School of Chemical & Biomedical Engineering Nanyang Technological University

AY2012/2013 CH4701 Final Year Design Project Cumene Plant Design Group 13
Group Members Bee Sui Chan Lim Ye Chiek Goh Chern Chiat Jeanette Hong May Hurn Soon Wei Jian Tan Ming Feng Tham Wai Lap Tong Kok Wah Matriculation No. U0920483D U0920454G U0923366F U0920486F U0922921E U0922022F U0920457J U0920472J

TABLE OF CONTENTS
TABLE OF CONTENTS ...................................................................................................................................................................... i LIST OF TA BLES................................................................................................................................................................................. ii LIST OF FIGURES ............................................................................................................................................................................... ii EXECUTIVE SUMMARY................................................................................................................................................................. iii SECTION 1.0 PROCESS DESIGN A ND SIMULATION .................................................................................................... 1

1.1 Reaction Kinetics ..1 1.2 Thermodynamic Package Validation1 1.3 Process Description..2

SECTION 2.0

OPTIMIZATION OF DESIGN VA RIA BLES .............................................................................................. 2

2.1 Classification of Dominant and Local Design Variables .....2 2.2 Dominant Variable Economic Trade-Offs ...3 2.3 Optimization of Dominant Design Variables ...4 2.4 Optimization of Local Design Variables ..6

SECTION 3.0

HEAT INTEGRA TION ..................................................................................................................................... 8

3.1 Determination of Energy Requirements and T min ..8 3.2 Development of Heat Exchanger Network ...9 3.3 Other Considerations in Development of Heat Exchanger Network .10 3.4 Economic Comparison of Stage 2 and 3....11

SECTION 4.0

DETAILED DESIGN OF MAIN REACTOR ............................................................................................. 12

4.1 Reactor Design Parameters .12

SECTION 5.0

SAFETY, HEA LTH, AND ENVIRONM ENT ............................................................................................ 13

5.1 Fire and Explosion Assessment ..13 5.2 Chemical Exposure Assessment .14 5.3 Environmental Assessment .14 5.4 General Safety M easures ....15 5.5 Considerations for Non-Steady State Plant Operation...16 5.6 Hazard and Operability Study (HAZOP) for M ain Reactor ...19

SECTION 6.0 SECTION 7.0

RECOMMENDATIONS ................................................................................................................................. 22 CONCLUSION.................................................................................................................................................. 22

REFERENCES......................................................................................................................................................................................A APPENDIX............................................................................................................................................................................................ B

LIST OF TABLES
Table 1 Table 2 Table 3 Table 4 Table 5 Table 6 Table 7 : List of plant-wide design variables and respective categorizat ion as dominant/local ........................................... 3 : Economic co mparison between stage 2 and 3 ............................................................................................................ 11 : Justificat ions for choice reactor design parameters ................................................................................................... 12 : General process flow conditions for the main reactor ............................................................................................... 13 : F&EI values of main process units with corresponding degree of hazard and main risk factor ........................ 13 : General hazards of raw materials and products for cumene manufacture ............................................................. 14 : HAZOP table for main reactor ...................................................................................................................................... 20

Table A 1: Equipment Design Parameters, Capital and Energy Costs for Economic Optimum.B Table A 2: Equipment Sizing, Cost Correlations, and Unit Price Data a.C Table A 3: Stream Table for Final Design ..D

LIST OF FIGURES
Figure 1: Temperature vs benzene fract ion for saturated liquid and gas phase of benzene-cumene system......................... 1 Figure 2: Profit vs main reactor pressure........................................................................................................................................... 3 Figure 3: Profit vs main reactor temperature .................................................................................................................................... 3 Figure 4: Profit vs total benzene ......................................................................................................................................................... 4 Figure 5: Profit vs main reactor volu me ............................................................................................................................................ 4 Figure 6: Profit vs main reactor volu me at different pressures ...................................................................................................... 5 Figure 7: Profit vs reactor volume at d ifferent temperatures ......................................................................................................... 5 Figure 8 Profit vs total benzene at different reactor volu mes ........................................................................................................ 5 Figure 9: Profit vs column 2 (T-101) cu mene fractions in distillate stream ................................................................................ 6 Figure 10: Pro fit vs transalkylator pressure at different temperatures .......................................................................................... 7 Figure 11: Pro fit vs transalkylator volu me at d ifferent B/DIPB rat ios ......................................................................................... 7 Figure 12: Total annualized cost vs min imu m temperature d ifference ........................................................................................ 9 Figure 13: Co mposite curve of hot and cold streams ...................................................................................................................... 9 Figure 14: Heat exchanger network design to meet minimu m energy requirements.............................................................. 10 Figure 15: Finalized heat exchanger network ................................................................................................................................. 11 Figure 16: Contribution of various unit operations to total capital cost for stage 2 & 3 ......................................................... 12 Figure 17 : Contribution of various unit operations to total energy cost for stage 2 & 3........................................................ 12 Figure 18: Typical configuration of a natural draft spray tower.................................................................................................. 15 Figure 19: HAZOP schemat ic fo r main reactor and associated boiler ....................................................................................... 19

ii

EXECUTIVE SUMMARY
The goal of this project is to design and optimize a cu mene production plant with an output of 200,000 tons per year or 231.12 kilo moles per hour. Cu mene which is used in the manufacturing o f phenol, nylon-6,6 and resins, is produced from the alkylat ion of benzene with propylene over an acid catalyst. An undesirable side reaction occurs where cu mene is further alky lated to di-isopropyl benzene (DIPB) by propylene. Section 1 of this report further discusses the detailed reaction kinetics that take place. Also discussed is the choice of a suitable thermodynamic package as an important input needed for co mputer simu lation using Aspen HYSYS. A detailed process description for the final plant design as shown in the inserted process flow diagram is included at the end of the section. Section 2 deals with the dominant and local design variables that are thus classified based on their impact on economic profit. Optimization is done with the purpose of obtaining the maximu m econo mic profit that is technically feasible. The design of the plant was done in 3 stages; Stage 1 involved identifying and optimizing the dominant design variables without DIPB recycle to extinction, which led to Stage 2 where a DIPB recycle stream and init ial heat integration were added. Stage 3 was focused on improving energy efficiency by using heat integration methods to further modify the Stage 2 design. In this report, only the results from Stage 2 and 3 are d iscussed. The dominant variables identified are the main reactor temperature, pressure and volume, and the total amount of benzene fed to the main reactor. These variables have the greatest effect on plant economics as they affect propylene conversion and thus raw material costs that form the bulk o f expenditure. The optimized variables for the main reactor were found to be inlet temperature of 300 C, pressure of 30 bar and volume of 51 m3 , using a total benzene flow rate of 335 kg mo le/hr (B/P ratio o f 1.36). Local variables revolve around specificat ions for the distillation colu mns and transalkylator in the DIPB recycle loop. Though local variables are of less significance in co mparison to dominant variab les, they were also optimized as their total sum contributed to a large part of capital and operating costs. Section 3 delves into the approach used to determine the min imu m temperature difference, T min between the hot and cold streams for heat integration. A Tmin of 20C corresponding to the min imu m total annualized cost (TAC) was obtained using the Aspen Energy Analy zer. Pairing of process streams and heat exchanger network design were then developed and shown in the form of grid diagrams. A co mparison of Stage 2 and 3 econo mics and steam consumption was done to quantify the benefits of the imp lemented heat integration. Section 4 describes the considerations for detailed engineering design of the main reactor. In general, the reactor consists of a multi-tubular packed bed that utilizes shell cooling which is linked to a steam generating boiler. It was designed in a similar way to a shell-and-tube heat exchanger using a triangular pitch layout. The mechanical drawing of the reactor is inserted in this report. Safety, health, and environmental concerns are addressed in Section 5. Fire and exp losion and chemical exposure analysis were conducted using Dow indices to grade the degree of hazards associated with major p rocess units. The main reactor and propylene storage tank were identified as process units with the highest risk po tential due to several risk factors. Env iron mental hazards identified include flare emissions and hot water disposal. To prevent and mitigate these hazards, general safety measures were outlined. Special safety procedures involved in the commissioning, start-up, shut-down and emergency shut-down of the plant were also discussed. Finally, a separate Hazard and Operability Study was conducted on the main reactor to ensure its safe operation, which is of greatest concern as it is operated at high temperatures and pressures that may lead to a reaction runaway.

iii

SECTION 1.0
1.1

PROCESS DESIGN AND SIMULATION

Reaction Kinetics
The main reaction for our process is shown in (1), where p ropylene reacts with benzene over an acid catalyst

to produce cumene. Cu mene is then further alky lated by propylene in side reaction (2) which produces diisopropylbenzene (DIPB), an undesirable side product. Other side reactions that involve trace impurities are not considered in this study. Both reactions (1) and (2) are exothermic. It is known that the activation energy of side reaction (2) is higher than (1), hence operation at higher temperature will favor the side -reaction and reduce the singlepass selectivity. In order to achieve an overall select ivity of 100%, a third, mildly endothermic reaction (3) is designed to take place in the transalkylator to convert any DIPB back to the cumene, indicat ing a need of recycling DIPB to extinction in the process loop. The relevant reaction kinetics as shown below are applied in the simulat ion along with specified catalyst properties and range of reaction. (1) (2) (3) ( )

1.2

Thermodynamic Package Validation

The accuracy of a process simulat ion outcome greatly depends on the thermodynamic models chosen. Hence,

the thermodynamic package for our process was carefully studied based on graphical comparison. The Peng -Robinson (PR) EOS model [1] and NRTL model [2] have been used in previous studies of the same p rocess and were selected to do a comparison with experimental data fro m DECHEMA. Th is was done by plotting a temperature versus composition (T xy ) graph for the three pairs of heavy key and light key co mponents of the respective distillat ion colu mns using VLE data fro m DECHEMA. Those values obtained from HYSYS simu lation that using PR and NRTL models are under the same physical conditions. Figure 1 shows that the PR model results in data closest to experimental values for the benzene-cumene system in Co lu mn 2, indicating higher accuracy for appro ximat ion of real conditions. Similar results were obtained fro m the other pairs of propylene-benzene and cumene-DIPB. Th is result also corresponds to Carlsons recommendation which indicates that PR or SRK is the most suitable one for modeling a non-polar real mixture [3]. Therefo re, the PR model was chosen as the basis used in HYSYS simulation.
Figure 1: Temperature vs benzene fraction for saturated liquid and gas phase of benzene-cumene system

