Individual Design of the Vapour Recovery System Charlie Lower Group 6

Abstract

This report gives an extensive overview into the design of the vapour recovery system for the large-scale production of methanol. From optimizing the system manually and also with the aid of ASPEN process modeling software, it was found that a fixed-plate shell-and-tube heat exchanger used as a condenser required heat to be removed at a rate of 8949 kW. The condenser features carbon-steel tubes and a stainless-steel shell. A 0.0254 m square pitched bundle of 368 tubes at a length of 4.88 m and outside tube diameters of 0.0254 m allow for sufficient cooling over 143.2 m2 of heat transferrable area. The condenser is to be placed before the splitter of the purge and recycle streams to ensure maximum possible treatment of the liquids entrained in the flashed vapours. The capital cost of the condenser was calculated to be 59k with installation at 35.4k. The operating cost, calculated as a function of the cooling water flowrate is 175k per annum.

Introduction
In a real working system, it is unrealistic to achieve perfect separation of the feed components to the desired product components. Instead, components are distributed throughout all streams leaving the process envelope. Although the separation section of the process is optimized such that maximum possible separation is achieved, there will still be desirable product present in the flash vapours from the flash column preceding the vapour recovery system. A vapour recovery system ensures that these desired vapours are reintroduced to the process to minimize wastage and to improve the efficiency of the process as a whole. The design brief states that a column efficiency of 85% is to be achieved. This suggests that at least 15% of the feed liquids will be entrained in the flash vapours leaving the flash column hence a largely significant quantity of the desired methanol is available for recovery as opposed to only purging. Ideally, the vapour recovery system can be designed is such a way that carries these desirable vapours to the recycle stream and back into the reactor feed. Recycling methanol from the flash column does mean that recycle and reactor input flowrates increase which in turn will increase capital and operating costs. However methanol poses many health risks when exposed to the environment due to its toxicity even in the smallest doses. It is therefore necessary to minimize the amount of methanol present in the purge stream, which will be treated as waste. There are two underlining factors that need to be established before optimization of the vapour recovery system can begin, these being positing of the system in the existing process and also the type of system or technology to be incorporated.

1 Placement of the Vapour Recovery System & Available Technologies 1.1 Placement of the Vapour Recovery System
Correct placement of the vapour recovery system is essential for correctly recovering the methanol from the flash column. There are three positions in which the system can feature in the existing process, however some are more advantageous than others. These can be seen schematically in figure 1.1.1. To Recycle
1

2
3

Purge

Flash Vapours Figure 1.1.1. Potential locations for placement of the vapour recovery system in the existing process. Integrating the vapour recovery system to position 1 would mean that the methanol being removed is from the recycle stream. This suggests that less methanol would be fed back into the reactor which keeps operating costs down due to a reduced reactor inlet flowrate however there will still be desired methanol vapours present in the purge stream. This untreated methanol means a significant amount of product wastage. Department of Chemical Engineering 2013/14

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Individual Design of the Vapour Recovery System Charlie Lower Group 6

Placement at position 2 would see treatment of the methanol vapours present in the purge stream. This seems feasible however similar position 1, one stream is left untreated i.e. the recycle stream, which also contains a significant amount of the desired methanol vapours form the flash column. It is clear that the vapour recovery system must be placed in a position that treats both the recycle and purge streams to achieve maximum recovery. After identifying the flaws with positions 1 and 2, it is clear to recognize why position 3 is the most favourable option. Position 3 ensures that as much methanol as possible can be removed from the flash vapours before entry to the splitter partitioning the recycle and purge streams. I.e. the desired methanol vapours are being recovered before reaching the purge and recycle streams to allow for maximum extraction as opposed to only treating one and not the other of the streams.

1.2 Reaction Separation Systems

Reaction separation systems involve the addition of other chemicals or substances, which then react with one or more of the components present when introduced to a given stream. Substances such as acids and alkalis are often used for neutralization mechanisms. Precipitants are also used to aid the precipitation of a dissolved solute. These methods are more commonly used to treat waste product streams as the components in the stream undergo chemical changes. This is not desirable as the objective is to purify components rather than change their physical properties suggesting that this technology is not suitable.

