US8883012

USOO8883 012B2
(12) United States Patent (10) Patent No.: US 8,883,012 B2

B00000 et al. (45) Date of Patent: Nov. 11, 2014
(54) REDUCED FOULING OF REVERSE OSMOSIS USPC ........... 210/690: 210/651; 210/652:210/660;
MEMBRANES 210/670: 210/692
(58) Field of Classification Search
(75) Inventors: Francis Boodoo, Bala Cynwyd, PA USPC ......... 210/650–652, 660, 670, 677, 690, 691,
(US); Fabio Chaves De Sousa, Sao 21 Of 692
Paulo (BR); James A. Dale, Cardiff See application file for complete search history.
(GB); Carmen Mihaela Iesan, Fagaras
(RO) (56) References Cited
U.S. PATENT DOCUMENTS
(73) Assignee: Purolite Corporation, Bala Cynwyd, PA
(US) 3,454,493 A 7/1969 Kun et al.
4,076,622 A 2f1978 Costin
(*) Notice: Subject to any disclaimer, the term of this (Continued)
patent is extended or adjusted under 35
U.S.C. 154(b) by 0 days. FOREIGN PATENT DOCUMENTS
(21) Appl. No.: 12/015,429 JP 51-88.473 8, 1976
JP 52-621.83 5, 1977
(22) Filed: Jan. 16, 2008
(Continued)
(65) Prior Publication Data OTHER PUBLICATIONS
US 2008/O173583 A1 Jul. 24, 2008 Dickert, Charles. Kirk-Othmer Encyclopedia of Chemical Technol
ogy: “Ion Exchange'. John Wiley & Sons, Inc. vol. 14, (c) 1995, pp.
Related U.S. Application Data 1-51*
(60) Provisional application No. 60/885,855, filed on Jan. (Continued)

19, 2007, provisional application No. 60/908,172,
filed on Mar. 26, 2007. Primary Examiner — Katherine Zalasky
(74) Attorney, Agent, or Firm — Fish & Richardson P.C.
(51) Int. C.
BOLD I5/04 (2006.01) (57) ABSTRACT
CO2F L/42 (2006.01) The present invention provides a new water purification
CO2F L/58 (2006.01) method and system using reverse osmosis. In particular, the
BOID 6/02 (2006.01) present invention provides methods and water purification
CO2F I/44 (2006.01) systems using an ion exchange resin and absorbent media for
BOIJ 4 I/OO (2006.01) pretreatment of water being fed to a reverse osmosis treat
CO2F IOI/IO (2006.01) ment system, where the pretreatment reduces fouling of, or
CO2F 9/OO (2006.01) deposits or chemical attack on the membrane Surfaces and
(52) U.S. C. passageways. Particularly, a macroporous resin having an
CPC ........... C02F I/441 (2013.01); C02F 2001/422 average pore diameter in the range of 1,000 to 500,000 Ang
(2013.01); C02F 2101/10 (2013.01); C02F stroms and a crush strength or Chatillon value of at least 24
2303/16 (2013.01); C02F I/42 (2013.01); C02F g/bead (710 um bead diameter) is used.
9/00 (2013.01); C02F 2001/425 (2013.01);
C02F2303/185 (2013.01) 14 Claims, 10 Drawing Sheets
Chile Bisulfite dosing Reverse

Dosing if chlorine is Osmosis
2 presert: System
1.
Surface 4 Peneate
Water iodic
Feed Water
Mutiaedia Multicontamiriant 5 micron (typically
Fie Coato Medias Fite 70-80%)
(Suspendcd f reduction of
Soids SDI, colloidal SDvalue E.
Filtration particulates, at this point to waste
organic flatter. typically (typically
2 20-30%
Typical Surface Water Pretreatment System with Invention

US 8,883,012 B2
Page 2
(56) References Cited OTHER PUBLICATIONS

U.S. PATENT DOCUMENTS Purolite Technical Bulletin, “Organic fouling of anion ion exchange
resins.” (2002), available at <http://www.purolite.com, accessed
4,895,659 A * 1, 1990 Semmens et al. ............. 210,638
4.969,991 A * 11, 1990 Valadez ....................... 210,962 Feb. 8, 2014.*
5,259,972 A 11, 1993 Miyamaru et al. Comstock, Daniel, “Cleaning and Scale Prevention in Reverse
5,374,357 A * 12, 1994 Comstock et al. ............ 210,666 Osmosis Systems.” Ultrapure Water Magazine, Sep. 2000, pp. 29.
5,470.461 A * 11, 1995 Ban et al. ....... 210,188 31-34, 36.
5,512,604 A * 4, 1996 Demopolis . 521 142 Siverns, Steve, “Using Ultrafiltration as a Pretreatment Before RO.”
6,258,278 B1* 7, 2001 Tonelli et al. ................. 210,652
6,323,249 B1 11, 2001 Dale et al. Ultrapure Water Magazine, May 2006, (4pgs).
7,291,578 B2 11/2007 SenGupta et al. Mierzejewski, Marek, “Industrial Applications. Using Mircofiltration
2002fO153319 A1 10, 2002 Mukhopadhyay as RO Pretreatment.” Ultrapure Water Magazine, Oct. 2004, pp.
2003. O146161 A1* 8, 2003 Herman ........................ 210,657 29-35.
2004/0129623 A1* 7, 2004 Miers et al. ................... 210,264 “Hydranautics Design Limits.” Hydranautics: High Performance
2004/O262206 A1 12, 2004 Gettman
Membrane Products, Jan. 23, 2001, www.hydranautics.com/docs/
FOREIGN PATENT DOCUMENTS trc/Dsgn Lmt.pdf (1 page).
JP 4-108587 4f1992
JP 4-210288 7, 1992 * cited by examiner
U.S. Patent Nov. 11, 2014 Sheet 1 of 10 US 8,883,012 B2
Chlorine Coagulant Polymer Acid or Reverse

Dosing Dosin Dosin Scale
5 Inhibitor Osmosis
Surface Pereate
Water Product
Feed Water
CARFTER Multimedia Activated 5 micron SPE;
Coagulation f Filter Er Fite
Flocculation - Sludge (Fioc Suspended
Settling typical
water losses of 5%)
Solids
Filtration)
E.
3.
SP value
at this point
it.
renova to Waste
typically
3 to 5 ical
(typically
20.30%)
Fig. 1.- Typical Conventional Surface Water Pretreatment System

Coagulant
Dosing for Ultrafiltration Acid Or
Chlorine Organics System Scale Reverse
Dosing removal Inhibitor Osmosis
3 Feed System
Surface Permeate
Water SDI value Product
Feed at this point Water
typically (typically
2.5 70-80%)
Reject Reject
Water Water
to Waste to Waste
(typically (typically
5 to 15%) 20-30%)
Fig. 2-Newer Ultrafiltration Membrane Pretreatment to RO Systems

Chlorine Bisulfite dosing Reverse

Dosing if chlorine is Osmosis
2. present System
1.
Surface 4 Perneate
Water Product
Feed Water
Multimedia Multicontaminant 5 micron (typically
Filter Coltro Medias Fite 70-80%)
(Suspended for reduction of Reiect
Soids SDI, coloidal SDI value NE
Filtration) particulates, at this point to Waste
organic matter. typically (typically
to 2 20-30%)
Fig. 3 - Typical Surface Water Pretreatment System with Invention

Colloidal
SiO2
Figure 4
Density
index)
Figure 5
Figure 6
NTU
Turbidity
Figure 7
s
5
9 4
in 3 SE
isC 2s
1
3 O
Virgin #1 Virgin #2
an Coll.SiO2 Inlet
Pilot Runs - - H. Coll.SiO2 Outlet
Figure 8
4.
123
0.
Pilot Runs-Days
- -
Figure 9
SF
O
s
es
1.5 save
1 aa.
m
E O.5 -E
O
o
O N
N N &
S
s S CN
g d
g CN
kc
Pilot Runs - Days
Figure 10
2
s
2
2
Pilot Runs - Days
Figure 11
O
O 200 400 600 800 1000 1200
Bed Volumes
Figure 12
14.0%
120%
100%
80%
60%
40%
20%
O%
O 18.9 37.8 75.6 89.78 113.4 132.3 160.7
Bec Volumes
Figure 13
8h 12h 16h 20h 24h 28h 32h 48h 72h 96h

Operating hours
Figure 14
ls
9. 2
E
O.
O
4h 8h 12h 16h 20h 24h 28h 32h 48h 72h 96h

