TITLE: MEMBRANE FILTRATION PROCESS WITH HIGH WATER RECOVERY
FIELD
[0001] This specification relates to reverse osmosis and nanofiltration
processes for water purification.
BACKGROUND
[0002] The following background discussion is not an admission that
anything discussed below is citable as prior art or common general knowledge.
[0003] High efficiency reverse osmosis processes ("HERO"; see, for
example, United States Patent Nos. 5,925,255 and 6,537,456) can achieve
higher water recovery rates compared to conventional reverse osmosis
processes. HERO relies on a series of pretreatment steps prior to reverse
osmosis filtration, which includes use of weak acid cation resin columns,
degasification and pH adjustment.
[0004] Other processes may involve the use of microfiltration, ultrafiltration,
ion exchange and chemical precipitation to achieve greater water recovery (see,
for example, United States Patent Nos. 5,501 ,798, 6,1 13,797 and 6,461 ,514).
INTRODUCTION
[0005] The following discussion is intended to introduce the reader to the
more detailed discussion to follow, and not to limit or define any claim.
[0006] Reverse osmosis and nanofiltration are filtration methods that can
be used to purify water by removing or reducing total dissolved solids (TDS) and
residual organic compounds from various water sources, such as from natural
water sources, municipal water supply or industrial effluents. Reverse osmosis
(RO) relies on a diffusive mechanism to separate relatively large molecules and
ions from a solution by applying pressure to the solution on one side of a
semipermeable membrane. Nanofiltration (NF) is typically a cross-flow filtration
technology which ranges somewhere between ultrafiltration (UF) and reverse
osmosis. The filtration process takes place on a selective separation layer
formed by a semipermeable membrane. Both reverse osmosis and nanofiltration
are a pressure driven separation process. The driving force of the separation
process is the pressure difference between the feed (retentate) and the filtrate
(permeate) side at the separation layer of the membrane.
[0007] In reverse osmosis and nanofiltration processes, efficiency and
water recovery is often limited by mineral scale formation from hardness
compounds, such as calcium, magnesium, barium, iron, fluoride, sulfate,
carbonate and silica or silicate salts on membrane surfaces. Residual organic
compounds and biological proliferation can also cause membrane fouling. In a
conventional RO or NF water purification process, the water recovery rate
(referring to the percentage of the permeate recovery from the feed water) is
often limited to the range of 65-80%, depending on the influent water quality. As
such, a large amount of the membrane concentrate (or "reject") has to be further
treated or disposed of at a high cost.
[0008] Described herein, a membrane filtration process includes first
pretreating an influent solution using a method effective to remove suspended
solids, such as ultrafiltration, microfiltration or multimedia filtration, to produce a
pretreated solution. Next, pH of the pretreated solution is adjusted to at least 8.3
or lower by injecting CO2 into the pretreated solution, to produce a conditioned
solution. In addition to adjusting pH of the pretreated solution, injection of CO2
also serves to increase bicarbonate concentration in the conditioned solution.
The conditioned solution is flowed through a membrane filtration unit, to produce
a permeate solution and a retentate solution. The membrane filtration unit
comprises reverse osmosis or nanofiltration membranes. The retentate solution
is then treated in a precipitation clarifier to cause precipitation of solids, to
produce a supernatant solution and a reject solution. At least a portion of the
supernatant solution is recirculated by combining it with the influent solution prior
to the step of pretreating.
[0009] The conditioning and precipitation steps provide for the removal of
hardness and silica-related fouling components; some portion of organic
compounds can also be removed during precipitation in the precipitation clarifier.
The process can increase water recovery rate for reverse osmosis and
nanofiltration processes.
DRAWINGS
[0010] FIGS. 1 to 3 are schematic views of examples of filtration
apparatuses.
[001 1] For simplicity and clarity of illustration, where considered
appropriate, reference numerals may be repeated among the drawings to
indicate corresponding or analogous elements.
DETAILED DESCRIPTION
[0012] Referring to FIG. 1, an example of a filtration apparatus is shown
generally at 100. The filtration apparatus 100 includes an influent solution 102.
The influent solution 102 is introduced to a pretreatment chamber 104. The
pretreatment chamber 104 includes suitable means effective to remove
suspended solids from the influent solution 102, using ultrafiltration,
microfiltration or multimedia filtration, for example.
