1. DESIGN OF MALEIC ANHYDRIDE (MAN) PRODUCTION PLANT
PLANT DESIGN I (CBB 4013)
INTERIM ORAL PRESENTATION
SEMESTER MAY 2012
DESIGN OF MALEIC ANHYDRIDE (MAN) PRODUCTION PLANT
GROUP 4
AFIQ NOOR BIN TUAH
MOHD FADHLI BIN SAYUTTI
CHE MUHAMMAD BUKHARI BIN CHE MOHD RAZALI
CHE FATIN HUMAIRA BINTI CHE YUSUF
NUR HANIE BINTI ZAMRI

2. OUTLINE PRESENTATION Introduction Literature Review
Preliminary Hazard Analysis
Conceptual Design Analysis
Process Flow Diagram
Heat Integration
Conclusion

3. INTRODUCTION

4. BACKGROUND OF DESIGN PROJECT
Two main feedstock
Benzene
n-Butane
Product
Maleic Anhydride

5. BACKGROUND OF DESIGN PROJECT
Application of MAN
Source:

6. BACKGROUND OF DESIGN PROJECT
N-Butane Oxidation to Produce MAN
The partial oxidation of n-butane is very exothermic:
C4H10(g) +3.5O2(g)C4H2O3(g)+4H2O(g) ∆H = -1236kJ/mol
C4H10(g) + 6.5O2(g) 4CO2(g) + 5H2O(g) ∆H = kJ/mol
C4H10(g) + 4.5O2(g) 4CO(g) + 5H2O(g) ∆H = kJ/mol

7. Alternate Feed Stock (Butane):
PROBLEM STATEMENT
Drawbacks of Benzene as Feedstock:
Health hazards from unreacted benzene vapor
Rising cost of benzene
Rising demand in other industries
Alternate Feed Stock (Butane):
Low cost
Easy availability
Less hazardous to health

8. OBJECTIVES
To design a Maleic Anhydride production plant using mixed butane as raw material

9. SCOPE OF STUDY Feed Preparation Oxidation Reaction
Crude Maleic Anhydride Recovery
Crude Maleic Anhydride Purification
Energy Recovery

10. LITERATURE REVIEW

11. FEED INFORMATION PROPERTIES MARKET STUDY Physical Properties
Chemical Properties
MARKET STUDY
Price

12. FEED PHYSICAL PROPERTIES
PHASE BEHAVIOR
Density (liquid)
600 kg/m³
Molar Mass
58.12 g/mol
Melting Point
-140 to -134 °C
Boling Point
-1 to 1 °C 
LIQUID PROPERTIES
Heat capacity, cp
J/(mol K)
GAS PROPERTIES
98.49 J/(mol K) at 25°C

13. FEED CHEMICAL PROPERTIES
Oxidation of butane form CO2 & H2O, carbon/CO may also form when O2 is limited:
2 C4H10 + 13 O2 → 8 CO2 + 10 H2O
n-Butane is the feedstock for catalytic processing of MAN:
2 CH3CH2CH2CH3 + 7 O2 → 2 C2H2(CO)2O + 8 H2O
Undergo free radical chlorination providing 1-chloro- & 2-chlorobutane and more highly chlorinated derivatives
Relative rates of chlorination are due to differing bond dissociation energies (2 central carbon atoms have the slightly weaker C-H bonds)

14. FEED PRICE
Source:

15. PRODUCT INFORMATION PROPERTIES MARKET STUDY Physical Properties
Chemical Properties
MARKET STUDY
Price
Demand

16. PRODUCT PHYSICAL PROPERTIES
PROPERTY
VALUE
Formula
C4H2O3
Formula Weight
98.06
Melting Point
52.85 °C
Boiling Point
202 °C
Specific Gravity, solid
1.48
Flash Point,
Open cup
Closed cup
110 °C
102 °C
Autoignition Temperature
477 °C
Heat Capacity, solid
kJ/K mol

