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Recovery of Sulfur Dioxide from Stack Gas (Design of a Sulfur Dioxide Absorber)
Table of Contents Section 1. The Design Problem 1.1 Statement of the Design Project..3 1.2 Description of the Process...4 1.3 Summary of Design Tasks...5 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...8 2.2 Functional Block Diagram.9 2.3 Process Flow Diagram...10 2.4 Process Flowsheet...10 2.5 Basic Assumptions 2.5.1 Operating mode, Product and Feed Specifications, Process Conditions.11 2.5.2 Battery Limits...11 2.5.3 Definition of Incoming and Outgoing Streams.12 2.6 Material and Energy Balances 2.6.1 Mass Process Stream Summary.12 2.6.2 Energy Process Stream Summary. 2.6.3 Detailed Calculations of the Material and Energy Balances...14 Section 3. Chemical Engineering Design 3.1 Calculation Flow Diagram.. 3.2 Summary of Assumptions.22 3.3 Chemical Engineering Design Calculations22 3.4 Definition of Variables...27 Section 4. References..28
Section 1. The Design Problem 1.1 Statement of the Design Project You are a member of a group of design engineers designing equipment for the recovery of SO2 from stack gases. The group leader has asked you to determine the optimum size of the SO2 absorption tower where the stack gas is entering at 100,000 ft3/min and minimize the SO2 content from 0.3% to 0.01%. Specifically, you are tasked to determine the height and crosssectional area of the optimum absorption tower and to present your recommendations in the form of a formal report. Your group has held several meetings to discuss the proposed overall design. Following is a list of conditions, assumptions, and data on which the group 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 zinc oxide process will be used for recovering the SO2. In this process, a solution of H2O, NaHSO3, and Na2SO3 is circulated through the absorption tower to absorb the SO2. This mixture is then treated with ZnO, and the ZnO3 formed is filtered off, dried, and calcined to yield practically pure SO2. The ZnO from the calciner is reused, and the sulphite-bisulphite liquor from the filter is recycled. The absorption tower will contain nonstaggered grids of the following dimensions: Clearance = 3.81cm Height = 10.16cm Thickness = 0.635cm Free cross-sectional area = 85.8 % Active absorption area per cubic foot of volume a = 13.7 ft2/ft3
The average density of the gas at the tower entrance can be assumed to be 0.8650 kg/m3. The sulphite-bisulphite liquid has a density of 70 lb/ft3 and can be considered as having a zero equilibrium SO2 vapour pressure at both the inlet and outlet of the tower. The sulphite-bisulphite liquid must be supplied at a rate of 675 lb/hft2 of column crosssectional area.
The optimum design can be assumed to be that corresponding to a minimum total power cost for circulating the liquid and forcing the gas through the tower. It maybe assumed that this optimum corresponds to the optimum that would be obtained if fixed charges were also considered. The following simplified equations are applicable for grids of the dimensions to be used: Equation (1) Equation (2) 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. The gas blower has an overall efficiency of 55 percent The pump has an overall efficiency of 65 percent. 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. To absorb the SO2, a solution of H2O, NaHSO3 and Na2SO3 is circulated through the absorption tower. The sulphite-bisulphite liquor is pumped to the top of the tower and compressed to 35 psig. The following reaction occurs between sulphur dioxide and sodium sulphite within the absorption tower: Equation (3) 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 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. 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.