[0013] After pretreatment, pH of the pretreated solution 106 is adjusted to
at least about 8.3 or lower by injecting CO2 134. Optionally, an anti-scalant
agent 112 can be added to prevent membrane scaling. Examples of anti-scalant
agents include polyacrylic acids, hydrolyzed polymaleic anhydride, acrylic or
maleic acid based copolymer and terpolymer, and metal sequestering agents
such as ethylenediaminetetraacetic acid (EDTA), sodium hexametaphosphate
(SHMP), 1-hydroxyethylidene-1,1-diphosphonic (HEDP), and 2-
phosphonobutane-1 , 2, 4-tricarboxylic acid (PBTC).
[0014] After conditioning, a conditioned solution 114 flows to a membrane
filtration unit 116. The membrane filtration unit 116 includes either reverse
osmosis (RO) or nanofiltration (NF) filtration membranes, or both. The
membrane filtration unit 116 produces a high purity permeate solution 118, and a
retentate solution 120.
[0015] The retentate solution 120 is introduced to a precipitation clarifier
122 and is treated to cause precipitation of solids. In the precipitation clarifier
122, pH of the retentate solution 120 can be increased to between about 9.5 and
12.0, or between about 10.0 and 11.5. The pH can be adjusted by adding an
alkali 124, for example, sodium hydroxide or lime. Furthermore, a precipitation
seed agent 126, such as CaC0 3 and CaS0 4 powders or slurry, can be added
initially to act as crystallization nuclei to speed up precipitation within the
precipitation clarifier 122.
[0016] Optionally, a coagulant agent and/or flocculant agent 128 can be
added, to speed up solid-liquid separation within the precipitation clarifier 122. In
the precipitation clarifier 122, once the precipitant "seed" is formed, the removal
of suspended solids can be enhanced through the use of coagulant and/or
flocculant. Coagulation and flocculation are mechanisms that are used to
chemically increase particle size to enhance precipitation. Coagulation is charge
neutralization by positively-charged coagulant. Both inorganic and polymer
based coagulants can be used to build particle size by neutralizing the negative
surface charges on particles via double layer compression and electrostatic
attraction. Flocculation is a physical bridging mechanism that relies primarily on
the size of the flocculant molecule more than its charge. Although cationic
flocculants may be used, anionic charged flocculants are preferable because pH
in the precipitation clarifier 122 is highly alkaline and there is an affinity between
inorganic solids and anionic flocculants.
[0017] Precipitation in the precipitation clarifier 122 can provide for the
removal of significant hardness and silica related fouling components. For
example, at a pH of 10.0 to 1.5 and with coprecipitation in the precipitation
clarifier 122, ions including barium, iron, manganese, magnesium, aluminum can
be removed to a relatively very low level, calcium can be removed in a form such
as calcium carbonate and calcium sulfate, and a significant portion of silica or
silicate salts can be removed by forming Si-Ca-Mg complex precipitates.
Increasing temperature by heating or steam injection can further enhance silica
removal in the precipitation clarifier 122.
[0018] The precipitation clarifier 122 produces a supernatant solution 130
and a reject solution 132. The reject solution 132 can be drained, either
periodically or continuously, from a lower part of the precipitation clarifier 122
where precipitated solids accumulate.
[0019] At least a portion of a supernatant solution 130 from the
precipitation clarifier 122 is recirculated by combining the supernatant solution
130 with the influent solution 102, prior to the step of pretreating in the
pretreatment chamber 104.
[0020] In addition to adjusting pH of the pretreated solution 106, the C0 2
injection 134 also serves to increase bicarbonate concentration in the
conditioned solution 114 prior to flowing to the membrane filtration unit 116,
which will enhance the precipitation of calcium in the retentate solution 120
downstream once pH is increased to between about 9.5 and 12.0, or between
about 10.0 and 11.5, in the precipitation clarifier 122.
[0021] There are other advantages to using C0 2 injection for reducing
scaling on membrane surfaces compared to use of sulfuric or hydrochloric acids,
for example. C0 2 is generally not corrosive to pipes and equipment, and it is not
stored as an acid solution. C0 2 injection serves as two purposes: adjust pH and
provide bicarbonate for subsequent hardness removal in the precipitation clarifier.
C0 2 is also more cost effective and environmentally friendly compared to use of
acid to decrease pH, and then supplementing sodium carbonate to the
precipitation clarifier 122.
[0022] The filtration apparatus 100 can include further components, which
have been omitted from FIG. 1. For example, one or more pumps can be
provided upstream of the membrane filtration unit 116 to pressurize the
conditioned solution 114, and/or a heat exchanger can be provided upstream of
the precipitation clarifier 122 to increase the temperature of the retentate solution
120 before introduction to the precipitation clarifier 122.
