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Water Management in Process Plants David Puckett Débora Campos de Faria Miguel J. Bagajewicz

Water Management in Process Plants

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Water Management in Process Plants. David Puckett Débora Campos de Faria Miguel J. Bagajewicz. Sources of Refinery Wastewater. Caustic Treating. NH 3 and H 2 S Water Contamination. Distillation. Water Contamination with Organics. Amine Sweetening. NH 3 and H 2 S Water Contamination. - PowerPoint PPT Presentation

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Page 1: Water Management in Process Plants

Water Management in Process Plants

David PuckettDébora Campos de Faria

Miguel J. Bagajewicz

Page 2: Water Management in Process Plants

Sources of Refinery Wastewater

Caustic Treating

Distillation

Amine Sweetening

Merox Sweetening

Hydrotreating

Desalting

NH3 and H2S Water Contamination

Water Contamination with Organics

NH3 and H2S Water Contamination

NH3 and H2S Water Contamination

Water Contamination with NH3, H2S, and Organics

Saline Water Contamination

Page 3: Water Management in Process Plants

Water Management Methods Wastewater produced in industrial processes

can be handled in three fashions.

End-of-Pipe Cleanup

Reuse

Regeneration

Page 4: Water Management in Process Plants

Regeneration Methods API separator and activated carbon to

remove organics from distillation and hydrotreating wastewater.

Reverse osmosis to removesaline contamination from desalting wastewater.

Chevron wastewater treatment to remove acid gas contamination from caustic treating, sweetening, and hydrotreating wastewater.

Page 5: Water Management in Process Plants

Wastewater Optimization Current methods of optimizing water reuse

and regeneration rely on several assumptions.

Operating and capital costs are functions solely of treated water flow rate.

Fixed process outlet concentrations.

Page 6: Water Management in Process Plants

Wastewater Optimization

22% of the amount of contaminant removed,89% of the FCI

51% of the amount of contaminant removed,78% of the FCI

AFCI

$458000

BFCI

$408000

CFCI

$317000

Page 7: Water Management in Process Plants

Wastewater Optimization Depending on the contaminants present and

the treatment processes used, the assumption that regeneration costs are dependent solely on flow rate may not be valid.

The optimum solution for a water allocation problem must take into account factors other than flow rate.

Page 8: Water Management in Process Plants

Removal of Organics

Distillation

Hydrotreating

Wastewater Contaminated with Organics

API Separator and Activated

Carbon Adsorber

Wastewater Free of Organics

Page 9: Water Management in Process Plants

API Separator Removes multi-phase contamination through

differences in specific gravity.

Page 10: Water Management in Process Plants

API Separator Appropriate for use with any contaminant that

forms a distinct phase in the process water.

Oil and Light Organics

Organic and InorganicSediment

Page 11: Water Management in Process Plants

API Separator Simulation The basis of the separation

is Stokes’ Law.

For a given contaminant in water, rate of settling is determined solely by contaminant particle size.

Quality of separation can be improved through flocculation and coagulation.

9

2 2

fpS

grV

Buoyant Force

Gravitational Force

Drag Force

Page 12: Water Management in Process Plants

API Separator Simulation Process water contaminant concentration

does not change quality of separation. Percentage of contaminants removed on a

volume basis determined based on a normal distribution of particle radii.

dr

dr

er

erRr

Rr

r

2

2

2

2

23

0

23

min

21

34

21

34

Page 13: Water Management in Process Plants

Quality of Separation vs. Length

Volume Percent of Contaminants Removed

0

20

40

60

80

100

0 10 20 30 40 50 60

Separator Length (m)

Vol %

of C

onta

min

ants

Separator Depth = 1 mSeparator Width = 2 mEntrance to Separator at 0.5 mProcess Water Flow Rate = 1 m3 / sContaminant SG = 0.95Mean Contaminant Diameter = 0.5 mm

Quality of separation improves with increasing length, but with diminishing returns.

Page 14: Water Management in Process Plants

Quality of Separation vs. Specific Gravity

Volume Percent of Contaminants Removed

0

20

40

60

80

100

0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5

Contaminant SG

Vol %

of C

onta

min

ants

Separator Depth = 1 mSeparator Width = 2 mSeparator Length = 25 mEntrance to Separator at 0.5 mProcess Water Flow Rate = 1 m3 / sMean Contaminant Diameter = 0.5 mm

Separation quality is poor for contaminants similar in density to water.

