INSTITUTO TECNOLÓGICO DE CIUDAD MADERO

DEPARTMENT OF CHEMICAL AND BIOCHEMICAL ENGINEERING

CHEMICAL ENGINEERING

HETEROGENEOUS REACTORS
PERIOD
JANUARY- JULY

MALEIC ANHYDRIDE PRODUCTION FROM BENZENE

MEMBERS
GUZMAN GUTIERREZ ORLANDO GIOVANNI
19070870
JIMENEZ BARRIOS FERNANDA MAYELA
19070910
PILA OLMEDO NESTOR EMMANUEL
20070255
VEGA MEDINA JAHYR ORLANDO
19070872
TEACHER
ING. VICENTE MUJICA CAMPOS
 CIUDAD MADERO, TAMAULIPAS. MAY 05, 2024

INDEX
1.BACKGROUNDS .........................................................................................................................3
1.1. Description. ................................................................................................................................3
1.2. Physical Properties ....................................................................................................................3
1.3. Chemical Properties. .................................................................................................................3
2.TARGET OR OBJECTIVE .........................................................................................................4
3. USES AND ECONOMICS ..........................................................................................................4
4. PROCESS DESCRIPTION .........................................................................................................5
5. MAIN REACTIONS ....................................................................................................................6
6. PROCESS FLOW DIAGRAM....................................................................................................7
9. AUXILIARY SERVICES DIAGRAM ........................................................................................8
8. STOICHIOMETRIC AND MASS BALANCE FOR A PBR-01 ...............................................9
9. STOICHIOMETRIC BALANCE .............................................................................................16
10. ENERGY BALANCE ..............................................................................................................18
11. COUPLING BETWEEN MASS AND ENERGY BALANCE ..............................................19
.........................................................................................................................................................23
12. ECONOMICAL EVALUATION OF THE PLANT PROJECT ............................................23
13. EARRING (EBIDTA), PRODUCTION COST, PROFITABILITY, AND CASH FLOW. ..25
14. MODEL SOLUTION IN POLYMATH ............................................................................26
15. SUGGEST & CONCLUSIONS .........................................................................................29
16. CREATIVE AND CRITICAL THINKING ......................................................................29
17. BIBLIOGRAPHY ..............................................................................................................29
1.BACKGROUNDS

1.1. Description.
Maleic anhydride (MAN) is an organic compound with the chemical formula C 4H2O3 which
main features are two carbonyl groups and a double bond. This chemical is a strong irritant
to skin, eyes, and mucous membranes of the upper respiratory system. It is also known by
other names such as 2,5- furandione, dihydro-2,5-dioxofuran, toxilic anhydride, and cis-
butenedioic anhydride.

1.2. Physical Properties

At room temperature, this organic compound it is a white crystalline solid with a pungent
odor which begins melting at 52.8 °C and boils at 202 ºC. However, for handling reasons,
during production, it is a liquid or gas.

This chemical compound is soluble, from greatest to lowest, in acetone, benzene, toluene, o-
xylene and kerosene among other organic components.

1.3. Chemical Properties.

Due to the extremely reactive double bond, maleic anhydride reacts readily (hydrolyzes) with
water to formmaleic acid (MA) at about 60 ºC and fumaric acid (FA) at 100 ºC. Fumaric acid
crystallizes and is not readily soluble in water. Thermal treatment and catalyst are used to
enhance formation of fumaric acid by maleic acid isomerization.

By limiting the aqueous maleic acid concentration to 40 % and the temperature to less than
85 ºC, fumaric acid will not form in > 0.1 % weight of the reaction mixture.
2.TARGET OR OBJECTIVE
The purpose of this project is the modeling and simulation of the maleic anhydride production
process through partial oxidation of benzene.

• Our target is to design a plant able to produce 40,000 ton/year of maleic anhydride.
• Our plant will be operating 8,000 h/year and 760 hours will be required in case of
preventive and corrective maintenance and God’s acts.
• Utilization Factor (U.F)

3. USES AND ECONOMICS

It’s used as a copolymer in the manufacture of polyester and other resins, and as a component
of pharmaceuticals and pesticides.