17. PRODUCT CHEMIICAL PROPERTIES
Acid Chloride Formation
Alkylation
Amidation
Hydration & Dehydration
Isomerization
3 Active Sites & 1 Double Bond with 2 Carbonyl O2

18. PRODUCT DEMAND Demand in Asia: 184,370 TPA
Production Rate in Malaysia (TCL Malaysia):
1997 – 35,000 TPA
2008 – 60,000 TPA
Capacity : 30,000 TPA
Source: &

19. PRODUCT PRICE Maleic Anhydride Price: 1476.92 USD/tone Conversion:
𝑈𝑆𝐷 𝑇𝑜𝑛𝑛𝑒 x 𝑇𝑜𝑛𝑛𝑒 𝑘𝑔 x 𝑅𝑀 𝑈𝑆𝐷 = 4.7 𝑅𝑀 𝑘𝑔
Source:

20. SITE LOCATION
Criteria
Selection Process
Decision

21. SITE LOCATION: Criteria
Location with respect to the marketing area
Raw material supply
Transport facilities
Availability of labor
Availability of utilities: water, fuel, power
Availability of suitable land
Environmental impact & effluent disposal
Local community considerations
Climate
Political and strategic considerations

22. SITE LOCATION: Selection Process
Factors
Site Location
Pasir Gudang Industrial Area, Johor
Teluk Kalong Industrial Area, Kemaman, Terengganu
Raw Materials
Butane
Imported
GPP, PGB
Utilities
Power
Sultan Iskandar Power Station
Paka Power Plant
Water
Johor Waterworks Department, Loji Air Sungai Layang, Syarikat Air Johor
Terengganu Waterworks Department, Bukit Sah, Sg Cherol, Seberang Tayor, Kemasik
Steam
(Unknown)
Centralised Utilities Facilities (CUF), Kerteh
Natural Gas
Gas Processing Plant (1,2,3,4), Kerteh
Gas Processing Plant (5,6), Paka

23. SITE LOCATION: Selection Process
Factors
Site Location
Pasir Gudang Industrial Area, Johor
Teluk Kalong Industrial Area, Kemaman, Terengganu
Available Area
44.16 ha ha
Land Price
RM – / meter2
RM – / meter2
Transportation
Seaport
Johor Port
Kemaman Port
Roadway
PLUS Highway (Bukit Kayu Hitam-Singapore)
Highway Pasir Gudang- Tanjung Kupang-Tuas Singapore
Karak Highway (Kuantan-KL)
East – Coast Expressway (K.Terengganu-Teluk Kalong- Gebeng-Kuantan-KL)
Railway
To Singapore and North Peninsular Malaysia.
Kerteh Petrochemical Complex – Kuantan Port branch out to Teluk Kalong Industrial Area (Kuantan Port-Gebeng-Kemaman Port- Kerteh)

24. SITE LOCATION: Selection Process
Factors
Site Location
Pasir Gudang Industrial Area, Johor
Teluk Kalong Industrial Area, Kemaman, Terengganu
Training Centre
Institut Latihan Perindustrian Pasir Gudang
Terengganu Advanced Technical Institute, Pusat Latihan Petroliam PETRONAS

25. SITE LOCATION: Decision
TELUK KALONG INDUSTRIAL AREA
Natural gas easily obtained from PETRONAS Gas Berhad (PGB) at Kerteh & Paka
Utilities directly supplied by Centralised Utilities and Facilities (CUF) at Kerteh
Existence of major transportation networks offers wider range of marketability options, locally and internationally
Strategically located: Kemaman Port allows ease of transportation all over the world with all year round deep water sea port
Economical local manpower due to the existence of several training centre institutions