Page 15: Water Management in Process Plants

Quality of Separation vs. Particle Diameter

Volume Percent of Contaminants Removed

0

20

40

60

80

100

0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Contaminant Particle Diameter (mm)

Vol %

of C

onta

min

ants

Separator Depth = 1 mSeparator Width = 2 mSeparator Length = 25 mEntrance to Separator at 0.5 mProcess Water Flow Rate = 1 m3 / sContaminant SG = 0.95

Quality of separation improves with increasing particle diameter, but with diminishing returns.

Page 16: Water Management in Process Plants

Quality of Separation vs. Wastewater Velocity

Volume Percent of Contaminants Removed

0

20

40

60

80

100

0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Wastewater Velocity (m/s)

Vol %

of C

onta

min

ants

Separator Depth = 1 mSeparator Width = 2 mSeparator Length = 25 mEntrance to Separator at 0.5 mContaminant SG = 0.95Mean Contaminant Diameter = 0.5mm

Quality of separation improves with decreasing velocity. A velocity of zero would give perfect separation.

Page 17: Water Management in Process Plants

Quality of Separation vs. Settling Distance

Volume Percent of Contaminants Removed

0

20

40

60

80

100

0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Height of Separator Entrance (m)

Vol %

of C

onta

min

ants

Separator Depth = 1 mSeparator Width = 2 mSeparator Length = 25 mContaminant SG = 0.95Process Water Flow Rate = 1 m3 / s

Quality of separation improves with decreasing settling distance. Separators that handle oil will have entrance as close to water surface as possible.

Page 18: Water Management in Process Plants

Equipment Cost vs. Flow rateEquipment Cost for API 40 Oil Removal

$2,000.00

$4,000.00

$6,000.00

$8,000.00

$10,000.00

$12,000.00

$14,000.00

0 0.2 0.4 0.6 0.8 1

Flow Rate (m3 / s)

Equi

pmen

t Cos

t ($

at M

&S In

dex

of 1

000)

75% Drop in Concentration85% Drop in Concentration95% Drop in Concentration98% Drop in Concentration99% Drop in Concentration99.5% Drop in Concentration

Separator Depth = 1 mSeparator Width = 2 mMean Particle Diameter = 1 mmProcess Water Flow Rate = 0.5 m3 / s

Equipment cost is sensitive to both flow rate and separation quality.

Page 19: Water Management in Process Plants

Operating Cost vs. Flow rateOperating Cost for API 40 Oil Removal

$0.00

$20,000.00

$40,000.00

$60,000.00

$80,000.00

$100,000.00

$120,000.00

0 0.2 0.4 0.6 0.8 1

Flow Rate (m3 / s)

Ope

ratin

g Co

st ($

/ yr

)

Separator Depth = 1 mSeparator Width = 2 mMean Particle Diameter = 1 mmProcess Water Flow Rate = 0.5 m3 / s

Operating cost is sensitive only to flow rate.

Page 20: Water Management in Process Plants

API Separator Performance With a normal distribution of particle

diameters, quality of separation can be solved analytically.

A bit impractical to implement.

Page 21: Water Management in Process Plants

API Separator Performance

Varying h

Varying L

Varying SG

Varying Dp Varying F/A

The approximation is quite close for all variables. The worst fit is for changes in settling height.

Page 22: Water Management in Process Plants

API Separator Equipment Cost

Equipment cost is dependent on flow rate, quality of separation, specific gravity of contaminant, contaminant particle size, settling distance, and the price of steel.

Varying F and %QS

Varying ΔSG, Dp, h

Page 23: Water Management in Process Plants

API Separator Operating Cost

Operating cost is dependent solely on flow rate.

Page 24: Water Management in Process Plants

Activated Carbon Removes soluble contaminants through

adsorption onto the activated carbon surface.

Page 25: Water Management in Process Plants

Activated Carbon Appropriate for use with liquid or gaseous

contaminants that are water soluble or form emulsions.

Dissolved Organics

Insoluble Organics of < 150 micronsDroplet Size

Dissolved Gases

Page 26: Water Management in Process Plants

Activated Carbon Simulation Separation will follow the

Langmuir isotherm.

For the Langmuir isotherm, the rate of adsorption, assuming negligible pore holdup and spherical adsorbate particles, is as follows.

CKCKNNII

IIISI 1

rr

rrdCdNt

CDC I

I

IPP

PIPI

2

2

Page 27: Water Management in Process Plants

Activated Carbon Simulation For a fixed bed adsorber,

process water should reachequilibrium with activatedcarbon prior to end of bed.

