MaxH2O Desalter Technology – Innovative Solution for Brine

Minimization

Alex Drak, IDE Technologies, Hamatechet St., Hasharon Industrial Park, Kadima,
6092000, Israel, alexd@ide-tech.com, +972 9 8929835
Roi Zaken Porat, IDE Technologies, Kadima, Israel
Marco Kerstholt, Royal HaskoningDHV, Umhlanga, South Africa
Gerard van Houwelingen, Royal HaskoningDHV, Amersfoort, the Netherlands
Tomer Efrat, IDE Technologies, Kadima, Israel

Keywords: MaxH2O Desalter, brine minimization, reverse osmosis, fluidized bed

reactor, sparingly soluble salts precipitation, mine-impacted effluent

Abstract

Reject brine, with a high content of dissolved salts, is a by-product of the brackish
water and industrial wastewater desalination processes. With the growing demand for
water, increasing amounts of brine are produced from the brackish water and
industrial wastewater desalination plants, leading to significant adverse impacts on the
environment. Effective management of desalination reject brine is imperative to
ensure more efficient disposal and reuse.
Sustainable improvement in reject brine management is based on brine minimization,
which can be achieved through the recovery of valuable materials such as salts,
metals, and chemicals. A recently developed MaxH2O Desalter technology allows
minimizing the quantity of produced brine from brackish water and industrial
wastewater desalination plants, recovering some of the salts for further reuse.
The brine chemistry is the main challenge to minimizing the quantity of produced
brine. As the concentration of the brine salts increases, there is an increased risk of
desalination process failure due to precipitation of salts on all available surfaces. The
recently developed MaxH2O Desalter technology, comprising a reverse osmosis (RO)
system with an integrated salt precipitation unit, overcomes this limitation. The
technology provides a solution for difficult brackish waters and industrial
wastewaters, and successfully overcomes the various challenges, e.g. scaling by
sparingly soluble salts, and organic and bio fouling. The integrated salt precipitation
unit removes only the salts that can harm the desalination process, minimizing the
reject brine quantity as much as possible in RO technology.

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This paper presents the recent pilot results for two water sources: brackish water
brine, and mine impacted effluent. The results show that with these types of water, the
system can reach maximum recovery as governed by osmotic pressure, and is no
longer limited by water chemistry. In the case studies presented, the developed system
successfully removed calcium carbonate, silica and calcium sulfate from the brine,
maintaining the saturation index of these salts in a range that does not harm the RO
membranes. The produced crystals have more than 90% dry solids content, and do not
require further sludge dewatering.

Introduction

Technological progress and population growth increases the need to generate water
from available sources such as sea and brackish water. The technologies available for
water production/desalination can be divided into two major types – membrane
technology, primarily reverse osmosis (RO), and thermal technologies such as
multiple effect distillation and multi-stage flash distillation. Over the last decade,
membrane technology has become the preferred technology, due to the relatively
lower capital and operational expenditures of this technology compared to thermal
technologies.
All desalination technologies produce the same by-product – concentrate or brine. The
amount of brine produced varies depending on the source of the water being
desalinated. In seawater desalination plants, the brine constitutes almost 50 percent of
the quantity of seawater that is pumped from the sea to desalination plant. In brackish
water desalination plants, the brine constitutes between 15 percent and 30 percent of
the brackish water pumped to the desalination plant.
The produced brine has a negative environmental impact and should be discharged to
authorized sites. Seawater brine is generally returned to the sea, while brackish water
brine sometimes has to be pumped over long distances, discharged to evaporation
ponds or injected into dedicated injection wells. Although the amount of brine in the
brackish water desalination plants is relatively low, the brine discharge in these
facilities is far more problematic.
As more desalination facilities are established, the problem of brine discharge is
becoming increasingly severe, and it is necessary to minimize the amount of brine
produced as much as possible. One of the solutions for brine minimization is salt
extraction. This solution is preferable from an environmental point of view, and is
likely to dominate the market in the coming years. For this to happen, this technology
must be economical. Meanwhile, it has been shown that the extraction of many salts
such as chlorine, bromine, sodium hydroxide, calcium carbonate, magnesium
hydroxide and magnesium oxide is technically feasible from seawater desalination
brine. According to the WateReuse Research Foundation (Mickley, 2008), the main
factor that impedes the recovery of salts from seawater desalination brine is the