1.3 Membrane Technology

Membrane separation systems feature a physical separation of components into permeate and retentate streams. It is possible to achieve gaseous separations by differences in solubilities and diffusivities through non-porous polymers. This is a feasible technology however optimization becomes very difficult, as fouling is very common. Another disadvantage of membrane separation is the slow flux through the membranes. In order to increase this flux, the pressure drop through the membranes would need to be increased. This would increase the compression costs largely and is therefore not feasible for this process.

1.4 Adsorption Column

Adsorption processes involve one or more components bonding to the surface of a material known as the adsorbent; this bonding usually occurs due to weak intermolecular forces, however chemical bonding is possible and is known as chemisorption. The selectivity of an adsorption column depends on the properties of the components and the adsorbent used. For example, polar molecules will adsorb preferentially onto a polar adsorbent than non-polar molecules, hence exacting a separation between them (Perry & Green, 2007, pp.16-11). By looking at the dipole moments of the individual components, it can be seen that methanol and water are both highly polar whilst all other components are either non-polar or only very weakly polar, as in the case of carbon monoxide (Atkins & De Paula, 2010, p.936). Therefore, this would suggest that a highly selective separation could be achieved, however, the adsorbent needs reactivation in order to remove the adsorbed molecules and provide a fresh surface for further adsorption. This is easily achieved using thermal reactivation, however this is a very energy intensive and environmentally damaging process which often causes degradation of the adsorbed compounds preventing them from being recycled (Perry et al. 2007, pp.16-63). Due to the energy intensity and hence cost associated with regenerating the adsorbent, an adsorption column is not suitable for this process.

1.5 Absorption Column

Absorption columns involve counter-contacting of a liquid and gaseous stream in order to transfer components from one stream to the other dependent on the solubilities of the components to the solvent used. Henrys law constants for the components in liquid water at 25oC show that methanol is very soluble in water whilst all other components are relatively insoluble; hence a very good separation could be exacted using liquid water to remove the methanol. However, by introducing an additional water stream, the recycled product going to the liquid recovery system would contain a large amount of water, which would significantly increase the size and cost of the liquid recovery system.

1.6 Condenser
A Condenser is a device or unit used to condense a substance from its gaseous to its liquid state, typically by cooling it. In so doing, the latent heat is given up by the substance, and will transfer to the condenser coolant. Condensers are typically heat exchangers, which have various designs. Condensers take advantage of the difference in boiling points between components in order to condense certain components and use gravity to separate the liquid and vapour phases. Methanol and water have significantly higher boiling points than all other components in the system and hence can be easily condensed without excessive cooling. Additionally, the majority Department of Chemical Engineering 2013/14

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Individual Design of the Vapour Recovery System Charlie Lower Group 6

of the other gases will pass through the condenser without being removed in the liquid stream, except for a small percentage, which may dissolve in the liquids. However, the gases are still present in the condenser and will end up being cooled by the cooling water. Additionally a large temperature difference is required in order to transport a large quantity of heat without a high flow rate of cooling water. For these reasons, a condenser will be used for the vapour recovery system.

2 Design of the Condenser 2.1 Optimum Conditions of Operation

In order to calculate the process operating conditions of the condenser, knowledge of the energy input and output of the condenser is used to determine the heat duty necessary for optimum operation of the vapor recovery system. The heat duty of the condenser allows the cooling water flowrate of the condenser to be determined; this is achieved by means of an energy and material balance including all process streams over the condenser. Figure 2.1.1 shows a schematic view of the material balance needed to perform energy calculations over the condenser. All molar flowrates for each component in their respective process streams are found using the results from the ASPEN simulation process model. -1
VAPOURS 33 bar, 50 C
0

CH4 (v) CO2 (v) CO (v) H2 (v) N2 (v) H2O (l) CH3OH (l)

1.23258 kmol s -1 0.38572 kmol s -1 0.20608 kmol s -1 1.85084 kmol s -1 0.24133 kmol s -1 0.04943 kmol s -1 0.33076 kmol s

