Alternative Process: Side reactions

The production of ammonium carbamate involves several chemical reactions using the
reactants, carbon dioxide and ammonia. The primary reaction and the rate of reaction for which
the process depends upon will follow is shown in equations 1 and 2.
2 NH 3(liquid )+ CO 2(gas) NH 2 CO 2 NH 4 (solid)

R 1=1.661011exp

C
( 61000
RT )

Co2

C NH 3

(Eq 1)

(Eq 2)

While this reaction is rather quick and moves towards completion at lower temperatures and
moderate pressures, care must be taken to reduce the amount of secondary reactions that occur
between these reactants. In fact, carbon dioxide within an aqueous solution will react with
aqueous solutions forming a moderately acid solution. These side reactions are shown below in
equations _-_.

However at low temperatures anhydrous ammonia is known to interact with aqueous solutions as
shown in equations

Within the conversion reactor the potential for secondary reactions involving the formation of
ammonium salts, primarily ammonium bicarbonate and ammonium carbonate, will be present.
These reactions are described in equations

It is important to be able to control these reactions in order to have optimal ammonium

carbamate production. As such, it will be extremely detrimental to the process to control the
temperature, pressure, and the concentration of ammonia within the conversion reactor.
Moreover the dominant reaction within the reactor will be ammonium carbamate at low CO2
loadings and excess NH3. At higher CO2 concentration equilibrium shifts to bicarbonate
formation. Therefore the reactor must be capable of kinetics involved to be able to successfully
produce an irreversible formation of ammonium carbamate.

Comparison of reactor
Scaled up design- Michael Warren
Overview of process:
The process design follows a pilot plant referenced by ____. The system operates using
an aqueous diffusion reactor capturing the post-combusted carbon dioxide from an operating
power plant using an aqueous solution of ethanol and ammonia to produce solid ammonium
carbamate. First, the inlet gas is cooled using refrigerated water in order to meet reaction
conditions. At low temperatures (~70F), carbon dioxide has a greater affinity for the solution
allowing for greater absorption and conversion. The solution is created using a liquid mixer in
which aqueous ammonia is met with ethanol. The solution is then pumped at a suitable flow rate
into the reactor. The reactor itself is specifically a diffusion reactor also know as a bubble
reactor. The reactor is filled with the solution and allows the inlet gas to be diffused into the
liquid at a steady flow rate. An optimum flow rate of diffusion is required to maintain a high
conversion of CO2. The reactor is pressurized in order to contain the possibility of the
production of gaseous ammonia and as such the reactor will not be vented as described in the
pilot scale. The vessel will however operate at a higher pressure (~50bar) and remain closely at
low temperatures. Cooling is required in order to prevent the reactor from experiencing an
increase in heat due to the exothermic reaction occurring. Ammonium carbamate is produced in
the reactor alongside other ammonium salts products such as bicarbonate and carbonate. The
outlet stream from the reactor passes a valve to return the slurry to atmospheric pressure where it
will be pumped to a centrifuge. The centrifuge is configured to allow industrial ventilation of the
remaining gas as well as any ammonia gas produced. The excess liquid stream is pumped and
recycled back into the process at steady rates. Saturated ammonium carbamate will continue to a
refrigerated granulation unit in order to break the solid crystals while not allowing
decomposition to urea or to its previous reactants.
Key Equipment:
Reactor: (MATT?)
Centrifuge
The process will require two perforated basket centrifuges that will separate the liquid-solid
solution while allowing the excess gases to be safely recovered. The solution contains the
produced ammonium carbamate, ammonium salts, and excess solvent. This type of centrifuge
was applicable due to large amounts of liquid within the inlet stream and the densities of the
solutes. The inlet stream is introduced to the rotating basket and meets a filter made of noncorrosive material such as 150 micro stainless steel wire cloth. The saturated solids will be caked

and removed by centrifugal force along with the mother liquor. The excess solution and gas will
flow through the caked solid and into a feed line that will be further pumped to a recycle holding
tank.. The dimensions of the centrifuge are ______________ as determined by the inlet rate of
flow and the amount of solid production. It is assumed that the centrifuge will achieve 95%
separation efficiency. Due to the nature of centrifuges, a separate unit is required in the case of a
shutdown of production caused by a faulty or damaged unit. The unit will require utility for the
motor and may need refrigeration necessary to prevent further exothermic reactions
Granulation unit (optional w/ single centrifuge)
Produced ammonium carbamate may require for the use of a granulation unit.
Mixer:
The process will need a large scale mixer to mix the aqueous ammonia with ethanol to create the
specific concentrations needed for the reaction. The unit will need to withstand the erosion
environment created by large concentrations of aqueous ammonia and will most likely be
constructed from stainless steel. The mixers dimensions are ______________. Utility will be
required to power the stir rod.
Compression and pumps:
The process involves multiple compressors and pumps to appropriately move the streams
throughout the plant. A CO2 compressor is required to move 3.9 MMCF of gas per hour at low
pressures. A compressor of this sort is used within the urea production industry and should have
existing LP and HP models available. The ventilation system also requires a similar compressor
in order remove around 3 MMCF from the recycle tank. The compressor will feed the excess gas
into a disposal system to safely discard any harmful gases. A pumping system is also necessary
to move the solutions

Utility