CHE 210 – Final Project

December #, 2019
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CHE 210 – Final Project
Styrene Production

Executive Summary

The first step in optimizing the design of the plant was determining its value, in this case

the net present value (NPV) of the base case process. Determining the NPV required

calculation of the cost of equipment (mainly reactor) and raw materials. For the original

design, the NPV was -$64 million. As part of initial analysis, it was determined which

factors had the biggest impact on the value of the plant. The factors identified as the largest

contributors to the economics were the cost of raw materials and the Reactor Volume. To

provide a clear economic evaluation of the process, I considered on the impact of the key

design variables: Reactor Volume, Conversion, Temperature and Pressure. In this way,

comparing the equivalent annual operating cost obtained for each case it was determined

the better choice: Temperature 840 K, Pressure 1.5 bar and Conversion 0.7. The

comparison among different configurations was helped to determine which conditions

optimized yield and conversion, thereby reducing the cost in raw materials. Thus, I found

that a CSRT reactor operating at 840 K and 1.5 bar as the optimum while fitting the process

constraints with a conversion of 0.7.

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Table of Contents

Executive Summary:…………………………………………………………………….. 1

Introduction:…………………………………………………………………………….. .3

Brief History of Product …………………………………………………………………. .3

Process ……………………………………………………………………………………4-6

Overall Strategy …………………………………………………………………………. .6

Main Body: ……………………………………………………………………………… 7

Reactor Volume vs. Conversion …………………………………………………………. 7

Reactor Volume vs Temperature…………………………………………………………. 8

Reactor Volume vs Pressure …………………………………………………………….. .9

Profit vs Conversion …………………………………………………………………….. .10

Economic Analysis ……………………………………………………………………10-11

Appendix:………………………………………………………………………………... 10

Calculations ……………………………………………………………………… …...11-16

Excel Spreadsheets …………………………………………………………………….17-18

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Introduction

Styrene is the monomer used to make polystyrene, which has a multitude of uses, the most

common of which are in packaging and insulated Styrofoam beverage cups. Styrene is

produced by the dehydrogenation of ethylbenzene. There is very little ethylbenzene sold

commercially, because most ethylbenzene manufacturers convert it directly into styrene.

The start of process design begins with deciding what the process type will be. The next

step is developing a broad design concept and properly economic analysis. The present

project is focus on to perform a preliminary design and economic analysis for the styrene

plant. Styrene is the precursor to polystyrene, which is used in plastics, protective coatings,

polyesters, resins, and chemical intermediates. Styrene also can be used as the yeast-like

fungus Exophiala jeanselmei that can be used to treat air polluted with styrene. The IUPAC

name for styrene are Vinyl benzene, Cinnamene, Styrol, Phenylethene, Diarex HF 77,

Styrolene, Styropol, Vinylbenzene, Phenylethylene is an organic compound with the

chemical formula C6H5CH=CH2.

Figure 1. Main Reaction Process

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This derivative of benzene is a colourless oily liquid that evaporates easily and has a sweet

smell, although high concentrations have a less pleasant odour. Styrene is the precursor to

polystyrene and several copolymers. The chemical structure of the styrene is shown in the

figure 1.

The rate expression for the reaction to form the styrene is given as:

Where PEB, Pstyrene, and PH2 are the partial pressures of ethylbenzene, styrene, and H2 and

the equilibrium constant (in units of bar) is given as:

æ 32000 J/mol ö
K p = 3000exp ç - ÷
è RT ø

Where T is the absolute temperature (in K) and the rate constant k (in units of mol/L/s/bar)

is given as:

æ 62000 J/mol ö
k = 2x104 exp ç - ÷
è RT ø

Steam (H2O) is added to the feed to reduce the formation of coke (carbon) via the

reactions:

𝑪𝟔 𝑯𝟓 − 𝑪𝑯𝟐 𝑪𝑯𝟑 → 𝟖𝑪 + 𝟓𝑯𝟐

𝑪 + 𝟐𝑯𝟐 𝑶 → 𝑪𝑶𝟐 + 𝟐𝑯𝟐

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Sufficient water is added so that the concentration of carbon can be assumed to be zero, i.e.,

any carbon that is formed is immediately reacted to form CO2 and H2. The first column

recovers all of the H2, CO2, and H2O in the gas phase, with all of the hydrocarbons removed

in Stream 5. The second column recovers all of the styrene in the bottoms at a

concentration of 99% (the remainder is unreacted ethylbenzene).