-1

Q VAPFLASH 33 bar, 75 C
0

CH4 (v) CO2 (v) CO (v) H2 (v) N2 (v) H2O (v) CH3OH (v) CH4 (l) CO2 (l) CO (l) H2 (l) N2 (l) H2O (l) CH3OH (l)

1.23088 kmol s -1 0.38197 kmol s -1 0.20602 kmol s -1 1.85062 kmol s -1 0.24119 kmol s -1 0.00392 kmol s -1 0.07381 kmol s
-1

Condenser

LIQREC 33 bar, 50 C
0

0.00170 kmol s -1 0.00376 kmol s -1 0.00006 kmol s -1 0.00022 kmol s -1 0.00015 kmol s -1 0.04550 kmol s -1 0.25695 kmol s

Figure 2.1.1. Schematic diagram of material balance over the condenser. Subscripts v and l denote vapour and liquid phases respectively. VAPFLASH, VAPOURS and LIQREC denote the flashed vapour stream from the flash column, vapour stream leading to recycle/purge streams and liquid recovery stream respectively.

The objective is to determine ! , the cooling rate of the condenser i.e. the rate at which heat must be removed from the condenser for optimum process operation. Beginning with first principles for an open steady-state system, the energy balance is given by equation 3.1.1. (2.1.1) !!! ! ! !! ! !! ! !!! For this process, there are no moving parts in the system and no energy is transferred by electricity or radiation, so ! ! is equal to zero. No significant vertical distance separates the inlet and outlet ports, so !!! is considered to be approximately zero. Phase changes and nonnegligible temperature changes occur, so !!! is also considered to be approximately zero (relative to !! ). The energy balance then reduces to equation 3.1.2 (Felder & Rousseau, 2000, p.363). (2.1.2) ! ! !! ! !! !! ! !! !!
!"# !"

Equation 2.1.2 shows that the cooling rate is equal to the total change in enthalpy over the condenser, which is the sum of the specific enthalpies of each component multiplied by their respective flowrates exiting the condenser minus the sum of the specific enthalpies of each component multiplied by their respective flowrates entering the condenser. The specific enthalpy of a component is expressed as the integral of the respective components heat capacity at constant pressure. !! (2.1.3)
!! ! !!" ! !! ! !! ! ! !! ! ! ! !! ! !
!!

!!" !"

(2.1.4)

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Individual Design of the Vapour Recovery System Charlie Lower Group 6

Heat capacities of individual components are expressed as a polynomial in terms of temperature where constants !! , !! , !! and !! corresponding to each component are found from literature (Felder et al. 2000, p.635-637). Combing equations 2.1.3 and 2.1.4 to give equation 2.1.5 allows for manual calculation of the individual specific enthalpies.
!! !
!! !! ! !

!! ! !! ! ! !! ! ! ! !! ! ! !"
! ! ! ! !! !!

!! ! !! ! ! !! ! ! ! !! ! ! ! !! ! !

! ! ! ! ! ! !! ! !! !! ! !! !! ! ! !! !! ! ! !! !! ! ! !! !! ! !! !! ! ! !! !! ! ! !! !! ! ! ! ! ! ! !

(2.1.6) (2.1.7)

Before determining the individual specific enthalpies of components, it is necessary to select reference states for each component. This simplifies calculations as the reference states are chosen such that they are equal to the states of given components in any of the process streams. For this process, the reference states are given in Table 2.1.1. Notice that the individual specific enthalpies for each component at their reference states are equal to zero.
Table 2.1.1. Reference state conditions for each component in the process. 0 Component Physical State Temperature [ C] Pressure [bar] CH4 Liquid 50 33 CO2 Liquid 50 33 CO Liquid 50 33 H2 Liquid 50 33 N2 Liquid 50 33 H 2O Vapour 50 33 CH3OH Vapour 50 33

