INVISTA DBA Dibasic Acid

For Flue Gas DesulfurizationN b 17 2010 Novem

ber 17, 2010

© 2010 INVISTA
Disclaimer

**The information set forth herein is furnished free of charge and is based on technical d

INVISTA believes to be reliable, provided that INVISTA makes no representation or warracomp y leteness or accuracy thereof. The information is intended to be used for information

only and on a without prejudice basis and should not be viewed as giving technical advicor otherwise. It is intended for use by persons having technical skill, at their own discre

who will make their own determination as to its suitability for their purposes prior to use

precaution information contained herein is given with the understanding that those using 

themselves that their particular conditions of use present no health or safety hazards As themselves that their particular conditions of use present no health or safety hazards. As 

material, evaluation of any compound under end-use conditions prior to specification is eNothing herein is to be taken as a license to operate under or a recommendation to infripatents. In no event will INVISTA be responsible for damages of any nature whatsoever the use of or reliance upon the information contained herein or the product to which the 

refers. NO REPRESENTATION OR WARRANTIES, EXPRESSED OR IMPLIED, OF MERCHANFITNESS FOR A PARTICULAR PURPOSE, OR ANY OTHER NATURE ARE MADE HEREUNDERESPECT TO THE INFORMATION CONTAINED HEREIN OR THE PRODUCT TO WHICH THINFORMATION REFERS. The data and information contained herein are the exclusive prINVISTA and nothing herein shall be construed as authorization or license to use print oINVISTA and nothing herein shall be construed as authorization or license to use, print, osuch data or information.Unless explicitly stated, no license or immunity under any patent is either granted or impthis presentation or through the technical information provided herein.

© 2010 INVISTA
INVISTA overview

• INVISTA: one of the world’s largest integrated producers 

pol dfb ymers and fibers

– Primarily nylon, spandex and polyester applications

• Subsidiaries of Koch Industries, Inc. acquired INVISTA fr

DuPont in 2004 and combined it with KoSa

• History of innovation and leadersh

• Enriching daily life: Enriching daily life: clothing carpe

clothing, carpe

luggage, plastic bottles, automobiairbags and more

• More th 00 d an 700 unique patents and

significant intellectual property

• www.INVISTA.com

© 2010 INVISTA
INVISTA’s shareholder

• INVISTA is an independently managed, 

wh ll d b idi f K h I d t i I holly owned subsidiary of Koch Industries, Inc. 

• Koch Industries, Inc. is one of the largest 

privately held companies in the world

• Koch companies: 60 countries, approximately 70,000 em• Businesses/industries:

– Refining and Chemicals Refining and Chemicals – Polymers and Fibers Polymers and Fibers– Process and Pollution Control – Commodity Trading 

Equipment and Technologies and Services

– Minerals – Forest & Consumer Prod

Forest & Consumer Prod

– Fertilizers – Ranching

• www.kochind.com

© 2010 INVISTA
Role of INVISTA DBA in flue gas desulfurization (FG

• Organic acid additives have been successfully used in coal-burn

power plant wet scrubbers since the 1980’s

• Drivers for the use of DBA in FGD Systems

– Regulatory compliance– Reduce cost (maintenance, energy, capital)– Flexible fuel strategy Flexible fuel strategy

• O ga c ac d add t es suc o e rgani

c acid additives such DBA 

offer:

– Improved scrubbing efficiency & operational flexibility– Improved reliability– Reduced operating cost

© 2010 INVISTA
Utility of DBA additive in FGD systems

• Retrofit to existing wet scrubbers

– Improve performance

– Overcome design limitation– Increase operational flexibility– T h l f h i f t fit li ti Tec

hnolo

gy o

f c

h

oice 

for re

trofit applications

• Original equipment for new wet scrubbers

– Reduce capital cost (minimize the amount of overdesign necessary to 

meetin

g SO

2-removal requirements)