A possible process flow diagram for production of styrene using some equipment such as

reactor (CSTR), 3-phases separator and Styrene Column:

Figure 2. PFD for Styrene Production.

The costs for the reactant and the sales price for the product are shown below:

Species Cost ($/lb)

Ethylbenzene 0.60

Styrene 0.80

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 Hydrogen 0.50

The capital cost for the reactor can be estimated as:

Cost (in $/yr) = 70,000*V0.62

where V is the volume of the reactor in L. This expression assumes a linear depreciation

over 10 years of operation.

The general strategy that I used to perform the economic evaluation was based on doing

mass balances for every single stream that involves whole process, knowing my product

specifications:

And with the general equation for a CSTR:

𝐹𝐴𝑜 𝑋𝐴 = −𝑟𝐴 𝑉

It could be obtaining the Reactor Volume. Thus, after gathering these values, we were able

to calculate the Cost of Manufacturing for the year using the following formula:

𝑪𝒐𝒎 = 𝑭𝑪𝑰 + 𝑪𝑹𝑴

Where:

Com : Cost of Manufacturing for the year

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FCI: Fixed Capital Cost (Reactor)

CRM : Cost of Raw Materials

This formula gave us a total cost of $64,971,027.25 per year.

Main Body

The optimization of economic cost for this process requires finding a minimum value for

the Estimating Annual Operational Cost (EAOC). The minimum value is given for optimal

conditions along with the continuous parameters of temperature, pressure and conversion.

The first step to optimizing this process was finding the better conversion of ethylbenzene

to get the specifications (Figure 3).

Conversion vs. Reactor Volume

T=840 K , P=1.5 bar
700
600
Reactor Volume (L)

500
400
300
200
100
0
0.4 0.5 0.6 0.7 0.8 0.9 1
Conversion

Figure 3. Optimal Conversion for Styrene Process (T=840 K , P=1.5 bar)

Then, doing the whole mass balance for all streams involves and to calculate the reactor

volume and then to do a comparison among results obtained. A preliminary analysis of the
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impact of temperature and pressure was done through the optimal case; the trends are

shown in Figure 4 and Figure 5.

Reactor Volume vs Pressure

T=840 K, X=0.875
5

4
Pressure (bar)

0
10 20 30 40 50 60 70
Reactor Volume (L)

Figure 4. Pressure trend of reactor showing the increase of Reactor volume.

A decrease in pressure results in increasing the Reactor Volume , as the primary reaction is

an equilibrium reaction.

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 Reactor Volume vs Temperature
P=1.58 bar , X=0.875
950

900
Temperature (K)

850

800

750

700

650
0 100 200 300 400 500 600 700 800
Reactor Volume (L)

Figure 5. Temperature trend of reactor showing the increase and decrease

with respect to styrene production and reactor volume

While a decrease in temperature results in decreasing the styrene production, since the

reaction is endothermic and also an increasing of Reactor Volume.

The next graphic shows a relation between profits generates ($/Yr), which means Sales

Revenues of Styrene and Hydrogen, and Conversion throughput reactor. A maximum point

indicates the best conversion to generate a higher profit

$
𝑃𝑟𝑜𝑓𝑖𝑡𝑠 ( ) = 80,622,068.37
𝑌𝑟

𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 = 0.875

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 18000000
16000000
14000000
12000000
Profits ($/Yr) 10000000
8000000
6000000
4000000
2000000
0
0.7 0.75 0.8 0.85 0.9 0.95 1
Conversion

Figure 6. Profits ($/Yr) vs. Conversion throughput reactor.

Applying the strategy above, three cases for the reactor volume were compared. The three

reactor volumes were 145.5 L, 197.5 L, and 608.2 L. The data for these cases is shown

below in Table 1. EAOC, Temperature and Pressure can be compared among them and see

the better choice for maximum profits. The higher increase in styrene production requires

more reactor volume and Temperature ≤ 1000K and Pressure ≤ 30 bar.