[0023] Using the filtration apparatus 100, water recovery rate can be
increased in comparison to a conventional arrangement in which there is no
recirculation. For illustration purposes, if reverse osmosis water recovery rate is
Y P, the reverse osmosis reject ratio is YR, the drain ratio is YD, and the
supernatant recirculation ratio is R (and the reject portion of pretreatment
chamber 104 is ignored), then:
Y P = 100% - YD (1)
R = YR- YD (2)
[0024] For normal RO water purification process, there is no recirculation
(R = O), so the water recovery rate is
Y P = 100% - Y R (3)
[0025] If the reverse osmosis reject ratio is 20%, then the water recovery
rate is 80%. However, using the filtration apparatus 100, as there is solid-liquid
separation in the precipitation clarifier 122, the supernatant solution 130 is
recirculated back to the pretreatment chamber 104. Suppose the reverse
osmosis reject ratio is 20%, and the supernatant recirculation ratio R is 10%,
then according to equation (3) the water recovery rate YP will be 90%. This ratio
can be further increased if hardness removal in the precipitation clarifier 122 is
efficient. Thus, as an approximation, a process using the filtration apparatus 100
can increase the water recovery rates from about 65-80% for a conventional
filtration process to about 90-95%. The increase in water recovery also reduces
costs associated with disposal of the reject solution.
[0026] Referring to FIG. 2, another example of a filtration apparatus is
shown generally at 200. The filtration apparatus 200 is similar to the filtration
apparatus 100. However, prior to being introduced to the pretreatment chamber
204, the influent solution 202 can be injected with C0 2 234a to decrease pH of
the influent solution 202 prior to pretreatment. Furthermore, the supernatant
solution 230 can be injected with C0 2 234b to decrease pH of the supernatant
solution 230 prior to combining the supernatant solution 230 with the influent
solution 202. By decreasing the pH, remaining particles in the supernatant
solution 230 are dissolved before being combined with the influent solution 202.
[0027] Referring to FIG. 3, another example of a filtration apparatus is
shown generally at 300. The filtration apparatus 300 is similar to the filtration
apparatuses 100 and 200. However, the filtration apparatus 300 is a "two-pass"
system, in which permeate solution 318 is flowed to a secondary membrane
filtration unit 316a. The secondary membrane filtration unit 316a produces a high
purity secondary permeate solution 318a, and a secondary retentate solution
320a. At least a portion of the secondary retentate solution 320a is combined
with the retentate solution 320 prior to being introduced to the precipitation
clarifier 322.
[0028] In some examples of this "two-pass" arrangement, the membrane
filtration unit 316 can comprise NF membranes, followed by the membrane
filtration unit 316a, which can comprise RO membranes. In other examples, the
membrane filtration units 316, 316a can each comprise RO membranes.
[0029] Generally, the membrane filtration units 116, 216, 316, 316a can
each comprise one or more RO or NF membrane modules, arranged in parallel
or in series. For example, the membrane filtration unit 116, 216, 316, 316a can
comprise two-stage or multi-stage reverse osmosis filtration modules.
[0030] Selection of CO2 injection points and pH control parameters can
significantly influence cost effectiveness of the filtration process. In an open
atmosphere system, it may not be economical to decrease pH to below 8.0 prior
to RO/NF filtration in the membrane filtration unit 116, 216, 316, as a portion of
injected C0 2 can escape to the atmosphere. However, if CO2 is added in a
closed system under pressure, the pressure will force the following equation
towards the right, allowing the pH to drop to a desired level.
C0 2 + H20 - H2CO3 ®HCO3 + H+ (4)
[0031] Thus, if the pretreatment chamber 104, 204, 304 is designed as an
open system (e.g., immersed MF/UF), CO2 can be injected to decrease pH to
around 8.0 to 8.5 prior to entering the pretreatment chamber 104, 204, 304 (e.g.,
C0 2 234a).
[0032] Further, as described above, CO2 can be injected to closed piping
between the pretreatment chamber 104, 204, 304 and the membrane filtration
unit 116, 216, 316 at 134, 234, 334 to decrease pH and simultaneously also
supplement sufficient carbonate/bicarbonate for subsequent precipitation of
calcium in the precipitation clarifier 122, 222, 322. Thus, in the retentate solution
120, 220 320, bicarbonate will be dominant as shown in following equation:
C0 2 + H20 - H2CO3 <- HCO3 + H+ (5)
[0033] As described above, the retentate solution 120, 220 320 is directed
to the precipitation clarifier 122, 222, 322 for hardness and silica removal. It can
be more efficient and desirable to convert as much bicarbonate to carbonate as
possible, by way of heating or decreasing pressure, or both, prior to using an
alkali to increase pH in the precipitation clarifier 122, 222, 322.