For clarity, an inlet-outlet enthalpy table is created which enables one to identify which specific enthalpies need to be calculated. The individual flowrates are taken directly from the schematic flowchart in Figure 2.1.1.
Table 2.2.2. Input and Output flowrates and Specific Enthalpies of each component in the process. -1 -1 -1 -1 Component Physical State !!" [kmol s ] !!"# [kmol s ] !!" [kmol s ] !!"# [kmol s ] CH4 Vapour 1.23258 1.23088 !! !! CH4 Liquid 0.00170 0 CO2 Vapour 0.38572 0.38197 !! !! CO2 Liquid 0.00376 0 CO Vapour 0.20608 0.20602 !! !!" CO Liquid 0.00006 0 H2 Vapour 1.85084 1.85062 !! !!! H2 Liquid 0.00022 0 N2 Vapour 0.24133 0.24119 !! !!" N2 Liquid 0.00015 0 H 2O Vapour 0.00392 !!" H 2O Liquid 0.04943 0.04550 0 !! CH3OH Vapour 0.07381 !!" CH3OH Liquid 0.33076 0.25695 0 !!

It is now apparent which specific enthalpies need to be calculated in order to determine the cooling flowrate. The following example calculation corresponds to the specific enthalpy of methanol in its vapour state at constant pressure. The calculations for all other specific enthalpies (!! ! !!" ) are carried out in the same fashion and are summarised in Table 2.1.2. Equation 2.1.8 is solved using equations 2.1.3 and 2.1.7; where !! and !! denote final and initial temperatures respectively. !! (2.1.8)
!!!!!!!!!!!!!!!!!!!!!! !

Substituting in known constants ! , ! , ! and ! for vapourised methane from literature.

! ! !"!!"!!"!! !" ! !"!!"!!"!! ! !!!"#!!"!! !" ! ! !" ! !!!"#!!"!! !" ! ! !!!""#!!"!! !" ! ! ! ! !!!""#!!"!! !" !
!

!!

!!!! !! !!! !"

! !!!!!!!!"!!" !" ! ! ! ! !!!!!!!!"!!" !" !

!

! !! ! !!!"#$% kJ mol-1 Department of Chemical Engineering 2013/14

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Individual Design of the Vapour Recovery System Charlie Lower Group 6

Table 2.1.2. Input and Output flowrates and calculated Specific Enthalpies of each component in the process. -1 -1 -1 -1 Component Physical State !!" [kmol s ] !!"# [kmol s ] !!" [J kmol ] !!"# [kmol s ] CH4 Vapour 1.23258 0.94350 1.23088 0.94350 CH4 Liquid 0.00170 0 CO2 Vapour 0.38572 0.96608 0.38197 0.96608 CO2 Liquid 0.00376 0 CO Vapour 0.20608 0.73051 0.20602 0.73051 CO Liquid 0.00006 0 H2 Vapour 1.85084 0.72143 1.85062 0.72143 H2 Liquid 0.00022 0 N2 Vapour 0.24133 0.72898 0.24119 0.72898 N2 Liquid 0.00015 0 H 2O Vapour 0.00392 0.84798 H 2O Liquid 0.04943 1.8550 0.04550 0 CH3OH Vapour 0.07381 1.20110 CH3OH Liquid 0.33076 2.1595 0.25695 0

It is now possible to calculate the cooling flowrate of the condenser as all necessary input and output flowrates and specific enthalpies are known. Recalling equation 2.1.2;
! ! !! !
!"#

!! !! !
!"

!! !!

! ! !!!"!#$ ! !!!"#$% ! !!!"#$% ! !!!""#$ ! !!!"#"$ ! !!!"#$% ! !!!"#!$ ! !!!"#$% ! !!!"#$$ ! !!!"#$# ! !!!"#"$ ! !!!""# ! !!!!"#$ ! !!!"#" ! !!!"#$$ ! !!!"#$% ! !!!"#$% ! !!!""#$ ! !!!"#"! ! !!!"#$% ! !!!"#$% ! !!!"#$% ! !!!"##$ ! !!!"#$# ! !!!!"#$ ! !!!"#$! ! !!!!"#$% ! !!!"##"! ! !!!!"#$!%" ! !!!!"#$%% ! ! ! !! ! !!"!#!!"

i.e. Heat is to be removed from the condenser at a rate of 8289 kW After simulating the process using the ASPEN process modeling software, the results give the cooling rate of the condenser to be 8949 kW. This is reassuring as this means manual calculations and computer-generated results only differ by approximately 7.3%. For consistency and ease of manipulation, ASPEN results will be used from this point onwards which confirms that the cooling flowrate of the condenser is 8949 kW.