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economics of extraction. Additional factors include facility location, product purity,
staffing, safety, material handling and storage.
The available alternative for brine minimization is a combination of technologies –
reverse osmosis, followed by thermal evaporation, followed by thermal
crystallization. Due to the significant differences in the cost of these technologies
(Table 1), the most economical approach would be to increase the load on the reverse
osmosis as much as applicable, and maximize its recovery, thus decreasing the size of
the thermal crystallization unit to the minimum.
Table 1 – Comparison of brine minimization technologies
Technology CAPEX, Energy Final brine
USD/m3/day Consumption,
kW/m3 product
Reverse Osmosis 500 – 1,000 3–4 Up to 10% TDS
brine
Thermal 2,000 – 5,000 8 – 20 Up to 20% - 25%
Evaporation TDS brine
Thermal 8,000 – 12,000 40 - 60 Up to solids
Crystallization

Two factors generally limit the use of reverse osmosis technology – osmotic pressure
and water chemistry, i.e. saturation of sparingly soluble salts in the produced brine
such as calcium carbonate, calcium sulfate or silica. Seawater RO desalination plants
already operate at the maximum threshold limit of the osmotic pressure, and no
further brine minimization is possible with current reverse osmosis membranes. In
brackish water desalination plants, the brine chemistry limits the amount of brine
produced and acts as the main limiting factor in terms of the possible recovery. The
final brine obtained at these facilities is far from the maximum threshold limit of the
osmotic pressure. Therefore, in brackish water desalination plants, there is a clear
potential for the use of reverse osmosis technology at much higher recoveries. If
reverse osmosis technology can be upgraded to overcome the brine chemistry
limitation, the upgraded RO technology can be used far more effectively before
switching to more expensive thermal technologies.
A recently developed MaxH2O Desalter technology, containing an RO system with
an integrated salt precipitation unit, overcomes the brine chemistry limitation. The
technology provides a solution for difficult brackish waters and industrial wastewaters
and successfully overcomes the various challenges, e.g. scaling by sparingly soluble
salts, and organic and biofouling. The integrated salt precipitation unit removes only
the salts that can harm the desalination process, without the addition of chemicals, and
produces scaling pellets of more than 90 percent dry solids content. These pellets do
not require further sludge dewatering treatment, thus minimizing the reject brine
quantity as much as possible by RO technology. The new technology minimizes the
quantity of produced brine from brackish water and industrial wastewater desalination
plants, recovering part of the salts, which can then be reused.

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 MaxH2O Desalter – Technology Description

The developed system contains an RO system with an integrated salt precipitation and
removal unit. The process provides a solution for difficult industrial wastewater and
brackish water requiring high recovery operation, and successfully overcomes the
various challenges, e.g., scaling of sparingly soluble salts, and organic and bio
fouling. The integrated salt precipitation and removal unit removes only the salts that
can harm the desalination process and, without the addition of chemicals, produces
scaling pellets of more than 90 percent dry solids content. These pellets do not require
further sludge dewatering treatment. In addition, the reverse osmosis unit is operated
at high shear velocity, minimizing the negative effect of concentration polarization,
thus improving the RO process efficiency. The developed process minimizes the brine
quantity to the maximum threshold limit of the osmotic pressure, with minimum
operational expenditures (Drak et al., 2016).

