MED BRINE TREATMENT FOR GEOTHERMAL INJECTION

Authors: Thomas Peter Sephton1, Dr. William Bourcier2, Larry Lien3, Richard Simonis4

1
Sephton Water Technology, Inc., USA, [email protected]
2
Lawrence Livermore National Lab, USA, [email protected]
3
Membrane Development Specialists, USA, [email protected]
4
Rocky Point Environmental Services, USA, [email protected]

Presenter: Thomas Peter Sephton

ABSTRACT

The purpose of this study and pilot project was to develop a method to dispose brine concentrate from a geothermal
waste heat Multi-Effect Distillation (MED) process by injection into the geothermal aquifer. This would provide
environmentally safe brine disposal roughly 2,000 meters below ground into an already hypersaline aquifer. It could
also provide a benefit to the geothermal resource by augmenting the 80% to 90% geothermal recharge in practice.

An existing two effect Vertical Tube Evaporator (VTE) pilot plant has been testing the use of waste heat from
geothermal steam vented at atmospheric pressure by power plants at the Salton Sea in the Southern California desert
in order to reclaim water from that large brine lake for environmental or potable reuse. Disposal of brine concentrate
at the inland site is problematic because rising salinity in the brine lake already threatens a critical ecosystem there.

Since the geothermal plants already reinject most of the the geothermal fluid after flashing steam to run turbines,
co-injection seems a logical local solution. However, the chemical compatibility of the MED brine with the
geothermal aquifer is critical to the geothermal operation. This project investigated the compatibility of the MED
brine from Salton Sea feed water with the geothermal aquifer. High sulfate and magnesium in Salton Sea feed water
were identified as the primary challenges. For example, sulfate would form gypsum when contacting high calcium
in geothermal fluids causing wells to plug.

This project lab tested ion exchange and thermal softening methods, before settling on a nonofiltration approach.
Nanofiltration methods were pilot tested with Salton Sea water resulting in a sequential UF/NF process to pre-treat
raw Salton Sea water before MED yeilding a brine concentrate compatible with the Salton Sea geothermal aquifer.
A subsequent bench test improved the nanofiltration permeate recovery to 95%.

Keywords: Geothermal, Distillation, MED, VTE, nanofiltration

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REF: IDAWC19-Sephton
I. INTRODUCTION

The triple flash geothermal power production process has been in use for over forty years on the Salton
Sea Known Geothermal Resource in Southern California’s Imperial Valley. In addition to flashing hot
geothermal brine at three pressures ranging from 270 psig to 48 psig to supply steam turbines, the process
includes a final non-power producing flash at atmospheric pressure before the spent brine is reinjected
into the geothermal aquifer to reheat and be reused. Steam from this atmospheric pressure flash has been
vented to the atmosphere for the last forty years, however, while not econmic to drive a steam turbine, the
near 100°C temperature provides a good watse heat source to drive a Multi-Effect Distillation (MED)
process at very low energy cost.

In prior work [1], a 15 effect MED process was pilot tested with a two-effect Vertical Tube Evaporator
(VTE) plant using the adjacent high salinity (50+ g/liter TDS) Salton Sea as source water. The pilot testing
acheived a high recovery rate of 86% with a performance ratio of 14 [2]. This leaves a 14% fraction of
highly concentrated brine to be disposed of without damage to this inland environment. The triple flash
geothermal process returns 80% to 90% of the geothermal brine used for power to the salt saturated
geothermal aquifer roughly 2,000 meters below ground. This offers an opportunity to make up that deficit
with concentrated Salton Sea brine discharged from the MED process, however the chemical compatibility
of the MED brine with the geothermal aquifer is critical to the geothermal operation. This project
investigated the compatibility of the MED brine, lab tested methods, then pilot tested a sequential UF/NF
process to pre-treat raw Salton Sea water before MED yeilding a brine concentrate compatible with the
Salton Sea geothermal aquifer.