Operating hours
Figure 15
90%
80%
70%
60%
50%
40%
30%
20%
Coll.SiO2
SD
Organics
US 8,883,012 B2
1. 2
REDUCED FOULING OF REVERSE OSMOSIS reject stream contains virtually all the contaminants that are
MEMBRANES larger in size than the pores of the membranes except for a
Small amount which leaks through into the finished permeate
CROSS REFERENCE TO RELATED water. Thus, the reject water stream will contain most of the
APPLICATIONS 5 dissolved salts originally present in the feed water along with
any loose deposits or foulants formed at the membrane Sur
The present invention claims priority to U.S. Provisional faces but which are carried away with the reject water. The
Application No. 60/885,855, filed Jan. 19, 2007, and U.S. bulk of deposits and foulants generally attach themselves to
Provisional Patent Application No. 60/908,172, filed Mar. 26, the membrane Surfaces and eventually cause enough restric
2007, both of which are herein incorporated by reference in 10 tion of flow through the membranes to warrant the need to
their entirety. clean the membranes chemically. However, frequent chemi
cal cleaning of membranes can shorten their useful lives and
FIELD OF THE INVENTION increase associated operating costs.
To maintain efficient operation, system designers strive to
The present invention relates generally to water purifica- 15 keep the membrane Surfaces and passageways as clean and
tion using reverse osmosis and nanofiltration membranes. In free from fouling, deposits, and microbial clogging as prac
particular, the present invention provides methods and water tical. As the membranes and passageways become fouled, the
purification systems using an ion exchange resin system for resistance to the flow of water increases, resulting in a higher
pretreatment of water being fed to a reverse osmosis or nano pressure drop and, consequently, higher pumping costs. As
filtration membrane treatment system, where the pretreat- 20 the pressure drop across the membrane increases, the Volume
ment reduces fouling of the membrane Surfaces and passage of treated (permeate) water decreases while its salinity
ways. increases. Correspondingly, the Volume of reject water sent to
drain increases. This expected loss in efficiency is compen
BACKGROUND OF THE INVENTION sated for in permeate production by increasing the size of and
25 cost of the system. The membrane industry uses a term,
Reverse osmosis (RO) and nanofiltration (NF) membrane referred to as the “Silt Density Index,” or (SDI) value of the
systems routinely provide desalinated or demineralized water feed water processed by the membranes, to determine the
to the power, chemical process, semiconductor, and pharma total Surface area of membranes elements needed to treat a
ceutical industries. Desalination of brackish and seawater for specific volumetric flowrate of water. Numerical values range
potable use similarly employs these membrane systems, and 30 from 1 to 7, with a value of 1 representing minimum fouling,
will play an even greater role as world population grows and while increasing values represent rapidly deteriorating foul
clean water becomes more scarce. ing conditions. For SDI values ranging from 3 to 5, which are
Despite the rapid growth rate, the cost of membrane treated typical of Surface water Supplies containing more colloidal
water continues to be affected by a number of operational contaminants, the industry standard is to allow for a flowrate
issues related to contaminants generally present in the water 35 of no more than 8 to 14 gallons of water per day per square
Supply. Central to the problems are the semi-permeable mem foot of membrane surface area (8 to 14 GFD). For better
branes which are essentially discrete filters, with RO mem quality waters with SDIs ranging from 1 to 3, such as well
branes capable of rejecting matter having an average diameter water supplies which typically have SDI values less than 3,
larger than 0.0001 micron (1 Angstrom). Such as atoms and more efficient designs can be made with water flow rates
molecules, and NF membranes rejecting dissolved species 40 ranging from 14 to 20 gallons of water per square foot of
having an average diameter greater than 0.0005 micron (5 membrane surface area (14 to 20 GFD). The larger amount of
Angstroms). membrane Surface area needed for water with higher fouling
Contaminants larger than these sizes, such as Suspended or potential equates to higher capital cost for more membranes
colloidal particulates (e.g., silt, clay, colloidal species of elements and pressure vessels to hold the membranes, apart
silica, organics, aluminum and iron) and large organic mol- 45 from the increased space needed to accommodate the equip
ecules (e.g., humic and fulvic acids) naturally presentin many ment. In addition, operating costs are also higher in terms of
water Supplies, are readily rejected. These contaminants extra water purchases for the higher volume of water that
become concentrated in the reject water stream from the must be rejected and for higher waste discharge fees. To
membrane plants, and have the potential to build-up to con maintain permeate production above some minimum level.
centrations at which they can deposit and foul the sensitive 50 the membrane plant must also be taken out of service peri
Surfaces and pores of the membranes. odically so that routine chemical cleaning of the membranes
Additionally, sparingly soluble salts of calcium, barium, can be performed to remove foulants, deposits, and microbial
and strontium sulfates and carbonates or salts of calcium slime masses. Generally, chemical cleaning of the membrane
phosphate or fluoride can potentially exceed their solubility is advised when the pressure drop across the membranes
during such concentration in the reject stream and precipitate 55 (known as the transmembrane pressure or TMP) increases by
as Scale on the Surface of the membranes. Metals present in about 15%, or when permeate water production decreases by
the feedwater Such as iron, manganese, and aluminum can about 15%, or when the salinity (or total dissolved solids) of
become oxidized by oxygen intrusion, and Such metal oxides the permeate increases by about 15%. (see Daniel Comstock,
can deposit on the surface of the membranes. If bacteria are Ultrapure Water Magazine, September 2000, pp. 30-36).
allowed to enter via the feedwater or via the membranes, for 60 Conventional membrane systems usually allow for a large
example, due to inadequate sanitization after maintenance fraction of the water to be sent to waste as reject, typically 20
work is performed, bacterial slime masses can quickly to 30% of the influent water for brackish water and as high as
develop if enough nutrients (organic matter) are available. 65% for seawater treatment. This represents a major operat
Such biofilms can coat the membrane Surfaces and signifi ing cost component but is necessary, in part, not to exceed the
cantly increase pressure drop across the membranes. 65 solubility or safe limits for silica especially, and other con
Processing water through the RO system results in a sub taminants like bacteria and sparingly soluble compounds like
stantial fraction of the water being rejected to waste. This Sulfate and carbonate salts of barium, strontium, and calcium
US 8,883,012 B2
3 4
and similar metals. RO Membrane systems incorporate a water if provisions are made for the feed of suitable chemical
number of pretreatment steps to minimize fouling, Scaling, coagulant ahead of the membranes. Ultrafiltration and micro
and biological problems. Suspended Solids several microns in filtration used as pretreatment before RO are further dis
size or larger, are relatively easy to remove by traditional cussed in “Using Ultrafiltration as a pretreatment before RO”
filtration methods, Such as those using sand or mixtures of 5 by Steve Siverns (Ultrapure Water Magazine, May 2006) and
sand with various other filtration medias Such as anthracite in “Industrial Applications Using Microfiltration as RO Pre
and garnet. On the other hand, colloidal particulates varying treatment' by Mark Mierzejewski (Ultrapure Water Maga
in size from as low as 0.008 micron (80 Angstroms) to about zine, October 2004, pg 29-35), both of which are herein
1 micron (10,000 Angstroms) in diameter present a much incorporated by reference. However, these pretreatments
larger removal challenge. Such colloidal particulates can 10 have the disadvantages associated with increased operator
remain Suspended indefinitely in the water phase and canthus error, a large capital investment, high maintenance costs, and
largely slip through the Void spaces in Such filtration media. the additional waste of water from the UF unit.
While ion exchange resins are useful as prefilters for soften The removal of dissolved silica from the water stream is
ing the water (i.e., strong acid cationic resins) and for remov also of major interest due to its limited solubility of approxi
ing organics (i.e., strong base resins), they have not been 15 mately 150 mg/l at ambient temperatures and the difficulty of
available for removing colloidal particulates. While the crush removing this contaminant using many standard pretreatment
strength of the resins used for water softening or removal of methods. Monomeric silica, a major form of silica present in
dissolved organic matter is high, on the average ranging from water, can polymerize into larger molecules. These can then
175 to 500 grams average per bead, high porosity deposit on the membrane Surfaces depending on the pH and
macroporous resins available in the past for the removal of temperature of water. Calcium or iron if present, can co-react
colloids (e.g., Rohm & Haas IRA-938) were very easily with silica or catalyze the reaction to significantly increase
crushed. Therefore, they were unacceptable for use in a pre the potential for silica deposition on the membranes.
filter for a membrane filter due to rapid increase in pressure U.S. Patent Publication 2002/0153319 (herein incorpo
drop across the resin and the increased risk of particulate rated by reference) describes what is referred to as the
fouling of the membranes by broken-off pieces of resin itself. 25 "HERO,” or High Efficiency RO” process for high purity
The crush strength of the macroporous resin previously used water production where traces of silica and boron can be
for colloidal removal, IRA-938, was measured at 8 grams per detrimental to downstream ion exchange mixed beds Supply
bead, which is extremely low compared to standard ion ing high purity water required for semiconductor manufac
exchange resins which are more robust, having breaking turing. Instead of removing silica, the technology concen
weights ranging from 175 to 500 grams per bead. Because of 30 trates on removing co-precipitating divalent contaminants in
the major crushing and physical breakdown problems of IRA the water Such calcium, barium, and strontium. The technol
938, this resin could not be commercially used and produc ogy also endeavors to increase the solubility of silica by
tion was discontinued. raising the pH of the water to about 10. The principal plat
A typical conventional pretreatment system for a Surface forms of the technology are (a) to remove cations, which in
water source will usually include several unit operations 35 combination with other species present at high pH, tend to
including: precipitate sparingly soluble salts on the membrane Surfaces
(a) Chlorine dosing into the feedwater supply for microbial and (b) to eliminate non-hydroxide alkalinity to the maxi
control; mum extent feasible. To accomplish this, the preferred
(b) Coagulant and polyelectrolyte flocculant chemical dos embodiment of the 319 application implements a number of
ing upstream of either a clarifier or a static mixer to 40 costly pretreatment steps including use of two weak acid
reduce Suspended solids and some of the colloidal par cation vessels in series, one operating in the hydrogen form
ticulates and organic matter; and the other in the Sodium form, along with a de-carbonator
(c) Downstream multimedia filters consisting of sand, vessel to release CO2 generated by the hydrogen form weak
anthracite and garnet to filter out residual Suspended acid cation vessel. These units require on-going (i.e., daily)
Solids; 45 skilled operator attention for acid and caustic chemical han
(d) One or more activated carbon filters for removal of dling and control, water sampling and testing. After the decar
residual chlorine to avoid damage to the membranes and bonator, the water must be re-pumped at additional cost and
for removal of any residual organic matter present (e.g., caustic must then be injected to raise the pH to preferably
humic and fulvic acids); above 10 before the water is fed to the RO. The increase in
(e) An ion exchange water softener using a strong acid 50 solubility of silica caused by increasing the pH and by elimi
cation resin in the Sodium form for removal of hardness; nating divalent cations from the water allows concentrations
(f) Alternatively to (e), above, the chemical feed of acid in excess of the normal solubility limit of 150 ppm to be
and/or a scale inhibitor for controlling scaling from cal -maintained in the reject concentrate from the RO, with suc
cium and barium salts of carbonate and Sulfate; cessful operation reported at 450 ppm silica and higher. As a
(g) A final 5-micron filter cartridge to catch any residual 55 result, the 319 application proposes that RO systems can be
suspended solids just before the water is fed to the mem operated with significantly increased permeate recovery
branes. reported from 85 to 95% depending on levels of other con
In recent years the industry has resorted to increasingly taminants in the water. Another major cost issue with the
more expensive techniques for controlling colloidal particu invention described in the 319 application is its poor perfor
lates, utilizing ultrafiltration (UF) and microfiltration mem 60 mance on raw waters which contain a hardness to alkalinity
branes (MF) with pore diameter greater than 0.001 micron ratio that is Substantially less than one. Under Such condi
(10 Angstroms) and 0.1 micron (1000 Angstroms) respec tions, the capacity of the weak acid cation resin to remove the
tively as prefilters ahead of the reverse osmosis units. UF divalent hardness cations present is very poor as the resin can
membrane prefilters have done a good job controlling colloi only remove divalent cations that are associated with alkalin
dal particulates compared to the traditional clarification and 65 ity.
multimedia filtration methods outlined above. Additionally There is therefore a need in the art for additional or
UF membranes have the ability to reduce organic matter in the improved pretreatment methods and membrane systems that
US 8,883,012 B2
5 6
have a reduced size or cost compared to prior art methods resin is chloromethylated and then aminated, wherein the
(i.e., reduced set-up costs, reduced operational costs, and macroporous resin comprises a basic anion-exchange resin.
reduced costs associated with regeneration of the pretreat In yet another preferred embodiment, the macroporous
ment material). It would be advantageous to provide a pre resin was formed from the polymerization of a solution of (a)
treatment method or membrane system that removes silica a monoethylenic monomer, (b) a polyethylenic monomer, (c)