Figure 1 - MaxH2O Desalter process scheme

The operation principle of the MaxH2O Desalter is the recirculation of treated water
through the RO system at high shear velocity, and continuous precipitation of
supersaturated salts from the recirculated brine. This significantly reduces the salt
concentration build up near the RO membrane wall and prevents the precipitation of

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sparingly soluble salts on the membranes. The brine flows through the salt
precipitation unit downstream, where it reduces the saturation of sparingly soluble
salts, thus enabling continuous cycles through the RO system until reaching maximal
brine osmotic pressure.
The salt precipitation unit used in this process has decades of experience in potable
water softening (Van Ammers et al., 1986) and has been implemented for the
recovery of phosphate and heavy metals, as well as fluoride (Van Dijk et al., 1991).
The principle of fluidized bed reactor operation is as follows: the reactor is partially
filled with suitable 0.2 – 0.5 mm seed particles; the RO brine is pumped upward
through the bed of particles to maintain this in a state of fluidization. The seed
particles are used as crystallization sites; they provide the high surface area that
lowers the energy required for precipitation. The antiscalant that prevents the scaling
in the RO elements, together with sparingly soluble salts, adsorbs and precipitates on
the seed particles, creating the salt-coated crystals. As the crystals become
progressively heavier, they gradually travel towards the bottom of the bed.
Periodically, without interrupting the operation of the reactor, the lower portion of the
bed, with 0.8 – 1.0 mm size crystals, is discharged into a transportable container with
a perforated bottom, and fresh seed material is introduced. No filter or other
mechanical dewatering equipment is required; the dry solids concentration in the
obtained crystals is more than 90% and they can be used for soil neutralization, road
building, as an animal feed additive, in cement making and other applications (Giesen
et al., 2009).

Case study - Brackish water desalination plant brine minimization

The MaxH2O Desalter technology was tested in a brackish water desalination plant in
Israel. The plant operated at the typical recovery of 80 percent for brackish water
desalination plants. (The composition of brackish water and 80 percent brine water is
shown in Table 2). As shown, the major challenge of this water type was super
saturation with respect to calcium carbonate and silica. An additional challenge was
the presence of aluminium, manganese and iron in the brackish water, which
prevented the increase of the recovery above 80 percent in the current plant.
Table 2 - Brackish water composition
Parameter Unit Brackish water Current 80% brine
concentration water concentration
Alkalinity mg/L as 290 1,481
CaCO3
Chloride mg/L 3,005 16,415
Calcium mg/L 184 1,080
pH 7.41 7.72
Conductivity mS/cm 8.87 26.82
Silica mg/L 14.8 70

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 Parameter Unit Brackish water Current 80% brine
concentration water concentration
Calcium Carbonate Log SI 0.39 1.23
Silica SI % 12.6% 59.2%

The first series of experiments were performed with brackish water, without
antiscalant. The experiments were repeated four times, i.e. four complete cycles were
performed. In each cycle, the maximum possible recovery that was achieved was
governed by osmotic pressure. The results obtained are shown in Figures 2 and 3. The
total recovery of 93 percent was reached in the brine stream that corresponds to feed
pressure of more than 60 bar (880 psi) (Figure 2).

Figure 2 - Brackish water experiment – Recovery and feed pressure changes

The changes in the calcium carbonate supersaturation are shown in Figure 3. As

shown, the actual calcium carbonate saturation index (Log SI) decreases to almost 1.0
at the end of every cycle, compared to the theoretical Log SI value that should have
risen to values above 2. The reduction in the actual Log SI value is an indication of
calcium carbonate removal during the process.

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 Figure 3 - Brackish water experiment – Calcium carbonate Log SI changes

The second series of experiments were performed with 80 percent brine from the
desalination plant. The experiments were repeated eight times, i.e. eight complete
cycles were performed. Contrary to the brackish water experiments, these experiments
were performed with antiscalant that was already added to the desalination plant feed
stream. No additional antiscalant was added during the experiment. The results
obtained are shown in Figures 4 and 5. The total recovery of 60 to 70 percent was
reached in the brine stream, which corresponds to a total recovery of 92 to 94 percent.
The feed pressure at the end of the cycle increased to values above 50 bar (735 psi)
(Figure 4).

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 Figure 4 - 80 percent brine water experiment – Recovery and feed pressure changes

The changes in calcium carbonate supersaturation are shown in Figure 5. As shown,

the actual calcium carbonate Log SI decreases compared to the theoretical Log SI
value, but not to a great extent. The reason for this behavior is probably the effect of
the antiscalant present in the brine solution. This effect should be further examined
and reduced. Possible solutions include increasing the brine residence time in the
fluidized bed reactor by recirculating part of the reactor effluent, selecting the proper
antiscalant with increased adsorption characteristics, or adding an antiscalant
adsorption accelerator such as caustic soda.

