dry sorbent injection of trona for sox mitigation...title dry sorbent injection of trona for sox...

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Copyright 2006, Solvay America, Inc. Solvay Chemicals, Inc. John Maziuk What is Trona? Trona is a ore that is mined underground Trona is naturally formed sodium sesquicarbonate Na 2 CO 3 NaHCO 3 2H 2 O Green River formation Numerous beds of Trona Contain billions of tons of Trona

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Page 1: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

What  is  Trona?

lTrona  is  a  ore  that  is  mined  undergroundlTrona  is  naturally  formed  sodium  sesquicarbonate

lNa2CO3• NaHCO3•2H2OlGreen  River  formationlNumerous  beds  of  TronalContain  billions  of  tons  of  Trona

Page 2: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Solvay  Chemicals  Operationsl Solvay  Chemicals,  Inc.  Currently  Mines  

Trona  Ore  at  an  Approximate  Depth  of  1500’  

(457m)l 12’  (3.67m)  Thick  and  

of  Very  High  Qualityl Provide  Ore  for  Many  

Yearsl Use  Both  Longwall  

Mining    and  Bore  Miners

Page 3: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Room  and  Pillar  Mining

Page 4: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

The  Surface  Plant

Page 5: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Trona  Dry  Sorbent  Injection  (DSI)

l “Popcorn  Effect”l ...5 to  20  times  the  original  surface  area

l 2(Na2CO3• NaHCO3•2H2O)  →

3Na2 CO3  +   CO2  +  5H2O

Page 6: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Trona  SEM  After  Calcination

Page 7: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Trona  DSC

Page 8: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Trona  DSI  Chemistry

2(Na2CO3• NaHCO3•2H2O) +3SO3 →3NaSO4 +5H2O  +  4CO2  

2(Na2CO3• NaHCO3 •2H2O)  +  3SO2  → 3Na2SO3    +  4 CO2  +  5H2O

3Na2SO3  +  1.5O2→ 3Na2SO4

Page 9: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Parameters  -­ Constraints  That  Affect  Sorbent  Utilization:

l Sorbent Injection Ratel NSR (Normalized Stoichiometric Ratio)l Sorbent Particle Sizel Sorbent Residence Time In The Flue Gas Streaml Sorbent Penetration And Mixing Within The FlueGas

l Particulate Control Device Usedl Other Acids

Page 10: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Trona  DSI  with  Baghouse

SO2  Removal

0%20%40%60%80%100%

0 0.5 1 1.5 2 2.5NSR

%  Removal

Trona Soda  Ash

Page 11: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Impact  of  Particle  Size  on  TronaPerformance  @325oF

 Effect  of  Sorbent  Size  @  NSR  1Source:  Solvay  Chemicals

0

20

40

60

80

100

11 14 32 65 93

microns

%SO2  Removal

Page 12: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Trona  DSI  @  Baghouse  Conditions

l PSD  is  very  important  to  SO2  Removal  Efficiency.

SO2  Removal  

00.20.40.60.81

1 2 3 4 5 6 7 8 9 1

NSR

%  SO2  R

emoval

T200<38  micron

Page 13: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Case  Study  at  a  Glass  Furnace  in  California

l A  Glass  Plant  Was  Having  Operational  Problems  With  A  Dry  Sorbent  SOx Mitigation  System

l Sodium  Bicarbonate  Crystals  Were  Being  Milled  And  Then  Dry  Injected    Into  The  Duct  From  The  Furnace  Just  Prior  To  The  Hot  Side  ESP

l The  Perf  Plates  Would  Plug  Quickly  Causing  Frequent  Shutdowns

l After  XRD  And  DSC  Analyses  They  Lowered  The  Injection  Temperature  By  Adding  Outside  Air.    

l The  Lower  Injection  Temperature  Delayed  The  Pluggage  By  Several  Days  But  Did  Not  Solve  The  Problem

Page 14: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

ESP  Perf  Plates  Using  Sodium  Bicarbonate  >700oF

Page 15: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Perf  Plates  Using  Sodium  Bicarbonate  at  550oF