1.3

Process Description
Fresh propylene consisting of 95 mol% propylene and 5 mol% propane stored as pressurized liquid is mixed

with the benzene stream, wh ich consists of pure and recycled ben zene. The liquid mixture at high pressure and lo w temperature (37.43C, 31.95 bar) is heated up by heat exchangers (E-100, E-101) and 1 heater (E-102). Subsequently, it is divided into 2 streams that are vaporized by heat exchanger (E-103) and vaporizer (E-104) respectively. The saturated vapor streams are then comb ined and heated by another 2 heat exchangers (E-105, E-106) and furnace (H100) to achieve the desired reactor feed inlet temperature of 300C and pressure of 30 bar. The reactant stream enters the vertical, mult i-tubular packed bed reactor (R-100) fro m the top and exits at the bottom. A catalyzed, exothermic reaction occurs that achieves a high propylene conversion rate. As it enters the reactor, the process stream is initially heated up by the circulat ing shell-side flu id (Dowtherm A) to kick-start the reaction, after which the process stream temperature rises due to heat produced from the exothermic reaction. The temperature is controlled to be below 400C to prevent catalyst deactivation by subsequent heat removal by Dowtherm A, wh ich is circulated co-currently with the process stream at a high flow rate. The heated Dowtherm A that exits the reactor is used to generate high pressure steam by heating up boiler feed water in an external bo iler (E -107). The cooled Dowtherm A is then returned to the reactor shell at the desired temperature. The product stream fro m the reactor is cooled by the feed -effluent heat exchanger (FEHE, E-106) and divided into 2 streams that are cooled to saturated liquid by heat exchanger (E-105) and 1 condenser (E-108) respectively. The saturated liquid streams are co mbined and further co oled by 2 heat exchangers (E-109, E-103) consecutively. The pressure of the process stream is then reduced by a pressure reducing valve before it is fed as a liquid to the 3 distillation columns for separation. The first column (T-100) distills over propylene and propane gas as top prod ucts which are flared, while the bottom stream in liquid phase is mixed with the transalkylator outlet stream. This mixed stream is then cooled by heat exchanger (E-100) before being fed to the second distillation colu mn (T -101). The distillate of the second column (T101) that is rich in benzene is split into a benzene recycle stream that rejoins the fresh benzene as feed to the main reactor and a benzene feed stream to the transalky lator, which consists of a small fract ion of the total benzene d istillate. The bottom product is fed to the third column (T-102) after being cooled by cooler (E-114). The cu mene product with purity of 99.9 mo l% and less than 0.03 mo l% of DIPB is recovered as the distillate in T-102, and subsequently cooled by cooler (E-117) before being stored. Meanwhile, the bottom DIPB product is mixed with the benzene stream fro m the second column (T-101) as mentioned previously. The benzene-DIPB mixture is then heated by the main reactor e ffluent in heat exchanger (E-109) and a heater (E-118) befo re being fed to a single tube, adiabatic transalkylator (R -101). In R-101, a mildly endothermic, transalkylation reaction produces a product stream rich in cu mene which is cooled by the reactant stream in heat exchanger (E-101). This stream is mixed with the bottom product of the first column (T -100) as mentioned above, thus completing the DIPB recycle loop.

SECTION 2.0
2.1

OPTIMIZATION OF DESIGN VARIABLES

Classification of Dominant and Local Design Variables

The identification of plant-wide degrees of freedom allowed the listing of different design variables as shown

in Tab le 1 below. The economic impact o f d ifferent variables was studied by obtaining plots for profit, J versus the respective variables for Stage 2 of the plant design. Do minant variab les were classified as those which caused a change in J that was greater than $0.05 mil upon its variation, whereas local variab les caused a change of less than $0.01 mil.

For all studies, the production rate was maintained at 200 000 tons per annum with 1% tolerance and the benzene to propylene ratio (B/P) at the reactor feed stream was adjusted by controlling the total amount of benzene in the reactor feed mixture.
Table 1: List of plant-wide design variables and respective categorization as dominant/local

Design variables Main reactor pressure (Main P) Main reactor temperature (Main T) Benzene to Propylene ratio for feed to reactor (B/P ratio) Main reactor volume (Main V) Main reactor length to diameter ratio (L/D ratio) Column operating pressure Column impurity specifications Feed stage location of columns Transalkylator temperature (Trans T) Transalkylator pressure (Trans P) Transalkylator volume (Trans V) Transalkylator L/D ratio Benzene to DIPB ratio (B/DIPB ratio)

Category: Dominant/local Dominant Dominant Dominant Dominant Local Local Local Local Local Local Local Local Local

Impact on J Change of J > $0.05 millions

Change of J < $0.01millions

2.2

Dominant Variable Economic Trade -Offs

The engineering design trade-offs for each dominant variab le are shown in Figure 2-5 belo w. Plant profit is

calculated by: Profit per annum, J ($/yr) = Revenue Raw material costs TAC + Steam credit (4) Total annualized cost, TAC ($/yr) = (Total capital cost/3 + Total energy cost per year); 3-year payback period (5)

Figure 3: Profit vs main reactor pressure

Figure 2: Profit vs main reactor temperature

Figure 2 shows the impact of main reactor pressure on J. For this study, the main reactor temperature, volume and total benzene in reactor feed mixture we re set at 320o C, 50m3 and 380 kg mo le/hr respectively. As pressure was increased fro m 25 to 32bar, the total conversion of propylene in main reactor increased from 92% to 98%, while cumene selectivity remained high and almost constant at 96%. Th is caused the raw material cost to decrease fro m $58.37 mil to $57.66 mil. The total annualized cost (TAC) increased, but in a smaller extent fro m $5.98 mil to $6.15 mil, mainly due to increase in the capital and energy costs of the furnace and BFW heat exchanger. The decrease of raw material cost outweighed the increase in TAC, resulting in increased J. Figure 3 shows the impact of main reactor temperature on J. For this study, the main reactor pressure, volume and total benzene in reactor feed mixture were set at 30 bar, 50 m3 and 380 kg mole/hr respectively. As temperature increased fro m 300 to 330o C, total propylene conversion and cumene single-pass selectivity remained high

and almost unchanged, both at around 97%, because the reactor maximu m temperature was maintained around 399400o C by adjusting the shell-side fluid in let temperature. Hence, raw material cost remained almost unchanged at $57.70 mil. However, TA C increased fro m $59.02 mil to $63.18 mil due to main ly due to increase in capital and energy costs of the furnace and BFW heat exchanger. Therefore, J decreased by approximately $0.3 mil over the entire range of study. Figure 4 shows the impact of total benzene in reactor feed mixture on J. For this study, the main reactor temperature, p ressure and volume were set at 300o C, 30 bar, and 50 m3 respectively. As total benzene in the feed mixtu re increased from 300 to 380 kg mo le/hr (B/P ratio increased fro m 1.12 to 1.55), total conversion of propylene increased fro m 95% and slowly achieved a maximu m value of 97%. Init ially, raw material cost decreased fro m $58.06 mil due to increased conversion, but eventually achieved a min imu m value of $57.76 mil at maximu m conversion. Cu mene single-pass selectivity also increased fro m 94% to 96% as increasing excess benzene
Figure 4: Profit vs total benzene

consumed propylene in the main reaction. Meanwhile, TA C

increased linearly fro m $5.64 mil to $5.87 mil, mainly due to increased capital and energy costs of the vaporizer, FEHE and benzene recycle line. The J value was dominated by decrease of raw material cost at first, but this was eventually outweighed by the increased TAC, causing J to first increase and then decrease. Figure 5 shows the impact of main reactor volu me on J. For th is study, the main reactor temperature, pressure and total benzene in mixture were set at 300o C, 30 bar and 340 kg mole/hr. Reactor tube length was set at 15 m in order to achieve the aspect ratio range of 5-10. As volu me increased fro m 35 m3 to 70 m3 by increasing the number of tubes, total conversion of propylene gradually increased from 93% to a maximu m of 98% due to increased residence time, whereas cumene single-pass selectivity remained high and almost unchanged at 96%. This was reflected by raw material cost that gradually decreased from $58.22mil to a constant value of
Figure 5: Profit vs main reactor volume

$57.57 mil. Meanwhile, TA C increased almost linearly fro m

$57.48 mil to $64.23 mil due to increase in reactor capital cost and furnace capital and energy cost. Hence, J was first increased by savings in raw material cost before decreasing due to increased TAC.

2.3

Optimization of Dominant Design Variables

The dominant variables were optimized first as they have the greates t effect on plant economics. Their

resulting optimal values formed the base case for subsequent optimization of local design variables

Figure 6 shows the optimization main

J vs main reactor volume at different pressures
46.10
J, $ Millions 46.00 45.90 45.80 45.70

reactor pressure. The reactor temperature and total benzene in feed mixture we re set at 300o C and 340 kg mole/hr. Cu mene single-pass selectivity remained high at around 96%. For fixed reactor volu mes of 40 m3 to 57 m3 , J increased with increased pressure due to increased propylene conversion and decreased raw material cost. However, as maximu m conversion was approached, the raw material cost savings gradually

45.60
45.50

27 bar
35

29 bar
65

30 bar
75

became constant. Further increase in pressure would result in higher J, but incurs higher risk of reactor overpressure, fire and explosion. Therefore, 30 bar was chosen as the optimal pressure. Figure 7 shows the optimization of main

45 55 Main reactor volume, V (m 3 )

Figure 6: Profit vs main reactor volume at different pressures

J, $Millions

46.30 46.20 46.10 46.00 45.90 45.80

J vs m ain reactor volume at different tem peratures

reactor feed temperature. The reactor p ressure and total

T 320

T 300

T 310

benzene in feed mixtu re were set at 30 bar and 340 kg mole/hr. Cu mene single-pass selectivity remained high at around 96%. At smaller volu mes of 30 m3 to 37 m3 that were constrained by shorter residence times , higher temperatures resulted in higher J, since raw material cost savings due to increased convers ion dominated over the increase in energy costs. However, when residence time was further increased with volu me,

45.70
25 35 45 55 65 Main reactor volume, V (m3)

maximu m conversions could be achieved at lower temperatures, thus saving on energy costs without sacrificing raw material cost savings. Hence, the lower

Figure 8: Profit vs reactor volume at different temperatures

o

limit of the catalyst operating range, 300 C was chosen as the optimal temperature. Based on the optimal temperature, 300C and pressure, 30 bar, that were limited due to react ion constraints, the total benzene in the reactor feed mixtu re was varied for different reactor volu mes. Fro m the previous studies shown above, it was known that optimu m conditions were appro ximately 50 m3 for reactor volu me and 340 kg mole/hr for total benzene flow rate. Hence, the reactor volu me and total benzene flow rate were varied at smaller intervals for greater Reactor volume (m )
(kgmole/hr) 3

accuracy. Figure 8 shows the three determining plots that gave the optimal parameters for reactor volu me: 51 m3 (746 tubes at 15 m tube length) and total ben zene: 335 kgmole/hr (B/P ratio of 1.36).

