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SPE-179580-MS

An Integrated German MEOR Project, Update: Risk Management and Huffn

Puff Design
H. Alkan, SPE, Wintershall Holding GmbH, N. Klueglein, BASF SE, E. Mahler, BASF SE, F. Kgler, Wintershall
Holding GmbH, K. Beier, Freiberg University, W. Jelinek, SPE, Wintershall Holding GmbH, A. Herold, BASF SE,
S. Hatscher, SPE, Wintershall Holding GmbH, B. Leonhardt, SPE, Wintershall Holding GmbH

Copyright 2016, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Improved Oil Recovery Conference held in Tulsa, Oklahoma, USA, 1113 April 2016.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
This paper provides an update on a microbial enhanced oil recovery (MEOR) project conducted by Wintershall and BASF.
Overall nutrient development and planning of a single well field trial (huffnpuff, HnP) including risk management are
described. A nutrient solution is tailored to stimulate growth and metabolite production of a reservoir community of various
indigenous microbial species in a Wintershall operated oil field with challenging reservoir characteristics, including high
salinity (160,000 ppm). Up-scaled imbibition experiments performed with sandstone cores using MEOR-oil systems are
compared with injection brine-oil systems and assessed for the implications on incremental oil. The results of sandpack and
coreflood experiments performed with optimized nutrient solutions are discussed regarding incremental oil recovery and
responsible EOR mechanisms. A MEOR modelling concept developed using STARS/CMG is used to estimate additional oil
production under various feeding strategies after the calibration of the EOR mechanisms assigned.
As the laboratory and numerical works have indicated the feasibility of the MEOR field application, emphasis has been put on
risk issues ranked in the register of the project. The key risk is potential souring of the reservoir due to the activation of the
sulphate reducing bacteria (SRB) growing on the metabolites generated by the MEOR target community. Conventional
mitigation measures have been tested in short and long-term experiments. An innovative solution had been developed to assure
H2S free application without any consequences to the reservoir and to the MEOR application.
A single well pilot application is planned in a pre-selected well of the Wintershall field studied with two main objectives: (1)
proof of the concept of risk mitigation and (2) stimulation of growth and metabolite production. Identification of operational
issues as well as data gathering to improve the forecasting methods towards full-field predictions are secondary objectives. A
monitoring plan has been initiated to establish a baseline in terms of microbiological and petro-dynamic parameters.
Temperature and volumetric distributions have been predicted based on the results of an injectivity test performed in the well.
The data is used to design the HnP operation and the surface setup for the injection rate of 100 m3/day nutrient solution under
well-defined conditions.

Introduction
The abundance of the published/presented and submitted papers on Microbial Enhanced Oil Recovery
(MEOR) to related journals and conferences is a clear indication of its continuing actuality. Its economical
feasibility is the obvious reason; another one is the progress in its understanding and prediction with the
help of the related science especially microbiology. The classical introduction to MEOR is to mention its
history starting almost at the same time as modern reservoir engineering. The use of microbes for oil
production was suggested in 1927 by Beckmann and the first systematic research on the subject was made
by ZoBell in the late 1940s leading to a patent. Soviet scientists also contributed on the early development
of MEOR until the 1980s (Donaldson et al., 1989). A significant increase in research on MEOR has been
observed after 1980. The trend is still upwards and it can be estimated that it will continue due to the
current situation in oil prices.
2 SPE-179580-MS

The objective of EOR methods is to recover more oil. Since mid of the recent century, many EOR
methods have been proposed, developed and applied. Obviously, two prerequisites for the application of
EOR in a field are technical and economical feasibility. There are many new ideas and technologies
proposed for EOR, however, the implementation of EOR is closely related to the demand of oil and thus
to the oil price. Many papers report on why and how MEOR may produce more oil (Jackson et al., 2014,
Kaster et al., 2012). Also, many publications discuss successful field results (Gao and Zekri, 2011).
Maudgalya et al. (2007) provide an excellent overview of the MEOR works up do date. However, MEOR
is still cited among other EOR methods as a marginal tertiary production technology. A potential reason
for that seems yet to be its image as a black box technology and its very strong dependency on other
disciplines, primarily on microbiology.
However, technology developments strengthen the position of MEOR as an economically viable
application option. In general, EOR is capital intensive, primarily due to high injectant costs. The cheapest
injectant for producing oil is water. Many of the EOR technologies are only applicable when the price of
oil is higher than US$ 30-40 per barrel. However, MEOR can be economic for the oil prices as low as
US$ 10 per barrel, provided that it is designed and applied properly.
Wintershall and its mother company BASF decided to jointly develop MEOR several years ago. The
project was considered in the innovation pipeline of Wintershall-BASF in early 2008 and after two years
of learning, idea generation and consulting, it was decided to support MEOR as one of the principal R&D
projects. The main reasons for this selection are its suitability for the mature fields of Wintershall due to
low-cost CAPEX and OPEX and its innovation perspectives, in addition to the capabilities on research
and development in the area of oilfield microbiology.
This paper provides an update on a MEOR project conducted by Wintershall and BASF. Planning of
HnP test including risk management and preliminary results are described.

MEOR Studies in Wintershall; Methodology

For several years, Wintershall and BASF have been conducting a collaborative R&D project in order
to (1) understand the interplay between microbiological, physical and chemical phenomena during
MEOR, (2) develop nutrient formulations to stimulate the microbial activity to enhance oil recovery and
define key reservoir and process parameters for the implementation of a field trial, (3) improve the
screening methods and methodology for MEOR applications and (4) commercialize the methodology for
the application in mature fields of Wintershall and/or its partners. The project was initiated with a literature
survey, followed by active sampling of injection and production fluids from mature oil fields of
Wintershall. This activity gave a challenging opportunity to discover natural microbial flora in reservoirs,
which had been poorly studied until now, and it helped to delineate reservoir conditions in terms of MEOR
applicability. The list of the fields and technical feasibilities according microbiological analysis is given
in Table 1. This analysis demonstrated promising microbiological activity for a MEOR technical
feasibility in three of the reservoirs analyzed. As can be considered from the table, the critical parameter
for the MEOR applications seems to be temperature rather than salinity. The field A was selected for
further analysis in terms of MEOR.
The project was divided into a usual EOR study structure emphasizing five work packages as described
in Alkan et al., 2014. The first work package was the microbiology study as common for all MEOR
projects. This topic is mainly conducted by BASF. The microbiology work package of the project consists
mainly of the following stages: sampling, cultivation and enrichment of microorganisms, characterization
of microbiological communities, optimizing the feeding strategies and defining EOR effects with batch
experiments. The second work package was devoted to dynamic tests including sandpacks and corefloods
to screen and to evaluate the dynamic performance of the microbial consortia stimulated by various
nutrient solutions. As no commercial simulator is able to model the MEOR effects, the third work package
covered the development of a numerical simulator. The implementation of the numerical modelling into
reservoir simulator CMG STARS was another task of this work package. In the fourth package, the
SPE-179580-MS 3