and/or other colloidal particulates. It would also be advanta a free-radical initiator, and (d) 20-40 pph poly(alkylene
geous to provide a system that Substantially reduces the Silt oxide) pore-forming agent or a mixture of the 20-40 pph
Density Index (SDI) value of the water. poly(alkylene oxide) with toluene, pore forming agents. In
one embodiment, the poly(alkylene oxide) is a copolymer of
SUMMARY OF THE INVENTION 10 ethylene oxide and propylene oxide. In a preferred embodi
ment, the poly(alkylene oxide) is present from 20-33 pph.
The present invention provides a novel method and pre In another embodiment, the macroporous resin has pore
treatment system which protects the RO or NF membranes diameters ranging from 10,000 to 200,000 Angstroms. In
from fouling, deposits, or chemical precipitation, any of another embodiment, the macroporous resin has pore diam
which can shorten the useful life of the membranes. 15 eters ranging from 10,000 to 200,000 Angstroms and a mean
In one embodiment, the present invention comprises a pore diameter (D50) of 31,000 to 70,000 Angstrom. In
method of purifying water comprising: a) pretreating the another embodiment, the macroporous resin has pore diam
water by passing the water through a vessel containing a resin eters ranging from 5,000 to 100,000 Angstroms.
component, wherein the resin component comprises a highly In another embodiment, the macroporous resin has a crush
macroporous resin having a substantial number of pores hav strength or Chatillon value of 175 g/bead average to 475
ing a pore diameter in the range of 1,000 to 500,000 Ang g/bead average, or higher. In another embodiment, the
stroms and a crush strength or Chatillon value of at least 24 macroporous resin has an average pore diameter in the range
g/bead (710 um bead diameter); and b) feeding the water of 10,000 to 500,000 Angstroms, a pore volume of at least
exiting the resin component to a reverse osmosis membrane 0.60 ml/g (dry), and a crush strength or Chatillon value of at
or a nanofiltration membrane to produce permeate water. 25 least 24 g/bead (i.e., an orthoporous resin). In another
Another aspect of the present invention provides a method embodiment, the macroporous resin has a pore diameter in
of treating water comprising: a) feeding water into a vessel the range of 10,000 to 200,000 Angstroms, a pore volume of
containing a resin component, wherein the resin component at least 0.60 ml/g (dry), and a crush strength or Chatillon
comprises a highly macroporous resin with high porosity and value of at least 24 g/bead. In yet another embodiment, the
high crush strength (i.e., having an average pore diameter 30 macroporous resin has a pore diameter in the range of 5,000
range from 10,000 to 500,000 Angstroms and a crush strength to 100,000 Angstroms, a pore volume of at least 0.60 ml/g
or Chatillon value of at least 24 grams per bead); b) feeding (dry), and a crush strength or Chatillon value of at least 24
the water from the resin component into a reverse osmosis g/bead to 175 g/bead.
system or a nanofiltration system to produce permeate water; In one preferred embodiment, resin component reduces the
and c) when chemical cleaning of the resin component is 35 Silt Density Index (SDI) and/or the colloidal particulate con
advised, regenerating the resin component using one solution tent of the water by at least 25%. Preferably, the SDI is
of a single chemical or mixture of chemicals for simultaneous reduced by at least 50%. Even more preferably, the SDI is
regeneration or rejuvenation of the resin component. reduced by at least 75%. In one preferred embodiment, the
Another aspect of the present invention provides a method SDI after step b) is less than 2.5. Even more preferably, the
of treating water containing dissolved silica is provided, 40 SDI after stepb) is less than 2.0, and even more preferably, the
where the comprises: a) feeding water into a vessel containing SDI after step b) is less than 1.5.
a resin component, wherein the resin component comprises In another preferred embodiment, the resin component
an iron-impregnant or iron-containing media which is an iron further comprises an iron-impregnant or iron-containing
oxide attached to an ion exchange resin; b) feeding the water media. Preferably, the resin component reduces the dissolved
from the resin component into a reverse osmosis system, a 45 silica of the water treated by at least 20%. In a preferred
nanofiltration system, a demineralization unit, a cooling embodiment, the iron-impregnant or iron-containing media is
tower, or a boiler, and c) when chemical cleaning of the resin an iron salt. In another preferred embodiment, the iron-im
component is advised, regenerating the resin component with pregnant or iron-containing media is an iron oxide attached to
an alkali solution or an alkaline and brine solution. Regen an ion exchange resin.
eration may be accomplished using one solution of a single 50 In yet another embodiment, the resin component further
chemical or mixture of chemicals for simultaneous regenera comprises one or more strong base resins. Preferably, the
tion or rejuvenation of the resin component. In one embodi resin component reduces the total organic carbon (TOC) con
ment, the iron-impregnant media comprises ArsenX'. tent of the water treated by at least 20% or more, preferably
In one embodiment, the pore Volume of the macroporous 40% or even more preferably 60%. In a preferred embodi
resin is at least 0.36 ml/g (dry). In another embodiment, the 55 ment, the resin component comprises two different strong
pore volume is 0.36-0.6 ml/g. In yet another embodiment, the base resins or a resin with two different strong base functional
pore volume is 0.36-1.5 ml/g. groups such as a BiQuat resin (a resin having two quaternary
In another embodiment, when chemical cleaning of the ammonium groups selected from triethylammonium, tripro
resin component is advised, the method also comprises regen pylammonium, and trihexylammonium.
erating the resin component using one solution of a single 60 In yet another embodiment, the resin component further
chemical or mixture of chemicals for simultaneous regenera comprises a strong acid resin. Preferably, the resin compo
tion or rejuvenation of the resin component. In yet another nent reduces the divalent cation content of the treated water
preferred embodiment, the chemical regenerant is used more by at least 20%.
than once (i.e., at least two times, at least four times, or more). In yet another embodiment, step b) removes contaminants
In another preferred embodiment, the macroporous resin is 65 from the water and these contaminants include at least two of
Sulfonated and comprises a strong-acid cation-exchange colloidal particulates having a diameter of at least 8 nm,
resin. In another preferred embodiment, the macroporous dissolved organic matter, dissolved divalent or trivalent metal
US 8,883,012 B2
7 8
cations, dissolved Sulfate or arsenate, and dissolved silica or BRIEF DESCRIPTION OF THE DRAWINGS
phosphate. More preferably, at least three contaminants are
removed. FIG. 1 shows a flow sheet of a typical conventional pre
In another embodiment of the present invention, the treatment system for reverse osmosis membrane systems uti
method of purifying or treating water further comprises pres lizing Surface water as feed.
Surizing the water entering the vessel containing the resin FIG. 2 shows a flow sheet of a second conventional typical
component to pressure values ranging from 5 to 200 pounds pretreatment system for reverse osmosis membrane systems
per square inch by means of a pressure pump. In yet another using an ultrafiltration membrane utilizing Surface water as
feed.
embodiment, the water pressure during step b) is at least 5
pounds per square inch and the flow rate through the vessel 10 FIG.3 shows a flow sheet of a preferred embodiment of a
allows for at least 8 to 20 gallons per square foot flow through Surface waterpretreatment system of the present invention.
the reverse osmosis membrane or a nanofiltration membrane FIG. 4 shows the reduction and removal capacity of one
Surface per day. embodiment of the resin component for reduction of colloidal
In a preferred embodiment, the step of regenerating com silica (average of 50% removal).
prises recirculating the chemical regenerant by recovering the
15 FIG. 5 shows the reduction and removal capacity of one
embodiment of the resin component for reduction of Silt
effluent from the vessel containing the resin component and Density Index (average of 49% reduction).
re-introducing it to the vessel to make repeated passes FIG. 6 shows the reduction and removal capacity of one
through the resin component. embodiment of the resin component for reduction of organic
In a preferred embodiment, the chemical regenerant com matter (average of 74% removal).
prises a solution of a chloride ion, an alkali bases, or a mixture FIG. 7 shows the capacity of one embodiment of the resin
of a chloride salt and an alkali base. In another preferred component for turbidity reduction (average of 31%).
embodiment, the chemical regenerant comprises a mixture of FIG. 8 shows the reduction and removal capacity of one
Sodium chloride and caustic Soda. In yet another preferred embodiment of the resin component for reduction of colloidal
embodiment, the chemical regenerant is used more than once 25 silica (average of 50% removal). Data is shown for a test pilot
(i.e., at least two times, at least four times, or more). system comprised of two 1 liter cartridges containing two
In yet another embodiment, the resin component further Volumes of the resin component used alternately to treat the
comprises at least one of polystyrene or acrylic polymer same Surface water Supply containing naturally varying influ
matrix-based anion exchange resin; an iron-impregnant or ent colloidal silica values ranging from 0.5 to 4.5 ppm, with
iron-containing media Such as an iron Salt or an iron oxide 30 the water after treatment through the cartridge containing
attached to an ion exchange resin; or a strong acid cation reduced values of colloidal silica ranging from 0.1 to 2.8 ppm,
exchange resin. representing and average of approximately 50% reduction in
In anther preferred embodiment, the average reduction in colloidal silica. Flow through each cartridge was controlled at
12 bed Volumes per hour, with each cartridge treating a total
dissolved silica of the effluent water compared to the water 35 of 864 liters before being removed for regeneration or reju
fed into the vessel is at least 20%. In anther embodiment, the Venation of the resin component. During the time that one
water fed into the vessel has at least 1 ppm silica. In yet cartridge was removed for regeneration, the alternate car
another embodiment, the water is fed into a demineralization tridge was installed. Cartridge 1 effluent values are repre
unit in step b) and wherein the chemical regenerant of step c) sented by designations, “Virgini 1”, “C1Reg.1, and
is a caustic solution effluent from the anion vessel of the 40 “C1Regi2 with “C1Reg.1” and “C1Reg2' representing the
demineralizer. values after regenerations 1 and 2. Cartridge 2 effluent values
In yet another embodiment, the method of purifying or are represented by designations, “Virgini2 and “C2Regi1
treating water further comprises pressurizing the water enter representing values for first use and after first regeneration.
ing the vessel containing the resin component to pressure FIG. 9 shows the reduction and removal capacity of one
values ranging from 5 to 200 pounds per square inch by 45 embodiment of the resin component for reduction of Silt
means of a pressure pump. In yet another embodiment, the Density Index (average of 49% reduction). Data is shown for
water pressure during step b) is at least 5 pounds per square a test pilot system comprised of two 1 liter cartridges con
inch, and the flow rate through the vessel allows for at least 8 taining two Volumes of the resin component used alternately
to 20 gallons per square foot flow through the reverse osmosis to treat the same Surface water Supply containing naturally
membrane or a nanofiltration membrane Surface per day. In a 50 varying influent colloidal silica values ranging from 0.5 to 4.5
further embodiment, the water is fed into a boiler in step b) ppm, with the water after treatment through the cartridge
which is operating at over 800 psi. containing reduced values of colloidal silica ranging from 0.1
In another embodiment, the water is fed into a demineral to 2.8 ppm, representing and average of approximately 50%
ization unit in Step b), wherein the resin component further reduction in colloidal silica. Flow through each cartridge was
comprises a strong base resin. 55 controlled at 12 bed volumes per hour, with each cartridge
In yet another embodiment, the regenerant may be recir treating a total of 864 liters before being removed for regen
culated by recovering the effluent from the vessel containing eration or rejuvenation of the resin component. During the
the resin component and re-introducing it to the vessel to time that one cartridge was removed for regeneration, the
make repeated passes through the resin component. alternate cartridge was installed. Cartridge 1 effluent values
Another aspect of the present invention comprises a water 60 are represented by designations, “Virginil 1, "C1Reg.1, and
treatment system using the resins as described herein and one “C1Regi2 with “C1Reg.1” and “C1Reg2' representing the
or more of a polystyrene or acrylic polymer matrix-based values after regenerations 1 and 2. Cartridge 2 effluent values
anion exchange resin; an iron-impregnant or iron-containing are represented by designations, “Virgini2 and “C2Regi1
media; or a strong acid cation exchange resin in fluid connec representing values for first use and after first regeneration.
tion to a reverse osmosis membrane or a nanofiltration mem 65 FIG. 10 shows reduction and removal capacity of one
brane, wherein the resin component can be regenerated using embodiment of the resin component for reduction of organic
a single chemical regenerant Solution. matter (average of 74% removal). Data is shown for a test
US 8,883,012 B2
9 10
pilot system comprised of two 1 liter cartridges containing FIG.16 shows the field pilots with multiple regenerations,
two Volumes of the resin component used alternately to treat reusing different regenerants. The Virgin resin reduced the
the same Surface water Supply containing naturally varying colloidal silica, SDI and organic matter by 60%, 42% and
influent colloidal silica values ranging from 0.5 to 4.5 ppm, 73% respectively. Reduction in the colloidal silica, SDI and
with the water after treatment through the cartridge contain organic matter after additional loading and regeneration
ing reduced values of colloidal silica ranging from 0.1 to 2.8 cycles are shown.
ppm, representing and average of approximately 50% reduc
tion in colloidal silica. Flow through each cartridge was con DETAILED DESCRIPTION
trolled at 12 bed volumes per hour, with each cartridge treat 10
ing a total of 864 liters before being removed for regeneration Resin Component
or rejuvenation of the resin component. During the time that The present invention comprises a resin component which
one cartridge was removed for regeneration, the alternate is a highly macroporous resin that can be used for the pre
cartridge was installed. Cartridge 1 effluent values are repre treatment of water being fed to a membrane treatment system.
