design of maleic anhydride (man) production plant group 4 afiq noor bin tuah 11857 mohd fadhli bin...

DESIGN OF MALEIC ANHYDRIDE (MAN)

PRODUCTION PLANT

GROUP 4AFIQ NOOR BIN TUAH 11857MOHD FADHLI BIN SAYUTTI 12012CHE MUHAMMAD BUKHARI BIN CHE MOHD RAZALI 11908CHE FATIN HUMAIRA BINTI CHE YUSUF 11907NUR HANIE BINTI ZAMRI 12140

1

PLANT DESIGN I (CBB 4013)INTERIM ORAL PRESENTATION

SEMESTER MAY 2012

OUTLINE PRESENTATION

Introduction

Literature Review

Preliminary Hazard Analysis

Conceptual Design Analysis

Process Flow Diagram

Heat Integration

Conclusion

INTRODUCTION

4

BACKGROUND OF DESIGN PROJECT

Two main feedstock

Benzene n-Butane

Product

Maleic Anhydride

5


Source: http://www.icis.com/Articles/2003/10/10/525310/chemical-profile-maleic-anhydride.html

Application of MAN

http://www.icis.com/Articles/2003/10/10/525310/chemical-profile-maleic-anhydride.html

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 = -2656 kJ/mol

C4H10(g) + 4.5O2(g) 4CO(g) + 5H2O(g) ∆H = -1521 kJ/mol


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

PROBLEM STATEMENT

OBJECTIVES

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

Feed Preparation

Oxidation Reaction

Crude Maleic Anhydride Recovery

Crude Maleic Anhydride Purification

Energy Recovery

SCOPE OF STUDY

LITERATURE REVIEW

FEED INFORMATION

PROPERTIES• Physical Properties• Chemical Properties

MARKET STUDY• Price

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 132.42 J/(mol K)GAS PROPERTIES

Heat capacity, cp 98.49 J/(mol K) at 25°C

FEED PHYSICAL 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)

FEED CHEMICAL PROPERTIES

Source: http://price.alibaba.com/search/priceSearch.htm?q=butane

FEED PRICE

http://price.alibaba.com/search/priceSearch.htm?q=butane

PRODUCT INFORMATION

PROPERTIES• Physical Properties• Chemical Properties

MARKET STUDY• Price• Demand

PROPERTY VALUEFormula C4H2O3

Formula Weight 98.06

Melting Point 52.85 °C

Boiling Point 202 °C

Specific Gravity, solid 1.48

Flash Point,Open cupClosed cup

110 °C102 °C

Autoignition Temperature 477 °C

Heat Capacity, solid 0.1199 kJ/K mol

PRODUCT PHYSICAL PROPERTIES

Acid Chloride Formation

Alkylation

AmidationHydration & Dehydration

Isomerization3 Active Sites & 1 Double Bond with 2 Carbonyl O2

PRODUCT CHEMIICAL PROPERTIES

Capacity : 30,000 TPA

PRODUCT DEMAND

Demand in Asia:184,370 TPA

Production Rate in Malaysia (TCL Malaysia): i. 1997 – 35,000 TPAii. 2008 – 60,000 TPA

Source: http://www.thirumalaichemicals.com/maleic.html & http://www.tclresearch.com/library/presentation.pdf

http://www.thirumalaichemicals.com/maleic.html

http://www.thirumalaichemicals.com/maleic.html

http://www.tclresearch.com/library/presentation.pdf

Maleic Anhydride Price: 1476.92 USD/tone

Conversion:

1476.92 x 0.001 x 3.1824 = 4.7

Source: http://price.alibaba.com/price/priceLeafCategory.htm?categoryId=100001625&spuId=100070280

PRODUCT PRICE

http://price.alibaba.com/price/priceLeafCategory.htm?categoryId=100001625&spuId=100070280

http://price.alibaba.com/price/priceLeafCategory.htm?categoryId=100001625&spuId=100070280

