CONTROL OF SULFUR DIOXIDE

AND SULFUR TRIOXIDE USING

MAGNESIUM-ENHANCED LIME
Joseph Potts and Erich Loch
Cinergy Corporation
Lewis Benson, Robert Roden and Kevin Smith
Carmeuse North America

Overview Of Talk
Background on control of SO3 with Mg(OH)2
and Ca(OH)2

Magnesium-enhanced lime FGD process with

byproduct Mg(OH)2

Results of 800 MW and 1300 MW

demonstrations of SO3 control with byproduct
Mg(OH)2

Description of 1300 MW byproduct Mg(OH)2

and SO3 control system

SO3 control costs byproduct Mg(OH)2 vs.

commercial Mg(OH)2
Control of SO2 and SO3 Using Magnesium-enhanced Lime

SO3 Emission from Coal-fired

Plants
From oxidation of SO2 in furnace and
SCR
Up to 3% oxidation, 70 ppmv SO3
Can foul heat transfer surfaces
Can cause visible plume
TRI substance

Control of SO2 and SO3 Using Magnesium-enhanced Lime

Background on SO3 control with

Mg(OH)2
Furnace injection of magnesium
hydroxide to control SO3
Reacts selectively with SO3 to form watersoluble MgSO4, but not with SO2

Decades of experience in oil-fired units

Some use in coal-fired units
Increases melting point of slag

Control of SO2 and SO3 Using Magnesium-enhanced Lime

Magnesium-Enhanced Lime FGD

Process Description
Wet FGD process (Thiosorbic process)
Uses lime reagent with 3-6 wt.% MgO,
balance CaO
Mg increases SO2 removal and allows low
L/G
21 L/G (3 l/Nm3) for 91% removal with 4% sulfur
coal

Low chemical scaling potential

Liquid in absorber only 10% gypsum-saturated
Lime is source of Mg for byproduct Mg(OH)2
Control of SO2 and SO3 Using Magnesium-enhanced Lime

800 MW and 1300 MW

Demonstrations of Furnace
Injection of Mg(OH)2
DOE/NETL program by URS co-

sponsored by EPRI, First Energy, AEP,

TVA, and Carmeuse
Objectives
90% SO3 removal
Reduce plume opacity
Study balance-of-plant effects on:
Slag accumulation
SCR catalyst
ESP
Fly ash composition

Control of SO2 and SO3 Using Magnesium-enhanced Lime

Mg(OH)2 Injection Locations

Furnace
Mg(OH)2
Injection
Locations

Selective
Catalytic
Reduction

ESP

Wet
FGD

Control of SO2 and SO3 Using Magnesium-enhanced Lime

800 MW and 1300 MW

Demonstrations of Furnace
Injection of Mg(OH)2
800 MW unit
AH, ESP (100 SCA), magnesium-enhanced
lime wet FGD
Baseline SO3 32-39 ppmv at ESP outlet

1300 MW unit
SCR, AH, ESP (400 SCA), magnesiumenhanced lime wet FGD
Baseline SO3 37 ppmv at economizer
outlet, 65 ppmv at SCR outlet

Control of SO2 and SO3 Using Magnesium-enhanced Lime

SO3 Removal in 800 MW

Furnace
SO3 Removal at ESP Outlet

100%
90%
80%
70%
60%
50%
40%

Long-term test

30%

Short-term test

20%
10%
0%
0

2
3
4
5
6
Mg:SO3 Ratio (baseline on ESP outlet SO3)

Control of SO2 and SO3 Using Magnesium-enhanced Lime

SO3 Removal in 1300 MW

Furnace
100%
90%

SO3 Removal

80%
70%
60%
50%
40%
30%
20%
10%
0%
0

1
2
3
4
5
6
7
Mg:SO3 Molar Ratio based on economizer outlet SO 3 concentration

Control of SO2 and SO3 Using Magnesium-enhanced Lime

SO3 Removal Across 1300 MW

Furnace and SCR
SO3 Removal at ESP Outlet

100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
0

Mg:SO3 Molar Ratio (based on baseline SCR outlet SO 3)

Control of SO2 and SO3 Using Magnesium-enhanced Lime

800 MW and 1300 MW

Demonstrations of Furnace
Injection of Mg(OH)2
No adverse impact on SCR catalyst or
slagging
ESP impact
800 MW adverse when SO3 reduced to 34 ppmv
1300 MW - no adverse impact
Opacity monitor readings reduced from 16-20%
to 10-15%

Byproduct and commercial Mg(OH)2

gave similar results
Control of SO2 and SO3 Using Magnesium-enhanced Lime

800 MW and 1300 MW

Demonstrations of Furnace
Injection of Mg(OH)2
Visible opacity significantly reduced
Flyash composition within spec for
sulfate

