Vinyl Chloride Production Senior Design Presentation

Jeremy Dry Bryce Lawson Phuong Le

Group 10

Israel Osisanya Deepa Patel Anecia Shelton

Project Purpose
To design an environmentally safe vinyl chloride production plant. Questions: What is Vinyl Chloride? How its being produced? How much does it cost to be environmentally friendly?

Vinyl Chloride
99% of VCM is used to manufacture polyvinyl chloride (PVC). PVC consumption is second to low density polyethylene. VCM production results in a number of unwanted by-products.

VCM Plant Emissions in the United States

0.0008 0.0007 0.0006

lb/lb VCM product

0.0005 0.0004 0.0003 0.0002 0.0001 0 1 2 3 4 5 6 7 8 9

1 2 3

Formosa-LA Oxyvinyls-D-TX Oxyvinyls-L-TX

4 5 6

Georgia Gulf-LA Westlake Monomers-KY Formosa-TX

7 8 9

Borden-LA Dow-LA Dow-TX

Manufacturing Methods
Vinyl Chloride Vinyl Chloride Vinyl Chloride Route) Vinyl Chloride from Acetylene from Ethane from Ethylene (Direct from Ethylene (EDC)

Balanced Process for Vinyl Chloride Production

Direct chlorination Oxychlorination EDC pyrolysis Overall reaction CH2CH2 + Cl2 ClCH2CH2Cl (EDC) CH2CH2 + 2 HCl + O2 EDC+ H2O 2 EDC 2 CH2CHCl (VCM) + 2 HCl 2 CH2CH2 + Cl2 + O2 2 CH2CHCl + H2O

No generation of HCl 95% of the worlds VCM is produced utilizing the balanced process

Balanced Process for Vinyl Chloride Production

HCl recycle

Air or O2 Oxychlorination

Light ends

Ethylene

EDC purification

EDC pyrolysis EDC recycle Heavy ends

VCM purification

VCM

Cl2

Direct chlorination

Direct Chlorination and Oxychlorination P&ID

CAUSTIC SCRUBBERS DC REACTOR OXYREACTOR

Vinyl Chloride Plant Reactor Design

Theoretical reactor design equations Literature kinetic data used to calculated rate constants Numerical Integration used to calculated specified parameters

Reactor Design

d dFk = wk 4 dz

2 t

Fk = molar flow rate z = tube length dt = tube diameter wk = iri

ri = kf[Ck]-kr[Ck]

Oxychlorination Chemistry
Set R-1 R-2 R-3 R-4 R-5 Reaction DCE formation TCE formation C2H4 combustion CuCl oxidation CuCl2 regeneration Stoichiometry C2H4 + 2CuCl2 C2H4Cl2 + 2CuCl C2H4 + 3CuCl2 C2H4Cl3 + 3CuCl +0.5H2 C2H4 + 3O2 2CO2 + 2H2O 2CuCl + 0.5O2 CuO-CuCl2 CuO + CuCl2 CuO + 2HCl CuCl2 + H2O

Plus nine other main by product formation reactions Excel Reactor Model of Oxychlorination

Oxychlorination Reactor Results

Oxy Reactor Effluent Flow Rates (lb-mol/hr) EDC Water TEC CO2 Ethylene Oxygen HCl Acetylene 1341 1341 1.26 140 5.5 2.76 0.015 0.13 Chloral CCl4 Methyl Chloride Chloroform Chloroethane Chloroprene Vinyl Acetylene Dichloromethane 0.25 1.25 0.12 0.11 0.11 0.10 0.09 0.10

Oxychlorination Reactor Parameters

Reactor Temperature (oC) Reactor Pressure (psig) Reactor Volume (ft3) Tube Diameter (in) Tube Length (ft) Residence Time (hr)

