Title Page PROCESS SYSTEMS ENGINEERING GROUP SCHOOL OF ENGINEERING

PROCESS SYSTEMS ENGINEERING MSc

Academic Year 2011 - 2012

PSE 01: PROCESS PLANT OPERATIONS

OWOLOBI EMMANUEL OYEPHO

PROCESS PLANT OPERATIONS

31 October 2011

Shell Middle Distillate Synthesis Plant in Malaysia. The plant uses natural gas from remote fields as feedstock

Process Description The SMDS plant is based on the non-catalytic partial oxidation of natural gas with oxygen, at about 1600K and 30 to 50 bar to produce syngas. Syngas is produced from the natural gas and subsequently goes series of tubular fixed-bed F-T reactor for hydrocarbon synthesis which is a modernized version of the classical FischerTropsch synthesis. The syngas undergoes catalytic reforming in the multi-tubular fixed-bed reactor with a temperature of between 570-620K and a pressure of between 30-50 bar. The synthesis of long-chain waxy alkanes is favoured so that a high overall selectivity towards distillate is achieved. The heavy alkanes is are subsequently converted in a combined hydro-isomerisation and hydro-cracking step to produce desired products, mainly transportation fuel. In the final stage of the process, the products mainly gas oil, kerosene and naphtha are separated by distillation. By varying the operating conditions in the hydro-cracking and subsequent distillation step, the product slate can be shifted towards a maximum kerosene mode or towards a maximum gas oil mode, depending on market requirement. is utilized to convert the syngas to paraffin which is mostly liquid fuel. The process is shown in the simplified block diagram below.

Task 3: Continuous Single Effect Evaporator

Vapour, V T1, yV, HV Feed F TF, xF, hF

P1 T1 Heat-exchange tubes

Steam S TS, HS Condensate S, TS, hS Concentrated product L T1,xL,hL

Figure 3.1: continous single effect evaporator. The diagram above illustrate the operation of a continuous single effect evaporator used to concentrate the solution. Parameters Feed rate = F = 10000kg/h Weight fraction of the solute in the feed = xF = 0.009 Weight fraction of the solute in liquid product = xL = 0.016 Feed entry temperature = TF = 295K Inlet saturated steam pressure = 196.8kPa Saturation temperature of steam = TS = 393.2K Overall heat transfer coefficient = 1604W/m2K. Specific heat capacity = 4.14kJ/kgK. Assumptions

1. The boiling point of the dilute solution in the evaporator is assumed to be that of water at 101.325kPa, T1 = 373.2K. T1 is the reference temperature.

Taking overall material balance of the operation we have F=L+V 10000 = L + V For material balance on the solute alone FxF = LxL 10000(0.009) = L(0.016) L= = 5625kg/h. 3.2 3.1

Put L = 5625kg/h into equation 3.1 10000 = 5625 + V V = 10000 5625 = 4375kg/h

The specific enthalpy of the feed can be calculated from hF = CPF(TF T1) 3.3

where CPF = specific heat capacity of the feed. T1 = boiling point of the dilute solution hF = 4.14(295 = 373.2)

323.748kJ/kg.

The overall heat balance across the evaporator is FhF + SHS = LhL + VHv + Shs Rearranging FhF + S(HS hs) = LhL + VHv

The enthalpy change of steam is the latent heat of steam at 196.8kPa = HS hs

FhF + S = LhL + VHv

3.4

HV is the latent heat of water at 101.325kPa and saturation temperature of 373.2K, reading from steam tables its value is 2257kJ/kg The latent heat of steam at a pressure of 196.8kPa and saturation temperature of 393.2K reading from steam tables is 2202kJ/kg. Substituting in equation 3.4 10000( 323.748) + S(2202) = 4375(2257) 2202S 3237480 = 9874375 2202S = 13111855 S= = 5954.5kg/h The heat transferred is Q = S = 13111855kJ/h. =


= 3642182W. From Newtons law of cooling, Q = UA(TS T1) Substituting into 3.5 3642182 = 1604 A (393.2 373.2) A= = 113.5m2

