Evaluating Ceramic Microfiltration for SAGD Produced

Water Processing
Name: Bo Wu, ID: 10094435

1. Introduction
This paper explores the theory, research and application of ceramic membranes for the
treatment of produced water in SAGD processing plants. Ceramic membrane hold the
potential as a game-changing technology, due to the potential to simplify the water
treatment process by replacing several currently used treatment technologies. Ceramic
membrane have inherent properties such as superior thermal and chemical stability,
and is able to accomplish current and pending regulatory objectives with no chemical
pre-treatment [6].
Produced water, which originates from reservoir formations and is brought to the
surface during the recovery of hydrocarbons, constitutes the largest waste stream in oil
and gas production. Over 90% of produced water needs to be processed once it arrived
at the upstream facility, before it is re-injected into the formation [15, 4]. In general,
produced water treatment is done via de-mineralizing and de-oiling. Various
technologies exist for treatment of oilfield produced water, with a series of operations to
remove both organic and inorganic contaminants. Traditional technologies used in
current SAGD processing plants include clarifiers, dissolved air flotation, filters, and
hydro-cyclones [9].
Membranes occupies one category in the oil industrys water treatment technology
family. Sub-category include ceramic membranes, polymeric membranes, and
biomimetic membranes [22]. While polymeric membranes are commonly used, and
have the advantages of low energy requirements and high efficiency, they have serious
disadvantages, like poor thermal stability and chemical incompatibilities. SAGD
produced water, with its high temperature, necessitates membranes made from ceramic
materials, such as metal oxides, clay and zeolite [11].
Ceramic microporous materials are very effective for reducing concentrations of oil and
suspended solids from produced water. They are particularly suitable for treating
corrosive and high temperature oil- and surfactant-contaminated water streams. Zeolite
membranes formed on commercial tubular strands have a 99% ion rejection ability [3].
As a result, membrane technology is used in industrial processes, wastewater
treatment, and oil field water treatment plants. Later parts of the paper will explore
ceramic membrane technologies developed specifically for SAGD produced water
treatment.
The biggest challenge in the adoption of ceramic membranes in SAGD is the
irreversible fouling of membranes, which severely reduces the membranes efficiency
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and life. Oily aqueous solutions typical of produced water can contain surfactants, which
adsorb onto the membrane. Various chemical and physical methods have been
proposed to modify membranes in order to reduce membrane fouling and improve
solute rejection and flux rate. Findings from these studies will also be discussed in this
paper.
2. Theory
The general principle of membrane separation is the transport of selected material and
the exclusion of other through physical and chemical differences. A concentration
gradient is established when a solution contacts a membrane, which serves as a driving
force for the solution to pass the membrane. Typical membrane operation include
microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO),
electrodialysis (ED), membrane electrolysis (ME), and diffusion dialysis (DD) [17].
In membrane separation, feedwater flows across a membrane surface. Under hydraulic
pressure, water molecules permeate through the membrane while particles, dispersed
oil, ions and organic molecules are prevented from passing the membrane due to size
exclusion [2]. The permeate will be collected as purified water for beneficial uses such
as feedwater to the boiler, while the concentrate is disposed of by deep well injection or
trucking. Figure 1 shows the separation of contaminants from water via different
membrane operations.

Figure 1. General membrane operation for water treatment.

2.1 Filtration Operation: Dead-end and Cross Flow

There are two main mode of operation in membrane filtration, whereby one is the deadend mode, and the other is the cross-flow mode.
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Dead-end filtration: all the fluid passes through the membrane perpendicular to the
membrane surface and particles larger than the pore sizes of the membrane are
rejected. The trapped particles eventually build up a "filter cake" on the surface of the
membrane, which reduces the efficiency of the filtration process [11]. Back flushing
washes away the filter cake and cleans the membrane for another cycle of filtration.