1.4 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
Phase
Density (kg/m3)
Melting point ( C)
Boiling Point ( C)
Ca(HSO3)2
202.22
Solid
NA
NA 0.189(0 C), 0.173(20) 0.066 (100C) 0.0043 0.21g (20C) 0.145 insoluble 7.5(25C) 42(6C) 4.76(0C) 42.7 (100C) 67.8 0.94 0.00016 insoluble
NA
NA
NA
NA
NA
CaO
56.08
Solid
2211
2572
2850
-635.090
-604.030
NA
Calcium sulfite Calcium sulfate Carbon dioxide Nitrogen Oxygen Sodium bisulfite Sodium sulfate Sodium sulfite Sulfur dioxide Water Zinc Oxide Zinc Sulfite *NA not available
CaSO3 CaSO4 CO2 N2 O2 NaHSO3 Na2SO4 Na2SO3 SO2 H2O ZnO ZnSO3
120.17 136.14 44.01 28.00 16.00 104.061 142.04 126.043 64.06 18 81.408 145.44
Solid Solid Gas Gas Gas Solid Solid Solid Gas Liq. Solid Solid
NA 2960 770 1.251 1.429 1480 2664 2633 3.049 1000 5606 NA
600 1460 -78 -210 -218.79 150 888 500 -72.7 1975 NA
NA 0.5-5 NA 3.1
1.4.2 Kinetic Data and Reaction Stoichiometry Absorber T=148.89C, P=1 atm Equation (4)
( ) ( )
Equation (5)
Liming Tank
( )
Equation (6)
Gasifier ( ( Zinc Oxide Mixer ) T=30C Equation (9) Calciner: T=800C Equation (10) ) Equation (7) Equation (8)
Fig.1 Number of Transfer Units as a function of mole fraction ratio Source: J.M.Coulson,J.F Richardson. Particle Technology and Separation
183.14 lbmol/min Desulfurized Gas 183.67 lbmol/ min Stack Gas 1.74 lbmol/min Water 1.77 lbmol/min Sulfur Doixide and Water
183.14 lbmol/min Desulfurized Gas sodium sulfite-bisulfite liquor Sodium bisulfite water Sulfur dioxide Zinc oxide
0.0001lbmol/min Calcium Oxide 1.74lbmol/min Make-up Water 183.67 lbmol/min Stack gas
Figure 3. Block Diagram for the Recovery of Sulfur Dioxide Using the Zinc Oxide Process
Calcium Oxide
13
Make-up Water
10
S02
12 2 4
D01
6 7 11 23 15 16 I
22
Evaporated Water
C01
3
S03 R01
8
21
S04 R02
18
F01
19 17
24 17
S01
9 20 5 13
14
Stack Gas
Process Equipment Summary C01: Sulfur Dioxide Absorber R01: Liming Tank D01: Rotary Dryer R02: Gasifier F01: Calciner R03: Zinc Oxide Reactor P01: Sulfite-Bisulfite Liquor C01 S01: Clarifier R01 P02:Sludge S01 S02:Clarifier R02 P03: Effluent S01 S03: Rotary Drum Filter S02 P04: Recycled Sulphite-Bisulphite Solution S04 S04: Rotary Drum Filter R03
10
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 continuously. The following criteria were used to determine the mode of operation of the plant. 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 the ideal gas theory. It is also assumed that CaSO4 filter cake from the rotary drum filter has a moisture content of 6%. It is also assumed that all unbound moisture are removed in the rotary drier containing zinc sulphate, , and only the bound water is left. 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 30% SO2-70% H2O. Purification of the recovered SO2 is not included in the process.
Calcium Oxide Water
Stack Gas
REACTION
SEPARATION
Product
waste waste
2.5.3 Definition of Incoming and Outgoing Streams Streams Definition Input Feed Stack Gas This consists of 100,000ft3/min at 300F and 1 atm stack gas containing 0.3%v/v SO2, 11% CO2, and the balance being N2, O2, and H2O. Make-up water This is the water used to replenish losses in the dryer and during filtration. This stream requires 1.7381lbmol/min of H2O Lime 1.13x10-4lbmol/min of lime, CaO ,is used to absorb the sodium sulfate formed in the absorption column. Output Purified Stack The purified stack stream has a reduced SO2 content from 0.3%v/v to Gas 0.01mole %. This stream contains a total of 183.1372lbmol/min. Recovered SO2 The recovered SO2 stream contains 30 mole%SO2 and 70 mole%H2O. CaSO4 waste This stream has contains a small amount of water and insoluble CaSO4. Evaporated This is the water that is evaporated from the dryer which is not Water recovered anymore. This stream contains 0.4964lbmol/min H2O. 2.6 Material and Energy Balances 2.5.1 Stream Nr. : Name: Comp MW SO2 64.00 CO2 44.00 O2 32.00 N2 28.00 H2O 18.00 Total Stream Nr. : Name: Comp MW H2O 18.00 Na2SO3 126.043 NaHSO3 104.061 Na2SO4 142.04 Total Mass Process Stream Summary 1 Stack gas lb/min 35.26 888.90 485.48 3726.44 263.82 5399.9 IN lbmole/min 0.55 20.20 15.17 133.09 14.66 183.67 2 OUT Desulfurized Gas lb/min lbmole/min 1.17 0.018 888.80 20.20 485.47 15.17 3726.40 133.09 263.72 14.66 5365.56 183.14 4 Make-up Water lb/min 31.29 IN 5 Exit Soln from Absorber lb/min lbmole/min 263.96 14.66 110.87 0.016 374.85 1.07 1.13E-4 15.73
