This work was performed as a task assignment under the FCC Environmental Program, Subtask 5 ,01

ADVANCED         CONTROL ASSESSMENT

Prepared for

U.S. Department of Energy

Pittsburgh Energy Technology Center

Prepared by

Jay Ratafia-Brown

Science Applications International Corporation

Contract No. DE-AC22-87PC79338

March 1989

EX)REVORD

This work was performed as a task assignment under the FCC Environmental Program, Subtask 5 .01. Participants in the preparation of this report inc lude :

       PETC

  Subtask Manager, Charles Drummond

  Technical Coordinator, Diane Revay Madden

  BRSC/SAIC

  Subtask Coordinator, David Henzel

  Principal Author and Investigator, Jay Ratafia-Brown

This report contains information confidential to DOE/PETC• and should not be distributed without PETC permission,

TABLE op CON•rmrtS

Section

1  .     INTRODUCTION AND SUMMARY. .. 1-1

1 . 1 Purpose of Project. .. 1-1

1 . 2 Major NOX Emissions . 1- 1

1 . 3 Current NOX Control Regulations in U.S. , Germany and Japan. . . 1- 7

       1 . 4 Acid Rain Legislation's Impact on Potential NOX Control. .                                    . 1- 10

1 . 5 Need for NOX Control. .. 1 - 11

       1 . 6 Overview of NOX Control Technologies. . .         . 1 - 12

7 Strategies for Developing/Uti1izing NOX Control

Technologies. .  . . . . . . . 1- 15

2  .     SCR TECHNOLOGY REVIEW AND     RECOžoŒNDATIONS. . . . . . . . . . . . . . . .  . 2 - 1

       2 . 1 SCR Overview. .                                    . 2 - 3

2 . 2 SCR Design Configurations. . . . . . . . . . . . . . . . . . 2 - 3

2 . 3 SCR System Performance. . . . . . . . . . . . . . . . . . . . 2 - 6 4 Catalyst Activity and Longevity. .

2 . 5 Recent Operating Experience and Lessons Learned in

              Japan and Germany                                . 2 - 13

        2 . 6 Process Integration and Retrofit Factors      . . . 2 -15

    7 Catalyst Data. . . . . . . . . . . .              . . . . 2 - 17

2 . 8 SCR Economics. .. 2 - 18

2  . 9 SCR R&D Requirements. . . . 2 - 31

3  . 1 SNCR Overview. . . . . . . . . .      . 3 - 1

3  . 2 Design Data. .   3 - 1

. 3 -4

. 3 - 6

. 3 - 10

. 3 - 10

4  .     ELECTROCATALYTTC NOX REDUCTION - SOLID ELECTROLYTE

        DECOMPOSITION CELLS . .                                  . 4- 1

       4 . 1 Technology Overview. . .                        . . . 4- 1

        4. 2 Solid Electrolyte Material. .                         .4-5

        4. 3 Other Electrolyte Materials. . .                     . 4-8

        4 . 4 Electrode Materials. .                            . 4- 10

      4 . 5 Integrated Design Configurations. . . . . .         . 4- 13

     4 . 6 R&D Considerations. . . . . . .                       . 4-13

5  .     ELECTRO-CATALYTIC REDUCTION USING INTENSE ELECTRIC FIELDS AND

DISCHARGES . .  . 5 - 1

6  .     ENHANCED DRY SCRUBBING FOR INTEGRATED NOX CONTROL. .  . 6 - 1

6.1  Technology Overview. . . . . . . . . . . . .  . 6 - 1

6.2  Alternative Dry Scrubbing Additives.    . 6 -6

6 . 3 R&D Requirements. . .. 6 - 14

i

                              TABLE    CONTENTS

(Continued)

    GAS SEPARATION MEMBRANES . .  . 7 - 1 7 . 1 Technology Overview. . .. 7 - 1

7 . 2 Current Membrane R&D. .. 7 -4

7  . 3 Conceptual Process Designs. .   . 7 - 5

  7 . 4 R&D Gaps and Recommendationss. . . . . .               . 7 - 10

8  .     8 . 1 Background. .. 8 - 1

     8 . 2 Japananese Experience. .                             . 8 - 3

     8 . 3 Recent U.S. R&D. .                                   . 8 - 7

8 . 4 R&D Considerations. . . . . . . . . . .                  . 8- 21

REFERENCES

Section. 1-32

Section. 2 -43

Section. 3 - 13

Section. 4- 16

   Section                 . . . . . . 6 - 16

      Section                                           . . . . 7 - 11

Section. 8 - 25

Figure

1-1  Sample NOX Control Technology Review Form. . . . .      . . . . . . . . . . . . . 1 - 2

