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Treatment
Manual monitoring
Continuous, on-line monitoring
Other monitoring techniques
Most industrial water treatment systems are dynamic. They constantly undergo
changes because of seasonal variations in water chemistry, varying plant operating
conditions, new environmental laws, and other factors. Because of this, proper
monitoring is essential to ensure that the water treatment program applied to a
boiler, cooling, wastewater or other industrial water system is satisfactorily controlled
so that the desired results are achieved.
Some of the value added benefits obtained through proper monitoring of a water
treatment program include:
MANUAL MONITORING
Because of the dynamic nature of many water treatment systems and the
worldwide need for improved reliability and quality, a higher degree of
precision is required in the monitoring and control of water treatment
programs than that obtained through manual monitoring. To achieve the
degree of precision needed, continuous on-line monitoring with automatic
instrumentation is required.
Specific Conductance
For heavy fouling conditions (found in some industrial cooling towers and
boilers, waste treatment plants, and some processes, such as metal
treatment baths) an electrodeless (toroidal) conductivity probe (Figure 36-1)
must be used. The toroidal probe uses inductance to sense conductivity
changes in a process solution.
pH
The probe houses the electrodes and exposes them to the test stream.
Probes are manufactured in many different configurations. Common
configurations include two or three electrodes. Mild steel, stainless steel, and
polyvinyl chloride (PVC) are common probe materials. Probes are available as
standard and retractable assemblies and are usually provided with standard
pipe connections.
Electrodes are made from many different metals, such as stainless steel, mild
steel, Admiralty brass, and 90-10 copper-nickel. Electrodes fasten onto the
probe, and the probe and electrode assembly are inserted into the test
stream.
Turbidity
O2 + 2H2O + 4e- ®
Sodium
For calibration of the specific ion analyzer, both electrodes are immersed in a
known standard solution. The electrodes are also immersed in another
standard with a tenfold higher concentration of sodium ions for determination
of the electrode slope. Modern microprocessor technology has provided
advanced calibration techniques that verify electrode stability during
calibration.
There are several specialty systems designed to monitor the rate of fouling
and corrosion in industrial equipment, including those discussed in the following
sections.
The heat probe includes two temperature sensors that measure probe surface
temperature and bulk water temperature. The temperatures are monitored
by a meter with a light-emitting diode (LED) display. The temperature
meter has an analog output for a recorder or data logging device.
As the test section fouls, less heat is dissipated into the bulk water and the
tube skin temperature decreases. The result is an increase in the temperature
difference (DT) which can be related to fouling factor Rf by the following
equation:
DTfinal - DTinitial
Rf =
Heat Flux
(Btu/hr/ft2)
The MonitAll is equipped with flow control valves to maintain a constant flow
rate and insertion tubes to increase velocity in the clear flow cell.
Model Condenser. The Betz Model Condenser, Figure 36-12, is a test device
used primarily to simulate surface condenser fouling and corrosion. It consists
of a horizontal, cylindrical stainless steel shell with one, two, or four
removable tubes. The tubes run the length of the shell and terminate at the
tube sheets. An electric heater is located in the bottom of the shell to
generate a constant heat flux. Temperature sensors are located in the shell
and tube discharges to monitor temperature difference.
Condenser operating conditions, such as heat flux and tubeside velocity, are
simulated by the model condenser. Shell temperature and tube discharge
temperature are monitored continuously. As foulant accumulates on the
internal tube surfaces, less heat is transferred through the tube wall. As a
result, the shell temperature increases and the tube discharge temperature
decreases. At a constant flow rate, the increase in the temperature
difference can be related to a fouling factor by the same equation given for
the MonitAll. Typically, tubes are removed and sent to a laboratory for
further analysis.
Test Heat Exchanger. A test heat exchanger (Figure 36-13) is used to
monitor the fouling and corrosion tendencies of a particular cooling water
stream. Cooling water passes through two remov-able tubes contained in a
cylindrical shell. The tubes, which are available in many different materials,
can be arranged for two single-pass or one two-pass operation. Steam or hot
condensate flows into the shell and heats the water flowing through the
tubes. The condensate exits the shell through a flowmeter that is used to
monitor heat input.
The monitoring station consists of two units: a data acquisition cabinet and a
piping and instrumentation cabinet. Figure 36-14 shows the data acquisition
cabinet, with the panel door open, connected to the piping and
instrumentation cabinet.