26. POSSIBLE PROCESS ROUTE
Option 1
Option 2

27. POSSIBLE PROCESS ROUTE: Option 1
Mixture of butane & air fed to reactor
Butane reacts with O2 to form MAN
Reactor effluent sent to absorber & contacted with H2O
Light gases are removed and MAN converted to maleic acid
Liquid effluent sent to 2nd reactor (maleic acid broken down to MAN & H2O)
Reactor effluent sent to distillation column to separate MAN & H2O

28. POSSIBLE PROCESS ROUTE: Option 2
Gas mixture of O2 & n-butane fed to reactor
Partial oxidation to MAN by contacting feed gas with VPO catalyst
The cooled gas flows to absorber and contacted with DBP as solvent
Absorption liquor flows to stripper column
Liquid side draw of crude MAN is removed from rectifying zone
The crude product flows to distillation column & form low boiling materials

29. Preliminary hazard
analysis

30. Colleferro Maleic Anhydrate Plant, Italy
PREVIOUS ACCIDENTS
Colleferro Maleic Anhydrate Plant, Italy
The temperature in the kettle increased rapidly and unexpectedly - exploded.
Due to an incomplete discharge of water at the end of the washing phase.
The introduction of maleic anhydride, contacting water at temperature higher than 100˚C caused the release of heat, which increased the evaporation rate.

31. LOGIC TREE FOR MAN INCIDENT
Fire
Explosion of kettle and column
Localizes collapse
Pressurization of kettle and column
Rupture of the kettle tube bundle and inlet of steam
Obstruction of the head condenser (no condensation of head vapors)
Reaction of the feed in the kettle with an undesired substance
Abnormal water in the kettle (exothermic reaction)
Inlet of steam in the kettle due to poor seal on heating bundle
Inlet of steam from the jacketed pipe between kettle and bottom
Inlet of demineralized water in the column due to seal defects of the condenser tube bundle
Residue of wash water in the kettle due to pipe or discharge valve blockage
Inlet of wash water in the kettle due to imperfect closing of the inlet valve
Combustion of the product in the kettle or in the column

32. IDENTIFICATION OF HAZARD
Chemicals
Flammability
Toxicity
Reactivity
Exposure Standard
Auto- ignition Temp oC
Flash
Point oC
LEL
(%)
UEL
Oral (LD50)
Inhalation (LC50)
Dermal
(LD50)
TWA
Propane`
468.0
-104.0
2.4
9.5
N/A
Reacts strongly with oxidizing agents.
1000 ppm
i - Butane
432.0
-82.0
1.4
8.3
57 parts per hundred (pph)
Rat
Stable but acts as oxidizing agent at elevated temperature of C
800 ppm
n- Butane
430.0
-60.0
1.8
8.4
658 g/m3/4hr

33. IDENTIFICATION OF HAZARD
Chemicals
Flammability
Toxicity
Reactivity
Exposure Standard
Auto- ignition Temp oC
Flash
Point oC
LEL
(%)
UEL
Oral (LD50)
Inhalation (LC50)
Dermal
(LD50)
TWA
Maleic Anhydride
447
110
1.4
1.7
1030mg/kg
Rat
N/A
2620m g/kg
Rabbit
Stable except when in contact with water. Reacts violently with amines, alkali metal ions and bases.
0.25 ppm (8 hours)
Carbon Dioxide
None
2000 ppm
Human
Stable under normal condition
5000 ppm

34. IDENTIFICATION OF HAZARD
Human Exposure
Workers are exposed to mixture of acid anhydrides
An individual showed an acute asthmatic reaction after exposure to dust containing maleic anhydride (Lee et al., 1991).
Human exposed to maleic anhydride showed respiratory tract and eye irritation at concentrations of 0.25 to 0.38 ppm (1 to 1.6 mg/m3) maleic anhydride (Grigor’eva, 1964).
maleic anhydride is a severe irritant to the eyes, skin and respiratory tract which can, upon exposure, produce intense burning sensations in the eyes and throat with coughing and vomiting.