– Increase SO

2 removal efficiency (95% +)

– Increase limestone utilization or use lowergrade limestone

– Reduce coal cost – Reduce maintenance cost– Contin

gency plannin

g for spray header or recirculation pump problem

© 2010 INVISTA
Limitations of wet limestone scrubbers

• Dissol dl d l d lve

d limestone provi

des liqui

d-p

hase

neutralizing capability (LOW solubility)

• At high pH, SO

2 dissolves and is rapidly neutralized

Li t

Gas 

– Neutralization of SO

2 consumes liquid-phase

neutralizing capability

• Rapid depletion of neutralizing capacity at surface of droplet 

Limes

tone

& water

– Replenished more slowly by diffusion of dissolved reagent from interior 

of droplet to the surface

• De

p g letion of dissolved rea

gent from interior

– Limited replenishment due to low solubility of limestone and slow 

dissolution rate

• When dissolution of limestone cannot keep up with consumption of liquid When dissolution of limestone cannot keep up with consumption of liquidphase neutralizing capacity, pH drops and SO

2 adsorption slows

© 2010 INVISTA
Chemistry of wet limestone scrubbers (simplified)

Without DBA• CaCO

3 (limestone) is virtually insoluble, 

but dissolves to provide a small amount 

With DBA• DBA “predissolves” limeston

• CaDBA is soluble and provid

of SO

2-neutralizin

g capacity • CaDBA is soluble and provid

SO

2-neutralizing capacity tha

CaCO

3 + DB

A CaDB

A + 

CaCO

3(solid) CaCO

3(aq)

SO

2(g) SO

2(aq)

H

2SO

3 + CaDBA CaSO

H

2SO

3

SO

2(g) SO

2(aq)

SO

2(aq) + H

2

O

H

2SO

3

H

2SO

3 + CaCO

3

C

a

S

O

4

SO

2(aq) + H

2

O

CaSO

3 + H

2O + CO

2

C

a

S

O

3

+

Air

• Liquid-phase neutralizing capacity is 

depleted by SO

2 neutralization

• Rate of replenishment depends on • More liquid-phase neutralizin

l bl f l

CaSO

3 + Air CaSO

4

C

a

S

O

3

+

Air C

a

S

O

4

Rate of replenishment depends on

limestone dissolution

• When LS dissolution cannot keep up with 

SO

2 neutralization, pH drops and SO

2

bbi

available 

for SO

2 neutralizati

• Rate of replenishment is incr• pH does not drop as much, s

scrubbi

n

g stops effi i i i d ffi

ciency is improve

d

© 2010 INVISTA
Typical FGD unit with DBA addition

Flue g

DBA

(solution

Flue gas in

Reagent

or flake)

Reaction

tank

Dewater

Limestone

Grinding

Reagent

storage

tank

Water (recycle)

© 2010 INVISTA
Typical benefits of DBA on FGD scrubber

100

Improved SO

2 removal 

efficiency

cy

Lower liquid/gratio for reduce

95

al Efficienc 100

nt) 140

Chloride tolerance

3

ratio for reduceenergy consum

90

O2 Remova 859095

val Efficiency (perce

No additive 100

120

G, gallons/kcf

S

7580

0 20000 40000 60000

Chloride, ppm

SO2 Removo add t e 500 ppm DBA 1000 ppm DBA 80 100

0 500 1000 

DBA Additive, ppm

L/

85

0 500 1000 1500 

ppm DBA

© 2010 INVISTA
Potential DBA benefits to FGD (on Large Utility Boilers)

Parameter

Wet Scrubber on Large Utility Boilers without DBA

Wet Scrubber owith DBA

SO2 Removal efficiency 80-90% (typical) 90-98% 1Limestone consumption

Increasing limestone feed to improve SO2 removal may result in poor 

limestone utilization.