3.5

Task 4
D1 (1) P1 Feed F,TF T1 (2) P2 T2 D2 (3) P3 T3 D3

Steam Condensate F-D 1 X X Condensate Condensate

F-D 1-D2

Product F-D1-D2-D3

Figure 4.1: Triple-effect evaporation Known parameters Feed rate = F = 4kg/s Mass fraction of the solute in feed = XF = 10 wt = 0.1

Vapour Pressure at effect 3 = P3 = 0.13bar=13kPa Temperature in effect 3 = T3 = 325K Mass fraction of the solute in the product = XL = 50 wt Temperature of inlet steam to effect 1 = T0 = 394K Pressure of inlet saturated dry steam = 205kPa Heat transfer coefficient of effect 1 = U1 = 3.1 kW/m2.K Heat transfer coefficient of effect 2 = U2 =2.0 kW/m2.K Heat transfer coefficient of effect 3 = U3 = 1.1 kW/m2.K Specific latent heat of steam to effect 1 = Specific latent heat for steam to effect 2 = Specific latent heat for steam to effect 3 = Specific latent heat for steam leaving 3 =
3 0

= 0.5

= 2200 kJ/kg = 2249 kJ/kg = 2293 kJ/kg

= 2377kJ/kg.

Assumptions 1. 2. 3. 4. 5. 6. Equal amount of heat is tranfered in each effect. Equal rate of evaporation. Approximately equal area for heating. Heat to raise temperature of feed from TF to T1 is neglected. The feed entry temperature TF is 294K Specific capacity of all liquors = 4.18kJ/kg.K

Taking an overall material balance, F = (D1 + D2 + D3) + L

4.1 4.2

4 = (D1 + D2 + D3) + L Taking a material balance on the solute alone, FxF = xLL 4(0.1) = L(0.5) L= = 0.8kg/s.

Put L = 0.8kg/s in equation 4.2, we have 4 = (D1 + D2 + D3) + 0.8 (D1 + D2 + D3) = 4 0.8 = 3.2kg/s 4.2(i)

For steam saturated at 205kPa, T0 = 394K,

0

= 2200kJ/kg

For liquid product at 0.13bar (13kN/m2), T3 = 325K,

3

= 2377kJ/kg

Total temperature difference is = T0 T3 = 394 325 = 69K.

For equal heat transfer, Q1 = Q2 = Q3 U1A1 T1 = U2A2 T2 = U3A3 T3 For equal area, A1 = A 2 = A3, Equation 4.3 reduces to U1 T1 = U2 T2 = U3 T3 Substituting the values of U1, U2 and U3 in equation 4.4, 4.4 4.3

3.1 T1 = 2.0 T2 = 1.1 T3 From equation 4.5, 3.1 T1 = 2.0 T2 T2 = T1 = 1.55 T1

4.5

4.5(i)

Also from equation 4.5 3.1 T1 = 1.1 T3 T3 = T1 = 2.8 T1 4.5(ii)

Total temperature change is given as T1 + T2 + T3 = T = 69 4.5(iii)

Put equations 4.5(i) and 4.5(ii) into equation 4.5(iii) T1 + 1.55 T1 + 2.8 T1 = 69 5.35 T1 = 69 T1 = = 13K

T2 = 1.55(13) = 20K T3 = 2.8(13) = 36K Since the feed enters at ambient temperature, it is necessary to have a greater value for T1 than the one obtained from the analysis above. Assuming T1 = 18K, T2 = 17K, T3 = 34K, then T1 = T0 18 = 394 T1 = 394 T1 T1 18 = 376K T2

T2 = 17K = T1 T2 = 376

17 = 359K T3

T3 = 34 = T2 T3 = 358 Hence,

34 = 325K

T0 = 394K, T1 = 376K, T2 = 359K, T3 = 325,

3

0 1 2

= 2200kJ/kg, = 2249kJ/kg = 2293kJ/kg

= 2377kJ/kg

Making heat balance over effect 1 S

0

= FCp(T1

Tf) + D1

S(2200) = 4(4.18)(376

294) + D1(2249) 4.6

2200S = 1371.04 + 2249D1 Making heat balance over the second effect, D1
1

+ (F D1)Cp(T1 T2) = D2

D1(2249) + (4 D1)4.18(376 359) = D2(2293) 2249D1 + 284.24 71.06D1 = 2293D2 4.7

2177.94D1 + 284.24 = 2293D2 Taking heat balance over the third effect, D2
2

+ (F D1 D2)Cp(T2 T3) = D3

2293D2 + (4 D1 D2)4.18(359 325) = 2377D3 2293D2 + 568.48 142.12D1 142.12D2 = 2377D3 2150.88D2 142.12D1 + 568.48 = 2377D3 From equation 4.2(i) D1 + D2 + D3 = 3.2 kg/s D1 = 3.2 D2 D3 4.9 4.8