Maleic Anhydride is used in following synthetic processes:

• Synthesis of fumaric, malic, succinic, maleic acids.
• Defoliants (e.g. endotal)
• Fungicides (canton, etc.)
• Insecticides (kalbofos)
• Production of polyester and alkyd resins for construction industry
• As an additive to lubricating oils to reduce friction

Fig 1.1 Net Commercial Balance according to the federal entity

4. PROCESS DESCRIPTION

Benzene is vaporized in E-601, mixed with compressed air, then heated in a fired heater, H-
601, prior to being sent to a packed-bed catalytic reactor, R-601, where the reactions take
place.

All the reactions are highly exothermic. For this reason, the ratio of air to benzene entering
the reactor is kept very high. A typical inlet concentration (Stream 6) of approximately 1.5
vol% of benzene in air is used. Cooling is achieved by circulating molten salt (a mixture of
sodium nitrite and sodium nitrate) cocurrently through the shell of the reactor and across the
tubes containing the catalyst and reactant gases. This molten salt is cooled in two external
exchangers—E-602 and E-607—prior to returning to the reactor.

The reactor effluent, Stream 7—containing small amounts of unreacted benzene, maleic
anhydride, quinone, and combustion products—is cooled in E-603 and then sent to an
absorber column, T-601, which has both a reboiler and condenser. Any water in the solvent
leaving the bottom of the absorber, T-601, reacts with the maleic anhydride to form maleic
acid, which must be removed and purified from the maleic anhydride. The bottoms product
from the absorber is sent to a separation tower, T-602, where the dibutyl phthalate is
recovered as the bottoms product and recycled back to the absorber. A small amount of fresh
solvent is added to account for losses. The overhead product from T-602 is sent to the maleic
acid column, T-603, where 95 mol% maleic acid is removed as the bottoms product.
5. MAIN REACTIONS

All the reactions are highly exothermic. For this reason, the ratio of air to benzene entering
the reactor is kept very high. A typical inlet concentration (Stream 6) of approximately 1.5
vol% of benzene in air is used. Cooling is achieved by circulating molten salt (a mixture of
sodium nitrite and sodium nitrate) cocurrently through the shell of the reactor and across the
tubes containing the catalyst and reactant gases. This molten salt is cooled in two external
exchangers—E-602 and E-607—prior to returning to the reactor.

The reactor effluent, Stream 7—containing small amounts of unreacted benzene, maleic
anhydride, quinone, and combustion products—is cooled in E-603 and then sent to an
absorber column, T-601, which has both a reboiler and condenser. In T-601, the vapor feed
is contacted with recycled heavy organic solvent (dibutyl phthalate), Stream 9.

This solvent absorbs the maleic anhydride, quinone, and small amounts of water. Any water
in the solvent leaving the bottom of the absorber, T-601, reacts with the maleic anhydride to
form maleic acid, which must be removed and purified from the maleic anhydride. The
bottoms product from the absorber is sent to a separation tower, T-602, where the dibutyl
phthalate is recovered as the bottoms product, Stream 14, and recycled back to the absorber.
A small amount of fresh solvent, Stream 10, is added to account for losses. The overhead
product from T-602, Stream 13, is sent to the maleic acid column, T-603, where 95 mol%
maleic acid is removed as the bottoms product.
6. PROCESS FLOW DIAGRAM
9. AUXILIARY SERVICES DIAGRAM
8. STOICHIOMETRIC AND MASS BALANCE FOR A PBR-01
𝐹𝐴 = 𝐹𝐴 0(1 − 𝑋𝐴)

𝑑𝐹𝐴 = −𝐹𝐴 0 (𝑑𝑋𝐴)

MASS BALANCE FOR A PBR-01

𝐼𝑁𝐿𝐸𝑇 − 𝑂𝑈𝑇𝐿𝐸𝑇 ± 𝑃𝑅𝑂𝐷𝑈𝐶𝑇𝐼𝑂𝑁 = 𝐴𝐶𝐶𝑈𝑀𝑈𝐿𝐴𝑇𝐼𝑂𝑁

From an open system and steady state, we have that:

𝐼𝑁𝐿𝐸𝑇 − 𝑂𝑈𝑇𝐿𝐸𝑇 ± 𝑃𝑅𝑂𝐷𝑈𝐶𝑇𝐼𝑂𝑁 = 𝐴𝐶𝐶𝑈𝑀𝑈𝐿𝐴𝑇𝐼ON

𝐹𝐴0 − 𝐹𝐴0 + 𝑑𝐹𝐴 ± (−𝑅𝐴 )(𝑑𝑊) = 0

𝐹𝐴0 𝑑𝑋𝐴 − (−𝑅𝐴 )(𝑑𝑊) = 0

Design equation for a 𝐹𝐴 0𝑑𝑋𝐴 = (−𝑅𝐴 )(𝑑𝑊)
Packed Bed Reactor
dXA = (−RA ) dX𝐴 (−RA)
= = =
d𝑊 FA0 dθ CA0

Production of the Maleic Anhydride

Then:

𝐹𝐶 = 46.56 𝑘𝑚𝑜𝑙/ℎ
Where
𝐹𝐶 = 𝑀𝑎𝑙𝑒𝑖𝑐 𝐴𝑛ℎ𝑦𝑑𝑟𝑖𝑑𝑒
𝐹𝐴0 = 𝐵𝑒𝑛𝑧𝑒𝑛𝑒

From Mass Balance:

A + B -----> C + D + E

Benzene + 4.5 O2 ----------------> Maleic Anhydride + CO + H O

2 2

4003.29601 kg/hr 146491.701 m3/hr 5000.005 kg/hr

51.2454686 kmol/hr 229.451586 kmol/hr 50.9892413 kmol/hr
6617.38373 kmol/hr

From Stoichiometric Balance we found that:

We have a ratio from kg- benzene/m3 of air = 0.0273278 kg/m3
We found that we have a ratio from gr-benzene/m3 of air = 27.33 gr/m3

Mass Balance for each equipment

PM Maleic Anhydride 98.08 kmol/kg

PM Benzene 78.11 kmol/kg
PM Air 29.96 kmol/kg
PM Oxygen 32 kmol/kg
PM Nytrogen 28 kmol/kg
PM Dibutyl Phthalate 278.3 kmol/kg
PM Quinone 166.22 kmol/kg
PM Maleic Acid 116.1 kmol/kg
PM Carbon dioxide 44 kmol/kg
PM Water 18 kmol/kg
1. Benzene Feed Drum (V-601)