35. PREVENTION Personal Protection for Exposure Control
To control or even avoid the exposure of those chemicals
Wearing eye/face protection to avoid eye contact with the chemicals.
Proper skin protective equipment such as coveralls or lab coats must be worn to prevent from skin exposure
The safety design of the facilities
Spill detection methods
Emergency notification procedures
Community contacts for notification and advice on evacuation needs
Fire prevention and protection
Provisions for spill containment/clean-up
Environmental protection
Compliance with applicable local regulations or laws
Risk reduction
Hazard Elimination
Consequence Reduction
Likelihood reduction

36. REGULATIONS & GUIDELINES
Several related local acts and regulations for compliance before operating new plant:
Occupational Safety and Health Act (OSHA) 1994
to reduce work related injuries, illness and death and incidentally to cut resulting costs
Environment Quality Act (EQA) 1974
prevention, abatement and control of pollution and enhancement of environment by restricting discharge of waste which applied to the whole Malaysia
Factories and Machinery Act (FMA) 1967
to provide for the control of factories with respect to matters relating to the safety, health and welfare of person

37. CONCEPTUAL DESIGN
ANALYSIS

38. SELECTED PROCESS: OPTION 2

39. PRELIMINARY REACTOR OPTIMIZATION
REACTION PATH
SELECTION OF CATALYST
OPERATING PARAMETER

40. REACTION PATH
C4H10 (g) O2 (g)­­­­­­­  C4H2O3(g) + 4 H2O (g) ∆H = kJ/mol (1)
C4H10 (g) O2 (g)  4 CO2 (g) + 5 H2O (g) ∆H = kJ/mol (2)
C4H10 (g) O2 (g)  4 CO (g) + 5 H2O (g) ∆H = kJ/mol (3)

41. SELECTION OF CATALYST Catalyst: Divanadyl Pyrophosphate, (VO)2P2O­­7
Reason:
The only commercially viable catalyst.
High selectivity to maleic anhydride
Able to selectively activate n­-butane during the rate determining step.
Thermally stable at high temperature
Temperature
yield
Conversion
Selectivity
400
0.561
0.85
0.66
406
0.532
0.888
0.5991
411
0.496
0.83
0.5976
412
0.554
0.918
0.6035
419
0.423
0.873
0.4845
421
0.518
0.5833

42. OPERATING PARAMETER Temperature Pressure Heating Medium
400°C
Based on literature study on optimum operating range
Safety consideration
Pressure
170kPa
Oxidation reaction is not pressure dependent
Cheaper cost
Heating Medium
Molten Salt
High heat capacity
Stable at high temperature and not flammable
Inlet Feed concentration
1.7 mol% of N-butane
LFL and UFL (1.86%-4.61%)
Conversion, selectivity and yield of Maleic Anhydride
Conversion : 85%
Selectivity : 0.66
Yield : 0.561

43. PROCESS SCREENING LEVEL 1: MODE OF OPERATION
LEVEL 2: INPUT-OUTPUT STRUCTURE
LEVEL 3: REACTOR SYSTEM
LEVEL 4: SEPARATION SYSTEM

44. LEVEL 1: MODE OF OPERATION
Batch Process
A one-time process, units are designed to start & be stopped frequently once the process is done
Continuous Process (chosen for MAN)
Units are designed to be working continuously & only be stopped during cleaning or maintenance time

45. Why Continuous Process is Chosen?
LEVEL 1: MODE OF OPERATION
Why Continuous Process is Chosen?
Production Rate
Our capacity: 31,375 metric ton/year (bigger than 10 million pound per year/ metric ton per year)
Market Study
MAN is not seasonable product (widely use in industry in all year long)
Demand for MAN will continue to grow
Operational Problem
The plant only involve vapour & liquid phase with no slurry
The equipment is not periodically started & stopped for cleaning purpose

46. LEVEL 2: INPUT-OUTPUT STRUCTURE
A simplified representation of process flow sheet which focuses on raw material feed, products and by-products
Decisions suggested by Douglas:
Should we purify the feed stream before they enter the process?
Should we remove or recycle a reversible by-product?
Should we use a gas recycle and purge stream?
Should we not bother to recover and recycle some reactants?

