Department of Chemical Engineering University of San Carlos Talamban, Cebu City

Recovery of Sulfur Dioxide from Stack Gases (Design of a Sulfur Dioxide Absorber)

A design project submitted in partial fulfilment of the requirements in the course

ChE 514 Process Equipment Design

By Gabutina, Maria Camille A. Navida, Marjon T. Obiedo, Elena A.

September 28, 2012

Table of Contents Section 1. The Design Problem 1.1 Statement of the Design Project..3 1.2 Description of the Process...3 1.3 Summary of Design Tasks...4 1.4 Design Data 1.4.1 Pure Component Properties..6 1.4.2 Kinetic Data and Reaction Stoichiometry...... 7 1.4.3 Equilibrium Data...7 Section 2. Process Design 2.1 Input/Output Diagram..10 2.2 Functional Block Diagram11 2.3 Process Flow Diagram...12 2.4 Process Flowsheet...13 2.5 Basic Assumptions 2.5.1 Operating mode, Product and Feed Specifications, Process Conditions.13 2.5.2 Battery Limits...13 2.5.3 Definition of Incoming and Outgoing Streams.14 2.6 Material and Energy Balances 2.6.1 Mass Process Stream Summary.14 2.6.2 Energy Process Stream Summary..16 2.6.3 Detailed Calculations of the Material and Energy Balances...17 Section 3. Chemical Engineering Design 3.1 Calculation Flow Diagram39 3.2 Summary of Assumptions.42 3.3 Chemical Engineering Design Calculations42 3.4 Definition of Variables...51 Section 4. References...52

Section 1. The Design Problem

1.1 Statement of the Design Project A team of design engineers is tasked to design an absorber for the recovery of SO2 from stack gases. Specific objectives of the design would be to determine the optimum size of the SO2 tower where the stack gas is entering at a rate of 100 000 ft3/min and minimize the SO2 content from 0.3% to 0.01%. The height and cross-sectional area of the optimum absorption tower should also be determined. The optimum design can be assumed to be that corresponding to a minimum total power cost for circulating the liquid and forcing the gas into the tower if fixed charges were also considered. The plant will be operated 16 hours a day and 294 days in a year.

1.2

Description of the Process

A stream of stack gases that contains 0.3 percent by volume SO2 enters the absorber at a temperature of 300F and a pressure of 1 atm using a gas blower. After several meetings to discuss the proposed overall design, following is a list of assumptions, and data on which the team has decided to base the design: 100,000 ft3/min of gas at 300 oF and 1 atm are to be treated. The entering gas contains 0.3 percent by volume SO2 and 11.0 percent CO2, with the balance being N2, O2 and H2O. The average molecular weight of the entering gas is 29.4. The mole percent of SO2 in the exit gas is to be 0.01 percent. The entering and exit pressures of the absorption column may be assumed to be 1 atm for the purposes of calculating the SO2 pressures.

The average density of the gas at the tower entrance can be assumed to be 0.0.054lb/ft3. The sulphite-bisulphite liquid has a density of 70 lb/ft3 and can be considered as having zero equilibrium SO2 vapour pressure at both the inlet and outlet of the tower and the sulphitebisulphite liquid must be supplied at a rate of 675 lb/hft2 of column cross-sectional area. To absorb the SO2, a solution of H2O, NaHSO3 and Na2SO3 is circulated through the absorption tower. The following reaction occurs between sulphur dioxide and sodium sulphite within the absorption tower: (1) Recovery of SO2 in the design project uses the zinc oxide process where the mixture is treated with ZnO, and the ZnO3 formed is filtered off, dried, and calcined to yield practically pure SO2. The SO2 from the calciner is reused, and the sulphite-bisulfite liquor from the filter is
3

recycled. The pressure of the exit gas from the absorption tower is still maintained at 1 atm. The SO2 concentration of this exit gas stream should be reduced to 0.01 mole per cent. Nonstaggerred grids are to be used as packing material and have the following specifications: Clearance = 1.5 in Height=4 in Thickness=0.25 in Free cross-sectional area=85.80% Active absoption area per cubic foot volume=13.7 ft2/ft3 The following simplified equations are applicable for grids of the dimensions to be used: (2) (3) Where:

The liquid is put into the absorption tower by means of a nozzle at the top of the tower. The pressure just before the nozzle is 35 psig. Assume the pump for the liquid must supply power to lift the liquid to the top of the tower and compress the liquid to take care of the friction in the lines and other minor losses. A safety factor of 10% is added to the power consumption of the pump to take care of friction losses. The gas blower has an overall efficiency of 55 percent The pump has an overall efficiency of 65 percent.

1.3 Summary of Design Tasks 1.3.1 Process Design Carry out overall material and energy balances for the whole process and individual material balances for major equipment involved for a continuous operation. Construct a process flow diagram of the whole process, showing the major equipment involved and the input and output streams.

1.3.2 Chemical Engineering Design Prepare a chemical engineering design on the height and cross-sectional area of the tower for the absorption of SO2 into the sulphite-bisulphite solution, taking into account the heat and mass transfer involved.

1.3.3 Mechanical Design Prepare a mechanical design of the SO2 absorber, specifying the auxiliaries of the tower. The vertical absorption tower contains non-staggerred grids that facilitate good contact between the gas and liquid phases. Choose the appropriate materials of construction for the absorber that are resistant to corrosion and high temperature. 1.3.4 Safety Prepare a brief description of the process and the materials used, showing their possible hazardous properties. Provide descriptions for the prevention of danger in process, damage in equipment and also injury to people. 1.3.5 Process Control Prepare a brief description on how the process is controlled, identifying the variables that are controlled in the process. Construct a process flow sheet presenting the control loops chosen and positioned for the process.

1.4 Design Data 1.4.1 Pure Component Properties Table 1. Technological and Medical Data of Pure Components
PURE COMPONENT PROPERTIES Technological Data Physico-Chemical Data Component Name Thermodynamic Properties Medical Data

Formula

Mol. Weight (lb/lb.mol)

Phase

Density (kg/m3)

Solubility in water (g/100mL)

Melting point ( C) -78 -210 -218.79 150 500 -72.7 1975 NA

Boiling Point ( C)

Hf298 (kJ/ mol)

Gf298 (kJ/ mol)

LD50 (oral) g/kg

Carbon dioxide Nitrogen Oxygen Sodium bisulfite Sodium sulfite Sulfur dioxide Water Zinc Oxide

CO2 N2 O2 NaHSO3 Na2SO3 SO2 H2O

44.0095 28.0000 15.9994 104.0609 126.0427 64.0638 18.0153 81.3794 190.4814

Gas Gas Gas Solid Solid Gas Liq. Solid Solid

770 1.251 1.429 1480 2633 3.049 1000 5606 NA

0.145 insoluble 7.5(25C) 42(6C) 67.8 0.94 0.00016 insoluble

-57 -195.79 -297.39 104 900 -10 100 2360 NA

-393.509 0 0 -1127.25 -1104.99 -296.83 -285.83 -348 789.86

-394.359 0 0 NA NA -300.194 -237.572 NA NA

NA 3.1

2 2.825 3 90 7.950 NA

ZnO ZnSO3.2.1/2 Zinc Sulfite H2O *NA not available

1.4.2 Kinetic Data and Reaction Stoichiometry Absorber T=148.89C, P=1 atm (4) Zinc Oxide Mixer (5) Calciner: T=800C (6) 1.1.1 Equilibrium Data

The equilibrium data used in this design is based on the experimental results obtained by Jerzy et al (1995). The equilibrium of the physical dissolution of SO2 in the solution of sodium sulphitessulphate, which takes place according to the relation (7) can be described by Henrys constant defined by the following equation: (8) Where is the partial pressure of SO2, H is is the Henrys constant, and is the activity of SO2. Johnstone et al (1938) proposed that the gas-equilibria in the SO2-NaHSO3-Na2SO3 system is described using the following relation: (9) The parameter in eq.(3) is called the equilibrium coefficient of the system and is a function of concentration of sodium ions, degree of conversion of sulphite to bisulphite, and temperature. Terms and denote concentrations of bisulphite and sulphite ions, respectively. The following equilibrium correlation is valid only at 308-363K, with a relative error of 12.4%. ( )

Figure 1. Partial pressures of SO2 over aqueous solutions of sodium sulphite-bisulphite as measured by Johnstone et al (1938) and those determined by Buzek and Jaschik (1995).