Figure 7 Profit vs total benzene at different reactor volumes

2.4
2.4.1

Optimization of Local Design Variables

Optimization of columns All 3 colu mns were designed using the short-cut distillat ion column in HYSYS with the reflu x ratio specified

as 1.5 times of minimu m reflu x and the total number of trays as 3 t imes of the min imu m. Colu mn d iameters we re sized according to Fairs method, whereas other tray, sieve and weir sizing parameters were taken fro m industrial ru les of thumb. Co lu mn purity specificat ion, operating pressure and feed position were variables that were considered in the column design. The effect of purity specifications for both the product streams of colu mn 1 (T-100) and the top stream of column 2 (T-101) were studied together since they are consecutively lin ked. The specifications for the bottom stream of T-101and the top stream of colu mn 3 (T -102) were already set to meet the cu mene product requirements and cannot be further optimized. Hence, actual variables were the benzene impurity fraction in the d istillate and the propane impu rity fraction in the bottoms for T-100, the cu mene impurity fraction in the distillate for T-101, and the cu mene impu rity fraction in the bottoms for T-102.

46.20 46.10

J vs T-101 Distillate - Cumene Impurities

J ,($ Millions/yr)

46.00 45.90 45.80 45.70 45.60 45.50 0 0.01 0.02 0.03 0.04 0.05 0.06 T-101 Condenser Cumene Fraction 0.07 0.08 0.09 0.1
T-100 Prop Frac 0.001;Ben Frac 0.001 T-100 Prop Frac 0.025;Ben Frac 0.001 T-100 Prop Frac 0.01;Ben Frac 0.1 T-100 Prop Frac 0.01;Ben Frac 0.001 T-100 Prop Frac 0.001;Ben Frac 0.1 T-100 Prop Frac 0.025;Ben Frac 0.1

Figure 9: Profit vs column 2 (T-101) cumene fractions in distillate stream

Figure 9 shows J vs. cumene impurity specificat ions in T-101 for various specification co mbinations of T-100. For T-100, increased propane fraction at the bottom stream brings down with it more unconsumed propylene . This small amount of propylene is eventually recycled back to the main reactor and results in savings to raw material cost. However, mo re inert propane also accumulates in the system and increases heating costs. From this trade -off, an optimal value of 0.025 for the propane impurity fraction was obtained. The amount of be nzene in the distillate o f T -100 should be minimized to prevent loss of raw material. However, fo r increased benzene fraction in the distillate, the column can be operated at lower pressure which in turn reduces T-100 reboiler heat load. Thus, there is a tradeoff between benzene loss and reboiler duty, resulting in an optimal benzene impurity fraction of 0.01. For all T-100 co mb inations, a more stringent cumene impurity specification for T -101 resulted in higher J. Less cumene in the d istillate stream of T -101 prevents benzene fro m stripping down to the bottom product and thus affecting the purity of the cu mene product in T-102. Furthermore, the d istillate stream of T -101 is recycled back to the main reactor and also diverted to the transalkylator. A higher cu mene fraction in the feed stream to the reactor increases the vaporizer and T-100 reboiler duty. Thus, the cumene impurity fraction of T-101 was set at a stringent value of 0.001. In T-102, the cumene fraction at the bottom can be slightly relaxed to reduce colu mn height. Increased cumene impurity at the bottom brings down with it mo re DIPB that is subsequently channeled to the transalkylator. More

cumene feed to the transalkylator would typically decrease the equilibriu m conversion, but in this case the effect is offset by increasing the amount of benzene that is entering the transalkylator fro m T -101. This ultimately results in more DIPB converted back to cumene and savings in raw material costs. However, increasing the cumene fraction in the bottom stream increases condenser duty as more energy is needed to condense more cu mene vapor. This trade-off results in a minimum TAC corresponding to an optimal cumene fraction of 0.01. The operating pressure of T-101 and T-102 were specified at low pressures in the range of 1.5-2.5 bar to achieve easier separation and to min imize reboiler duty. The optimu m pressure of T-100 was found to be at a higher pressure of 7.5 bar as the benefit fro m reduced reboiler duty was offset by benzene loss in the distillate strea m. The feed position for T-100, T-101 and T-102 are at the 6th , 10th , and 23rd plate respectively, each corresponding to minimum reboiler duty in their respective columns. 2.4.2 Opti mization of transalkylator Local variables identified for the transalkylator that was operated in liquid phase were operating temperature, pressure, volume, and feed B/DIPB ratio. The optimizat ion of these variables is summarized in Figures 10 and 11 below.
J vs. transalkylator pressure at different temperatures (at 2.25m3 and B/DIPB ratio 2.0)

Figure 11: Profit vs transalkylator pressure at different temperatures

Figure 10: Profit vs transalkylator volume at different B/DIPB ratios

Figure 10 shows the optimizat ion of transalky lator pressure and temperature with respect to J. Increased pressure had little effect on equilibriu m conversion but incurred higher pump capital and energy costs. Meanwhile, equilibriu m conversion was increased by higher temperatures, wh ich resulted in raw material costs savings and reduced capital and energy costs for the condenser of column 2 and the reboiler of colu mn 3. Th is outweighed the increased in heating costs, leading to increased J at h igher temperatures. Optimal operating conditions were chosen to be 30 bar and 238o C. Pressures lower than 30 bar resulted in viscosity calculation issues as the reactants start to vaporize. The temperature was set slightly below 240o C to avoid catalyst deactivation. Figure 11 shows the optimizat ion of transalky lator volu me and different B/DIPB ratio s with respect to J. This study was conducted at the optimal pressure and temperature obtained earlier. Decreased B/DIPB rat io and increased volume of up to 2.75 m3 caused increased equilibriu m conversion, wh ich resulted in raw material costs savings and reduced capital and energy costs for the condenser of colu mn 2 and the reboiler of co lu mn 3 as mentioned

above. The B/DIPB rat io has to be at least 2.0 to prevent problems due to sticky flo w. Optima l B/ DIPB ratio and volume was chosen to be 2.0 and 2.75 m3 respectively for the highest J. Further increase in volu me would only take up space and increase the reactor capital cost as equilibrium conversion reaches a maximu m at 88%. 2.4.3 Optimization of length-to-diameter aspect ratios Optimization of the main reactor and transalky lator L/ D ratio share the same approach. Using fixed optimal volumes, the d iameter of the reactor was varied and the corresponding tube length that achieved the desired volu me was calculated. The results showed that a longer design (higher L/D ratio) resulted in lower profit due to increased capital cost of the reactor. For the main reactor, an L/D rat io of 5-10 [4] for efficient heat transfer to appro ximate shelland-tube heat exchanger was used as a standard, whereas for the transalkylator, typical aspect ratios for single-tube plug flow reactors based on literature were in the range of 1-5 [5]. Hence, for both the main reactor and transalky lator, the minimum L/D ratios for standard industrial manufacture were chosen as approximately 5 and 1 respectively.

SECTION 3.0

HEAT INTEGRATION

Heat integration involved several steps with the aim to ach ieve minimu m energy requirement (M ER) with the least capital cost incurred. Started with determining MER, we proceeded to determine the minimu m t emperature difference (T min ), pinch temperatures and matching streams with considerations, then finally reducing the number of heat exchangers (HE) to achieve the final heat exchanger network (HEN) design.

3.1 3.1.1

Determination of Energy Requirements and T min MER determination

MER was calculated prior to the design of HEN. Selection and data extraction of major process streams were

essential steps for MER calculat ion. M ER value of 1.68 MW of excess heat available was obtained by the difference between the enthalpy of hot and cold streams [6].

3.1.2

Tmin determination

Energy Targeting: QHmin and QCmin of the process for a given T min were considered as the energy targets. A higher Tmin will incur higher energy costs as streams that are unable to be matched will need to be heated or cooled by utilities. Energy requirements affect the operating cost. Area Targeting: On the other hand, a lo wer T min will result in h igher heat exchanger cap ital costs due to a smaller temperature d ifference driving fo rce that would require greater network area to achieve the desire d heat exchange duty. This area is to the sum of all heat exchanger areas of each segment based on heat capacity with all heat availab le utilized and the calculat ion was made using th e Baths formula [7] as shown in equation 6 belo w, where Q is the amount of energy transferred at n-th interval and U is the heat transfer coefficient at n-th interval. As T min increases fro m 10C to 50C, the area decreases constantly from 837.5 to 484.9 m2 . The size of heat exchangers, heaters and coolers affect the capital cost.
( ) ..... (6)

There was a trade-off between utility requirements and heat exchanger area for vary ing Tmin. To co mpare the effect of operating vs. capital costs, a plot of TAC which totaled the operating and capi tal costs against Tmin was plotted as shown in Figure 12. Fro m the plot, we can see that from 10C to 20C of Tmin, TA C decreased as energy saving outweighed increased capital cost. Beyond 20C, capital cost outweighed utility savings and TAC increased. The optimal Tmin of 20C corresponding to the lowest TAC of $1.28 mil/yr was obtained before proceeding to exchanger network (HEN) design.

TAC vs Tmin
1.46 1.44 1.42 1.40 1.38 1.36 1.34 1.32 1.30 1.28 1.26
0 10 20 30 40 50 Tmin ( C)

400 350 Temperature (C)

Temperature vs Enthalpy
QH, min = 18.88

TAC ($ Mil /yr)

300 250
200 150 100 50 0
QC, min = 12.88

Cold Hot 0.00 20.00 40.00 60.00 Enthalpy ( x10 9 J/hr) 80.00

Figure 13: Total annualized cost vs minimum temperature difference

Figure 12: Composite curve of hot and cold streams

3.1.3

Pinch Temperature Analysis Hot and cold p inch temperatures of 183.7C and 163.7C were determined using HYSYS Energy Analy zer.

The pinch temperature(s), minimu m hot utility requirement (Q Hmin ) and min imu m co ld utility requirement (QC min ) were further verified manually using the Temperature Interval (TI) and Composite Curve (CC) method. Figure 13 shows the Composite Curves that consist of temperature-enthalpy profiles of heat availability ("hot composite curve") and heat demands (the "cold composite curve"). The minimu m energy target for the process was achieved by overlapping the hot and cold composite curves, separating them by T min of 20C. This overlap shows the maximu m process heat recovery possible, ind icating that the remaining heating and cooling needs are Q Hmin of 18.88x109 J/hr (5254 MW) and QCmin of 12.88x109 J/h (3579MW).

