Bosch–Meiser process
The Bosch–Meiser process is an industrial process for the large-scale manufacturing of urea, a valuable nitrogenous chemical. It was patented in 1922 and named after its discoverers, the German chemists Carl Bosch and Wilhelm Meiser.
The whole process consists of two main equilibrium reactions, with incomplete conversion of the reactants.
- The first, called carbamate formation: the fast exothermic reaction of liquid ammonia with gaseous carbon dioxide at high temperature and pressure to form ammonium carbamate :
- The second, called urea conversion: the slower endothermic decomposition of ammonium carbamate into urea and water:
Reactant recycling
Because the urea conversion is incomplete, the urea must be separated from the unconverted reactants, including the ammonium carbamate. Various commercial urea processes are characterized by the conditions under which urea forms and the way that unconverted reactants are further processed.Conventional recycle processes
In early "straight-through" urea plants, reactant recovery was done by letting down the system pressure to atmospheric to let the carbamate decompose back to ammonia and carbon dioxide. Originally, because it was not economic to recompress the ammonia and carbon dioxide for recycle, the ammonia at least would be used for the manufacture of other products such as ammonium nitrate or ammonium sulfate, and the carbon dioxide was usually wasted. Later process schemes made recycling unused ammonia and carbon dioxide practical. This was accomplished by the "total recycle process", developed in the 1940s to 1960s and now called the "conventional recycle process". It proceeds by depressurizing the reaction solution in stages and passing it at each stage through a steam-heated carbamate decomposer, then recombining the resulting carbon dioxide and ammonia in a falling-film carbamate condenser and pumping the carbamate solution back into the urea reaction vessel.Stripping recycle process
The "conventional recycle process" for recovering and reusing the reactants has largely been supplanted by a stripping process, developed in the early 1960s by Stamicarbon in The Netherlands, that operates at or near the full pressure of the reaction vessel. It reduces the complexity of the multi-stage recycle scheme, and it reduces the amount of water recycled in the carbamate solution, which has an adverse effect on the equilibrium in the urea conversion reaction and thus on overall plant efficiency. Effectively all new urea plants use the stripper, and many total recycle urea plants have converted to a stripping process.In the conventional recycle processes, carbamate decomposition is promoted by reducing the overall pressure, which reduces the partial pressure of both ammonia and carbon dioxide, allowing these gasses to be separated from the urea product solution. The stripping process achieves a similar effect without lowering the overall pressure, by suppressing the partial pressure of just one of the reactants in order to promote carbamate decomposition. Instead of feeding carbon dioxide gas directly to the urea synthesis reactor with the ammonia, as in the conventional process, the stripping process first routes the carbon dioxide through the stripper. The stripper is a carbamate decomposer that provides a large amount of gas-liquid contact. This flushes out free ammonia, reducing its partial pressure over the liquid surface and carrying it directly to a carbamate condenser. From there, reconstituted ammonium carbamate liquor is passed to the urea production reactor. That eliminates the medium-pressure stage of the conventional recycle process.
Side reactions
The three main side reactions that produce impurities have in common that they decompose urea.Urea hydrolyzes back to ammonium carbamate in the hottest stages of the synthesis plant, especially in the stripper, so residence times in these stages are designed to be short.
Biuret is formed when two molecules of urea combine with the loss of a molecule of ammonia.
Normally this reaction is suppressed in the synthesis reactor by maintaining an excess of ammonia, but after the stripper, it occurs until the temperature is reduced. Biuret is undesirable in urea fertilizer because it is toxic to crop plants to varying degrees, but it is sometimes desirable as a nitrogen source when used in animal feed.
Isocyanic acid HNCO and ammonia results from the thermal decomposition of ammonium cyanate, which is in chemical equilibrium with urea:
This decomposition is at its worst when the urea solution is heated at low pressure, which happens when the solution is concentrated for prilling or granulation. The reaction products mostly volatilize into the overhead vapours, and recombine when these condense to form urea again, which contaminates the process condensate.