simulation of the field pilot is planned. The planning and execution of a field pilot is the last work package
of the MEOR Studies.
Table 1 Wintershall fields screened for MEOR based on microbiological analysis

Field Temperature C TDS*, g/L Technical Feasibility

A 35-40 160 High
B 50-55 180 High-Medium
C 78-82 100 Low
D 80-82 130 Low
E 50-55 <1 High
F 80-85 40-60 Low
*Total dissolved salts

Microbiology
Cultivation and enrichment of microorganisms
In order to find a bacterial community with MEOR potential, original injection water from the reservoir
is sampled under sterile and anoxic conditions at the field site and shipped immediately to the laboratory.
For cultivation of anaerobic microorganisms, anoxic injection water (100 ml) is filled into serum flasks
with a total volume of 200 ml under anoxic and sterile conditions. The water is supplemented with
100 mM MES (2-(N-morpholino) ethanesulfonic acid) buffer (anoxic, sterile filtered) and pH is adjusted
to the corresponding reservoir brine pH. The bottles are closed with butyl rubber stoppers and crimped.
Different anoxic and sterile nutrients are supplied to the bottles with sterile syringes and bottles are
incubated at the reservoir temperature without shaking. The growth is monitored by measuring optical
density (OD600) and metabolite production via HPLC (high performance liquid chromatography) or GC
(micro gas chromatography). The following carbon sources have been tested to stimulate bacteria: sucrose,
glucose, fructose, molasses, sugar syrup, whey extract, glycerol, acetate, polymer mix and casaminoacids.
Sucrose in combination with yeast extract showed good and reproducible growth and therefore this
nutrient combination was chosen for further experiments.

Characterization of MEOR community

The obtained enrichment cultures were analyzed for optimal growth conditions and metabolite
production and were identified as follows: DNA (Deoxyribonucleic Acid) was isolated from the
enrichments after 10 days of incubation and with 16S rDNA analysis via 454 sequencing, the identity of
the organisms could be revealed. Most enrichments contained more than one species but in all cases
dominated by strictly anerobic, fermentative bacteria commonly found in high-salt reservoirs (Oren 2014).
A typical composition of the bacterial community of the field studied after 10 days of incubation is shown
in Figure 1.
4 SPE-179580-MS

Halanaerobiaceae
Halobacteriodaceae
Others

Figure 1 Composition of the bacterial community after 10 days of incubation of original injection water amended with
sucrose and yeast extract

During incubation, a drop in pH is observed. This is due to the bacterial formation of organic acids,
especially formate and acetate but also butyrate and occasionally lactate that can be detected after 4 days
(Figure 2). Furthermore, ethanol is produced in significant concentrations during bacterial fermentation.
The metabolites are produced very fast over the first few days onto a stable concentration level. Gas
production was measured in the headspace and CO2 and H2 production was observed. The total amounts
of the single metabolites produced may vary because of natural fluctuations in the bacterial cell number
and/or community in the original injection water. Still, in all cases a fast and reliable consumption of
sucrose with the concurrent increase in biomass and metabolites was observed.

6 Sucrose Formate Acetate Butyrate Ethanol

5
Metabolite Amount [g/L]

0
0 4 7
Time [days]
Figure 2 Metabolite production during growth of MEOR community incubated at 42C with sucrose and yeast extract;
sucrose consumption, acid and alcohol production shown over time

Optimizing the feeding strategies

In Figure 3, a typical growth curve of the halophilic community grown with sucrose and yeast extract
can be seen. Highest OD600 is reached after ~46 hours and slowly decreases afterwards. Cell enumeration
via MPNs (most probable number) indicates a maximum cell number of ~2x1010 cells/mL. Sucrose is
completely consumed by the cells after 3 days with a maximum rate of 0.2 g sucrose per hour in the used
100 mL setup. pH decreases from 6.3 to ~5.7.
SPE-179580-MS 5

7 1,8

1,6
6
1,4
5

Optical density [OD600]

1,2
pH / Sucrose [g/L]

4 1,0

3 0,8

0,6
2
sucrose 0,4
pH
1
OD600 0,2

0 0,0
0 20 40 60 80 100 120 140 160 180
Time [hours]
Figure 3: Growth characteristics of MEOR community during incubation with sucrose and yeast extract at 37C.

EOR mechanisms
Additional oil recovered by MEOR is subject of various papers and research projects. In some papers,
new concepts are attributed to MEOR (Kowalewski et al. 2006, McInerney, Nagle, and Knapp 2005). This
is due to the additive combination of various EOR mechanisms. In the field studied, following effects
have been determined to be primarily important during MEOR:
1. The change of the viscosity of the oil and water phases
2. Wettability change
3. Bioplugging
4. Change of interfacial tension (IFT)
The combination and degree of these effects are depending on the following factors:
o Dominant microbial community
o Nutrient composition and feeding strategy
o Reservoir thermodynamics
o Injection characteristics
A discussion on the EOR effects observed for the field studied after the nutrient feeding is provided in the
following chapters.