305 58 461 2 1320 0.05

DC Reactor Modeling Results

DC Reactor Kinetic Results Modeling Literature Values Results Conversion of ethylene Selectivity to EDC 99.93% 99.8% 99.94% 99.4% DC Reactor Parameters Reactor Temperature (oC) Reactor Pressure (psig) Reactor Volume (ft3) Tube Diameter (in) Tube Length (ft) Residence Time (hr) 120 15 90 2 115 0.018

EDC Purification P&ID

WATER WASH HEAVIES COLUMN LIGHTS COLUMN

EDC Pyrolysis P&ID

CRACKING FURNACE FURNACE FEED FLASH EFFLUENT QUENCH SECTION

EDC Pyrolysis Reactor Modeling Results

Conversion of EDC per pass is maintained at 50-55% Increasing cracking severity beyond this level results in insignificant increase in conversion and a decrease in selectivity to VCM. Conversion can be increased by the addition of CCl4 Modeling results produced conversion equal to 60% Major by products of EDC pyrolysis: Acetylene, benzene, 1-3 butadiene, vinyl acetylene, chloroprene.

VCM Purification P&ID

HCl COLUMN VCM COLUMN FEED FLASH

Pro II Simulation PFD

S5 S4 OP1 F1 S34

1 M1 2 3 4 5 6 S1 S25 SC1 S12 S28 S11 7 S29 S33 S6 9 10 11 S30 F3 S31 S3 M6 15 S26 T1 S22 S24 S2 E1 SC2 S23 SP3 S61 F2 M7 16 17 S35 T2 30 S40 S44 T3 42 T4 S64 S38 12 13 14 8 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 S36 1 S41

1 S59 2 3 4 5 6 7 8 9 10 11 12 S55 13 14 15 16 17 18 S56 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 2 3 4 5 6 7 8 9 10 11 12 13 S58 14 15 16 17 18 19

1 S62 S60

S52 S53 S54 S39 S49 S43 R1 S45 E3 F6 S51 E4 F7

S27 M5

S48 S42 M8

F5

E2

F4

S63

S50

20

S57

Liquid Liquid

Heat Integration
Pinch Design Method

Optimization method that reduces energy cost Utilizes process to process heat transfer Optimal pinch temperature 316oF

Heat Integration
Grand Composite Curve
1000 900

QHmin

Temperature (F)

800 700 600 500 400 300 200 100 0 0 50 100 150 200 250 300 350

Pocket of Heat Recovery

QCmin

Duty (MMBtu/hr)

Heat Integration Results

Hot Utility 401 308 MM Btu/hr Cold Utility 251 158 MM Btu/hr Energy Reduction Results in a savings of $2.4 Million/year!

Waste Stream Treatment

Location of Waste Streams

EDC Purification/Pyrolysis Oxychlorination Reaction Section Direct Chloriantion Caustic Scrubber

Contents of Waste
Liquid Waste Ethylene EDC C2HCl3 VCM Vapor Waste Ethylene EDC Carbon Tetrachloride CHCl3 Dichloromethane C2HCl3 C2H2 VCM C2HCl3O Vinyl Acetylene Chloroethane

Types of Waste Treatment

Condenser Catalytic Incinerator Absorber/Scrubber Thermal Incinerator Flare

Waste Treatment Selected

Multiple Treatment Process Selected Consists of thermal incineration, absorption column, and caustic scrubbing unit

Treatment PFD
CO2, NOx Water Cl2, H2O, HCl CO2, NOx Incinerator Liquid Waste Water + HCl NaOH

Absorption

CO2, NOx Cl2

Water + NaCl + NaOCl

Caustic Scrubbing

Vapor Waste

Products of Waste Treatment

Water and HCl (solution) Water, NaCl, and Sodium Hypochlorite (solution) Carbon Dioxide and Nitrous Oxides

Incineration Unit Design

Auxiliary Fuel Flowrate Needed (Qf) Qf = Qw (X/Y) where, X = 1.1Cpo(Tc Tr) Cpi(Ti Tr) hw Y = hf 1.1Cpo(Tc-Tr) Qf = 331 lb/hr