Table. 1 Results from the preliminary economic analysis

Preliminary Economic Analysis

Reactor Volume (L) 45.94 197.5 608.2

Temperature (K) 840 900 950

Pressure (bar) 1.5 2 2.5

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 Conversion 0.7 0.9 0.95

EAOC ($/Yr) 64,971,027.25 65,290,886.37 67,161,702.37

As we can see, the better choice for a maximum profit for this process it is shows below:

Reactor Volume (L) 45.94

Temperature (K) 840

Pressure (bar) 1.5

Conversion 0,7

EAOC ($/Yr) 64.971.027,25

It demonstrates the less is EAOC, the maximum profit we can obtain.

Appendix

Next calculations were taking for the best choice for an optimal economic cost

The first step was doing the mass balance for whole process, the data for this is shown

below in Table 2.

𝑇𝑜𝑛 1000 𝑘𝑔 1 𝑑𝑎𝑦 1ℎ 𝑘𝑔

𝐸𝑡ℎ𝑦𝑙𝐵𝑒𝑛𝑧𝑒𝑛𝑒 𝐹𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 200 [ ][ ][ ] = 2.31
𝑑𝑎𝑦 1 𝑇𝑜𝑛 24 ℎ 3600 𝑠 𝑠

𝑔
2314.8 𝑠 𝑚𝑜𝑙
𝐸𝑡ℎ𝑦𝑙𝐵𝑒𝑛𝑧𝑒𝑛𝑒 𝐹𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 𝑔 = 21.80 𝑠
106.17
𝑚𝑜𝑙

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 𝑔
𝑙𝑏 𝑔 𝑔 347.22 𝑠 𝑚𝑜𝑙
𝑊𝑎𝑡𝑒𝑟 𝐹𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 0.15 = 0.15 ∗ 2314.8 = 𝑔 = 19.29
𝑙𝑏 𝑔 𝑠 18 𝑠
𝑚𝑜𝑙

1 2 3 4 5 6 7

Ethylbenzene 21.80 21.80+X 6.54+0.3X 0 6.54+0.3X X 6.54-0.7X

Styrene 0 0 ---- 0 ----- 0 -----

Water 19.29 19.29 ---- --- 0 0 0

Hydrogen 0 0 ---- --- 0 0 0

Carbon Dioxyde 0 0 ---- --- 0 0 0

6
Let 𝑁̇𝐸𝐵 = 𝑋

3
95.95 % of EthylBenzene  Styrene ∴ 𝑁̇𝑆𝑡𝑦𝑟𝑒𝑛𝑒 = (15.26 + 0.7𝑋)(0.9595)

5 3 7
𝑁̇𝑆𝑡𝑦𝑟𝑒𝑛𝑒 = 𝑁̇𝑆𝑡𝑦𝑟𝑒𝑛𝑒 = 𝑁̇𝑆𝑡𝑦𝑟𝑒𝑛𝑒 = (15.26 + 0.7𝑋)(0.9595)

Stream 7

7
𝑁̇𝑆𝑡𝑦𝑟𝑒𝑛𝑒
7 7 = 0.99
𝑁̇𝑆𝑡𝑦𝑟𝑒𝑛𝑒 + 𝑁̇𝐸𝐵

Therefore,

7 7
0.01𝑁̇𝑆𝑡𝑦𝑟𝑒𝑛𝑒 = 0.99𝑁̇𝐸𝐵

Thus,

(15.26 + 0.7𝑋)(0.9595)(0.01) = 0.99(6.54 − 0.7𝑋)

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Solving the last equation, we obtain:

𝑚𝑜𝑙
𝑋 = 2.88
𝑠

Note: All numbers are in units of (mol/s)