The change of the viscosity of the oil and water phase

An improvement of mobility ratio in the reservoir is due to the increase of viscosity of the aqueous
phase and/or the decrease of the viscosity of the oil phase assuming that there is no beneficial change in
relative permeabilities. The rheology of the aqueous phase in the presence of nutrients is investigated
during the growth of the MEOR microorganisms. The viscosity of the aqueous phase after MEOR
treatment shows slightly pseudoplastic rheology which can be an advantage in the reservoir in terms of
conformance control. Some of the measurements were performedwith cell-containing fluid samples while
some of the measurements were performed with cell-free, filtered samples (0.2 m pore size). In both
cases, a significant increase in viscosity in comparison to formation water was observed. The reason for
this is that the bacteria are producing exopolymeric substances (EPS) e.g. polysaccharides during growth,
which are secreted in the surrounding medium. Figure 4 shows an overview of the viscosities measured
at shear rate 7 s-1 for the incubation period between 4 and 7 days where the microbial activity is at its
maximum. A trend due to various measurement procedures (with cells/filtered) is not a priori. A challenge
6 SPE-179580-MS

in improved rheology of the aqueous phases is its stability over time. For the measurement given in the
Figure 5, the viscosity reached its highest value at the 7th day of incubation. After the 8th day, it decreases
slowly reaching half of its maximum after 50 days in the reservoir. This is an obvious issue for the
reservoir engineering design of the field applications.
In a MEOR treatment, it is known that various byproducts may lead to a change in oil viscosity. Gases
and alcohols are metabolites formed by the bacteria after nutrient additions and those metabolites
(especially CO2) can dissolve into the oil and reduce its viscosity. Changes in the composition of the oil
and its physical properties as a result of microbial activity are already reported in the literature. According
to laboratory as well as field applications, after microbial treatment, the ratio of low carbon number
alkanes to high carbon number alkanes increases and viscosity decreases (He, et al., 2003; Wankui et al.,
2006). There is also geochemical evidence that suggests that low molecular weight alkanes may be derived
from fatty acids in certain oil types, thus creating an oil phase with lower viscosity (Hinrichs et al., 2006).
In our batch experiments performed with dead oil and various combination of MEOR fluids and bacterial
communities, a significant reduction in oil viscosity was observed in the case of oil combined with nutrient
and bacterial community (Figure 6). As can be concluded from the figure, the mixing of grown metabolites
only with oil does not make any change; the cells are clearly playing a role in decreasing the oil viscosity.
On the other hand, in our MEOR formulation, microbial growth and metabolism results in CO2 and H2
production. The gas amount varies between 30 and 80 mol/L depending on the nutrient concentration
with approximately 80% being CO2. With the assumption that this amount dissolves directly into the oil,
a reduction of the viscosity of the oil phase of up to 3 cP could be achieved, significantly contributing to
the oil mobility. The assumption that CO2 directly dissolves into the oil is an acceptable one, as the CO2
is generated at pore level in close proximity of in-situ fluids. Additionally, the solubility of CO2 in oil is
approximately 6-7 times higher than its solubility in water with given salinity; thus the CO2 will most
likely dissolve preferentially in the oil phase. Viscosity measurements conducted at reservoir pressure and
temperature by mixing reservoir oil and corresponding amounts of CO2 support this statement.

25
Apparent Viscosity @ 7 s-1 [mPa.s]

20

15

10

0
1 2 3 4 5 6 7 8 9 10 11

Figure 4 Measured viscosities of the grown culture after 4 to 7 days at a shear rate of 7 s-1 with a co-axiale cylinders
rheometer (horizontal axis: number of experiment).
SPE-179580-MS 7

12

Apparent Viscosity @ 7 s-1, [mPa.s]

10

0
0 20 40 60 80 100 120
Time [days]
Figure 5 Measured viscosities of a grown culture at 37C as function of time at 7 s-1.

48 1 week 9 weeks 25 weeks

47

46
Oil Viscosity [mPas]

45

44

43

42

41

40

39
Oil+IW Oil+Nutrient Oil+Nut+MC Oil+Metabolite Oil

Figure 6 Effect of the metabolites on the viscosity of oil. IW = Injection water; MC = microbial community

Wettability change
Wettability alteration is always considered as one of the MEOR effects leading to additional oil. To
investigate the potential of wettability alteration and its magnitude, imbibition experiments were
performed with sandstone cores having various petrophysical properties and initial states i.e. nutrients
with different concentrations, cells in the cores and/or in surrounding solutions. Amott type glass flasks
are used and reservoir temperature is applied. The recovery is compared with experiments performed with
sterile formation water. Obviously, thereby only an indirect measure of a potential change in wettability
is achieved as the released oil is a function of other factors like IFT, permeability and gravity. However,
if these factors are kept constant, wettability can be considered as the influencing parameter. More than
150 experiments were performed using different combination of settings. The data are scaled based on the
formulation proposed by Li and Horne, 2002, which means normalizing the recovery in terms of all acting
8 SPE-179580-MS

parameters. The advantage of this model in comparison to other approaches is that it considers all the
influencing effects of permeability, porosity, capillary pressure, wettability and the gravity on the
spontaneous imbibition. They derived a dimensionless time (with almost all the parameters) and a
normalized recovery for an oil-water-rock system:

k e Pc ( S wf S wi )
*

td = c d t
e L2c (1)
And

R * = cR (2)

Where c is the ratio of the gravity force to the capillary force:

a0
c=
b0 (3)