Figure 2. Dead-end filtration

Typical usage of dead-end filtration technique is for dilute solutions, as fouling is an

issue, and membrane needs a replacement following a finite number of backwashes.
This filtration technique typically has low capital cost but high operating cost.
Cross-flow filtration: the fluid feed stream runs parallel to the membrane, causing a
pressure differential across the membrane to develop. Some of the particles will pass
through the membrane, while the rest continues to flow across the membrane. The
cross flow cleans the membrane and prevents buildup of a filter cake [17]. An important
variable in cross flow filtration is the cross flow velocity, which is the flow rate per unit
cross section area of the flow. The higher the velocity, the lower the retention time, and
the lower the foulant concentration on the membrane surface.

Figure 3. Cross-flow filtration

Typical usage of cross-flow filtration technique is for high solid content solutions, such
as oilfield produced water. The membrane has extended lifetime compared to dead-end
filtration operation if regularly cleaned. This filtration technique typically has high capital
cost but reasonable operating cost [4].

3 Membrane Process Microfiltration

Microfiltration can remove suspended solids down to 0.1 m in size through mechanical
sieving [8]. It is suitable for use as a pre-filter to a water recycling system, or as a prefilter for reverse osmosis. The pore size of the membrane range from 10 to 0.1 m [13].
Microfilter membranes come in many shapes, such as hollow fibers, flat sheet, tubular,
and spiral wound. Microfilter membranes are effective against particles and sediment for
produced water treatment, but cannot filter out the monovalent chemicals (eg. Na+, Cl-),
dissolved organic matter, and small colloids [23].
Microfilter membranes can operate in either cross-flow filtration or dead-end filtration.
The most widely used process design for microfiltration is dead-end flow [1]. As
particles accumulate on the membrane surface, the pressure required to maintain the
flow increases, leading to the necessity to do periodic replacements. Backwash is
usually used to clean the membranes and it is carried out for short durations (3sec to
3min) frequently (between 5min to 1hr) [9]. A clean in place operation can also be
performed to clean the membrane.
4 Ceramic Membrane
4.1 Properties
Ceramic membranes are much more resilient than polymeric membranes for use in
harsh operating conditions, such as heavy oil facilities. Their advantage lies in
chemically and thermally stability, mechanical strength, ease of regeneration after
fouling, and high potential flux rates [5]. Industrial ceramic membranes are usually in a
tubular configuration, with the feed water flowing inside the membrane channels and
permeating through the membrane to the outer layer.
The desirable characteristics of ceramic membranes for produced water desalination
include high porosity, surface hydrophilicity, and adequate temperature and pressure
tolerance [11]. Ceramic membranes are capable of removing particulates, organic
matter, oil and grease, and metal oxides. Ceramic membranes alone cannot remove
dissolved ions and dissolved organics. To improve removal efficiencies of dissolved
organic carbon and small particulates, it is helpful to inject chemical coagulant upstream
from the membrane. In addition, a strainer or cartridge filter needs to be placed prior
ceramic membranes for removing large particulates [19].
Ceramic membranes can be classified as microporous membranes (pore size <2.0 nm),
mesoporous membranes (2.0 nm - 50 nm), and macroporous membranes (pore size
>50 nm) [23]. See Figure 4 for typical ceramic membrane industrial usage.

Figure 4. Ceramic membrane in tubular form

Advantages of ceramic membranes include a very hydrophilic, higher flux due to welldefined pore distribution, and better recovery performance of the membrane due to
better resistance stress [7]. Disadvantages include sealing problems due thermal
expansion of ceramic membrane, brittleness and the necessity for module housing.
Among the many flux-influencing factors, including feed water quality, concentration of
suspensions, membrane porosity, and pore size distribution, pore size selection is
critical in meeting desired permeate water quality and water flux. Water flux increases
exponentially with an increase in pore size [22]. As a result, selecting of ceramic
membranes with appropriate pore size and size distribution is crucial to the
achievement of high water flux.
Infrastructure requirements are similar to other membrane processes, and include a
tank for the feed water, a feed pump, rack for the membrane modules, a tank for the
filtrate water, and pumps for the backwash systems. Nonetheless ceramic membranes
currently have a higher capital cost than polymeric membranes, due to complication in
the membrane production and lower popularity [9]. For example, zeolite membranes are
about 1050 times more expensive than the equivalent polymeric membranes [12].
Energy requirements for ceramic membranes are lower compared polymer membranes.
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Energy requirements for ceramic membranes are lower compared polymer membranes.
However, ceramic membranes do require frequent backwashes, and the backwash
waste will require disposal.
4.2 Use in oil removal
Numerous research studies have been conducted on using ceramic membranes to treat
produced water contaminated with oil. These research studies have shown that ceramic
membranes generally perform better than polymeric membranes on oil-containing
waters [6, 7, 10, 13]. The latter is found to be more prone to fouling and degradation.
Organic matter, oil and grease, and metal oxides can be removed using ceramic
membranes, but dissolved ions and dissolved organics cannot be separated [6]. See
Figure 5 for a typical ceramic membrane module in an oil processing plant.