47. LEVEL 3: REACTOR SYSTEM Type of Reactor Advantages Disadvantages
Fixed-bed reactor
High catalytic conversion
Easy to operate
Difficult in temperature control within the reactor
Appearance of hotspot
Channelling of gas
Difficulty in unit cleaning or service
Difficulty in catalyst replacement

48. LEVEL 3: REACTOR SYSTEM Type of Reactor Advantages Disadvantages
Fluidized-bed reactor
Uniform particle mixing
Uniform temperature distribution
Avoid hot spot
Good temperature control
Higher capacity for MAN production
Easier in catalyst replacement
Higher pumping power requirement
Back mixing problem
Lack of understanding
Scale up problem
Erosion of internal components
Entrainment of particles
High catalyst volume demand

49. LEVEL 3: REACTOR SYSTEM Fluidized bed Reactor is too complex
Desired production of MAN is within capacity
Fixed Bed Reactor
Cheaper initial capital cost
Sufficient time for maintenance

50. LEVEL 4: SEPARATION SYSTEM
Feed Purification
Stages
Product Recovery
Product Purification

51. Mean relative volatility
FEED PURIFICATION
Separation of Propane (A), iso-butane (B) and n-butane (C)
Other component neglected as their composition are very small
Heuristic 3 : A component composing a large fraction of the feed should be removed first.
Distillation
Colum
75°c
10 bar 1 2 3
Input
Distillate Product
Bottom Product
A/BC B/C .... (1)
Component
Feed (wt%)
Feed flowrate
Mean relative volatility
Propane
1.54
230.9
2.5
iso-butane (LK)
29.5
4423.7
1.3
n-Butane (HK)
67.7
1.0
Isobutene
0.13
19.5
0.9
1-butene
0.20
30.0
0.8
Neopentane
0.11
16.5
0.7
Isopentane
0.77
115.5
0.6
n-Pentane
0.08
12.0
0.425
ABC
AB/C (2)
From posibble sequence, there are two routes for the distillation at feed purification
1st route as it need two distillation column to seperate the C
2nd routes is only using one distillation column

52. PRODUCT RECOVERY Solvent = Dibutyl Phthalate (C16H22O4)
High solubility to MAN
Availability = Port Klang, Malaysia
Cost =
Offgas to utility
ABSORBER
100% η
STRIPPER 13 14 16 15 17 19
Lean solvent
T= 70 °C
P= 160 kPa
Product
Feed mixture
Rich solvent
T= 245 °C
P= 12 kPa
Homogeneous mixture (gas phase)
High solubility of MAN (product) with the solvent
Low vapor pressure of solvent to be used inside the stripper for the solvent recovery (high temperature of stripper operating parameter)
Stripper operates same as distillation column (no stripping gas injected)
Purified solvent to solvent tank

53. Mean relative volatility
PRODUCT PURIFICATION
Component
Feed (wt%)
Feed flowrate
Mean relative volatility
Maleic Anhydride (HK)
99.1
3961.5 3
Water (LK)
0.9
180.2 5
Product purification
110°c
10bar 19 20 21
Input
Distillate Product
Bottom Product
Separation of Maleic Anhydride (A) and water (B).
Heuristic 3 : A component composing a large fraction of the feed should be removed first.
AB A/B
From posibble sequence, only one route for the distillation at product purification.
Maleic Anhydride and water shall be directly seperated.

