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BATCH 2014
Hassan Ali
M Mohtashim


M Umair Awam
Naveed Aqeel
Shakeel Ahmed
S.M Daniyal Naeem
Mashood ul Haq
Hamza Ishtiaque
Abid Hussain





Experimental setup and steps of measurement


Well A

Well B


SPE 121695

Laboratory Measurement of pH of Live Waters at High Temperatures and Pressures


This paper describes a new technique for measuring pH on live formation water samples in the
laboratory at high temperature and pressure. The technique involves adding pH sensitive dyes to
pressurized single phase water samples collected using a formation tester and spectroscopically
determining the pH in the laboratory at reservoir conditions. Due to the lack of standard
laboratory techniques for such measurements at high temperatures and pressures, current practice
involves flashing the single phase water sample to ambient conditions, analyzing the flashed
water and gas phases, and then using water chemistry models to predict pH at reservoir
conditions. Uncertainties in the thermodynamic models for formation waters at high temperature
and pressure, as well as uncertainties associated with the flash process and possible precipitation
of salts can propagate as errors into scale and corrosion models. It is proposed that the direct pH
measurement on live water samples described here be used as an additional input for the water
chemistry models to improve confidence in their predictions. This will allow for more efficient
selection of completion materials and planning for scale treatment and mitigation.
Water sampling in exploration wells is usually done to obtain information regarding the scaling
and corrosion potential of the water, understand reservoir connectivity, and establish the salinity
of the water for petrophysical evaluation. Corrosion potential of the water is important for
material selection for tubing, pipeline, and process equipment. Scaling potential is critical for the
selection of an optimal development strategy to prevent scale formation by choice of operating
conditions, to select and deploy scale inhibitors when needed, or both. Correct water resistivity is
important for interpreting openhole wireline logs accurately.


In this report, we present results of live water pH measurement technique on formation water samples
from two offshore Gulf of Mexico wells for pressures to 20,000 psi and temperatures to 242F. Results
are compared to predictions from two commercial thermodynamic models that use the flashed gas and
water analysis data as inputs. The experimental setup for pH measurement of live water samples can also
measure the sensitivity of pH to pressure and temperature. Comparison of the laboratory pH measurement
to real-time in situ downhole pH measurements made on the same formation water with a formation
tester showed good agreement. This is an example of the implementation of the chain of custody concept,
which compares a measurement made downhole with that made in the laboratory on the same sample
using the same technique, to validate the representativeness of the sample as it is transported from
downhole to the laboratory
Experimental Set Up and Steps of Measurement:
Fig. shows a schematic of the experimental set-up to measure pH of live waters at reservoir temperature
and pressure. Pressurized sample chambers are used to hold the samples (deionized water, formation
water, and the dye solution). The formation water chamber has a heated jacket to maintain it at reservoir
temperature. The high-pressure, high-temperature optical cell is fluidically connected to the sample
chambers and optically coupled to a bench-top spectrophotometer using fiber optic cables. The
temperature of the optical cell and the sample in it is controlled by the oven. The first step involves precharging the lines and the optical cell with deionized water at reservoir pressure and heating to reservoir
temperature and recording the optical spectrum. Next, the formation water is used to displace the
deionized water taking care to maintain the pressure in the system. The optical spectrum of the formation
water is compared with the deionized water spectrum to check for any suspended solids or oil drops, the
presence of which would cause the light to scatter and yield a high optical density signal. Typically the

two spectra overlay each other unless there is a slight color due to presence of ferrous ions in the
formation water. This recorded spectrum is used as the baseline spectrum for all subsequent runs. The
next step involves transferring a controlled volume of the dye solution into the formation water chamber
and mixing it to create a 7.5% v/v solution of dye in formation water. The formation water in the lines
and in the optical cell is then displaced with this formation water-dye mixture solution, again ensuring
that the pressure in the system is maintained. The pH is calculated from the recorded spectra of the
formation water-dye mixture solution as outlined in the theory section. By varying the pressure and
temperature and recording the spectra at each setting, one can obtain pH as a function of these
parameters. The optical signal is continuously monitored to detect light scattering caused by any solid or
gas coming out of solution because of change in pressure and temperature.