The effective mobility Me=ke/e and the capillary pressure Pc were defined directly at the saturation of
imbibition water front and the dimensionless time includes all important parameters that can be
involved in the MEOR effect. With respect to the linear correlation between the imbibition rate and the
reciprocal of the recovery by spontaneous imbibition, the parameters 0 and 0 could be obtained.
Therefore, the capillary pressure and the effective mobility ratio can be calculated with these constants
and the approach of scaling the dimensionless time versus the normalized recovery can be applied.
Figure 7 shows a result of a couple of experiments scaled with the approach given above. Three sets of
experiments are shown in the figure. Experiments performed with normally applied nutrient concentration
are noted 1C and the experiments in which doubled nutrient concentration are used are noted 2C. An
experiment conducted using sterilized formation water as aqueous phase is also shown in the figure. Dead
oil from the studied field was used in all experiments and diluted with hexadecane to obtain comparable
viscosities to the oil at reservoir conditions. As can be seen from the Figure 7, the normalized recovery in
the MEOR setup is higher (55 65% OOIP) than in the sterile case (~35% OOIP). No consistent difference
between the two nutrient concentrations is observed. The jump in the imbibition curves begins
approximately at the first day and the recovery reaches the highest value at the third day. It should be
noted that the growth of the objective community under defined feeding strategy is always occurring in
the first 2-3 days (as shown in Figure 2) and therefore growth matches the imbibition curves.
In Karimi et al., 2012 both macroscopic and microscopic approaches are provided to investigate the
wettability alteration induced by bacteria and microbial formulations. One of the conclusions of this work
is that bacteria use organic compounds to adsorb on the glass surfaces during the aging process and
partially or totally remove the thin adsorbed oil film. Subsequently, there is a shift towards a more water
wet state. This is in line with our findings in imbibition experiments. The metabolites alone without cells
make no significant difference in imbibition, on the other hand, the presence of the cells in the core (cores
prepared with non-sterile formation water) accelerate the imbibition behavior. This is a strong indication
of the wettability effect of the growing bacteria as a result of the MEOR treatment. More work consisting
of imbibition experiments and contact angle measurements with materials of various wettability are being
done to be able to better explain the physical reasons of the phenomena.
SPE-179580-MS 9

Figure 7 Scaled results (according to Li and Horne, 2002), of three sets of imbibition experiments all conducted at 37C

Bioplugging
It is consensus that bio-plugging can be the most efficient EOR mechanism within MEOR and in a
previous paper, the results of the experiments performed in micromodels (Alkan et al., 2014) were
presented as direct experimental confirmation of the potential bioplugging in the field formulation studied.
Further micromodel experiments are conducted with various designs mimicking porous media. The
conformance control is especially important for the reservoir under study as it exhibits a high degree of
heterogeneity so we are trying to understand this effect with additional experiments.
Jackson et al., 2014 report on a dramatic improvement in oil recovery when a biofilm treatment was
used to modify the permeability of the highest permeable tube in a set of composite slim tube experiments.
It is reported that despite the high permeability contrast in this composite slim tube set up, substantial oil
was recovered from the slim tube with the lowest permeability. Such kind of experiments are difficult to
apply for MEOR formulations because of the generated gases which result in three phases in the porous
media (water, oil, gas) making the interpretation of the results extremely difficult. Therefore, the focus of
this study was mainly on direct measurement of the formation and geometry of the biofilm and cell
attachment on the pore surfaces creating reduction in the permeability. Bacterial growth was investigated
in both batch cultures and under dynamic conditions. To visualize cell adhesion and also biofilms, specific
fluorescent dyes were used. In batch experiments with high concentrations of nutrients, agglomeration of
cells was very distinct after three weeks, with cell clumps reaching a diameter of up to ~70 m. The cell
clumps were mostly loosely associated to the sand particles. Up to this time point, mostly single cells were
visible in the medium, whereas after four weeks of incubation, many cells were observed being attached
to the surface of some particles. With low nutrient concentrations the adsorption of the cells onto sand
surfaces was much more pronounced throughtout the incubation time of four weeks.
The slow decrease of the nutrient concentration with a concurrent increase in produced metabolites
observed in batch experiments was simulated in a continuous loop of a sandpack setup to investigate EPS
formation and cell attachment. Good growth was observed inside the column with highest activity between
day 3 and day 6. Cell numbers of the fermenting community increased from ~1.106 cells/mL to ~8.108
cells/mL at day 7 in both the lower and upper part of the column. After 28 days, the column was opened
10 SPE-179580-MS

and samples for fluorescence microscopy and Scanning Electron Microscope (SEM) were taken from
various parts of the column. Using SEM, we saw that the bacteria directly attached to the sand particles
throughout the sand column (see Figure 8). Details of this work are given by Klueglein et al., 2016. Such
visual observations supported by the experiments performed in micromodels mimicking simplified pore
structures, confirms the expectations in terms of bio-plugging effects for conformance control and thus
oil recovery. Numerical studies using the approximated geometrical data from the above described studies
show the permeability decrease in theoretical models. A positive aspect is that the biofilm formation or
cell attachment is strongly dependent on the shear stresses. As mentioned in previous studies as well (Park
et al., 2011) at higher local velocities, biofilm formation rate decreases drastically. This is a favorable
aspect in terms of conformance control and undesired plugging around the wellbore. The biofilm is
preferentially formed in the channels with higher conductivity in which the flow velocities are lower; the
biofilm formation and cell attachment are not expected to occur near the wellbore region and low
permeability regions in a highly heterogeneous reservoir.

Figure 8 SEM pictures of the biofilm formation from the samples taken from dynamic experiments

Figure 9 shows the results of a numerical study performed with a MEOR simulator, BUGSIM, on a
generic reservoir model consisting of layers with permeabilities of strong contrast (between 1 and
1500 mD). On the left side, the oil saturation after continuous water injection of 2080 days is shown, on
the right the same model with 1000 days water injection followed by nutrient injection of 360 days and
720 days water injection. It can be concluded that in the MEOR case, a lower and more homogeneous
distribution of the lower oil phase is possible, which would result in additional oil at the end of the
production period by the plugging effect. Using reservoir models calibrated by experimental data
additional recoveries up to 10% are obtained only activating the bioplugging effect.

Figure 9 The effect of bioplugging on sweep efficiency (oil saturation) in a generic model after (left) 2080 days continuous
water injection (right) 1000 days water injection + 360 days nutrient injection after+continuous water injection
SPE-179580-MS 11

Change in Interfacial Tension (IFT)

The IFT between MEOR solutions and oil are measured by using a state of the art pendant drop
tensiometry with some limitations caused by the turbidity created by the cells and metabolites. These
measurements together with the IFT between formation water and oil from the reservoir studied are given
in Figure 10. The oil phase constitutes from the dead oil from the reservoir studied with a viscosity of
40 mPa.s. As can be concluded from the figure, the IFT between nutrient solution and oil is about
25 mN/m for both concentrations used in the measurements, but slightly lower for the samples with double
nutrient concentration. The value is lower than the IFT between original formation water and oil. Note
that these concentrations are equal to those discussed for potential field applications.After the third day of
the incubation, the IFT decreases down to approximately 15 mN/m or lower and stays approximately
constant. It can be concluded from the figure that the effect of the decreased IFT on the recovered oil
should be very small depending on the capillary number of the reservoir rock. The analysis of this effect
is made in detail in Alkan et al. 2014.