SITE LOCATION

Criteria

Selection Process

Decision

1. Location with respect to the marketing area2. Raw material supply3. Transport facilities4. Availability of labor5. Availability of utilities: water, fuel, power6. Availability of suitable land7. Environmental impact & effluent disposal8. Local community considerations9. Climate10. Political and strategic considerations

SITE LOCATION: Criteria

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

(Unknown) Gas Processing Plant (1,2,3,4), KertehGas Processing Plant (5,6), Paka

SITE LOCATION: Selection ProcessFactors Site Location

Available Area 44.16 ha 352.70 ha Land Price RM 86.00 – 237.00 /

meter2RM 45.00 – 105.00 / meter2

Transportation Seaport Johor Port Kemaman Port

Roadway PLUS Highway (Bukit Kayu Hitam-Singapore)Highway Pasir Gudang-Tanjung Kupang-Tuas Singapore

Factors Site Location

SITE LOCATION: Selection Process

Training Centre Institut Latihan Perindustrian Pasir Gudang

Terengganu Advanced Technical Institute, Pusat Latihan Petroliam PETRONAS

SITE LOCATION: Selection ProcessFactors Site Location

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

TELUK KALONG INDUSTRIAL AREA

SITE LOCATION: Decision

POSSIBLE PROCESS ROUTE

Option 1

Option 2

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

POSSIBLE PROCESS ROUTE: Option 1

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

POSSIBLE PROCESS ROUTE: Option 2

PRELIMINARY HAZARDANALYSIS

Colleferro Maleic Anhydrate Plant, Italy

i. The temperature in the kettle increased rapidly and

unexpectedly - exploded.

ii. Due to an incomplete discharge of water at the end of the

washing phase.

iii. The introduction of maleic anhydride, contacting water at

temperature higher than 100˚C caused the release of heat,

which increased the evaporation rate.

PREVIOUS ACCIDENTS

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

LOGIC TREE FOR MAN INCIDENT

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 N/A N/A Reacts strongly with oxidizing agents.

1000 ppm

i - Butane 432.0 -82.0 1.4 8.3 N/A 57 parts per

hundred (pph)

Rat

N/A Stable but acts as oxidizing agent at elevated temperature of 435 0C

800 ppm

n- Butane 430.0 -60.0 1.8 8.4 N/A 658 g/m3/4hr

Rat

N/A Stable but acts as oxidizing agent at elevated temperature of 435 0C

800 ppm

IDENTIFICATION OF HAZARD

Maleic Anhydride

447 110 1.4 1.7 1030mg/kg

Rat

N/A

2620mg/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 None None None N/A 2000 ppm

Human

N/A Stable under normal condition

5000 ppm

Chemicals Flammability Toxicity Reactivity

Exposure Standard

Auto-ignition Temp oC

Flash

Point oC

LEL

(%)

UEL

(%)

Oral (LD50) Inhalation (LC50)

Dermal

(LD50)

TWA


• Human Exposure i. Workers are exposed to mixture of acid anhydridesii. An individual showed an acute asthmatic reaction

after exposure to dust containing maleic anhydride (Lee et al., 1991).

iii. 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).

iv. 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.


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

PREVENTION

Several related local acts and regulations for compliance before operating new plant:

1. Occupational Safety and Health Act (OSHA) 1994- to reduce work related injuries, illness and death

and incidentally to cut resulting costs 2. 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

3. 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

REGULATIONS & GUIDELINES

CONCEPTUAL DESIGN ANALYSIS

SELECTED PROCESS: OPTION 2

PRELIMINARY REACTOR OPTIMIZATION

REACTION PATH

SELECTION OF CATALYST

OPERATING PARAMETER

C4H10 (g) + 3.5 O2 (g) C4H2O3(g) + 4 H2O (g) ∆H = -1236 kJ/mol (1)

C4H10 (g) + 6.5 O2 (g) 4 CO2 (g) + 5 H2O (g) ∆H = -2656 kJ/mol (2)

C4H10 (g) + 4.5 O2 (g) 4 CO (g) + 5 H2O (g) ∆H = -1521 kJ/mol (3)

REACTION PATH

Catalyst: Divanadyl Pyrophosphate, (VO)2P2O 7 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 0.888 0.5833