3.2

Development of Heat Exchanger Network

The problem was div ided at the pinch; each part designed separately starting at the pinch and moving away.

For pairing above pinch, CPC CPH and for belo w pinch, CPH CPC. By maximizing all exchanger loads, supplying external heating above the pinch, and external cooling below the pinch, the HEN design was comp leted as shown below in Figure 14.

Stream C1 Liq to 27 C2 Liq to 32 C3 Liq to 36 18 to 19

M CP H (kW/C (MW)

M CP H (kW/C) (MW)

183.7

101.5

40.7

2 0.132

0.132 183.7 127.9

2 68.8

32 1.915

183.7

168.1

1.915 167.8 3 167.6 1.404

6769 3.385

27 0.620
19 to 22 22 to 25

339.5 316.7 277.4 190.2 221.2 239.1 268.3

316.7 277.4 221.6

183.7 183.7 183.7 183.7 183.7 183.7 178.4 129.2

5

65 2.546 26 2.442 24 0.156 19 0.731 2 0.087

158.2

155.1 140.8 174.3 148.6 36.8

26 0.745 24 1.023 19 0.182 2 0.055 21 1.981

0.081

28 to 30 32 to 34 42 to 44

0.047
3 2
sa

8 to 11

163.7 168.9 54 2.190 204.1 7 1.216 22 2.157 2 0.117 34 0.987 300.0 238.0 192.8 231.7 181.7 200.2 184.8
4
sa

x1= 30.0 x2= 20.0 x3= 204.1 4.1 163.7 163.7 163.7 163.7

y1= 21.0 y2= 19.0 y3= 14.1

0
1

132.1 1.981 109.8 150.8 129.2 54 1.868

11 to 14

3 0.731

0.156

0.664

1.023

0.087 5 0.620

0.182

14 to 17

1 1.536 2 0.117

40 to 41 C1 Vap to 26 C2 Vap to 31 C3 Vap to 35

158.4

2 0.008

0.008

0.987 4265 3.067 221.2 3 220.6

8

220.5

163.7

2.829 1763 3.317 235.7 4 0.772

0.238 235.3 6 233.8 163.7

2.546

Figure 14: Heat exchanger network design to meet minimum energy requirements

3.3
3.3.1

Other Considerations in Development of Heat Exchanger Network

Stream matching considerations

Forbidden matches [8]: The condenser and reboiler streams were not allowed to be matched in heat exchange due to reasons of operability for start-up and control. These resulted in coolers and heaters that needed to be added to the 6 of the streams (C1 Vap to 26, C1 Liq to 27, C2 Vap to 31, C2 Liq to 32, C3 Vap to 35 and C3 Liq to 36) from the columns [9]. Imposing such criteria on our design affected the energy recovery of the network and resulted in an energy penalty of 5.692 MW from the existing MER system [6]. Stream 8 to 17 was segmented into 3 sections (8 to 11, 11 to 14, and 14 to 17): From source temperature of 36.8C to final target temperature of 300C, there was phase change involved for streams 11 to 14, as such there is a large variation in heat capacity across the phase change. By dividing this stream into 3 segments, a more accurate CP was achieved compared to taking the average CP, resulting in a more accurate HEN designed. Tmin violation was better avoided and calculation of heat transfer coefficients was simplified. Stream split of 11 to 14 between 129.2C to 204.1C: The stream split was necessary to ensure saturated condition in all outlet streams. [10] 3.3.2 Minimizing number of heat exchanger units Calculated N min =16, and the orig inal HEN Nact =23 indicated there are 7 independent heat paths. These paths were then broken by transferring duty fro m s mall cooler or heater to nearby heat exchanger, further reducing the number of heater and cooler required for the system. The network temperatures were checked whenever a path was broken to ensure no Tmin v iolations. The T min for the Final HEN Design (Figure 15) after earlier considerations and minimization of is around 25 C.

10

M CP H (kW/C) (MW) C1 Liq to 27 2.2 0.132 Stream C2 Liq to 32 32.4 1.915 3.385 0.620 2.546 339.5 y1= 0.0 19 to 22 64.8 316.7 277.4 316.71

101.5 127.9 168.1

3 4 5

40.7 0.132 1.915 3.385 68.8 167.6

C3 Liq to 36 6769.3 18 to 19 27.3

1
22 to 25 28 to 30 32 to 34 42 to 44 8 to 11 11 to 14 26.0 23.9 19.4 1.6 21.4 54.1 3.187 1.179 0.912 0.143 1.981 4.058 204.1 277.4 190.2 221.2 239.1 272.6 1.009

y2= 0.0 155.1 140.8

2
0.912

174.3 148.6 129.2 98.4 92 36.8 129.2

2
0.660

6
1.179

1
3.186

x1= 40.8 x2= 13.3 204.1

0.143

1
14 to 17 40 to 41 C1 Vap to 26 22.5 1.6 33.9 2.157 0.125 0.987 3.067 3.317 300.0 272.4 0.997

3.1

3
238.0 192.8 221.2 235.7 0.987 3.067 3.317 0.620

2
1.536

4
0.125

158.4 163.7 220.5 233.8

3
4

C2 Vap to 31 4265.0 C3 Vap to 35 1762.9

Figure 15: Finalized heat exchanger network

3.4

Economic Comparison of Stage 2 and 3

The effect of heat integration was evaluated by economic comparison as shown in Table 2 below.
Table 2: Economic comparison between stage 2 and 3

Criteria Raw material cost ($/yr) Product sales ($/yr) Conversion (%) Selectivity (%) Energy consumption per kg product (kJ/kg) Steam credit ($/yr) Total energy cost ($/yr) Total capital cost ($) Total annualized cost, TAC ($/yr) Profit, J ($/yr)

Stage 3 % increase / decrease 57,780,965 108,178,200 97.38 100% overall selectivity due to DIPB recycle to extinction 0.0191 0.0106 -44.47 1,861,230 1,369,356 -26.43 1,952,721 748,619 -61.66 7,202,558 7,341,905 +1.93 6,214,803 4,565,277 -26.54 46,043,661 47,201,314 +2.51

Stage 2

After heat integration, steam credit was reduced by 26.4% as heat was recovered directly and less steam was produced. Energy costs were reduced by 44.5% due to increased energy efficiency. Total capital cost increased by 1.93% mainly due the addition of more heat exchangers. Since savings in energy costs far outweighed the additional capital costs incurred, TAC was reduced by 26.5% and J was increased by 2.51% ($1.16 mil).

11

Contribution of Various Unit Operations to Total Capital Cost for Stage 2 and 3

Stage 2 Capital
Stage 2

Stage 3 Capital

Figure 16 shows that the contribution of heat exchangers increased from 23% to 24% in the total capital cost as the replacement of fro m the original 2 coolers and 1

Stage 3

Reactor Columns 45% Pumps Transalkylator

23% 8.70546

24%
45%

1%
6%

1%
6%

heater with 5 heat exchangers was more costly.

0.39379 87.87644
25% 24%

Heat Exchangers, Heaters & Coolers

$7,202,557/yr

$7,341,905/yr

Figure 16: Contribution of various unit operations to total capital cost for stage 2 & 3

Figure 17 shows that the contribution of heat exchangers in total energy cost dropped from

Contribution of Various Unit Operations to Total Energy Cost for Stage 2 and 3 Stage 2
1%

Stage 2 Energy

Stage 2 Energy
Stage 3
11%

Columns

50% to 11%. Such great savings were mainly due to increased heat

49%

Pumps

efficiency of the new HEN design. In Stage 3, colu mns became the

50%
88% Heat Exchangers, Heaters & Coolers

highest in energy consumption as most of the reboilers were still using high pressure steam for operation.

1%

$3,813,950/yr

$2,117,975/yr

Figure 17 : Contribution of various unit operations to total energy cost for stage 2 & 3

SECTION 4.0
4.1

DETAILED DESIGN OF MAIN REACTOR

Reactor Design Parameters

Description A multi-tubular, packed bed reactor with cooling was chosen to approximate a shell-and-tube heat exchanger design for efficient heat removal. Smaller tube diameters provide larger surface area for heat transfer but increase pressure drop an d capital cost for a fixed reactor volume. 3 inch (7.62 x 10-2 m) outer diameter tubes were chosen to optimize capital cost, pressure drop and heat removal. Triangular pitch layout was chosen as it can accommodate more tubes than a square pattern. This layout also produces high turbulence and hence a higher overall heat transfer coefficient. [11] The reactor was placed vertically to facilitate loading and removal of solid catalysts in the packed bed. An aspect ratio of 4.85 (L=15.00 m, D=3.09 m) was chosen to approximate typical heat exchanger aspect ratios of 5-10. Further increase in length was constrained by standard manufacturing limits and stability of vertical configuration. [5] Standard segmental baffles with 25% baffle cut were chosen. Optimum baffle spacing of 0.625 m (approximately one-fifth of the shell diameter) was chosen to promote cross -flow between shell-fluid and process tubes while ensuring the maximum allowable pressure drop of 300 kPa (0.1 times of operating pressure) was not exceeded. [12] Co-current flow between the process stream and shell side fluid (Dowtherm A) was chosen as Dowtherm is initially used as a heating medium to kick-start the reaction, after which it acts as a cooling medium to remove heat from the exothermic reaction. The area about the shell inlet nozzle was enlarged to reduce Dowtherm velocity and resulting impingement of tubes. A flared shell inlet nozzle and an impingement plate were also used to further reduce impingement effects. [12]

Table 3: Justifications for choice reactor design parameters

Design choice Reactor type

Tube diameter

Pitch layout Configuration Length-todiameter aspect ratio Baffle cut and spacing

Fluid flow

Impingement

12

Table 4: General process flow conditions for the main reactor

Flow Condition Process stream inlet temperature Process stream outlet temperature Shell-side fluid inlet temperature Shell-side fluid outlet temperature Tube-side pressure drop Shell-side baffled pressure drop Heat transfer area Heat duty Tube side heat-transfer coefficient Shell side heat-transfer coefficient Overall heat-transfer coefficient Velocity in tubes Nominal Re in tubes Velocity in shell Nominal Re in shell

Value 300.0 C (573.15 K) 339.2 C (612.35 K) 330.2 C (603.35 K) 335.0 C (608.15 K) 8.51 x 103 Pa 283.98 x 103 Pa 2678.77 m2 5580 x 103 W 70.18 W/(m2 .K) 1214.46 W/(m2 .K) 13.34 W/(m2 .K) 6.55 x 10-2 m/s 13460.59 (Turbulent) 1.58 m/s 386967.93 (Turbulent)

Calculation methods Tube-side pressure drop: Erguns equation for packed beds Tube-side heat transfer coefficient: Gn ielinskis correlation [13] fo r packed beds to calculate Nu for turbulent flow reg ime. Heat transfer coefficient determined from obtained Nu.

