Ler Importante Rochas Carbonáticas

materials
Article
Experimental Study on the Dissolution Characteristics and
Microstructure of Carbonate Rocks under the Action of
Thermal–Hydraulic–Chemical Coupling
Jinzhu Meng , Sili Chen *, Junxiang Wang, Zhi Chen and Jingyu Zhang
School of Architecture and Civil Engineering, Shenyang University of Technology, Shenyang 110870, China
* Correspondence: [email protected]
Abstract: Microdamage in a rock induces a change in the rock’s internal structure, affecting the
stability and strength of the rock mass. To determine the influence of dissolution on the pore structure
of rocks, the latest continuous flow microreaction technology was used, and a rock hydrodynamic
pressure dissolution test device simulating multifactor coupling conditions was independently devel-
oped. The micromorphology characteristics of carbonate rock samples before and after dissolution
were explored using computed tomography (CT) scanning. To conduct the dissolution test on 64 rock
samples under 16 groups of working conditions, 4 rock samples under 4 groups were scanned by
CT under working conditions, twice before and after corrosion. Subsequently, the changes in the
dissolution effect and pore structure before and after dissolution were quantitatively compared and
analyzed. The results show that the dissolution results were directly proportional to the flow rate,
temperature, dissolution time, and hydrodynamic pressure. However, the dissolution results were
inversely proportional to the pH value. The characterization of the pore structure changes before
and after sample erosion is challenging. After erosion, the porosity, pore volume, and aperture of
rock samples increased; however, the number of pores decreased. Under acidic conditions near the
surface, carbonate rock microstructure changes can directly reflect structural failure characteristics.
Consequently, heterogeneity, the presence of unstable minerals, and a large initial pore size result
in the formation of large pores and a new pore system. This research provides the foundation and
assistance for predicting the dissolution effect and evolution law of dissolved pores in carbonate
Citation: Meng, J.; Chen, S.; Wang, J.;
rocks under multifactor coupling, offering a crucial guide for engineering design and construction in
Chen, Z.; Zhang, J. Experimental
Study on the Dissolution
karst areas.
Characteristics and Microstructure of
Carbonate Rocks under the Action of Keywords: carbonate rock; thermal–hydraulic–chemical coupling; dissolution effect; computed
Thermal–Hydraulic–Chemical tomography scanning; microstructure
Coupling. Materials 2023, 16, 1828.
https://doi.org/10.3390/ma16051828
Academic Editor: Vit Smilauer

1. Introduction
Received: 4 January 2023 With the improvement of the social economy, some of the subterranean projects are
Revised: 21 February 2023
starting to gain traction. Karst gradients, foundation instability, karst water flow, and karst
Accepted: 21 February 2023
collapse have a detrimental impact on the foundations of structures and pose a considerable
Published: 23 February 2023
risk to the safety and financial investment of engineered construction. Moreover, due to the
anisotropy of rock, its interior contains holes, cracks, microcracks, and microplanes, and its
mesocharacteristics will significantly affect its strength, stability, and seepage characteristics.
Copyright: © 2023 by the authors.
Hence, to conduct engineering construction in karst areas and to improve the stability
Licensee MDPI, Basel, Switzerland. of engineering structures and later safety maintenance, the characteristics of the rock
This article is an open access article dissolution law in soluble rock areas must be understood. Moreover, there should be
distributed under the terms and research on rock pore structure and prediction of its development trends to assure early
conditions of the Creative Commons identification and safety evaluation of karst geological disasters. These are crucial for the
Attribution (CC BY) license (https:// safe development of rock mass engineering and are vital for material research.