sented by designations, “Virgini 1”, “C1Reg.1, and 15 The membrane treatment system may be a reverse osmosis
“C1Regi2 with “C1Reg.1” and “C1Reg2' representing the membrane system or a nanofiltration membrane system. This
values after regenerations 1 and 2. Cartridge 2 effluent values resin component contains one or more ion exchange resin
are represented by designations, “Virgini2 and “C2Regi1 and/or adsorbent media layered or mixed together in an ion
representing values for first use and after first regeneration. exchange vessel. In some embodiments, the resin component
FIG. 11 shows the capacity of one embodiment of the resin can be described as a multi-contaminant control mixture
component for turbidity reduction (average of 31%). Data is since multiple contaminants are removed from the water
shown for a test pilot system comprised of two 1 liter car stream by the resin. These contaminants include, but are not
tridges containing two Volumes of the resin component used limited to, colloids, dissolved organic matter, dissolved silica,
alternately to treat the same Surface water Supply containing and divalent and trivalent cations. As used herein, the resin
naturally varying influent colloidal silica values ranging from 25 component may also include adsorbents.
0.5 to 4.5 ppm, with the water after treatment through the The resin component is effective for the simultaneous
cartridge containing reduced values of colloidal silica rang removal or reduction in concentration of one or more of the
ing from 0.1 to 2.8 ppm, representing and average of approxi following contaminants from a water Supply or process
mately 50% reduction in colloidal silica. Flow through each Stream:
cartridge was controlled at 12 bed volumes per hour, with 30
i. Colloidal particulates ranging in diameter from 0.008
each cartridge treating a total of 864 liters before being micron (80 Angstroms) and greater consisting typically
removed for regeneration or rejuvenation of the resin compo of colloidal species of silica, organic matter, iron, man
nent. During the time that one cartridge was removed for ganese, aluminum, copper, lead, nickel, and other met
regeneration, the alternate cartridge was installed. Cartridge 1 als;
effluent values are represented by designations, “Virgini 1. 35
ii. Dissolved organic matter (naturally occurring organic
“C1Reg.1”, and “C1Regi2 with “C1Reg.1” and “C1Reg2”
representing the values after regenerations 1 and 2. Cartridge matter Such as humic, fulvic and tannic acids);
2 effluent values are represented by designations, “Virgini2. iii. Dissolved divalent or trivalent metals cations such as
and “C2Regi1 representing values for first use and after first calcium, magnesium, barium, strontium, iron, manga
regeneration. 40 nese, aluminum, copper, lead, and nickel;
FIG. 12 shows the capacity of one embodiment of the resin iv. Dissolved anionic species including Sulfate and bicar
component for dissolved silica removal using a high capacity bonate; and
iron-impregnated resin. This Figure shows that an average of V. Dissolved silica, phosphate, arsenate, and similar oxya
8000 mg silica per liter of resin were removed to 50% break nions.
through point when treating a typical influent water contain 45 Preferably, two or more of the above contaminants are
ing 16.8 ppm silica at a pH of 8.2 and a flow rate of 12 bed reduced or removed. Even more preferably, three or more of
Volumes per hour. the above contaminants are reduced or removed. Even more
FIG. 13 shows the capacity of one embodiment of the resin preferably, four or more of the above contaminants are
component for dissolved silica removal using a high capacity reduced or removed. Most preferably, five or more of the
iron-impregnated resin. The silica is removed from the blow 50 above contaminants are reduced or removed. The number of
down form a 2400 psig steam generator. The silica removal contaminants removed by the resin component will depend
capacity under adverse elevated levels of silica of 77 ppm and on the identity and concentrations of contaminants in the raw
pH of 9.5 is shown at significantly faster velocity of 57 bed water, and the other elements in the water purification system
Volumes per hour. Capacity achieved was approximately being used. Such as a pretreatment filter.
6000 mg silica per liter of resin to 50% silica breakthrough. 55 In one embodiment, a single porous resin that reduces or
FIG. 14 shows the removal of silica from NSF53 Challenge removes colloidal contaminants is used.
water at pH 7.7. This test provides a loading of approximately In an embodiment, the resin component comprises a
17 grams of silica per liter of resin after 96 hours and a silica porous resin to reduce or remove colloidal contaminants and
breakthrough of approximately 60% at the end of the test. a strong base resin that removes dissolved organic contami
FIG. 15 shows the removing and regenerating of silica with 60 nants.
reused regenerant at pH 8.0. This test provides a loading of In another embodiment, the resin component comprises a
approximately 34 grams of silica per liter of resin after 96 porous resin to reduce or remove colloidal contaminants, a
hours and a silica breakthrough of approximately 52% at the strong base resin that removes dissolved organic contami
end of the test. During a second loading cycle with the same nants, and an adsorbent media that removes dissolved silica.
challenge Solution and effluent sample, silica loading was 26 65 Two or more of the resins may have been previously com
grams silica per liter of resin, or approximately 76 percent of bined. Such as a resin combining organic removal and
the loading for the first test. removal of colloidal contaminants.
US 8,883,012 B2
11 12
In another embodiment, the resin component may contain iv. a strong acid cation exchange resins primarily for
two or more strong base resins. In anther embodiment, the removal of dissolved divalent or trivalent metals cations
resin component contains a strong acid component as a soft Such as calcium, magnesium, barium, strontium, iron,
ener resin. manganese, aluminum, copper, lead and nickel.
As used herein, the phrase “reduces contaminant’ means 5 In a preferred embodiment, the resin component comprises
that at least 25% of the measurable contaminant (or contami a combination of a macroporous resin with high porosity and
nants) is removed from the water stream. More preferably, at high crush strength and one or more of ii., iii, and iv.
least 40% of the contaminant is removed. More preferably, at Macroporous Resin of High Porosity and High Crush
least 60% of the contaminant is removed. Even more prefer 10
Strength
ably, at least 70% of the contaminant is removed, and even In one embodiment, the macroporous resin used as part of
more preferably, at least 80% of the contaminant is removed. the resin component is a colloidal scavenger resin with high
Most preferably, at least 90% or more of the contaminant porosity and high crush strength Such as described in U.S. Pat.
concentration is removed when comparing the contaminant No. 6,323,249 to Dale, et al., herein incorporated by refer
concentration in the inlet of the vessel or device compared to 15 ence. The diameter of the large macropores in this resin
the outlet of the vessel or device. typically range from 5,000 to 100,000 Angstroms, or more
As used herein, the phrase “removes contaminant’ means preferably 10,000 to 200,000 Angstroms and are ideal for
that at least 95% of the measurable contaminant (or contami removal of colloidal particulates by a combination of adsorp
nants) is removed from the water stream. More preferably, at tion and ion exchange phenomena. Preferably, the mesh size
least 98% of the contaminant is removed. Even more prefer of this resin is 16 to 50 U.S. mesh. Either cation oranion type
ably, at least 99% of the contaminant is removed, and even resins can be utilized as the base resin. When using an anion
more preferably, at least 99.5% of the contaminant is resin as the base, the capacity for removal of dissolved
removed. Most preferably, at least 99.9% or more of the organic matter is increased significantly. The synthesis of the
contaminant concentration is removed when comparing the macroporous resin of the present invention is described
contaminant concentration in the inlet of the vessel or device 25 herein below.
compared to the outlet of the vessel or device. The macroporous resin also has a pore Volume of at least
As used herein, the terms "diameter' and "size, when 0.36 ml/g (dry). The pore volume may be greater than about
referring to colloids, are both defined as the average diameter 0.6 ml/g dry, or the pore volume may be between 0.36 and 1.5
of the colloidal particles. ml/g dry.
The resin component is also effective for reducing the Silt 30
The macroporous resin has a high crush strength, which is
Density Index (SDI) value of the water or process stream in defined as a Chatillon value of at least 24 g/bead (710 umbead
preparation for treatment of the water by a reverse osmosis, diameter). More preferably, the Chatillon value is at least 50
nanofiltration, or similar membrane system. The SDI value is g/bead, and even more preferably at least 100 g/bead. More
a numeral value derived from a standard industry test in which preferably, the Chatillon value is a least 200 g/bead. The high
the flowing sample of feed water to be tested is kept at a 35
crush strength is an important aspect of the present invention
constant pressure of 30 psig and is passed through a 0.45
micron filter element. The time taken to fill a standard 500 ml since resins having lower crush strength have the disadvan
container is recorded for an initial reading taken immediately tage that, due to the need to contain and operate the resins in
at the beginning of the test and another reading taken 15 pressurized vessels and the need to subject the beads to
minutes after. A mathematical formula is used to compare and 40 repeated exhaustion and regeneration cycles, the beads tend
compute a numerical value referred to as the Silt Density to fracture. Potentially the fractured bead then can be eluted
Index (SDI) value. Numerical values range from 1 to 7, with from the vessel and foul the membrane filter; the efficacy of
1 being excellent and representing minimum fouling, while the remaining resin is also reduced for resins having lower
increasing values represent rapidly deteriorating fouling con crush strength.
ditions. The typical percentage of reduction of the SDI value 45 In another embodiment, the macroporous resin used as part
of a water stream passing over the resin component ranges of the resin component is an orthoporous resin with high
from 25% to 100%. Preferably, the SDI is reduced by at least porosity and high crush strength such as described in U.S.
40%. Even more preferably, the SDI is reduced by at least Provisional Patent Application No. 60/908,172, herein incor
50%, and even more preferably, the SDI is reduced by at least porated by reference. The orthoporous resins used in the
60%. Even more preferably, the SDI is reduced by at least 50 present invention have particularly large pores compared with
70%, and even more preferably, the SDI is reduced by at least typical macroporous resins. The pore size affects the diffu
80%. Even more preferably, the SDI is reduced by at least sion and flow kinetics through the resin material. The ortho
90%, and most preferably, the SDI is reduced by at least 95%. porous resins can beformed by generating an interpenetrating
In a preferred embodiment, the resin component uses a polymeric network (IPN). This is done by (a) preparing an
combination of two or more of: 55 initial macroporous copolymer, (b) re-swelling, and (c) poly
i. a macroporous resin with high porosity and high crush merizing. When an orthoporous resin is used, the average
strength, primarily for removal of colloidal particulates pore diameter is between about 10,000-500,000 Angstroms.
and some dissolved organic matter, The orthoporous resins of the present invention are formed
ii. a strong base or weak base anion exchange resins of in several steps. A first step involves the synthesis of a copoly
polystyrenic or acrylic polymer matrix primarily for 60 merby (a) Suspending droplets of a homogeneous mixture of
removal of dissolved organic matter and anionic species monomers with a free radical initiator and porogen(s). Such as
Such as Sulfate and bicarbonate; an aliphatic alcohol- i.e., methyl isobutyl carbinol, isobutyl
iii. an iron-impregnated or iron-containing media using alcohol, etc.—(b) in an aqueous Solution, and then (c) ther
Substrates such a cation or anion resin, alumina, natural mally polymerizing. A second step involves combining (re
Zeolite, sand or similar filtration media primarily for the 65 swelling) the 0" order IPN, as made in the first step, with
removal of dissolved silica, arsenic, phosphate and simi another monomer mixture and polymerizing in aqueous Sus
lar oxyanions by an adsorption mechanism; and pension, to createa 1" order IPN. A third step combines the 1
US 8,883,012 B2
13 14
order IPN with additional monomer, to create a 2" order IPN. and the need to Subject the beads to repeated exhaustion and
In one embodiment, a 3' order IPN is formed by using the 2' regeneration cycles, the beads tend to fracture. Potentially the
order IPN as a seed. fractured bead then can be eluted from the vessel and foul the
Preferably, the mixture of polymerisable monomers used membrane filter; the efficacy of the remaining resin is also
to form the copolymer and to form the IPN comprises a reduced for resins having lower crush strength.
monoethylenically unsaturated monomer, or monomers, and Iron-impregnated or Iron-containing Media
a polyvinylidene monomer. Initiators, Suspension agents, sta Optionally, an iron-impregnated or iron-containing media
bilizers, etc. may be added to the monomer mixture or aque may be incorporated in the resin component. Granular iron
ous phase as appropriate. oxide or iron hydroxide based adsorbents have been marketed
One preferred macroporous resin is formed when styrene, 10 for a number of years for arsenic removal and show a good
divinylbenzene and a porogen are mixed together with a capacity for dissolved silica adsorption, and may be used in
polymerization initiator to form the monomer solution. Free the resin component of the present invention. However, many
radical initiators are most desirable. Free radical generating popular products based primarily on pure iron oxide or
compounds which may be used to effect polymerization of hydroxide have a tendency to break down generating fines
the monomers include peroxides Such as benzoyl peroxide, 15 which can then foul downstream equipment. Therefore, pre
lauoryl peroxide, tertiarybutyl peroxide, peroxy-compounds ferred iron-impregnated or iron-containing media useful in
Such as potassium persulfate, sodium perborate and ammo the present invention includes iron-impregnated cation and
nium persulfate and azo compounds such as azo-bisisobuty anion resins such as ArsenX' (manufactured by The Purolite
ronitrile, 2,2-azobis-(2-methyl-butyronitrile), 2-t-butylazo Co., Philadelphia) as described in U.S. Pat. No. 7,291,578 and
2-cyano propane. Suitable concentrations are from 0.01 to Resintech ASM-10HP (manufactured by Resintech, New Jer
5.0%, more preferably 0.02 to 3.0%. The monomer phase is sey) as described in U.S. Patent Publication 2006/0037913