1-2  General Combustor/Boi1er NOX Control Me thods. . .. 1-13

1- 3  Advanced Flue Gas Denitrification Technologies. . . . . . . . . . . . 1 14

I - 14      Distribution of Annual NOX Emissions by Design Period and Firing Arrangement. .. 1-18 1-5      Comparison of Total NO* Emissions and Unit Capacity. .. 1-18

1-6 Coal -Fired Utility Boilers NOX Retrofit Potential. .. 1-20 1-7 NOX Control Components. . . . . . . . .. . . 1 - 28

1-8        Existing Boiler/NOX Control Technology Representation

Direct NOX Conversion/Reduction Technology Application. . . . .1 29

1-9        Existing Boiler/NOX Control Technology Representation

NOX Separation Technology Application with Secondary

Concentrated NOX Reduction.. 1-31

2-2a "High Ash" SCR Design Configuration. . .

2-2b "Low Ash" SCR Design Configuration. . .

2 -2c         "Cold-Side" SCR Design Configuration. . . . . . . . . . .. 2 -4

2 - 3      Conditions for the Formation of Ammonium

         Sulfate/ Bisulfate. . . . .. 2 - 8

2 -4 General Arrangement of SCR Catalyst (16) .. 2 - 9

2  - 5 Catalyst Space Velocity vs. NO* Removal Efficiency. .. . . 2 - 11 2 - 6 Catalyst Space Velocity vs. Initial NOX Concentration. ,. 2-12 2 - 7 Possible SCR System Ductwork Layout (2) .. . . 2- 16 2 - 8 German SCR Capital Costs (14) .. 2-29

2-9  Comparison of German Estimated Annualized Costs of SCR for "High Ash" Configuration vs . "Cold-Side"

Configuration (14) . .. 2-30

2-10  Retrofit NOX Control Costs : High Sulfur Coal. .. 2-32

(continued)

Figure

2-11  Combination of SNCR and SCR NOX Control Technologies

Effect of SNCR Removal Efficiency, on Required SCR

Catalyst Volume (23) ,  . . . . . . . . . 2 - 3 3

2-12  SCR R&D Requirements. 2- 34

2-13  SCR R&D Requirements Existing High Temperature SCR.  . 2-35

2  - 14  SCR R&D Requirements Low Temperature SCR,  . 2-36

2-15  SCR R&D Requirements Combined SCR (NOX Control) and

S02 Control .. 2-37

2-16  SCR R&D Requirements Economic Trade-off Analyses. . . . . 2 38

2- 17 Krantz Lignite Coke SCR System. . .  . 2 -39

3-1         SNCR NOX Reduction Results at Mainz-Wiesbaden Power

Plant: NOX Reduction Efficiency and NH3 Breakthrough

@ Full Boiler Load (23) .. 3-5

3-2       Full -Scale Urea Injection Test Results. . . .  .. 3-8

3-3 Pilot -Scale Tests with Lime -Urea Hydrates and Mixtures, . . . . , .3 9

Schematic Representation of Solid Oxide Electrolyte Cell for Flue Gas Cleanup. ..4-2

4-2  Model of the Cathodic Electro-Reduction of NO. ..4-6

4-  3     Temperature Range of Decomposition for Various Gases with

Bench-Scale Zirconia Cell at an Applied Voltage of 950 mV,, 4-7

4-4         Comparison of the Rate of Decomposition of NO for

Standard Zirconia vs. Blackened Zirconia. . . . . . . .. 4-9

4-  5     Decomposition of NO Using Various Experimental Electrodes. .4-11

4-6  Decomposition of NO Using Experimental Electrodes, .. 4-12

4-7  Essential Elements of a Baseline Commercial SOx-NOx Removal System. . . . . .

6-1  Niro Proposed Reaction Mechanism. .. 6-5

6-2  Effect of SOx/NOx Ratio on NOX Removal in ANL' s

            20                                    Spray Dryer Test. . .6-5

iv

( continued)

6- 3       Effect of Baghouse Pressure Drop on SOX and NOX

Removals in ANL' s 20 MW Spray Dryer Test.  . . . .6 12

6  -4    Nitrates/ Nitrites as a Function of Critical Process

Variables. .  . 6 -12

7-1 Flow Diagram of a Gas Separation Membrane FCC System using a Partial Vacuum on the Permeate Side of the

Membrane . .  . 7 -6

7  -2    Flow Diagram of a Gas Separation Membrane FGC System using Pressure on the Feed Side of the Membrane & a

Partial Vacuum on the Permeate Side .  . 7 - 8

7-3        Flow Diagram of a Gas Separation Membrane FGC System

Using a Sweeping Vapor. .. 7 - 9

8-1 Common Chelating Agents. . .. 8- 2

8  -2    Nitric Oxide Removal in the Double -Alkali Scrubber Chemistry. . 8-9

8-  3     Dependence of NOx/SOx Removal Mechanism on pH.  . 8 - 10

8-4        Summary of Reactions That Can Take Place as a Result of

Interactions Between Nitrite and Bisulfite Ions. .  . 8 - 13

8- 5 DOW Chemical  Schematic of Field Trial Apparatus . . . . . . . . . . . .8 17

