Académique Documents
Professionnel Documents
Culture Documents
Summary: New membrane processes for water • Hot water steam injection/stripping
deaeration.
treatment are continually being sought after for
• Oxidation/reduction reaction chemicals.
their simple and continuous operation. A new
• Ion exchange processes.
approach for removing dissolved gases from
make-up supplies utilizes hydrophobic hollow Removing dissolved gases from water with Gas
fiber membranes. These membranes have many Transfer Membranes (GTM®) is a proven, low
characteristics that enhance or replace other flow rate laboratory technology. Recent
degassing methods. This paper reports carbon advances in GTM® design now make them
dioxide and dissolved oxygen removal feasible for high flow rate industrial systems2, 3.
efficiencies for a 100 gpm gas transfer Using these systems alone or in conjunction with
membrane unit installed in a nuclear power other membrane processes offer new or
plant’s make-up system. improved options for water treatment.
hydrogen sulfide gas, improving drinking water membrane is gas permeable and water
taste. And, utilities remove oxygen from boiler impermeable. The hollow fiber configuration,
feed makeup to prevent corrosion. Removing with the gas phase inside the fiber, offers high
these gases prior to, or during ion exchange surface area for maximum contact time. The
demineralization, can have a significant impact patented Liqui-Cel ® design4,5 tested includes
on operating performance and efficiency. The an internal baffle to promote turbulent flow in and
• Aeration (open and forced draft). diameter with 0.05 micron gas permeable pores.
www.ionics.com
three streams are identifiable: Station is located in Waterford, CT. The station
consist of three independent units. Unit 1 is a
• Feed stream.
General Electric 650 MW boiling water reactor
• Process effluent.
(BWR) design, commissioned in 1970. Unit 2
• Concentrate waste stream.
and 3 are pressurized water reactors (PWR). Unit
2 is a Combustion Engineering 850 MW design
As illustrated in Figure 1, the tube interior commissioned in 1975. Unit 3 is a Westinghouse
operates under vacuum, nitrogen sweep gas or 1150 MW design, commissioned in 1986.
both in combination. Dalton’s Law of Partial
Pressure and Henry’s law of Gas Solubility1, 6 The plant’s makeup water is deoxygenated and
define the mechanisms that drive dissolved gas demineralized by a service contract company.
removal by GTM®. In short, reducing the gas Unit 1 and 2 share the same makeup water
concentration over the water allows the treatment system and operates independently
dissolved gases to expand into the hydrophobic from Unit 3’s makeup system. We selected Unit
hollow fiber and be swept away. Reducing the 3’s makeup system for the test site based on its
CO2 and O2 gas concentration is accomplished design and Northeast Utilities’ long history for
by applying a vacuum, using inert nitrogen supporting and testing new technology7, 8.
GAC
SAC
SBA
SBA
MB
200 gpm
N2 To Storage with
GTM
Nitrogen Blanket
Cl2
Vacuum
Carbon Catalyzed
Deoxygenation
Reject Reject
www.ionics.com
Table 1 Millstone Municipal Raw Water Supply Table 2 RO Permeate Quality
On
Cations Anions TDS as Ions 5 - 7 mg/l
(mg/l as CaCO3) (mg/l as CaCO3)
Conductivity: 5 - 13 µmhos
Ca+2 8 - 30 HCO3-1 6 - 13 HCO3-1 < 1.0 mg/l
Mg+2 3-5 Cl-1 6 - 14 CO2 as CO2: 6 - 12 mg/l
Na+1 8 - 16 SO4-2 2 - 19 O2 as O2: 6 - 8 mg/l
K+1 1-2 NO3-1 0-2 TOC as C: 0.2 - 0.4 mg/l
TDS as 45 - 65 Conductivity: 50 - 90 pH: 6.1 - 8.1
Ions: mg/l µmhos
CO2 as 0.75 - 1.5
O2 as O2: 6 - 8 mg/l
CO2: mg/l
SiO2 as higher hardness and alkaline feeds, acid
SiO2: 2 - 5 mg/l TOC as C: 2 - 6 mg/l
pretreatment reduces the Langlier Saturation
pH: 6.1 - 8.1 Turbidity: 0.01 - 2.0 NTU
Index (LSI)9 in the RO reject stream, preventing
calcium carbonate membrane scaling. Although,
Ultrafiltration. The UF utilizes an 80,000
injecting acid minimizes CA membrane
molecular weight cut off polysulfone membrane
hydrolysis and reduces the scaling potential, it
in a hollow fiber configuration. The system,
creates free carbon dioxide, refer to Eq. (1).
operating between 85% to 90% recovery,
effectively pretreats the city supply to minimize
Every 1 ppm H2SO4 added to the RO feed
colloidal fouling on the down stream RO
Eq. ( 1 )
membranes. The UF membranes are chemically
cleaned on a daily to monthly basis depending
on the city water quality. Cleaning requirement is
determined by effluent silt density index greater
than five, increasing pressure drop or flux
increases the CO2 concentration by 0.89 ppm.
decline.