lbmole/min 1.74
340.76
15.73
31.29
1.74
12
Stream Nr. : Name: Comp MW CaO 56.08 CaSO4 136.14 H2O 18.00 NaHSO3 104.061 Na2SO4 142.04 CaSO3 120.14 Total Stream Nr. : Name: Comp MW SO2 64.00 H2O 18.00 NaHSO3 104.061 CaSO4 136.14 Total Stream Nr. : Name: Comp MW H2O 18.00 NaHSO3 104.061 CaSO4 136.14 Na2SO3 126.043 ZnO 81.408 Total Stream Nr. : Name: Comp ZnSO37/2H2O H2O Na2SO3 Total
6 IN 7 Calcium Oxide Sodium Bisulfite lb/min lbmole/min lb/min lbmole/min 6.32E-3 1.13E-4 4.727E-3 2.626E-4 0.023 2.25E-4
6.32E-3 1.13E-4 9 SO2 recycle lb/min lbmole/min 7.21E-3 1.13E-4 4.73E-4 2.63E-4
0.028
4.88E-4 10
7.68E-3 12 Water
3.76E-4
Liquor w/ SO2 absorbed lb/min lbmole/min lb/min 263.88 14.66 111.93 1.07 0.014 1.13E-4 15.73 41.15 41.15
2.37E-4
1.31E-4
375.82
0.53 0.53
15 Zinc Sulfite lb/min lbmole/min 110.46 0.53 250.92 13.94 66.80 0.53 428.18 15.00
16 Zinc Sulfite lb/min lbmole/min 110.46 0.53 8.95 0.50 119.41 1.03
13
Stream Nr. : Name: Comp MW H2O 18.00 CaSO4 136.14 Na2SO3 126.043 SO2 64.00 Total Stream Nr. : Name: Comp ZnSO37/2H2O H2O SO2 Total Stream Nr. : Name: Comp MW H2O 18.00 CaSO4 136.14 Na2SO3 126.043 Total
17 Sodium Sulfite lb/min lbmole/min 242.1 13.45 66.80 33.92 342.82 0.53 0.53 14.51
33.92 56.78
0.53 1.8
0.015
1.20E-4
20 Sulfur Dioxide lb/min lbmole/min 33.92 22.86 56.78 22 0.53 1.27 1.8
110.46
0.53
lbmole/min 0.50
8.95
0.50
2.37E-3 1.31E-4
24 Calcium Sulfite lb/min lbmole/min 6.76E-3 3.75E-4 0.015 1.13E-4 0.014 1.13E-4 0.036 6.01E-4
2.6.2 Energy Process Stream Summary 2.6.3 Detailed Calculation of the Material and Energy Balance BALANCE FOR THE FEED Component balance: yS02 + yCO2 + yO2 + yN2 + yH2O= 1 eq. 11 Molecular weight balance: ySO2(MWSO2) + yCO2(MWCO2) + yO2(MWO2) + yN2(MWN2) + yH2O(MWH2O) = 29.4 eq. 12 Amount of O2: yO2(left in the feed)= yO2(total) yO2(combusted)
14
yO2 = (0.21/0.79)(yN2) yCO2 eq. 13 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 eq. 14 Substitute eqn. 13 12 0.003(64) + 0.11(44)+ [0.21/0.79 yN2 0.11]32 + 28yN2 + 18yH2O = 29.4 eqn. 15 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
15
6 Ca-balance: ( SO2-balance: ( ( ) ) ( ( ) ) ( ( ) ) ( ( ) ) )
O2-balance: ( ( Inert: ( )[ ( ( ( ) )] ) ) ) ( ( ) ) ( ( ) )
16
( (
) ( )
) (
) ( )
)]
)]}
17
( ) {[ ( ) [ ( ) (
)]
)]}
)]
( [ (
( )
)]}
)]
( ) ( ) [ (
] {[
)]
)]}
)[
)]
18
N2-balance: ( ) ( ) eqn.27
CO2-balance: ( ) ( ) eqn. 28
H2O-balance: ( ) ( ) eqn. 29
19
Where
Assume feed entering at T = 298.15 K Solve for the standard heat of formation from equations (1) and (2). Data for the Standard heat of formation of each component can be found in table C1 of Vanness and Smith Thermodynamics book Component ( ) -1 105 469.78 -285 830 -296 830 0 -1 387 100 -1 127 738.236
(-1 127 738.236) [(-1 105 469.78) + (-285 830) + (-296 830)]
(33) ( ) ( ) (34)
20
( Solve for ( ) ( )
From table C4 of of Vanness and Smith Thermodynamics book Basis : 1 hour of operation
Component
n 910.266 3.470 1.0986 0.012 64.22 7985.148 1212 3.535 4.038 4.796 15.420 24.117 3.502 4.467
( ( (
) ) )
(910.266)( 3.535) + (3.470)( 4.038) + (1.0986)( 4.796) + (0.012)( 15.420) + (64.22)( 24.117) + (7985.148)( 3.502) + (1212)( 4.467) 8.314 ( 38 164.04) 317 295.8 J/mol K , from equation (6)
Solving for
300. 83 K
21