creativecommons.org/licenses/by/ There have been several karst-related studies, including those on karst landforms [1,2],
4.0/). hydrogeology [3,4], karst environment [5,6], and so on. Since the 1970s, researchers have
Materials 2023, 16, 1828. https://doi.org/10.3390/ma16051828 https://www.mdpi.com/journal/materials

Materials 2023, 16, 1828 2 of 22
been studying the experimental dissolution of carbonate rock under temperature, mechan-
ical, and chemical conditions [7]. The research includes carbonate rock dissolution and
precipitation [8–11], dissolution reaction law and dynamic process [12,13], the dissolu-
tion mechanism of karst development features [14–16], and the dissolution rate of rock
samples and their influencing factors [17–21]. The main factors affecting the dissolution
effect of carbonate rocks are found to be temperature [22], flow rate [23,24], hydrodynamic
pressure [20,25–27], and pH value [28]. Based on macromechanism research through dis-
solution tests, there are numerous test methods for observing the internal mesostructure
of materials in the research of the mesocharacteristics of rocks, such as scanning electron
microscopy (SEM), nuclear magnetic resonance (NMR), and CT [29–31]. NMR and CT
can be used to analyze, as well as detect, rock samples of any shape and size with a small
number of samples, high speed, a nondestructive process, and high accuracy. NMR can
directly detect fluid and its distribution in rock samples. Additionally, the porosity of
the rock sample can also be measured more accurately using this technique, including
analyzing the size distribution, connectivity, and mobile fluid of the rock. Furthermore,
it has obvious advantages in quantitatively characterizing the pore defects in rock, and
realizes the quantitative evaluation of the damaged state of rock [32,33]. Zhang et al. [34]
revealed the evolution of pore size, pore volume, and permeability during the dolomite
reservoir dissolution process. Meanwhile, Xiao et al. [35] show that regardless of whether
the pore structure is good or bad, it is better to use the pore composition to evaluate the
pore structure. Diffusion-weighted imaging (DWI) has always been of interest to schol-
ars. Fheed proposed using DWI as it can show the arrangement of fissures in rock cores
or allow conclusions to be drawn regarding the permeability of a reservoir sample. In
order to resolve the specifics of naturally bendy carbonate pore networks consisting of
narrow dissolution channels, determining a major fluid flow direction is necessary [36–39].
Krzyżak et al. proposed a more advanced technique of diffusion tensor imaging (DTI) for
characterizing rock core samples. Upon obtaining the diffusion tensor (DT), the parameters
of the DT could be observed in both 2D and 3D. Each parameter was explained, and its
value in characterizing pore space was examined [40,41]. Meanwhile, Fheed also applied
zero echo time (ZTE) imaging using a high-field 9.4 T MRI scanner to study the relationship
of the local water saturation level and the sample microstructure. In comparison with
high resolution 3D micro-CT images, ZTE seems to be especially suitable for studying
porous and fractured carbonate rocks [42]. In comparison, the ray method of CT scanning
is ideal for studying the internal structure of minerals and geotechnical materials. This
technology was developed in the 1970s and was initially used for nondestructive testing
in the medical field [43]. However, in the 1990s, computer science and technology made
significant advances, while industrial CT gradually increased. With the rapid development
and maturity of technology recently, it has been popularized and applied to geotechnical
engineering from medical and industrial fields and gradually applied to civil engineering,
water conservancy and hydropower, and other fields as a nondestructive testing technology.
Raynaud [44] was the first to use X-ray CT scanning to analyze the scanning sections of
rock samples. He discovered that rock volume deformation correlated with changes in ray
density. The formation of microcracks accompanies rock salt microdamage, and the micro-
pores in rock salt change accordingly, affecting the change in rock salt density. CT observed
structural changes in rock in a nondestructive, real-time, and dynamic manner without
requiring a complex sample preparation process or causing structural damage [45]. Berg
et al. [46], Wildenschild and Sheppard [47], Blunt et al. [48], and Luquot and Gouze [49]
provided a necessary method for studying the internal mesostructural evolution of rock
salt during dissolution and for evaluating the changes of secondary pores formed by karst
under various conditions to study the pore system in reservoirs. To better understand fluid
flow in complex porous media, Garing et al. [50], Bird et al. [51], Bultreys et al. [52], Cnudde
and Boone [53], Rabbani et al. [54], Dong et al. [55], Freire-Gormaly et al. [56], and Noiriel
et al. [57] extracted three-dimensional pore network information using segmentation, bina-
rization, skeleton, and other methods. They defined it using porosity distribution, pore
Materials 2023, 16, 1828 3 of 22
radius, pore throat radius, pore throat length, and coordination number. Rötting et al. [58]
discovered that significant dissolution occurred only under certain conditions and pore
sizes. Then, Krebs et al. [59] and Yao et al. [60] used NMRI and microfocused computed
tomography (µCT) techniques to image rock samples before and after dissolution. Both
realized 3D visualization and fine characterization of rocks using µCT as reference visu-
alization technology since it can measure the scale as well as the relationship between
pore and fracture accurately. They further completed the fine description of the scale by
including spatial development as well as distribution characteristics of pores and fissures.