Absorption Column Design

Amount of Solvent (Water) L = G*(Yi Yo)/(Xo Xi) L = 154,000 lbs/hr Column Diameter (Dt) 4VM v DT = fU f (1 Ad / A) v Dt = 5.7 ft

Absorption Column Design Contd

Number of Theoretical Stages (NOG)
N OG ln{[( A 1) / A][(Yi KX i ) /(YO KX i )] + (1 / A)} = ( A 1) / A

NOG = 20

Overall Height of a Transfer Unit (HOG) HOG = G/KyaS HOG = .75

Absorption Column Design Contd

Hpack Packing Height = NOG*(HOG)

Hpack = 15 ft

Caustic Scrubbing Design

L DT NOG HOG Hpack = = = = = Design 45,000 lbs/hr 4.5 ft 12 .83 10 ft

Waste Water Treatment

Waste Water Streams

DC Caustic Scrubber (L/hr) Water NaCl HCl Chloral EDC CCl4 TCE 280 48 Water Wash Drum (L/hr) 41,000 0 200 26 680 180 170

Limits and Treatment Options

EPA Limit (mg/L) HCl Chloral EDC CCl4 TCE 5 1 .005 .005 .005 Treatment Options GAC Incinerator w/Afterburner GAC -GAC Boiling -GAC Fluidized Bed Incineration -Incineration -GAC

Granular Activated Carbon

EPA Recommended Control Technology Ability to remove > 99% of contaminants Simple design and operation No hazardous waste byproducts Ability to operate at low temperatures and pressures

GAC Operation
Makeup Carbon In Effluent

Water Flow Carbon Column Influent

Carbon Movement

Column Specifications
Carbon Mass Adsorber Volume Adsorber Area Velocity Contact Time Equilibrium Saturation 21000 lb 170 ft3 36 ft2 7 ft/min 27 min 19 days

Carbon Regeneration
Carbon In 200-300oF 300-450oF 400-1000oF 1000-1600oF 1600-1800oF 1600-1800oF Rabble Teeth Gas Out Rabble Arm

Carbon Out

HAZOP Studies- Safety Concern

Purpose: Reduce risk at workplace Identify risks, prevent and reduce impact Subdivide into small sections Deviations, Causes, Consequences, Safe Guard and Actions

PFTR Reactor

Plant Location Location Factors

Raw Materials
Distance Abundance

Total Tax
Corporate Income Tax Sales Tax Property Tax Corpus Christi, TX

Wages Utilities Land Cost

Taft, LA

Factor Rating Maximization

TX LA Factor Weight % Raw Material 3 miles 17 miles Distance 30 4 2 Abundance 25 40% 32% Total Tax 20 1.03 0.95 Wages 12 $2.7/MMBtu $2.5/MMBtu Utilities 8 $1270/acre $640/acre Land Cost 5

Factor Rating Maximization

Weight % x Value % = Factor Rating Taft, LA
0.64

Corpus Christi, TX
0.96

Plant Capacity
Forecasting

Economic Analysis 4.09 billion lb/yr

Economic Analysis 6.44 billion lb/yr Risk & Probability Analysis

Economic Analysis 10.5 billion lb/yr

Decision

Forecasting
Price s of Chlorine v s. Ye ar
220 Prices of Chlorine ($/ton)

Find Mean Value & Std. Dev Apply to Monte Carlo Simulation

200

180 y = 2.112x - 4017.7 R2 = 0.9548

160

140 1975

1980

1985

1990 Year

1995

2000

2005

Forecasting
Year 2004 2005 2006 2007 2008 2009 2010 2011 Std. Dev. Ethylene ($/ton) 492.5 499.4 506.2 513.1 519.9 526.7 533.6 540.4 24.17 Chlorine ($/ton) 212.2 214.1 216.1 218.0 219.9 221.8 223.8 225.7 10.56 Oxygen ($/ft3) 0.001445 0.001436 0.001427 0.001418 0.001409 0.001400 0.001391 0.001382 0.000102 VCM ($/ton) 499.2 506.2 513.2 520.2 527.2 529.2 535.2 543.21 26.15

