8.

5
8.4 pH DATA: THREE-SHIFT SUBGROUP CONTROL CHART
UCL
AVERAGES

8.3
8.2 MEAN
8.1
LCL
8.0
7.9
MEAN

0.5 pH DATA
DISTRIBUTION
RANGES

0.4 UCL
0.3
0.2
MEAN
0.1
0.0
0 2 4 6 8 10 12 14 16 20 24 28 DATE

40
PERCENT OF DATA

30 NORMAL
DISTRIBUTION
20

10 -4 -3 -2 -1 +1 +2 +3 +4 std.

7.9 8.0 8.1 8.2 8.3 8.4 8.5 pH

0
<7.90 7.95 8.05 8.15 8.25 8.35 >8.40

Monitoring and Controlling

Industrial Processes
Second Edition

Marvin D. Silbert and Henry K. Miyamoto

2002
ISBN 0-9695133-1-3
 Monitoring and Controlling Industrial Processes

Table of Contents

Preface............................................................................................................................................. i
Legal Notice ................................................................................................................................... ii
Table of Contents..........................................................................................................................iii
1 Why Do We Need to Look Deeper? ..................................................................................... 1
1.1 Troubleshooting ............................................................................................................................ 2
1.2 Historical Data .............................................................................................................................. 3
1.3 Performance Indicators ................................................................................................................. 4
2 Data Formats ......................................................................................................................... 5
2.1 Tabulation ..................................................................................................................................... 6
2.1.1 Significant Figures ................................................................................................................... 6
2.2 Graphical Trends........................................................................................................................... 7
2.2.1 Scatter Plots.............................................................................................................................. 7
2.2.2 Runs Charts .............................................................................................................................. 7
2.2.3 Curve Fitting ............................................................................................................................ 8
2.2.4 Auto-Scaling............................................................................................................................. 8
2.2.5 Multi-Parameter Plotting .......................................................................................................... 9
2.3 Histograms.................................................................................................................................... 9
3 Data Distributions ............................................................................................................... 12
3.1 The Normal Distribution............................................................................................................. 12
3.2 The Poisson Distribution............................................................................................................. 17
3.3 The Binomial Distribution .......................................................................................................... 19
3.4 Combining and Comparing Distributions ................................................................................... 22
3.5 Precision, Accuracy, Bias and Repeatability............................................................................... 26
4 Medians and Percentiles ..................................................................................................... 29
4.1 Percentiles................................................................................................................................... 29
4.2 Data Sorting ................................................................................................................................ 29
4.3 The Box and Whisker Plot.......................................................................................................... 30
5 Time-Series Analysis ........................................................................................................... 32
5.1 Random Movements ................................................................................................................... 32
5.1.1 Positive First Difference Test ................................................................................................. 32
5.1.2 Turning Points Test................................................................................................................. 32
5.1.3 Runs Test ................................................................................................................................ 33
5.2 Periodicity................................................................................................................................... 35
5.3 Trends ......................................................................................................................................... 35
6 Statistical Process Control .................................................................................................. 36
6.1 Process Capability ...................................................................................................................... 36
6.2 Control Charts............................................................................................................................. 38
6.2.1 Moving Averages.................................................................................................................... 43
6.3 Median Control Chart ................................................................................................................. 45
6.4 CuSum Control Chart ................................................................................................................. 46
6.5 Sum and Difference Control Charts ............................................................................................ 46
6.6 Attribute Control Charts ............................................................................................................. 47
6.6.1 Control Charts for Defects...................................................................................................... 47