Figure 10 Interfacial tensions of the MEOR formulation versus dead oil at various incubation time measured by pendant
drop tensiometry.

Dynamic Recovery Experiments

To test the performance of the MEOR formulation tailored for the field under dynamic conditions,
sandpack and coreflood experiments are performed. A detailed information on these experiments are
provided in Alkan et al., 2014. Sandpack experiments were conducted in glass columns with a diameter
of 5 cm and a bed length of 30 cm with either natural quartz sand or artificial glass beads. For both types
of porous media, grain sizes of 100-200 m were used which is a common portion in natural porous media.
The relatively large dimensions of these sandpacks allow for the detection of small MEOR effects since
the resolution of the additional oil is improved. Optionally, glass columns featured ports along their length
allowing for additional differential pressure measurements or direct sampling opportunities are used.
The sandpacks were operated under anaerobic and sterile conditions at reservoir temperature (37C)
and atmospheric pressure. All fluids used were either purged with nitrogen or heated and cooled under a
nitrogen-atmosphere prior to use. Concentrations of dissolved oxygen were monitored non-invasively
using optical sensors in order to account for an anaerobic atmosphere.The differential pressure along the
length of the sandpack or chosen sections was recorded during the injection phases with an electronic
differential pressure transmitter. Microbial analysis included microbial community fingerprinting using
Denaturating Gradient Gel Electrophoresis (DGGE) as well as quantitative Polymerase Chain Reaction
12 SPE-179580-MS

(qPCR) and (fluorescence) microscopy, the cell activity was assessed via a cell viability assay targeting
the intracellular ATP molecules.
After reaching initital oil saturation Soi with oil injection, an aging period of 7 days is given. The
residual oil saturation Sor, is determined after water injection of 4 pore volumes (PV) at minimum. The
nutrient injection (minimum 1 PV) and subsequent static incubation (5-10 days) cycle is repeated up to
three times, followed by a final waterflood (minimum 1 PV). Fluid permeabilities were determined at
different applied flow rates and their corresponding differential pressures according to the Darcy Equation
under laminar and linear flow conditions for Newtonian fluids: Microorganisms were introduced into the
sandpack using non-sterile injection water in the waterflooding step. Therefore, a microbial community
similar to the planktonic reservoir community was established within the sandpack. Alternatively, sterile
injection water was used and an enrichment culture showing a good potential for MEOR was injected as
5 % inoculum along with the nutrients in the first nutrient flooding step.
In order to separate MEOR effects from experimental artifacts and from the rheological and chemical
EOR properties of the nutrient solution, control experiments were conducted.
A number of corefloods were also conducted under reservoir temperature (37C) and pressure
conditions (30 bar). Bentheim sandstone cores with a permeability of around ~2 D were used. Sterilization
of the cores took place via heating of the core in-situ in the coreholder, the remaining setup was sterilized
chemically. The experimental procedure regarding the injection patterns was similar to the sandpack
experiments.
In all dynamic experiments, a bacterial growth level similar to batch experiments is obtained. The sand
packs conducted using glass beads to mimic the porous media, gave recoveries up to 18% of the original
oil in place (OOIP). Using quartz sand for porous media reduced the OOIP from 35-40 % down to 25%
presumably due to pronounced water wetness of the quartz. Obviously, this unrealistic level of remaining
oil makes the evaluation of any EOR contribution difficult. Although there is clear indication of additional
oil recovery due to the application of MEOR, the recovery factors are less compared to glass bead
experiments being between 6 to 10%.
The recoveries of five core floods conducted with MEOR formulation vary between 3 and 5% of OOIP.
In one of the core floods, a recovery up to 11% was obtained. It should be noted that in two experiments
liquid metabolites only were injected into the cores to test their ability of recovering oil hoping to isolate
the individual mechanisms.
Evaluation of the sand packs and corefloods allows following discussion on the mechanisms and
influence of MEOR on recovering oil: The sand packs and cores are considered to be homogeneous which
means that the bio-plugging effect should not have a substantial contribution on the recovery.Yet, it should
be noted that bioplugging is supposed to be the main effect in a reservoir with sizeable permeability
variation. However, in all experiments it was concluded that a fraction of the cells remained in the porous
media; a result confirmed by the pressure difference and qPCR (corefloods and sandpacks) as well as
DAPI measurements (corefloods only) and ATP measurements alongth different lengths of the porous
medium (sandpacks only). Despite the retention of cells within the porous media, the negatively charged
quartz surface may have resulted in electrostatic repulsion of the bacterial cells those membranes are
generally negatively charged in dependency of factors such as the microbial species, ionic strength and
pH of the surrounding media (Jacobs et al., 2007). A resulting delay of bacterial adsorption to the sand
grain surfaces might also result in a slower formation of a stable biofilm. Since the reservoir mineralogy
is more complex containing significant amounts of clay and carbonates compared to the porous media
used in the lab experiments, attraction forces between cells and rock surfaces are expected to be different.
The effect of IFT is the minor one according the discussion given by Alkan et al., 2014, no quantifiable
effect is expected in such porous media material where the capillary forces play negligible role. The two
mechanisms that appear to be predominant are viscosity and wettability changes. It seems that the change
in wettability effect does not play any role in sand packs where the initial wettability (even after aging) is
strongly water wet (experiments with sand), and potentially in corefloods just a minor role. The main
mechanism contributing to the recovery is likely to be the change in the phase viscosities. Going back to
SPE-179580-MS 13

the viscosities, the reduction in oil viscosity is due to the dissolution of gas and liquid metabolites in oil.
In high pressure corefloods gas evolving from the (at start of the experiment dead) oil after releasing the
oil to atmosphere can be interpreted as an indication of gas dissolution in oil. Another indication is the
differences in pressure development observed between the experiments conducted at atmospheric and high
pressure conditions. In the experiments at atmospheric conditions, the pressure development in the core
is relatively high in comparison to high pressure experiments in which a small difference was observed as
an indication of the dissolution of CO2 in oil.
As discussed earlier, apart from a viscosity decrease of the oil phase, an increase of the apparent
viscosity of the water phase was observed repeatedly during batch incubations with a maximum after
around eight to ten days of incubation. The viscosifying effect of biopolymers was most pronounced under
low shear rates following a pre-shear: Both of these conditions might not apply to dynamic experiments
since a) the applied flow velocities (between 1-3 m/d) were slightly higher than associated reservoir flow
leading to higher shear rates on a pore level and a) appropriate pre-shear is not given due to the restricted
length of the sandstone cores and sandpack as well as the static incubation phases where shear is absent.
In summary, it can be concluded that individual MEOR mechanisms could partly be confirmed by the
dynamic lab experiments but are expected to be more pronounced under reservoir conditions.

