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DECLARATION (12 pt bold) The substance of this thesis is original work of the author and due reference and acknowledgement has been made, whenever necessary, to the work of others cited in this thesis. No part of the thesis has been submitted or accepted for any degree at the Petroleum Institute or at any other institution worldwide and is not concurrently submitted or will be submitted in candidature for any other degree. Sign here Type your name here Candidates name and signature with date All 12 pt Times New Roman; double space; top margin = 3.5 inch

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ACKNOWLEDGEMENT (12 pt bold) -- optional This Masters Thesis is dedicated to Used to acknowledge those who have supported you during your graduate studies. This is not typically the place to recognize those who assisted you in your academic research. That is done on the required Acknowledgements page

Abstract

Table of content

ACKNOWLEDGEMENTS................................................................................................ ii LIST OF Figures ............................................................................................. iv LIST OF TABLES...............................................................................................................v LIST OF ABBREVIATIONS/NOTATIONS.................................................................... vi ABSTRACT......................................................................................................................

Chapter 1: Introduction Chapter 2: Review of literature 2.1 Background 2.1.1 Fluid rock interaction 2.1.2 Velocity analysis and petrophysics properties correlation 2.1.3 Images analysis to study rock texture? 2.1.4 Importance of fluid analysis?? 2.2 Summary of Previous Research 2.3 Defining the Research Topic Chapter 3: Investigation methods and principles 3.1 Images analysis Thin Section SEM 3D-images 3.2 (Acoustic )Velocities or (Vp and Vs) 3.3 Porosity and permeability 3.4 ICP fluid analysis

Chapter 4: Experimental work (Experiments) Chapter 5: Results 5.1Sample C17 5.1.1 Images analysis Thin Section SEM 3D-images 5.1.2 Acoustic Velocities (Vp and Vs) 5.1.3 Porosity 5.1.4 Permeability 5.1.5 ICP fluid analysis 5.2 Sample D19 5.2.1 Images analysis Thin Section SEM 3D-images 5.2.2 Acoustic Velocities (Vp and Vs) 5.2.3 Porosity 5.2.4 Permeability 5.2.5 ICP fluid analysis Chapter 6: Analysis 6.1 Sample C17 6.2 Sample D19 6.3 Comparison between Sample C17 and D19 6.4 Comparison with previous studies 6.5 Implication

Chapter 7: Conclusion Chapter 8: Recommendation and further work

Chapter 1: Introduction Carbonate sediments are the most common hydrocarbon reservoirs in the world; representing 60% of the total reservoirs (Gosh and Sen, 2012). Characterization of carbonate reservoir is considered to be very complex due to lack of research in rock physics of carbonate rocks (Vanorio and Mavko, 2011) and carbonate reservoirs heterogeneity. Carbonate aquifers are also difficult to characterize due the carbonate heterogeneity. Carbonate reservoirs and aquifers are mostly affected by diagenesis processes such as compaction, dissolution, precipitation and cementation (Assefa et al., 2003 and Koesoemadinata and George, 2003). Diagenetic processes, affecting carbonate rocks can be reactivated during the production as a result of fluid-rock interaction. In the case of primary oil recovery, (i.e. without external fluids injected in the rock), the induced flow and pressure may introduce some changes in the original porosity and permeability. Whereas, when injecting external fluids in the rock, for example to enhance production, this process might introduce a disequilibrium in the host rock system that can lead to physical and chemical changes in the reservoir (Vialle and Vanorio, 2011). In the case of carbonate aquifers, similar concept is applied during the production. During the production from the aquifers the induced flow and pressure may introduce some changes in the original porosity and permeability. These

physical and chemical changes might lead to changes to porosity () and permeability ( The aim of the research is to better understand fluid-rock interaction in carbonate rocks that lead to porosity and permeability variation as a result of potential changes in producing hydrocarbon and/or water reservoirs. In this study we test the ability of detecting porosity and permeability changes using acoustic velocities (Vp and Vs).This research might contribute to oil and gas industry and to hydrology study of aquifers by improve the understanding of how fluid-rock interaction would affect reservoir quality. Consequently, this might help in monitoring hydrocarbon production in carbonate reservoir and hydrological study of carbonate aquifers . Chapter 2: Review of literature 2.1 Background 2.1.1 Fluid rock interaction 2.1.2 Velocity analysis and petrophysics properties correlation 2.1.3 Images analysis to study rock texture? 2.2 Defining the Research Topic Two main objectives are identified for this study. First objective is to investigate a potential correlation between fluid-rock interaction, and porosity permeability changes. The motivation of this objective is draw a clear understanding about this correlation since previous reviewed studies has some limitations as mention in literature review section. For example Vega's et al. (2011) study show small changes in porosity that might be due to fluid rock interaction, whereas the permeability was not considered. Vega's study was

carried in a pure mineral which is not a good representation of a real carbonate reservoir/ carbonate aquifers, so repeating experiment with the carbonate samples might add significance value to reservoir characterization. Vialle and Vanorio experimental study also show a potential correlation between fluid-rock interaction and porosity and permeability changes. However, Vialle and Vanorio study was focusing mainly in a mudstone samples without considering petrophysical properties variation in real reservoir rock. In my study, I choose two samples that are slightly differ in term of pertophysical properties. One of the tested hypotheses in this part is the ability of geochemistry and sample imaging analysis in improving the investigating fluid rock interaction mechanism. Second main objective of this study is to test the applicability of detecting porosity and permeability changes by acoustic velocity laboratory scale (high frequency wave). An important hypothesis to be tested in this study is the ability of acoustic velocities in detecting porosity and permeability changes at laboratory scale.