A constant length of bedis required for adsorption.

Page 28: Water Management in Process Plants

Water Treatment Rate vs. Adsorbant Surface Area

Activated Carbon Adsorption

05

10152025303540

200 700 1200 1700 2200

Adsorbant Surfac e Area (m2 / kg)

Max

Wat

er T

reat

ed (

m3

/ hr

)

Contaminant Diffusivity = 5 * 10 ^ -11 m2 / sLangmuir Coefficient = 0.06 m3 / kgSaturation Adsorption = 0.4 kg / kg adsorbantInlet Contaminant Concentration = 0.25 kg / m3

Greater adsorbant surface area results in faster adsorption and a faster rate of treatment.

Page 29: Water Management in Process Plants

Time in Service vs. Adsorber Diameter

Activated Carbon Adsorption

0200400600800

1000120014001600

0 0.5 1 1.5 2

Adsorber Diameter (m)

Tim

e Be

twee

n Re

gene

rati

ons

(hrs

) Contaminant Diffusivity = 5 * 10 ^ -11 m2 / sLangmuir Coefficient = 0.06 m3 / kgSaturation Adsorption = 0.4 kg / kg adsorbantInlet Contaminant Concentration = 0.25 kg / m3

A greater diameter has more adsorbant per unit length and thus will take longer to saturate.

Page 30: Water Management in Process Plants

Time in Service vs. Adsorber Height

Activated Carbon Adsorption

0

50

100

150

200

250

300

0 5 10 15 20 25

Adsorber Height (m)

Tim

e Be

twee

n Re

gene

rati

ons

(hrs

)

Contaminant Diffusivity = 5 * 10 ^ -11 m2 / sLangmuir Coefficient = 0.06 m3 / kgSaturation Adsorption = 0.4 kg / kg adsorbantInlet Contaminant Concentration = 0.25 kg / m3

The saturation wave travels through the adsorber at a constant speed.

Page 31: Water Management in Process Plants

Outlet Concentration vs. Inlet Concentration

Activated Carbon Adsorption

0

0.01

0.02

0.03

0.04

0.05

0.06

0 0.2 0.4 0.6 0.8 1

Inlet Conc entration (kg / m3)

Out

let

Conc

entr

ation

(kg

/

m3)

Contaminant Diffusivity = 5 * 10 ^ -11 m2 / sLangmuir Coefficient = 0.06 m3 / kgSaturation Adsorption = 0.4 kg / kg adsorbant

Outlet concentration from adsorber is dictated by adsorption thermodynamics.

Page 32: Water Management in Process Plants

Equipment Cost vs. Flow Rate

Activated Carbon Adsorption

$0.00

$2,000.00

$4,000.00

$6,000.00

$8,000.00

$10,000.00

$12,000.00

0 5 10 15 20 25

Flow Rate (m3 / hr)

Equi

pmen

t Co

sts

($)

Contaminant Diffusivity = 5 * 10 ^ -11 m2 / sLangmuir Coefficient = 0.06 m3 / kgSaturation Adsorption = 0.4 kg / kg adsorbantInlet Contaminant Concentration = 0.25 kg / m3

Wastewater pump and column diameter must scale for flowrate.

Page 33: Water Management in Process Plants

Operating Costs vs. Flowrate

Activated Carbon Adsorption

$0.00

$50,000.00

$100,000.00

$150,000.00

$200,000.00

$250,000.00

0 5 10 15 20 25

Flow Rate (m3 / hr)

Ope

rati

ng C

osts

($

/ yr

)

Contaminant Diffusivity = 5 * 10 ^ -11 m2 / sLangmuir Coefficient = 0.06 m3 / kgSaturation Adsorption = 0.4 kg / kg adsorbantInlet Contaminant Concentration = 0.25 kg / m3

A greater flow rate means more regenerations per year in addition to increased pumping work.

Page 34: Water Management in Process Plants

Equipment Cost vs. Inlet Concentration

Activated Carbon Adsorption

$0.00

$2,000.00

$4,000.00

$6,000.00

$8,000.00

$10,000.00

0 0.2 0.4 0.6 0.8 1

Inlet Conc entration (kg / m3)

Equi

pmen

t Co

sts

($)

Contaminant Diffusivity = 5 * 10 ^ -11 m2 / sLangmuir Coefficient = 0.06 m3 / kgSaturation Adsorption = 0.4 kg / kg adsorbantInlet Contaminant Flow Rate = 7.035 m3 / hr

No changes in the adsorber need to be made to accommodate a greater inlet concentration.