Prediction of the Oil Recovery Performance

Numerical evaluation is an inevitable part of a field application. Numerical work is being performed
via lumped as well as discretized models. The model of Bryant and Lockhart (2002) is used to describe
the reaction engineering constraints in order to optimize the inoculation versus residence time. The
necessary input data are provided by growth curves obtained by feeding nutrients to defined
microorganisms of the corresponding reservoir. The prediction of the production performance of the
planned field pilot is performed by the numerical implementation established and validated by Wintershall
using STARS/CMG as the supporting tool (Alkan et al., 2015). The new MEOR model is calibrated with
laboratory data including growth curves, measured metabolite properties and dynamic experiments, which
are later up-scaled for the field pilot. The following EOR effects are considered: changes in both water
and oil phase viscosities, decrease in IFT and bio-plugging. Sensitivity runs performed on a 5-spot
injection pattern generic model of the field chosen for the pilot show that the dominating effect on
additional oil recovery would be the flow diversion by the plugging preferential water injection paths
through microbial growth. Table 2 provides a list of the contributing mechanisms with their calculated
recoveries for an injection strategy of injecting 0.3 PV nutrient solution following a water injection period
of 4 years. The traffic light notation indicates, how high the recovery factor is above the waterflooding
case: The green light for cases with recoveries greater than 5, yellow for RF in the range of 3.5 till 5, red
for cases below 3.5 till 2 and black for cases with recovery less than 2.After the nutrient injection which
takes 100 days, a water injection of four years is repeated.
For the viscosifying effect in the water phase and bio-plugging, minimum and maximum measured
and/or observed values from the laboratory works were applied as various scenarios. The polymer and the
plugging effects were noted as polymer 12 and 23 and plugging 10 and 100, corresponding to the minimum
and maximum values measured respectively evaluated. The minor effects of IFT reduction and effect of
CO2 on oil viscosity can be concluded from the Table 2 when they are applied independently. It should be
noted that the CO2 effect is based on the minimum measured CO2 generation value being 30 mol/L of
nutrient solution. Also, the potential decrease in oil viscosity due to mixing with liquid metabolites is not
considered in the modelling. With the applied feeding strategy, the ultimate recovery reaches to 8%
approximately by using the effects at their maximum. The recovery is calculated to be approximately 6%
when the applied effects remain at their minimum. The calculations are repeated with various injection
strategies by actualizing the measurements when necessary.
With the results from the simulations and having the modest CAPEX and OPEX being confirmed
especially in the latest phase namely preparation of the pilot, a unit price of approximately US$ 10/bbl
14 SPE-179580-MS

additional oil appears to be likely. A net present value calculation performed for the field studied with the
assumptions of a constant oil price of US$ 40/bbl and an additional recovery of only 5% resulted in a
value of 15 Mio US$ for an application of 20 years.

Table 2 Results of the runs performed with 5-spot generic model with isolated and combined EOR effects

WF Waterflooding

Independent Effects
1 Polymer23
2 Polymer12
3 IFT
4 CO2
5 Plugging 10
6 Plugging 100
7 Polymer23 + SR

Combined Effects
Two
8 Polymer12 + IFT
9 Polymer12 + CO2
10 Polymer12 + Plugging 10
11 Polymer12 + Plugging 100
12 Polymer23 + Plugging 100 + SR
13 IFT + CO2
14 IFT + Plugging 10
15 IFT + Plugging 100
16 CO2 + Plugging 10
17 CO2 + Plugging 100

Three
18 Polymer12 + IFT + CO2
19 Polymer12 + IFT + Plugging 10
20 Polymer12 + IFT + Plugging 100
21 Polymer23 + IFT + Plugging 100 + SR
22 IFT + CO2 + Plugging 10
23 IFT + CO2 + Plugging 100

All
24 Polymer12 + IFT + CO2 + Plugging 10
25 Polymer12 + IFT + CO2 + Plugging 100
26 Polymer23 + IFT + CO2 + Plugging 100 + SR

Risk Issues/Management
In the early stages of the project, a risk register was prepared. This has been continuously maintained
during the course of the project. Following technical risks were determined to exhibit high risk for the
continuation of the project:

o Reservoir souring due to the potential activation of SRBs

o Well not suitable for the pilot
o Plugging of the near wellbore portion of the reservoir by extensive growth of bacteria
o Insufficient growth of bacteria in the reservoir
o High adsorption of the injected nutrients on the reservoir rock
o Microbially Induced Corrosion (MIC) due an extended application in the field