54. PRELIMINARY MASS BALANCE
Mass Balance around Reactor
Mass Balance around Feed Distillation Column
Mass Balance around Flash Vessel
Mass Balance around Absorber
Mass Balance around Stripper
Mass Balance around Product Distillation Column

55. MASS BALANCE AROUND REACTOR
INPUT
OUTPUT

56. MASS BALANCE AROUND FEED DISTILLATION COLUMN

57. MASS BALANCE AROUND FLASH VESSEL

58. MASS BALANCE AROUND ABSORBER
Offgas
Feed
ABSORBER
Rich Solvent
Lean Solvent

59. MASS BALANCE AROUND STRIPPER
Feed
Product
STRIPPER
Solvent Recovery

60. MASS BALANCE AROUND PRODUCT DISTILLATION COLUMN

61. PRELIMINARY ENERGY BALANCE
Energy Balance around Reactor
Energy Balance around Feed Distillation Column
Energy Balance around Stripper
Energy Balance around Product Distillation Column

62. ENERGY BALANCE AROUND REACTOR
Entalphy for propane (input) = ΔHf°(i) + cp(i) (T­i – Tref)
= ( )
= kJ/mol
Entalphy for propane (ouput) = ΔHf°(i) + cp(i) (T­i – Tref)
= ( )
= kJ/mol

63. ENERGY BALANCE AROUND REACTOR
Q = ΔH
= (ΣnoutH­out – ΣninH­in) / 3600
= ( )/3600
= kW or MW

64. ENERGY BALANCE AROUND FEED DISTILLATION COLUMN
Condenser
Reboiler

65. ENERGY BALANCE AROUND STRIPPER
Condenser
Reboiler

66. ENERGY BALANCE AROUND PRODUCT DISTILLATION COLUMN
Condenser
Reboiler

67. ECONOMICS EVALUATION ECONOMIC POTENTIAL
CUMULATIVE DISCOUNTED CASH FLOW DIAGRAM
PROFITABILITY ANALYSIS

68. ECONOMIC POTENTIAL EP 1 = Product Value – Cost of Raw Material
= 147,462,876 RM/year -66,286,494 RM/year
= 81,176,382 RM/year
EP 2 = EP 1 + By Product Value
= 81,176,382 RM/year + 0
= 81,176,382 RM/year
EP 3 = EP 2 – Utility Cost
= 81,176,382 RM/year- 19,954,598 RM/year
=61,221,784 RM/year

69. CUMULATIVE DISCOUNTED CASH FLOW DIAGRAM
Pay Back Period = 6th year
Future worth = RM1,900,234,524

70. PROFITABILITY ANALYSIS
ITEMS
PRICE (RM/YEAR)
RAW MATERIAL
66,286,494
PRODUCT
147,462,876
CAPEX
132,114,000.00
OPEX
92,603,095.90
FUTURE WORTH
PAYBACK PERIOD

71. PROCESS FLOW
DIAGRAM
(BEFORE
HEAT INTEGRATION)

72. HEAT INTEGRATION

73. STREAM DATA

74. PROBLEM TABLE ALGORITHM
QC = kW
Tpinch: 400°C

75. COMPOSITE CURVE
QC = kW

76. GRAND COMPOSITE CURVE
Process Recovery: kW

77. HEAT EXCHANGER NETWORK

78. TOTAL ENERGY SAVING Cold utility Hot utility Before integration (kW)
After integration (kW)
Energy saved (kW)
Percent of energy saved (%)
50.6
100

79. PROCESS FLOW
DIAGRAM
(AFTER
HEAT INTEGRATION)

80. PROCESS FLOW DIAGRAM

81. MATERIAL BALANCE TABLE

82. CONCLUSION

83. CONCLUSION
Our design of MAN production plant using n-butane as raw material is feasible with the process route selected & realistic with the demand & market of MAN with the following specifications:
Plant Site Location: Teluk Kalong Industrial Area, Kemaman, Terengganu
Capacity: 30,000 TPA
Production Rate: 31,375 TPA
Purity: 98%
Future Worth: RM1,900,234,524
Pay Back Period: 6th year
Energy Recovery: 100% Hot Utility, 50% Cold Utility