Shell-side pressure drop and heat-transfer coefficient: Kerns method [4] Overall heat transfer coefficient: Equation 12.2 of Chemical Engineering Design, 5th edition [4]

SECTION 5.0
5.1

SAFETY, HEALTH, AND ENVIRONMENT

Fire and Explosion Assessment

The Dow Fire and Exp losion Index (F&EI) [14] was used to gauge the risk potential of a fire or exp losion

event occurring in several major process units as shown in Table 5 below.

Table 5: F&EI values of main process units with corresponding degree of hazard and main risk fact or

Process Unit Main reactor Propylene storage tank Furnace Benzene storage tank

F&EI 168 156 135 106

Degree of Hazard Severe Heavy Heavy Intermediate

Main risk factor Exothermic reaction involving flammable vapors (400C, 30 bar) Storage of liquefied flammable gas under compression (25C, 15 bar) Fired heating that is potential ignition source (300C, 30 bar) Storage of flammable liquid at atmospheric conditions (25C, 1 bar)

As shown in Table 5, the main reactor has the highest fire or explosion risk potential and is further discussed using the Hazard and Operab ility Study (HAZOP) in Sect ion 5.6. Using bow-tie risk analysis for the top event of reactor cooling loss, the safeguards imp lemented reduced the estimated frequency of a dangerous reaction runaway to only once in 1481 years, thus minimizing the risk of such an occurrence. The propylene storage facility poses a heavy hazard as leaked propylene may form a vapor cloud that risks ignition by open flames or sparks. Therefore, efficient ventilation is necessary to dissipate the vapor concentration to below flammable levels. The furnace is a potential ignition source for flammab le mixtures. Hence, there needs to be adequate spacing between the fu rnace and other process units, especially the storage tanks where large quantities of chemicals are kept. Ign ition sources should be eliminated in classified hazardous areas where flammable materials are stored. Co mpared to the other process units, the benzene storage facility has the lo west risk potential as it exists as a liquid at at mospheric conditions, and leakages can be contained more effect ively. Overall, this quick analysis highlights a few major risk factors such as elevated process conditions, inherent chemical properties, quantity of flammable material, and distance of ignit ion point to possible leak sources.

13

5.2

Chemical Exposure Assessment

The general hazards of chemicals involved in cu mene production, all of which are hydrocarbons, are extracted

from their Material Safety Data Sheets and summarized below.

Table 6: General hazards of raw materials and products for cumene manufacture

Chemical & Formula Name Benzene (C6 H6 ) Propylene (C3 H6 ) Propane (C3 H8 )

*Flammability Rating 3 4 4

**OEL (ppm) 8hrs (TWA) 1 500 1000 15mins (STEL) 5 N/A N/A General Hazards Carcinogenic effect; Toxic to blood, bone marrow, central nervous system (CNS), liver and urinary system As asphyxiant; May cause unconsciousness, nausea and depression of all the senses As asphyxiant; May cause damage to the nervous system, heart and central nervous system

Cumene 3 25 50 Toxic to lungs, the nervous system and mucous membranes (C9 H12 ) DIPB Vapors and liquid are irritating to eyes, respiratory tract and 2 0.5 2.5 (C12 H18 ) mucous membrane; Cause headache and unconsciousness *Based on NFPA 704 standards **Occupational Exposure Limits Among the substances involved, benzene is the most hazardous to human health as it is a carcinogen. To prevent toxic effects, Personal Protection Equip ment (PPE) such as clean suits and masks are to be worn. For asphyxiants such as propylene and propane, it is essential that workers obtain proper Permit -To-Work (PTW) before entering confined spaces that may contain such gases. The PTW can only be issued after ensuring o xygen and toxic gas levels in the confined space are within acceptable limits. If necessary, workers should be equipped with PPE such as breathing apparatus and gas monitoring devices. The Dow Chemical Exposure Index (CEI) [15] was used to investigate a few release scenarios and determine the largest airborne quantity resulting from such a release. The hazard distance was subsequently determined based on the respective chemical Emergency Response Planning Guidelines (ERPG) values. Generally, storage in vapor form or pressurized tank is the most significant in terms of CEI value and corresponding hazard distance. Co mparable to the fire and explosion hazard analysis, release scenarios involving the main reactor and liquefied propylene storage tanks both resulted in the most severe hazards, with maximu m hazard distances of up to 10 km. This further enfo rces the need to put in p lace stringent preventive measures for these two process units. In summary, personnel must ensure that all work being carried out in the chemical plant is in accordance to Standard Operating Procedures (SOP) and in co mpliance with government rules and regulations to ensure the wellbeing of workers.

5.3

Environmental Assessment
Two major environ mental hazards that are of concern fo r our process are emissions due to flaring o f waste

gases and disposal of heated water. The co mposition of the waste gas stream is appro ximately 71.16% propane, 24.44% propylene, and 4.40% ben zene for a total mass flow rate of 768.83 kg/hr. Products of flaring mainly consist of carbon dio xide and water vapor, with so me amounts of carbon mono xide (CO), carbon particles (soot), unburned hydrocarbons, and other partially altered hydrocarbons that are releas ed as emissions. Nitrogen o xides (NO x) are also emitted due to oxidation of at mospheric nit rogen. Industrial emissions contribute to air pollution and need to be kept below the published standards set by the Singapore National Environmental Agency (NEA) [16]. In order to reduce emissions, part of the waste gas can be used to supplement natural gas burned in other process units such as the furnace. This adds fuel credit to the overall process and reduces the amount of hydrocarbons that are flared. Flares sho uld be operated at maximu m co mbustion efficiency with min imu m excess air. High combustion efficiencies of up to 98% are

14

able to reduce the amount of intermediate products formed fro m inco mplete co mbustion, resulting in less than 2% of hydrocarbon and CO emissions. Furthermore, usage of excess air is minimized to reduce the amount of NO x produced and to optimize fuel consumption [17]. Next, the disposal of heated water is a major concern since water is used in large quantities to control the temperature of processes in cumene production. The hot water effluent consists of heated cooling water discharged from condensers and coolers, and boiler b low down water. Direct discharge of heated water into a public sewer or water course can potentially increase the temperature of natural aquatic environments and cause harm to marine life. According to NEA regulat ions, the temperature of trade effluent needs to be cooled down to below 45C before discharge into any public sewer [16]. Cooling towers may be used to reduce the temperature of heated water befo re discharge. There are many categories of cooling towers, one of which is the natural draught spray tower [18] as shown in Figure 18. In general, the environmental impact of any chemical process needs to be carefully weighed and minimized in order to maintain the health of our ecosystem and achieve sustainable development in the long term.
Figure 18: Typical configuration of a natural draft spray tower.

5.4

General Safety Measures

General safety measures are very important in protecting personnel or the environ ment fro m hazardous events

that could stem fro m failure in equip ment design, containment and storage, poor risk management systems o r inexperience of employees. 5.4.1 Preventive measures

Design of equipment - Process and storage vessels were designed at higher set values than normal maximu m operating conditions, resulting in greater tolerance to disturbances in the system. For examp le, the reactor vessel thickness was designed to withstand conditions up to 428C and 35 bar, providing a tolerance range of 28C and 5 bar above normal operating conditions of 400C and 30 bar. Additional allowances were also made for corrosion and wind -load for vertically placed vessels. Inventory minimization - The storage of raw materials and products should be optimized to reduce the availability of materials for a fire, exp losion or chemical release, while ensuring sufficient supply for continuous plant operation. For a fixed production rate, inventory minimizat ion should be b alanced against the need for higher transportation frequency by analyzing the associated cost and risk factors. Equipment spacing - The plant layout of process units should take into consideration the radius of exposure resulting fro m a hazardous event. Adequate spacing is needed to prevent escalation of a loss event due to a domino effect in adjacent units and to provide access to emergency equipment. When limited by space constraints, other methods such as fireproofing of steel structures, barricading control rooms and tanks, etc. may be employed [19]. Redundancy systems Back-up equip ment is provided for essential services such as the reactor cooling circulation pump, remote control valves and emergency power supply. This great ly reduces the frequenc y of hazardous events due to equipment failure.

15

Maintenance & training Regular maintenance of process control equipment is needed to increase their reliab ility. Similarly, regular training of personnel ensures their co mpliance to standard operating proc edures and raises awareness of potential hazards. 5.4.2 Mitigation measures

Drainage and containment In general, flammab le liquids are stored in tanks that contain less than 15,000 gallons (56.78 m3 ) to reduce the amount of flammab le material that wou ld be involved in a spill [20]. Dikes are designed to direct the spill to an impounding basin. De -inventory or evacuation of liquid fro m leaking equipment to a secondary storage tank can also be used to reduce and terminate leakage. Dispersion Process areas should be designed to have good natural or mechanical ventilat ion to prevent the aggregation of flammable or to xic vapors that may lead to a hazardous event. Inert gases such as nitrogen or carbon dio xide can be used to lower the concentration of oxygen needed for combustion. Vents can be directed to a flare system that burns off the leaked gases. Emergency response Emergency response efforts should be focused on preventing further escalation and human exposure. Mitigation systems such as automatic shutdown, water curtains, and foam may be imp lemented. Early warning systems and evacuation plans that are regularly rehearsed can reduce the risk of public exposure. If human exposures do occur, quick response and medical preparedness are crucial to prevent loss of lives.