Page 35: Water Management in Process Plants

Activated Carbon Aerogel

Activated Carbon Adsorption

$0.00

$50,000.00

$100,000.00

$150,000.00

$200,000.00

$250,000.00

0 0.2 0.4 0.6 0.8 1

Inlet Conc entration (kg / m3)

Ope

rati

ng C

osts

($

/ yr

)

Contaminant Diffusivity = 5 * 10 ^ -11 m2 / sLangmuir Coefficient = 0.06 m3 / kgSaturation Adsorption = 0.4 kg / kg adsorbantInlet Contaminant Flow Rate = 7.035 m3 / hr

A greater inlet concentration has the same effect as a greater flow rate. More contaminant must be adsorbed necessitating more regenerations.

Page 36: Water Management in Process Plants

Activated Carbon Performance Outlet concentration can be calculated

analytically.

Page 37: Water Management in Process Plants

Activated Carbon Equipment Cost

Equipment cost is dependent on flow rate, inlet concentration, column measurements, and the prices of steel and activated carbon.

Varying F and CIN

Varying D Varying H

Page 38: Water Management in Process Plants

Activated Carbon Operating Cost

Operating cost is dependent only on flow rate and concentration.

Varying F

Varying CIN

Page 39: Water Management in Process Plants

Removal of Salts

DesaltingWastewater

Contaminated with Salts

Reverse Osmosis

Separation

Wastewater Free of Salts

Page 40: Water Management in Process Plants

Reverse Osmosis Removes salts from process water by forcing

water against the salt concentration gradient.

Page 41: Water Management in Process Plants

Reverse Osmosis Suitable for the removal of any soluble

contamination.

Soluble Salts

Soluble Organics

Microorganisms

Page 42: Water Management in Process Plants

Reverse Osmosis Simulation Separation proceeds based

on Fick’s First Law.

For reasonably dilute solutions, the van’t Hoff approximation of osmotic pressure can be used.

Quality of separation is fixed by type of membrane used.

Pz

N PWI

iMRT

Page 43: Water Management in Process Plants

Flow Rate vs. Membrane Area

Purified Water Flow Rate

0

0.0005

0.001

0.0015

0.002

0.0025

0.003

0.0035

0 50 100 150 200 250 300 350 400 450 500

Membrane Area (m2)

Wat

er F

low

Rat

e (m

3/s)

Membrane Thickness = 0.002 mMembrane Permeability = 1.92 * 10-9 ((m3 m) / (m2 sec atm))Brine Pressure = 10 atmBrine Ion Concentration = 100 mol / m3

Ion Rejection Percentage = 0.99

Flow rate and membrane area are linearly related, as would be expected from Fick’s Law.

Page 44: Water Management in Process Plants

Flow Rate vs. Membrane Thickness

Purified Water Flow Rate

0

0.002

0.004

0.006

0.008

0.01

0.012

0.014

0 0.0005 0.001 0.0015 0.002

Membrane Thickness (m)

Wat

er F

low

Rat

e (m

3/s)

Membrane Area = 100 m2

Membrane Permeability = 1.92 * 10-9 ((m3 m) / (m2 sec atm))Brine Pressure = 10 atmBrine Ion Concentration = 100 mol / m3

Ion Rejection Percentage = 0.99

Flow rate and membrane thickness are inversely related, as would be expected from Fick’s Law.

Page 45: Water Management in Process Plants

Flow Rate vs. Brine Pressure

Purified Water Flow Rate

-0.0004-0.0002

00.00020.00040.00060.00080.001

0.00120.0014

1 3 5 7 9 11 13 15

Brine Pressure (atm)

Wat

er F

low

Rat

e (m

3/s)

Membrane Area = 100 m2

Membrane Thickness = 0.002 mMembrane Permeability = 1.92 * 10-9 ((m3 m) / (m2 sec atm))Brine Ion Concentration = 100 mol / m3

Ion Rejection Percentage = 0.99

Flow rate is zero when the pressure gradient is equal and opposite to the osmotic pressure gradient.

Page 46: Water Management in Process Plants

Flow Rate vs. Rejection Percentage

Purified Water Flow Rate

00.00010.00020.00030.00040.00050.00060.00070.00080.0009

0.25 0.35 0.45 0.55 0.65 0.75 0.85 0.95

Rejection Percentage

Wat

er F

low

Rat

e (m

3/s)

Membrane Area = 100 m2

Membrane Thickness = 0.002 mMembrane Permeability = 1.92 * 10-9 ((m3 m) / (m2 sec atm))Brine Pressure = 10 atmBrine Ion Concentration = 100 mol / m3

A higher rejection percentage results in a larger osmotic pressure gradient.