Chapter 3: Investigation methods and principles 3.1 Images analysis Thin Section SEM 3D-images and image processing using Sakhr program 3.2 Porosity and permeability 3.3 (Acoustic )Velocities or (Vp and Vs) 3.4 ICP fluid analysis

Chapter 4: Experimental work (Experiments) In order to accomplish the research objectives several steps were followed as shown in Figure 2 Sample ID: C17 Sample selection Sample ID: D19 Fluid preparation Experiment 2 Fluid preparation Experiment 1 Experiment 2

Figure 2: Procedure followed in research 4.1 Sample selection Two reservoirs samples were selected from set of samples that we have in rock physics lab. The samples are from . Field, Thamama zone??). In total we have 58 samples from four different wells. Initially 10 samples were selected from 56 recorded samples in the data sheet. The selection first was depending on samples availability since most of the samples were already in use for another experiment and others are used as test samples for equipment calibration on the lab. From the 10 available samples I choose four samples that can be used for experimental purposes. The remaining six samples were either destroyed or not applicable for experimental purposes since they are very small (with an approximate length of 6 cm). In addition to that, most important criteria that restrict my choices are the petrophyiscal properties which are Klinkenberg-corrected (Kg) permeability in mD and porosity in % collected by Mr. El Amin Mokthar (Table 1).

The four initial selected samples were chosen to have variation in porosity and permeability values (low porosity and permeability value, mid porosity and permeability and high porosity and permeability value). After that I narrow my selection to only two samples due to time constrains. Selected samples range between high porosity and permeability values to medium porosity and permeability. Sample C17 was chosen for its high porosity (32.6%) and relatively low permeability (98 mD) so I can detect fluid behavior with a relative high porous media and low ability of fluid flow. For this sample, the low permeability value may allow the fluid to interact longer with the host rock. Sample D19 has relative medium porosity (23.8 %) with low permeability (42 mD). D19 has been selected to examine a mid-properties value compared to previous sample. 4.2 Fluid preparation Initially three fluids were proposed which are carbonated water, saline water and distilled water. Due to time constrains and equipment availability I end up using one fluid. Used fluid in Experiment 1 and 2 was distilled water. Distilled water was expected to be the most reactive solution compares to other proposed solutions. The distilled was used for accelerating diagenesis process and alteration to test if fluid changes will lead to porosity permeability changes.

4.3 Experiment 1 Experiment 1 is a repetition of the work done by Vega et al. (2011) but using carbonate sample reservoir rock instead of pure calcite and dolomite minerals. This experiment conducted to show potential detectable change in porosity and permeability for carbonate sample as Vega's experiment show potential observable changes in pure calcite and dolomite minerals porosities. Slight modification was made to the experiment since at that time we did not have a controllable pump. The experiment set up is shown in figure (3) Figure shows the experiment set up used in Vegas et al. 2011 experiment.

Sample soaked in distilled water

Pump Input water

Output water

Figure 3: Experiment 1 setup

Sample analytical techniques were carried before starting the experiment; such as thin section analysis, SEM/back scattering/ EDS images, 3D CT scan. To repeat and check the experiment in Vega et al (2011) for a reservoir rock, I used sample C17 that has highest porosity and permeability. The high porosity and permeability of sample C17 might help in observing possible changes better than D19. The used sample was initially dry then it is soaked in an elementary flask that filled with distilled water. In addition to that distilled water was pumped to the sample and this induces some movement on the preexisting fluid on the elementary flask. Sample was subjected to flow for 30 min then we turn off the pump and keep the sample soaking on the fluid. In consequence, the flow rate in this experiment is not considered as a major controlling factor since there is no real flow through the samples. This procedure was repeated for different experiment 1 stages (exposure time) table 2. For example in 2 hour exposure time: the first 30 min was flowing a fluid through sample , second 30 min soacking the sample on the fluid without flow then this procedure is repeated for the next hour. Experiment 1 carried for six stages which are: 1 hour, 2 hours, 3 hours, 4 hours, 5 hours and 6 hours of exposure time. The flow rate in this experiment was not controlled as mentioned before and it was about (6 ml/min). The input and output solution were collected in order to capture any potential changes in element composition (ICP-Ms analysis). Velocity, porosity and permeability measurements were taken after each experiment stage (exposure time). At the end of experiment 1, CT scan was carried again to capture possible changes.

Table 2: Experiment 1 procedure. An example of the carried procedure (1 hour of exposure time and 2 hour of exposure time). The procedure was repeated in each experiment stage. So at any exposure time each one hour is divided to 30 min of fluid flow and 30 min of soaking the sample without flow.

Exposure time

Analytical techniques before carrying the experiment

Analytical techniques after each exposure time

Remarks

At the start point

Velocity measurements Porosity and permeability measurements ICP-MS for sample CT scanner and SEM for sample

1hrs

Velocity measurements Porosity and permeability

30 min with fluid flow 30 min sucking the

measurements Collecting fluids for ICP-MS analysis 2 hrs Velocity measurements Porosity and permeability

sample

30 min with fluid flow 30 min sucking the

measurements Collecting fluids for ICP-MS analysis

sample 30 min with fluid flow 30 min sucking the

sample

Experiment 2 In Experiment 2 I used the setup shown in figure 6. This setup adds more accuracy and control to the experiment; the sample is placed in a core holder which ensures maximum contact between fluid and sample. For this experiment setup, I decided to saturate the sample before each flowing stage in order to accelerate the changes if it they occur.