A discrepancy between the measurements of partial pressures by Johnstone et al (1938) and by Buzek et al(1995) can be observed in Figure 1. The data obtained by Buzek et al (1995) will be used in the design of the absorption tower since they used more accurate measuring techniques compared to Johnstone et al(1938).

Section 2. Process Design 2.1 Input/Output Diagram

Stack Gases: 322,864.3246 lb/h 2118.0277lb/h SO2 53,350.2918 lb/h CO2 56,675.9314 lb/h O2 186,558.2743 lb/h N2 24,161.7994 lb/h H2O

Desulfurized Gas: 320,816.6931 lb/h 70.3962 lb/h SO2 53,350.2918 lb/h CO2 56,675.9314 lb/h O2 186,558.2743 lb/h N2 24,161.7994 lb/h H2O

Zinc Oxide Process

Make-up H2O(l) to absorber 1,909.3444lb/h

SO2 -H2O mixture: 3,831.9318 lb/h 2,047.6315 lb/h SO2 1,784.3003 lb/h H2O Evaporated Water 125.0441lb/h H2O

TOTAL IN: 324,773.6690 lb/h

TOTAL OUT: 324,773.6690lb/h

Figure.2 Input-Output Diagram for Zinc Oxide Process

2.2 Functional Block Diagram

Zinc Oxide 2989.7463lb/h ZnO

Desulfurized Gas: 320,816.6931 lb/h 70.3962 lb/h SO2 53,350.2918 lb/h CO2 56,675.9314 lb/h O2 186,558.2743 lb/h N2 24,161.7994 lb/h H2O
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Stack Gases: 322,864.3246 lb/h 2118.0277lb/h SO2 53,350.2918 lb/h CO2 56,675.9314 lb/h O2 186,558.2743 lb/h N2 24,161.7994 lb/h H2O
5 3

Evaporated H2O 125.0441 lb/h H2O

1

SYNTHESIS 1atm 122F

SEPARATION 1 atm 200C

11

RECOVERY 1atm 800C

12

Make-up H2O to absorber 1909.3444 lb/h H2O

Inlet SulphiteBisulphite Soln: 23,834.7678 lb/h 10,762.8235 lb/h H2O 6,932.3506 lb/h Na2SO3 6,139.5936 lb/h NaHSO3

Zinc Sulphite Slurry: 28,872.1456 lb/h 9,323.2954 lb/h H2O 6,932.3506 lb/h Na2SO3 6,139.5936 lb/h NaHSO3 6088.2389 lb/h ZnSO32 H2O

Zinc Sulphite 6821.6781 lb/h ZnSO3.2 H2O

SO2 -H2O mixture: 3831.9318 lb/h 2047.6315 lb/h SO2 1784.3303 lb/h H2O

Recycled Sulphite-Bisulphite Solution 8,853.4791lb/h H2O 6,932.3506 lb/h Na2SO3 6,139.5936 lb/h NaHSO3 TOTAL IN: 324,773.6690 lb/h TOTAL OUT: 324,773.6690 lb/h

Figure 3. Block Diagram for the Recovery of Sulfur Dioxide Using the Zinc Oxide Process

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2.3 Process Flow Diagram

Desulfurized Gas: 320,816.6931 lb/h 70.3962 lb/h SO2 53,350.2918 lb/h CO2 56,675.9314 lb/h O2 186,558.2743 lb/h N2 24,161.7994 lb/h H2O
10

Make-up H2O to absorber 1909.3444 lb/h H2O

Inlet SulphiteBisulphite Soln: 23,834.7678 lb/h 10,762.8235 lb/h H2O 6,932.3506 lb/h Na2SO3 6,139.5936 lb/h NaHSO3
3

Zinc Oxide 2989.7463 lb/hr

Zinc Oxide Reactor 1 atm 77F

Zinc Sulphite Slurry: 8 28,872.1456 lb/h 9,323.2954 lb/h H2O 6,932.3506 lb/h Na2SO3 6,139.5936 lb/h NaHSO3 6088.2389 lb/h ZnSO32 H2O

Absorber 1 atm 122F

Stack Gases: 322,864.3246 lb/h 2118.0277lb/h SO2 53,350.2918 lb/h CO2 56,675.9314 lb/h O2 186,558.2743 lb/h N2 24,161.7994 lb/h H2O
1

Dryer 212F 1 atm

Zinc Sulphite: 6,821.6781 6,088.2389 lb/ ZnSO3.5/2 H2O 388.6670 lb/h ZnO 344.7722 lb/h H2O
11

Evaporated H2O 125.0441 lb/h H2O

Rotary Kiln 572F 1 atm

12

SO2 -H2O mixture: 3831.9318 lb/h 2047.6315 lb/h SO2 1784.3303 lb/h H2O

Exit SulphiteBisulphite Soln: 25,882.3993 lb/h 10,187.0213 lb/h H2O 2,903.7247 lb/h Na2SO3 12,791.6623 lb/h NaHSO3
6

Rotary Filter 77F 1 atm

Filtered Zinc Sulphite: 6,946.7222 lb/h 469.8163lb/h H2O 388.6670 lb/h ZnO 6088.2389 lb/h ZnSO3 5/2 H2O

Recycled Sulphite-Bisulphite Soln: 21,925.4234 8,853.4791 lb/h H2O 6,923.3506 lb/h Na2SO3 6,139.5936 lb/h NaHSO3

Figure 4. Process Flow Diagram of Zinc Oxide Process

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2.4 Process Flow Sheet

1
77.3

Make-up Water to the absorber

5 1

Desulfurized Gas Evaporated Water

122

2 1
122

1
572

H02

R01
1 77.3 9

10

212

1 77.3

D01
11 212 1 12 572 1

SO2 & H2O

C01 Stack Gas H01

1 122 1 4 122 1

S01
6 77 1

F01

P01

P02

Figure 5. Process Flow sheet for Zinc Oxide Proce

Process Equipment List C01: Sulfur Dioxide Absorber D01: Rotary Dryer H01: Heat Exchanger 1 H02: Heat Exchanger 2 F01: Rotary Kiln P02: Recycled Sulfite-Bisulfite Liquor R01: Zinc Oxide Reactor S01: Rotary Filter

Process Flow Scheme Project: Design of a Sulphur Dioxide Absorber Stream Number Temperature(F) Pressure(atm)

Designers Gabutina,M.C.A. Navida,M.T. Obiedo,E.A.