SELECTION OF CATALYST

•400°C

•Based on literature study on optimum operating range

•Safety consideration

Temperature

•170kPa

•Oxidation reaction is not pressure dependent

•Cheaper cost

Pressure

•Molten Salt

•High heat capacity

•Stable at high temperature and not flammable

Heating Medium

•1.7 mol% of N-butane

•LFL and UFL (1.86%-4.61%)

Inlet Feed concentration

•Conversion

: 85%

•Selectivity

: 0.66

•Yield

: 0.561

Conversion, selectivity and yield of Maleic Anhydride

OPERATING PARAMETER

PROCESS SCREENING

LEVEL 1: MODE OF OPERATION

LEVEL 2: INPUT-OUTPUT STRUCTURE

LEVEL 3: REACTOR SYSTEM

LEVEL 4: SEPARATION SYSTEM

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


Why Continuous Process is Chosen?

Production Rate

• Our capacity: 31,375 metric ton/year (bigger than 10 million pound per year/4 535.9237 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


A simplified representation of process flow sheet which focuses on raw material feed, products and by-products

Decisions suggested by Douglas:

1. Should we purify the feed stream before they enter the process?2. Should we remove or recycle a reversible by-product? 3. Should we use a gas recycle and purge stream?4. Should we not bother to recover and recycle some reactants?

LEVEL 2: INPUT-OUTPUT STRUCTURE

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


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


Fixed Bed Reactor

Cheaper initial capital cost

Sufficient time for maintenance


Desired production of MAN is within capacity

Fluidized bed Reactor is too complex

Stages

Feed Purification

Product Recovery

Product Purification

LEVEL 4: SEPARATION SYSTEM

Distillation

Colum

75°c

10 bar

1

2

3

Input

Distillate Product

Bottom Product

ABC AB/C ....(2)

A/BC B/C.... (1)Component Feed (wt%) Feed

flowrateMean relative

volatility

Propane 1.54 230.9 2.5iso-butane (LK)

29.5 4423.7 1.3

n-Butane (HK)

67.7 10152.0 1.0

Isobutene 0.13 19.5 0.91-butene 0.20 30.0 0.8Neopentane 0.11 16.5 0.7Isopentane 0.77 115.5 0.6n-Pentane 0.08 12.0 0.425

• 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.

• 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

FEED PURIFICATION

ABSORBER100% η

STRIPPER100% η

13

14

16

15

17

19

• 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)

T= 70 °CP= 160 kPa

T= 245 °CP= 12 kPa

Feed mixture

Offgas to utility

Lean solvent

Rich solvent

Product

Purified solvent to solvent tank

• Solvent = Dibutyl Phthalate (C16H22O4)

• High solubility to MAN

• Availability = Port Klang, Malaysia

• Cost =

PRODUCT RECOVERY

• 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.

Product purification

110°c

10bar

19

20

21

Input

Distillate Product

Bottom Product

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

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

PRELIMINARY MASS BALANCE

INPUT OUTPUT

MASS BALANCE AROUND REACTOR

MASS BALANCE AROUND FEED DISTILLATION COLUMN

MASS BALANCE AROUND FLASH VESSEL

Propane = 0.0 kmol/hiso-butane = 1.3 kmol/hn-butane = 10.8 kmol/hisobutene = 0.2 kmol/h1-butene = 0.2 kmol/hNeopentane = 0.1 kmol/hIsopentane = 0.3 kmol/hn-Pentane = 0.1 kmol/hOxygen = 591.9 kmol/hNitrogen = 3189.0 kmol/hWater = 390.4 kmol/hMaleic Anhydride = 40.4 kmol/hCarbon Dioxide = 41.6 kmol/hCarbon Monoxide = 41.6 kmol/hDibutyl Phthalate = 0.0 kmol/h