added to an aqueous phase for Suspension polymerization of herein incorporated by reference. During manufacture of
the monomers. Salt may be added to the aqueous phase to ArsenX' resin, nanoparticles of iron oxide are deposited
decrease the water solubility of the monomers. deep within the matrix of the resin beads. The resin beads
Various Suspension agents and stabilizers such as polyvi 25 provide a robust matrix to which the nanoparticles are firmly
nylalcohol, methyl cellulose, carboxymethyl cellulose, bonded and allow efficient diffusion of water and its contami
hydroxyethyl cellulose, poly(Vinyl pyrrolidine), polyacrylate nants into and out of the beads. Thus instead of adding iron
salts, polymethyacrylate salts, dimethyldialkylammonium salt to the silica containing water to treat silica in thermal
polymers, nitrite and dichromatic salts, calcium phosphate brines, the silica-containing water is simply passed through a
salts, carbonate salts, Sulfate salts, bentonite clays, gum ara 30 bed of the iron-containing impregnated media, allowing the
bic, lignoSulfonates, gelatine and Xanthan gums in amounts silica to diffuse into the matrix of the iron-impregnated resin
ranging from 0.01 to 1.0% by weight of the monomers may be to become complexed by adsorption onto the nanoparticles of
added to the aqueous dispersion to aid in maintaining the iron oxide.
monomers dispersed as droplets while polymerizing the same While ArsenX' resin was primarily developed for removal
as beads. 35 of arsenic and other oxyanions by adsorption, it shows good
Orthoporous copolymers can be sulfonated with sulfuric capacity for silica removal, like other iron-based adsorbents,
acid, oleum, Sulfur trioxide, or chlorosulfonic acid to form a but without the physical breakdown issues of granular prod
cation exchanger or, alternatively, it may be chloroalkylated ucts. Indeed, water treatment practitioners initially recog
and Subsequently aminated to form an anion exchanger. nized the adsorption of silica by Such iron-containing prod
A wide variety of amines including primary, secondary, 40 ucts during the removal of arsenic from drinking water
and tertiaryalkylamines, or arylamines can be employed in systems. But to practitioners its ability to remove silica was
the amination reaction. Polyalkylenepolyamines such as eth viewed as merely providing undesirable competition to the
ylenediamine, diethylenetriamine, triethylene-tetramine, tet adsorption of arsenic from the water since, depending on the
raethylenepentamine, propylenediamine, and iminobispro water chemistry, ArsenX' resin typically shows adsorption
pylamine can also be used. Aminoalcohols and 45 capacities for silica of only about 1000 to 2000 bed volumes
dimethylaminoethanol are also useful, as well as hexameth of water treated versus typical arsenic capacity of as much as
ylenetetraamine. A preferred embodiment employs a trialky 40,000 to 100,000 bed volumes. Therefore, the capacity of
lamine as the aminating agent, producing a quaternary anion ArsenX' resin for silica has previously been viewed as more
exchanger. Generally, the alkyl radical does not contain more of a nuisance contaminant since the silica competed with
than 4 carbon atoms. 50 arsenic, the contaminant of interest, for the same adsorption
In Some embodiments, a strong base anion exchange using sites on the media. A proprietary method of regeneration of
a trimethylamine resin is preferred. Weak base anion ArsenX' resin is available for stripping or eluting silica,
exchange resins may also be prepared; these resins are pre phosphate, and arsenic from the media, utilizing simple brine
pared in the same manner as the strong base resins with the and caustic Solution consisting usually of 2% caustic and 1%
exception that the tertiary-amine is replaced with non-tertiary 55 brine. Heating the Solution, preferably to temperatures up to
amines, such as dimethylamine, diethylamine, monomethy 50° C., and passing 2-20 bed volumes, preferably approxi
lamine, ethanol amines, etc. mately 6 bed volumes, slowly through the resin bed at a
The macroporous resin described in this embodiment of flowrate of about 2 bed volumes per hour increases the
the invention has a particularly high crush strength. Thus, in removal efficiency of silica and the other contaminants.
one embodiment, the Chatillon value is at least 200 g/bead 60 Although ArsenX' can be used and disposed of after a single
average (710 um bead diameter). More preferably, the Cha use, in a preferred embodiment, it is regenerated repeatedly
tillon value is at least 300 g/bead. More preferably, the Cha after exhaustion and reused multiple of times before final
tillon value is a least 400 g/bead. In one embodiment, the disposal. This embodiment is desirable due to the lower over
crush strength is 475 g/bead. The high crush strength is an all cost. Therefore, ArsenX' resin is a preferred component
important aspect of the present invention since resins having 65 in the resin component for processes where the raw water
lower crush strength have the disadvantage that, due to the stream contains dissolved silica, especially at elevated con
need to contain and operate the resins in pressurized vessels centrations. Iron-impregnated or iron-containing media hav
US 8,883,012 B2
15 16
ing an iron oxide attached to an ion exchange resin where the reduced footprint requirement compared to conventional
ion exchange resin has a crush strength of at least 24 g/bead treatment systems, and the removal or reduction of contami
(and preferably higher) can be used for removal of dissolved nants that are not addressed by the conventional or UF pre
silica in various systems that, because of the pressure require treatment systems such as removal or reduction of dissolved
ments, do not allow for use of crushable medias. These sys Sulfate, arsenate, phosphate, and similar oxyanions.
tems include reverse osmosis systems, nanofiltration sys An advantage of the method and system described in the
tems, demineralization units, cooling towers, boilers, etc. present invention is the compact size available for the vessel
The resin component may contain, for example, a containing the resin component. The resin component can use
macroporous resin of high porosity and high crush strength, a regenerable ion exchange/adsorbent resins layered or mixed
strong base anion exchange resin, and ArsenX' resin. The 10 together in a compaction exchange vessel. The ability to use
resin component may contain two or more components from a vessel having a small footprint allows for lower cost vessels
a single category. For example, it may contain two strong acid and Smaller space requirements for the purification system
cation exchange resins for the removal of different metal without reducing the flow rate of the water in the system.
cations. These components may be homogeneously mixed or Another advantage of the method and system described in
formed into layers within the vessel containing the resin 15 the present invention is the lower cost associated with oper
component. Other configurations of the components are also ating the purification process. In previous pretreatment meth
envisioned. ods, an operator was generally required to oversee the pro
The resin component must be able to withstand the pres cess. For example, a conventional hot lime softener/clarifier
sure applied to the vessel without crushing. The crush used to reduce silica contamination requires heating the
strength of the macroporous resin within the resin component water, a large space, and skilled operators to continuously
must be at least 24 g per bead average. More preferably, the monitor and adjust chemical feed. Similarly, the purification
crush strength is at least 50 g per bead. More preferably, the technology described in US Patent Application 2002/
Chatillon value for the macroporous resin is a least 100 g per 0153319 requires a number of costly pretreatment steps
bead. Even more preferably, the Chatillon value for the including use of two weak acid cation vessels in series, one
macroporous resin is a least 200g per bead average. 25 operating in the hydrogen form and the other in the Sodium
Other components in the resin, which will add to the overall form, along with a decarbonator vessel to release CO2 gener
crush strength, must also be stable to crushing. Preferably, the ated by the hydrogen form weak acid cation vessel. These
resin component, which contains a macroporous resin and units require on-going skilled operator attention on a daily
optionally other resins or absorbent components, has high basis for acid and caustic chemical handling and control,
crush strength, defined as a Chatillon value of at least 24 g per 30 water sampling and testing. In contrast, the resin component
bead. More preferably, the Chatillon value for the resin com does not require significant operator oversight.
ponent is at least 50g per bead. More preferably, the Chatillon Contaminants
value for the resin component is a least 100 g per bead. Even Surface waters typically have elevated levels of suspended
more preferably, the Chatillon value for the resin component solids with turbidity values greater than 1 nephelometric tur
is a least 200g per bead. Commonly-used ion exchange resins 35 bidity units (NTU) and dissolved organic matter consisting
Such as strong-acid cation exchange resins and basic anion largely of humic and fulvic acid compounds at concentrations
exchange resins have crush strengths significantly greater of several parts per million. Present in most of these surface
than what is defined herein as a “high' crush strength. The waters are varying levels of colloidal particulates comprised
adjective "high’ is used, herein, to mean in comparison to of silt, clay, silica, iron, aluminum and organic matter. As a
other large-pore macroporous resins capable of adsorbing 40 result, surface waters typically have Silt Density Index values
colloidal materials, and not all available or common resins greater than 5. Typical concentrations of colloidal silica range
without regard to their porosity. from 0.2 to 3 ppm. The resin component of the present inven
Advantages tion is particularly useful in removing these contaminants
The resin component allows for the use of a smaller size Such that the fouling, chemical deposits, and chemical pre
RO membrane system for treating the same flow-rate of water 45 cipitation on the RO membrane are reduced.
compared to conventional systems; reduction in SDI by the Silica Removal
methods and system of the present invention to values lower The resin component of the present invention is particu
than 2 units, allows for designata flux rate of 14 to 18 gallons larly useful in removing silica. Removal or reduction of dis
per square foot of membrane surface per day (GFD) com solved silica in the feed water has always been of major
pared to the allowable flux of 8 to 14 GFD when SDI values 50 interest in RO purification. Silica has a solubility of approxi
exceed 2 units (see Hydranautics Design Limits, www.hydra mately 150 mg/l at ambient temperatures and can form diffi
nautics.com/docs/tre/Dsgn Lmt.pdf). Thus, the number of cult to remove deposits on the membrane Surfaces if its solu
membranes needed and the size of the membrane system bility limit is exceeded in the reject/concentrate wastewater
needed is thus reduced. stream from RO system. Thus the higher the influent silica,
There is significantly lower wastage of water using the 55 the more reject water must be wasted. In fact, the need to
methods and systems of the present invention. The wastage is prevent silica deposits and biological fouling are, in part, the
typically less than 1%. Such as water used for periodic regen major reasons for the large percentage of reject water from the
eration of the resin component compared to on-going back typical RO system, ranging generally from 20 to 30%. For
wash and flushing water needs of UF systems ranging from 5 waters with high silica (i.e., 30 to 70 ppm, or higher), this can
to 15%. 60 be especially problematic, requiring the generous dosing of
The use of the resin component in the methods and systems silica dispersant chemicals ahead of the RO and inefficient
of the present invention also allows for the reduction in the design for even higher rates of water rejection, approaching
number of unit operations or treatment steps needed com 50% or more. Vendors of silica dispersants generally claim
pared to conventional treatment systems and in associated Success in controlling silica at about 200 percent of Satura
labor and operating costs. 65 tion, but membrane manufacturers usually set their own inter
Additional benefits include a lower capital cost when com nal alarm point at 100% of saturation to minimize silica
pared to conventional and UF pretreatment systems, a deposits (see Hydranautics Chemical Pretreatment for RO
US 8,883,012 B2
17 18
and NF March 2002). http://www.membranes.-com/docs/ ducible, and consistent. The mercury-intrusion method has
tab/TAB111.pdf. Cleaning membranes for silica deposits long been used to find the distribution of sizes of capillary
which tend to be hard and crust-like can be very costly in pores in a porous solid by forcing in mercury, the radius being
terms of downtime, the expensive chemicals that are needed, found from the pressure and the percentage from the Volume
and the risk of permanent damage and shortened life of the of mercury absorbed at each pressure. The method is based on
membranes. the relationship that the pressure required to force pure mer
Silica can be partially removed from surface waters in cury into a capillary of diameter dis (-4 O cos 0)/d, where O
conventional hot lime softeners/clarifiers in which the silica is is the Surface tension of mercury and 0 is the contact angle of
co-precipitated with magnesium hydroxide to form sludge. mercury with the porous solid (Proc. Nat. Acad. Sci. U.S.A.
Such systems have not enjoyed widespread use however, 10 (1921) 7:115). Since, for a particular solid the surface tension
since they are generally limited to large plants due to the and the contact angle are constants, penetration of mercury
requirements including heated water, a large space, and the into the pores, at a known pressure, indicates the correspond
need to continuously monitor and adjust the chemical feed. In ing pore diameter while the amount of mercury intruded,
addition, the exiting pH of the treated water, usually over 10, indicates the porosity or Volume of pores of a given diameter.
must be adjusted downward by acid addition to avoid post 15 As used herein, the term "crush strength,” refers to the
precipitation of Solids and to avoid damage to the RO mem mechanical load required to break individual resin beads, and
branes. In helping to solve the dissolved silica problem, the is used interchangeably with the term “friability.” Crush
potential for fouling by colloidal particulates is increased as strength is the statistical average of the individual crush
Such systems have a tendency to retain colloidal and Sus strengths of a sample comprising at least 10 but generally 25
pended solids in the carryover from the hot lime softener. The beads, each bead having a particle diameter of 710 um+35
typical downstream multimedia can do a good job of remov um, wherein crush strength is the applied force at which the
ing Suspended Solids but has only minor capability to remove bead Snaps or crushes.