These risks have been studied extensively especially in the last year of the project approaching the pilot.
The well bore integrity test was performed with ultrasonic Imaging Tool (USIT) which showed severe
integrity problems due to corrosion below 600 m depth in the well. The well had to be worked over causing
SPE-179580-MS 15

a delay in the execution of the pilot. A second post job USIT measurement confirmed the successful re-
establishment of well integrity.
The likelihood of complete plugging in the near wellbore region caused by massive growth of bacteria
is rated now very low based on an extensive literature survey and experimental studies mentioned in
related sections.
The experiments conducted with batch and dynamic experiments using representative formation
material and cores demonstrated that there should be sufficient bacterial growth in the reservoir. New
insights on the bacterial growth will be gained during the pilot, where samples will be taken after the
incubation period.
Static adsorption tests performed with representative amount of reservoir rock on the basis of specific
surface area did not show significant loss in nutrient concentration due to the adsorption on the rock. It
should be noted that the clay content is relevant for adsorption. The mineralogy of the reservoir area where
the well for the pilot was selected, shows a clay content lower than 5% and therefore should not cause any
significant adsorption problems.
The quantification of MIC was decided to be investigated as part of the pilot as it has no direct
implication to the in-situ performace.
In the risk management of the project, the main focus has been on the potential souring due to increase
of H2S generation in the reservoir. It is very well known that microorganisms may play an important role
in the transformation of sulfur in its various oxidations states. The relevant example of this cycle in the
oil industry is the biogenic production of H2S. Toxicity of H2S, accelerated corrosion of pipelines,
production and processing equipment, and decrease in efficiency of secondary oil recovery due to
plugging of the oil bearing strata by biomass and precipitated metal sulfides are some of the problems
associated with reservoir souring. Furthermore, the necessity for the removal of H2S prior to the sale or
use of oil and gas, as well as before recycling of the produced water increases the cost of production. The
generated H2S first dissolves in the produced phases and thus is transported to the surface.
Thermochemical sulphate reduction and dissolution of sulphidic components of the reservoir rock are
considered as one contributing factor (Tang et al. 2009). However, sulphate-reducing bacteria (SRB) are
believed to be the major players in souring of oil reservoirs. As SRBs have also been detected in the both
formation and injection waters in addition to 4 mM sulfate present in the reservoir brine, a risk contingency
plan against the H2S generation had to be developed before starting the pilot in the selected field.
Successive and multi-disciplinary analysis show that the carbon sources, which will be injected as
nutrients for the identified beneficial microorganisms in the studied field, can play a critical role in the
reservoir ecology. It is observed that organic acids produced during microbial sugar conversion (acetate,
lactate, formate) may be a substrate for SRBs initiating natural souring due to H2S production. Nitrate
(sodium nitrate) as well as some other chemicals (i.e. molybdate) were tested as potential mitigating
chemicals as the classical mitigation using biocides is no option for MEOR.
Nitrate is currently often used as inhibitor against H2S formation. Typically, nitrate provides more
energy than sulfate when used as a bacterial electron acceptor and promotes the growth of nitrate-reducing
bacteria (NRBs) which out-compete SRBs. There are many examples of successfully using nitrate in oil
fields (Arensdorf et al., 2009, Kuijvenhofen et al., 2007).
Having studied the existing literature, nitrate was selected as the first chemical to be tested under
laboratory conditions. However, it was soon realized that adverse effects of nitrate are especially iron and
calcite precipitations and furthermore unreliable NRB activity.
Because of the significant negative side effects of nitrate in our system, we were challenged to find a
different H2S inhibitor. Other known inhibitors were tested, including tungstate and molybdate.
Molybdate was been found to be a cheap and reliable solution during our experimental trials. Figure 10
shows the inhibition of H2S as function of the molybdate concentration combined with our MEOR nutrient
mix. A final concentration 0.1 g/L of molybdate was chosen to be injected into the reservoir together with
the nutrient solution. Here it should be noted that this amount of molybdate has no negative effects on the
MEOR properties and no mineral precipitation was observed.
16 SPE-179580-MS

800

700 0,1
0,05
600 0,025
0
500
H2S [ppm]

400

300

200

100

0
0 10 20 30 40 50
Time [days]
Figure 10 Effect of molybdate concentration (g/L) on the H2S generation in the field studied.

Proof of Concept; Field Pilot

The proof of concept of the methodology and formulations developed is realized in two steps: the first
one is a small scale HnP and the second one a multi-well test (or a larger HnP) in the same field. The field
is located in Northern Germany and is a sandstone reservoir with a shale content gradient increasing from
east to west, producing since mid 1950s. The current average water cut is around 96% with a recovery
factor calculated to be 43%. The general reservoir characteristics of the field as well as the main chemical
components of the injected water are given in Table 3. A 60 years old production well with a perforation
depth around 950 m has been assigned for the pilot test.
The small scale HnP is intended to verify the developed feeding and mitigation strategy targeting the
main risk of potential souring. As indicated in the sections above, all MEOR applications should consider
the potential activation of SRBs causing H2S production and subsequent souring of the reservoir. This is
especially important if the formation water naturally contains sulfate or sulfuric species. As this pilot is
designed as HnP and negligible mixing of injected water with formation water is expected, the
characteristics of injection water had to be also considered. Although the injection water is comparable to
reservoir water in terms of microbiological and chemical composition, the 66.5 mg/L sulfate content is
slightly higher than the content in the original reservoir brine. In addition to that, the presence of the SRBs
in the injection water was confirmed by laboratory experiments. The secondary objective of the HnP is to
warrant the growth of the target MEOR bacteria consortia in the reservoir, which has to be stimulated and
actived to show metabolites and therefore MEOR effects. Oil mobilization is not a focus in this trial.
The plan of the HnP is to inject 400 m3 nutrient solution into the reservoir over several days with a
subsequent shut-in period of 10 - 15 days to allow sufficient incubation time for the bacterial community.
The back-produced water will be microbiologically and chemically analyzed. To be able to detect
differences caused by the nutrient injection, baseline measurements prior to the field test are indispensable.
For this, samples of both the injection water and the production water have been taken on monthly basis
starting half a year prior to the field test. The waters are analyzed for both chemical (pH, redox potential,
dissolved organic carbon (DOC), iron and salt content, gasses and organic acid content) and also
microbiological parameters (optical density, cell numbers of several metabolic groups (MPN), bacterial
identity and bacterial activity (ATP)). Some other parameters monitored are: ionic composition, particle
numbers, water cut and cell numbers of different metabolic groups on DNA level (qPCR). Three month
before starting the field test, the baseline samples are taken twice per month to closer investigate possible
SPE-179580-MS 17

natural fluctuations. Especially important is to monitor the natural occurring amount of H2S in the water
to permit distinction from potentially newly formed H2S during our field trial. Fluctuations in both
injection and production water have been low so far for both, chemical and microbial parameters. In the
injection water, small amounts of organic acids were seen and H2S could be only detected once in the
injection water (data not shown).