The piping and instrumentation cabinet (wet side) includes the MonitAll hot
tester, a flow sensor, two corrosion probes, a conductivity sensor, a pH
sensor, coupon holders, stainless steel piping, and a drain line. A small
electrical enclosure within the cabinet supplies the electrical power for the
MonitAll and the space heater provided for climate control.
Halogen Residuals
Visual Inspection
Fiber Optics. A fiber optics device (Figure 36-18) is commonly used for
equipment inspection. A lens on each end of the fiber optics bundle provides a
clear, undistorted, color image. Video equipment and 35 mm cameras may be
used with a fiber optics system.
The methods included in this handbook are suitable for on-site analysis. They
involve the use of apparatus and chemicals that are evaluated, approved, and
supplied by GE Water & Process Technologies. Lists of required materials are
provided with each titrimetric, spectrophotometric, and colorometric
procedure. In some cases, other appropriate equipment may be substituted
for the apparatus listed. Substitution of reagents, unless otherwise noted, is
not recommended. Microbiological tests and tests which are not suitable for
on-site analysis have been excluded from this text.
For most tests, the samples should be cooled to room temperature (21-
26°C, 70-80°F) prior to testing. They should also be filtered through 0.2-
2.5 µm filters, if required.
METHODS OF ANALYSIS
Titration Methods
Historically, titration has been the most common method of plant control
analysis. Titration is based on the use of a buret, from which a standard
solution is added to the sample until an "end point" is reached. The end
point is generally indicated by a color change or detected by potentiometric
device (e.g., pH meter).
Photometric Methods
Photometers or spectrophotometers provide the most accurate means of
measuring the color of a reacted sample. In field analysis applications, simple
filter photometers have been replaced by monochromator-based
spectrophotometers. The essential components of a spectrophotometer include
the following:
Colorimetric Methods
When elements are present in minute or trace quantities, the use of parts
per million results in small decimal values. Therefore, it is more convenient to
use parts per billion (ppb) in these cases. One part per billion is equal to
one-thousandth of one part per million (0.001 ppm). For example, in studies
of steam purity using a specific ion electrode to measure sodium content,
values as low as 0.001 ppm are not uncommon. This is more conveniently
reported as 1.0 ppb.
In recent times, the convention for reporting analytical results has been
shifting toward the use of milligrams per liter (mg/L) as a replacement for
parts per million and micrograms per liter (µg/L) as a replacement for parts
per billion.
Test procedures and calculations of results are based on the milliliter (mL)
rather than the more common cubic centimeter (cc or cm3). The distinction
between the two terms is very slight. By definition, a milliliter is the volume
occupied by 1 g of water at 4°C, whereas a cubic centimeter is the volume
enclosed within a cube 1 cm on each edge (1 mL = 1.000028 cm3).
Thus, if the solution density is close or equal to 1, then ppm = mg/L. This is
normally the case in dilute, aqueous solutions of the type typically found in
industrial water systems. Control testing is usually conducted without
measurement of a solution's density. For common water samples, this poses
no great inaccuracy, because the density of the sample is approximately 1.
Milligrams per liter (mg/L) and parts per million (ppm) begin to diverge as
the solution density varies from 1. Examples of this are a dense sludge from a
clarifier underflow (density greater than 1) or closed cooling system water
with high concentrations of organic compounds (density less than 1). All of
the analytical methods discussed in this text contain calculations required to
obtain the results in milligrams or micrograms per liter.
The use of equivalents per million is not recommended for normal plant
control. Parts per million is a simpler form of expressing results and is
accepted as the common standard basis of reporting a water analysis.
However, whenever extensive calculations must be performed, the use of
equivalents per million greatly simplifies the mathematics, because all
constituents are on a chemical equivalent weight basis. The remainder of this
section provides a discussion of parts per million and equivalents per million
for those who desire a working knowledge of these methods of expression for
purposes of calculations.
The units of ppm and epm are commonly combined in normal reporting of
water analyses, and many different constituents are frequently reported on a
common unit weight basis. For example, calcium (equivalent weight 20.0) is
reported in terms of "calcium as CaCO3" (equivalent weight 50.0). The test
for calcium is calibrated in terms of CaCO3, so the conversion factor 2.5
(50/20) is not needed. Hardness, magnesium, alkalinity, and free mineral acid
are often reported in terms of CaCO3; the value reported is the weight of
CaCO3 that is chemically equivalent to the amount of material present.
Among these substances, ionic balances may be calculated. When constituents
are of the same unit weight basis, they can be added or subtracted directly.