colloidal particulates, leaving the possibility of intolerable The crush strength of the macroporous resin of the present
fouling of the membranes. invention, when the resin has been aminated to form a strong
Silica removal on iron oxide is a long established technol 25 base anion exchange resins is at least about 24 g/bead pref
ogy that has been used in purification of hot thermal brines, erably at least 30 g/bead, more preferably at least 40 g/bead,
where an iron salt such as ferric chloride is used to form a and even more preferably at least 50 g/bead. Similarly, the
sludge of iron oxide/hydroxide on which silica present in the crush strength of the macroporous resin which has been
brine is allowed to precipitate and is then filtered out. The formed into a strong acid-type cation exchange resins (i.e.,
formation of an iron/silica sludge creates a similar problem to 30 Sulfonic acid groups, e.g. sodium polystyrene Sulfonate or
that formed with the hot lime softener, i.e., the difficulty of polyAMPS), other strong base resins (i.e., trimethylammo
efficiently filtering out suspended and colloidal solids before nium groups (i.e., polyAPTAC) weak acid resins (i.e., car
the water reaches the reverse osmosis membranes. boxylic acid groups), and weak base resins (i.e., amino
The resin component of the present invention can be used groups, such as polyethylene amine).
to reduce dissolved silica in the feedwater to the membrane 35 Crush strength can be measured using the Chatillon test.
system, allowing a potential for recovery of a higher percent The Chatillon test is named for an apparatus manufactured by
age of the water as permeate (approaching 85 to 95 percent), John Chatillon and Sons, New York, N.Y. and designed to
and thus requiring much less water to be wasted as reject. measure resin friability. This instrument measures the force
Silica in the reject stream must be controlled at no more than (grams) required to crack or fracture a resin bead when it is
150 ppm to avoid precipitation on the membrane surfaces. So 40 placed between two parallel plates. The plates are gradually
for example, if the influent water had a silica content of 50 brought together at a uniform rate until the resin “breakpoint
ppm, silica in the reject water can only be concentrated 3 is reached. The purpose of this test is to simulate the frictional
times (i.e. 150/50) so as not to exceed the 150 ppm limit; this and pressure forces exerted on individual resin beads under
equates to a rejection volume of/3 or approximately 33% of actual use conditions.
the water (if the Small amount of silica leakage in the perme 45 Specifications for testing include converting the resin into
ate is ignored). So permeate recovered is about 66%. If how the proper form (hydrogen or sodium for cation resins and
ever, the silica were reduced to say 25 ppm in the influent chloride form for anion resins) by well known standard pro
water, the reject can now be concentrated to 6 times (i.e. cedures. The converted resin is screened to a -20+30 U.S.
150/25); this equates to a much reduced reject water volume mesh cut size and then allowed to fully hydrate in deionized
of approximately /6th of the total influent water or about 16.7 50 water for at least 15 minutes prior to testing. Actual testing is
percent. Thus the percentage recovered as permeate increases done on a single resin bead (covered by a small drop of water)
to about 83%). Using this example, it can be seen that the in the Chatillon instrument using the lowest practical speed of
volume of useful permeate increased by over 25% compared descent of the crushing plate. The individual fragmentation
to the initial level, while the reject water volume decreased by forces are recorded from the instrument ingrams per bead and
50% of its initial levels. Any throughput fees relevant for 55 the results are presented as an average (20 beads minimum,
disposal of the reject water would be expected decrease by typically 30 beads), a standard deviation, a 95% confidence
50% while any revenues from sale of the permeate would interval, and the percentage of beads which meet a minimum
increase by over 25%. friability standard.
Analysis of Resin Pore Structure and Crush Strength (Fri Analysis of Treatment Efficacy
ability) 60 The propensity of a membrane to become fouled by par
The pore structure of macroporous resins is formed by ticulates in the feed water can be determined using a standard
voids or channels between the polymer lattice work. The pore test called the Silt Density Index (SDI). In this test, a sample
structure has been found to have a characteristic pore distri of the feed water is passed through a 0.45-micron filter and a
bution and range. Numerous methods of pore measurement measurement is taken of how fast the filter becomes fouled.
have been applied to macroporous resins; none are truly abso 65 From this, an SDI value is calculated. Typical values range
lute. Characterization by the mercury-intrusion technique, from 1 to 6. A high value means the water presents a high
particularly within a series, has been found to be direct, repro fouling risk. Membrane Suppliers generally require an SDI
US 8,883,012 B2
19 20
value of no more than 4 if a performance guarantee is to be regenerate the resin component, it is noted that a greater
given, and generally prefer that the SDI value be no greater ability to reuse the regenerant mixture allows for substantial
than 3. Properly designed conventional pretreatment systems cost saving.
generally achieve values below 5 and may sometimes achieve The ability to repeatedly reuse the regenerant mixture very
values or 3 or lower. A common indicator of suspended Solids significantly reduces the cost associated with operating the
particles present in the water is turbidity, measured in units resin component system, including cost savings in chemical
referred to as Nephelometric Turbidity Units (NTU). NTU regenerant, associated labor, waste water disposal fees, and
are defined as the intensity of light at a specified wavelength any chemicals needed to neutralize the alkali waste to comply
scattered or attenuated by suspended particles or absorbed at with discharge regulations.
a method-specified angle (i.e., 90°) from the path of the 10 In another preferred embodiment the chemical regenerant
incident light compared to a standard. Most RO designers is repeatedly recirculated through vessel containing the resin
specify a maximum turbidity of 1 NTU. For long term, reli component, collecting the eluent from the vessel and using a
able operation, maximum values of SDI and Turbidity of 2.5 pump to return the Solution to the inlet of the vessel to again
SDI units and 0.5 NTU respectively are preferred. pass through the bed or Volume of resin, and then repeating
In the present invention, the SDI of water exiting the vessel 15 this procedure multiple of times. Preferred rates of recircu
containing the resin component is less than 4. More prefer lating the chemical regenerant are from 2 to 40 bed Volumes
ably, it is less than 3.5, even more preferably, it is less than 3, per hour, with a more preferred rate ranging from 8 to 40 bed
and even more preferably, it is less than 2.5. In a preferred Volumes per hour. Recirculation at higher rates than normally
embodiment, the SDI is less than 2.0, and in an even more used in the single pass method of the recirculation allows for
preferred embodiment, the SDI is less than 1.5, and in an even considerable savings in time, as well as savings in associated
more preferred embodiment, the SDI is less than 1.0. Another labor cost, and the operating flexibility to minimize the time
method of analyzing the SDI is provided in a ratio of the SDI during which the resin component vessel is unavailable for
values for influent and effluent water of the vessel. processing of the feed water to the membranes.
Cleaning Conventional methods of regeneration do not use the recir
An advantage of the resin component of the present inven 25 culation method of regeneration, as it is counter-intuitive in
tion is the simplicity of regeneration. This is found through that the effluent containing contaminants eluted or stripped
the time saving, reduced operator costs, and in many cases, from the resin are essentially reintroduced to the resin on
reduced cost of regenerant(s). Using a single Volume of reintroducing the regenerant. Conventional single pass of the
chemical regenerant, Such as a mixture of sodium chloride regenerant is designed to progressively strip the contaminants
and caustic soda, all ion exchange resins and/or adsorbent 30 from the resin as the regenerant travels through the resin bed
media within the resin component are simultaneously regen from one end to the other. As more fresh regenerant displaces
erated or rejuvenated. The single regenerant is applied either the spent regenerant, the overall fraction of contaminants
at ambient or elevated temperatures up to 100° C. stripped from the resin into the regenerant continuously
In one embodiment, the chemical regenerant comprises a increases, allowing greater and greater efficiency of stripping
mixture of chloride salts, such as potassium, calcium or 35 the contaminants. The fraction of the contaminants left on the
ammonium chloride, and an alkali or base. Such as caustic resin attains chemical equilibrium with the fraction extracted
potash, ammonium hydroxide, sodium carbonate, potassium by the regenerant; a similar chemical equilibrium exists for
carbonate, ammonium carbonate, and sesquicarbonates of the chemical regenerant, with the regenerant essentially dis
Sodium or potassium. placing the contaminant from the resin in proportion to the
In another embodiment, the regenerant chemical com 40 selectivity of the resin for the contaminant and the regenerant.
prises a chloride brine solution. Demineralization of water is a reference base for the ion
In another embodiment, the regenerant chemical com exchange process in which 95 to 99 percent of the dissolved
prises an alkali base. solids present in the raw water must be removed. Similarly
The resin component may be cleaned on a once-through softening of water by ion exchange for use as boiler feedwater
basis. In this embodiment, the regenerant mixture is passed 45 or for supply to RO systems requires removal of hardness to
once through the vessel containing the resin component and is very low levels of about 1 part per million, typically repre
then disposed of. Preferable flow rates range from 2 to 8 bed senting about 99 percent removal from the raw water. For
Volumes per hour, a bed Volume being defined as the equiva Such processes, it is intolerable to reuse or recirculate the
lent liquid volume occupied by the combined volume resins regenerant if such quality is to be consistently achieved.
and adsorbents in the vessel; even more preferred are flow 50 Therefore, the embodiments comprising reuse and/or recir
rates ranging from 2 to 4 bed Volumes per hour. culation of the regenerant are not applicable to aspects of the
Using one regenerant mixture to regenerate all resins and invention in which strong acid cation resins in the Sodium
adsorption medias results in Savings on costs for regenerant, form are utilized for removal of divalent and trivalent cations,
labor, associated dilution and rinse water, and waste water Such as calcium and magnesium when softening for RO is
disposal costs including any chemical cost for neutralization 55 required. However, the reuse and/or recirculation of the
of the alkali nature of the waste to comply with discharge regenerant is appropriate for cases in which the resin compo
regulations. nent includes resins and/or adsorbents for the removal of
In addition, the regenerant mixture may be re-used to dissolved silica, colloidal silica, and organic matter. In Such
regenerate the resin component in Subsequent regenerations. cases, the concentrations and quantities of alkali and brine
In one embodiment, a single regenerant mixture is used 2, 3, 60 used for regeneration represent a very large excess over sto
4, 5, 6, 7, 8, 9, 10 or more times to clean the resin component ichiometric requirements (a few hundred percent), and in
when chemical cleaning is advised. Additional fresh chemi Such cases the percentage of contaminants removal achieved
cals may be added to the regenerant mixture for the Subse by the present invention (typically 25 to 75%) do not require
quent regenerations to make up for any unavoidable losses to the highest purity of regenerant to be used to achieve the
maintain the original concentration of the regenerant. While it 65 targeted level of quality. In addition, extraction of silica from
is understood that re-using the regenerant mixture a certain the resin component is greatly facilitated by the very high
number of times is not required each time it is advised to solubility of silica in a caustic Soda solution (greater than 25
US 8,883,012 B2
21 22
percent). Reuse of the regenerant is preferred embodiment of of the problem of fouling by suspended solids, colloidal par
the invention as the operating cost of the resin component ticulates, organic compounds, and biological matter from the
system can be reduced to a small fraction of the cost com RO unit to the UF unit. This means that the UF unit must be
pared to using the regenerant just once, thus providing even periodically backwashed and also chemically cleaned when
more cost savings benefits over conventional pretreatment the buildup of foulants causes too much of a decrease in
systems. operating efficiency. A significant problem is the waste of a
General Description of Embodiments portion of the incoming water used for periodic flushing of
FIG. 1 shows the conventional pretreatment approach, uti foulants from the surfaces of the membranes, with typical
lizing a clarifier, multimedia filter, and carbon filter while percentages ranging from 5 to 15% of the influent total being
FIG. 2 shows the use of a UF membrane system as pretreat 10 fed to the UF. This is in addition to the 20 to 30 percent of the
ment. The conventional system, Such as the one described in water that is additionally wasted as reject from the down
FIG. 1, is labor intensive, subject more to operator error, and stream RO unit, amounting to total water losses ranging from
occupies a large footprint. The UF pretreatment unit, such as 25 to 45%. While this is generally not a problem for desali
the one described in FIG. 2, is capital intensive and itself nation of seawater or municipal wastewater, it is a major
wastes significant amounts of water in addition to the waste 15 concern to operators of RO plants in arid regions of the world
from the RO itself. where water Supply is quite limited. Some membrane system
In the conventional treatment system shown in FIG. 1, suppliers offer a third smaller membrane system to further
chlorine or sodium hypochlorite solution (refer to item 1a) is treat the reject stream from the first UF in an effort to reduce
usually dosed into the feed water at about 1 to 2 ppm free water losses. However, this adds further to the already larger
chlorine in order to control microbial growth. A coagulant extra capital costs needed for the main UF, making Such
Such as aluminum sulfate (2a) and a polyelectrolyte polymer systems affordable to only a limited number of users.
chemical (3.a) are dosed in ppm concentrations ahead of the The invention, as described by the embodiment shown in