Table 3 Reservoir and injection water characteristics of the chosen Wintershall field in Northern Germany

Property (Unit) Measurement

Brine
Density (kg/m3) 1110
Salinity (g/L) 155
Viscosity @ 37C (mPa.s) 1.18
Oil
Density @ atm pressure (kg/m3) 880
Viscosity @ atm pressure (mPa.s) 40
Viscosity @ res. pressure (mPa.s) 25
IFTwo @ 37C (mN/m) 40
Reservoir
Initial temperature (C @ 750 m tvdss) 37
Current pressure (bar @ 750 m tvdss) 30
Bubble point (bar) 37.6
Major injection water components (mg/L)
Iron 86
Sulfate 66.5
Phosphate <2
Nitrate <1
Calcium 14000
Sodium 45900
pH 5.7

An injectivity test was performed prior to the application in the same well in order to evaluate the near
wellbore characteristics as well as for the selection of some parameters of the planned surface (e.g. filters).
The permeability, skin and potential boundary effects were obtained by pressure transient anaylsis. No
significant issues for the planned operation have been found. As additional quality control for the HnP
heavy water (deuterium oxide, D2O) is used as tracer premixed with the nutrient. Deuterium is a non-
radioactive isotope of hydrogen. The injected fluid is dosed with 100 ppm D2O; a concentration allowing
better interpretation of the production of the injected amount of nutrient solution after the incubation
phase.
Another challenge regarding the application has been the reservoir temperature distribution around the
wellbore. This is valuable information as the growth of the bacteria is strongly depending on the
temperature in the reservoir. As can be seen from the Figure 11, the microbiological activity of the
objective community is optimal at near initial reservoir temperature and decreases significantly when
incubated below 30C.
The injection water temperature is approximately 15C. Although some heating of the injection water
will occur in the wellbore and in the reservoir, the lower injection temperature causes a cooling down
18 SPE-179580-MS

effect in the near-wellbore region resulting in poor growth of the bacteria. To quantify this effect,
numerical studies were conducted. The properties of the wellbore and the reservoir section were coupled
with the parameters of the planned injection. The first step was to calculate the heat transfer in the wellbore
in order to estimate the temperature of the fluid entering the reservoir at the bottomhole. The calculated
value matched very well the temperature measurements during the injectivity test. The second step was to
calculate the cooling down effect and its extent into the reservoir. It was determined that after the injection
period, a radius of approximately 4 m will cool down to 26C and this reservoir portion remains at this
temperature during the incubation period. This is due to the fact that the rock has already reached the same
temperature as the water, which means that there is no heat transfer from the matrix into the water
anymore. Beyond the 4 m radius, the temperature transitions towards original reservoir temperature
(~42C @ sand face in this well) with a very strong gradient. Various simulators were used to check the
validity of the results. The calculated lower temperature very near to the wellbore is critical for the growth
of bacteria. However, it holds only a small portion (about 10%) of the total injected fluid. It was concluded
that this is negligible and no precautions for heating of the injected fluid at surface were taken.
The surface facilities for HnP have been designed and constructed considering the existing hardware
at the wellhead. The injection water is provided from an injection line nearby. The concentrated nutrient
solution will be mixed with the injection water at the designed ratio using a dosage pump and a static
mixer. The resulting solution will be injected into the reservoir with a pump at given rate. The size of the
filters were selected to allow the bacteria passing through.
6,E+05
20C
25C
5,E+05
30C
37C
4,E+05
40C
ATP [RLU]

3,E+05

2,E+05

1,E+05

0,E+00
0 2 4 6 8 10 12 14 16 18
Time [days]
Figure 11 Bacterial activity (ATP) during growth at different incubation temperatures

Conclusion
An update of the ongoing Wintershall-BASF project on MEOR is provided. Following conclusions can
be drawn from the current status of the project:
Recent laboratory measurements confirmed previous data on the individual mechanisms of the
MEOR concept developed for the Wintershall oil field studied. As known from literature, the
additional MEOR recovery is due to the combined effect of these mechanisms (IFT reduction,
plugging, wettability change, etc.). Based on numerical modelling studies using generic models
calibrated with data from the laboratory, the incremental recovery due to MEOR can be as high as
8% of OOIP for the field studied.
The risk issues in potential field applications have been studied and managed. The main item was
the reservoir souring as a result of H2S generation in the reservoir under MEOR nutrient addition.
An innovative solution is now being used as part of the MEOR feeding strategy. Laboratory results
SPE-179580-MS 19

from both, short as well as in long term experiments confirm successful mitigation of souring risk
using this strategy.
The field pilot is a small scale HnP in a selected well in the field studied. The recompletion of the
well followed by an injectivity test have completed the preparation of the well. The test will be
performed in the near future to test the MEOR feeding and H2S mitigation strategy. The pre-test
surveillance has been started to establish the baseline.
The cost of the nutrients as well as of the surface facilities to be used in the planned pilot show the
obvious advantage of MEOR. The economic analysis prove that MEOR is feasible considering the
costs to be as low as US$ 10/bbl additional oil in case it is planned and applied properly. The field
specific feeding strategy as well as risk management are the crucial issues.

Acknowledgement
The authors appreciate the technical support provided by D. Burkhardt, A. Fingerle, G. Glaser, S. Emig,
H. Platsch and S. Reimann. The valuable discussions with F. Visser, A. Behr, M. Amro and F. Bruns are
also appreciated.

Nomenclature
tD = dimensionless time used in this study
c = constant, ratio of the impact of gravity and capillary forces defined by the constants a0 and b0
a0 = coefficient associated with capillary forces, M/T
b0 = coefficient associated with gravity, M/T
ke = effective permeability of the two phases at Swf (considered as one phase), L2
= porosity
Pc*= capillary pressure at Swf , M/LT2
Me*= effective mobility of the two phases at Swf, ML/T,
Swf = water (or the wetting phase) saturation behind imbibition front
Swi = initial water (or the wetting phase) saturation
e = the effective viscosity of the two phases (considered as one phase), M/LT
Lc = characteristic length, L
R* = normalized oil (or the nonwetting phase) recovery
R = recovery by spontaneous imbibition in the units of pore volume
t = imbibition time, t

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