Figure 4: Experimental setup for experiment 2 (courtesy of El Amin Mokhtar, 2012) Before starting experiment 2, CT scan was carried for sample C17 and D19. The initial suggested flow rate for reservoir simulation is 1 ft/day. The proposed flow rate in this experiment was lowered to a minimum rate (1 ft/day which is approximately equal to 0.24 ml/min) to avoid hydraulic fracturing. In this experiment the sample was subjected to the assigned flow rate directly since the sample is placed in a core holder. The initial used pressure was 200 psi which is the limit capability of the available lines (plastic lines). At the start point before placing the sample, I flashed the system with distilled

water, Methanol and Ethanol to ensure that there is no any oil or salt contaminated in the lines and to ensure that the only effect on the sample is the distilled water. After placing saturated sample inside the core holder the distilled water was flowed through the sample. Fluid flow followed a timing schedule shown in table 3 for sample C17 and table 4 for sample D19. After each flow time the sample was removed from the system and dried to take porosity, permeability and velocity at dry condition. The input and output fluid were collected for ICP analysis of elements composition. The system flashed with distilled water Methanol and Ethanol again after each stage (injected pore volume). The flowing schedule in this experiment depended on the filled pore volume. From the initial porosity measurements we calculated the actual sample pore volume then we multiplies it by the needed injected pore volume to get the required time for the experiment. For example at the first stage (5 injected pore volume) Total number of pore that need to be filled= actual sample pore volume * injected pore volume Total number of pore that need to be filled = 15.782 *5= 78.91 ml Time required to fill the pore= Total number of pore that need to be filled /flow rate Time required to fill the pore= 78.91 ml / 0.2 (ml/min) Time required to fill the pore= 394.55 min ~ 6.5 hours

Table 3: Experiment 2 stages for sample C17 . Filled pore volume 5 50 75 100 150 Sample pore volume Used flow rate 15.782 15.928 15.964 16.051 16.08 0.2 0.2 0.2 0.2 0.2 Time ( hours) 6.5 66 98 134 201

Table 4: Experiment 2 stages for sample D19. Filled pore volume 20 50 80 120 Sample pore volume Used flow rate 15.55 15.641 15.696 15.914 0.2 0.2 0.2 0.2 Time ( hours) 26 65 105 159

After carrying experiment 2 for both samples, CT scan was carried to capture any possible changes.

Chapter 5: Results 5.1Sample C17 5.1.1 Images analysis

Thin section C17 is Calcite foraminifers packstone (Figure 5). Calcite composition of the sample observed clearly as the sample is stained with red lizarin (Figure 6). In the stained part; most of the grains reflect red to pinkish color which is an indication to calcite. The thin section of sample C17 is full of micrite (Figure 5). Most of the observed pores in this thin section are cemented with Calcite. The thin section quality is considered as poor quality, since the diagenesis sequence cannot observe clearly even at very high magnification.

Figure 5: Sample

C17, foraminifers Figure 6: C17 thin section, where half of the section is stained with red lizarin. In the stained part most of the grains reflect pinkish color which is an indication of calcite cementation.

packstone full of micrite

SEM/ backscattering/ EDS SEM and backscattering images of the sample were captured to get an idea about pore structure type, grain shape and approximate porosity. The SEM, EDS and backscattering analysis were applied by cutting small piece of the sample. From the SEM images at very low resolution ( 500 Mm) (Figure7) macro porosity observed. Increasing the resolution to (50 Mm) shows more detailed of sample C17 internal structure. At resolution of 50 Mm the observed grains are surrounded to irregular grains with micro porosity (Figure 8) between the grains. Some of the grains are covered by micritic grain and this is confirms the abundance of micritic grains that observed in the thin section part of sample C17.

Figure 7: Overview of C17 SEM image at Figure 8: Irregular (Calcite??) grains very low resolution, Macro pores spaces covered with micritic grains. Yellow circles observed. indicate the micro pore spaces (less than 30 Mm)

Backscattering images of the same sample at resolution of (500 Mm) give an indication of micro and macro porosity supporting the SEM images figure 9.

Figure 5: Backscattered image of sample C17, where the black dots (background) represent the pore space and white to very light grey represent the grains.

The EDS (energy dispersive x-ray spectroscopy) report of sample C17 shows that the sample is mostly consist of Calcium carbonate figure 10. EDS analysis of sample composition might would help in understanding the interaction mechanism.

Quantitative results
50

Weight%

40 30 20 10 0 C O Ca

Element

Weight%

Atomic%

CK OK Ca K Totals

16.90 46.99 36.11 100.00

26.82 56.00 17.18

Figure 10: EDS analysis of sample C17 most of the sample is consist of calcite.

