NITRIC ACID DESIGN PROJECT

SHIVAM PANDYA

UNIT 1

INTRODUCTION

Basis :Design A Chemical Plant To Produce 280 tonnes/day Of 60% (Wt) Nitric Acid. PROCESS DESCRIPTION:
Single pressure process operates at about 1000 kPa Air compressor to provide high pressure air to the reactor Ammonia vaporizer and super heater before the reactor Reactor vessel with gauze catalyst for ammonia oxidation at 1000 kPa and 900-950 C Heat exchanger to cool down the reactor exit stream An absorption column to produce nitric acid A stripper to release the dissolved nitrogen oxides from nitric acid solution

BLOCK FLOW DIAGRAM:

FIG 1.1 BFD NITRIC ACID PRODUCTION

 PROCESS EQUIPMENT:
AIR COMPRESSOR Air is compressed in two stages. The first-stage compression is a low-pressure compression from atmospheric pressure up to 310 kPa. An axial compressor is used which takes its shaft drive from a steam turbine. The second compression utilizes a centrifugal-type compressor. The centrifugal compressor is more efficient for the air flowrate (36 000 kg/h) and outlet pressure (1090 kPa) desired. The centrifugal compressor takes its shaft drive from the expansion of tail gas. Intermediate to the two compression stages is an intercooler which allows the air temperature to be lowered from 180C to 45C, with a pressure loss of 10 kPa. The temperature drop enables a more efficient second compression stage.Compressor intercooler area = 130 m2.

AMMONIA VAPORIZER A shell and tube-type heat exchanger with two passes per shell on the tube side. This unit should contain internal baffles. Operating pressure is 1240 kPa, with a design pressure of approximately 1400 kPa. This exchanger is made from mild steel. Ammonia vaporizer heatexchange area = 83 m2

AMMONIA SUPERHEATER A shell and tube-type heat exchanger of similar mechanical construction to the ammonia vaporizer. Also constructed from mild steel. Ammonia superheater heat-transfer area = 30 m2.

REACTOR The reactor is a pressure vessel operating in the range 1050 kPa to 1100 kPa. The design pressure should be about 1400 kPa. The vessel must be designed to ensure even passage of the feed gas mixture over the platinum/rhodium catalyst gauze. A Random Pack flow distributor (Englehard Industries) would be suitable. The catalyst gauze and accompanying platinum filter gauze are fixed in position by lateral supports across the width of the reactor. The catalyst gauze and filter gauze are both 80 mesh, plain weave-type sheets (about 25 of each for a total mass of 24

kg). In the reaction section, the walls of the reactor should be lined with refractory material to prevent wear on the outer walls. The bottom section of the reactor is jacketed. Air is preheated in this jacket prior to mixing with ammonia. The bottom section of the reactor also contains a shell and tubetype heat exchanger. This exchanger provides the final stage of tail-gas preheating. Tail gas enters at 235C and the reaction gases leave the exchanger section of the reactor at 645C. The reactor shell, jacket and associated heat exchanger are all constructed from mild steel. Reactor exchanger heat-transfer area = 72m2.

STEAM SUPERHEATER This unit superheats saturated steam from 250C (and 4000kPa) to 380C. The product steam is of medium pressure and suitable quality for in-house application and also for export. The superheater cools the reaction gases from the reactor exit temperature of 645C to 595C. Design pressure on the shell side is approximately 5000 kPa. The steam superheater is constructed from mild steel.Steam superheater heat-transfer area = 15 m2.

WASTE-HEAT BOILER A shell and tube-type exchanger required to heat pressurized (4000 kPa) hot water from 117C to a saturated vapour at 250C. Design pressure on the tube side is approximately 5000 kPa. The waste-heat boiler cools reaction gases from 595C to 280C. It is made from mild steel. Waste-heat boiler heat-transfer area = 110 m2.

TAIL-GAS PREHEATER A shell and tube-type exchanger. It takes reaction gases leaving the platinum filter at about 315C and 1020 kPa, and subsequently reduces their temperature to 185C. The cooling medium is tail gas. It enters at about 50C and leaves the tailgas pre-heater at 235C. The design pressure for this unit is approximately 1200 kPa. It is constructed from mild steel. Tail-gas preheater heat-transfer area = 89 m2

COOLER/CONDENSER This unit is the first to be constructed of type 304L stainless steel. It condenses weak nitric acid from the gaseous mixture

and cools the remaining gases from an inlet temperature of 185C to 60C. This shell and tube-type heat exchanger uses deionized water as its cooling medium. It has a design pressure of about 1200 kPa. Cooler/condenser heattransfer area = 97m2.

OXIDATION UNIT The oxidation unit is an empty pressure vessel that takes input reaction gases and blends in additional air from the bleaching column. The extra oxygen provided enables further oxidation to occur and raises the gas mixture temperature to 140C. At the top of the oxidation unit is a mist eliminator to prevent carry over of acid vapour by entrainment. At the bottom of the vessel is the weak-acid drain. The oxidation unit is constructed from SS304L and has a design pressure of 1200 kPa.