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2.5 Basic Assumptions 2.5.1 Operating mode, Product and Feed Specifications, Process Conditions The plant processes 100,000ft3/min of stack gas at 300F and 1 atm with 0.3% v/v SO2 to produce a purified stream containing 0.01 mole% SO2. The plant operates 24 hours a day, 7 days a week, and 365 days a year. The following criteria were used to determine the mode of operation of the plant.(Sinnott,1999) Criteria Batch Continuous System 6 6 1 Production rate < 5x10 kg/h >5x10 kg/h 2 No. of Products multiple Single SINGLE 3 Fouling severe not severe NOT SEVERE 4 Catalyst life short Long LONG 5 Process Design uncertain Proven PROVEN 6 Market New product established ESTABLISHED One of the first basic assumptions for the stack gas is that the volume per cent given is equal to its mole per cent. This is based on Amagats law. 2.5.2 The battery limits The process will primarily focus on the purification of stack gas containing 0.01% SO 2 and the recovery of SO2 as a mixture of SO2 and H2O. Purification of the recovered SO2 is not included in the process.
Desulfurized Gas Water

Stack Gas

REACTION

SEPARATION

Product

waste

Figure 6. Battery Limits for Zinc Oxide Process

13

2.5.3 Definition of Incoming and Outgoing Streams Table 2. Incoming and Outgoing Streams
Equipment Name Absorber Zinc Oxide Reactor Rotary Filter Rotary Dryer Rotary Kiln Code C01 R01 S01 D01 F01 No. <1> <3> <4> <7> <6> <9> <11> Incoming Streams Temp. Pressure (F) (atm) 122 1 122 1 122 1 572 1 77 1 212 572 1 1 No. <2> <4> <8> <9> <10> <11> <7> <12> Outgoing Streams Temp. Pressure (C) (atm) 122 1 122 1 77.3 77.3 212 212 572 572 1 1 1 1 1 1

2.6 Material and Energy Balances 2.6.1 Mass Process Stream Summary
Stream Nr: Name: Comp SO2 CO2 O2 N2 H2O TOTAL MW 64.0638 44.0095 32.0000 28.0000 18.0153 lbmol/hr 33.0612 1,212.2449 1,771.1229 6,662.7955 1,341.1837 11,020.4082 1 Stack Gas IN 2 OUT Desulfurized Gas lbmol/hr 1.0988 1,212.2449 1,771.1229 6,662.7955 1,341.1837 10,988.4458 lb/h 70.3962 53,350.2918 56,675.9314 186,558.2743 24,161.7994 320,816.6931

lb/h 2,118.0277 53,350.2918 56,675.9314 186,558.2743 24,161.7994 322,864.3246

Stream Nr: Name: Comp H2O Na2SO3 NaHSO3 TOTAL MW 18.0153 126.0427 104.0609

3 Inlet Sulphite-Bisulphite Soln lbmol/hr 597.4275 55.0000 59.0000 711.4275 lb/h 10,762.8235 6,932.3506 6,139.5936 23,834.7678

4 Exit Bisulphite Soln lbmol/hr 565.4651 23.0376 122.9248 711.4275 lb/h 10,187.0123 2,903.7247 12,791.6623 25,882.3993

5 IN Make-up Water to Absorber lbmol/hr 105.9847 lb/h 1,909.3444

105.9847

1,909.3444

14

Stream Nr: Name: Comp H 2O Na2SO3 NaHSO3 ZnO ZnSO3.5/2H2O TOTAL MW 18.0153 126.0427 104.0609 81.3794 190.4814

6 Recycled Sulphite-Bisulphite Soln lbmol/hr lb/h 491.4428 55.0000 59.0000 8,853.4791 6,932.3506 6,139.5936

7 Zinc Oxide lbmol/hr lb/h

8 Zinc Sulphite Slurry lbmol/hr 517.5215 55.0000 59.0000 lb/h 9,323.2954 6,932.3506 6,139.5936 388.6670 6,088.2389 28,872.1456

36.7384 605.4428 21,925.4234 36.7384

2989.7463 2989.7463

4.7760 31.9624 668.2599

Stream Nr: Name: Comp H2O Na2SO3 NaHSO3 ZnO ZnSO3.5/2H2O TOTAL MW 18.0153 126.0427 104.0609 81.3794 190.4814

9 Filtered Zinc Sulphite lbmol/hr 26.078769 lb/h 469.8163

10 OUT Evaporated Water lbmol/hr 6.9410 lb/h 125.0441

4.7759878 31.96238 62.817137

388.6670 6,088.2389 6,946.7222

6.94100

125.0441

Stream Nr: Name: Comp H2O ZnSO3.5/2H2O ZnO H2O SO2 TOTAL MW 18.0153 190.4814 81.3794 18.0153 64.0638 lbmol/hr 31.9624 4.7760 19.1378

11 Zinc Sulphite lb/h 6,088.2389 388.6670 344.7722 6,821.6781

12 OUT SO2-H2O mixture lbmol/hr 99.0437 lb/h 1784.3003

31.9624 131.0061

2047.6315 3831.9318

15

2.6.2

Energy Process Stream Summary

Table 3. Energy Process Stream Summary for each Equipment IN Equipment Stream Nr Qi (Btu) QR (Btu) Q (Btu) 1 3.53E+11 C01 1.58E+08 -2.11E+10 3 4.45E+04 4 5.11E+07 R01 -3.73E+06 -5.87E+07 7 1.13E+07 S01 D01 F01 8 9 11 -7.49E+04 -4.54E+03 4.75E+06 0 0 -2.96E+07 0 1.56E+09 1.99E+08

Total (Btu) 3.53E+11 -7.49E+04 -7.49E+04 1.56E+08 1.98E+10

Stream Nr 2 4 8 6 9 10 11 7 12

OUT Qp (Btu) 3.53E+11 51072240 -7.49E+04 -7.04E+04 -4.54E+03 2.80E+06 4.75E+06 8.75E+06 1.98E+10

Total (Btu) 3.53E+11 -7.49E+04 -7.49E+04 1.56E+08 1.98E+10

16

2.6.3 Detailed Calculation of the Material and Energy Balance BALANCE FOR THE FEED Summation of mole fractions in the feed: yS02 + yCO2 + yO2 + yN2 + yH2O= 1 Average Molecular Weight equation: ySO2(MWSO2) + yCO2(MWCO2) + yO2(MWO2) + yN2(MWN2) + yH2O(MWH2O) = 29.4 Amount of O2: yO2(left in the feed)= yO2(total) yO2(combusted) yO2 = (0.21/0.79)(yN2) yCO2 substitute eqn. 13 to eqn.11 0.003 + 0.11 + [0.21/0.79 yN2 0.11] + yN2 + yH2O = 1 0.21/0.79 yN2 + yO2 + yH2O = 0.997 Substitute eqn. 13 12 0.003(64) + 0.11(44) + [0.21/0.79 yN2 0.11]32 + 28yN2 + 18yH2O = 29.4 Substitute eqn. 14 15 32(0.21)/0.79 yN2 + 28yN2 + [8(0.997-1/0.79)yN2] = 27.888 13.72151899yN2 = 9.942 yN2 = 0.7246 yO2 = 0.0826 yH2O = 0.0798 (17) (16) (14) (15) (13) (12) (11)

17

BALANCE FOR THE INPUT/OUTPUT DIAGRAM

BALANCE FOR THE OUTLET GAS STREAM Assumptions: No water will transfer from the liquid phase to the gas phase Doing inert balance, we could obtain the amount of desulfurized gas leaving the tower. [ [ ] ]

Since we got the amount of desulfurized gas leaving the tower, we could now use this to determine the mole fractions of each component in the stream. N2-balance:

)
18

CO2-balance:

H2O-balance:

O2-balance:

BALANCE AROUND THE INPUT/OUTPUT DIAGRAM Assumptions: 87% conversion in the zinc oxide mixer 20% moisture left in the filter cake (mass H2O/mass wet solid) 10% moisture left in the dried solids (mass H2O/mass wet solid)

19

Since the conversion of ZnO to ZnSO3 is 87%, we can get the amount of zinc oxide supplied.