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 Figure 5 - 80 percent brine water experiment – Calcium carbonate Log SI changes

The main findings of the pilot study are:

• The pilot operated continuously with brackish water brine, without scaling on
the RO membrane throughout the trials, removing calcium and alkalinity in the
pellet reactor.
• The total recovery of 92% – 94% was reached.

Case Study – Mine Impacted Effluent Minimization

The developed technology was tested with mine impacted effluent that is metal-rich
water with a high sulfate content and high calcium sulfate scaling potential. The
effluent composition, together with product water requirements, are presented in
Table 3. The major challenge of this wastewater was supersaturation with respect to
calcium sulfate. An additional challenge with this type of wastewater is the presence
of metals and organic material, which prevents a conventional RO system from
reaching high recovery.

Table 3 – Mine Impacted Effluent Composition & Product Requirements

Parameter Unit Mine Impacted Effluent Product
Concentration Requirements
pH 5.70 5.5 – 9.0
Alkalinity ppm as CaCO3 < 5.0

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 Parameter Unit Mine Impacted Effluent Product
Concentration Requirements
Total dissolved solids ppm 3,157 < 500
Conductivity at 25C microS/cm 3,960
Calcium ppm 294
Magnesium ppm 1.3
Sodium ppm 734
Potassium ppm 35.6
Chloride ppm 96 < 200
Fluoride ppm 0.62 < 1.0
Sulfate ppm 2,020 < 250
Boron ppm 0.49 < 0.75
Total suspended ppm 12.8
solids
Turbidity NTU 18
Iron ppm 1.96
Aluminum ppm 0.858 < 5.0
Manganese ppm 0.082 < 0.2
Copper ppm 0.587
Dissolved organic ppm 6.1
carbon
Chemical oxygen ppm as O2 35.0
demand
Oil and grease ppm 1.39
Calcium sulfate % 57% at 25 C
saturation index

The pilot is operated at the following process parameters:

• Reverse Osmosis permeate flux – < 40 LMH
• Reverse Osmosis instantaneous (local) recovery – 15%
• Salt precipitation reactor hydraulic loading rate – 60 - 100 m3/hr/m2
• Gravity media filter hydraulic loading rate – < 12 m3/hr/m2

The Figures below present the continuous operation of the pilot with mine impacted
effluent. Figure 6 shows the total recovery achieved in the pilot study. It can be seen
that recovery above 90% was achieved in every cycle. RO feed pressure, at the end of
the cycle, was only 25 – 28 bar, meaning that further increase in recovery is possible.

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Since about 70% of the salts in the wastewater are calcium and sulfate that are
partially removed in the salt precipitation reactor during the process, the recovery of
the system can be significantly increased until reaching the limit of the osmotic
pressure. In order to reduce the duration of each cycle for operation at recoveries
higher than 90%, it is probably worth splitting the system into two systems, each
operating at 90% recovery and providing a total recovery of about 99%.
100% 100

90% 90

80% 80

70% 70

Feed pressure [bar]

Recovery [%]

60% 60

50% 50

40% 40

30% 30

20% 20

10% 10

0% 0
0 10 20 30 40 50 60 70 80 90
Experiment time [hr]
Total recovery Local recovery Brine stream recovery Feed Pressure

Figure 6 - Achieved Recovery and Feed RO Pressure during the Pilot Study

Figure 7 shows the sulfate concentration changes during the pilot study. The green
triangles are the theoretical sulfate values if calcium sulfate is not removed during the
process. The blue rhombuses are the actual sulfate values measured during the study.
It can be seen that theoretical sulfate concentrations would reach the values of 27,000
– 32,000 mg/L, while the actual sulfate concentrations measured are 15,000 – 17,000
mg/L. Part of the sulfate reduction can be attributed to calcium sulfate crystallization
in the salt precipitation unit.