Laboratory set up for pH measurement at reservoir temperature and pressure

Well A
The zone of interest in Well A is a thick permeable water zone several thousand feet above the oil
productive target and is considered a potential water supply source for secondary recovery. The
actual pH conditions can have a significant impact on equipment design selection based on the
corrosion potential.
Tables 1 and 2 summarize the key details for the two samples (A -1 and A-2) collected in this zone.
The reconditioned samples were flashed to obtain the gas/water ratio (GWR) to generate a gas
stream that is analyzed by gas chromatography and a water stream that is analyzed for all the ions.
For these two samples, the dissolved gas was negligible (very low measured GWR), so no gas
composition is reported as there was not enough gas to conduct a gas chromatographic analysis.
Note the change in pH value from the immediate flash condition to room temperature at which ion
analysis is done, primarily caused by CO2 exchange with ambient air. Solid precipitation was not
observed for these flashed samples. Table 2 lists the key species analyzed for the two streams that
are used as inputs in the model predictions. The electroneutrality imbalance was less than 3% for the
two samples.

Table 1: Sample collection details and physical properties measured by flash process.

Table 2: Analysis of flashed gas and water phase at 77F

Table 3 shows the comparison of the pH measured in-situ by formation tester and the pH measured by
live water pH measurement technique. Note the difference between the pH measured by flash process and
the pH measured by live water pH measurement process, also the pH measured by live water pH
measurement process and that measured in-situ by formation tester have very small difference.

Table 3: Summary of pH measurements and model predictions for samples from Well A
Well B
The zone of interest in Well B is a water-bearing section below the oil target and considered
representative of water that may accompany oil production at sometime in the field life. Since there was
no downhole in situ pH measurement made on this sample during sample acquisition, the Chain of
Custody validation could not be implemented for this case. Another point to note is that the reservoir
pressure for this formation is 19,542 psi, which is beyond the calibrated range (10,000 psi) for the
spectroscopic pH method. This limit is not an equipment or process limit, but is a limit imposed by the
pressure range for which the calibration of the dye constants was done.

Table 1: Sample collection details and physical properties

Fig. 4 plots the experimentally measured pH of the live water sample in the laboratory at reservoir
temperature (242 F) and pressures ranging from reservoir pressure of 19,542 psi to 8,000 psi. The optical
measurements showed no evidence of solids or gas coming out of solution in the optical cell while the
pressure was decreased. Fig. 4 also includes plots of the predictions from the two models that were made
using the flashed water ion analysis and flashed gas analysis as inputs.

The live pH measurements compare well with predictions from Model 1 with differences of 0.1 to 0.2
units that are acceptable given the inherent error bars for the measurement and model predictions. Model
2 also agrees well at the lower pressures, but shows larger discrepancies from both measurements as well
as Model 1 predictions at higher pressures.


A novel method for pH measurements for live waters in the laboratory has been described. Measurements
made on reconditioned reservoir samples are presented for pressures to 20,000 psi, temperature to 242F,
and ionic strength to 3 gmol/kg. Comparisons of measurements with predictions from two models
showed good agreements for the most part with differences of less than 0.2 units. These differences
underscore some of the uncertainties involved in using surface-flashed water sample measurements to
predict reservoir condition pH and scaling. Measurement of pH on live waters is done prior to the flash
process and so is more robust. The set-up also allows measurements of pH at different temperatures and
pressures. The optical cell used for the pH measurement can monitor appearance of scale or gas bubbles
and hence the set up can potentially be used to map these boundaries for live water samples. The
inclusion of all these robust measurements as inputs for models that simulate multiphase equilibrium is
expected to increase confidence in predictions. Finally, the implementation of the Chain of Custody
concept for water samples is demonstrated by comparing the downhole in situ pH measurement during
sample acquisition with the pH measurement on the same reconditioned water sample in the laboratory.
This allows validation of the sample collection, transfer, and reconditioning processes, and assures
representativeness of the collected sample prior to doing further measurements on it in the laboratory.