Since the amount of water left in the filter cake is 20(w/w)% moisture, we can get the mole fraction of water in the filter cake. But we should remember that the solids contain 87% ZnSO3 and 13% ZnO. This is because of the conversion in the zinc oxide mixer.

We could also do the same process to get the mole fraction of water left in the solids that are coming out in the drier.

Therefore the amount of water that is evaporated from the drier is:

Also from the decomposition reaction of zinc sulphite in the calciner,

we can solve for the stream coming out of the calciner.

20

Doing Over-all mass balance in the input/output diagram, we can get the amount of water needed to replenish the losses.

Then,

DETAILED CALCULATION FOR THE EQUIPMENT BALANCES: Zinc Oxide Mixer

Since the conversion of ZnO to ZnSO3 is 87%:

21

From the reaction:

)(

22

Rotary Filter

23

DRYER

24

CALCINER
Stream 7

Stream 11

Stream 12

25

From the reaction:

( (

) )

26

Detailed Energy Calculations From the general energy balance for an open system [( ) ] (29)

Assuming steady state condition, sum of kinetic and potential energy is zero and there's no shaft work, equation (29) reduces to (30) In the absorber, the reaction between the stack gas and the sodium sulphite-bisulphite liquor takes place at 323K or at 121.73 F. Since the stack gases enters at 300F and the sulphitebisulphite liquor enters at 298.15K or 77F, the heat required to bring down the gas temperature and increase the liquid temperature at P = 1 bar will be computed using equation (31) (31)

Since the initial and final temperature is already given and the heat capacity, Cp can be eadily calculated using it, then equation (31) could be simplified to (32) Presented below is the heat capacity of the entering gas at 300F. Heat capacity contstants obtained from table C1 of of Vanness and Smith Thermodynamics book are shown below. Basis: 1 hour of operation Table 4. Heat capacity, Cp of the stack gases at 300F Componet CO2 SO2 N2 H2 O O2 Mass (lbm) 53350.2918 2118.0277 186558.2743 24161.7994 56675.9314 A 29370 33375 29105 33359 29103 B 34540 25864 8614.9 26798 10040 C -1428 932.8 1701.6 2609.3 2526.5 D 26400 10880 103.47 8888 9356 Cp(Btul/lbmF) -2.2808E+04 11573.88551 45867.66965 110647.6027 59436.67011

The heat capacity, Cp is solved using equation (33) (33)

27

For the heat capacity of the stack gases at 323 K or 121.73 F, heat capacity data is presented below Table 5.Heat capacity, Cp of the stack gases at 121.73 F Component Mass (lbm) A B C 53350.2918 29370 34540 -1428 CO2 2118.0277 33375 25864 932.8 SO2 186558.2743 29105 8614.9 1701.6 N2 24161.7994 33359 26798 2609.3 H2 O 56675.9314 29103 10040 2526.5 O2

D 26400 10880 103.47 8888 9356

Cp(Btu/lbmF) -13109 6908.24 26965.7 65285.3 34915.2

For the liquid (sodium sulphite-bisulphite liquor) heat capacity at 298.15 K or 77 F Table 6.Heat capacity, Cp of the sodium sulphite-bisulphite liquor at 298.15 K or 77 F Component Mass (lbm) A B C D Cp(Btu/lbmF) 6139.384978 116400 0 0 0 4.68325298 NaHSO3 6932.600585 197210 -4.00E-11 0 0 6.550786583 Na2SO3 10762.80862 276370 -2090.1 8.125 -0.014116 87.25916149 H2 O For the liquid (sodium sulphite-bisulphite liquor) heat capacity at 323 K or 121.73F Table 7. Heat capacity, Cp of the sodium sulphite-bisulphite liquor at 323 K or 121.73F Component Mass (lbm) A B C D Cp(Btu/lbmF) 6139.384978 116400 0 0 0 4.68325 NaHSO3 6932.600585 197210 -4.00E-11 0 0 6.55079 Na2SO3 10762.80862 276370 -2090.1 8.125 -0.014116 104.335 H2 O A summary of the heat capacities of the entering stack gases and the sodium sulphite-bisulphite liquor at different temperatures is shown below Table 8.Heat capacity, Cp of the sodium sulphite-bisulphite liquor at 323 K or 121.73F Component Mass (lbm) Cp at 77F Cp at 300 F Cp at 121.73 F 53350.2918 NA -2.2808E+04 -13109 CO2 2118.0277 NA 11573.88551 6908.24 SO2 186558.2743 NA 45867.66965 65285.3 N2 24161.7994 NA 110647.6027 65285.3 H2 O 56675.9314 NA 59436.67011 34915.2 O2 6139.384978 4.68325298 NA 4.68325 NaHSO3 6932.600585 6.550786583 NA 6.55079 Na2SO3 10762.80862 87.25916149 NA 104.335 H2 O *NA not applicable

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Use equation (31) to solve for the heat, Q required to decrease the temperature of the stack gases and increase the temperature of the sodium sulphite-bisulphite liquor given the heat capacities of each component For the stack gases from 300 F to 121.73 F, heat that needs to be removed is

[ -2.2808E+04)+( 2118.0277)( 11573.88551)+( 186558.2743)( 45867.66965)+( 24161.7994)( 919924.1691)+( 56675.9314)( 59436.67011)](121.73 -300) -2.39003E+12 Btu Therefore, the heat, Q that needs to be removed from the stack gases in order to reach a temperature of 121.73 F or 323 K is Q = -2.39003E+12 Btu.

Use the same equation to solve for the heat required to raise the temperature of the sulphitebisulphite liquor to 121.73 F or 323 K from 77 F or 298.15K using the data from table _.

[ 6139.384978)( 4.68325298)+( 6932.600585)( 6.550786583)+( 10762.80862)( 87.25916149)](121.73 -77) 39338.1718 Btu Therefore, the heat, Q that needs to be added to the sodium sulphite-bisulphite liquor in order to reach a temperature of 121.73 F or 323 K is Q = 39338.1718 Btu.

Energy Balance around the Absorber Main Reaction around Absorber (34)

(35) Where

29

Since the temperature of the gas has been brought down from 300 F to 121.73 F , its new initial temperature is 121.73 F, and since heat of formation of substances are not available at that temperature rather it is available at 77 F, its temperature will be brought down to 77 F which is in this case, assumed to be the reference temperature then a path will just be made to reach the final temperature.

Hr

And (36) ( ( )) (37) (38) (39)

(
(

) (40)

30

In solving for , heat capacity of each reactants at its initial temperature is needed. Data from the previously calculated heat capacities of the gases and the liquid at each initial temperature which is 121.73 F is used.

