1. p. 1 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. AIM:Develop the proposal of a block diagram and main operating conditions for a monoethanolamine plant. Reactions:

2. p. 2 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. “The reaction of ethylene oxide with ammonia takes place slowly and is accelerated by water.” BASIC DATA (Ullmann’s Encyclopedia of Industrial Chemistry) “The reaction is highly exothermic; the enthalpy of reaction is about 125 kJ per mole of ethylene oxide. ” “All the reaction steps have about the same activation energy and show a roughly quadratic dependence of the reaction rate on the water content of the ammonia – water mixture used. ” “In all conventional processes, reaction takes place in the liquid phase,...” TB (ºC) TC (ºC) NH3-33133 EO10196 H2O100374 MEA170405 DEA268463 TEA335499

3. p. 3 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. PERFORMANCE Type of reaction? Maximum selectivity Mixed reactions: NH3, MEA: Multiple in series EO: Multiple in parallel Conversion target? Multiple in series reactions: low conversion (50%?) Performance choice?

4. p. 4 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. FLOW PATTERN CONCENTRATION Feed Product PF CONCENTRACIÓN Feed Product CSTR For safety reasons, ethylene oxide must be metered into the ammonia stream ; in the reverse procedure, ammonia or amines may cause ethylene oxide to undergo an explosive polymerization reaction.

5. p. 5 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. CONCENTRATION NH3 >> EO Performance choice: maximum selectivity Stoichiometric ratio?

6. p. 6 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. TEMPERATURE “All the reaction steps have about the same activation energy and show a roughly quadratic dependence of the reaction rate on the water content of the ammonia – water mixture used. ” Performance choice: maximum selectivity Selectivity does not depend on temperature: maximum T (reduces reactor volume). “The reaction is highly exothermic ; the enthalpy of reaction is about 125 kJ per mole of ethylene oxide. ” Intensive cooling required.

7. p. 7 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. PRESSURE “All the reaction steps have about the same activation energy and show a roughly quadratic dependence of the reaction rate on the water content of the ammonia – water mixture used. ” Objetivo: máxima selectividad Selectivity does not depend on pressure: minimum P required to keep liquid phase (temperature depending). “In all conventional processes, reaction takes place in the liquid phase,...”

8. p. 8 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. PRACTICAL REACTOR Liquid phase reaction. Homogeneous catalytic. Flow pattern: PF (NH3 and MEA) and CSTR (EO). Highly exothermic: cooling required High pressure. “The reaction of ethylene oxide with ammonia takes place slowly and is accelerated by water.” High residence time. Multi-tubular cooled reactor, with multiple intermediate EO feed points.

9. p. 9 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. DIAGRAM SEPARADOR

10. p. 10 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. Ullmann’s Encyclopedia of Industrial Chemistry “All the reaction steps have about the same activation energy and show a roughly quadratic dependence of the reaction rate on the water content of the ammonia – water mixture used. Therefore, product composition depends solely on the molar excess of ammonia and not on water content, reaction temperature, or pressure. The product distribution as a function of the molar ratio of the reactants is shown in Figure.”

11. p. 11 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. “In all conventional processes, reaction takes place in the liquid phase, and the reactor pressure must be sufficiently large to prevent vaporization of ammonia at the reaction temperature.” Ullmann’s Encyclopedia of Industrial Chemistry “In current procedures, ammonia concentrations in water between 50 and 100 %, pressures up to 16 MPa (160 bar), reaction temperatures up to 150 °C, and an excess up to 40 mol of ammonia per mole of ethylene oxide are used. ” “Today, ethanolamines are produced on an industrial scale exclusively by reaction of ethylene oxide with excess ammonia, this excess being considerable in some cases ”

12. p. 12 Wording Basic data Analysis Performance Flow pattern Concentration Temperature Pressure Practical reactor Diagram Actual process Ullmann 1 Ullmann 2 Ullmann 3 Monoethanolamine Integrated Process Design. UVa. Ullmann’s Encyclopedia of Industrial Chemistry