clarifier (4a) to create and to concentrate a gelatinous sludge FIG. 3., uses a compact small footprint multimedia vessel for
of aluminum hydroxide. The large Surface areas of the sludge simultaneous reduction of a variety of contaminants as
can then trap any suspended and colloidal particulates present 25 described hereinabove, including colloidal particulates, the
in the incoming Surface water. The sludge is then routed to a Silt Density Index value of the water, dissolved organic mat
quiescent Zone of the clarifier where it is largely removed by ter, metals, dissolved anions such as Sulfate, arsenic, phos
settling to the bottom of the clarifier where it is periodically phate, and dissolved silica. It requires minimum operator
removed, then dried and disposed. Organic matters of the attention, generates comparatively much Smaller Volume of
humic and falvic acid varieties which are typically present in 30 waste water and the capital cost is significantly lower than that
Surface water are also partially removed by becoming trapped for either a UF or conventional pretreatment system.
in the sludge produced by addition of the coagulant. The embodiment described by FIG. 3, when compared to
Any residual floating sludge that is carried over from the the conventional system as described in FIG. 1, does not
overflow of the clarifier is subsequently removed on the include the clarifier and activated carbon units, similar to the
downstream multimedia filter (5a). Typical composition of 35 UF pretreatment system in FIG. 2 above. Chlorine or sodium
the filter media are sand, anthracite and garnet, which gener hypochlorite solution (refer to item 1c) is optionally dosed
ally provide more efficient filtration than a single media filter into the feed water at about 1 to 2 ppm free chlorine in order
such as a sand filter. The water is then routed to an activated to control microbial growth. Any residual sludge or other
carbon filter (6a) for removal of any residual chlorine. Most Suspended solids are removed on the downstream multimedia
membranes have very limited tolerance for oxidizing agents 40 filter (2c). Typical, but non-limiting composition of the filter
Such as chlorine and continuous exposure to even Small con media include sand, anthracite and garnet, which generally
centrations can shorten their useful life significantly. The provide more efficient filtration than a single media filter such
activated carbon also removes organic matter that is still as a sand filter. If the water has been dosed with chlorine or
present in the water at that step in the treatment process. The similar oxidant, the water is then dosed with sodium bisulfite
water is then finally routed through a 5 micron rated filter (8a) 45 to remove any residual chlorine present at this point (3.c) since
for removal of any last traces of suspended solids before it is most RO membranes have very limited tolerance for oxidiz
fed to Reverse Osmosis System (9a). Generally, the goal at ing agents such as chlorine and continuous exposure to even
this point is to have water with maximum limits for turbidity Small concentrations can shorten their useful life signifi
and SDI values of 1 and 4 or better respectively. cantly. A resin component (4c) of one or more specialized ion
The number of unit operations in the pretreatment process 50 exchange resins and/or adsorbent medias is installed down
as described in FIG.1 makes this operator-intensive, requir stream of the Sodium bisulfite dosing point. The resin com
ing daily operator attention for efficient operation. Routine ponent contains a macroporous resin as described herein.
tasks by operators would include refilling of chemical solu Either cation oranion type resins can be used as the base resin.
tions for chlorine, coagulant, polymer, and acid or scale When an anion resin is used as the base, its capacity for
inhibitor, adjustment of chemical dosage for changes in the 55 removal of dissolved organic matter is increased significantly.
Source water quality, calibration and repair of all chemical The resin component (4c) is housed in a vessel. The vessel
dosing systems, removal of sludge from the clarifier, back may be any container known in the art that can contain the
wash of the multimedia filters; periodic change out of micron resin component at the pressure required in the system. The
filters and activated carbon media, observing, adjusting and water is then finally routed through a 5 micron rated filter (5c)
recording of plant flow rates and periodic chemical cleaning 60 or similar for removal of any last traces of Suspended solids
of the membranes when they become fouled. before it is fed to the Reverse Osmosis System (6c). Prefer
FIG. 2 shows the newer UF pretreatment system that is in ably, the waterfed to the RO system has a maximum limits for
use on especially larger RO systems. This system eliminates turbidity and SDI values of 1 and 4 or better respectively.
the use of the clarifier, multimedia, and activated carbon units When it is desired to remove dissolved silica as well as
as described in FIG. 1 above. A coagulant (2b) is still dosed 65 colloidal particulates, a preferred embodiment of the present
ahead of the UF system (3.b) to more efficiently trap incoming invention comprises the incorporation of an iron-impregnated
organic matter. In essence, using a UFSystem transfers much or iron-containing media Such as cation oranion resin, natural
US 8,883,012 B2
23 24
Zeolite or alumina in the resin component (4c). A strong acid bic, lignoSulfonates, gelatine and Xanthan gums in amounts
cation resin can be incorporated for removal of divalent and ranging from 0.01 to 0.5% by weight of the monomers may be
trivalent cations. After exhaustion, all resins can be regener added to the aqueous dispersion to aid in maintaining the
ated with the same regenerant mixture of brine and caustic, monomers dispersed as droplets while polymerizing the same
either at ambient or elevated temperatures. 5 as beads.
Formation of Macroporous Resin The mixture is heated at 70° C. to 90° C. for from 6 to 15
Conventional gel resins formed by copolymerization of hours filtered, washed, and dried. Following filtration, wash
monovinylidene and polyvinylidene monomers contain ing and drying, the crosslinked copolymer resin can be Sul
micropores, where the pore structure is defined by the dis fonated with sulfuric acid, oleum, Sulfur trioxide, or chloro
tance between the crosslinked polymeric chains. 10
Sulfonic acid as the Sulfonating agent to form a cation
Macroporous resins contain significant non-gel porosity in exchanger or, alternatively, it may be chloroalkylated and
addition to normal gel porosity, within the polymer lattice. Subsequently aminated to form-an anion exchanger.
This non-gel porosity arises from channels present between A wide variety of amines including primary, secondary,
the gel lattices. These microscopic channels are separate and and tertiary alkylamines orarylamines can be employed in the
distinct from the micropores, which are present in all 15
crosslinked copolymers, as is well known to those skilled in anination reaction. Polyalkylenepolyamines such as ethyl
the art. While the channels are themselves relatively small, enediamine, diethylenetriamine, triethylenetetramine, tetra
they are large when compared with the micropores of the gel ethylenepentamine and propylenediamine can also be used.
type resins. Aminoalcohols and dimethylaminoethanol are also useful. A
As noted above, the macroporous resins can be formed by preferred embodiment employs a trialkylamine as the ami
the process described in U.S. Pat. No. 6,323,249, herein nating agent, producing a quaternary anion exchanger. Gen
incorporated by reference. The macroporous resins produced erally, the alkyl radical does not contain more than 4 carbon
by the process described in U.S. Pat. No. 6,323,249 have atOmS.
extremely large-sized pores, but their narrower distribution of When the water stream to be purified has colloidal silica
pore sizes gives them Sufficiently high crush strength for most 25 and other such colloidal particulate matter which needs to be
purposes. The narrower pore distribution, in the useful size removed prior to reverse osmosis, a strong base anion
range for the removal of colloidal matter, means that there are exchange prepared with trimethylamine resin is preferred.
few uselessly small pores and needlessly large pores present. Although resins with a strong base functionality are preferred
The macroporous resins are formed by copolymerizing for the removal of colloidal silica and other such colloidal
monoethylenically unsaturated monomers with polyvi 30 particulate matter, weak base anion exchange resins having
nylidene monomers in the presence of mixture of relatively the same macroporous structure will also perform. Such weak
moderate amounts of a water-soluble polymeric porogen with base anion exchange resins are prepared in the same manner
a low molecular-weight, good Swelling porogen. as the strong base resins with the exception that the trimethy
Useful monoethylenically unsaturated monomers include lamine is replaced with dimethyl amine, diethyl amine,
styrene, vinyltoluene, methyl-styrene, tertiary butyl styrene, 35 monomethyl amine, ethanol amines etc. These weak base
vinyl pyridine, 2-methyl-5-vinyl pyridine, vinylidine chlo anion exchange resins, aside from the differences in ion
ride, tetrafluoroethylene, vinyl acetate, vinyl stearate, vinyl exchange functional groups, are essentially identical in mor
bromide, vinyl anisole, vinyl naphthalene, acrylic and meth phological structure as the strong base anion exchange resins,
acrylic esters and other derivatives. Styrene is preferred. particularly about their large pore sizes.
Useful polyvinylidene monomers for use as a crosslinking 40 Methods of producing ion-exchange resins from corre
agent include divinylbenzene, diisopropenylbenzene, ethyl sponding crosslinked copolymer resins are known in the art.
eneglyocol dimethacrylate, hexanediol diacrylate, allyl meth Anion exchange resins produced by chloromethylating poly
acrylate, divinylketone, divinyl Sulfone, trimethylolpropane, styrene and Subsequently aminating are disclosed in U.S. Pat.
trimethacrylate, and trivinylbenzene. Divinylbenzene is pre Nos. 2,591,573; 2,591,574; 2,616,099; 2,616,877; 2,629,710;
ferred, and is preferably present in an amount of from 2 to 45 2,631,999; 2,632,000; 2,642,417; 2,725,361; 2,794,785;
100%, more preferably 2 to 16%. 3,422,160; 3,311,602; 2,953,547; 4,225,677; and 3,425,990.
One preferred macroporous resin is formed when styrene, Strongly acid cation exchangers obtained by Sulphonation of
divinyl benzene and the porogen are mixed together with a crosslinked polymers, such as for example crosslinked poly
polymerization initiator to form the monomer solution. Free styrenes are disclosed in U.S. Pat. Nos. 2,366,007, 2,466,675,
radical initiators are most desirable. Free radical generating 50 2,500,149, 2,631,127 and 2,664,801. All U.S. patents and
compounds which may be used to effect polymerization of published applications cited herein are hereby incorporated
the monomers include peroxides Such as benzoyl peroxide, by reference.
lauoryl peroxide, tertiary-butyl peroxide, hydrogen peroxide, The macroporous resin removes colloidal particulate mat
per-compounds such as potassium persulfate, sodium perbo ter, such as silica, from the water stream by providing novel
rate and ammonium persulfate and azocompounds such as 55 macroporous resins characterized by pore diameter ranging
aZo-bisisobutyronitrile, 2,2-azobis-(2-methylbutyronitrile), in size from 4,000 to 500,000 Angstroms, or more preferably
2-t-butylaZo-2-cyano propane. Suitable concentrations are 4,000 to 200,000 Angstroms, or even more preferably from
from 0.01 to 5.0%, more preferably 0.02 to 3.0%. The mono 10,000 to 200,000 Angstroms and having particularly high
mer phase is added to an aqueous phase for Suspension poly crush strength and high pore Volume. The anion exchange
merization of the monomers. Salt may be added to the aque 60 resins can be used to remove colloids or particulate matter,
ous phase to decrease the water Solubility of the monomers. Such as colloidal silica or hydrous oxides, or can be used in
Various Suspension agents and stabilizers such as polyvi conjunction with cation exchange resins to simultaneously
nylalcohol, methyl cellulose, carboxymethyl cellulose, achieve deionization and colloidal removal. In addition, the
hydroxyethyl cellulose, poly(Vinyl pyrrolidine), polyacrylate anion exchange resins of the invention are capable of effec
salts, polymethyacrylate salts, dimethyldialkylammonium 65 tively removing acids of relatively high molecular weight
polymers, nitrite and dichromatic salts, calcium phosphate Such as, for example, humic acid, and are capable of removing
salts, carbonate salts, Sulfate salts, bentonite clays, gum ara viruses from aqueous solutions.
US 8,883,012 B2
25 26
Definitions water Supply pretreatment system contained softening and
The term “single chemical regenerant’ means both a single clarification using chlorine, aluminum Sulfate and calcium
chemical regenerant and a mixture of chemicals using a single hydroxide, followed by sand filtration and activated carbon.
regenerant. Prior to use, the water was filtered through a 1-liter cartridge
The term highly macroporous resins, as used herein, means filter of spiral wound cotton fiber to remove suspended solids
resins with pores with large diameters. The average pore matter. The filtered water was then passed at a flowrate of 12
diameter of a highly macroporous resin ranges at least about BV/Halternately through two 1 liter cartridges, each contain
1,000 Angstrom and typically has an average pore diameters ing 1 liter of the resin component and comprised of a 50:50
(D50) of at least about 20,000 Angstroms. mixture of Purolite A501P, a macroporous anion resin of high
Orthoporous resins, as the term is used herein, are highly 10 porosity and high crush strength as described in U.S. Pat. No.
macroporous resins having a substantial number of pore 6,323,249 to Dale, et al., and Purolite A-860, a macroporous
diameters ranging from 10,000 to 500,000 Angstroms. acrylic strong base anion resin, both resins manufactured by
As used herein, the term “simultaneous.” means at the same Purolite Intl. Ltd. During the test period, the influent water
time or within a few minutes. When used in conjunction with composition varied naturally; colloidal silica ranged from 0.5
resin regeneration or rejuvenation, “simultaneous regenera 15 to 4.5 ppm, dissolved organic matter ranged from 0.6 to 2.5
tion or rejuvenation” means that the regeneration or rejuve ppm, turbidity ranged from 0.2 to 0.65 NTU, and silt density
nation occurs in a single process step by the addition of a index (SDI) ranged from 0.25 to 4.75 SDI units. Colloidal
single regenerant. It is understood that one chemical regen silica concentration, silt density index, concentration of
eration process may proceed at a different rate than another organic matter, and turbidity were each measured at both the
chemical regeneration process. inlet and outlet of the ion exchange vessel. FIG. 4 shows the
The term about or approximately means within an average reduction in colloidal silica over the test period of
acceptable error range for the particular value as determined approximately 50%, with colloidal silica being reduced from