1 2 3 4 5 6 7

Ethylbenzene 21.80 24.68 3.08 0 7.40 2.88 4.53

Styrene 0 0 20.72 0 20.72 0 20.72

Water 19.29 19.29 5.30 5.30 0 0 0

Hydrogen 0 0 39.08 39.08 0 0 0

Carbon Dioxyde 0 0 7.00 7.00 0 0 0

CSTR Balance

𝑑𝑁̇𝑆𝑡𝑦𝑟𝑒𝑛𝑒
= −20.72 + 𝑅1 𝑉
𝑑𝑡

𝑅1 𝑉 = 20.72

𝑑𝑁̇𝐸𝐵
= 24.68 − 20.72 − 3.08 − 𝑅2 𝑉
𝑑𝑡

𝑅1 𝑉 = 0.87

𝑑𝑁̇𝐻2 𝑂
= 19.29 − 16𝑅2 𝑉 − 𝑁̇𝐻2 𝑂
𝑑𝑡

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 𝑁̇𝐻2 𝑂 = 19.29 − 16(0.87) = 5.30

𝑑𝑁̇𝐻2
= 21𝑅2 𝑉 + 𝑅1 𝑉 − 𝑁̇𝐻2
𝑑𝑡

𝑁̇𝐻2 = 21(0.87) + 20.72 = 39.08

𝑑𝑁̇𝐶𝑂2
= 8𝑅2 𝑉 − 𝑁̇𝐶𝑂2
𝑑𝑡

𝑁̇𝐶𝑂2 = 8(0.87) = 7.00

For optimal preliminary economic cost:

𝑇 = 840 𝐾

𝑃 = 1.5 𝑏𝑎𝑟

The rate expression for the reaction to form the styrene is given as:

If,

−32000 𝐽/𝑚𝑜𝑙
𝑘𝑝 = 3000𝑒𝑥𝑝 [ ] = 30.70 𝑏𝑎𝑟
𝐽
8.314 × 840 𝐾
𝑚𝑜𝑙 𝐾

And,

𝐽 𝑚𝑜𝑙
−62000 2.789 𝐿
4
𝑘𝑝 = 2 × 10 𝑒𝑥𝑝 [ ]= 𝑚𝑜𝑙
𝐽 𝑠
8.314 × 840 𝐾 𝑏𝑎𝑟
𝑚𝑜𝑙 𝐾

Rearranging

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 𝑚𝑜𝑙
𝑚𝑜𝑙 2.789 𝐿 𝑋𝑆𝑡𝑦𝑟𝑒𝑛𝑒 𝑋𝐻2 𝑃2
𝑅1 𝑉 = 20.72 = 𝑠 [𝑋𝐸𝐵 𝑃 − ]𝑉
𝑠 𝐾𝑝
𝑏𝑎𝑟

̇
𝑁𝐸𝐵 3.08
𝑋𝐸𝐵 = = = 0.041
̇
𝑁𝑇𝑜𝑡𝑎𝑙 75.17

̇
𝑁𝑆𝑡𝑦𝑟𝑒𝑛𝑒 20.72
𝑋𝑆𝑡𝑦𝑟𝑒𝑛𝑒 = = = 0.2756
̇
𝑁𝑇𝑜𝑡𝑎𝑙 75.17

𝑁𝐻̇ 2 39.08
𝑋𝐻2 = = = 0.5198
̇
𝑁𝑇𝑜𝑡𝑎𝑙 75.17

Substituting in last equation,

𝑚𝑜𝑙
𝑚𝑜𝑙 2.789 𝑠 0.2756 ∗ 0.5198 ∗ 1.5 𝑏𝑎𝑟 2
𝑅1 𝑉 = 20.72 = [0.0410 ∗ 1.5 𝑏𝑎𝑟 − ]𝑉
𝑠 𝐿 30.70 𝑏𝑎𝑟
𝑏𝑎𝑟

𝑉 = 145.5 𝐿

Calculation for Estimating Annual Operational Cost (EAOC) $/Yr:

$
𝐸𝐴𝑂𝐶 ( ) = 𝐹𝐶𝐼 + 𝐶𝑅𝑀
𝑌𝑟

FCI:

Cost (in $/yr) = 70,000*(145.5 L)0.62

Cost (in $/yr) = 1,534,903.90

Cost of Raw Materials 𝐶𝑅𝑀 :

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 𝑇𝑜𝑛 1000 𝑘𝑔 1 𝑙𝑏 240 𝑑𝑎𝑦𝑠 $ $
𝐶𝑅𝑀 = 200 [ ][ ][ ] [0.60 ] = 63,436,123.35
𝑑𝑎𝑦 1 𝑇𝑜𝑛 0.454 𝑘𝑔 1 𝑌𝑟 𝑙𝑏 𝑌𝑟