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 6.6.2 Control Charts for Defectives................................................................................................. 49
6.7 What do you do with a bad data point?....................................................................................... 51
7 The Electronic Log Sheet.................................................................................................... 53
7.1 Off-the-Shelf Products ................................................................................................................ 56
7.2 Do More than Plot Data .............................................................................................................. 56
7.2.1 The Appearance is Important.................................................................................................. 58
7.2.2 Incorporating the Graphics into the Text ................................................................................ 59
7.2.3 Significant Figures ................................................................................................................. 60
8 Applications in the Field ..................................................................................................... 61
8.1 Laboratory Samples vs. Field Instrumentation............................................................................ 61
8.1.1 Cost ........................................................................................................................................ 61
8.1.2 Reliability ............................................................................................................................... 61
8.1.3 Availability ............................................................................................................................. 61
8.1.4 Sensitivity............................................................................................................................... 62
8.1.5 Service Requirements............................................................................................................. 62
8.1.6 Calibration and Stability......................................................................................................... 62
8.2 Monitoring the Controlled System.............................................................................................. 63
8.2.1 If all additions are stopped ..................................................................................................... 63
8.2.2 Removal process is stopped.................................................................................................... 64
8.2.3 Isolating the system ................................................................................................................ 65
8.2.4 Transients ............................................................................................................................... 65
8.3 Mode of Addition........................................................................................................................ 65
8.3.1 Continuous Addition:.............................................................................................................. 65
8.3.2 Intermittent or Batch Addition:............................................................................................... 65
8.4 Steady-State vs. Batch Operation................................................................................................ 66
8.5 The Continuously Varying Process ............................................................................................. 68
8.6 Relationships Among Parameters ............................................................................................... 69
9 Applying Quality Methods ................................................................................................. 70
9.1 Quality Assurance ....................................................................................................................... 70
9.1.1 Established Procedures........................................................................................................... 70
9.1.2 Repeatability, Reproducibility and Bias: ................................................................................ 71
9.1.3 Record Keeping:..................................................................................................................... 71
9.1.4 Chain of Command: ............................................................................................................... 71
9.1.5 QA Manual ............................................................................................................................. 72
9.1.6 ISO-9000 Compliance ............................................................................................................ 72
9.2 Introducing a Statistically-Based Program.................................................................................. 73
9.2.1 Continuous Processes ............................................................................................................. 73
9.2.2 Batch Processes ...................................................................................................................... 75
9.2.3 Linking Statistical and Quality-Assurance Programs ............................................................. 76
9.3 Meeting Performance Indicators ................................................................................................. 76
9.4 Troubleshooting and Assigning Priorities ................................................................................... 76
9.4.1 Cause-and-Effect Analysis ..................................................................................................... 76
9.5 Assigning Priorities..................................................................................................................... 78
9.6 A Concluding Thought................................................................................................................ 79
Bibliography ................................................................................................................................ 80
Index ............................................................................................................................................. 81
Appendices ................................................................................................................................... 83

Rev: 2007-May-27

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Optimizing Water Treatment
for Plant Utilities, Offsites
and Electrical Generation

Marvin D. Silbert

(c) 2006
Marvin Silbert and Associates

ISBN 0-9695133-8-0
 Table of Contents

Table of Contents...................................................................................................... i

INTRODUCTION ................................................................................................... 1
1 What is this Liquid called Water? ..................................................................................... 2
1.1 The Hydrologic Cycle............................................................................................................... 2
2 Why Do We Need Water Treatment? ............................................................................... 8
2.1 Scaling ...................................................................................................................................... 8
2.2 Corrosion ................................................................................................................................ 15
2.3 Microbiological Species.......................................................................................................... 25
2.4 Natural Organic Material ........................................................................................................ 27
2.5 Hydrocarbons.......................................................................................................................... 28
2.6 Solids ...................................................................................................................................... 29
2.7 … in the Real World ............................................................................................................... 31

WORKING WITH WATER................................................................................ 32

3 Disinfection ........................................................................................................................ 33
3.1 Chlorination ............................................................................................................................ 33
3.2 Dechlorination......................................................................................................................... 35
3.3 Alternative Biocides................................................................................................................ 36
4 Solids Removal .................................................................................................................. 39
4.1 Clarification ............................................................................................................................ 39
4.2 New and Specialized Clarifier Designs................................................................................... 42
4.3 Selecting The Chemistry For The Clarification Process ......................................................... 44
4.4 Lime Softening........................................................................................................................ 45
4.5 Particle Filtration .................................................................................................................... 49
4.6 Membrane Filtration - Microfilters ......................................................................................... 57
5 Organic Removal............................................................................................................... 58
5.1 Processes to Separate Oil and Water ....................................................................................... 58
5.2 Adsorption .............................................................................................................................. 60
5.3 Biological Treatment............................................................................................................... 62
5.4 Ion-Exchange Resins............................................................................................................... 62
5.5 Alumina, Silica ....................................................................................................................... 63
5.6 Ultrafiltration .......................................................................................................................... 63
6 Demineralization / Deionization....................................................................................... 64
6.1 Ion Exchange .......................................................................................................................... 64
6.2 Electrodeionization ................................................................................................................. 77
6.3 Reverse Osmosis ..................................................................................................................... 80
6.4 Electrodialysis......................................................................................................................... 87
6.5 Evaporative Processes............................................................................................................. 88
6.6 Desalination ............................................................................................................................ 89
7 Chemical Additions to the System ................................................................................... 92
7.1 Acid Addition to Reduce Scaling when Water is Heated........................................................ 92
7.2 Lime Addition of Counteract Soft-Water Corrosion............................................................... 93
7.3 Crystal Modifiers / Sludge Conditioners to Counteract Scaling ............................................. 93
7.4 Chelant Treatment................................................................................................................... 95
7.5 Chemical Feed Equipment ...................................................................................................... 95
7.6 Chemical Feed Kinetics and Equilibrium ............................................................................... 99
8 Optimizing the Water-Treatment Plant........................................................................ 103
 8.1 Matching the Plant to the Water............................................................................................ 103
8.2 Storage and Distribution Of DI Water .................................................................................. 108
8.3 Moving toward Zero Liquid Discharge................................................................................. 108
8.4 Zero Liquid Discharge .......................................................................................................... 110
8.5 Make or Buy?........................................................................................................................ 111