by one of ordinary skill in the art, which will dependin part on an average influent value of 1.5 ppm to an average effluent
how the value is measured or determined, i.e., the limitations value of 0.75. FIG. 5 shows the average reduction in the SDI
of the measurement system, i.e., the degree of precision 25 from an average influent value of 3.0 to an average effluent
required for a particular purpose, such as a pharmaceutical value of approximately 1.5. FIG. 6 shows the average reduc
formulation. For example, “about can mean within 1 or more tion in dissolved organic matter from an average influent
than 1 standard deviations, per the practice in the art. Alter value of 0.92 ppm to an average effluent value of 0.25 ppm.
natively, “about can mean a range of up to 20%, preferably FIG. 7 shows the average reduction in turbidity from an
up to 10%, more preferably up to 5%, and more preferably 30
influent value of 0.22 NTU to an average effluent value of
still up to 1% of a given value. Alternatively, particularly with approximately 0.15 NTU. FIGS. 8, 9, 10 and 11 show the
respect to biological systems or processes, the term can mean change in influent values and the corresponding changes in
within an order of magnitude, preferably within 5-fold, and effluent values for colloidal silica, silt density index, organic
more preferably within 2-fold, of a value. Where particular matter, and turbidity respectively.
35
values are described in the application and claims, unless
otherwise stated, the term “about meaning within an accept Example 2
able error range for the particular value should be assumed.
As used herein and in the appended claims, the singular The invention was demonstrated by treating Philadelphia
forms “a” “an, and “the include plural referents unless the city water Supply containing approximately 2 ppm silica, a
context clearly indicates otherwise. Thus, for example, refer 40 pH of 8.2, total dissolved solids of approximately 210 ppm,
ence to “a molecule' includes one or more of such molecules, and a total organic matter content raging from 1.5 to 2.5 ppm
“a resin' includes one or more of such different resins and measured as total organic carbon (TOC). The water was arti
reference to “the method’ includes reference to equivalent ficially spiked with additional silica to achieve 16.8 ppm of
steps and methods known to those of ordinary skill in the art silica in keeping with typical levels experienced in many part
that could be modified or substituted for the methods 45 of the United States where ROs are used with attendant silica
described herein. deposition problems. The resin component, comprising a 16
to 50 US mesh size sample of 1 liter of ArsenXP (with
EXAMPLES experimental code of D9908) was installed in a cartridge and
the water was passed through the resin component at a flow
The following examples are included to demonstrate pre 50 rate of 12 bed volumes per hour. The influent and effluent
ferred embodiments of the invention. It should be appreciated dissolved silica concentration was measured periodically
by those of skill in the art that the techniques disclosed in the until the breakthrough of silica in the effluent reached 50
examples which follow represent techniques discovered by percent of the influent value as displayed in FIG. 12. A mass
the inventor to function well in the practice of the invention, balance was done to determine the fraction of silica that was
and thus can be considered to constitute preferred modes for 55 loaded on the resin. At the 50% breakthrough point for silica
its practice. However, those of skill in the art should, in light in the effluent, after approximately 1200 liters of water had
of the present disclosure, appreciate that many changes can be been treated, the total silica loaded on the resin was deter
made in the specific embodiments which are disclosed and mined to be approximately 8 grams of silica per liter of resin.
still obtain a like or similar result without departing from the
spirit and scope of the invention. 60 Example 3
Example 1 Water from the blowdown water stream of a 2400 psig
steam generator boiler was recovered and treated for reuse by
The invention was demonstrated using a continuously passing through a 1 liter cartridge filled with 1 liter of the resin
flowing Surface water Supply from a river with naturally vary 65 component comprising ArsenX' (with experimental code
ing composition with respect to colloidal silica, organics mat D-9908) at a relatively flow rate of 57 bed volumes per hour.
ter, turbidity and silt density index (SDI) values. The river The blowdown water contained a very high concentration of
US 8,883,012 B2
27 28
silica at average of 77 parts per million and a relatively high carbon. Prior to use, the water was filtered through a 1-liter
pH of 9.5. The influent and effluent silica concentrations were cartridge filter of spiral wound cotton fiber to remove sus
measured periodically until the silica concentration in the pended solids matter. The filtered water was then passed at a
effluent was approximately equal to that in the influent water. flowrate of 12 BV/H through the two cartridges for a total of
A mass balance was done to determine the fraction of silica 72 hours. During the test period, the influent water composi
that was loaded on the resin and this was determined to be tion varied naturally; colloidal silica ranged from 0.5 to 4.5
approximately 6,000 milligrams of silica per liter of resin ppm, dissolved organic matter ranged from 0.6 to 2.5 ppm,
with a total of 161 liters of water treated as displayed in FIG. turbidity ranged from 0.2 to 0.65 NTU, and silt density index
13. The loading was 8.7 g SiO, per liter of media and a silica (SDI) ranged from 0.25 to 4.75 SDI units. Colloidal silica
breakthrough of approximately 60% at the end of the test. 10 concentration, silt density index, concentration of organic
matter, and turbidity were each measured at both the inlet and
Example 4 outlet of the ion exchange vessel.
The average results of the two pilots showed that the virgin
A 18 ml sample of D9908 iron-impregnated anion resin, resin had reduced the colloidal silica, SDI and organic matter
also known as ArsenXnp, was put into a glass column and a 15 by 60%, 42% and 73% respectively as shown in FIG. 16. The
challenge solution, referred to as a NSF53. Challenge solu resin samples were then regenerated with a 10% sodium
tion was passed through the resin at a flow rate of 20 BV/Hat chloride/2% caustic Soda Solution containing 160 grams
ambient temperature. The challenge solution contained 51 NaCl mixed with 32 grams of NaOH at a flow rate of 2 BV/H
ppm Ca, 17.8 ppm Mg, 114 ppm Na, 67 ppm SO 1.64 ppm at ambient temperature. The cartridges were then subjected to
PO 97.6 ppm HCO 140 ppm Cl, 22 ppm SiO, and had a pH second and third loading cycles with the same feedwater
of 7.7. Effluent samples were taken every 4 hours for a total described above and regenerated twice with the same regen
time of 96 hours and the samples were analyzed for silica erant solution. Average reduction rate for colloidal silica, SDI
concentration and pH. The results are shown in FIG. 14, and organic matter for the two cycles were 50%, 49% and
indicating a loading of approximately 17 grams of silica per 79% respectively (i.e., Alk. Brine (4 reg)).
liter of resin after 96 hours and a silica breakthrough of 25 Two additional loading and regeneration cycles were then
approximately 60% at the end of the test. performed with the same influent water but with a regenerant
solution comprised of 10% NaCl for a dosage of 160 grams
Example 5 NaCl per liter of resin and at 40° C. instead of ambient
temperature as the previous experiments. The average reduc
A 18 ml sample of D9908 iron-impregnated anion resin, 30 tion rates for colloidal silica, SDI and organic matter for these
also known as ArsenXnp, was put into a glass column and a two experiments were 37%, 64% and 74% respectively (i.e.,
challenge solution, referred to as a NSF53. Challenge solu 40 C Brine (2 reg)).
tion was passed through the resin at a flow rate of 20 BV/Hat Four additional loading and regeneration cycles were then
ambient temperature. The challenge Solution contained 46.8 performed with the same influent water but with a regenerant
ppm Ca, 13.8 ppm Mg, 117 ppm Na, 60 ppm SO, 0.01 ppm 35 Solution comprised of a two step approach, with the first step
PO, 125 ppm HCO, 140 ppm Cl, 29 ppm SiO, and had a pH comprised of 10% NaCl/2% NaOH at dosages of 160 grams/
of 8.0. Effluent samples were taken every 4 hours for a total liter and 32 grams/liter respectively and heated to 40°C. The
time of 96 hours and the samples analyzed for silica concen second step comprised a solution of just 10% NaCl at a
tration and pH. The results are shown in FIG. 15, indicating a dosage of 64 grams/liter at ambient temperature. Average
loading of approximately 34 grams of silica per liter of resin 40 reduction in colloidal silica, SDI and organic matter were
after 96 hours and a silica breakthrough of approximately 62%, 44% and 75% respectively (i.e., 40 C Alk. Brine, Brine
52% at the end of the test. The sample of resin was then (4 reg)).
regenerated coflow with 6 bed volumes of 4% caustic soda Two additional loading and regeneration cycles were then
solution at ambient temperature at a flow rate of 2 BV/H. The performed with the same influent water but with a regenerant
resin was then Subjected to a second loading cycle with the 45 identical to the last four cycles above, but at ambient tempera
above mentioned challenge solution and effluent sample ture instead of heating to 40°C. Average reduction of colloi
again taken and analyzed. Silica loading on the resin for the dal silica, SDI and organic matter were 64%, 39% and 71%
second cycle was 26 grams silica per liter of resin, or approxi respectively (i.e., Alk. Brine, Brine (2 reg)).
mately 76 percent of the loading for the first test. As demonstrated in this example, the reduction of organic
50 matter after multiple loading and regeneration cycles is simi
Example 6 lar for each of the tested regenerants. For the best reduction in
SDI, regeneration using 40C brine is the best, and alkalibrine
The ease of regenerability and the ability to reuse the also good. For the best reduction in colloidal silica, regenera
regenerant a multiple of times was demonstrated using two tion using alkali brine and brine is the most preferred. While
field pilots, each comprised of a 1 liter cartridge containing a 55 temperature control is not needed, extra brine step is helpful.
50:50 mixture of Purolite A-501 P. a macroporous anion resin For the best reduction in turbidity, regeneration using alkali
of high porosity and high crush strength as described in U.S. brine at ambient temperature provided a 32% reduction.
Pat. No. 6,323,249 to Dale et al., and Purolite A-860, a What is claimed is:
macroporous acrylic strong base anion resin, both resins 1. A method of purifying water containing colloidal par
manufactured by Purolite Intl. Ltd. 60 ticulates of organic matter comprising:
This aspect of the invention was demonstrated using a a) pretreating the water by passing the water through a
continuously flowing Surface water Supply from a river with vessel containing a resin component, wherein the resin
naturally varying composition with respect to colloidal silica, component comprises a highly macroporous anion
organics matter, turbidity and silt density index (SDI) values. exchange resin having a plurality of pores having a pore
The river water supply pretreatment system consisted of soft 65 diameter in the range of 4,000 to 500,000 Angstroms and
ening and clarification using chlorine, aluminum Sulfate and a crush strength or Chatillon value of about 24 g/bead to
calcium hydroxide, followed by sand filtration and activated about 50 g/bead (710 um bead diameter);
US 8,883,012 B2
29 30
b) feeding the water exiting the resin component to a 6. The method of claim 1, wherein the macroporous resin
reverse osmosis membrane or a nanofiltration mem has a pore diameter in the range of 5,000 to 100,000 Ang
brane to produce permeate water; and Stroms and a pore Volume of at least 0.6 ml/g (dry).
c) periodically regenerating the resin component by 7. The method of claim 1, wherein the macroporous resin is
removing contaminants comprising colloidal particu chloromethylated and then aminated.
lates of organic matter from the resin by passing a solu 8. The method of claim 1, wherein the resin component
tion of sodium chloride through the vessel, further comprises one or more strong base resin(s).
wherein the resin component reduces the organic colloidal 9. The method of claim 1, wherein regeneration comprises
particulate matter and the Silt Density Index (SDI) con recirculating the sodium chloride by recovering the effluent
tent of the water by at least 20 percent of the influent 10
from the vessel containing the resin component and re-intro
values, the solution of sodium chloride is essentially free ducing it to the vessel to make repeated passes through the
of sodium hydroxide and the flow of water from the resin resin component.
component to the reverse osmosis or nanofiltration 10. The method of claim 1, wherein the resin component
membrane is continuous.
2. The method of claim 1, wherein the macroporous resin 15
further comprises at least one of polystyrene or acrylic poly
has a pore volume of at least 0.36 ml/g (dry). mer matrix-based anion exchange resin.
3. The method of claim 2, wherein the macroporous resin 11. The method of claim 1, wherein the sodium chloride
has an average pore diameter in the range of 10,000 to 500, solution is added to the resin componentatarate of 2 to 20 bed
000 Angstroms, and a pore volume of at least 0.60 ml/g (dry). Volumes per hour, wherein the bed volume is the equivalent
4. The method of claim 2, wherein the macroporous resin liquid volume occupied by the resin in the vessel.
has a pore diameter in the range of 10,000 to 200,000 Ang 12. The method of claim 1, wherein the anion exchange
resin is in chloride form.
stroms and a pore Volume of at least 0.60 ml/g (dry). 13. The method of claim 1, wherein the colloidal particu
5. The method of claim 1, wherein the macroporous resin is lates of organic matter comprise humic, fulvic, or tannic
formed from the polymerization of a solution of (a) a mono acids.
ethylenic monomer, (b) a polyethylenic monomer, (c) a free 25
radical initiator, and (d) 20-40 pph poly(alkylene oxide) pore 14. The method of claim 1, wherein sodium hydroxide is
forming agent or a mixture of the 20-40 pph poly(alkylene excluded from the solution of sodium chloride.
oxide) pore-forming agent with toluene. ck ck ck ck ck

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USOO8883 012B2

(12) United States Patent (10) Patent No.: US 8,883,012 B2

(60) Provisional application No. 60/885,855, filed on Jan. (Continued)

Chile Bisulfite dosing Reverse

Typical Surface Water Pretreatment System with Invention

(56) References Cited OTHER PUBLICATIONS

Chlorine Coagulant Polymer Acid or Reverse

Fig. 1.- Typical Conventional Surface Water Pretreatment System

Fig. 2-Newer Ultrafiltration Membrane Pretreatment to RO Systems

Chlorine Bisulfite dosing Reverse

Fig. 3 - Typical Surface Water Pretreatment System with Invention

Pilot Runs - Days

8h 12h 16h 20h 24h 28h 32h 48h 72h 96h

4h 8h 12h 16h 20h 24h 28h 32h 48h 72h 96h

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