2. Benzene Feed Pumps (P-601 A/B)

3. Benzene Feed Vaporizer (E-601)

4. Air compressor (C-601)

5. Feed heater (H-601)

6. Packed Bed Reactor (R-601)

7. Benzene feed vaporizer (E-603)

8. Dibutyl Feed Pumps (P-603 A/B)

9. MA Scrubber (T-601)

10. Maleic Anhydride Tower Condenser (E-604)

11. Maleic Anhydride Reflux Drum (V-602)

12. Dibutyl Reflux Pumps (P-605 A/B)

13. Dibutyl Scrubber (T-602)

9. STOICHIOMETRIC BALANCE

Rate law
1. 𝑟1𝐶 = 𝑘1𝐶𝐴C𝐵4.5
2. – 𝑟3𝐶 = 𝑘3𝐶𝐶C𝐵3

New rates

𝑟𝐴 = 𝑟1 𝐴
𝑟𝐵 = 𝑟1 𝐵 + 𝑟3 𝐵
𝑟𝐶 = 𝑟1 𝐶 + 𝑟3 𝐶
𝑟𝐷 = 𝑟1 𝐶 + 𝑟3 𝐷
𝑟𝐸 = 𝑟1 𝐸 + 𝑟1 𝐸

Relative rates
1st reaction
3rd reaction
10. ENERGY BALANCE

No Isothermal with heat transfer

Qgen – Qrem = Qaccum

𝑑𝑡
(-Ra)(dw)(-ΔHrxn) – (UA(Tm-TR)= Σ 𝐹𝑖 𝐶𝑝𝑖 𝑑𝑤

𝑑𝑡 (−Ra)(dw)(−ΔHrxn) – (UA(Tm−TR)
= 𝑑𝑡
𝑑𝑤 Σ 𝐹𝑖 𝐶𝑝𝑖 𝑑𝑤

Packed Bed Reactor R-601

✓ Steady State, no isothermal with heat exchange
✓ ü Energy Balance with dW
11. COUPLING BETWEEN MASS AND ENERGY BALANCE

From mass balance

From energy balance

𝑸𝒕𝒓𝒂𝒏𝒔𝒇 = 𝑼𝑨 (𝑻𝒎 − 𝑻𝒓𝒆𝒂𝒄𝒕)

Parameters of the PBR-601 (Shell and tube vertical design)

D=3.8 m
L=7 m
U=100m2𝑤h K=360m2kJh K
Tm = 414°C = 687.15 K
Treact = 460°C = 733.15 K

𝐴=𝜋∗𝐷∗𝐿
𝐴 = 𝜋 ∗ 3.8𝑚 ∗ 7𝑚

𝐴 = 83.566565 𝑚2
D2
𝑉=𝜋∗ ∗𝐿
4
3.82
𝑉=𝜋∗ ∗ 7𝑚
4
𝑉 = 79.388046 𝑚3
Catalyst volume

D = 0.0254 m
r = 0.0127 m
Ltube = 6.4 m

𝑉𝑡𝑢𝑏𝑒 = 𝜋 ∗ 𝑟2 ∗ 𝐿
𝑉𝑡𝑢𝑏𝑒 = 𝜋 ∗ (0.0127𝑚)2 ∗ (6.4𝑚)
𝑉𝑡𝑢𝑏𝑒 = 0.0032429 𝑚3
We have 12,100 tubes, so
𝑉𝑡𝑢𝑏𝑒𝑠 = 𝑉𝑡𝑢𝑏𝑒 ∗ 12100
𝑉𝑡𝑢𝑏𝑒𝑠 = 0.0032429𝑚3 ∗ 12100

𝑉𝑡𝑢𝑏𝑒𝑠 = 39.239427 𝑚3
12. ECONOMICAL EVALUATION OF THE PLANT PROJECT

Production Cost for Maleic Anhydride

Average

1. Raw material 74 0.92

2. Labor (operators+ managers) 5.8 0.072

3. Utilities 12 0.15

4. Package 3.5 0.043

5. Maintenance (people & spare 4.2 0.050

parts)
6. Safety & laboratory people 0.5 0.006

TOTAL AVERAGE 100 1.241 dls/kg

 From Raw Material
𝑑𝑙𝑠
1. Benzene cost= 0.87 𝑡𝑜𝑛
𝑘𝑔
Catalyst production= 40000
𝑦𝑒𝑎𝑟

Life- time= 4 years

2. Catalyst = Material + Installation

2.1 Material = 1,500,000 𝑑𝑙𝑠

600000 𝑑𝑙𝑠
2.2 Installation =
2100000 𝑑𝑙𝑠
𝑡𝑜𝑛
Production of catalyst= (4 years) (40 000 )= 160 000 000 kg
𝑦𝑒𝑎𝑟
2100000 𝑑𝑙𝑠
Cost production of catalyst= = 0.02
160000000 𝑘𝑔