Figure 5. Ceramic membrane PW treatment facility

Membrane fouling is one of the problems associated with the usage of membranes in
produced water treatment processes. However, due to the high chemical and thermal
stability of the ceramic membranes, it is possible to deploy chemical and thermal
cleaning methods on ceramic membranes. Feed streams containing high amount of
total dissolved solids can be treated using ceramic membranes, but high ionconcentration may cause irreversible fouling.
Based on several studies, it was concluded that ceramic membranes have better
performance, long operating life (typically over 10 years), and lower energy requirement
than polymer membranes [15].
Operating parameters have been reported for ceramic membranes for use in refinery
water treatment in Iran. When using tubular ceramic microfiltration membranes (made
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with Aluminum oxide of pore size 0.2m, recommended working conditions is 1.25 bar
for the transmembrane pressure, 2.25 for the cross flow velocity and 32.5C for
temperature [24]. Backwashing was found to be useful in preventing the decline in
permeate flux.
4.3 Material of Construction
Ceramic ultrafiltration and microfiltration membranes are made from metals such as
aluminum, titanium, silicium, or zirconium along with non-metals like oxides, nitrides, or
carbides [2]. Aluminium oxide and zirconium oxide are the most important materials for
ceramic membranes.
Typically, ceramic membranes have an asymmetrical structure with an effective top
layer formed by coating or casting. The mesoporous thin layer with thickness of 0.51.0mm will exclude any suspensions larger than the pore size [20].
4.4 Membrane Fouling and Flux Loss
Common problems for produced water purification by membranes are fouling and flux
decline, both of which significantly increase operating costs [15]. Membrane fouling is
associated with the composition of produced water such as the concentration of
suspended particulates, floating oil droplets, and dissolved salts.
In oilfield produced water, membrane fouling is a concern due to the high impurity
content, leading to flux decline [6]. A typical flux decline curve for different pore sizes is
shown in Figure 6. When the flux rate becomes unacceptable, the membrane will need
to be cleaned.

Figure 6. Reduction in flux following membrane fouling

5 SAGD Produced Water

Produced water from oil and gas production has a complex solution composition, which
varies over the life of a well production. The dissolved salts contain different cations and
anions in varying concentrations. The primary cations from dissolved salts include Na+,
K+, Ca2+, Mg2+, Ba2+, Sr2+ and Fe2+; the anions are mainly F-, Cl-, and HCO3 . See
Table 1 for typical Canadian heavy oilfield produced water contents.
Table 1. Typical water quality of produced water in Canadian heavy oil field

Parameter
Alkalinity (CACO3)
Hardness
TSS
TDS
Total O&G
Dissolved O&G
Filterable Organic Carbon
CO3
Cl
SO4
Ba
Ca
Mg
Fe
K
Na
Si

Range of Data (mg/L)

68-1196
3.3-11170
8-1955
2110-76185
3.3-1571
0-103.3
0.8-548
40.8-745.2
85-43500
0.10-820
0.1-118
0.4-2576
0.03-1200
0.05-46
11-884
520-36000
1.2-207

6 Application to SAGD
This section examines the use of ceramic membranes for SAGD projects in operation or
under construction in Canada. Ceramic membrane has attracted interest from the
SAGD industry primarily in its potential for the de-oiling of produced water. Regulation in
Alberta requires that at least 90% of the water used in steam generation come from
produced water [25]. As such, produced water treatment is critical.
Unlike produced water in conventional oil fields, SAGD produced water possess a
number of challenges to the treatment process:
-

The PW is hot for efficient energy usage, and is around 90-120C.