SECONDARY COOLER The secondary cooler takes the exit gases from the oxidation unit at 140C and cools them down to 65C, a suitable temperature for entry into the absorption column. It is a shell and tube-type heat exchanger constructed of SS304L. The cooling medium is circulating warm water from the warm-water loop. The inlet temperature is 50C and the exit temperature is about 80C. The design pressure for this unit is about 1200 kPa. Secondary cooler heat-transfer area = 140m2

ABSORBER The absorber is usually a sieve tray-type column. It has a design pressure of 1200 kPa and an operating pressure around 990 kPa. A bursting disc is used for pressure relief. Each tray is provided with cooling coils to allow the cooling of the absorption liquor. There are two independent cooling circuits, each using deionized water. The top section has an inlet temperature of 7C and an outlet temperature of 20C. The bottom section cooling loop has an inlet temperature of 20C and an exit of 40C. The use of two cooling circuits provides greater flexibility in manipulating absorption conditions in the column. The tail gas leaves the column at about 10C. Weak acid from the cooler/condenser is added to an appropriate tray midway up the column, and make-up water at 7C is added to the top tray. The acid drained from the bottom of the column contains

some dissolved nitrogen oxides. The column and its cooling circuits are all constructed from SS304L.

Bleaching Column The bleaching column is a smaller sieve tray-type column. Impure acid runs down the column from the top tray and air is bubbled up through the liquor to remove dissolved nitrogen oxides. The acid from the base of the column is the final desired 60%(wt.) product.

UNIT 2
Overall Material Balance

MATERIAL AND ENERGY BALANCE

Basis: 100% acid and hourly production ( 11667 kg ) Reaction:

NH3 + 2O2 HNO3 + H2O Ammonia Requirement : NH3 = Ammonia is 99% NH3 = 1988/0.99 = 2008 kg / 63) = 1988 kg

Air Requirement : Oxygen required = Nitrogen required = So, Air requirement = 35638 kg

Make-up Water Requirement : H2O Produced by reaction = Water in NH3 = 1988 H2O require = 4667 kg So, Make-up Water Requirement = 4667-2105-20 = 2542 kg kg

Tail Gas : tail gas = 28521 kg

Air 35638 Kg Ammonia 2008 Kg Make-up Water 2542 Kg PROCESS BASIS 1 HOUR

Tail Gas 28521 Kg Total Product (7000 Kg HNO3 + 4667 Kg H2O B FIG 2.1 OVERALL MATERIAL BALANCE

 UNIT MASS AND ENERGY BALANCE CALCULATION

Compresser :
A two-stage compressor with intercooler is used to supply air for the process. Air requirements total 35 638 kg. Stage one is low-pressure compression using an axial compressor. It takes air feed at approximately 35C and compresses it to 180C and 310 kPa. Stage two of compression is a high-pressure process employing a centrifugal compressor. It takes air from the intercooler at 45C and 300 kPa, and discharges it at 232C and 1090 kPa.

Theoretical Power

= P1 Q1 ln(P2/P1)

= 72226717 KJ Assuming the efficiency of the compressor is 65% So, Actual shaft power required = 72226717/0.65 =11118026 KJ

Intercooler Heat Duty = m Cp ( Tin Tout) = 35638 = 5051686 KJ Cooling Water Flow Rate = Heat Duty/Cp ( Tout Tin) = 5051686/4.184 = 60370 Kg

 Ammonia Vaporizer :
The ammonia vaporizer receives liquid ammonia from the adjacent plant at - 15C and 1240 kPa and vaporizes it at 35C using warm water. The warm-water loop circulates water from the ammonia vaporizer to the secondary cooler. Water enters the ammonia vaporizer at 80C and exits at about 50C.

Enthalpy Of Ammonia 1240 kPa @ -15 C = -850 KJ/Kg C = 525 KJ/Kg Heat Require To Vaporize Ammonia = m (H out H in) =2008 = 2660600 kJ Required circulation rate from the warm-water loop: mw = Heat Duty/Cp (Tin Tout) =2660600/4.184 = 21200 Kg

Ammonia Superheater :
The ammonia superheater takes the saturated ammonia vapour at 35C and superheats it to 177C for mixing with air downstream. Superheated steam at 380C and 4000 kPa is the heating medium. Average heat capacity for ammonia vapour in the range 35C to 177C is 2.25 kJ/ (kg K).