Page 16: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Sodium  Sulphate  III

Page 17: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Case  Study  at  a  Glass  Plant  in  California  (continued)

l The  Glass  Company  Decided  To  Test  Tronal T200  Performed  Much  Better  At  The  >700oF  Injection  Temperature  Rangel Higher  SOx Removalsl Higher  Utilization  Efficiencyl Air  Cooling  At  The  Injection  Point  Is  Not  Necessaryl Milling  T200  Had  Only  A  5%  Utilization  Efficiency  Improvement  Over  Sodium  Bicarbonate

l No  Plugging    Occurred

Page 18: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Trona  DSI  

SO2  Removal  w/  Trona  @  Glass  Plant

50%

60%

70%

80%

90%

100%

1.051.051.191.401.501.501.501.501.501.501.501.502.74

NSR

SO2  Removal

Page 19: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Trona  DSI

SOx  Removal  w/  Trona  @  Glass  Plant

50%55%60%65%70%75%80%85%90%95%100%

530 550 700 700 710 710 720 725 750 750 750 805 805o F

Page 20: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Perf  Plate  Before  Hot  Side  of    ESP  in  Previous  Slide  After  Two  Weeks  of  T200  DSI  and  still  

“clean  as  a  whistle”

Page 21: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Test  Data,  continuedFigure  5:

Gavin  Unit  2:  SO3  Reduction  Lime  and  Trona  Data:  SCR  Out  of  Service

0%10%20%

30%40%50%60%70%

80%90%100%

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0Moles  Sorbent  :  Moles  SO3

%  SO3  Reduction  Measured  at  ESP  

Outlet

Trona  -­  No  ESP  Conditioning

Trona  ESP  Conditioned

Lime

Page 22: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Trona  DSI  Benefits

l High  Removals  With  Low  Cost  Positionl Low  Initial  Capitall Low  Sorbent  Costl High  SOx    Removal

l Saved  The  Glass  Plant  $$$/Ton  Of  SOx Removal  Costs  Via  SBC

l Milling  Improved  T200  SOx Removal  Efficiency  By  5  -­ 10%

l Spent  Sorbent  And  Unused  Sorbent  Can  Be  Sent  Back  To  Furnace

Page 23: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Typical  Trona  DSI  Loading/Storage  System

Page 24: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

Dry  Sorbent  Injection  (DSI)

l Dry  Sorbent  Injection  Of  T200  Is  A  Very  Cost  Effective  Way  To  Mitigate  Acid  Gas  Emissions.    l Low  Capitall Does  Not  Require  Heating  Of  Tanks  Or  Linesl Requires  Few  Mechanical  Partsl Compatible  With  ESPs,  Baghouses  And  Most  Wet  Scrubbers

l Will  React  With  Acid  Gases  Over  A  Wide  Temperature  Range  (2750F  -­ 18000F)

l Trona  Sorbent  Specifically  Designed  To  Be  Used  For  Neutralization  Of  Acid  Gases  That  Can  Be  In  Emissions  From  Boilers,  Kilns,  Combustors,  Furnaces  And  Incinerators.

Page 25: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

DSI  of  Trona    

l Because  Of  The  Positive  Effect  Sodium  Has  On  The  Resistivity  Of  Particles  It  Is  Not  Detrimental  To  The  Operation  Of  An  ESP  And  Can  Actually  Enhance  It’s  Operation

l Trona  Will  Act  As  A  Precoat  On  Baghouse  Filter  Media    

l Trona  for  DSI  is  A  Fine  (D50 30-­35µ) Material  That  Can  Be  Easily  Aerated  For  Pneumatic  Transfer

l Trona  for  DSI  Can  Be  Used  As  Is  Or  Milled  To  A  Smaller  Size.  

Page 26: Dry Sorbent Injection of Trona for SOx Mitigation...Title Dry Sorbent Injection of Trona for SOx Mitigation Created Date 11/22/2015 10:14:52 PM

Copyright  2006,  Solvay  America,  Inc.Solvay  Chemicals,  Inc. John  Maziuk

The  End