There is high oil content in the water, typically >100ppm
The oil is sticky and forms tight emulsions in the water due to naphthenic crudes

Nonetheless, high effluent quality is demanded by the steam generator and fouling is a
major concern for the boilers. Husky Energy notes in a 2011 conference that dissolved
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organics is not effectively removed by any of the current upstream processes. Refer to
Figure 7 for the process flow diagram of a SAGD processing facility. Note that the
cyan/blue stream indicates produced water.

Figure 7. SAGD process flow diagram

6.1 Husky Energy

Operating experience of SAGD de-oiling system by Husky Energy resulted in
observations that frequent upsets has increased the TOC loading in the boiler feedwater
steam. The steam generator (OTSG) tubes experienced fouling as a result of poor BFW
quality, causing decreased tube life, increased pigging, and in some cases tube rupture.
Less steam and poor quality steam is generated as a result, and the production of crude
is reduced.
Husky Energy has implemented a ceramic membrane technology pilot at the Sunrise
SAGD Project (300,000bpd), which is expected to come on stream in 2015. Ceramic
membranes has the potential to replaces current processes in both primary and
secondary de-oiling, including de-silication [24]. The eater treatment strategy was
proposed by the EPC WorleyParsons, which recommended replacement of
conventional de-oiling with ceramic membrane de-oiling for more efficient BFW
treatment.

6.2 ConocoPhillips Canada

ConocoPhillips Canada, in collaboration with the vendor Veolia Water Solutions,
initiated a two year field test of ceramic membranes for SAGD PW treatment. The test
location is the Surmont Phase 1 SAGD facility, and occurred from 2009-2011 [25].
Veolia Water has developed a technology called ROSS specifically for SAGD PW
applications (see figure 8). The advantage of this technology is in combining deoiling
and silica removal using ceramic membranes.

Figure 8. Veolias ceramic membrane technology

Veolia Waters ceramic membrane is marketed under the name CeraMem, and comes
with several desirable qualities, including:
- Ability to operate at high temperatures (>100C)
- Able to withstand high temperature cleaning and harsh chemical treatment
- Able to withstand fluid with pH ranging from 3-11, and can withstand backflush
- Able to treat emulsified oil without chemical usage
- Long membrane life (>10 years)
- High process flux
The results of the field trial is shown in Table 2. Overall performance is satisfactory. The
membrane is able to operate between 10-20 days before cleaning is needed [25]. The
field had encountered upset conditions as well, but the author notes that it is infrequent
for upsets to occur. With ceramic membranes, upsets can occur unpredictably, can be
severe (increasing the O&G and TSS by 1000%), and fouls the membrane rapidly.
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Table 2. Water quality in the feed and permeate for Veolias field study

Attributes
Reactive Silica
Turbidity
Oil and Grease
Total organic carbon

Feed
250-350
10-150
5-65
350-450

Permeate
< 30
<2
<1
250-350

As a result of this study, Veolia has proposed a new process flow for SAGD PW
treatment, which retains the FWKO /Treater, as well as the skim tank as a buffer, and
replaced the ORF, IGF, and WLS process.
6.3 Lab Scale Study
Petroleum Technology Alliance Canada sponsored a bench scale experiment of
ceramic membranes capability in deoiling produced water in 2010, which was
conducted at SAIT. The final paper has been peer reviewed by Thomas Harding from
the University of Calgary. This study utilized produced water from Huskys upgrader in
Lloydminster and uses a testing apparatus with configuration as shown in Figure 9.

Figure 9. Process flow schematic of the bench scale ceramic membrane study

The aim of the study is to use PW with an oil and grease concentration of 1700 to 9000
mg/L to test for water quality parameter. Samples with oil and grease concentration of
1700ppm and 3600ppm showed reduction in concentration to 5ppm in the permeate,
regardless of the membrane pore size, length or surface area. Removal efficiency was
99.7% - 99.9% for all membranes [26]. One sample, with oil and grease concentration
at 9000 ppm and a viscosity 1.88 cP, showed a concentration ranging from 5.0 11ppm
oil and grease in the permeate.
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