Put 4.9 into 4.7 and 4.8 2177.94(3.2 D2 D3) + 284.24 = 2293D2 6969.408 2177.94D2 2177.94D3 + 284.24 = 2293D2 4.10

7253.648 = 4470.94D2 + 2177.94D3 From 4.8

2150.88D2 2150.88D2 2008.76D2

142.12(3.2 D2 454.784

D3) + 568.48 = 2377D3 142.12D3 = 2377D3 4.11

142.12D2

2519.12D3 = 454.784

From equation 4.10, D3 = Put 4.12 into 4.11, we have 2008.76D2 2519.12 = 454.784 2519.12(7253.648 4470.94D2) = 454.784 2177.94 4.12

2008.76 2177.94D2

4374958.754D2 18272809.75 + 11262834.37D2 = 9990492.265 15637793.12D2 = 19263302.02 D2 = D3 = D1 = 3.2 = 1.23kg/s = 0.811kg/s 1.28 0.811 = 1.159kg/s

From equation 4.6, Put D1 = 1.159 2200S = 1371.04 + 2249(1.159) 2200S = 3977.631 S = 1.81kg/s The area in each effect necessary to transmit the necessary heat required under the given temperature difference can be obtained as A1 = A2 = A3 = = = = = 67.6m2 = 72.40m2 = 77.70m2.

Task 5

Mole fraction benzene in vapour, yA

0.8 0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8 Mole fraction benzene in liquid, xA 1

Below is the table of the equilibrium data given above Table 5.1 Mole fraction of benzene in liquid, xA 0.00 0.12 0.26 0.40 0.58 0.78 1.00 Fractional vaporisation = xn The operating line equation is given by ym 1 ! 1.28 xm  0.028 From equation 5.1, the slope of the line is therefore F  1 = V xF , xD , xw = 2.3 5.1 Mole fraction of benzene in Vapour, yA 0.00 0.26 0.48 0.64 0.79 0.90 1.00

The operating line equation becomes y ! 3.3 xF  2.3 x where xF = mole fraction of benzene in the liquid feed = 0.6 Lets locate another point in the operating line equation. Since the slope is negative lets get the corresponding value of y when x is less than the feed value say 0.5. y ! 3.3(0.6)  2.3(0.5) ! 0.83 By plotting the points A(0.6,0.6) and B(0.5,0.83) on a graph using excel, the point of intersection of the operating line and the equilibrium line is 5.2

1.2

Mole fraction of benzene in vapour,y

0.8

0.6

equilibrium line x= y line operating line

0.4

0.2

0 0 0.2 0.4 0.6 0.8 Mole fraction of benzene in liquid, x 1 1.2

Task 6

Mole fraction benzene in vapour, yA

0.8 0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8 Mole fraction benzene in liquid, xA 1

Table 6.1 Mole fraction of benzene in liquid, xA 0.00 0.12 0.26 0.40 0.58 0.78 1.00 Let the basis be 100kmol By taking an overall material balance we have 100 = D W 6.1 Mole fraction of benzene in Vapour, yA 0.00 0.26 0.48 0.64 0.79 0.90 1.00

A balance on the more volatile component benzene gives 100 xF = D xD  xw W Substituting the values of xF , xD , xw into equation 6.2 gives 40 = 0.9D 0.1W 6.3 6.2

From equation 6.1,

D = 100 6.4 Put 6.4 into 6.3 40 = 0.9(100 W) 40 = 90 0.8W W = 62.5kmol. From equation 6.4 D = 100 62.5 = 37.5 The top operating line is given as yn 1 ! R x xn  D R 1 R 1 6.5 0.1W

Where R = reflux = 5kmol/kmol product yn 1 ! 5 0.9 xn  5 1 5 1 0.15 6.6

yn 1 = 0.83 xn

Equation 6.6 is the top operating line drawn through the points A(0.9,0.9) and B(0,0.15). The equation of the bottom operating line is ym 1 ! W Lm xm  Lm  W Lm  W xW 6.7

Since the vapour is saturated, L m = Vm = 100 RD 5(37.5)

= 287.5kmol Substituting in equation 6.7 gives ym 1 ! 287.5 62.5 xm  0.1 287.5  62.5 287.5  62.5 6.8

ym 1 ! 1.28 xm  0.028

Equation 6.8 is the bottom operating line equation and is represented by a line drawn through C(0.1,0.1) at a slope of 1.28 Using Excel the two operating lines were drawn as shown by the graph below.