II. GEOCHMICAL MODELLING

Dr. William Bourcier led a study that reviewed the chemistry of the geothermal aquifer at the Salton Sea
and used computer modelling to identify constraints that MED brine concentrate from Salton Sea feed
would have to meet to be suitable for injection in that aquifer. The geothermal fluid produced from the
aquifer has a high TDS of 300,000 mg/kg with sodium (53,000 ppm), potassium (16,700 ppm), and
chloride (151,000 ppm). Notable was a very high concentration of calcium (27,400 ppm). The fluid has
very low concentrations of sulfate (~60 ppm), and magnesium (~35 ppm). By comparison, raw Salton Sea
feed without pretreatment had TDS at 59,000 mg/kg with sodium (13,000 ppm), potassium (380 ppm),
chloride (20,000 ppm), and comparatively high sulfate (12,000 ppm). Magnesium is also comparatively
high in the Salton Sea at 1,600 ppm. The primary constraints on MED brine concentrate identified were:

1. Sulfate concentration must be at or below the present levels in the geothermal fluid, at 64 ppm.
Higher levels will cause precipitation of calcium sulfate due to the high amount of calcium in the
fluid, and the known trend for calcium sulfate to get less soluble with temperature.
2. Magnesium concentration must also be equal or lower than the value of about 35 ppm measured
in the geothermal brine. Magnesium at higher concentrations is likely to precipitate upon
heating, potentially damaging the geothermal reservoir.
Dr. Bourcier also conferred with the geothermal power producer who identified sulfate and magnesium
as their main sources of concern along with total suspended solids. Dr. Bourcier identified several
methods to remove sulfate, magnesium, and other constituents from the MED brine, including ion
exchange, thermal softening, and nanofiltration. After lab tests of ion exchange with Salton Sea brine
and further discussion among all authors, nanofiltration pretreatment of Salton Sea feed was chosen as
the most likely approach to succeed with major reductions of both magnesium and sulfate.

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III. BRINE PRETREATMENT PROCESS DEVELOPMENT

Nanofitration (NF) was tested as a method to remove hardness (calcium and magnesium) from Salton Sea
feed water prior to treatment using the VTE. The NF step would potentially allow a much higher recovery
in the VTE, lower operating costs for VTE cleaning, and reduce the need for anti-scaling agents. There
was also the possibility of producing a calcium sulfate by-product in the NF treatment step that would be
marketable for drywall manufacture.

Tests were carried out both at the CalEnergy pilot test site near Calipatria, California as well as at the
Separation Engineering facility near San Diego (using fluids transported from the Calipatria site). The
goals of the NF work were to measure the extent of hardness removal (Ca and Mg rejection) for the NF
membranes for Salton Sea feed, to determine the water recovery possible without scaling, and to supply
the data needed for preliminary cost estimates for a full-scale NF system.

Salton Sea water, pre-treated using ultrafiltration to remove particulates plus acid addition (HCl) to
prevent calcite scaling, was fed into a nanofiltration system that used 4040 elements (4 inch diameter, 40
inch length) at 5-10 GPM feed input. The membranes were obtained from membrane Development
Specialists (MDS) and were the DK-type NF polymer available from GE-Osmonics. The compositions of
permeate and concentrate were monitored for TDS, pH, calcium and magnesium. Data from these tests
are shown in Figure 1. Overall, the test results show a desired 99% or higher rejection of hardness.

Figure 1: Test results for NF tests carried out at CalEnergy site at Salton Sea. 2009-2010

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First Round Nano-filtration Test at VTE Pilot Plant

Dr. Bill Bourcier ran bench tests of seawater softening with a strong acid cation exchange resin (Purolite
C-100). The specificity of the resin for calcium and magnesium in seawater was poor so ion exchange was
rejected as a pre-treatment method in favor of nano-filtration.

Dick Simonis and Bill Bourcier ran a test of nano-filtration with 85° F seawater feed at 50% recovery to
reduce sulfate, calcium, and magnesium. Genesis LF was used as an anti-scalant. The membranes scaled
up after three hours of operation with Salton Sea water so the test was aborted. A decision was taken to
try pre-softening to reduce calcium that could form calcium sulfate and ultra-filtration pre-treatment on
the theory that particulates in the feed allowed nucleation of precipitates. New nano-filtration membranes
and a set of ultra-filtration membranes were ordered.

A membrane post mortem by Larry Lien restored membrane flow with acid washing indicating the scaling
problem was from calcium carbonate. Dick Simonis recommended pretreatment of Salton Seawater with
HCl to lower the pH from 8 to 6.5 combined with ultra-filtration prior to nano-filtration to remove
particulates that might interfere with the anti-scalant. This would be a 3 pass process.