NPW & ROI

NPW =
k =1
n

n 1

(1 + i )

CFk

CFn + VS + I W

(1 + i )

TCI

TCI = CFk (1 + r ) k + (Vs + I w )(1 + r ) n

k =1

Where TCI= total capital investment CF = cash flow i = interest rate = 0.05 Vs = savage value Iw = working capital

Economic Analysis
Plant Capacity 4.09 billion lb/yr 6.44 billion lb/yr 10.5 billion lb/yr

TCI

$47,110,000

$68,886,000

$77,154,000

NPW

$133,739,000

$284,828,000

$161,759,000

ROI

0.24

0.25

0.20

Risk Analysis
Monte-Carlo simulation

Mean and Standard Deviation Random Number Generation NPW Risk Measurement Probability

Decision: Plant Capacity Detailed Economic Analysis

Monte Carlo
Assume normal distribution Perform random walks
Norminv(Rand(), Mean, Std. Dev.)

Stop the iterations when the data converges

Approximately 1000 trials

Reduce error compared to analytical approach

Procedure
Random Number Generation Raw material Cost Total Product Cost

Income from selling VCM

Gross Income

Net Present Worth

Cash Flow

Net Profit

Risk & Probability

Project Risk Curves

1

Cummulative Probability

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 -6000 -4000 -2000
6.44 billion lb/yr

2000
4.09 billion lb/yr

4000
10.5 billion lb/yr

6000

Net Present Worth ($106)

Comments
Capacity of 4.09 billion lb/yr:
41.7% chance of negative NPW

Capacity of 6.44 billion lb/yr:

31.5% chance of negative NPW

Capacity of 10.5 billion lb/yr:

36.8% chance of negative NPW

Probability vs. Net Present Worth

0.35 0.3 0.25
Probability

Highest Probability of positive NPW

0.2 0.15 0.1 0.05 0

-4500 -3000 -1500 0 NPW ($10 )
6

1500

3000

6.44 billion lb/yr

4.09 billion lb/yr

10.5 billion lb/yr

Decision
Plant Capacity of 6.44 billion lb/yr:

Highest NPW Highest ROI Lowest risk: 31.5 % of losing money High probability of making money

Detailed Economic Analysis

Plant Capacity: 6.44 billion lb/yr Plant Equipment: Four Heat Exchangers Four Distillation Towers Seven Flash Tanks Three Reactors Adsorption System Incineration Unit Total Equipment Cost: $15.3M

Total Capital Investment Total Equipment Cost Variables Equipment Installed Incineration Unit (install) Instrumentation & Control Piping (installed) Electrical (installed) Total Building Cost Office Process Building (5-Unit) Service Building Storage Building Maintenance Unit/Shop Administration/Accounting Environment/Research Total Yard Improvement Site Cleaning Grading Fencing Walkways Total Land Cost Total Direct Plant Cost Engineering & Supervision Construction Expenses Contractor's Fee Contingency Total Indirect Cost Fixed Capital Investment Working Capital Total Capital Investment Description 47% of TEC (P&T) Flow Rate Correlation 18% of TEC (P&T) 50% of TEC (P&T) 11% of TEC (P&T) $15,284,100 Cost ($) 7,183,527 10,500 2,751,138 7,642,050 1,681,251 19,268,466
2

$45/ft (Brick Building) in 3000 ft 2 2 $15/ ft (Steel Building)in 4600 ft /Unit 2 2 $45/ ft (Brick Building) in 2000 ft 2 2 $15/ ft (Steel Building)in 4000 ft /Unit 2 2 $45/ ft (Brick Building) in 1500 ft 2 2 $45/ ft (Brick Building) in 2500 ft 2 2 $45/ ft (Brick Building) in 3000 ft