5.5
5.5.1

Considerations for Non-Steady State Plant Operation

Dynamic operation Dynamic operation contributes to more than 5 times of chemical industry accidents in comparison to normal

steady state operation, main ly due to operators unfamiliar with these infrequent activities and necessity of parameter deviation [21]. Thus, general safety considerations for commissioning, normal start-up, shut-down, and emergency shut-down activities are important and will be briefly described in this section. 5.5.2 Commissioning Co mmissioning after co mplet ion of mechanical construction or after turnaround requires a functional check of the auxiliary items, utilit ies, and equip ment to ensure that process units will perform as intended. It starts with physical inspection of auxiliary items such as pipe supports, insulation and protective coating of high temperature equipment to ensure they are manufactured and assembled as specified, followed by verification of ut ility capacity to provide cooling water, lo w pressure steam, Dowtherm A and boiler feed water for all heat transfer requirements. Subsequen tly, commissioning of equipment is performed by running inert materials such as water and inert gas through the units to examine operating limit stability and for possible leakage. The tested equipment and piping are subsequently cleaned and dried by purging with compatible inert gas before start-up. The final stage of commissioning focuses on safety precautions and control systems. Sensors, analyzers, interlocks, alarms, control loops system as illustrated in Figure 19 fo r the main reactor as well as other units are calibrated and inspected in this stage. Finally, a safety review checklist on all above items is performed. If all requirements are met, the plant is ready for start-up, otherwise modifications are implemented as required and the commissioning process is repeated. 5.5.3 Start-up Normal start-up of the plant is performed after co mmissioning where reactant materials are brought into service and monitored until processes run as normal by the end of start -up. During start-up, process parameters may

16

violate constraints valid for steady state operations. Thus, safeguarding elements such as interlocks are removed to avoid unreasonable shut-downs which in turn increase the risk of start-up. A co mp lex process network is bro ken down in several unit operations for simplicity during start-up operation. As a general procedure, the distillation colu mns (T100, T-101, T-102) are started up first as they consist of reversible unit operations which can be operated on a stand alone basis without any continuous feed. Feed is charged into the 3 colu mns and brought to operating conditions under total reflux until the units are ready to be put online [22]. Subsequently, for better control and inventory optimization, non -reversible unit operations, such as the main reactor are started up next. The reactor is charged with benzene and cu mene with is recycled over the entire process section including the reactor feed system, reactor, and recovery system. The recovery of benzene is driven to production state condition to ensure the recovery system can process the reactor effluent without significant process upsets once propylene is introduced into the reactor. The temperature of the reactor is controlled by heat exchange with Dowtherm A in the main reactor, whereas the reactor feed temperature is controlled by the pre-heater and furnace before stable heat integration co mes into place. Finally, the required amount of propylene in correct rat io to benzene is supplied continuously into the reactor as soon as the benzene flo w rate an d reactor feed temperature reach the target values in steady state operations. One concern during start-up is process runaway from expected trajectories. The dynamic behaviour of the process system is a function of init ial p rocess conditions, process distu rbances and the trajectories of the manipulated process variables. Thus, correct start-up conditions and sufficient control o f the man ipulated variables must be verified. Hazards present during the commissioning phase must be guarded against during start -up. In addition, the start-up phase is characterized by peak physical and physiological stress for operating personnel as extra physical activit ies and accurate observations are needed. 5.5.4 Shut-down Shut-down is a sequence of steps used to bring a chemical process from operational to non-operational status through a relatively short period of dynamic operation. In general the operational steps of shut -down include emptying, purging, cleaning, cooling and verifying the safety of the non -operational environ ment for maintenance personnel to work in. As an initiation step, the fresh feed to the main reactor is shut off, the ben zene recycled to the reactor fro m separation units will gradually decreased and finally ceased. For separation units, the reflu x flo w rate is adjusted proportionally with reduced feed flow rate. The reboiler is turned off first, followed by the condenser. All the liquid is then drained out from the colu mn and reflu x d ru m before being cooled to room temperature by flushing with inert nitrogen [23]. The decontamination process following shut-down common ly encounters a problem, which is the flammability and toxicity of process chemicals. As mention in Section 5.1, chemicals present in the process are all flammable, which poses a hazard when a mixtu re of these chemicals and air co me into contact with an ignition source. Hence, the decontamination process has to avoid flammable range operation and leakage using proper purge systems. Chemical inventory minimization is also considered during the shut-down process to make sure off-grade product is produced in the least amount. 5.5.5 Emergency shut-down Emergency shut-down differs fro m normal shutdown in that it is an unplanned shut -down caused by any of the critical process parameters exceeding its operating window, unexpected utilit ies failure, or equip ment failu re. These deviations can potentially trigger catastrophic consequence such as a fire and explosion. Thus, safety interlock systems,

17

such as emergency auto shut-down of the reactors during high and unnoticeable temperatures are present to avoid dangerous conditions. Safety interlocks in the reactor section of this project is a combination of manual shutdown valves and sophisticated computer systems that rely on signals from sensors and programmable logic controllers which control valves for shutdown. Events such as loss of power, loss of coolant, relief valve failure, reactor runaway and loss of reaction can trigger auto matic shut-down of the reactor. In general, if the failed equip ment can be bypassed individually fro m the normal process with redundant units, other operations may still be continued, but if it is a critical unit operation like the main reactor, it can t rigger the shut-down of the entire plant. Production will be resumed once the sudden shut-down is attended by proper investigation on the root causes of the emergency situation, and recommendations for preventing recurrence founded and implemented.

18

5.6

Hazard and Operability Study (HAZOP) for Main Reactor

Figure 19: HAZOP schematic for main reactor and associated boiler

19

19

Table 7: HAZOP table for main reactor

Project name: Section: Item 1A Study Node Reactor (process stream) 2. Ex cessiv e Dow therm flow (Refer to 2B) 3. Feed inlet temperature low due to heat loss along pipeline 4. Feed inlet temperature low due to failure of upstream heating operations 1B High 1. Dow therm inlet temperature high (Refer to 2E) 1a. Cataly st deactiv ation 1b. Possible reaction runaw ay 2. No/ Low Dow therm flow (Refer to 2A) 3. Feed inlet temperature high due to ov erheating upstream 4. Tube fouling 3. 4. " " 2. " 1a. Thermocouple activ ates high temperature alarm to alert operator 1b. Refer to safeguards of 2E 2a. Refer to safeguard 1B.1a 2b. Refer to safeguards of 2A 3a. Refer to safeguard 1B.1a 4a. Refer to safeguard 1B.1a 2a. Refer to recommendation 1B.1a 2b. Refer to recommendations of 2A 3a. Refer to recommendations 1B.1a 4a. Refer to recommendations1B.1a 4b. Anti-fouling material for tubes 4c. Regular tube-cleaning 1C High High 1. Failure of thermocouples or high temperature alarm sy stem 1. Reaction runaw ay leading to 1. Secondary temperature detector triggers automatic fire and ex plosion shutdow n sy stem 1a. Emergency procedures and drills 1b. Shutdow n of reactor 1c. Regular inspection on secondary temperature detector and automatic shutdow n sy stem 2. Failure of operator to notice high temperature 1D 1E Reactor (process stream) High 1. Feed inlet pressure high due to upstream pump fault Pressure Low 1. Feed inlet pressure low due to upstream pump fault 2. " 2. " 2a. Proper training of operator 2b. Refer to recommendations of 1C.1 1. Low conv ersion leading to w aste of raw materials 1. Reactor ov erpressure 1a. Pressure indicator alerts operator 1b. Upstream back up pump operates 1a. Upstream back up pump operates 1b. Pressure indicator activ ates high pressure alarm to alert operator containment sy stem 2. Tubes/ product outlet nozzle blocked 1F High High 1. Safety v alv e fails closed 2. " 2a. Refer to 1E.1b,c 1. Rupture disc (RD) burst, discharged materials flow to 2a. Refer to 1E.1b,c,d 1a. Regular inspection on rupture disc 1b. Emergency procedures & drills " 2a. Proper training of operator 2b. Refer to recommendations of 1F.1 1. Reaction runaw ay , ex plosion 2. Failure of operator to notice high pressure 2. " 2. 1a. Regular inspection on pressure indicator sy stem 1b. Regular inspection on pumps 1a. Regular inspection on pumps 1b. Regular inspection on pressure indicator and alarm sy stem 1c. Regular inspection on safety v alv e 4. " 4. Refer to safeguard 1A.1a 3. " Process Parameter Temperature Low Deviation CH4701 FYDP PFR-100 Potential Causes 1. Dow therm inlet temperature low (Refer to 2D) Process: Reference Drawing: Possible Consequences 1. Reaction quenched, low /no conv ersion 2. " Safeguards 1a. Reactor thermocouple activ ates low temperature indicator to alert operator 1b. Refer to safeguards of 2D 2a. Refer to safeguard 1A.1a 2b.Refer to safeguards of 2B 3. Refer to safeguard 1A.1a. Cumene Production Figure 19 Recommendations 1a. Regular inspection on reactor thermocouple and temperature indicator 1b. Refer to recommendations of 2D 2a. Refer to recommendation 1A.1a 2b.Refer to recommendations of 2B 3a. Refer to recommendation 1A.1a 3b. Install insulation on pipeline to reduce heat loss 4a. Refer to recommendation 1A.1a 4b. Install temperature controller on upstream heating units 1a. Regular inspection on thermocouples and alarm sy stem 1b. Refer to recommendations of 2E

1c. Safety v alv e (SV) opens, discharged materials flow to 1d. Reactor design to w ithstand high pressure

ov erpressure leading to fire and containment sy stem

20

20

1G

Flow

No/ Low

1. Automatic control v alv e (FCV 1) fails closed

1a. No reaction / Low cumene 1a. Manual v alv e 1 (MV1) in parallel open production rate 1b. Pressure build up before FCV 1 1b. Feed stream flow meter and flow indicator alert operator 2a. Refer to safeguard 1G.1b 2b. Pipe casing along feed line 3a. Upstream back up pump operates 3b. Refer to safeguard 1G.1b 1a. Manual v alv e (MV2) in series closed 1b. Refer to safegaurd 1G.1b

1a. Regular inspection on v alv es 1b. Regular inspection on feed stream flow meter and indicator

2. Feed supply pipe ruptures / leak

2. Raw materials release to atmosphere

2a. Refer to recommendation 1G.1b 2b. Regular inspection to ensure pipeline integrity 3a. Regular inspection on upstream feed pumps 3b. Refer to recommendation 1G.1b 1a. Refer to recommendations of1G.1

3. Upstream feed pump failure/fault 1H Flow High 1. Automatic control v alv e (FCV 1) fails open

3. Refer to 1G.1a 1a. Flooding of dow nstream unit operations 1b. Pressure build up at dow nstream sy stems

2. Upstream feed pump fault 2A Reactor cooling sy stem Flow No/ Low 1. Automatic control v alv e (FCV 2) fails closed 2. Dow therm circulating pump fault 3. Dow therm supply pipe fully / partially blocked 4. Dow therm supply pipe ruptures / leak

2.