3D CT images Processed images using Sakher program 5.1.2 Acoustic velocity measurements Experiment1 Velocity measurements for the sample were taken at each experiment stage/exposure time at dry conditions. The Vp response of sample C17 was generally increasing with

increasing the exposure time if we compare the Vp value at zero time with the Vp value at the last stage ( after 6 hour of exposure time) figure 11 . However, the measured Vp values through experiment 1 was fluctuating; decreasing the first stage (after 1 hr of exposure time) then increase after 2 hour of exposure time. The measured Vp values decreases again with increasing the exposure time from 2 hour to 4 hour. At the last two stages the measured Vp was increasing with increasing of exposure time. (Comment on error)

Vp ( m/s) Vs exposure time (hrs)

2460.00 2450.00 2440.00 Vp ( m/s) 2430.00 2420.00 2410.00 2400.00 2390.00 2380.00 0 1 2 3 4 5 6 7 Time (hours)

Figure 11: The measured Vp values at dry condition with the increasing of the exposure time.The measured Vp Values were changin with increasing the exposure time, but this changes in Vp value were not follwing a general trend. The Vp values were fluctuating with increasing the exposure time. The measured Vs values for the same sample have more clear trend with increasing the exposure time. The Vs values increases with increasing the exposure time from 0 time to 2 hour of exposure time figure 12. Then the Vs values start to deacrese with increasing

the exposure time form 2 hour of exposure time to 6 hour of exposure time. Measured Vs for sample C17 shows a decreasing polynomial trend with increasing the exposure time.

Vs (m/s) versus time (hrs)

1500.00 1450.00 Vs (m/s) 1400.00 1350.00 1300.00 R = 0.8929 1250.00 0 1 2 3 4 5 6 7 Time (hrs)

Figure 12: Measured Vs vlaues of sample C17 in experiment 1 versus the exposure time. Vs values show a decreasing polynomial trend with increasing the exposure time Experimen 2 Velocity measurements for sample C17 were taken during the second experiment after each stage (injected pore volume) at dry conditions. Measured Vp increases with increasing injected pore volume (exposure time) figure 13. Vs for sample C17 shows an increasing polynomial trend with increasing the exposure time. The increasing of velocity give an indication that the sample becomes stiffer since the sound wave is traveling faster with less disturbance. Add bulk modulus

Vp (m/s) versus pore volume

2900 2850 2800 2750 2700 2650 2600 2550 2500 2450 2400 0 20 40 60 Injected pore volume R = 0.9534

Vp (m/s)

80

100

120

Figure 13: Measured Vp for sample C17 through experiment 2 at dry conditions. Vp readings are increasing with increasing the injected pore volume/ exposure time. Measured Vs values for sample C17 through the second experiment was fluctuating with increasing the injected pore volume figure 14. In general there was an increase if we compare the first value (zero injected pore volume) with the last value (100 injected pore volumes).

Vs (m/s) versus Pore volume

1500 1450 Vs (m/s) 1400 1350 1300 1250 0 20 40 60 80 100 120 injected pore volume

Figure 14: Vs measured values for sample C17 through experiment 2 at dry conditions. There is a general increase in the Vs values with increasing the injected pore volume/ exposure time.

5.1.3 Porosity

Experiment 1 Porosity measurements of sample C17 were taken after each stage (exposure time) at dry condition using the porosimeter. Porosity value is increasing with increasing the exposure time figure 15. Increasing of porosity could be an indication of partial dissolution. On the same experiment the velocity measurements were also increase and this not expected as the porosity is increasing also.

Porosity (%) versus Time (hrs)

25.8 25.6 Porosity (%) 25.4 25.2 25 24.8 24.6 24.4 0 1 2 3 4 5 6 7 Time (hrs) R = 0.8815

Figure 15: Porosity of sample C17 measured after each stage ( exposure time) at dry condition. The porosity measurements is incresing with increasing the exposure time.
Experiment 2

In the second experiment the porosity measurements were also taken after each stage ( exposure time/ injected pore volume). The main differences between experiment one and experiment 2 as mentioned in chapter ( 5) are : the sample was intially saturated in the second experiment and sample was subjected to fluid flow within closed system. Additional control in the second experiment might help in enhancing the reaction or changes on the sample. Porosity measurements of sample C17 on the second experiment were increasing with increasing the injected pore volume/ exposure time figure 16.

Porosity (%) versus Pore volume

26.2 26.1 Porosity (%) 26 25.9 25.8 25.7 25.6 25.5 0 20 40 60 80 100 120 Injected pore volume

Figure 16: Porosity measurements of sample C17 in experiment 2 at dry conditions. The porosity is incresing with increasing the injected pore volume.

5.1.4 Permeability Experiment 1 The permeability measurements were also taken at dry conditions after each stage (exposure time). Permeability values are generally decreasing with increasing the exposure time as shown in figure 17. However, we can observe a fluctuating trend of permeability values as the exposure time increase. From 2 hour exposure time to 4 hour exposure time the permeability value is increasing. At the same stages (from 2 hour exposure time to 4 hour exposure time) the Vp values is decreasing. From 4 hour of exposure time to 6 hour of exposure time the permeability is decreasing whereas, the Vp is increasing

Permeability Kg (mD) versus Pore volume

121 120.5 120 119.5 119 118.5 118 117.5 117 116.5 0 1 2 3 4 5 6 7 Time (hrs) Permeability Kg (mD)

Figure 17: Permeability measuremenst of sample C17 during experiment 1 at dry conditions. The permeability values in general is decreasing with an increaing of exposure time.