Page 47: Water Management in Process Plants

Flow Rate vs. Brine Concentration

Purified Water Flow Rate

-0.0004

-0.0002

0

0.0002

0.0004

0.0006

0.0008

0.001

0 50 100 150 200 250 300 350 400 450 500

Brine Concentration (mol/m3)

Wat

er F

low

Rat

e (m

3/s)

Membrane Area = 100 m2

Membrane Thickness = 0.002 mMembrane Permeability = 1.92 * 10-9 ((m3 m) / (m2 sec atm))Brine Pressure = 10 atmIon Rejection Percentage = 0.99

Again, flow rate is zero when the pressure gradient is equal and opposite to the osmotic pressure gradient.

Page 48: Water Management in Process Plants

Flow Rate vs. Temperature

Purified Water Flow Rate

0.000610.0006150.00062

0.0006250.00063

0.0006350.00064

0.0006450.00065

0.000655

273 278 283 288 293 298 303 308 313 318 323

Temperature (K)

Wat

er F

low

Rat

e (m

3/s)

Membrane Area = 100 m2

Membrane Thickness = 0.002 mMembrane Permeability = 1.92 * 10-9 ((m3 m) / (m2 sec atm))Brine Pressure = 10 atmBrine Concentration = 100 mol/m3

Ion Rejection Percentage = 0.99

The van’t Hoff approximation introduces a dependence of osmotic pressure on temperature.

Page 49: Water Management in Process Plants

Equipment Cost vs. Flow Rate at 1463 ppm Inlet

TDS = 50 mol / m3 Equipment Cost

$0.00

$500,000.00

$1,000,000.00

$1,500,000.00

$2,000,000.00

$2,500,000.00

$3,000,000.00

$3,500,000.00

$4,000,000.00

0 5 10 15 20 25 30 35

Flow Rate (m3 / hr)

Equi

pmen

t Cos

t ($

at M

&S In

dex

of 1

000)

80% Rejection

96% Rejection

99.2% Rejection

99.84% Rejection

Inlet = 1463 ppm80% = 293 ppm96% = 59 ppm99.2% = 12 ppm99.84% = 2 ppm

Membrane Thickness = 0.0001 mMembrane Permeability = 9.17 * 10-10 ((m3 m) / (m2 sec atm))Brine Pressure = 10 atmBase Ion Rejection Percentage = 0.8

Equipment cost increases exponentially with process water purity as membrane rejection is fixed so membranes must be worked in series to achieve higher purity.

Page 50: Water Management in Process Plants

Equipment Cost vs. Flow Rate at 59 ppm Inlet

TDS = 2 mol / m3 Equipment Cost

$0.00

$500,000.00

$1,000,000.00

$1,500,000.00

$2,000,000.00

$2,500,000.00

$3,000,000.00

$3,500,000.00

$4,000,000.00

0 5 10 15 20 25 30 35

Flow Rate (m3 / hr)

Equi

pmen

t Cos

t ($

at M

&S In

dex

of 1

000)

80% Rejection

96% Rejection

99.2% Rejection

99.84% Rejection

Inlet = 59 ppm80% = 12 ppm96% = 2 ppm99.2% = 0.5 ppm99.84% = 0.09 ppm

Membrane Thickness = 0.0001 mMembrane Permeability = 9.17 * 10-10 ((m3 m) / (m2 sec atm))Brine Pressure = 10 atmBase Ion Rejection Percentage = 0.8

Equipment costs are dependent on the relative inlet/outlet concentrations, not the absolute concentrations.

Page 51: Water Management in Process Plants

Operating Cost vs. Flow Rate at 1463 ppm Inlet

TDS = 50 mol / m3 Operating Cost

$0.00

$200,000.00

$400,000.00

$600,000.00

$800,000.00

$1,000,000.00

$1,200,000.00

$1,400,000.00

$1,600,000.00

0 5 10 15 20 25 30 35

Flow Rate (m3 / hr)

Ope

ratin

g Co

st ($

at M

&S In

dex

of 1

000)

80% Rejection

96% Rejection

99.2% Rejection

99.84% Rejection

Inlet = 1463 ppm80% = 293 ppm96% = 59 ppm99.2% = 12 ppm99.84% = 2 ppm

Membrane Thickness = 0.0001 mMembrane Permeability = 9.17 * 10-10 ((m3 m) / (m2 sec atm))Brine Pressure = 10 atmBase Ion Rejection Percentage = 0.8

The same trends as observed in equipment costs are observed in operating costs.

