An aqueous waste stream leaving a process contains 10.0 wt% sulfuric acid and 1 kg nitric acid per kg sulfuric acid. The flow rate of sulfuric acid in the waste stream is 1000 kg/h. The acids are neutralized before being sent to a wastewater treatment facility by combining the waste stream with an aqueous slurry of solid calcium carbonate that contains 2 kg of recycled liquid per kg solid calcium carbonate. (The source of the recycled liquid will be given later in the process description.) The following neutralization reactions occur in the reactor:

CaCO₃ + H₂SO₄ → CaSO₄ + H₂O ÷ CO₂

CaCO₃ + 2 HNO₃ → Ca (NO₁)₂ + H₂O + CO₂

The sulfuric and nitric acids and calcium carbonate fed to the reactor are completely consumed. The carbon dioxide leaving the reactor is compressed to 30 atm absolute and 40°C and sent elsewhere in the plant. The remaining reactor effluents are sent to a crystallizer operating at 30°C, at which temperature the solubility of calcium sulfate is 2.0 g CaSO₄/1000 g H₂O. Calcium sulfate crystals form in the crystallizer and all other species remain in solution.

The slurry leaving the crystallizer is filtered to produce (1) a filter cake containing 96% calcium sulfate crystals and the remainder entrained saturated calcium sulfate solution, and (ii) a filtrate solution saturated with CaSO4 at 30°C that also contains dissolved calcium nitrate. The filtrate is split, with a portion being recycled to mix with the solid calcium carbonate to form the slurry fed to the reactor, and the remainder being sent to the wastewater treatment facility.

(a) Draw and completely label a flowchart for this process.

(b) Speculate on why the acids must be neutralized before being sent to the wastewater treatment facility.

(c) Calculate the mass flow rates (kg/h) of the calcium carbonate fed to the process and of the filter cake; also determine the mass flow rates and compositions of the solution sent to the wastewater facility and of the recycle stream. (Caution: If you write a water balance around the reactor or the overall system, remember that water is a reaction product and not just an inert solvent.)

(d) Calculate the volumetric flow rate (T/h) of the carbon dioxide leaving the process at 30 atm absolute and 40°C. Do not assume ideal gas behavior.

(e) The solubility of Ca (NO₃)₂ at 30°C is 152.6 kg Ca(NO₃)₂ per 100 kg H₂O. What is the maximum ratio of nitric acid to sulfuric acid in the feed that can be tolerated without encountering difficulties associated with contamination of the calcium sulfate by-product by Ca(NO₃)₂?