1.2

1 Mole Fraction of benzene in vapour

0.8

0.6

y x=y line Top operating line

0.4 Bottom operating line 0.2

0 0 0.2 0.4 0.6 0.8 1 1.2

Mole fraction of benzene in liquid

Task 7: Drying For the first operation: W 1 = 0.25, w = 0.1, wc = 0.15, we = 0.05 f 1 = (w1 f c = (wc f = (w t = 15s The total drying time is t= f 1  f1  f c  ln c mA fc f1 1 0.2  0.1 0.1  ln mA 0.1 0.05 we) = 0.25 we) = 0.15 0.05 = 0.2 0.05 = 0.1

we) = 0.1 0.05 = 0.05

15 =

mA = 0.113 For the second operation: w1 = 0.32, w = 0.07, wc = 0.15, we =0.05 and; f 1 = (w1 we) = 0.32 0.05 = 0.27

fc = ( wc  we ) ! 0.15  0.05 ! 0.10 f = (w we) = 0.07 0.05 = 0.02

The total drying time is then: t = 29.29ks =

29.29 60

1000 60

= 8.14hours.

Task 8: Crystallization. Crystallization is one of the unit operations (separation processes) employed in the process industry to separate solutes (normally pure solids) from a homogenous liquids phase. Crystallization occurs primarily due to changes in solubility of the solute which is a result of temperature change. Commercially it can find application in industries such as sugar, salt and pharmaceutical industries. For this work, I considered a typical process in the pharmaceutical industry where crystallization is used. FRACTIONATIONAL CRYSTALLIZATION OF PLASMA PROTEINS Plasma proteins are made up of fibrinogens, globulins and albumins. These proteins have similar solution behaviour. These proteins can be separated by fractional crystallization by means of ethanol (an anti-solvent) addition at specified condition of temperature, PH and ionic strength. The operation utilizes the continuous fractionation system described by Chang (1988) and illustrates some of the solutions that are often employed to minimize the difficulties associated with the batch operation. Figure 8.1 shows one stage of the continuous precipitation train. In the continuous system, both ethanol and buffer for PH control are added to the solution by spraying a dispersion of fine droplets above the surface of the suspension in the MSMPR precipitator. Gradients in density and surface tension that exist within the droplets and the continuous solution phase would hinder dispersing the ethanol, in particular since the upper region of the tank are typically the least well-mixed. A better solution to the blending of the anti-solvent is by blending with the aid of a static mixer and external recycle line. A recycle line with an in-line static mixer was used to promote mixing of the protein solution as it was added. The solid-free protein solution is mixed into the recirculating suspension from the tank by continuously injecting it just upstream of the static mixer so that it was rapidly diluted into the stream recycling from the MSMPR. The flow rate of the recycle stream was about ten times that of the injected feed so a significant dilution is achieved in the recycle line. By employing a well-designed system an using an on-line PH control for the addition of buffers, several improvement were achieved beyond the standard batch process. First, yield and purity of albumin from the final fractionation step increased. Second larger particles were formed which eased recovery by centrifugation. Finally the time cycle was reduced significantly since longer time was required for the batch process. The use of the continuous system allowed operation at low supersaturation that minimized nucleation and co-precipitation. This favourably impacted both purity and yield since co-precipitation of albumin in stage 4 would result in yield loss. Further co-precipitation of fibrinogen and globulin in the final precipitation stage when recovering albumin will lead to loss of purity in the albumin.

References 1. Jones, A.G., Crystallization Process Systems, 2002, Elsevier, London. 2. Myerson, A.S., Handbook of Industrial Crystallization, 2002, ButterworthHeinemann, Oxford.