Basis: 1 hour of operation Table 9.Heat capacity of reactants (stack gases) Comp Mass (lbm) A B 53350.2918 29370 34540 CO2 2118.0277 33375 25864 SO2 186558.2743 29105 8614.9 N2 24161.7994 33359 26798 H2 O 56675.9314 29103 10040 O2 Using equation (37) to solve = -3.53465E+11 Btu

C -1428 932.8 1701.6 2609.3 2526.5

D 26400 10880 103.47 8888 9356

Cp(Btu/lbmF) -13109 6908.24 65285.3 65285.3 34915.2

, with Tinitital = 121.73 F and Tfinal = 77 F

Table 10. Heat capacity of reactants (sodium sulphite-bisulphite liquor) Component Mass (lbm) A B C D 6,139.5936 116400 0 0 0 NaHSO3 6,932.3506 197210 -4.00E-11 0 0 Na2SO3 10,762.8235 276370 -2090.1 8.125 -0.014116 H2 O For the sodium sulphite-bisulphite liquor, using equation (37) to solve 121.73 F and Tfinal = 77 F = -44524.43865 Btu

Cp(Btu/lbmF) 4.68325 6.55079 104.335

, with Tinitital =

Solve for the standard heat of formation from equations (38). Data for the Standard heat of formation of each component can be found in table C1 of Vanness and Smith Thermodynamics book.

31

Table 11. Heat of formation of the products and the reactants Component 410.33367 -6826.9323 -1992.1001 -4659.1918

( ) [( ) ( ) ( )]

157469713.9 Btu Solve for the heat capacity of the products at T = 121.73 F or T = 323K using equation (33). Calculated values are shown below. Table 12. Heat capacity of the products Component Lbm 53350.2918 CO2 70.3962 SO2 186558.2743 N2 24161.7994 H2 O 56675.9314 O2 12791.6623 NaHSO3 2903.7247 Na2SO3 10187.0123 H2 O Use equation (32) to solve for the heat of the products

Cp (Btu/lbmF) -13109 6908.23753 26965.6752 65285.2837 34915.196 4.68325298 6.55078658 104.334951

[ 53350.3)( -13109)+( 70.3421)( 6908.24)+( 186558)( 26965.7)+( 24161.8)( 65285.3)+( 56675.9)( 34915.2)+( 13076)( 4.68325)+( 14121.5)( 6.55079)+( 2704.44)( 104.335)](121.73-77) 3.52883E+11 Btu Therefore, the amount of heat in the products is 3.52883E+11 Btu.

The heat of the reactants, is just equal to the heat that needs to be removed in order to reach the reference temperature, therefore,
32

= = 3.53465E+11 Btu Finally, solve for the heat that has been removed or added during the reaction using equation (35) and the previously calculated heats of the reactant, the reaction and the products. The heat of reaction, is just equal to

(35) Rearraning,

3.52883E+11- (3.53465E+11 Btu + 157469713.9 Btu) -739302742.6 Btu

Therefore, Inlet = 3.53465E+11 Btu = 44524.43865 Btu 157469713.9 Btu -21053159653 Btu Total Q = 3.528833E+11 Btu

Outlet = 3.52832E+11 Btu = 51072240.02 Btu Total Q = 3.52883E+11 Btu

33

Energy Balance Around the Zinc Oxide Mixer (5) Since the ZnO fed comes from the calciner, it is assumed that the temperature of ZnO entering the zinc oxide mixer would be at T= 550F or T= 560.93K. Since the temperature of both the ZnO stream and the liquid outlet stream from the absorber are not T= 25C or T= 77F, same procedure as with the inlet stack gas was done.

Hr

With the Zinc oxide initial temperature T= 550F and liquid inlet stream of T= 121.73 F, equation (37) is used yielding = -62379141.8 Btu Table 13.Heat of Formation Data from Table C4 of Vanness and Smith Thermodynamics Book. Component -2434.390869 410.3336993 -6826.932263 -965.1517713 -4659.19177

Equation (38) is used to obtain = -3730345.706 Btu Solve for the heat of reactants, both the zinc oxide at T = 550F and liquid liquor with a temperature of T= 121.73 F. The heat that needs to be removed from the reactants is equal to the heat of the reactants. 62379141.8 Btu
34

Use equation (40) to estimate the final temperature Table 14.Heat Capacity Constants of the Products Component lbmol/min A B 0.5327 71427 87.015 0.9167 8.6254 0.9833 0.0796 197210 33359 116400 -5070 -4.00E-11 26798 0 286.1

C 0 0 2609.3 0 -0.5775

D 0 0 8888 0 0.00043

ZnO

163001155 -1.08E+06 75527.7639 -131.440117

Table 15. Iteration table Iteration number 0 1 2 3 4

T (R) 700 536.60 536.5868524 536.5868511 536.5868511

Cp (Btu/lbm F) -944866548 -795086178.1 -795073910.7 -795079095 -795079095

Therefore the liquid final temperature, based on the iteration method used is T= 536.5868511R or T= 76.91685114 F Table 16. Heat Capacity Data Component

lbmol/min 0.5327 0.9167 8.6254 0.9833 0.0796

Cp (Btu/lbm) 2.140125353 6.550786583 87.22959082 4.68325298 1.486713579

ZnO From the data above -74920.91222 Btu

35

Using equation (35) -58723717.01Btu Therefore Inlet 51072240.02 Btu 11306901.78 Btu Q = -58723717.01 Btu = -3730345.706 Btu Total = -74920.91222 Btu

Outlet = -74920.91222 Btu Total = -74920.91222 Btu

Energy Balance Around the Filter Since there is no reaction inside the filter, it is assumed that the heat of the substances going inside the filter is just equal to the heat of the substances going out of the filter. There is no heat added or removed, Q.

-74920.91222 Btu

Therefore Inlet
36

Total = Outlet = -70381.45955 Btu = -4539.060668 Btu Total =

For the Dryer Assume final temperature of the products is T= 212F which is the drying temperature. Since unbound water will be the ones that will be evaporated, latent heat of vaporization of water needs to be obtained to account for the phase change and sensible heat should be obtained also to account for the temperature change from the initial to the final temperature. Reactants are at T= 76.91685114F so its 4539.060668 Btu (based on the heat of stream 9).

For the latent heat of Vaporization of water, equation (36) is used which is known as the Clausius-Clapeyron Equation ( ) ( )( ) (41)

(42) Equation (41) is known as the Antoine equation and the value of its constants can be found at table B.2 of the Thermodynamics book of Vanness and Smith For water A= 16.3872 B= 3855.70 C= 230.170 T1= 25 C or 77F or 536.57R T2= 100C or 212F or 671.67R R= 1.9872 Btu/lbmol R

37

Using equation (42) followed by equation (41) = 18 212.4524 Btu/lbmol Table 17. Heat Capacity Data Component

lbmol/min 0.5327 0.319 0.0796 6.9410

Cp (Btu/lbm) 2.283658576 145.8980055 1.094635677 145.8980055

ZnO H2 O 156499855.5 Btu = 4539.060668 Btu = 18212.4524 Btu

Using Equation (35) Q = 156477104 Btu

Therefore Inlet 4539.060668 Btu Q = 156477104 Btu = 34 268.7166 Btu Total =156499855.5 Btu

2801576.002 Btu = 4746330.335 Btu Total = 156499855.5 Btu

38

Energy Balance Around the Calciner (6)

8725893.677 Btu The calcination temperature of anhydrous zinc sulphite is 550F . Assume products from the calciner are at T= 550F Table 18. Heat Capacity Data Component

lbmol/min 0.5327 0.6123 0.5327 1.6507

Cp(Btu/lbm F) 2.283658576 6.185897556 20131.35171 385.8867636

ZnO SO2 H2 O

Solve for the latent heat of vaporization of water at the given conditions Tinitial= 212 F and Tfinal = 550 F using the Antoine equation constants of water. Using equation (40) and (41) = 16875.20139 Btu Since the temperature of the reactant is not T= 77F, we will solve the Hr as shown.