"

2a. Upstream back up pump operates 2b. Refer to safeguard 1G.1b

2a. Regular inspection on upstream feed pumps 2b. Refer to recommendation 1G.1b 1a. Regular inspection on v alv es 1b. Regular inspection on flow meter and indicator 2a. Regular inspection on pumps 2b. Refer to recommendation 2A.1b 2a. Refer to recommendation 2A.1b 2b. Regular inspection to ensure pipeline integrity 3a. Refer to recommendation 2A.1b 3b. Regular inspection on containment sy stem 1a. Refer to recommendations 2A.1

1. Loss of cooling, temperature 1a. Manual Valv e (MV 3) in parallel open runaw ay 2. 3. 3a. Refer to 2A.1 3b. Release of Dow therm fluid to env ironment " " 1b. Dow therm pipeline flow meter and indicator alert operator 2a. Back up pump operates 2b. Refer to safeguard 2A.1b 3a. Refer to safeguard 2A.1b 3a. Refer to safeguard 2A.1b 3b. Containment sy stem 1a. Manual v alv e (MV 4) in series closes 1b. Refer to safeguard 2A.1b " 2a. Back up pump operates 2b. Refer to 2A.1b 1a. Check v alv e prev ents backflow

2B

High

1. Automatic control v alv e (FCV 2) fails open 2. Dow therm circulating pump fault

1. Reactor cools, conv ersion decreases 2.

2a. Regular inspection on pumps 2b. Refer to 2A.1b 1a.Regular inspection on check v alv e

2C

Rev erse

1. Backflow of Dow therm to reactor due to high backpressure

1. Possible temperature rise and reaction runaw ay

2D

Temperature

Low

1. BFW inlet flow ex cessiv ely high due to FCV 3 fails open 2. BFW inlet temperature low due to heat loss along pipeline

1. Reactor ov ercooling, low /no 1a. Manual Valv e (MV 6) in series closes conv ersion 2. " 1b. BFW flow meter and flow indicator alerts operator 2a. Insulation on pipeline to reduces heat loss

1a. Regular inspection on v alv es 1b. Regular inspection on BFW flow meter and indicator 2a. Regular inspection on pipeline insulation 1a. Regular inspection on v alv es 1b. Refer to recommendation 2D.1b 2a. Regular inspection on pumps 2b. Refer to recommendation 2D.1b temperature alarm sy stem

2E

High

1. BFW inlet low flow due to FCV 3 fails close 2. BFW no/low flow due to BFW supply pump failure/fault

1. Loss of cooling, temperature 1a. Manual Valv e (MV 5) in parallel open runaw ay 2. " " 1b. Refer to safeguard 2D.1b 2a. BFW supply back up pump operates 2b. Refer to safeguard 2D.1b indicator and alarm sy stem to alert operator

3. BFW inlet temperature high due to loss of temperature 3. control at BFW storage tank

3a. BFW storage tank themocouples activ ates temperature 3a. Regular inspection on BFW storage tank thermocouples and

21

21

SECTION 6.0

RECOMMENDATIONS

For fu rther study, a unit operation to separate propane from p ropylene may be included in the design in order to allo w recycling of propylene in the overall process. Potential separation methods include using extractive distillation with aqueous acetonitrile [24] or a hybrid adsorption-distillation process [25] among others. Heat integration can be improved by adjusting the column pressures to allow matching of condenser and reboiler streams in heat exchange. Based on current optimized conditions, stream matching of the condensers and reboilers was not possible due to temperature conditions. In addition, reactive d istillation is also a potential option to co mbine reaction and separation processes to reduce operating costs [1].

SECTION 7.0

CONCLUSION

This project was conducted in three stages to highlight the progression and improvement fro m the base model of a steady state cumene production plant. The base model also supported the identification of do minant and local variab les which were studied to yield optimal profit. The common trade-off encountered during the optimization of design variables was between raw material and total annualized costs. Raw material cost was affected by conversion and selectivity issues, whereas the total annualized cost was affected by capital and energy costs based on specified operating conditions. Introduction of the transalkylator in Stage 2 eliminated overall production of the DIPB by product, allowing further optimization of p rocess conditions to reduce reactant wastage and operating costs. Subsequent heat integration in Stage 3 utilized existing process streams to perform mutual heating and cooling operations, thus reducing reliance on utilit ies. The result was a reduction in total annualized costs of 26.5%, and a profit increment of 2.51% ($1.16 mil), with a final estimated profit of $47,201,314 per annum.

22

REFERENCES
[1] Ashok S. Pathak, San kalp Agarwal, Vivek Gera, Nitin Kaistha, Design an d Control of a Vapor-Phase Conventional Process and Reactive Distillation Process for Cumene Production, Ind. Eng. Chem. Res. 2011,50,33123326 [2] Luyben, W.L. Design and Control of the Cumene Process , Ind. Eng. Chem. Res.2010. 49,719-734 [3] Carlson E. C. Dont Gamble with Physical Properties for Simulations, Chemical Engineering Progress , 1996. [4] Sinnott R. K., Towler G., Chemical Engineering Design 5th ed. Elsevier, 2009. [5] Eigenberger G., Fixed Bed Reactors, Institut flir Chemische Verfa hrenstechnik, Universitiit Stuttgart, Stuttgart, Federal Republic of Germany. 2009<http://elib.uni-stuttgart.de/opus/volltexte/2009/4798/pdf/eig16.pdf> [6] Ian C. Kemp , Pinch Analysis and Process Integration, 2nd ed ., Elsevier Ltd, 2007. [7] Aspen Technology, Inc, Aspen Energy Analyzer Reference Guide, V7.1 , Burlington, MA., 2009. [8] Shenoy U. V. Heat Exchanger Network Synthesis: Process Optimization by Energy and Resource Analysis, Gulf Publishing Company, 1995. [9] Sloley Andrew W. Heat Integration Can Co mplicate Control. Sustainable Planet .(N.p.) 2010. <http://www.sustainableplant.com/2010/heat-integration-can-complicate-control/ > [10] Eaton, Ben A., et. al., The Predict ion of Flow Patterns, Liquid Ho ldup and Pressure Losses Occurring During Continuous Two-Phase Flow In Horizontal Pipelines, Journal of Petroleum Technology . V19,6, 1967. <http://www.onepetro.org/mslib/servlet/onepetropreview?id=00001525 > [11] Rajiv Mukherjee, Effectively Design Shell-and-Tube Heat Exchangers, Chemical Engineering Progress, 1998 [12] Richard L. S., Patrick M . B., et. al., Perrys Chemical Engineers Handbook, 8th ed, Chapter 11 , McGraw Hill Inc., 2008. [13]Koning G. W . Heat and Mass Transport in Tubular Packed Bed Reactor s at Reacting and Non -reacting Conditions, Twente University Press, 2002. [14] Scheffler N. E., Heit zig W. R., et. al. Dows Fire & Explosion Index Hazard Classification Guide, 7 th ed ., American Institute of Chemical Engineers (AIChE), 1994. [15] Dauwe R., Marshall J. T., Thayer J. C., et. al. Dows Chemical Exposure Index Guide, First Edition , American Institute of Chemical Engineers (AIChE), 1994. [16] Code of Practice on Pollution Control, Third Edition . National Environ ment Agency (NEA), 2000.<http://app2.nea.gov.sg/data/cmsresource/20090401728616415372.pdf > [17] Industrial Flares. United States Environment Protection Agency (EPA) http://www.epa.gov/ttnchie1/ap42/ch13/final/c13s05.pdf [18] Dobney P. W. AIRAH DA17 Cooling Towers . Australian Institute of Refrigerat ion, Air-Conditioning & Heating Incorporated, 2009. <http://mct.hugedev.com/wp-content/uploads/2010/09/Cooling-Tower-Types-Table-2.1.pdf > [19] Plant Layout . Health & Safety Executive (HSE) <http://www.hse.gov.uk/comah/sragtech/techmeasplantlay.htm > [20] Branan C. R. Rules of Thumb for Chemical Engineers , Gulf Professional Publishing. 2011. [21] Centre for Chemical Process Safety, Guidelines for Safe Process Operations and Maintenance . NY: A merican Institute of Chemical Engineers. 1995. [22] Verwijs J. W., Kosters P. H., et. al. Reactor Operating Procedures for Startup of Continuously -Operated Chemical Plants . AIChE Journal Vol. 41, No. 1. 1995. [23] Verwijs J. W., H. van den Berg and Westerterp K. R.Startup of an Industrial Adiabatic Tubular Reactor, AIChE Journal . Vol. 38 No. 12. 1992. [24] Bo Liao, Zhigang Lei, et. al., New process for separating propylene and propane by extractive distillation with aqueous acetonitrile. Chemical Engineering Journal , V84. 2001. <http://www.sciencedirect.com/science/article/pii/S1385894701001759 > [25] Ghosh T. K., Hon- Da Lin & Hines A. L., Hybrid adsorption -distillation process for separating propane and propylene, Ind. Eng. Chem. Res., 1993. <http://pubs.acs.org/doi/abs/10.1021/ie00022a024 >

APPENDIX
Table A 1: Equipment Design Parameters, Capital and Energy Costs for Economic Optimum

Heat Exchanger E-100 E-101 E-103 E-105 E-106 E-109 Cooler E-107 E-108 (Condenser) E-114 E-117 Heater E-102 E-104 (Vaporizer) E-118

Area (m2 ) 80.97 8.22 310.11 321.24 231.77 5.66 Area (m2 ) 327.15 53.36 17.24 122.39 Area (m2 ) 117.57 52.41 8.36

TEMA type BFU AEL BFU AEL AEL AEL

Duty (kW) 1853.68 149.76 3203.87 1553.68 605.60 142.49

U (kW/K.m2 ) 1175.81 1175.81 999.59 295.23 240.14 1175.81 U (kW/K.m2 ) 0.57 0.57 0.57 0.57 U (kW/K.m2 ) 0.57 0.57 0.57

Minimum T (K) 66.89 25.64 26.07 43.68 39.04 44.61 Minimum T (K) 30.00 30.00 30.00 30.00 Minimum T (K) 30.00 30.00 30.00

Energy Cost ($) -

Capital Cost ($) 126,907.38 28,688.03 303,787.36 310,832.42 251,402.27 22,507.93 Capital Cost ($) 314,538.55 96,783.22 46,437.63 166,000.05 Capital Cost ($) 161,724.75 95,650.73 29,009.98

Total Cost ($) 126,907.38 28,688.03 303,787.36 310,832.42 251,402.27 22,507.93 Total Cost ($/yr) 314,538.55 96,783.22 46,437.63 166,000.05 Total Cost ($/yr) 171,153.69 319,001.84 29,173.57 198,965.07

Duty (kW) 5574.71 909.33 293.81 2085.45 *Duty (kW) 38.07 (2003.38) 893.02 (4134.98) 0.54 (142.46)

SteamCredit ($/yr) 966,132.28 105,356.42 36,782.76 261,084.09 Energy Cost ($/yr) 9,428.94 223,351.11 163.59