For example, ppm total hardness as CaCO3 minus ppm calcium as
CaCO3 equals ppm magnesium as CaCO3. However, ppm magnesium as
Mg2+ equals 12.2 (magnesium equivalent weight) divided by 50.0
(CaCO3 equivalent weight) times the ppm magnesium as CaCO3.
In every case, it is necessary to define the unit weight basis of the results-
"ppm alkalinity as CaCO3" or "ppm sulfate as SO42- " or "ppm silica as SiO2".
Where the unit weight basis is different, calculations must be based on the
use of chemical equations.
The following rules outline where epm can be used and where ppm must be
used. In general, either may be used where an exact chemical formula is
known. When such knowledge is lacking, ppm must be used.
Number of
Formula Equivalent Weight
equivalents
POSITIVE IONS
Aluminum Al+3 3 9
Ammonium NH4+ 1 18
Calcium Ca2+ 2 20
Copper Cu2+ 2 31.8
Hydrogen H+ 1 1
Ferrous Ion Fe2+ 2 27.9
Ferric Ion Fe3+ 3 18.6
Magnesium Mg2+ 2 12.2
Manganese Mn2+ 2 27.5
Potassium K+ 1 39.1
Sodium Na+ 1 23
NEGATIVE IONS
Bicarbonate HCO3- 1 61
Carbonate CO32- 2 30
Chloride Cl- 1 35.5
Fluoride F- 1 19
Iodide I- 1 126.9
Hydroxide OH- 1 17
Nitrate NO3- 1 62
Phosphate
PO43- 3 31.7
(tribasic)
Phosphate
HPO42- 2 48
(dibasic)
Phosphate
H2PO4- 1 97
(monobasic)
Sulfate SO42- 2 48
Bisulfate HSO4- 1 97.1
Sulfite SO32- 2 40
Bisulfite HSO3- 1 81.1
Sulfide S2- 2 16
COMPOUNDS
Alum Al2(SO4)3 18H2O 6 111
Aluminum
Sulfate Al2(SO4)3 6 57
(anhydrous)
Aluminum
AI(OH)3 3 26
Hydroxide
Aluminum Oxide Al2O3 6 17
Ammonia NH3 1 17
Sodium
Na2AI2O4 6 27.3
Aluminate
Calcium
Ca(HCO3)2 2 81.1
Bicarbonate
Calcium
CaCO3 2 50
Carbonate
Calcium Chloride CaCl2 2 55.5
Calcium
Ca(OH)2 2 37
Hydroxide
Calcium Oxide CaO 2 28
Calcium Sulfate
CaSO4 2 68.1
(anhydrous)
Calcium Sulfate
CaSO4 2H2O 2 86.1
(gypsum)
Calcium
Ca3(PO4)2 6 51.7
Phosphate
Carbon Dioxide CO2 2 22
Chlorine Cl2 2 35.5
Ferrous Sulfate
FeSO4 2 76
(anhydrous)
Ferric Sulfate Fe2(SO4)3 6 66.6
Magnesium
MgO 2 20.2
Oxide
Magnesium
Mg(HCO3)2 2 73.2
Bicarbonate
Magnesium
MgCO3 2 42.2
Carbonate
Magnesium
MgCl2 2 47.6
Chloride
Magnesium
Mg(OH)2 2 29.2
Hydroxide
Magnesium
Mg3(PO4)2 6 43.8
Phosphate
Magnesium
Sulfate MgSO4 2 60.2
(anhydrous)
Magnesium
Sulfate (Epsom MgSO4. 7H2O 2 123.2
Salts)
Manganese
Mn(OH)2 2 44.5
Hydroxide
Silica SiO2 2 30
Sodium
NaHCO3 1 84
Bicarbonate
Sodium
Na2CO3 2 53
Carbonate
Sodium Chloride NaCl 1 58.4
Sodium
NAOH 1 40
Hydroxide
Sodium Nitrate NaNO3 1 85
Trisodium
Na3PO4. 12H20 3 126.7
Phosphate
Trisodium
Phosphate Na3PO4 3 54.7
(anhydrous)
Disodium
Na2HPO4. 12H2O 2 179.1
Phosphate
Disodium
Phosphate Na2HPO4 2 71
(anhydrous)
Monosodium
NaH2PO4. H2O 1 138
Phosphate
Monosodium
Phosphate NaH2PO4 1 120
(anhydrous)
Sodium Silicate Na2SiO3 2 61
Sulfuric Acid H2SO4 2 49
Sodium
NaPO3 1 102
Metaphosphate
Sodium Sulfate Na2SO4 2 71
Sodium Sulfite Na2SO3 2 63