2.2 Sizing
In order to size the condenser, the surface area available for heat transfer must be calculated. This is achieved using equation 2.2.1 (Felder et al. 2000, p.347). Where ! is the heat duty, ! is the heat transfer coefficient, !! is the surface temperature, !! is the surrounding temperature and ! is the desired surface area. Note that the surrounding temperature corresponds to ambient conditions of 25 oC and 1 bar.
!!!!!!!!!!!!!!!!!! ! ! !"#"$$$! ! ! ! ! !! ! !! !"#$ !" ! !" ! !! !

(2.2.1)

! ! ! !"#!!"!! !

The condenser is classified as a shell-and-tube heat exchanger. There are various models of such heat exchangers, for this process a fixed-tube model is to be used, shown in figure 2.2.1. Choice of tube inside-diameter, length and pitch was selected from literature (Peters et al. 2003, p.242) for similar scale and design current industrial production plants. Subsequently, these are 0.0254 m, 4.88 m and 0.0254 m square pitch respectively. The tubes will be made from Carbon Steel and the shell from Stainless Steel. To calculate the number of tubes, !! , required for the known surface area of heat transfer, equation 2.2.2 is used. Where !! is the tube outside-diameter and ! is tube length.
!!!!!!!!!!!!!!!! ! ! ! !"#!!"#!! ! ! !"#!!"# !!! ! ! !!!"#$!! !!!!!!

(2.2.2)

Therefore, the number of tubes required for sufficient cooling in the condenser is 368.! Department of Chemical Engineering 2013/14

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Individual Design of the Vapour Recovery System Charlie Lower Group 6

Figure 2.2.1. Cross-sectional drawing of the fixed-plate shell-and-tube condenser (NPTEL, 2012, p.6).

2.3 Equipment and Installation Costs

The purchase cost, or capital cost of the condenser can be found graphically as a function of the surface area. Figure 6-5 (Peters et al. 2003, p.242) illustrates how the purchase cost of a carbon steel shell-and-tube heat exchanger with identical dimensions (tube outside-diameter, pitch classification and size and tube length). From this graph, the purchase cost is estimated at 19000. However, to achieve a more accurate estimation of purchase price a scaling factor is used combined with the suitable cost index. Using equation 2.3.1 (Peters et al. 2003, p.242). also known as the six-tenths factor rule. ! denotes the ratio of capacities of the condenser in year b to year a, or in this case 2013 to 2000. ! represents the ratio of the cost indexes. The value of 729.68 (Unknown, 2008) was calculated by extrapolating the gradient of the slope. The value of 394.1 was taken directly from Table 6-2 (Peters et al, 2003, p.238).
!!"#$!! ! !!"#$!! !" !!! ! !"#!!" !"" !!! ! !"### ! !"#$%!!" !"#!! !"

(2.3.1)

Therefore the capital cost of the condenser for 2013 is 59000. The installation cost of the condenser is be calculated simply as a percentage of the capital cost. Table 6-5 (Peters et al. 2003, p.242) states that the installation cost for a heat exchanger is 60% of the capital cost. Therefore the installation cost of the condenser is 35400.

2.4 Operating Costs

The operating cost of the condenser is simply the cost of the cooling water needed as a continuous supply to the condenser. In order to calculate this, the cost of supplied cooling water is calculated as a function of the volumetric flowrate. First, a simple mass balance is carried out over the condenser.
VAPOURS 4774 t day
-1

VAPFLASH 5574 t day

-1

Condenser

COOLING WATER -8949 kW

LIQREC 800 t day

-1

Figure 2.4.1. Schematic flowchart of mass balance including cooling water stream over the condenser.