Reverse osmosis membranes do not remove
dissolved gases. Therefore, the RO permeate
Reverse Osmosis. The RO utilizes cellulose
contains equal amounts of CO2 as generated in
acetate (CA) membranes in a spiral wound
the feed water, adding undue ion exchange
configuration. Cellulose acetate membranes, on
loading on the down stream demineralizer10.
this water supply, have successfully
Conventionally, CO2 is removed by forced draft
demonstrated nine years operating experience
aeration or vacuum deaerators1.
without a single cleaning.
www.ionics.com
removed by the down stream ion exchange feed pH, temperature and vacuum/nitrogen
demineralizer. combinations. Over 2.5 million gallons were
treated during the GTM® test. As illustrated in
Figure 3, oxygen removal ranged between 78%
Table 3 Makeup Water Quality and 95%. Carbon dioxide removal, illustrated in
www.ionics.com
ppm. Based on the 65% to 95% CO2 removal pH probes were installed to measure the
efficiency, this equates to 0.3 ppm to 4.2 ppm pH difference across the GTM®. This allowed
GTM® effluent CO2 concentration. Carbon for a reliable in-line method to monitor CO2
dioxide concentration depends on the removal performance.
chemical relationship between alkalinity and pH,
Figure 5 illustrates that CO2 removal efficiency
refer to Eq. (7)10.
is linearly related to feed pH. At lower pH,
Eq. ( 7 )
with correspondingly higher feed CO2
concentrations, percent removal exceeds 85%.
This data, when extrapolated, shows that
optimum operating pH for CO2 removal is 4.7
(free mineral acidity) where all alkalinity is
converted to CO2. The data was collected at 21°
Based on this relationship, Equation (7) is to 22° C and vacuum at 27” Hg.
solved for [CO2], providing a method where by
carbon dioxide concentration is calculated, Figure 5 Carbon Dioxide Removal pH Effect
refer to Eq. (8).
Eq. ( 8 )
% Removal
Eq. ( 9 )
Assuming the alkalinity concentration does not improves as the feed water temperature
change through the GTM® unit, combining increases. As the water temperature approaches
Equation (8) and (9) calculates removal efficiency its boiling point, gas removal approaches 100%.
based on the influent (INF) and effluent (EFF) pH As water temperature approaches its freezing
change, refer to Eq. (10). point, gas removal approaches 0%. This data
was collected at influent pH 5.0 to 5.5 and
Eq. ( 10 ) vacuum at 27” Hg.
www.ionics.com
data indicates CO2 removal is at its lowest when During the test dissolved oxygen data was
using nitrogen and vacuum in combination. collected at varying temperatures and while
However, CO2 removal efficiency is at its highest applying nitrogen sweep gas with and without
when using nitrogen alone. The poor efficiency vacuum. The GTM® consistently reduced the
using nitrogen in combination with vacuum can dissolved oxygen below 1.1 ppm. The minimum
be due to nitrogen impurity, air in-leakage and dissolved oxygen concentration recorded was
difficulty controlling feed pH. 350 ppb utilizing nitrogen and vacuum. Utilizing
vacuum only, dissolved oxygen concentration
ranged between 900 to 700 ppb. In addition to
Figure 6 Carbon Dioxide Removal
Temperature Effect varying conditions, the GTM®’s effect on the
hydrazine usage for the down stream
deoxygenation process was investigated.
Figure 8 illustrates the logarithmic temperature
% Removal
www.ionics.com
shown in Figure 9, slightly improved overall O2
Figure 10 Hydrazine Dosage
removal compared to vacuum alone.
without sacrificing dissolved O2 effluent and low level carbon dioxide removal utilizing
quality. The data illustrated in Figure 10 a new membrane process. GTM® technology
requirement. Combining these processes dissolved gas removal methods. GTM®’s are
• Does not increase operation requirements. cost analysis versus achievable effluent
quality. The data presented here provides a
In order to achieve less than 3 ppb dissolved O2 strong foundation for GTM® technology that
with GTM® alone, multiple units in series, can be used to design future makeup water
combined with vacuum and nitrogen sweep gas treatment systems.
www.ionics.com
This paper was presented at IWC-95-41 8. T.F. Burns, C. Booth, “Utrafiltration
Pretreatment of Reverse Osmosis Make-up
References
Systems”, UTRAPURE WATER EXPO 88,
3. P. D’Angelo, “Oxygen Removal: Theory and 11. R.C. Dickerson, W.S. Miller, U.S. Patent 4,
Jul./Aug., 1995.
12. W.S. Miller, “Oxygen Removal by Catalyzed
4. R. Prasad, C. Runkle, H. Shuey, U.S. Patent Carbon Beds”, EPRI Condensate Polishing
5,264,171, “Method of Making Spiral-Wound Workshop, Richmond, VA, Oct. 31, 1995.
Ionics, Incorporated © 2004 Ionics, Incorporated. All rights reserved worldwide. The information contained in this publication is believed to be
65 Grove Street accurate and reliable, but is not to be construed as implying any warranty or guarantee of performance.
Watertown, MA 02472
617-926-2500
info@ionics.com
www.ionics.com
TP-513 E-US 1204 formerly ECOLO 507