Experiment 2 Permeability values for sample C17 in the second experimenst were also taken after each stage (injected pore volume/ exposure time). Generally we can said that the permeability is increasing with increasing the exposure time figure 18. For the same experiment and same sample the porosity measurements were also increasing with increasing of injected pore volume/exposure time.

Permeability Kg (mD) versus Pore volume

119.500 Permeability Kg (mD) 119.000 118.500 118.000 117.500 117.000 116.500 116.000 0 20 40 60 80 100 120 Injected pore volume

Figure 18: Permeability measurements of sample C17 through experiment 2. The permeability values generally increaing with increasing of injected pore volume/ exposure time. 5.1.5 ICP fluid analysis ICP-MS was used to examine changes elemental composition of the fluids injected, postexperiment as well as the solution used to saturate the rock at the beginning of the experiment. For the second experiment the fluid used to saturate the sample is the same the injected fluid (reference point/ zero point). The elemental composition analysis of the fluid through the experiment might help in understanding diagenesis or fluidrock interaction. The most important tracked elements are the Ca, Mg and Fe, since our samples are mainly carbonate (calcite C17). In each stage the input and output fluids were analyzed. The Input fluid (reference) for each stage is represented at the zero time; for example: for the second stage (after 2 hour of exposure time), the input fluid is represented at zero time and the output is represented at 2 hour point. Each element reading is normalized through the experiment stages. For example in the case of Ca

element I found the maximum reading of Ca through the experiment stages and divided the reading at each stage by this maximum number; similar procedure was applied for the remaining elements. Experiment 1 The ICP analysis of the input and output fluid shows that Ca element content is generally increases with increasing the exposure time. For the first two stages (after 1 hour of exposure time and after 2 hour of exposure time, the Ca content considered to be increasing compared to the reference point and increasing with respect to each other with increasing in exposure time. This increasing means that after exposure time of 2 hour we get more Ca content on the fluid than 1 hour of exposure time. This is might means that dissolution is increased with increasing the exposure time from 1 hour to two hours. Then by trying to compare output Ca content from 2 hours of exposure time to 4 hours we can say that the Ca output is decreasing by comparing output fluid content of these stages, but it is still increasing if we compare it with the input fluid content. This could mean that by increasing the exposure time the dissolution rate will decrease. However, the Ca content start to increase again at the last two stages of the experiment which again might give an indication to increasing in dissolution rate in the sample by the fluid. The Ca content of the output fluid for sample C17 in experiment 1 was fluctuating and increasing in general. However, this trend might not be really representative to the real fluid rock interaction since the exposure time is very low (maximum exposure time in experiment 1 is 6 hours). Fe and Mg content were almost following the same trend of the Ca content with increasing of the exposure time. Both Fe and Mg were generally increasing with increasing the exposure time figure 19.

Element content (normalized values) Vs Time (hrs)

Element content ( normalized values) 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 1 2 3 4 5 6 7 Time (hrs)

Ca Mg Fe

Figure 19: Ca, Fe and Mg readings of the input and output fluids injected to sample C17 in experiment 1. Al of them shows a general increasing with increasing the exposure time compared to the reference value (zero time). Experiment 2 For the second experiment Ca and Mg content were following similar trend with an increasing of injected pore volume/ exposure time. Ca and Mg content were generally increasing with increasing of injected pore volume/ exposure time compared to the reference point (zero injected pore volume/exposure time). However if we compare the output content of each stage together we can say that the output content get less as we increase the injected pore volume/ exposure time. This is mean that by increasing the injected pore volume/ exposure time the dissolution occurrence in the sample might decrease. On the other hand the Fe content show a general increasing compared to the reference value and compared to different stages (injected pore volume) figure 20

Element content (normalized values) Vs. injected pore volume

Element content (normalized values) 1 0.8 0.6 Ca 0.4 0.2 0 0 20 40 60 80 100 120 140 injected pore vloume Mg Fe

Figure 20: Ca, Mg and Fe content of the input and output injected fluid to sample C17 in experiment 2. All of them show a general increasing compared to the reference point (zero point) with an increasing of the injected pore volume/ exposure time. Ca and Mg output are considered to be decrease comparing the output fluid content of each stage together. However, the Fe content is increasing if we compare the output fluid content at each stage together

5.2 D19 5.2.1 Image analysis Thin section D19 is limestone sample with dolomite cementation. The dolomite content is clearly observed by the dolomite crystal shape figure 21, which is a typical shape of dolomite crystal (add reference). In the stained part of the sample the grains reflect white color which is an indication of dolomite content (add reference). Most of the grains are

recrystallized. Most of the observed pores in this thin section are cemented with calcite or dolomite. The thin section quality is considered as poor quality, since the diagenesis sequence cannot observe clearly even at very high magnification.

Figure 21: Sample D19, dolomite crystal with saddle shape is clearly observerd. This part of thin section is stained with red lizarin

SEM/ backscattering/ EDS SEM and backscattering images of the sample were captured to get an idea about pore structure type, grain shape and approximate porosity. The SEM, EDS and backscattering analysis were applied by cutting small piece of the sample. At 300 Mm resolution macro porosity could be observed, represented by dark areas (yellow circles) in the SEM image

figure 22. At resolution of 30 Mm we can clearly observe the dolomite crystal that has the same shape of dolomite crystal observed in the thin section figure 23.