8- 6 DOW Chemical  Electrolytic Cell. .  8 - 18

8  - 7   DOW Chemical  NO Absorption vs. Fe(ll) Conc. . . . . . . . . . . . . . . . .8 19

8-8  Effect of Initial pH and Reducing Temperature on Ferric

            Iron Reduction       PETC Data. . . . . . . . . . . . . . .. 8 - 20

8-9  Electrodialysis Cell Arrangement and Flows for Normal

Polarity. .8 - 22

8 - 10 PETC Flue Gas Cleanup Process Producing Na2S04. .. 8 -23

TABLES

2-1       Summary of Southern California Edison' s SCR DeNOx

System (12) . .. 2- 2

2  -2    Performance Comparison Between SCR Design Configurations for Coal -Firing     .. 2 - 5

2-3  Catalysts Containing Copper/Copper Oxides. . . . . . . . .   . .. 2 -19

2-4  Catalysts Containing Iron Compounds. . .. 2 - 20

2 - 5 Catalysts Containing Vanadium Oxides . . .. 2 -21

2 - 6     Cerium Containing Catalysts . . .. 2 -22

2 - 7 Catalysts Base Metal Oxide(s) on a Titanium Oxide Support. . . . 2 23 2 - 8 Zeolitic Catalysts. . . . . . . . . . . . . . . .  . 2 -24 2- 9 Recent U. S. SCR Cost Estimates . . .  . . . . . . . . . . . . . 2 - 2 6 2 - 10 Equipment Cost Breakdown for TJA Base SCR Application ( 18 )2 - 27 2-11 Operating Cost Breakdown for TVA SCR Application (18). 2 - 28

2  - 12 SCR Technology Data Fon:n. .. 2 -41

3-1 SNCR Technology Data Form.  . . . .3 - 2

3  - 2   Cost Comparison Between Original and Improved SNCR

Technology and SCR Technology for 500 MW Coal-Fired Plant. .  . 3- 11

vi

TABIZS

(continued)

Table

4-1   Solid Electrolyte Decomposition Cell Tech. Data Form

5-1 Electro-Catalytic Reduction Technology Data Form. . . . . . . . . . . , . .5 2

6-1  Enhanced Dry Scrubbing Technology Data Form. . .. 6 - 2

6-2  Recent Dry Scrubbing R&D to Promote NOX Control. .- . 6-7

6-3  Summary of Alternative Additives Tested for Line-Based

         Dry Scrubbing Systems.  . .  . . . . . . . 6 -8

7  -1    Gas Separation Membranes Technology Data Form. . . .. 7 -2

8-1 Absorption-Reduction Vet FGD/DeNOx Data Form. . . . . . . . . . . . . , . . .8 4

8  - 2   ANL Wet Scrubber Experimental Program. . . . . . . . .. 8 -8

8-3        Kinetic and Thermodynamic Data for Reversible NO

Coordination to Ferrous Chelates. .  . 8 - 12

                     ADVANCED     CONTROL ASSESSMENT

1  .     INTRODUCTION      SUMMARY

1.1  Purpose of Project

The purpose of this project is to review and assess the current status of commercial and advanced flue gas NOX control technologies for utility and large industrial boiler applications in support of P ETC' s program development for the Proof-of Concept Test and Evaluation of Advanced NOR Control Processes. Emphasis has been placed on the following areas :

o  Understanding the- current status of advanced technologies and their potential applicability;

o  Qualitative assessment of technology advan t ages and disadvantages ;

          Identification of data gaps and poorly understood phenomena;

O      Identification of recent significant technology advances; and   Strategic use of various technologies .

Each technology (or group of similar technologies) is evaluated in a separate section of the report . A general overview of a technology is initially provided, followed by a specific review of key technology operating mechanisms , components, materials, systems integration, etc . Results are provided from recent test programs sponsored by DOE and others . Large- scale design configurations are quantitatively examined ( if sufficient data was available) . R&D cons iderati ons and recommendations are provided. In addition, a technology assessment data sheet has been completed for all technologies reviewed; a blank form is shown in Figure 1•1. These data sheets can be updated on a regular basis and can be compiled into a separate quick reference resource .

The remainder of Section 1 briefly examines the broad-based NOX emissions issues and their impact on control technology, reviews the current control regulations in Germany and Japan and their overall approach co NOX control, assesses the need for more advanced NOX control technology , reviews the utility boiler NOX control market characteristics and examines key aspects of integrated NOX control technologies and implementation strategies.

1.2  Major NOX Emissions Issues

Recent research findings link nitrogen oxides (NO. N02 and N20, collectively called NOX) to a broad range