Improved SO2 rem

need for excess limlimestone utilizatio

Gyp q y sum 

quality Standard FGD solids Hi

g py her 

purity at n

Solids disposal (non-gypsum producers) Typical FGD solids

Less solids and lowto better limeston

Increasing liquid/gas ratio to improve

Improved SO2 remoperation at lower 

Slurry recirculation energy

Increasing liquid/gas ratio to improve

SO2 removal may increase energy use.

operation at lower reducing energy u

Scaling and plugging

Scaling and plugging may cause downtime and reduced removal efficiency.

Reduced scaling ain less downtime aefficiency

Chloride inhibition

Buildup of chloride reduces limestone utilization and scrubbing efficiency Higher efficiency e

Fuel (i.e. coal) selection

Choice of fuel may be limited by emission constraints

Improved SO2 rem

range of fuel optio

The DBA benefits described above are a general summary of modeling and industry experience. Actual benefits will vary with individual scrubber and operational parameters.1 – Percent reduction will depend upon FGD scrubber design and individual unit operational parameters.

© 2010 INVISTA
DBA consumption

DBA is slowly depleted through several different mechanism• Slow oxidation (chemical degradation)

- Oxidation and decarboxylation- Some oxidation products remain functional

• System purges (blow down) System purges (blow down)• Co-precipitation with solids in natural or inhibited oxidation scrubbe

– Not significant with forced oxidation

• Solution losses (process liquor entrained with solids)

The dominant mechanism(s) will be determined by mode o

of the FGD unit

© 2010 INVISTA
Testing DBA in FGD scrubbers

100

95

al Efficiency

90

SO2 Remov

85

0 500 1000 1500 2000

ppm DBA

The shape and curve will be unique for each scrubber and must determined by testing.

© 2010 INVISTA
Barriers to DBA testing and use

• People and time (motivated site advocate, support services) • Regulatory (e g potential impact on air and water permits) Regulatory (e.g. potential impact on air and water permits)• Aversion to change (potential disruption to operations, concern 

gypsum quality, new chemical, uncertainty about DBA benefits)

• Cost (of testing equipment and additive) Cost (of testing, equipment and additive)• Misalignment of corporate and site objectives (e.g. corporate g

minimize overall SO

2 compliance costs vs. site goal to minimize 

operating expenses) operating expenses)

• Implementation – lack of physical facilities to store and meter D

into system

• Lack of large scale testing facilities (i e no DBA storage tank) Lack of large scale testing facilities (i.e. no DBA storage tank)

© 2010 INVISTA
DBA addition and testing concepts

DBA

Hot water supply

Flush water supplied

to all required points

10001200

h)

2. DBA feed started

1. Baseline 

data acquired

Typical permanent facility

DBA

Storage 

Tank

Heater

Backpressure

Regulation

to all required points

DBA feed to 

i di id l

DBA

Storage 

Tank

Heater

Backpressure

Regulation

to all required points

DBA feed to 

i di id l

400600800

SO2 emissions (pph

3. Virtually immediate decrease in SO2 emissions

Recirculating

Pumps

Regulating

Valves

Flow

Meters

indi

vidual

FGD units

Recirculating

Pumps

Regulating

Valves

Flow

Meters

indi

vidual

FGD units

0

200

012345

Day

Temporary / test facility

Lime

DBA Trailer slurry 

Feed and control system

FGD 

DBA Trailer

Pump Regulating valve Flow meter

• Transfer lines electrically heated to prevent DBA crystallization

© 2010 INVISTA
Temporary facility for testing DBA

• DBA added directly from trailer to two scrubber reaction tanks to 

concentration of approximately 1200 ppm in scrubber

• The response was immediate. Performance was monitored as DB

concentration declined to develop efficiency curve

1 0

100%

0 50.81.0

O2 Emissions Baseline data (before DBA addition) Adding trailer #1 to 97% 98% 99%

val Efficiency

0 00.30.5

Relative SOAdding trailer #1 to reaction tank #1 Adding trailer #2 to 

reaction tank #2

94%95%96%

SO2 Remov

** As each scrubber is unique, it is important to run a test to determine scr

performance as a function of DBA concentration in the scrubber

0.0

02468

Time (hours)