Section 3. Chemical Engineering Design 3.1 Calculation Flow Diagram 3.2 Summary of Assumptions The calculation of the height and diameter of the tower is done using the method found in J.M.Coulson,J.F Richardson. Particle Technology and Separation Processes.Volume 3, 3rd Edition. 2002.Butterworth-Heinemann.Oxford p699. The solution coming in the absorber is assumed to contain only sodium sulphite and water only. The temperature of the incoming solution is at 25C. The diameter of the tower in design no.2 is based on the solubility of the product, NaHSO3, in water. 3.3 Chemical Engineering Design Calculations Design No. 1 Since there were no kinetic data given on the reaction of sulphur dioxide with the sulphitebisulphite solution, the strategy applied to the first design is based on the method found in the book by Coulson and Richardson (2002) which employs the use of Overall Number of Transfer Units(Nog) and Overall height of transfer units(Hog). In this method, a plot containing values of Nog versus the ratio of the inlet and outlet mole fractions of the desired component is used to estimate the Nog by assuming a value of mG/L. The suggested ratio by Colburn (1939) is from 0.7-0.8. This method is applicable for dilute systems where the composition of the component to be absorbed is less than 10%. In the problem, the composition of SO2 in the stack gas in 0.3% and thus the system qualifies as a dilute system. The overall transfer unit, , is where L is the tower height (m) And the overall height of transfer unit is, ( ) Equation (37) will lie between 0.70.8 Equation (36)
are molar flow rates per unit area on a solute free basis
as a function of
, , with
as parameter
From Table 12.5 from Coulson(2002), Volume 2 p 695 for plain grids,
Solving for the overall height of transfer unit, ( ) ( It is specified in the problem that, ( Where ) ( ) ( )( )( ) ) Equation (38)
The expression for the overall mass transfer coefficient is also given in the problem, ( ) ( )
Based on the Heuristics in Chemical Engineering by S. Walas(2002) , packings of random or structured nature are suited especially to towers under 3ft diameter and where low pressure drop is desirable. Since the calculated diameter is 2.64ft and operating pressure is at 1 atm, then the non-staggerred grids which are considered as structured packings can be used effectively in the design of the absorber.
24
The first design gives a diameter of 2.87ft and a height of 61.73ft. Multiplying the crosssectional area obtained to the mass velocity of the liquid gives the mass of solution passing through the column. ( )( )( )
The following calculations are used to determine the theoretical amounts of reactants in the solution needed to react with the SO2 and O2 in the stack gas. By doing this, the theoretical mass flow rate of solution passing through the absorber can be compared with the one obtained using Design No.1. If the flow rate obtained using Design No.1 is larger than the theoretical flow rate, then the area of the absorber can accommodate the flowing liquid. If otherwise, then another design should be considered. ( ) ( )( )
)(
( (
( )(
)( )
25
The theoretical amount of reactants needed to let the reactions in the absorber proceed amount to 76.7479lb/min and this amount does not include yet the carrier liquid which is water. The first design only allows 72.9lb/min of solution to pass through the column. It is obvious that the dimensions obtained from the first design cannot perform the job. Therefore, a second design is needed. Design No.2 The carrier liquid must be able to dissolve the main product of the reaction in the absorber which is sodium bisulphite. The amount of carrier liquid is based on the solubility of sodium bisulphite, assuming all other reactants are supplied according to stoichiometry. ( ( )( )( ) )
) ( )
26
The height is solved using the same graph from Coulson used in design no.1, now assuming .
From Figure 5, ( ( )( ) )( )
The new diameter and height obtained are 6.2097ft and 79.9 ft, respectively.
27
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. 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.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 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.
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