Figure 22: D19 SEM image, the yellow circle represent the macro porosity.

Figure 23: D19 SEM image, the blue circle represent the dolomite crystal.

The back scattered images of sample D19 confirm the occurrence of macro porosity at resolution of 500 Mm figure 20, where the black background represent the pore spaces and the white areas represent the grains figure 24.

Figure 24: Back scattered image of sample D19 at resolution of 500 Mm. Black background represent the pore space whereas the white to grey color represent the grains.

The EDS report for sample D19 shows that the sample mostly consists of calcite with dolomite. The dolomite content is indicated by Mg occurrence figure 25.

Element OK Mg K Ca K Fe K Totals

Weight% 58.90 15.21 25.25 0.64 100.00

Atomic% 74.39 12.64 12.73 0.23

Quantitative results
60

Weight%

50 40 30 20 10 0 O M g Ca Fe

Figure 25: EDS analysis of sample D19, most of the sample is calcite with dolomite content.

CT scan Processed images by Sakhr program.

5.1.2 Acoustic Velocities or (Vp and Vs) Velocity measurements for sample D19 were taken at each experiment stage (injected pore volume/exposure time). The velocity was measured at dry condition. Vp is increasing with increasing injected pore volume/ exposure time figure 26. This indicates that the sample stiffness might be increase.

Vp (m/s) versus Injected pore volume

3300 3250 3200 Vp (m/s) 3150 3100 3050 3000 2950 0 20 40 60 80 100 120 140 Injected pore volume R = 0.9202

Figure 26: Measured Vp for sample D19 in experiment 2. Vp measured at dry condition. The Vp increases with increasing the injected pore volume/ exposure time. Measured Vs values generally are increasing with increasing of the injected pore volume /exposure time. However, the values were not showing clear increasing trend with increasing the injected pore volume/ exposure time as the values fluctuating through the experiment figure 27.

Vs (m/s) versus injected pore volume

2150 2100 2050 Vs (m/s) 2000 1950 1900 1850 1800 1750 0 20 40 60 80 100 120 140 injected pore volume

Figure 27: Measured Vs values of sample D19 on dry conditions. Generally the Vs is increasing with increasing the injected pore volume/ exposure time.

5.2.3 Porosity Porosity measurements of the sample were taken at dry condition after each stage (after each injected pore volume/ exposure time). Porosity measurements of the sample are increasing with increasing the injected pore volume figure 28. The increases of porosity might be an indication of dissolution on the sample which leads to increase in pore spaces

Porosity (%) versus Injected pore volume

24.1 24 23.9 23.8 23.7 23.6 23.5 23.4 23.3 23.2 0 20 40 60 80 100 120 140 Injected pore volume Porosity (%)

Figure 28: Porosity measurements of sample D19 on experiment 2. The measurements were taken on dry conditions. Porosity values are increasing with increasing the injected pore volume/ exposure time. 5.2.4 Permeability The permeability measurements were also taken on dry condition and after each stage (after each injected pore volume/ exposure time). Generally the permeability value is increasing compared to the initial value at zero point. Increasing on permeability value is very sharp and clear at the first stage (after injecting 20 pore volumes) after that the permeability values are slightly fluctuating figure 29.

Permeability Kg (mD) versus Pore volume

62 60 Permeability Kg (mD) 58 56 54 52 50 0 20 40 60 80 100 120 140 Pore Volume

Figure 29: Permeability measurements of sample D19 on experiment 2. The readings were taken on dry condition. Generally the permeability is increasing. The permeability show sharp increasing after the first stage (after 20 injected pore volumes). Then the permeability reading is slightly fluctuating.

5.2.5 ICP fluid analysis ICP-MS was carried to examine changes elemental composition of the fluids injected, post- experiment as well as the solution used to saturate the sample. For the second experiment the fluid used to saturate the sample is the same the injected fluid (reference point/ zero point). Tracking possible the elemental composition changes might help in understanding diagenesis or fluidrock interaction. The most important tracked elements are the Ca, Mg and Fe, since our samples are mainly carbonate (calcite + Dolomite D19). The input and output fluid were collected at each stage of the experiment. The input fluid in each stage is the same fluid and it represented in figure 30 as the zero point. Each element reading is normalized through the experiment stages as mentioned in the ICP analysis for sample C17. Experiment 2 Both elements Ca and Mg are having the same trend. Ca and Mg content on the output samples considered to be increasing if we compare them to the initial value (zero value). Ca and Mg reach its maximum content on the output fluid in the second stage (after 20 injected pore volumes). Then the output content of Ca and Mg is decreased compared to the second stage values. As we increase the injected pore volumes/ exposure time, the output content of Ca and Mg element is decreases figure 30. Thats mean we are dissolving less Ca and Mg elements from the sample (D19). Most of the Ca and Mg elements have been washed from the sample at the first stage (after 20 injected pore volume). The Fe content is increasing compared to the initial value ( zero point). As we increase the injected pore volume/ exposure time, the amount of dissolved Fe from the sample/ output content is increase.

Element content (normalized values) Vs injected pore volume of the sample

Element content (Normalized values) 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 20 40 60 80 100 120 140 Injected pore volume of the sample

Ca Mg Fe

Figure 30: Ca, Mg and Fe content on the input (zero point) and output injected fluids. Ca and Mg have the same trend. Both are increasing compared to the intial point (zero point). However, Ca and Mg content are decreasing through the experiment. Fe content of the output fluid is increasing through the experiment.