Second Round Nano-filtration Test at VTE Pilot Plant

Dick Simonis installed ultra-filtration membranes in the pilot test unit and ran ~4,000 gallons of seawater
through at 50% recovery while dosing HCl to a pH of ~6.5. Dick Simonis and Bill Bourcier ran two nano-
filtration passes on ultra-filtrate at 85 deg F to reduce sulfate, calcium, and magnesium in the seawater to
concentrations compatible with the geothermal aquifer. Samples were taken for on-site and off-site lab
analysis. Bill Bourcier tested nano-filtration permeate samples on site for total hardness, calcium, and
sulfate. The 1st nano-filtration pass achieved better than 99% rejection of each. The second pass brought
calcium, magnesium, and sulfate below levels detectable in the on-site analysis. Based on published
detection limits, 2nd pass nano-filtration permeate would meet the targets for geothermal compatibility
after 6:1 concentration.

Dick Simonis and Bill Bourcier completed a 1st nano-filtration pass on ultra-filtrate from Salton Sea water
at about 50% recovery. Bill Bourcier tested nano-filtration permeate samples on site for total hardness,
calcium, and sulfate. Dick Simonis and Bill Bourcier ran a 2nd 50% recovery nano-filtration pass on
permeate from Salton Seawater already nano-filtered once to further reduce sulfate, calcium, and
magnesium in the seawater to concentrations compatible with the geothermal aquifer. 800 gallons of 2nd
pass permeate were stored for later concentration in the VTE. Bill Bourcier tested nano-filtration permeate
samples on site for total hardness, calcium, and sulfate.

Dick Simonis ran a nano-filtration test on ultra-filtrate from Salton Sea water to push for 75% recovery
per pass. The test was shut down due to precipitation blocking the membranes. Investigation of the choice
of anti-scalant showed that the Gensys LS in use was not the manufacturer’s best recommendation for
high sulfate brine. It was decided to try the recommended high sulfate anti-scalant, Gensys CAS.

In order to determine the maximum recovery possible with 2-stage NF, a sample of UF-treated Salton Sea
feed water was taken to a test facility in San Diego operated by Separation Engineering (SE). The tests
were carried out by Larry Lien of MDS, assisted by Tom Sephton and Bill Bourcier. For the testing at SE,
the first step was an NF step at 80% recovery using a sulfate anti-scalant (Gensys CAS) to prevent gypsum
precipitation. The concentrate from this step was then forced to precipitate the supersaturated gypsum by

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addition of lime particulate seeds. The precipitate was then separated and another NF step carried out to
75% recovery. The CAS anti-scalant from Gensys allows about a 5 times supersaturation of gypsum before
initialization of precipitation. With this process 95% of the initial feed is now essentially free of hardness
and can be treated to very high recovery using the VTE (80% in the first step, and 75% of the 20%
concentrate sums to 95%). It is also possible that the gypsum precipitate could be marketable for drywall
manufacture. The test results for the SE tests are shown in Figure 2.

Figure 2: Test results for 2-pass NF tests carried out at the Separation Engineering facilities. 2010

IV. DISTILLATION PILOT TESTING

The 2nd pass NF permeate was concentrated 12 fold in a VTE Pilot Plant with heat from 100°C geothermal
steam. Heat transfer performance data and samples of brine and distillate were taken at each one-fold
increase in brine concentration. Steady heat transfer performance indicated no scaling during brine
concentration. All samples were tested for pH and TSS/TDS plus ion analysis in a commercial lab.
Magnesium and sulfate levels were higher after introduction of the 2nd pass permeate to the VTE system.
This may be caused by dissolving these elements out of slurry deposits from prior raw feed testing.
Maximum sulfate was exceeded in the VTE brine concentrate only when going above 5 fold concentration.
Higher concentration would be desirable to match the 300,000 mg/liter TDS of local geothermal brine.

Concentration of Nano-filtration Permeate by VTE Pilot Plant

Concentration of 2nd pass NF permeate was accomplished with an isothermal brine concentration in VTE
1 at 100°C geothermal steam temperature conditions running permeate concentration from 1:1 up to 10:1
based on feed rate measurements. Heat transfer performance data were taken at each one-fold increase in
brine concentration with sampling of brine and distillate. As seen in Figure 3, there was no indication of
scaling during brine concentration with steady heat transfer recorded. The isothermal brine concentration
test of 2nd pass NF permeate in VTE 1 continued at at 100°C geothermal steam temperature conditions
running permeate concentration from 10:1 up to 12:1 based on feed rate measurements. There was no
indication of scaling. All samples were tested for pH and TSS/TDS on site.