ABSORBER

Feed Offgas

Rich Solvent

Lean Solvent

MASS BALANCE AROUND ABSORBER

STRIPPER

Feed Product




Solvent Recovery

MASS BALANCE AROUND STRIPPER

MASS BALANCE AROUND PRODUCT DISTILLATION COLUMN

Energy Balance around Reactor

Energy Balance around Feed Distillation Column

Energy Balance around Stripper

Energy Balance around Product Distillation Column

PRELIMINARY ENERGY BALANCE

Entalphy for propane (input) = ΔHf°(i) + cp(i) (T i – Tref) = -103.8 + 0.074 (300 -25)= -83.6 kJ/mol

Entalphy for propane (ouput) = ΔHf°(i) + cp(i) (T i – Tref) = -103.8 + 0.074 (400 -25)= -76.2 kJ/mol

ENERGY BALANCE AROUND REACTOR

Q = ΔH= (ΣnoutH out – ΣninH in) / 3600= (-76452537.53 - 27266534.1)/3600= -28810.8 kW or -28.8 MW

ENERGY BALANCE AROUND REACTOR

Condenser

Reboiler

ENERGY BALANCE AROUND FEED DISTILLATION COLUMN

Condenser

Reboiler

Gas (191.8°C --> 25°C) Gas (25°C) --> Liquid (25°C) Liquid (25°C --> 190.8°C) Components mCpdT (kJ/hr) mλ (kJ/hr) mCpdT (kJ/hr) Water -5484553.4 42873.4 54516.6 Maleic Anhydride -1103534.1 76674.3 96918.2 Q (KJ/h) -1158379.5 79547.7 51434.8 Qtotal (kw) -659.4

Gas (354.1°C --> 25°C) Gas (25°C) --> Liquid (25°C) Liquid (25°C --> 355.1°C) Components mCpdT (kJ/hr) mλ (kJ/hr) mCpdT (kJ/hr) Dibutyl Phthalate -4154.1 1463.3 4166.6 Q (KJ/h) -4154.1 1463.3 4166.6 Qtotal (kw) 2200

ENERGY BALANCE AROUND STRIPPER

Condenser

Reboiler

ENERGY BALANCE AROUND PRODUCT DISTILLATION COLUMN

ECONOMIC POTENTIAL

CUMULATIVE DISCOUNTED CASH FLOW DIAGRAM

PROFITABILITY ANALYSIS

ECONOMICS EVALUATION

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

ECONOMIC POTENTIAL

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

-500,000,000

0

500,000,000

1,000,000,000

1,500,000,000

2,000,000,000

2,500,000,000

Cumulative Discounted Cashflow at i=10%

Year

Cum

ulati

ve D

iscou

nted

Cas

h Fl

ow

Pay Back Period = 6th yearFuture worth = RM1,900,234,524

CUMULATIVE DISCOUNTED CASH FLOW DIAGRAM

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

70

PROFITABILITY ANALYSIS

PROCESS FLOW DIAGRAM(BEFORE

HEAT INTEGRATION)

HEAT INTEGRATION

STREAM DATA

QC = 14697.20 kW Tpinch: 400°C

PROBLEM TABLE ALGORITHM

QC = 14697.20 kW

COMPOSITE CURVE

Process Recovery: 29748.1 kW

GRAND COMPOSITE CURVE

HEAT EXCHANGER NETWORK

Cold utility Hot utility

Before integration (kW) 29743.82 44182.14

After integration (kW) 14697.20 0

Energy saved (kW) 15046.62 44182.14

Percent of energy saved (%) 50.6 100

TOTAL ENERGY SAVING

PROCESS FLOWDIAGRAM

(AFTERHEAT INTEGRATION)

80

PROCESS FLOW DIAGRAM

81

MATERIAL BALANCE TABLE

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:i. Plant Site Location: Teluk Kalong Industrial Area, Kemaman,

Terengganuii. Capacity: 30,000 TPAiii. Production Rate: 31,375 TPAiv. Purity: 98%v. Future Worth: RM1,900,234,524vi. Pay Back Period: 6th yearvii. Energy Recovery: 100% Hot Utility, 50% Cold Utility

CONCLUSION

design of maleic anhydride (man) production plant group 4 afiq noor bin tuah 11857 mohd fadhli bin...

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