Chapter 6: Analysis 6.1 Sample C17 The used techniques here which are thin section analysis, SEM images and EDS analysis show that sample C17 is mainly a calcitic limestone. Pore distribution for sample C17 from the thin section indicated an abundance of microporosity. Additionally the SEM images show the occurance of both micro porosity (below 30 Mm ) and macro porosity at (500 Mm ) as mentioned in chapter 5. However, the thin sections (approximately less than 1 cm~0.5 cm) and sample pieces (up to 2 mm in diameter) used for SEM images

may not be representative of the whole core plug and some features in the pore space distribution and pore structure might be missing. 3D CT scans of sample C17 taken at three stages: (1) before any treatment, (2) after the first experiment, and (3) after the second experiment were expected to help in detecting any changes in the sample through whole process. The 3D CT scan scanned the whole sample. Produced videos from these three stages were slightly helpful in tracking the changes qualitatively. As mention in the results part between the three stages the main changes were in the micoporosity. General decreasing in the microporosity was observed. Studying the produced images of the three stages using Sahker (image processing and analysis program) , I found that the microporosity were below the image resolution ( 40 Mm ) and, consequently, not detected. Comparing the porosity estimated from the program with the actual value at the end of each stage confirmed that there is a gap / missing data that the program was not able to read from the images due to the images quality. Estimated value from each stage was less than actual measured value by the porosimeter as shown in table 1. Table 1: Porosity values of sample 422-17 before any treatment, after the first experiment and after the second experiment estimated form Sakher program and measured by the porosimeter. Stage number Experiment Stage Estimated porosity value form Actual porosity Porosity difference Total Porosity

measured by Estimated Porosity porosimeter (%)

Sakher (%) 1 Before any 9.5 treatment 2 After first 11.1

(%)

24.4

14.9

25.6

14.5

experiment 3 After second experiment 10.9 26.1 15.2

The histogram and the maximum density probability of the grains (solid phase) in each stage shows that from stage 1 to stage 2 we have a general increasing in grains density probability whereas from stage 2 to stage 3 we have a general decreasing in grains density probability value. For example by taking 400 slices from the sample in each stage (starting from slice 1 to slice 400) the changes were as shown in table 2. Table 1: Grain probability distribution value of sample 422-17 before any treatment, after the first experiment and after the second experiment.

Experiment Stage

Grain maximum density probability

1.Before any treatment 2.After first experiment 3.After second experiment

0.045 0.056 0.043

Comparison between porosities at stage 1 and stage 2 cannot be made since the sample lost a small volume after the first experiment which might affect the probability distribution readings and total porosity. Moving from stage 2 to stage 3 we can observe a decreasing in the grain maximum density probability.

Moving from stage 2 to stage 3, there is also a loss in the sample volume after stage 3 (approximately 0.4 g) but it is very small compared to sample loss after stage 2 previous loss (approximately 4g). As the loss in C17 sample volume after stage is negligible, I assumed that there is no loss in the sample volume. The decreasing of the grain maximum density probability (from stage 2 to stage 3) with this assumption might indicate an occurrence of dissolution process. Comparing velocity and porosity results of the sample C17 in the second experiment, we can see that their behavior is against the expected trends. More reasonable expected trend is to have opposite response from porosity and velocity compared to each other; e.g.: if the porosity is increasing we will be more likely expecting to have a decreasing in velocity value. Increasing in porosity means that we have more open spaces that could be filled with water, air, gas or oil. The seismic wave traveling through the solid matter is

expected to be faster than traveling through gas or liquid mater. Increasing the porosity means that we are introducing a disturbance to the traveling wave and this would lead to decreasing in wave velocity. However, the velocity (Vp and Vs) were increasing with increasing exposure time /injected pore volume and this could be an indication to precipitation occurrence. As the velocity is increasing, the rock sample expected to be stiffer. Two reasonable ways in increasing the stiffness of the sample might be: first rearranging pore distribution and grains in a way that would add to rock stiffness , second the occurrence of precipitation process that might help in filling the pore spaces. As discussed in the chapter 5, ICP analysis of the fluids (input and output) for experiment 1 and experiment 2 shows an increase of Ca, Mg and Fe content on the output fluids compared to the input content (zero point). For Experiment 1 the Ca, Mg and Fe content of the output were increasing as the exposure time is increased from 0 to 2 hours of exposure time. The increases on the elements (Ca, Mg and Fe) content of the output fluid could indicate dissolution from the sample at the very first stages of the experiment. Then from 2 hours of exposure time to 4 hours the content is decreases which mean that we dissolve less of these elements from the sample, or we could have partial precipitation. From 4 hours of exposure tome to 6 hours of exposure time which again indicate occurrence of dissolution. As mentioned in the chapter 5, Ca and Mg content of the output fluids have similar trend in experiment 2. Ca and Mg content were generally increasing compared to the reference point (zero injected pore volume/exposure time). As the injected pore volume is increased/ exposure time the output fluid Ca and Mg content is decreases. The decreasing

