral, a purely siliceous lattice is neutral and possesses no acidity. 43. ZEOLITE CATALYSTS FOR AMINATION Zeolite Properties 2 Substituting part of the Si atoms by Al (+3), creates a negative charge at the Al-O tetrahedra, which is balanced by a metal cation (Lewis acid site) or a proton (Brnsted acid site). Thus these acid sites are localized and their concentration is proportional to the aluminum concentration in the lattice. Due to their open structure, the accessibility of acid sites is much larger than for amorphous materials of similar composition. High surface concentration of reactants and longer residence times of reactants in the pores generally additionally enhance the activity of zeolites. 44. ZEOLITE CATALYSTS FOR AMINATION Numerous zeolites have been tested as catalyst ranging in size from 'small pore' to 'large pore' zeolites. ZK-5 Rho Chabazite Erionite Offretite ZSM-5 Mordenite 45. ZEOLITE CATALYSTS FOR AMINATION Mordenite (MOR) Faujasite (FAU) Mazzite (MAZ) Beta (BEA) Large Pore zeolites 46. ZEOLITE CATALYSTS FOR AMINATION LargePorezeolites Zeolite structures, emphasizing the diameter of the 12-ring; (a) BEA, (b) FAU, (c) MOR, and (d) MAZ. 47. Amines Production WWW.GBHENTERPRISES.COM 48. Amines Production When ammonia is reacted with methanol, the products MMA, DMA and TMA are formed in consecutive reactions. The most widely used method for the production of methylamines is the reaction of methanol with ammonia at temperatures of about 400C in the presence of acidic solid catalysts. These catalysts are capable of dehydrating and aminating methanol. These catalysts are capable of dehydrating and aminating methanol. For example, modified -alumina, aluminosilicate and thorium oxide catalysts. 49. Amines Production Largest Producers of methylamines and their method of production 50. Amines Production Process Constraints As a result of the increasing demand for DMA all major producers and researchers are looking for a catalyst that increases the yield of DMA. Therefore, in many processes MMA and TMA are converted into DMA by being recycled into the feedstock. There are also byproducts that are produced during the catalytic reaction and they include ethanol, ethylamine, dimethylether, methane and etc. 51. Amines Production Process Overview Fresh methanol and ammonia feed are combined with recycled ammonia and methylamines (mainly MMA and TMA) are fed to a reactor containing a solid acid catalyst. The amorphous silica alumina catalysts produced by Albemarle are those most commonly used in the methylamine production process. These catalysts are highly active and stable but have no specific product selectivity. Various catalysts are available in the market under commercial names. 52. Amines Production Typical properties of KDC-6 catalyst produced by Albemarle 53. AMINE PRODUCTION PROCESSES The Nitto Chemical Methylamines Process Methylamines are produced conventionally by reacting gaseous methanol and ammonia in the presence of a catalyst such as silica-alumina. The reaction products have the thermodynamic equilibrium composition of monomethylamine, dimethylamine, and trimethylamine. To produce a product mix different from the equilibrium composition, unwanted methylamines recovered downstream must be recycled to the reaction to suppress their formation. 54. AMINE PRODUCTION PROCESSES The Nitto Chemical Methylamines Process Nitto Chemical (Japan) has developed a process that can produce a non-equilibrium product mix having a high dimethylamine content, e.g., 86% dimethylamine and 7% each of mono- and trimethylamines. The process is based on zeolite-type catalysts. A commercial methylamines plant based on it has been in operation since 1984. 55. AMINE PRODUCTION PROCESSES The Nitto Chemical Methylamines Process A conventional process to produce a product mix consisting of 34wt% monomethylamine, 46wt% dimethylamine, and 20wt% trimethylamine would require a total fixed capital about 14%higher and a product value about 7% higher than that of the Nitto Chemical process. 56. AMINE PRODUCTION PROCESSES The Nitto Chemical Methylamines Process To produce a product mix similar to the one prescribed for the Nitto Chemical process, the conventional process would be even more costly, because larger portions of the monomethylamine and trimethylamine product streams must be recycled to the reactor to suppress the formation of these two methylamines. 57. Amines: Markets and Applications 58. Amines: Markets and Applications 59. Amines: Markets and Applications 60. Amines: Gas Separation 61. Amines: Gas Separation Solvents Amine scrubbing technology was established over 60 years ago in the oil and chemical industries, for removal of hydrogen sulfide and CO2 from gas streams Commercially, it is the most well established of the techniques available for CO2 capture although practical experience is mainly in gas streams which are chemically reducing, the opposite of the oxidizing environment of a flue gas stream. and desorption characteristics. 62. Amines: Gas Separation Solvents There are several facilities in which amines are used to capture CO2 from flue gas streams today, one example being the Warrior Run coal fired power station in the USA where 150 t/d of CO2 is captured. Mono-ethanolamine (MEA) is a widely used type of amine for CO2 capture. CO2 recovery rates of 98% and product purity in excess of 99% can be achieved. There are, however, questions about its rate of degradation in the oxidizing environment of a flue gas and the amount of energy required for Regeneration. Improved solvents could reduce energy requirements by as much as 40% compared to conventional MEA solvents. There is considerable interest in the use of sterically-hindered amines which are claimed to have good absorption and desorption characteristics. 63. Conventional Amines Treating System 64. Amines: Gas Sweetening 65. Amines: Gas Sweetening 66. Amines: Gas Sweetening 67. Amines: Gas Sweetening 68. APPENDIX 69. Ethyleneamines Production 70. Ethyleneamines Production US 7,626,058 Scheme1 71. Ethyleneamines Production US 7,626,058 Scheme 2 72. Ethyleneamines Production US 7,626,058 Scheme 3 73. Ethyleneamine Profiles 74. Ethyleneamine Profiles 75. Ethyleneamine Profiles 76. Ethyleneamine Profiles 77. Ethyleneamine Profiles 78. Ethyleneamine Profiles Typical Physical Properties 79. Ethyleneamine Profiles Typical Physical Properties 80. Ethyleneamine Profiles Typical Physical Properties 81. Ethyleneamine Profiles Typical Physical Properties 82. Ethyleneamine Profiles 83. Ethyleneamine Profiles 84. Ethyleneamine Profiles 85. Ethyleneamine Profiles 86. Ethyleneamine Profiles 87. Ethyleneamine Profiles 88. Ethyleneamine Profiles 89. Ethyleneamine Profiles 90. Ethyleneamine Profiles 91. Reactions of Ethyleneamine 92. Ethyleneamine: Reaction Notes 93. Ethyleneamine: Reaction Notes 94. Ethyleneamine: Reaction Notes 95. Ethyleneamine: Reaction Notes 96. Ethyleneamines Applications Ethyleneamines are utilized in a wide variety of applications because of their unique combination of reactivity, basicity, and surface activity. They are predominantly used as intermediates in the production of functional products. The following table lists the major end-use applications for these versatile materials. 97. Ethyleneamine Profiles