Regarding the dissolution mechanism of carbonate rocks, previous studies on rock
salt primarily began at the macroscopic level. They explained the microscopic dissolution
and the “driving force” of pore development from the perspectives of dissolution kinetics
and diagenesis. Many factors were thought to control the change in pore structure caused
by dissolution, such as fluid temperature, pressure, pH value, porosity, permeability, and
crystal size, but the studies were mostly based on a single environmental equilibrium state,
with little research on multifactor control systems in different occurrence environments.
Furthermore, the solution preparation of the experiment’s reaction was complicated, the
reaction time was long, and the accuracy was low. The acid fluid moved and reacted in
the internal pores of the carbonate rocks during diagenesis. However, existing research
has contributed enormous knowledge to pore system reform under different pressure
and temperature conditions. Fredd and Foggler [61–63], Golfier et al. [64], and Tansey
and Balhoff [65] evaluated the micro-dissolution process, pore structure property change,
and micro-dissolution mechanism under the action of thermal–hydro–chemical coupling.
However, they ignored the relationship between rock and dissolution.
Consequently, to investigate the effect of dissolution on the pore structure of carbonate
rocks under thermal–hydraulic–chemical coupling conditions, the latest continuous flow
microreaction technology was used. Limestone samples from the Dalian coastal area were
chosen for the research. Furthermore, an independently developed rock hydrodynamic
pressure dissolution test device simulated multifactor coupling conditions. The degree of
influence of various influencing factors on rock mass dissolution under thermal–hydraulic–
chemical coupling conditions was investigated, and previous test device limitations were
overcome. The dissolution rate of carbonate rock and the chemical composition of karst
water were quantitatively studied using an orthogonal experimental design, linear regres-
sion analysis, and variance analysis on the test results. Hence, the relationship between
dissolution rate and influencing factors was quantified, and the results were obtained. Next,
CT was used to obtain slice images of the material’s internal structure. The mechanism
and distribution law of dissolved pores in rock salt dissolution was studied. The surface
morphology of rock samples before and after the dissolution was compared and analyzed
microscopically. Next, the characteristics of the microscopic dissolution process and pore
changes of carbonate rocks were investigated. The changes in microstructure parameters
before and after dissolution were quantitatively analyzed, providing a theoretical basis for
the cause, distribution, and prediction of dissolved pores in carbonate rocks.
2. Test Equipment and Experimental Methodology

2.1. Test Samples
The rock samples used in the experiment were gathered from the Dalian Bay shoreline.
This region’s karst formations, including karst caves, dissolved gaps, and dissolution
funnels, are the result of groundwater and seawater erosion as well as the effect of the
surrounding structure. Table 1 comprises a list of the samples’ mineral compositions that
were subjected to X-ray diffraction (XRD) analysis, and Figure 1 shows the results of whole-
rock XRD mineral analysis. The predominant mineral in the rock samples was calcite, with
a small amount of quartz.
surrounding structure. Table 1 comprises a list of the samples’ mineral compositions that
were subjected to X-ray diffraction (XRD) analysis, and Figure 1 shows the results of
Materials 2023, 16, 1828
whole-rock XRD mineral analysis. The predominant mineral in the rock samples was4cal- of 22
cite, with a small amount of quartz.
Table1.
Table XRDanalyses
1.XRD analysesof
ofcarbonate
carbonaterocks
rocks [7].
[7].