Heat Duty To Superheat Ammonia = m Cp (Tout Tin) =2008 = 641556 kJ

Enthalpy of superheated steam vapour at 4000 kPa @ 380C =3165 kJ/kg @ 250C =2800 kJ/kg Heat of condensation at 250C and 4000 kPa is 1714 kJ/kg Steam Requirement = Heat Duty/(
cond

+ (H380 H250))

= 641556/(1714 + (3165 2800)) = 308 kg

Reactor Feed Mixture

Preheated air at 262C and 1090 kPa is mixed with superheated ammonia at 177C and 1240 kPa. Heat capacity Ammonia at 177C Air at 262C Reactor feed temperature Energy required to heat ammonia = Energy loss by air m ammonia Cp (Tout Tin) = m air Cp (Tin Tout) 2008 x 2.38 (Tout - 177) = 29 700 x 1.05 (262 Tout) Tout= 250 C 2.38 kJ/(kg K) 1.05 kJ/(kg K)

Reactor :
The feed mixture oxidises over the platinum catalyst, thus converting the ammonia into nitrogen monoxide (NO) with a yield of 95%. The remaining 5% forms nitrogen gas and thus remains essentially inert to the reaction in all subsequent process units.

4NH3 + 5O2 4NH3 + 3O2

4NO + 6H2O 2N2 + 6H2O

Mass of nitrogen = Nitrogen in air + Nitrogen from reaction = [0.7491 x 2 97001 + [0.05 (2006/l 7 ) 141 = 2 2 331 kg Mass of inerts = constant = 356 kg Mass of nitrogen monoxide = 0.95 (2006/l 7) 30 = 3363 kg Mass of water = Water in air + Water from reaction = 353 + [0.95 (3 x 2006/17) (18/2)] = 3539 kg Mass of oxygen by difference =31 706 - (22 331 + 356 + 3363 + 3539) = 2117 kg Highly exothermic reaction yields approximately 14 000 kJ/kg ammonia. Average heat capacity of the reaction mixture (1.22 kJ/kg K) is calculated by multiplying the pure gas values by their weight%. Reaction mixture temperature = Tin + [(AH,,,,, FAmm)/(CP FTol)l = 250 + [(14000 x 2006)/(1,22x 31 706)] = 976C The reaction mixture then enters the heat exchange section of the

reactor providing energy to preheat the air feed and also providing the final preheat stage for the tail gas before it enters the expander. The design temperature for the reaction gas outlet is 645C. Total heat given out to the reactor internal exchangers is the sum of further reaction heat and also sensible heat in the reaction gases cooling from 972C to 643C

Steam Superheater :
Oxidation continues as the reaction gases cool, with the equilibrium increasingly favouring the formation of nitrogen dioxide and nitrogen tetroxide at the expense of nitrogen monoxide. The trend is initially gradual, but strengthens as the gases pass

through the tail gas preheater and cooler/condenser. During reaction in the superheater, approximately 5% of the nitrogen monoxide reacts with oxygen to form nitrogen dioxide. No nitrogen tetroxide is formed at this stage. The nitrogen, water, and inert gas components remain unchanged.

2NO + O2

2NO2

Mass of nitrogen monoxide = 0.95 x 3363 = 3195 kg Mass of nitrogen dioxide = 0.05 (3363/30) 46 = 258 kg Mass of oxygen by difference = 31 706 - (22 331 + 356 + 3569 + 3195+ 258) = 1997 kg

 The steam production section comprising the steam superheater and waste-heat boiler is designed to lower the reaction-gas temperature from 645C to 280C (further oxidation in these vessels will also continue to produce reaction heat). Steam of sufficient quality is to be produced for export to the adjacent ammonia and ammonium nitrate plants. Medium-pressure steam (at 380C and 4000 kPa) is preferred. The average heat capacity of the reaction gases in this temperature range is 1.19 kJ/(kg K). Reaction heat is 0.143 times the sensible heat.

Energy for steam raising = Sensible heat + Reaction heat = 1 .143 (Sensible heat) = Index FTotal Cp (Tout Tin) = 1.143 x 31 706 x 1.19 (645 - 280) = 15740825kJ The high-pressure boiler-feed water is preheated to 96C before entering the steam production circuit.

Steam raising capacity = Energy required to change from liquid (96C) to vapour (380C) = Heat available/[(H380 H250) + AH,,, + (Cp (250 Tin))] = 15 740 825/ [(3165 - 2800) + 1714 + (4.2 (250 - 96))] = 5775 kg Steam-superheater duty = F steam (H380 H250) = 5775 (3165 - 2800) = 2107875kJ

Reaction-gas exit temperature = Tin - [Heat duty/(Index FTotal) ] = 645 - [2 107 875/(1 .143 x1.19 x 31 706)] = 596 C Waste Heat Boiler :

Platinum Filter :

Tail Gas Preheater :

Cooler / Condenser : The cooler/condenser further cools the reaction gases so that water condenses with some nitric acid. The design concentration for the nitric acid produced from the cooler/condenser is 42% by weight.

It is assumed that all the water vapour is condensed. The other design specification for this unit is that of the gases leaving the cooler/condenser to the oxidation unit; 43% of the nitrogen monoxide has reacted to form nitrogen dioxide, and 20% of this gas has dimerized to nitrogen tetroxide.

It is important to note that since the cooler/condenser is the first of the vessels to be constructed of stainless steel, all susequent cooling water must be taken from the deionized-water circuit.