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Figure 3. Heat transfer performance in VTE 1 concentrating NF permeate to 12 fold

Figure 4. Major ions in NF permeate concentrating12 fold in VTE 1

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 Figure 5. Minor ions in NF permeate concentrating12 fold in VTE 1

Lab analysis of major ions, particularly sulfate and magnesium was needed to confirm whether the brine
concentrate will be suitable for geothermal injection. Samples from the isothermal brine concentration test
of 2nd pass nano-filtration permeate in VTE 1 were diluted and preserved with nitric acid and shipped out
to the Thermochem commercial lab for chemical analysis of major ions to confirm whether the brine
concentrate will be suitable for geothermal injection, see Figure 4 for major ions. Lab results received
showed 2nd pass nano-filtration permeate met targets with sulfate at 3.86 mg/liter and magnesium at 1.48
mg/liter in a brine calculated to be 19,400 mg/liter TDS, see Figure 5 for minor ions.

The 2nd pass permeate could, in theory, be concentrated 16 fold to 310,400 mg/liter TDS before exceeding
the maximum 65 mg/liter target for sulfate or 35 mg/liter for magnesium in the geothermal aquifer. In the
brine concentration test, magnesium and sulfate levels were higher after introduction of the 2 nd pass
permeate to the VTE system. This may be caused by dissolving these elements out of slurry deposits that
were not adequately removed from the VTE equipment after flushing several times with freshwater and
distilled water or by some unknown mechanism. Maximum sulfate was exceeded in the VTE brine
concentrate only when going above 5 fold concentration, see Figure 51. This level of concentration would
be adequate if the starting material were raw Salton Sea water, but nano-filtration reduced sodium and
chloride in the permeate along with the divalent ions targeted so a higher concentration would be desirable
to recover more distilled water and match the 300,000 mg/liter TDS of local geothermal brine. If the nano-
filtration pre-treatment were used for a large scale process, permeate should be distilled and concentrated
by separate clean VTE equipment that had not been exposed to raw Salton Sea water, slurry, or nano-
filtration reject brine.

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Concentration of Nano-filtration Reject by VTE Pilot Plant

The quantity of 1st Pass Nano-Filtration Reject saved from the final NF pilot test was about 1,500 gallons,
sufficient for only one chance at a concentration test with NF Reject as the feed source. The NF Reject
was expected to have elevated levels of scale forming ions such as calcium, magnesium, and sulfate.

A series of tests with freshwater feed were run to select an optimal operating condition and concentration
of the anti-scaling surfactant Linear Alkylbenzene Sulfonic Acid (LAS-99 from Pilot Chemical or LAS).
In prior tests, LAS concentrations of 10 mg/liter and above showed excessive foaming at the highest
operating temperatures in VTE 2 unless the brine recycle rate were reduced. VTE 1 was less prone to
foaming. A multi-effect simulation test of VTE 1&2 in two-effect operation with 2 mg/liter LAS in
freshwater, feed preheating by heat exchange with de-superheating condensate, forward feed from VTE 1
to VTE 2, and brine re-injection from VTE 2 back to VTE 1 was run at ½ the typical brine recycle rate or
¾ gpm per tube. This had no impact on heat transfer performance at lower operating temperatures, but
caused up to a 20% reduction in the measured heat transfer coefficient at higher temperatures. Similar
multi-effect simulation tests were run with LAS dosed at 10 mg/liter and at 20 mg/liter using the ¾ gpm
per tube brine recycle rate. The lower recycle rate and improved control of the LAS concentration in the
brine made it possible to operate without excessive foaming. LAS concentrations of 10 mg/liter and 20
mg/liter gave an improvement in the heat transfer coefficient of about 10% in VTE 2 over 2 mg/liter LAS.
There was minimal difference in VTE1. The performance benefit of higher LAS in VTE 2 was offset by
the need to operate at a reduced brine recycle rate, so the 2 mg/lit LAS condition was chosen with VTE 2
brine recycling at 1.5 gpm per tube.