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Individual Design of the Vapour Recovery System Charlie Lower Group 6

Figure 2.4.1 illustrates that the cooling water flowrate is independent of other streams entering and exiting the condenser i.e. the cooling water inlet and outlet flowrates are equal. In order to determine the volumetric flowrate of the cooling water, the relationship between the specific heat capacity, heat flowrate, density and temperature difference needs to be found. Equation 2.4.1 adapted from literature (Felder et al. 2000, p.243) demonstrates this relationship where ! is the desired volumetric flowrate. The design brief specifies that cooling water is supplied at 25 0C and 1 bar for 0.065 m-3. (2.4.1) !
!! !!! !"#"!!"!! !! ! ! !!!"##$!!! ! !! !!!"# !"!! !!! !!!! !""" !"!!!! !!"!! !!

Multiplying the volumetric flowrate by the supply price gives;

!!!"##$!!"!!"! ! !!!!""#!! !! ! !"#$!!! !!" !!

The annual operating cost of the condenser subject to the cooling water flowrate supply is 175k yr-1.

Conclusion
After completing the design of the vapour recovery system for the large-scale production of methanol, a greater and more detailed insight to the plant operation and economics was achieved. It was found that the use of a fixedplate shell-and-tube heat exchanger performing as a condenser, made from carbon-steel tubes and stainless-steel shell is deemed as a suitable choice for the vapour recovery system. The condenser is to be placed before the splitter of the purge and recycle streams to ensure maximum possible treatment of the entrained liquids in the flashed vapours. Heat is to be removed at a rate of 8949 kW, which provides an operating cost of 175k per annum. Other costs include capital purchase of the condenser at 59k and its installation of 35.4k.

Nomenclature
! !! ! !! ! !! ! !! !! !!" !!"#$ !! !!"#$ !! !! !! !!! ! !! !! ! !! !! ! ! ! ! !
!"#

!
!"

Surface Area [m ] Specific Heat Capacity Constants [-] -1 o -1 Specific Heat Capacity [J kg C ] -1 o -1 Specific Heat Capacity component i [J kg C ] Equipment Cost Year a [] Equipment Cost Year b [] Tube Outside-Diameter [m] Kinetic Energy [kJ] Change in Potential Energy [kJ] -1 Heat [kJ s ] Specific Enthalpy component i [W] Change in Enthalpy [W] Tube Length [m] -1 Molar Flowrate component i [kmol s ] Number of Tubes [-] 3 -1 Volumetric Flowrate [m s ] Heat Duty [W] Cooling Rate [W] -3 Density [kg m ] Sum out, Sum in [-] Temperature [ C]
o

!! !! !! !! !! ! ! ! ! ! ! !! !" !" !" !" !" !! !" !" !"

Outside Temperature [ C] o Surface Temperature [ C] o Initial Temperature [ C] o Final Temperature [ C] o Temperature Change [ C] Shaft Work [kJ] Ratio of Equipment Capacity [-] Ratio of Cost Index [-] Shell Shell Nozzle/Branch Stationary Tube Sheet Channel/Stationary Head Channel Nozzle/Branch Tube Tie Rods and Spacers Baffles Pass Partition Instrument Connection Expansion Bellows Support Saddles

References
Atkins P., De Paula J. (2010). Atkins' Physical Chemistry. 9th ed. Oxford: Oxford University Press. Felder R. M., Rousseau R. W. (2000). Elementary Principles Of Chemical Engineering. 3rd ed. New York: John Wiley & Sons. NPTEL. (2012). Process Design of Heat Exchanger. Chemical Engineering Design. 2 (1), Perry R. H., Green D. W. (2007). Perry's Chemical Engineers' Handbook. 8th ed. New York: McGraw-Hill. Peters M. S., Timmerhaus K.D. & West R. E. (2003). Plant Design and Economics for Chemical Engineers. 5th ed. Singapore: McGraw-Hill. Sinnott R. K. (1999). Coulson & Richardson's Chemical Engineering Volume 6. Oxford: Butterworth-Heinemann. Unknown. (2008). Plant Cost Index. Journal of Chemical Engineering. September (1),

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Resume (Equipment Specification Data)

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