Hr

39

Table 19. Heat of Formation Component

lbmol/min 0.5327 0.6123 0.5327 1.6507

2198.775405 -965.1517713 -1992.100055 -5775.723703

ZnO SO2 H2 O

(6)

The heat that of the substances going in to the calciner is equal to the heat of the substances going out of the drier, therefore = 8725893.677 Btu

The heat of reaction is just equal to the heat of decomposition, therefore, -29570194.88 Btu Heat of the products is solved using (37) 19832001225 Btu Using equation (35) Q = 19852828651 Btu

Therefore Inlet 8725893.677 Btu = -29570194.88 Btu = 446 331.1066 Btu Q = 19852828651 Btu Total = 19832001225 Btu
40

Outlet = 8747699.534 Btu = 19823253526 Btu Total = 19832001225 Btu

41

Section 3. Chemical Engineering Design 3.1 Calculation Flow Diagram

Determine absorber specifications

Determine constraints

Determine the total height and diameter of absorption column.

Determine inlet liquid flow rate.

Determine power requirement to pump inlet liquid and to the compress gas phase feed

Determine total power cost of pumping liquid and compressing the gas

NO

Satisfy specs and constraints?

Add pump and compressor power costs to fixed charges

YES
Determine minimum D and H that would give minimum total cost

Final Design

42

3.2 Summary of Assumptions The system is assumed to obey Henrys law, hence a straight equilibrium line is obtained. The flooding pressure drop is assumed to be 0.5 in H2O/ft of packing . The cost per kWh is based on the market value of electricity in Cebu City as of June 2012. Cost = P9.9578/kWh The amount of Na2SO3 going in the absorber is 55 lbmol/h. Fixed charges are assumed to be 15% of the total power costs.

3.3 Chemical Engineering Design Calculations In the design of an absorption column, there are a number of factors that need to be considered. First is the solubility of the gas phase component into the absorbing liquid phase. This dictates the amount of solvent to be used, and in this case, the amounts of sodium sulphite-bisulphite compounds which react with SO2. An good design would be the one that uses the minimum amount of solvent and reactants for a given conversion in order to give the minimum pumping costs. Another factor to be considered is the mass transfer properties of the system. This is still related to the solubility of the gas phase component which is the basis for designing the height of the column. Ultimately, the best possible design would be the one that has the minimum diameter and minimum height that satisfy the specifications and constraints of the design. The following steps were carried out in order to determine the possible pairs of diameter and height that satisfy the specifications and constraints stipulated in the design problem:

1. Determination of gas mass velocity Flooding pressure is estimated to be 0.5 in H2O/ ft of packing. The gas mass velocity at flooding can be obtained using the relation given in the problem (from equation 1):

2. Solving for the inner diameter of the column Absorbers used in the industry typically operate in the range of 60-75% of the flooding velocity. The gas mass velocity of the optimum design lies within this range, therefore, the diameter of the column that falls within it must be determined. For the calculations, increments of 2.5% will be used. For 65% of flooding velocity,
43

)(

)(

The diameter is then Table 3 shows a summary of the gas mass velocities and the respective diameters obtained. Table 3. Inner Diameter of column at different gas mass velocities % of Go,flooding (lb/ft2.h) 60 62.5 65 67.5 70 72.5 75 Go(lb/ft2.h) 7151.4960 7449.4750 7747.4540 8045.4330 8343.4120 8641.3910 8939.3700 Area(ft2) 45.3052 43.4930 41.8202 40.2713 38.8330 37.4940 36.2442 Diameter(ft) 7.5950 7.4416 7.2971 7.1606 7.0316 6.9093 6.7932

It can be seen in Table 3 that the least diameter can be obtained at 75% of the flooding velocity. The minimum diameter gives the least volumetric flow rate of the liquid to be pumped into the tower. Therefore, this gives the minimum cost for power for pumping. 3. Determination of Packing Height Now that the possible diameters of the column have been obtained, the height of packing is to be determined next. The equilibrium data used in this design is from the study by Buzek et al. (1995). The data is a plot of the partial pressure of SO2 in equilibrium with the sulphitebisulphite liquor in mol/kg H2O.

44

Figure 7. Equilibrium data of SO2 in sulphite-bisulphite liquor It was specified in the problem that the concentration of SO2 in the feed stream is 0.3% v/v. By Amagats law, this can be assumed to be equal to 0.3% mol/mol. The system pressure is at 1 atm so the partial pressure of SO2 in the feed is 0.003 atm. The liquid concentration at which a partial pressure of 0.003 atm is in equilibrium with is at 80 mol/kg. This is shown in Figure A.1 in Appendix A. The column must not operate at this point since there is no more driving force for the mass transfer of SO2 into the solution. The x-axis is a ratio of the square of the bisulphite ion concentration over the sulphite ion concentration, which allows the amounts of the sulphitebisulphite ions to be manipulated. The amount of sodium sulphite supplied, which is one of the reactants aside from H2O and SO2, is assumed to be constant, allowing the amount of sodium bisulphite to be manipulated. 3.1 Establishing the operating lines Before the operating lines can be established, the molality of the solution must first be calculated. At 60% of flooding velocity, ( ) ( )

45

( Assume lbmol/h of NaHSO3=65lbmol/h

)(

)(

)(

)(

( Solving for the molality of the solution,

)(

)(

It was calculated from the overall mass balance that the total amount of SO2 absorbed is 31.96lbmol/h. The reaction stoichiometry between the sodium sulphite, SO2, and water system is ( )

Therefore,

( )( )( )( )( )

46

[ {( ) ( ( }] ( ) ) )( )

The molalities at other gas mass velocities are solved in this manner. As a summary, Table 4. Molalities of the inlet and outlet liquid streams Na2SO3 IN (lbmol/h) 60.00 62.50 65.00 67.50 70.00 72.50 75.00 55 55 55 60 60 55 55 NaHSO3 IN (lbmol/h) 65 64 63 62 61 60 59 (mHSO3-)2/ (mSO3-) IN 1 1 1 1 1 1 1 (mHSO3- )2 /mSO3-) OUT 44.24 46.77 49.37 44.91 47.47 50.13 52.91

The bottom part is designated as point 1 while the top part of the column is designated at point 2. At point 1, x1 varies for each percent of flooding, and y1 =0.003 atm. At point 2, x2=1 and y2=0.0001 atm, as specified in the problem.

47

x1,y1

x2,y2

Figure 8. Operating line and equilibrium line at x1=44 mol/kg.