H-100 161.72 0.00 (2755.67) 0.57 30.00 0.00 198,965.07 (Furnace) *Value for duty in brackets is duty required for startup, equipment sizing is based on this duty. Condenser E-111 E-113 E-116 Area (m2 ) 10.67 149.96 283.73 Area (m2 ) 56.16 175.61 194.08 Duty(kW) 126.38 1775.93 3360.14 U (kW/K.m2 ) 0.85 0.85 0.85 U (kW/K.m2 ) 0.57 0.57 0.57 Minimum T (K) 13.90 13.90 13.90 Minimum T (K) 30.00 30.00 30.00 Tray spacing (m) 0.61 0.61 0.55 Energy Cost ($/yr) 529.87 7393.48 13944.55 Energy Cost($/yr) 98,584.42 209,444.41 224,112.53 Capital Cost ($) 33995.82 189437.73 286729.19 Capital Cost ($) 243,845.28 762,437.78 842,621.90

Total Cost ($/yr) 34,525.69 196,831.21 300,673.74 Total Cost ($/yr) 342,429.70 971,882.19 1,066,734.43

Reboiler E-110 E-112 E-115

Duty(kW) 957.03 2992.37 3307.08

Column T-100 T-101 T-102

Height (m) 5.12 16.09 22.68

Diameter (m) 1.22 1.52 1.83

Number of Tray 8 25 32

Feed tray 6 10 23

Reflux Ratio 1.91 1.66 0.37

Capital Cost ($) 80,748.14 256,621.45 410,345.11

Reactor R-100 R-101

Volume (m3 ) 51.00 2.75

Length (m) 15 3.38

Diameter (m) 3.09 0.97

Catalyst Weight (kg) 25500.00 1375.00

Catalyst Cost ($) 2,040,000.00 55,000.00

Capital Cost ($) 1,233,314.12 35,701.99

Pump P-100 P-101 P-102 P-103 P-104

Type Centrifugal Centrifugal Centrifugal Centrifugal Centrifugal

Power (kW) 23.65 12.80 1.80 1.48 10.21

Design Pressure (kPa) 31.75 31.75 30.00 30.00 31.75

Cost ($/yr) 125,535.12 107,730.93 49,794.88 44,204.75 101,156.77

Table A 2: Equipment Sizing, Cost Correlations, and Unit Price Dataa

Equipment Tower

Parameter Diameter Height Capital cost Heat transfer coefficient Differential temperature Capital cost Heat transfer coefficient Differential temperature Capital cost Heat transfer coefficient Differential temperature Capital cost Capital cost Catalyst cost b Bulk density Porosity

Calculation Method

Tray sizing utility (Fair's method) Trays with 2 ft spacing, 20% extra height for sump $17640(D)1.066 (L)0.802 (D,L in m) 0.852 kW/(K.m2 ) Condenser 13.9 C $7296 (area)0.65 0.568 kW/(K.m2 ) Reboiler, heater, 30.0 C vaporizer, cooler $7296 (area)0.65 Respective overall heat-transfer coefficient, U Heat exchangers Respective Tmin $7296 (area)0.65 $7296 (area)0.65 $20 kg -1 Reactor, transalkylator 1000 kg/m3 (main reactor), 500 kg/m3 (transalkylator) 0.5 $Cp(1.8 + 1.51Fp2.4) log(Cp) = 3.5793 + 0.3208 log(P) + 0.0285 log(P)2 Pump Capital cost Fp = 0.1682 + 0.3466 log(Q) + 0.4841 log(Q)2 outlet pressure(P) in barg, duty(Q) in kW Propylene feed (5% impure) $9 kmol-1 Raw material/products Benzene feed $25 kmol-1 Cumene product $65 kmol-1 Steam $9.83 GJ-1 Utilities Cooling water $0.16 GJ-1 Electricity $16.8 GJ-1 $4.83 GJ-1 (from coolers) Steam credit $6.67 GJ-1 (from R-100) a b Taken from Pathak et. al. [1] Catalyst price included in capital cost. All areas in m2 .

Table A 3: Stream Table for Final Design

Stream Number Temp C Pressure bar Vapor fraction Total kmol/h Total kg/h Flowrates kmol/h Propylene Propane Benzene Cumene DIPB Stream Number Temp C Pressure bar Vapor fraction Total kmol/h Total kg/h Flowrates kmol/h Propylene Propane Benzene Cumene DIPB Stream Number Temp C Pressure bar Vapor fraction Total kmol/h Total kg/h Flowrates kmol/h Propylene Propane Benzene Cumene DIPB 1 25.0 1.0 0.0 231.9 18111.8 0.00 0.00 231.88 0.00 0.00 19 318.0 29.7 1.0 351.3 36247.9 6.22 20.74 98.53 220.21 5.59 35-1 35.0 1.4 0.0 231.5 27812.8 0.00 0.00 0.24 231.15 0.07 2 26.5 31.8 0.0 231.9 18111.8 0.00 0.00 231.88 0.00 0.00 20-1 318.0 29.7 1.0 228.1 23532.9 4.04 13.47 63.97 142.96 3.63 35-2 35.0 1.0 0.0 231.5 27812.8 0.00 0.00 0.24 231.15 0.07 3 31.5 31.8 0.0 335.0 25803.8 2.30 8.36 324.23 0.10 0.00 20-2 318.0 29.7 1.0 123.2 12715.0 2.18 7.28 34.56 77.24 1.96 36 235.0 1.8 0.0 7.4 1192.0 0.00 0.00 0.00 0.07 7.29 4 31.5 31.8 0.0 335.0 25803.8 2.30 8.36 324.23 0.10 0.00 21-1 282.1 29.4 0.0 228.1 23532.9 4.04 13.47 63.97 142.96 3.63 37 236.8 30.0 0.0 7.4 1192.0 0.00 0.00 0.00 0.07 7.29 5 25.0 15.0 0.0 247.6 10443.4 235.20 12.38 0.00 0.00 0.00 21-2 282.7 29.6 0.0 123.2 12715.0 2.18 7.28 34.56 77.24 1.96 38 236.8 30.0 0.0 7.4 1192.0 0.00 0.00 0.00 0.07 7.29 6 27.0 31.8 0.0 247.6 10443.4 235.20 12.38 0.00 0.00 0.00 22 282.3 29.4 0.0 351.3 36247.9 6.22 20.74 98.53 220.21 5.59 39 147.0 30.0 0.0 23.6 2400.5 0.36 1.31 14.51 0.09 7.29 7 27.0 31.8 0.0 247.6 10443.4 235.20 12.38 0.00 0.00 0.00 23 277.7 29.0 0.0 351.3 36247.9 6.22 20.74 98.53 220.21 5.59 40 237.6 29.8 0.0 23.6 2400.5 0.36 1.31 14.51 0.09 7.29 8 31.3 31.8 0.0 582.6 36247.1 237.50 20.74 324.23 0.10 0.00 24 153.6 28.5 0.0 351.3 36247.9 6.22 20.74 98.53 220.21 5.59 41 238.0 29.7 0.0 23.6 2400.5 0.36 1.31 14.51 0.09 7.29 9 120.0 31.5 0.0 582.6 36247.1 237.50 20.74 324.23 0.10 0.00 25 154.0 7.8 0.0 351.3 36247.9 6.22 20.74 98.53 220.21 5.59 42 239.1 29.6 0.0 23.6 2400.5 0.36 1.31 8.99 11.13 1.77 10 126.1 31.3 0.0 582.6 36247.1 237.50 20.74 324.23 0.10 0.00 26 40.0 7.8 1.0 16.7 743.2 3.91 12.38 0.42 0.00 0.00 42* 239.1 29.6 0.0 23.6 2400.5 0.36 1.31 8.99 11.13 1.77 11 127.6 31.2 0.0 582.6 36247.1 237.50 20.74 324.23 0.10 0.00 26-1 29.6 1.0 1.0 16.7 743.2 3.91 12.38 0.42 0.00 0.00 43 145.6 29.2 0.0 23.6 2400.5 0.36 1.31 8.99 11.13 1.77 12-1 127.6 31.2 0.0 457.9 28492.4 186.69 16.31 254.87 0.08 0.00 27 189.5 7.9 0.0 334.6 35504.7 2.30 8.36 98.12 220.21 5.59 44 146.1 7.9 0.0 23.6 2400.5 0.36 1.31 8.99 11.13 1.77 12-2 127.6 31.2 0.0 124.6 7754.7 50.81 4.44 69.37 0.02 0.00 28 186.8 7.9 0.0 358.1 37905.2 2.66 9.68 107.10 231.34 7.36 45 41.2 2.2 0.0 16.2 1208.5 0.36 1.31 14.51 0.02 0.00 13-1 203.7 30.9 1.0 457.9 28492.4 186.69 16.31 254.87 0.08 0.00 29 106.1 7.4 0.0 358.1 37905.2 2.66 9.68 107.10 231.34 7.36 46 42.6 30.0 0.0 16.2 1208.5 0.36 1.31 14.51 0.02 0.00 13-2 203.9 31.1 1.0 124.6 7754.7 50.81 4.44 69.37 0.02 0.00 30 106.3 2.3 0.0 358.1 37905.2 2.66 9.68 107.10 231.34 7.36 47 42.6 30.0 0.0 16.2 1208.5 0.36 1.31 14.51 0.02 0.00 14 203.7 30.9 1.0 582.6 36247.1 237.50 20.74 324.23 0.10 0.00 31 41.2 2.2 0.0 119.3 8900.4 2.66 9.68 106.87 0.12 0.00 48 41.2 2.2 0.0 103.1 7691.9 2.30 8.36 92.35 0.10 0.00 15 274.3 30.5 1.0 582.6 36247.1 237.50 20.74 324.23 0.10 0.00 32 191.4 2.4 0.0 238.8 29004.7 0.00 0.00 0.24 231.22 7.36 49 42.7 31.8 0.0 103.1 7691.9 2.30 8.36 92.35 0.10 0.00 16 300.0 30.2 1.0 582.6 36247.1 237.50 20.74 324.23 0.10 0.00 33 175.8 2.3 0.0 238.8 29004.7 0.00 0.00 0.24 231.22 7.36 50 42.7 31.8 0.0 103.1 7691.9 2.30 8.36 92.35 0.10 0.00 17 300.0 30.2 1.0 582.6 36247.1 237.50 20.74 324.23 0.10 0.00 34 175.8 1.7 0.0 238.8 29004.7 0.00 0.00 0.24 231.22 7.36 50* 42.7 31.8 0.0 103.1 7691.9 2.30 8.36 92.35 0.10 0.00 18 339.0 30.1 1.0 351.3 36247.9 6.22 20.74 98.53 220.21 5.59 35 170.3 1.5 0.0 231.5 27812.8 0.00 0.00 0.24 231.15 0.07