$ $
𝐸𝐴𝑂𝐶 ( ) = 1,534,903.30 + 63,436,123.35 = 64,971,027.25
𝑌𝑟 𝑌𝑟

Profits selling Styrene and Hydrogen ($/Yr):

$ 𝑚𝑜𝑙 𝑔 3600 𝑠 24 ℎ 240 𝑑𝑎𝑦𝑠 1 𝑙𝑏 $

𝑆𝑡𝑦𝑟𝑒𝑛𝑒 ( ) = 20.72 [104.15 ][ ][ ][ ][ ] [0.8 ]
𝑌𝑟 𝑠 𝑚𝑜𝑙 1ℎ 1 𝑑𝑎𝑦 1 𝑌𝑟 454 𝑔 𝑙𝑏

$
𝑆𝑡𝑦𝑟𝑒𝑛𝑒 ( ) = 78,837,162.50
𝑌𝑟

$ 𝑚𝑜𝑙 𝑔 3600 𝑠 24 ℎ 240 𝑑𝑎𝑦 1 𝑙𝑏 $

𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 ( ) = 39.08 [2 ][ ][ ][ ][ ] [0.5 ]
𝑌𝑟 𝑠 𝑚𝑜𝑙 1ℎ 1 𝑑𝑎𝑦 1 𝑌𝑟 454 𝑔 𝑙𝑏

$
𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 ( ) = 1,784,905.88
𝑌𝑟

$
𝑃𝑟𝑜𝑓𝑖𝑡𝑠 ( ) = 𝑅𝑒𝑣𝑒𝑛𝑢𝑒 − 𝐶𝑜𝑠𝑡 = 80,622,068.37 − 64,971,027.25 = 15,651,041.12
𝑌𝑟

In conclusion, it was necessary to perform an economic analysis of this process to

determine whether or not the process is profitable. If the process is potentially profitable,

then it’s necessary to use this economic analysis to optimize the process to achieve

maximum profit. First, an equation describing the profit was developed, by setting two of

the three variables constant, the equation could then be analyzed in Microsoft Excel to

examine the relationship between a single variable and the profit, allowing for the

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optimization of that variable. Therefore, it’s an attractive economic opportunity for my

company to produce styrene under those conditions, because profits are higher and make up

for EAOC.

Excel Spreedsheat

Compound 1 2 3 4 5 6 7 Xi
Ethylbenzene 21,80 24,68 3,08 0 7,40 2,88 4,53 0,0410
Styrene 0 0 20,72 20,72 20,72 0 20,72 0,2756
Water 19,29 19,29 5,30 5,30 0 0 0 0,0705
Hydrogen 0 0 39,08 39,08 0 0 0 0,5198
Carbon Dioxide 0 0 7,00 7,00 0 0 0
75,17

Temperature (K) 840 Kp 30,7014112

Pressure (bar) 1,5 k1 2,78918194
Conversion 0,875
Selectivity 0,9595
Reactor Volume Capital Cost for the Reactor
R1V 20,7163191 V (L) 145,50437 Cost ($/yr) $ 1.534.903,90
R2V 0,87

V (L) Conversion V (L) Pressure (bar)

20,83 0,5 Conversion vs. Reactor Volume 67,66 1
29,22 0,6 T=840 K , P=1.58 bar 35,11 2
43,75 0,7 24,32 3
74,95 0,8 700 18,98 4
Volume of REactor (L)

145,5 0,875 600 15,83 5

190,34 0,9 500

606,69 0,95 400

300
200
Reactor Volume vs Pressure
100
5
T=840 K, X=0.7
0
0,4 0,5 0,6 0,7 0,8 0,9 1
4
Conversion
Pressure (bar)

3
V (L) Temperature (K)
701,92 650 2
283,15 700 Reactor Volume vs Temperature
132,64 750 1
69,23 800 P=1.58 bar , X=0.7
39,29 850 950 0
10 20 30 40 50 60 70
23,84 900 900
Temperature (K)

Volume of Reactor (L)

850
800
750
700
650
0 100 200 300 400 500 600 700 800
Volume of Reactor (L)

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