of Ca and Mg content indicates that we have a dissolution process, but as we increase the injected pore volume/ exposure time the dissolving mechanism is reduced. The reduction of dissolving mechanism could indicate partial occurrence of precipitation. Potential precipitation of ion in the sample can be supported by the increasing on Vp as mentioned before and general decreasing of Ca and Mg content on output fluid for Experiment 2. Decreasing of grain maximum density probability from stage 2 (after experiment 1) to stage 3 (after experiment 2) might mean an increasing in pore space/ total porosity and this analysis can be supported by the general increasing on actual measured porosity (from the porosimeter) in both experiments. Generally, we can say that there are observable changes in both experiments for sample C17. The changes indicated the occurrence of both mechanisms (dissolution and precipitation). The dissolution might have the higher influence on the rock fluid interaction as it is also shown in total porosity measurements of the sample through both experiment 1 and 2. However, the changes are clearer on experiment 2 as we had higher exposure time/ injected pore volume. 6.2 Sample D19 Thin section analysis, EDS and back scattering images of sample D19 before any treatments confirmed dolomite content on the sample as mentioned in chapter 5 Porosity and velocity changes for sample D19 showed a similar trend as sample C17 on experiment 2. Total porosity and Vp values increased through experiment 2. General increasing on total porosity might indicate a dissolution process whereas the increasing of

velocity might give an indication to precipitation process. As the velocity is increasing, the rock sample expected to be stiffer. Two reasonable ways in increasing the stiffness of the sample might be: first rearranging pore distribution and grains in a way that would add to rock stiffness, second the occurrence of precipitation process that might help in filling the pore spaces. The occurrence of dissolution and precipitation process is also supported by the input and output fluid analysis through the experiment. Ca content behavior in sample D19 is similar to sample C17. The increasing of Ca content in output fluid proposed a potential dissolution. General decreasing on the difference Ca content between input and output fluid could support the precipitation and decreasing of dissolution mechanism. For this sample 3D CT scan images and processed images were not very helpful as the resolution was very low. In sample D19 the resolution is much lower is much lower than the scale of pores and grains in this sample so it is very difficult to detect the pore space in this sample. However in some slices slight changes were observe in pore structure and size. 6. 3Comparison between sample C17 and D19 Both samples show similar responses to experiment 2. Sample C17 have higher initial porosity and permeability than and D19. Sample D19 shows slightly higher changes in porosity than sample C17, as we expected. The change in sample 427-19 was expected to be higher since it has lower permeability than C17. The low permeability might help in constraining the fluid movement while carrying the experiment and this might lead to a greater contact between fluid and rock surface.

The ICP analysis of the fluid shows that after running the experiment 2 for both samples and for 20 injected pore volumes, the Ca and Mg content reach the maximum amount. The output Ca and Mg content from sample D19 (approximately 10099.71 ppm after 20 injected pore volumes) is much higher than on sample C17 (approximately 1997.6 ppm after 20 injected pore volumes). This might also indicate that the low permeability value of sample D19 helped in trapping the fluid and increasing the possibility of rock fluid interaction/ dissolution. Another thing that should be considered is that both samples were saturated with input fluid before running the experiment. Then after running the experiment for 20 injected pore volume we got those results. The saturation of the sample before injecting any fluids might help in weakening the grains especially in the pore spaces where the fluid might get higher contact with the sample material. This might help in understanding why we get clearer results in experiment 2 for both samples than experiment 1 for C17. The permeability changes in both samples are not very clear. Permeability values are fluctuating but generally increasing for sample C17 and decreasing for sample D19 figure 31. However in the last two steps the changes on permeability values are very low and this might suggest that carrying the experiment for longer exposure time might lead to constant permeability value or might introduce other changes as we increase the exposure time.

Permeability of sample C17 and D19 Vs injected pore volume

140.000 Permeability Kg (mD) 120.000 100.000 80.000 60.000 40.000 20.000 0.000 0 50 100 150 Injected pore volume C17-EX2 D19-EX2

Figure 31: permeability values of sample C17 and D19 in experiment 2. Both show general increasing. Porosity for both samples in experiment 2 was increasing with increasing the injected pore volume/ exposure time figure 32.

Porosity (C17 and D19) Vs injected pore volume

26.5 26 porosity (%) 25.5 25 24.5 24 23.5 23 0 50 100 150 injected pore volume C17-EX2 D19-Ex2

Figure 32: Porosity measurements of sample C17 and D19 through experiment 2. Both porosity reading are increasing with increasing the injected pore volume/ exposure time. 6.4 Comparison with previous studies Comparing the results of my experiment with Vegas 2011 results, the measured acoustic velocity of the sample (pure calcite) in dry condition is generally decreasing with increasing exposure time figure 33.

Figure 33. Calcite (i) dry and (ii) saturated sample velocity change with different experimental order. Vega et.al (2011). In experiment 1 sample C17 velocity measurements were increases with increasing exposure time. Experiment 1 conditions were similar to the applied experiment in Vegas et. al (2011) research. The main difference is that tin Vegas 2011 experiment the used sample is pure calcite whereas, in my research I used carbonate sample from real reservoir. Heterogeneity of the sample used in my research my add complexity in fluid rock interaction mechanisms, understanding sample behavior and in tracing the petrophysical properties changes by acoustic velocity. Measured porosity form Vegas

research was not has a clear decreasing trend. On the other hand for the sample used in my research the porosity was increasing with increasing the exposure time. 6.5 Implication

Chapter 7: Conclusion Chapter 8: Recommendation and further work