The graphs for the other concentrations may be found in the Appendices, from Figure A.2 to A.4. 3.2 Determination of the value of the integral, The height of the column can be determined using the equation Where Gm is the molar gas mass velocity, Kga is the mass transfer coefficient multiplied by the effective surface area per unit volume, y1 is the bottom gas phase concentration, y2 is the exit gas concentration, and y* is the concentration of gas phase that is in equilibrium with the liquid phase at any point in the absorber. Since the integral cannot be evaluated analytically, a graphical solution is needed. To do this, a plot of y versus 1/(y-y*) is made and the area under this curve is the value of the integral.

48

At 60% flooding, x1=45 mol/kg Table 4. Values of y and corresponding equilibrium values
x1=45mol/kg y* 1/(y-y*) 0.0019 0.0012 0.0006 0.0004 0.00032 0.00028 0.0002 0.00015 0.0001 0.000045 909.09091 1250.00000 2500.00000 3333.33333 3571.42857 4545.45455 5000.00000 6666.66667 10000.00000 18181.81818

y 0.003 0.002 0.001 0.0007 0.0006 0.0005 0.0004 0.0003 0.0002 0.0001

0.0035 0.003 0.0025 0.002 y 0.0015 0.001 0.0005 0 0.00000 y = 6.724x-1.134 R = 0.9983

5000.00000

10000.00000 1/(y-y)

15000.00000

20000.00000

Figure 9. A plot of y versus 1/(y-y*)

49

Using Simpsons 3/8 Rule, [ From the plot, ]

Then,

Solutions for the other values are shown in the appendices. As a summary, 4. Determination of Column Height After evaluating the integral, the column height can now be determined. At 60% of flooding velocity and x1=44 mol/kg, (From Table 3),

The relation between the mass transfer coefficient Kg, and the gas mass velocity, Go was given in the problem through the equation:

50

The surface area per unit volume of packing for non-staggerred grids was also given as and the total system pressure,P, is at 1 atm. Finally,

)(

Table 6. Possible heights at operating at 60-75% of flooding gas mass velocity

% of flooding x1(mol/kg) I Gm(lbmol/h.ft2) Kga(lbmol/h.ft3.atm) Z(ft) 60% 45 9.6231 243.2482 36.8630 63.4997 62.50% 47 11.2439 253.3835 38.0868 74.8033 65% 49 18.1712 263.5188 39.3007 121.8416 67.50% 50 6.5422 273.6542 40.5054 44.1992 70% 47 11.2439 283.7895 41.7012 76.5181 75% 53 5.2280 293.9249 42.8885 35.8286

It is shown in Table 6 that the minimum height at any gas mass velocity is obtained when the sulphite-bisulphite liquor concentration is at 53 mol/kg. Therefore, the operating point at x 1,y1 should be (53, 0.003). It was stated previously that the optimum design would be the one that has the minimum diameter and minimum height. In this design, the optimum diameter, which is the minimum diameter, is obtained when the gas mass velocity is 75% of that of flooding and has a value of

The minimum height is also obtained at 75% of flooding velocity and is equal to

5. Calculating the power requirements for the pump and the compressor and power costs 5.1 Pump Power Requirements and Power Costs The power requirement of the pump is dependent upon the cross-sectional area of the column. Minimum pumping cost is obtained when the diameter is the smallest possible diameter. At 75% of flooding velocity, ( )

51

Applying 10% safety factor

For the power cost

Basis of 1 hour:

5.2 Compressor Power Requirement and Power Cost For the compressor power: (75) where:

52

http://newsinfo.inquirer.net/216687/cebu-power-rates-to-rise-by-p1kwh

Basis of 1 hour:

5.3 Total Costs ( Power Costs and Fixed Charges) Fixed charges, which include depreciation, local taxes, and insurance (Timmerhaus, 1991) is assumed to be 15% of the total power cost. The total cost per hour of operation is then,

6. Determination of other important parts of the absorber The following are other important factors that need to be considered in designing an absorption column: 6.1 Packing Support The function of the support plate is to carry the weight of the wet packing, whilst allowing free passage of the gas and liquid. The best design of packing support is one in which gas inlets are provided above the level where the liquid flows from the bed like the gas-injection packing support. It has a low pressure drop and no tendency of flooding. (Sinnott, 1999)

53

6.2 Liquid distributors The satisfactory performance of a column is dependent on maintaining a uniform flow of liquid throughout the column, and good initial liquid distribution is essential. For large diameter columns, the trough-type distributor can be used, and will give good liquid distribution with a large free area for gas flow. 6.3 Liquid redistributors Redistributors are used to collect the liquid that has migrated to the column walls and redistributes it evenly over the packing. They will also even out any maldistribution that has occurred within the packing. According to Walas(2002), liquid distributors are needed at least every 20ft of packing. For the design, the total packing height is 45.19ft.

The height of each of three equally sized packed beds is,

It was stated in the design problem that non-staggerred grids are to be used with the following specifications: Clearance=1.5 in Height=4 in Thickness=0.25 in The number of grids per packed bed is calculated by dividing the total height of the packed bed by the height plus the clearance of (n-1) grids plus the height of the topmost grid.

6.4 Liquid Hold-up An estimate of the amount of liquid held up in the packing under operating conditions is needed to calculate the total load carried by the packing support. 6.5 Liquid Level at the bottom and Vapor disengagement Walas(2002) suggests that 6 ft should be added to the bottom for liquid level and 4 ft above the tower for vapor disengagement. 6.6 Distance of top of liquid level(bottom) to gas inlet The distance of the top of the liquid level at the bottom of the tower to the gas inlet should be half of the column diameter, and should not be less than 0.6m. (Sinnott, 1999) 6.7 Distance of gas inlet to the bottom of the last packing support The distance between the gas inlet to the bottom of the first packing support (bottom to top) should be at least 1m or one column diameter. 6.8 Distance between packed beds An allowance of 1.5 ft is allotted for the liquid redistributor and the space between the packings. 6.9 Wetting rates

54

The packing wetting rate should be checked to make sure it is above the minimum recommended by the packing manufacturer. For structured packing, the minimum wetting rate is from 0.07x10 5 to 0.14 x 10-3 m3s-1/m2. To check if the liquid flow rate in the problem is above the minimum wetting rate, the following equation is used:

Since

then the system is well irrigated.

7.10 Maximum Allowable Vapor Velocity The maximum allowable vapor velocity is usually the velocity at flooding (Timmerhaus,1991). For the problem, the gas mass velocity at flooding is at 11, 919.160 lb/h.ft2.

55

Appendix A. Equilibrium line and operating lines at different x1 (liquid outlet concentration) values A.1 x1=44.24 mol/kg

56

A.2 x1=47 mol/kg

57

A.3 x1= 49 mol/kg

58

A.4 x1=45 mol/kg

59

A.5 x1=47 mol/kg

60

A.6 x1=50 mol/kg

61

A.7 x1=53 mol/kg

62

Appendix B. Determination of the value of the integral B.1 x1=45 mol/kg at 60% of flooding velocity Table B.1 Values of y and corresponding equilibrium values
y 0.003 0.002 0.001 0.0007 0.0006 0.0005 0.0004 0.0003 0.0002 0.0001 y* 0.0019 0.0012 0.0006 0.0004 0.00032 0.00028 0.0002 0.00015 0.0001 0.000045 1/(y-y*) 909.09091 1250.00000 2500.00000 3333.33333 3571.42857 4545.45455 5000.00000 6666.66667 10000.00000 18181.81818

0.0035 0.003 0.0025 0.002 y 0.0015 0.001 0.0005 0 0.00000 y = 6.724x-1.134 R = 0.9983

5000.00000

10000.00000 1/(y-y)

15000.00000

20000.00000

Figure B.1 A plot of y versus 1/(y-y*) Using Simpsons 3/8 Rule, [ ]

63

From the plot,

Then,

A summary of values for used in the computation of the integral is found in Table B.6, which is after the other graphs for the different x1 concentrations have been presented.