HCO3 + heat ®C0 3
2+ + C0 2 + H20 (6)
[0034] As shown in equation (6), heat forces bicarbonate to produce
carbonate and CO2. Pressure of the retentate solution 120, 220 320 can drop
substantially as it flows from the membrane filtration unit 116, 216, 316 to the
precipitation clarifier 122, 222, 322, and thus C0 2 can be evaporated/volatized.
Conversion of bicarbonate to carbonate, by either heating or pressure drop, or by
both, can reduce the requirement of dosing with alkali to increase pH for
precipitation. The volatized CO2 can also be collected and recycled for CO2
injection as described above.
[0035] The teachings herein may be suitable either for new water
purification installations or retrofit of existing reverse osmosis and nanofiltration
operations.

CLAIMS
We claim:
1. A membrane filtration process, comprising:
pretreating an influent solution to remove suspended solids, to
produce a pretreated solution;
adjusting pH of the pretreated solution to at least 8.3 or lower by
injecting C0 2 into the pretreated solution, to produce a conditioned solution;
flowing the conditioned solution through a reverse osmosis or
nanofiltration membrane filtration unit, to produce a permeate solution and a
retentate solution;
collecting the permeate solution;
treating the retentate solution to cause precipitation of solids, to
produce a supernatant solution and a reject solution; and
recirculating at least a portion of the supernatant solution by
combining the portion of the supernatant solution with the influent solution prior to
the step of pretreating.
2. The process of claim 1, further comprising, prior to the step of pretreating,
injecting C0 2 into the influent solution.
3. The process of claim 1 or 2, further comprising injecting CO2 into the
recirculated supernatant solution after the step of treating.
4. The process of any one of claims 1 to 3, further comprising, prior to the
step of flowing, adding an anti-scaling agent to the conditioned solution.
5. The process of any one of claims 1 to 4, wherein the step of treating
comprises adjusting pH of the retentate solution to between 9.5 and 12.0.
6. The process of any one of claims 1 to 4, wherein the step of treating
comprises adjusting pH of the retentate solution to between 10.0 and 11.5.
7. The process of any one of claims 1 to 6, wherein, in the step of treating,
the retentate solution is treated in a precipitation clarifier.
8. The process of claim 7, wherein the step of treating comprises adding an
alkali to the retentate solution in the precipitation clarifier.
9. The process of claim 7 or 8, wherein the step of treating comprises adding
a precipitation seed agent to the retentate solution in the precipitation clarifier.
10. The process of any one of claims 7 to 9, wherein the step of treating
comprises adding a coagulant agent to the retentate solution in the precipitation
clarifier.
11. The process of any one of claims 7 to 10, wherein the step of treating
comprises adding a flocculant agent to the retentate solution in the precipitation
clarifier.
12. The process of any one of claims 1 to 11, wherein the step of treating
comprises heating the retentate solution.
13. The process of any one of claims 1 to 12, wherein the step of treating
comprises reducing pressure of the retentate solution.
14. The process of any one of claims 1 to 13, wherein the step of treating
comprises collecting C0 2.
15. The process of claim 14, further comprising injecting the collected CO2
into the pretreated solution, the influent solution, or the recirculated supernatant
solution.
16. The process of any one of claims 1 to 15, wherein the step of pretreating
comprises using microfiltration, ultrafiltration or multi-media filtration.
17. The process of any one of claims 1 to 16, further comprising:
flowing the permeate solution through a secondary reverse osmosis
membrane filtration unit, to produce a secondary permeate solution and a
secondary retentate solution;
collecting the secondary permeate solution; and
recirculating at least a portion of the secondary retentate solution
by combining the portion of the secondary retentate solution with the first
retentate solution prior to step of treating.
18. The process of any one of claims 1 to 17, wherein, in the step of adjusting,
injecting C0 2 into the pretreated solution causes an increase in bicarbonate
concentration.
19. The process of claim 2, wherein injecting C0 2 into the influent solution
causes an increase in bicarbonate concentration.
20. The process of claim 3, wherein injecting CO2 into the recirculated
supernatant solution causes an increase in bicarbonate concentration.