3. Air
0.7457 𝐾𝑊
𝑃𝑂𝑇 = 3000𝐻𝑃 | | = 2237.1 𝐾𝑊
1 𝐻𝑃
𝐾𝑊𝐻
(2237.1 𝐾𝑊)(8000 𝐻) = 17.9𝑥106
𝑦𝑒𝑎𝑟

𝐾𝑊𝐻 0.075 𝑑𝑙𝑠 𝑑𝑙𝑠

17.9𝑥106 | | = 1.34𝑋106
𝑌𝑒𝑎𝑟 1 𝐾𝑊𝐻 𝑦𝑒𝑎𝑟
𝑑𝑙𝑠
1.34𝑋106 𝑑𝑙𝑠
𝑦𝑒𝑎𝑟
𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝐶𝑜𝑠𝑡 = = 0.0335
𝑘𝑔 𝑘𝑔
40𝑥106
𝑦𝑒𝑎𝑟
Raw material
𝑑𝑙𝑠
1. Benzene=0.87
𝑘𝑔
𝑑𝑙𝑠
2. Catalyst=0.02
𝑘𝑔
𝑑𝑙𝑠
3. O2(Air) = 0.0335
𝑘𝑔
𝑑𝑙𝑠
Total = 0.92
𝑘𝑔
13. EARRING (EBIDTA), PRODUCTION COST, PROFITABILITY,
AND CASH FLOW.

𝑑𝑙𝑠
Maleic Anhydride sale price = 1.54
𝑘𝑔

𝐶𝑜𝑠𝑡 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 = 1.24

𝐸𝑎𝑟𝑛𝑖𝑛𝑔 = 𝑆𝑎𝑙𝑒 𝑝𝑟𝑖𝑐𝑒 − 𝐶𝑜𝑠𝑡 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 = 1.54 − 1.24 = 0.30

𝑑𝑙𝑠
𝐸𝐵𝐼𝐷𝑇𝐴 = 0.30
𝑘𝑔
𝐸𝑎𝑟𝑛𝑖𝑛𝑔 𝑑𝑙𝑠 𝑑𝑙𝑠
= 40𝑥106 (0.30 ) = 12𝑥106
𝑦𝑒𝑎𝑟 𝑘𝑔 𝑦𝑒𝑎𝑟

𝐸𝐴𝐼𝐷𝑇𝐴 = 12𝑥106 (1 − 0.40) = 7.2𝑥106 𝑑𝑙𝑠

Initial Investment (Maleic Anhydride) = 75,000,000

𝑑𝑙𝑠
7.2𝑋106
𝑦𝑒𝑎𝑟
𝑅𝑂𝐼 = = 0.96 ∗ 100 = 96%
7.5𝑥106
1
𝑅𝑒𝑐𝑢𝑝𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = = 0.1 ∗ 100 = 10 𝑦𝑒𝑎𝑟𝑠
96%
 14. MODEL SOLUTION IN POLYMATH
Weight catalyst in Polymath
15. SUGGEST & CONCLUSIONS

The data obtained in the simulations and modeling of the reactor were close to the results
of the case study. Output streams can be optimized in some equipment, such as steam to
recycle matter and purify output streams. Include more equipment to make better use of
energy that is wasted or not used, such as turbines, cooling towers, etc.
As a team we took on the task of concluding this project through simulations such as the
Polymath program to corroborate the veracity of our data.

16. CREATIVE AND CRITICAL THINKING

The variables that can be changed in this system to improve the process are:

• The inlet temperature of the reactor to reach the reaction temperature.

• The inlet pressure of the reactor to increase conversion.
• Increase the flow rate of molten salt in the reactor.

17. BIBLIOGRAPHY

• Turton, R. et al. (2018) Analysis, synthesis, and design of Chemical Processes.

• Boston: Pearson Education, Inc.
• Fogler, H.S. (2022) Elements of chemical reaction engineering. Upper Saddle
River: Pearson.
• Çengel Yunus A., Boles, M.A. and Kanoğlu Mehmet (2024) Thermodynamics:
An engineering approach. New York, NY: McGraw Hill.
• Green, D.W., Southard, M. and Perry, R.H. (2019) Perry's Chemical Engineers'
o handbook. New York: McGraw-Hill.
• Walas, S.M. (2012) Chemical Process Equipment: Selection and Design.
• Amsterdam: BH, Butterworth-Heinemann, an imprint of Elsevier.
• Notes of class “Heterogenous Reactors” given by Eng. Vicente Mujica Campos