Page 52: Water Management in Process Plants

Operating Cost vs. Flow Rate at 59 ppm Inlet

TDS = 2 mol / m3 Operating Cost

$0.00

$200,000.00

$400,000.00

$600,000.00

$800,000.00

$1,000,000.00

$1,200,000.00

$1,400,000.00

$1,600,000.00

0 5 10 15 20 25 30 35

Flow Rate (m3 / hr)

Ope

ratin

g Co

st ($

at M

&S In

dex

of 1

000)

80% Rejection

96% Rejection

99.2% Rejection

99.84% Rejection

Inlet = 59 ppm80% = 12 ppm96% = 2 ppm99.2% = 0.5 ppm99.84% = 0.09 ppm

Membrane Thickness = 0.0001 mMembrane Permeability = 9.17 * 10-10 ((m3 m) / (m2 sec atm))Brine Pressure = 10 atmBase Ion Rejection Percentage = 0.8

The same trends as observed in equipment costs are observed in operating costs.

Page 53: Water Management in Process Plants

Reverse Osmosis Performance Outlet concentration defined by membrane

properties.

Page 54: Water Management in Process Plants

Reverse Osmosis Flow Rate

Page 55: Water Management in Process Plants

Reverse Osmosis Equipment Cost

Varying F and CIN

Equipment costs are dependent on flow rate, brine concentration, and membrane cost for single membrane. Cost scales based on bypass ratio and number of membranes in series for a series of membranes.

Page 56: Water Management in Process Plants

Reverse Osmosis Operating Cost

Varying F

Operating costs are dependent solely on flow rate. Cost scales based on bypass ratio and number of membranes in series for a series of membranes.

Page 57: Water Management in Process Plants

Removal of H2S and NH3

Wastewater Contaminated with H2S and

NH3

Chevron Wastewater Treatment

Wastewater Free of H2S and NH3

Caustic Treating

Amine Sweetening

Merox Sweetening

Hydrotreating

Page 58: Water Management in Process Plants

Chevron Wastewater Treatment Removes dissolved gases from wastewater

through stripping and absorption.

Chevron Waste Water Treatment PFD

Ammonia Stripper

Partial Condenser

Ammonia Stream

Water feed

Hydrogen Sulfide Stripper

Hydrogen Sulfide Stream

Partial Reboiler Partial Reboiler

Stripped water

Page 59: Water Management in Process Plants

Chevron Wastewater Treatment Suitable for the removal of any suitably

volatile contaminant.

Hydrogen Sulfide

Ammonia

Page 60: Water Management in Process Plants

Chevron Wastewater Treatment Simulation

Hydrogen Sulfide - Water Stripping

0

0.2

0.4

0.6

0.8

1

0 0.01 0.02 0.03 0.04 0.05 0.06

Liquid Mole Fraction Hydrogen Sulfide

Vapo

r Mol

e Fr

actio

n Hy

drog

en S

ulfid

e

m=L/Gb=Yo-XI(L/G)

Equilibrium Line

McCabe-Thiele Method can be used.

Page 61: Water Management in Process Plants

Quality of Stripping vs. Reboil Ratio

H2S Stripping

0.0070.00720.00740.00760.0078

0.0080.00820.00840.00860.0088

0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Reboil Rati o

Proc

esse

d W

ater

H2S

%

Inlet H2S Concentration = 1000 mol/m3Tray # = 6Outlet Gas = 50% H2S

Superior quality of separation achieved with less of the wastewater boiled.

Page 62: Water Management in Process Plants

Quality of Stripping vs. Number of Trays

H2S Stripping

0

0.005

0.01

0.015

0.02

1 3 5 7 9 11

Tray Number

Proc

esse

d W

ater

H2S

%

Inlet H2S Concentration = 1000 mol/m3Outlet Gas = 50% H2SReboil Ratio = 0.6

Superior separation achieved at greater number of trays, though diminishing returns are noted.

Page 63: Water Management in Process Plants

Quality of Stripping vs. Inlet Concentration

H2S Stripping

0

0.002

0.004

0.006

0.008

0.01

0.012

0.014

0.01 0.02 0.03 0.04 0.05 0.06 0.07

Inlet Water H2S %

Proc

esse

d W

ater

H2S

%

Inlet H2S Concentration = 1000 mol/m3Outlet Gas = 50% H2SReboil Ratio = 0.6Tray # = 6

An increase in inlet concentration will always increase the outlet concentration if all other factors remain constant.