Control of SO2 and SO3 Using Magnesium-enhanced Lime

Hydrated Lime [Ca(OH)2]

Injection for SO3 Control
12 micron avg. particle size, 16 m2/gram
Demonstrated at 1300 MW for control of
SO3 following SCR
Injected after air heater
Demonstrated at 1300 MW (Zimmer
station) with post-SCR SO3
concentrations
Injected after ESP
Captured in FGD absorber and completely
utilized
Control of SO2 and SO3 Using Magnesium-enhanced Lime

Control of SO2 and SO3 Using Magnesium-enhanced Lime

Magnesium-Enhanced FGD Process

with Byproduct Mg(OH)2
C le a n e d G a s
M a g n e s iu m
Enhanced
L im e

A b s o rb e r

W a te r

O x id iz e r

F lu e
G as

B e lt F ilte r

S la k e r

In e r ts

C o m p re s s e d
A ir

L im e
S lu r r y
Tank

G ypsum
B y p ro d u c t

P re -T re a te d
F G D E fflu e n t
B y p ro d u c t
M a g n e s iu m
H y d r o x id e
S y s te m

P r e c ip ita tio n
Tank
p H 9 .5 - 1 0

G ypsum
to O x id iz e r

M a g n e s iu m
H y d r o x id e

Control of SO2 and SO3 Using Magnesium-enhanced Lime

Byproduct Mg(OH)2 System at

Zimmer
L im e
4 TPH
C a (O H )2

F G D E fflu e n t
631 gpm

P r e c ip ita tio n
Tank
p H 9 .5 - 1 0 .5

P re -T re a te d
F G D E fflu e n t
to P o n d s
550 gpm
G ypsum
to O x id iz e r
7 TPH

M a g n e s iu m
H y d r o x id e S lu r r y
to S O 3 C o n tro l
3 T P H M g (O H )2

MgSO4 + Ca(OH)2 + 2H2O

CaSO42H2O (gypsum) +
Mg(OH)2
Control of SO2 and SO3 Using Magnesium-enhanced Lime

MagnesiumEnhanced Lime
Absorber
Babcock & Wilcox
atdesign
Zimmer
54 ft (16.5 m) high
Station
straight shell
L/G is 21 gal/1000
acfm (3 l/m3) for 91%
SO2 removal

Control of SO2 and SO3 Using Magnesium-enhanced Lime

Ex-Situ Oxidizer at Zimmer

Station

Control of SO2 and SO3 Using Magnesium-enhanced Lime

Byproduct Mg(OH)2 from

Magnesium-Enhanced Lime Wet
FGD Process
Byproduct process developed by
Carmeuse
Piloted in 1995 at Cinergys Zimmer
station with support of EPRI, Ohio Coal
Development Office and Cinergy
Two plants currently producing
byproduct Mg(OH)2

Pre-treats FGD wastewater

Reduces dissolved solids by 80%, metals
Control of SO2 and SO3 Using Magnesium-enhanced Lime

Composition of Byproduct
Mg(OH)2
Mg(OH)2, wt. %
Gypsum, wt. %
Inerts, wt. %
Total Suspended
Solids in slurry, %
BET Specific
Surface Area, m2/g
Median Particle
Size, microns

73
21
6
20
55
3

2 m ic ro n s

Control of SO2 and SO3 Using Magnesium-enhanced Lime

1300 MW SO3 Control System

Design Parameters at Zimmer
Station
Mg(OH)2 injection system design
3 TPH Mg(OH)2
Mg:SO3 ratio = 8
90% removal of furnace-generated SO3

Ca(OH)2 injection system

4 TPH Ca(OH)2
Ca:SO3 ratio 7.7
90% removal of SO3 post-SCR

Control of SO2 and SO3 Using Magnesium-enhanced Lime

SO3 Control Costs with Mg(OH)2

Study by Carmeuse of 1300 MW
byproduct Mg(OH)2 system
$5.4 million capital cost
O&M cost $67/ton Mg(OH)2
Compares with commercial Mg(OH)2 cost
of ~$210/ton
$2.5 million/yr savings
2 year payback
Wastewater pre-treatment at low cost

Control of SO2 and SO3 Using Magnesium-enhanced Lime

Conclusions
Injection of byproduct Mg(OH)2

demonstrated at 800 and 1300 MW for

90% capture of furnace-generated SO3
Byproduct Mg(OH)2 system being installed
in 1300 MW plant, start-up 1st quarter 2004
Byproduct process pre-treats FGD
wastewater
Byproduct Mg(OH)2 cost compares
favorably with cost of commercial Mg(OH)2
Hydrated lime controls SO3 formed during
SCR
Control of SO2 and SO3 Using Magnesium-enhanced Lime