1st Pass NF Reject was mixed with all available CaSO4 slurry to 1.5% TSS and used to charge VTE 1&2.
LAS was dosed at 2 mg/liter. Samples were taken for analysis. The pilot plant was brought to the Effect
15 low temperature condition of 51°C with geothermal steam heat. To provide a standard curve of brine
conductivity against concentration (TDS), the 1st Pass NF Reject slurry was concentrated isothermally up
to 4:1 with samples taken for analysis at 1:1, 2:1, 3:1, and 4:1 concentration factors. All major ions showed
a steady rise in concentration except calcium, which declined steadily across the test range indicating
precipitation of CaSO4. Sulfate was in 8.7 fold molar excess over calcium, so precipitation is not obvious
in the sulfate data. Also carbonate was converted fully to bicarbonate between 2:1 and 4:1 brine
concentration.

A multi-effect simulation test of 1st Pass NF Reject was run immediately after brine concentration. VTE
2 brine was held at the 4:1 concentration factor with 51°C effect 15 temperatures while taking thermal
performance data. VTE 1&2 were operated with 2 mg/liter LAS, feed preheating with geothermal
condensate to VTE 1, then to VTE 2, and brine re-injection from VTE 2 back to VTE 1. VTE 2 was run
at the typical brine recycle rate of 1.5 gpm per tube. The brine concentration was brought down with
excess blowdown and the operating temperatures raised for an Effect 11 and an Effect 7 simulation of a
forward feed multi-effect system. The supply of 1st Pass NF Reject ran out after the Effect 7 simulation
so the high temperature 100°C steam, low brine concentration condition could not be tested. Heat transfer
coefficients operating with 1st Pass NF Reject ran about 10% below a prior freshwater baseline test in both
evaporators. Slurry (as TSS) rose steadily during the isothermal brine concentration to 2.8%, but was
reduced to very low levels when driving down the brine concentration during the test.

To evaluate possible scaling of VTE 1 and VTE 2 during the multi-effect simulation test with 1st Pass NF
Reject feed, both evaporators were drained and recharged with freshwater and 10 mg/liter LAS. A baseline
multi-effect simulation test of VTE 1&2 was run in two-effect operation with feed preheating by

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geothermal condensate, forward feed from VTE 1 to VTE 2, and brine re-injection from VTE 2 back to
VTE 1. The same test procedure was repeated after draining, flushing, and recharging both evaporators
with freshwater and 2 mg/liter LAS. Heat transfer performance data was taken and compared with baseline
tests run with 10 and 2 mg/liter LAS in freshwater before the 1st Pass NF Reject test.

Figure 6. VTE 1 heat transfer coefficient concentrating NF Reject with freshwater tests for scaling

Figure 7. VTE 2 heat transfer coefficient concentrating NF Reject with freshwater tests for scaling

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The heat transfer coefficient was not reduced in VTE1 (Figure 6) under either test condition indicating no
measurable scaling during the test using 1st Pass NF Reject as feed. A slight reduction in heat transfer
performance was seen in VTE 2 (Figure 7). The NF reject feed source was very high in scale forming
ions. The multi-effect simulation with 1st Pass NF Reject feed tested the low temperature with high brine
concentration condition that would be used in a multi-effect system configured for forward feed. This
result supports a forward feed process, however there was not enough 1st Pass NF Reject to test all forward
or reverse feed conditions. Buildup of flakes in the VTE 1 strainer occurred in both freshwater tests
requiring strainer screen cleaning after each test run.

V. CONCLUSIONS

Pilot testing showed that a two pass NF process, after removal of all particulates by UF, can achieve the
very low levels of magnesium and sulfate required. The permeate from NF could be concentrated up to
12 fold in the VTE without scaling while recovering about 90% of the water as distillate. The UF/NF
pretreatment process on Salton Sea feed water can enable disposal of MED brine concentrate in the
geothermal aquifer without harm to the aquifer or the surface environment and with a possible recharge
enhancement benefit to the geothermal resource.

VI. REFERENCES

1. Sephton T. and Tiffenbach A. 2005. “VTE Desalination using Geothermal Energy at the Salton
Sea”. Proceedings of the 2005 Solar World Congress, Orlando Florida.
2. Sephton T. 2017. “Brine Lake VTE-MED Pilot with Geothermal Waste Steam”, International
Desalination Association 2017 World Congress Proceedings.

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