Page 64: Water Management in Process Plants

Equipment Cost vs. Flow Rate

H2S Stripping

$0.00

$5,000.00

$10,000.00

$15,000.00

$20,000.00

$25,000.00

$30,000.00

0 10 20 30 40

Flow Rate (m3 / hr)

Equi

pmen

t Co

st (

$)

Inlet Concentration = 0.0146

Inlet Concentration = 0.0259

Inlet Concentration = 0.0373

Inlet Concentration = 0.0471

Inlet Concentration = 0.0611

Outlet Gas = 50% H2SReboil Ratio = 0.6Tray # = 6

Equipment costs increase in stepped fashion based on need for additional tray to maintain specified outlet concentrations.

Page 65: Water Management in Process Plants

Operating Cost vs. Flow Rate

H2S Stripping

$0.00$1,000,000.00$2,000,000.00$3,000,000.00$4,000,000.00$5,000,000.00$6,000,000.00$7,000,000.00$8,000,000.00$9,000,000.00

0 10 20 30 40

Flow Rate (m3 / hr)

Ope

rati

ng C

ost

($)

Inlet Concentration = 0.0146

Inlet Concentration = 0.0259

Inlet Concentration = 0.0373

Inlet Concentration = 0.0471

Inlet Concentration = 0.0611

Outlet Gas = 50% H2SReboil Ratio = 0.6Tray # = 6

Operating costs insensitive to inlet concentration as primary operating costs is heating of large amounts of water.

Page 66: Water Management in Process Plants

Equipment Cost vs. Flow Rate

H2S Stripping

$0.00

$5,000.00

$10,000.00

$15,000.00

$20,000.00

$25,000.00

$30,000.00

$35,000.00

0 10 20 30 40

Flow Rate (m3 / hr )

Equi

pmen

t Co

st (

$)

Outlet Concentration = 0.012

Outlet Concentration = 0.01

Outlet Concentration = 0.009

Outlet Concentration = 0.008

Outlet Concentration = 0.007

Inlet H2S Concentration = 1000 mol/m3Outlet Gas = 50% H2SReboil Ratio = 0.6

Same trends as observed with varied inlet concentrations.

Page 67: Water Management in Process Plants

Operating Cost vs. Flow Rate

H2S Stripping

$0.00$1,000,000.00$2,000,000.00$3,000,000.00$4,000,000.00$5,000,000.00$6,000,000.00$7,000,000.00$8,000,000.00$9,000,000.00

0 10 20 30 40

Flow Rate (m3 / hr)

Ope

rati

ng C

ost

($ /

yr)

Outlet Concentration = 0.012

Outlet Concentration = 0.01

Outlet Concentration = 0.009

Outlet Concentration = 0.008

Outlet Concentration = 0.007

Inlet H2S Concentration = 1000 mol/m3Outlet Gas = 50% H2SReboil Ratio = 0.6

Same trends as observed with varied inlet concentrations.

Page 68: Water Management in Process Plants

Chevron Wastewater Treatment Simulation

Ammonia - Water Distillation

0

0.2

0.4

0.6

0.8

1

0 0.2 0.4 0.6 0.8 1

Liquid Mole Fraction Ammonia

Vapo

r Mol

e Fr

actio

n Am

mon

ia

m=Reflux Ratio

(YI,YI)

McCabe-Thiele Method can be used.

Page 69: Water Management in Process Plants

Distillation Quality vs. Number of Trays

NH3 Distillation

0

0.005

0.01

0.015

0.02

1 3 5 7 9 11

Tray Number

Proc

esse

d W

ater

NH

3 % Inlet NH3 Concentration = 1000 mol/m3

Outlet Gas = 98% NH3Reboil Ratio = 0.6Reflux Ratio = 0.6

Same trends as observed with stripping column.

Page 70: Water Management in Process Plants

Distillation Quality vs. Reboil Ratio

NH3 Distillation

0

0.001

0.002

0.003

0.004

0.005

0.006

0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Reboil Ratio

Proc

esse

d W

ater

NH

3 %

Inlet NH3 Concentration = 1000 mol/m3Outlet Gas = 98% NH3Reflux Ratio = 0.6Stripping Tray # = 6

Same trends as observed with stripping column.