64

x1=47 mol/kg Table B.2 Values of y and corresponding equilibrium values

y 0.00300 0.00200 0.00100 0.00060 0.00040 0.00030 0.00020 0.00010 y* 0.00210 0.00150 0.00070 0.00039 0.00023 0.00017 0.00010 0.00005 1/(y-y*) 1111.11111 2000.00000 3333.33333 4761.90476 5882.35294 7692.30769 10000.00000 18181.81818

0.00400 0.00350 0.00300 0.00250 0.00200 0.00150 0.00100 0.00050 0.00000 0 5000 10000 15000 20000 y = 28.822x-1.281 R = 0.9902

Figure B.2 A plot of y versus 1/(y-y*)

65

x1=49mol/kg Table B.3 Values of y and corresponding equilibrium values

y y* 1/(y-y*) 0.00300 0.001600 714.2857 0.00190 0.001000 1111.1111 0.00125 0.000700 1818.1818 0.00090 0.000490 2439.0244 0.00065 0.000350 3333.3333 0.00045 0.000210 4166.6667 0.00031 0.000150 6250.0000 0.00021 0.000100 9090.9091 0.00015 0.000070 12500.0000 0.00010 0.000047 18867.9245

0.00350 0.00300 0.00250 0.00200 y 0.00150 0.00100 0.00050 0.00000 0.0000 2000.0000 4000.0000 6000.0000 8000.0000 10000.0000 12000.0000 14000.0000 16000.0000 18000.0000 20000.0000 1/(y-y*) y = 3.2176x-1.056

Figure B.3 A plot of y versus 1/(y-y*)

66

x1=50 mol/kg Table B.4 Values of y and corresponding equilibrium values

y 0.0030 0.0025 0.0010 0.0008 0.0006 0.0005 0.0004 0.0003 0.0002 0.0001 y* 0.0025 0.0019 0.0007 0.0005 0.0004 0.0003 0.0003 0.0002 0.0001 0.0000 1/(y-y*) 2000.0000 1666.6667 2857.1429 3333.3333 4000.0000 5000.0000 6666.6667 6666.6667 9523.8095 18181.8182

0.0035 0.0030 0.0025 y = 98.716x-1.426 0.0020 0.0015 0.0010 0.0005 0.0000 0.0000 2000.0000 4000.0000 6000.0000 8000.0000 10000.0000 12000.0000 14000.0000 16000.0000 18000.0000 20000.0000

Figure B.4 A plot of y versus 1/(y-y*)

67

x1=53mol/kg Table B.5 Values of y and corresponding equilibrium values

y 0.0030 0.0020 0.0010 0.0008 0.0006 0.0004 0.0003 0.0002 0.0001 y* 0.0025 0.0016 0.0008 0.0006 0.0004 0.0003 0.0002 0.0001 0.0000 1/(y-y*) 2000.0000 2500.0000 5000.0000 4000.0000 5000.0000 6666.6667 8333.3333 10000.0000 18181.8182

0.0035 0.003 0.0025 0.002 y 0.0015 0.001 0.0005 0 0.00000 2000.00000 4000.00000 6000.00000 8000.00000 10000.00000 14000.00000 18000.00000 12000.00000 16000.00000 20000.00000 1/(y-y*) y = 6.724x-1.134

Figure B.5 A plot of y versus 1/(y-y*)

68

Table B.6 Summary of Values for the computation of

% of flooding x1 (mol/kg) (b-a) h x1 x2 x3 x4 f(x1) f(x2) f(x3) f(x4) I Gm Kga Z(ft)

60%

62.50%

65%

67.50%

70%

75%

45 17272.7273 5757.5758 909.0909 6666.6667 12424.2424 18181.8182 0.0030 0.0003 0.0002 0.0001 9.6231 243.2482 36.8630 63.4997

47 17070.7071 5690.2357 1111.1111 6801.3468 12491.5825 18181.8182 0.0036 0.0004 0.0002 0.0001 11.2439 253.3835 38.0868 74.8033

49 18153.6388 6051.2129 714.2857 6765.4987 12816.7116 18867.9245 0.0064 0.0004 0.0002 0.0001 18.1712 263.5188 39.3007 121.8416

50 16181.8182 5393.9394 2000.0000 7393.9394 12787.8788 18181.8182 0.0017 0.0003 0.0002 0.0001 6.5422 273.6542 40.5054 44.1992

47 17070.7071 5690.2357 1111.1111 6801.3468 12491.5825 18181.8182 0.0036 0.0004 0.0002 0.0001 11.2439 283.7895 41.7012 76.5181

53 16181.8182 5393.9394 2000.0000 7393.9394 12787.8788 18181.8182 0.0012 0.0003 0.0001 0.0001 5.2280 293.9249 42.8885 35.8286

3.4 Definition of Variables

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Greek letters

Subscripts

Section 4. References

Arthur Kohl, Richard Nielsan. Gas Purification. 5th Edition. 1960.Gulf Publishing Company, Texas p562 Don W. Green, Robert H. Perry. Perrys Chemical Engineers Handbook. 8th Edition. 2008. McGraw Hill, New York. G.S Parks, E. Hablutzel, L.E.Webster. The Heat of Formation of Zinc Oxide. Department of Chemistry Stanford University. 1927 H.F Johnstone, Alamjit D. Singh. Process for Recovering Sulfur dioxide from Waste Gas. Commonwealth Edison Company, Chicago, Ill. Patent number 2,161, 056. J.M. Smith, H.C. Van Ness, M.M. Abbott. Introduction to Chemical Engineering Thermodynamics.7th Edition. 2005. McGraw-Hill Education. New York. Chapter 4 J.M.Coulson,J.F Richardson. Particle Technology and Separation Processes.Volume 3, 3rd Edition. 2002.Butterworth-Heinemann.Oxford p699 L.E Greesingh, A.F Graefe, F.E Miller and H. Barber. Applicability of Aqueous Solutions to the Removal of SO2 from Flue Gas. Volume 1. Envirogenics Company. El Monte, California p229

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M. Schultes. Absorption of Sulfur Dioxide with Sodium Hydroxide Solution in Packed Columns. 1998. Wiley- VCH Verlag GmbH, D-69469 Weinheim p202 S. Walas. Heuristics in Chemical Engineering. 2002. Butterworth-Heinemann. Oxford p 7 Sinnot, R K (2005). Chemical Engineering Design, 4th edition, volume 6. Elsevier ButterworthHeinemann.7 William R. Parish. Process for Removing Sulfur Dioxide from Gas. 1978. Lakeland, FLA. Patent number 4, 206, 187. Jerzy Buzek, Manfred Jaschik. Gas-Liquid Equilibria in the System SO2-Aqueous Solutions of NaHSO3/Na2SO3/Na2SO4. Polish Academy of Sciences, Institute of Chemical Engineering, ul.Baltycka 5, 44-100 Gliwice, Poland.(1995).

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