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 35000

30000

25000
Sulfate concentration [mg/L]

20000

15000

10000

5000

0
0 10 20 30 40 50 60 70 80 90
Experiment time [hr]
Feed sulfate measured Feed sulfate calculated from total recovery

Figure 7 - Sulfate Concentration Changes during the Pilot Study

Figure 8 shows changes in the calcium sulfate saturation index during the pilot study.
The yellow circles are the theoretical calcium sulfate saturation index that would be
achieved if no calcium sulfate was removed during the process. The blue rhombuses
are the actual calcium sulfate saturation index achieved in the study, and calculated
based on measured calcium and sulfate concentrations. It can be seen that the actual
calcium sulfate saturation index at the end of the cycle was around 1,000% - 1,200%
for a very short period of time. This high supersaturation of calcium sulfate, without
scaling on the RO membrane, was achieved by maintaining a constant antiscalant
concentration in the recirculated RO brine. The antiscalant used in this study was
phosphonate based antiscalant, specifically designed to prevent calcium sulfate
precipitation in RO membranes. According to the antiscalant manufacturer, the
maximum calcium sulfate supersaturation that can be achieved in the presence of
antiscalant without scaling in RO membranes during continuous operation is 800%.
Due to the cycle operation of the developed technology, the RO membranes are
exposed to high supersaturation of calcium sulfate for a very short time. This short
time is probably insufficient for calcium sulfate to start the scaling process on the RO
membrane. In addition, the lower than saturation conditions prevailing in the RO
membrane at the beginning of the cycle can remove/dissolve the crystals that
precipitate at the end of the previous cycle.

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 5000%

4500%

4000%

3500%

3000%
SI Calcium Sulfate

2500%

2000%

1500%

1000%

500%

0%
0 10 20 30 40 50 60 70 80 90
Experiment time [hr]
Feed Actual SI Feed Theoretical SI

Figure 8 - Calcium Sulfate Saturation Index Changes during the Pilot study

Figure 9 shows the changes in the concentration of antiscalant during the pilot study.
The green triangles are the theoretical antiscalant concentration as phosphate, if there
is no deactivation of antiscalant. The blue rhombus are the actual antiscalant
concentration as phosphate kept in the recirculated RO brine. Antiscalant was
continuously added during the pilot study in order to maintain constant phosphonate
concentration of approximately 1 ppm as phosphate in the recirculated RO brine. This
concentration was sufficient to prevent scaling of calcium sulfate in the RO
membrane. The difference between the theoretical and actual antiscalant
concentrations are the amount of antiscalant that was adsorbed on the pellets in the
salt precipitation reactor.

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 100.0

10.0
Antiscalant concentration [mg/L]

1.0

0.1

0.0
0 10 20 30 40 50 60 70 80 90
Experiment time [hr]
Feed antiscalant measured Feed concentration calculated

Figure 9 - Antiscalant Concentration Changes during the Pilot Study

At the end of the pilot study, samples of pellets were analysed by High Resolution
Scanning Electron Microscopy (HR SEM). The pictures of pellets taken during the
HR SEM analysis are presented in Figure 10.

Figure 10 - Pictures of Pellets from HR SEM Analysis

HR SEM analysis revealed phosphorus and sulphur atoms on the produced pellets.
This is proof that antiscalant absorbs on the pellets and calcium sulfate precipitates on
the pellets.
Table 4 presents the partial product water analysis done in several tests. It can be seen
that the produced RO product meets the client product water requirements.
Table 4 - RO Product Water Quality and Product Requirements