Page 71: Water Management in Process Plants

Distillation Quality vs. Reflux Ratio

NH3 Distillation

0

0.005

0.01

0.015

0.02

0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Refl ux Ratio

Proc

esse

d W

ater

NH

3 %

Inlet NH3 Concentration = 1000 mol/m3Outlet Gas = 98% NH3Reboil Ratio = 0.6Stripping Tray # = 6

Increasing reflux ratio will improve the quality of the separation. Note the break in the graph at the minimum reflux ratio.

Page 72: Water Management in Process Plants

Equipment Cost vs. Flow Rate

NH3 Distillation

$0.00

$5,000.00

$10,000.00

$15,000.00

$20,000.00

$25,000.00

$30,000.00

0 10 20 30 40

Flow Rate (m3 / hr)

Equi

pmen

t Co

st (

$)

Inlet Concentration = 0.0146

Inlet Concentration = 0.0259

Inlet Concentration = 0.0373

Inlet Concentration = 0.0471

Inlet Concentration = 0.0611

Outlet Gas = 98% NH3Reboil Ratio = 0.6Reflux Ratio = 0.6Stripping Tray # = 6

Same trends as observed with stripping column.

Page 73: Water Management in Process Plants

Operating Cost vs. Flow Rate

NH3 Distillation

$0.00$1,000,000.00$2,000,000.00$3,000,000.00$4,000,000.00$5,000,000.00$6,000,000.00$7,000,000.00$8,000,000.00$9,000,000.00

0 10 20 30 40

Flow Rate (m3 / hr )

Ope

rati

ng C

ost

($)

Inlet Concentration = 0.0146

Inlet Concentration = 0.0259

Inlet Concentration = 0.0373

Inlet Concentration = 0.0471

Inlet Concentration = 0.0611

Outlet Gas = 98% NH3Reboil Ratio = 0.6Reflux Ratio = 0.6Stripping Tray # = 6

Same trends as observed with stripping column.

Page 74: Water Management in Process Plants

Equipment Cost vs. Flow Rate

NH3 Distillation

$0.00$5,000.00

$10,000.00$15,000.00$20,000.00$25,000.00$30,000.00$35,000.00$40,000.00

0 10 20 30 40

Flow Rate (m3 / hr )

Equi

pmen

t Co

st (

$)

Outlet Concentration =0.00982

Outlet Concentration =0.00685

Outlet Concentration =0.00582

Outlet Concentration =0.00534

Outlet Concentration =0.00528

Inlet NH3 Concentration = 1000 mol / m3Outlet Gas = 98% NH3Reboil Ratio = 0.6Reflux Ratio = 0.6

Same trends as observed with stripping column.

Page 75: Water Management in Process Plants

Operating Cost vs. Flow Rate

NH3 Distillation

$0.00

$2,000,000.00

$4,000,000.00

$6,000,000.00

$8,000,000.00

$10,000,000.00

0 10 20 30 40

Flow Rate (m3 / hr)

Ope

rati

ng C

ost

($ /

yr)

Outlet Concentration =0.00982

Outlet Concentration =0.00685

Outlet Concentration =0.00582

Outlet Concentration =0.00534

Outlet Concentration =0.00528

Inlet NH3 Concentration = 1000 mol / m3Outlet Gas = 98% NH3Reboil Ratio = 0.6Reflux Ratio = 0.6

Same trends as observed with stripping column.

Page 76: Water Management in Process Plants

Performance of Chevron Wastewater Treatment H2S Removal

NH3 Removal

Page 77: Water Management in Process Plants

Chevron Wastewater Treatment Equipment Costs

Varying F

Varying Tray Number

Varying D

Equipment costs strongly dependent on number of trays, column diameter, and the price of stainless steel.

Page 78: Water Management in Process Plants

Chevron Wastewater Treatment Operating Costs For both the stripping and the distillation

columns, operating costs follow the below relation.

Page 79: Water Management in Process Plants

Conclusions Capital costs for API separators are heavily

dependent on inlet/outlet concentration ratio. Operating costs for API separators are independent of concentration.

Capital costs for activated carbon adsorption are independent of concentration. Operating costs for activated carbon adsorption are heavily dependent on concentration.

Page 80: Water Management in Process Plants

Conclusions Both capital costs and operating costs for

reverse osmosis are heavily dependent on inlet/outlet concentration ratio.

Capital costs for Chevron Wastewater Treatment are dependent on concentration. Operating costs for Chevron Wastewater Treatment are nearly independent of concentration.

Page 81: Water Management in Process Plants

Water Management Questions?