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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
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OUTLINE PRESENTATION Introduction Literature Review
Preliminary Hazard Analysis Conceptual Design Analysis Process Flow Diagram Heat Integration Conclusion
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INTRODUCTION
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BACKGROUND OF DESIGN PROJECT
Two main feedstock Benzene n-Butane Product Maleic Anhydride
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BACKGROUND OF DESIGN PROJECT
Application of MAN Source:
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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
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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
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OBJECTIVES To design a Maleic Anhydride production plant using mixed butane as raw material
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SCOPE OF STUDY Feed Preparation Oxidation Reaction
Crude Maleic Anhydride Recovery Crude Maleic Anhydride Purification Energy Recovery
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LITERATURE REVIEW
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FEED INFORMATION PROPERTIES MARKET STUDY Physical Properties
Chemical Properties MARKET STUDY Price
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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
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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)
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FEED PRICE Source:
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PRODUCT INFORMATION PROPERTIES MARKET STUDY Physical Properties
Chemical Properties MARKET STUDY Price Demand
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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
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PRODUCT CHEMIICAL PROPERTIES
Acid Chloride Formation Alkylation Amidation Hydration & Dehydration Isomerization 3 Active Sites & 1 Double Bond with 2 Carbonyl O2
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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: &
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PRODUCT PRICE Maleic Anhydride Price: 1476.92 USD/tone Conversion:
𝑈𝑆𝐷 𝑇𝑜𝑛𝑛𝑒 x 𝑇𝑜𝑛𝑛𝑒 𝑘𝑔 x 𝑅𝑀 𝑈𝑆𝐷 = 4.7 𝑅𝑀 𝑘𝑔 Source:
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SITE LOCATION Criteria Selection Process Decision
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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
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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
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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)
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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
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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
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POSSIBLE PROCESS ROUTE
Option 1 Option 2
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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
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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
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Preliminary hazard analysis
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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.
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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
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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
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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
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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.
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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
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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
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CONCEPTUAL DESIGN ANALYSIS
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SELECTED PROCESS: OPTION 2
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PRELIMINARY REACTOR OPTIMIZATION
REACTION PATH SELECTION OF CATALYST OPERATING PARAMETER
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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)
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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
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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
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PROCESS SCREENING LEVEL 1: MODE OF OPERATION
LEVEL 2: INPUT-OUTPUT STRUCTURE LEVEL 3: REACTOR SYSTEM LEVEL 4: SEPARATION SYSTEM
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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
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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
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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?
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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
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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
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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
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LEVEL 4: SEPARATION SYSTEM
Feed Purification Stages Product Recovery Product Purification
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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
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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
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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.
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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
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MASS BALANCE AROUND REACTOR
INPUT OUTPUT
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MASS BALANCE AROUND FEED DISTILLATION COLUMN
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MASS BALANCE AROUND FLASH VESSEL
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MASS BALANCE AROUND ABSORBER
Offgas Feed ABSORBER Rich Solvent Lean Solvent
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MASS BALANCE AROUND STRIPPER
Feed Product STRIPPER Solvent Recovery
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MASS BALANCE AROUND PRODUCT DISTILLATION COLUMN
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PRELIMINARY ENERGY BALANCE
Energy Balance around Reactor Energy Balance around Feed Distillation Column Energy Balance around Stripper Energy Balance around Product Distillation Column
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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
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ENERGY BALANCE AROUND REACTOR
Q = ΔH = (ΣnoutHout – ΣninHin) / 3600 = ( )/3600 = kW or MW
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ENERGY BALANCE AROUND FEED DISTILLATION COLUMN
Condenser Reboiler
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ENERGY BALANCE AROUND STRIPPER
Condenser Reboiler
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ENERGY BALANCE AROUND PRODUCT DISTILLATION COLUMN
Condenser Reboiler
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ECONOMICS EVALUATION ECONOMIC POTENTIAL
CUMULATIVE DISCOUNTED CASH FLOW DIAGRAM PROFITABILITY ANALYSIS
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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
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CUMULATIVE DISCOUNTED CASH FLOW DIAGRAM
Pay Back Period = 6th year Future worth = RM1,900,234,524
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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
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PROCESS FLOW DIAGRAM (BEFORE HEAT INTEGRATION)
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HEAT INTEGRATION
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STREAM DATA
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PROBLEM TABLE ALGORITHM
QC = kW Tpinch: 400°C
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COMPOSITE CURVE QC = kW
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GRAND COMPOSITE CURVE Process Recovery: kW
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HEAT EXCHANGER NETWORK
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TOTAL ENERGY SAVING Cold utility Hot utility Before integration (kW)
After integration (kW) Energy saved (kW) Percent of energy saved (%) 50.6 100
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PROCESS FLOW DIAGRAM (AFTER HEAT INTEGRATION)
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PROCESS FLOW DIAGRAM
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MATERIAL BALANCE TABLE
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CONCLUSION
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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
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