In industrial urea manufacture (NH3 + CO2 → ammonium carbamate → urea), what is the effect of increasing the NH3/CO2 molar ratio in the synthesis section?
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AIncreased degree of conversion of CO2 to urea
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BDecreased degree of conversion of NH3 to urea
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CDecreased overall yield of urea
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DDecreased specific volume of the molten mass only, with no effect on conversion
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EShift to ammonia-free operation
Answer
Correct Answer: Increased degree of conversion of CO2 to urea
Explanation
Introduction / Context:Urea plants first form ammonium carbamate from ammonia and carbon dioxide, then dehydrate it to urea. Manipulating the NH3/CO2 ratio affects equilibria, corrosion, and physical properties. Understanding how excess ammonia influences conversion is central to process optimization and energy balance in high-pressure synthesis loops.
Given Data / Assumptions:
- Operating at high pressure and moderate temperature in the synthesis zone.
- Carbamate formation is favored by excess NH3.
- Downstream recovery strips/recycles unconverted NH3 and CO2.
Concept / Approach:Raising the NH3/CO2 ratio drives formation of ammonium carbamate and subsequently favors the dehydration route to urea, increasing the single-pass conversion of CO2. Although excess ammonia is later recovered, within the synthesis section this ratio shift improves conversion and can also beneficially affect melt properties (e.g., reduce specific volume/viscosity), but the primary textbook takeaway is the conversion gain for CO2.
Step-by-Step Solution:
Recognize key equilibrium: NH3 + CO2 + NH3 ⇌ NH4NH2COO (carbamate).Leverage excess NH3 to push equilibrium rightward.Higher carbamate formation supports greater conversion of CO2 to urea in the reactor.Therefore, select “increased degree of conversion of CO2 to urea.”Verification / Alternative check:Process design literature cites higher NH3/CO2 improving CO2 conversion at the expense of larger recycle duties—managed by stripper/condenser sections.
Why Other Options Are Wrong:
- Decreased NH3 conversion or overall yield: inconsistent with equilibrium shift toward carbamate/urea.
- Decreased specific volume only: while melt properties may change, the dominant effect tested is conversion increase.
- Ammonia-free operation: not applicable.
Common Pitfalls:Ignoring the recycle loop: higher NH3/CO2 aids conversion but increases ammonia recovery load; the question focuses on conversion effect within synthesis.
Final Answer:Increased degree of conversion of CO2 to urea