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 Quality Product
No. Units Test 49 Test 50 Test 51 Test 52
Parameter Requirements
1. Total dissolved ppm 29.2 41.2 33.0 33.0 <500
solids
2. Sodium ppm 12.0 15.0 12.0 12.0
3. Potassium ppm <1.0 <1.0 <1.0 <1.0
4. Calcium ppm 1.2 1.2 1.0 1.0
5. Magnesium ppm <1.0 <1.0 <1.0 <1.0
6. Arsenic ppm <0.0005 <0.0005 <0.0005 <0.0005
7. Selenium ppm <0.002 <0.002 <0.002 <0.002
8. Iron total ppm 0.005 0.005 <0.005 <0.005
9. Manganese ppm <0.0005 <0.0005 <0.0005 <0.0005 <0.2
10. Copper ppm 0.0014 0.0016 0.0017 0.0011
11. Lead ppm <0.0005 <0.0005 <0.0005 <0.0005
12. Chromium ppm <0.0005 <0.0005 <0.0005 <0.0005
13. Cadmium ppm <0.0002 <0.0002 <0.0002 <0.0002
14. Barium ppm <0.002 <0.002 <0.002 <0.002
15. Zinc ppm <0.005 <0.005 <0.005 <0.005
16. Aluminum ppm 0.005 <0.005 <0.005 <0.005 <5.0
17. Lithium ppm <0.0005 <0.0005 <0.0005 <0.0005
18. Silver ppm <0.0005 <0.0005 <0.0005 <0.0005
19. Cobalt ppm <0.0005 <0.0005 <0.0005 <0.0005
20. Nickel ppm <0.0005 <0.0005 <0.0005 <0.0005
21. Strontium ppm 0.006 0.006 0.004 0.004
22. Beryllium ppm <0.0002 <0.0002 <0.0002 <0.0002
23. Molybdenum ppm <0.001 <0.001 <0.001 <0.001
24. Tin ppm <0.002 <0.002 <0.002 <0.002
25. Chloride ppm 4.0 4.0 3.0 3.0 <200
26. Sulfate ppm 12.0 21.0 17.0 17.0 <250
27. COD ppm 2.0 2.0 2.0 2.0

The main findings of pilot study are:

• The pilot operated continuously with mine impacted effluent, without scaling
on the RO membrane throughout the trials, removing calcium and sulfate in the
pellet reactor.
• Recovery of 91% – 93% was reached.
• During the entire operation, antiscalant was added to the recirculated solution
to maintain the concentration of the anti-scalant at about 1 ppm as phosphate.

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 Conclusions

The developed technology was successfully tested with brackish water brine enriched
with calcium, carbonate and silica, and mine impacted effluent enriched with metals
and sulfate. The results show that the system can reach the recovery of over 90%,
removing an excess of sparingly soluble salts in the integrated salt precipitation unit,
without precipitation on RO membranes. The system operated without the addition of
chemicals other than antiscalant and pellets. The produced pellets have more than
90% dry solids content, and do not require further sludge dewatering treatment.
These results show the significant advantage of the developed system as a treatment
alternative for brackish water brine minimization and mine impacted effluent
treatment. The developed system saves operational costs by reducing chemical
consumption and the amount of sludge to be discharged, and investment costs by the
high recovery that can be achieved.
The ability of this technology to practically eliminate the recovery limitation of water
chemistry by precipitating the sparingly soluble salts on pellets, while operating the
RO at high velocity with inherently high shear forces, allows the RO unit to be
designed for its maximum production and recovery potential.

REFERENCES

Drak A., Zaken R., Efrat T., "High Recovery Reverse Osmosis System with
Integrated Salt Precipitation Cycle for Industrial Water Treatment Applications",
Proceedings of 77th International Water Conference (2016), San Antonio, USA.
Giesen A., Erwee H., Wilson R., Botha M and Fourie S., "Experience with
Crystallization as Sustainable, Zero-Waste Technology for Treatment of Wastewater",
Proceedings of International Mine Water Conference (2009), Pretoria, South Africa.
Mickley M., " Survey of High-Recovery and Zero Liquid Discharge Technologies for
Water Utilities ", WaterReuse Foundation (2008)
Van Dijk J.C., Wilms D.A., "Water Treatment without Waste Material: Fundamentals
and State-Of-The-Art of Pellet Reactors", Proceedings of IWSA World Congress
(1991), Copenhagen, Denmark.
Van Ammers M., Van Dijk J.C., Graveland A. and Nuhn P.A., "State of the Art of
Pellet Softening in the Netherlands", Water Supply (1986), Volume 40, pp. 223–235.

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