CLEANING AND MAINTENANCE ................................................................ 113

9 System and Component Cleaning.................................................................................. 114
9.1 When is a Cleaning Required................................................................................................ 114
9.2 Off-Line Procedures.............................................................................................................. 115
9.3 On-line Chemical Treatment................................................................................................. 121
9.4 Mechanical Cleaning Systems .............................................................................................. 121
9.5 Clean-Up of the Water .......................................................................................................... 123

COOLING WATER TREATMENT................................................................. 126

10 Classification of Cooling Systems .................................................................................. 127
10.1 Contact Cooling .................................................................................................................... 127
10.2 Non-Contact Cooling ............................................................................................................ 128
10.3 The Once-Through Cooling Systems.................................................................................... 130
10.4 The Open-Recirculating System ........................................................................................... 132
10.5 The Closed Recirculating System ......................................................................................... 136
10.6 … and in the Real World ...................................................................................................... 136
11 Chemical Treatment of Cooling Systems ..................................................................... 141
11.1 Once-Through Systems......................................................................................................... 141
11.2 Open-Recirculating Systems................................................................................................. 143
11.3 Closed Systems ..................................................................................................................... 147
12 Building Cooling Systems ............................................................................................... 151
12.1 The Mechanical or Compression Chiller .............................................................................. 151
12.2 The Absorption Chiller ......................................................................................................... 153
12.3 HVAC systems...................................................................................................................... 154
12.4 Free Cooling.......................................................................................................................... 154
12.5 Refrigeration and Ice Making ............................................................................................... 156
12.6 HVAC Chiller Performance.................................................................................................. 156
13 Steam Condensers ........................................................................................................... 164
13.1 Condenser Leakage ............................................................................................................... 165
13.2 Measuring Condenser Performance ...................................................................................... 169

BOILER WATER TREATMENT..................................................................... 176

14 Boiler Design and Operation.......................................................................................... 177
14.1 Boilers and Boiler Systems ................................................................................................... 177
14.2 Boiling As a Concentrating Mechanism ............................................................................... 180
14.3 Boiler Mass Balance ............................................................................................................. 182
14.4 Blowdown ............................................................................................................................. 185
14.5 Condensate Recycle .............................................................................................................. 189
14.6 Carryover in Steam ............................................................................................................... 191
14.7 Shutdown / Start-Up / Storage .............................................................................................. 194
14.8 The Need for Chemical Treatment........................................................................................ 196
14.9 The Better the Water, the Better the Control ........................................................................ 199
15 Boiler Alkalinity and pH Control .................................................................................. 202
15.1 Alkalinity Control for Carbon Steel...................................................................................... 202
15.2 Increasing System Alkalinity ................................................................................................ 205
15.3 Choosing an Amine to Give a Specified pH ......................................................................... 209
15.4 Dissolved Oxygen Control.................................................................................................... 215
15.5 Oxidizing Chemistry ............................................................................................................. 220

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16 Treatment of Low and Medium-Pressure Boilers........................................................ 223
16.2 Erosion-Corrosion / Flow-Accelerated Corrosion ................................................................ 230
17 Treatment of High-Pressure Boilers.............................................................................. 231
17.1 All Volatile Treatment (AVT) .............................................................................................. 231
17.2 Oxygenated Treatment (OT) ................................................................................................. 231
17.3 Phosphate .............................................................................................................................. 231
17.4 Optimizing High-Pressure Phosphate Programs ................................................................... 240
17.5 Hideout.................................................................................................................................. 241
17.6 Monitoring and Controlling an EPT Program....................................................................... 244

INDUSTRY APPLICATIONS............................................................................ 250

18 Oil and Gas ...................................................................................................................... 251
18.1 Oil-Containing Streams......................................................................................................... 251
18.2 Produced Water..................................................................................................................... 252
18.3 Refinery Process Waters........................................................................................................ 253
18.4 Treatment of Produced and Waste Waters............................................................................. 254
19 Metal Production and Finishing Industries .................................................................. 256
19.1 Metallic Wastes ..................................................................................................................... 256
19.2 Sludge Dewatering................................................................................................................ 258
20 Sanitary Wastes / Sweetwater ........................................................................................ 259
20.1 Aerobic Processes ................................................................................................................. 259
20.2 Anaerobic Processes ............................................................................................................. 259
21 Alkaline Processes ........................................................................................................... 263
21.1 Characteristics of High-pH Systems ..................................................................................... 265

ALPHABETICAL INDEX ................................................................................. 267

Rev: December 2006

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