94%

0 200 400 600 

ppm DBA

performance as

a function of DBA concentration in the scrubber

© 2010 INVISTA
Wastewater issues6,7

• Highly site specific

– Some sites are “zero discharge” – no issue– Others have varying outfall requirements (BOD, aquatic tox., e

• DBA is an organic diacid and contributes toward BOD / CO

– DBA is “readily biodegradable” – the most easily degradable cla– Some degradation occurs in the scrubber and downstream equ– Activated sludge ponds wetlands are all effective bio Activated sludge, ponds, wetlands are all effective bio-oxidizers 

oxidizers 

degrees

• Studies to date show no adverse effect on Se removal by b

Studies to date show no adverse effect on Se removal by b

at DBA levels up to 2000 ppm in the waste water7

• Several specialized firms can assist with wastewater treat

© 2010 INVISTA
INVISTA DBA supply update

• September 2008

– Hurricane IKE hits Texas gulf coast near Hurricane IKE hits Texas gulf coast near

Galveston

– Extensive flooding forces shutdown and 

damages INVISTA damages INVISTA s’ Orange TX facility Orange, TX facility

• 2009-2010

– INVISTA re

pgp ositions 

global adi

pic acid 

business for world-class competitiveness and growth

• First quarter 2011 First quarter 2011

– INVISTA anticipates re-start of the 

Orange, TX adipic acid facility

© 2010 INVISTA

Used with permission from The Orange Leade
INVISTA DBA

• INVISTA can provide free trial quantities of DBA 

solution – contact us for details

• T h i l d il bl i l d Technical documents available on request include:

– DBA shipping and handling guidelines for flue gas desulfurization– Measurement of buffer capacity of FGD scrubber liquid Measurement of buffer capacity of FGD scrubber liquid– Testing INVISTA dibasic acid (DBA) in wet scrubbers– DBA in FGD brochure

• If you face any hurdles planning your trial, please call 

us. INVISTA may be able to help!

Contact Us:1-800-231-0998

db i i t

© 2010 INVISTA

www.dba.invista.com
References

1. “The Role of Organic Acids in Flue Gas Desulfurization”, INVISTA publication.2. “Testing INVISTA Dibasic Acid (DBA) in Wet Scrubbers”, INVISTA publication

3. Overview on the Use of Additives in West FGD Systems, R.E. Moser and E.R. Owens

1991 SO2 Control Symposium. Vol 1. Electric Power Research Inst., Palo Alto, CA, 3A.1-3A.21

4. Incorporating Full-Scale Experience into Advanced Limestone Wet FGD Designs., P.C

(ABB Environmental Systems). Proceedings: 1991 SO2 control symposium. Volume Power Inst., Palo Alto, CA (United States) Nov 1992. p. 8A.43-8A.66

5. “Testing yp and Commercialization of Byproduct Dibasic Acids as Buffer Additives for Li

Gas Desulfurization Systems,” J. C. S. Chang and J. D. Mobley, J.A.P.C.A., 33(10) 95

6. Duke Power WFGD Retrofit Program: Compliance via Standardization and Selective S

Innovations, Jim McCarthy, Jurgen Dopatka, Phil Rader, Clark Bussell (Alstom and SPower-Gen International 2005. Available on the web at 

http://www.power.alstom.com/home/events/past_events/power_gen_international/__56769.pdf

7. ABMet Biological Selenium Removal from FGD Wastewater. Jill Sonstegard, Tim Pick

Environmental (includes the former Applied Biosciences Corp) Official Proceedings - 

Water Conference (2005), 66th, IWC.05.72/1-IWC.05.72/5. Available from www.esw

© 2010 INVISTA