135,000 375,000 90,000 62,500 67,500 112,500 135,000 977,500 220,000 4,650 81,000 22,500 328,150 63,500 35,921,716 4,890,912 6,266,481 3,209,661 6,419,322 20,786,376 56,708,092 13,144,326 69,852,418

$4400/acre (total of 50 acres) $465/acre (total of 10 acres) $9/ft (total of 9000 ft) 2 2 $4.50/ ft (total of 5000 ft ) $1270/acre (total of 50 acres) 32% of TEC (P&T) 41% of TEC (P&T) 21% of TEC (P&T) 42% of TEC (P&T) Direct+Indirect 86% of TEC (P&T) Direct+Indirect+Working Capital

Employee
Plant Chairman Managers Plant Manager Unit Managers Operational Engineers Computer Programmer Computer Engineer Chemical Engineers Process Engineers Electrical Engineers Environment Engineers Industrial Engineers Mechinical Engineers Maintainance Engineers Operator Supervisor Administration Financial Manager Production Manager Sales Manager Accounting Budget Analysts Finantial Analysts Tax Preparers Auditor Total

# of Employee $/yr 1 $105,000 1 5 1 2 5 5 3 3 3 2 2 30 5 1 1 1 2 1 2 2 $80,000 $73,000 $62,890 $74,310 $72,780 $73,000 $68,630 $62,000 $61,900 $63,500 $30,000 $68,000 $70,000 $60,000 $68,000 $60,000 $53,000 $62,000 $33,000 $35,000

Total $105,000 $80,000 $365,000 $62,890 $148,620 $363,900 $365,000 $205,890 $186,000 $185,700 $127,000 $60,000 $2,040,000 $350,000 $60,000 $68,000 $60,000 $106,000 $62,000 $66,000 $70,000 $5,137,000

Economic Summary
Total Product Cost-$1.59 billion Net Profit- $26.2 million NPW- $265 million ROI-23.7%

Environmental Impact vs. Profit

Waste Reduction Algorithm

Evaluate effects of design changes on environment Reactors can not be varied
Exothermic reactions allow heat integration

Variable design parameters

Oxygen usage Furnace temperature

Impact Calculations
Impact/hr Ii = Mj x xkjk
Mj = mass flow rate of stream j xkj = mass fraction of chemical k in stream j -k = characteristic potential impact of chemical k

Environmental Impact vs. Profit

190000

E I ( lb / H r)

Oxygen hot utility, Oxygen furnace, incinerator incinerator 185000 Oxygen hot utility, furnace All Oxygen
180000 175000

Oxygen All Air Oxygenincinerator furnace

170000

165000 -30 -20 -10 0 10 20 30

Profit (Million $)
Original Furnace Temperature Lower Furnace Temperature Higher Furnace Temperature

Sequestering CO2 Emissions

Enhanced oil recovery Brine aquifers injection Located beneath shale layer 3100 ft FCI is a function of CO2 flow rate
27.753 $/(kg/hr) = $11.4 million

OC is a function of CO2 flow rate and depth

0.0000912 $/(kg/hr)(ft) = $183,000/yr

VCM Plant Emissions in the United States

0.0008 0.0007 0.0006

lb/lb VCM product

0.0005 0.0004 0.0003 0.0002 0.0001 0.0000 1 2 3 4 5 6 7 8 9 10

2 3 4

Formosa-LA

Georgia Gulf-LA

Borden-LA

Capital Investment to achieve this emission reduction = $2.5 Million Oxyvinyls-D-TX 6 Westlake Monomers-KY 9 Dow-LA Decreased Net Profit = $1.3 Million/year
Oxyvinyls-L-TX 7 Formosa-TX 10 Dow-TX

Conclusion
Balanced Process Incineration and Carbon Adsorption 6.4 billion lbs/year Taft, LA Sequestration of CO2