Mineral Composition
Mineral Composition Quartz
Quartz Calcite
Calcite Else
Else
Mineral content (%)(%)
Mineral content 1.5 1.5 96.596.5 2.0
2.0
Note:
Note: Other substances
Other substances mainly
mainly include
include weak
weak crystallization
crystallization or amorphous
or amorphous substances.
substances.
Supplementaryfigure
Figure1.1.Supplementary
Figure figureof
ofthe
theX-ray
X-raydiffraction
diffractionwhole-rock
whole-rockmineral
mineralanalysis
analysis [7].
[7].
Table22lists
Table liststhe
thechemical
chemicalmakeup
makeupofofsamples
samplesobtained
obtainedfrom
fromX-ray
X-rayfluorescence
fluorescencespec-
spec-
troscopy. CaO is the main ingredient in the rock samples with 55.41% concentration,
troscopy. CaO is the main ingredient in the rock samples with 55.41% concentration, in-
indicating that these are carbonate rocks.
dicating that these are carbonate rocks.
Table 2. Main chemical composition content of the rock sample and LS (wt%) [7].
Table 2. Main chemical composition content of the rock sample and LS (wt%) [7].
Chemical
Components SiO𝐒𝐢𝐎 𝐂𝐚𝐎 𝐅𝐞2 O Loss on
Chemical 2 𝟐 CaO Fe 𝟐𝐎
3𝟑
𝐂𝐎
CO𝟐2 𝐌𝐠𝐎MgO 𝐀𝐥𝟐 𝐎Al
𝟑 2 O3 SrO SrO Cl Loss on Ignition
Cl
Components Ignition
Mineral content (%) 0.532 55.41 0.206 43.54 0.050 0.053 0.052 0.040 0.117
Mineral content (%) 0.532 55.41 0.206 43.54 0.050 0.053 0.052 0.040 0.117
Considering the low accuracy of CT scanning of large-sized specimens and the de-
mandConsidering
of subsequent the low accuracy
mechanical of CTthe
research, scanning
commonly of large-sized specimens
used large-sized and the
specimens werede-
mand of into
changed subsequent
Φ 12 mm mechanical
× 12 mm research, the commonly
micro-cylindrical used large-sized
rock samples specimens
(Figure 2a) were
using a drill
changed
core into Φ
machine. 12rock
The × 12 mmwere
mm samples micro-cylindrical
washed with rock samples
deionized (Figure
water and 2a)
thenusing
drieda in
drill
a
drying box at 105 °C for 12 h. The samples were weighed with an electronic balance usinga
core machine. The rock samples were washed with deionized water and then dried in
adrying
measuring 105 ◦of
box atrange C for 12 h.
0–120 The an
g and samples were
accuracy ofweighed
0.01 mg.with
Theyan electronic
were balance
numbered, andusing
the
a measuring range of 0–120 g and an accuracy of 0.01 mg. They were numbered,
weight W1 of the samples was recorded before dissolution. Figure 2b shows the solution’s and the
weight W1direction
infiltration of the samples
on thewas
rockrecorded
salt side.before dissolution. Figure 2b shows the solution’s
infiltration direction on the rock salt side.
Materials 2023,
Materials 16,16,
2023, x FOR PEER
x FOR REVIEW
PEER REVIEW 55 of 23
of 23
Materials 2023, 16, 1828 5 of 22
(a)
(a) (b)
(b)
Figure
Figure
Figure 2.2.2. Pictureofof
Picture
Picture ofrock
rocksamples:
rock samples:(a)
samples: rockspecimens;
(a)rock specimens; (b)
specimens;(b) location
(b)location map
locationmap of
mapof the
ofthe rock
therock sample.
rocksample.
sample.
2.2. Test
2.2.Test Device
TestDevice
Device
2.2.
2.2.1. Dissolution
2.2.1.Dissolution
DissolutionTestTest Equipment
TestEquipment
Equipment
2.2.1.
A set
Aset of YYDR-2
setofofYYDR-2 rock
YYDR-2rock hydrodynamic
rockhydrodynamic pressure dissolution
hydrodynamicpressure
pressure dissolutiontest
testequipment
equipment(Figure
(Figure3)3)
based A on microreaction technology was created usingdissolution test equipment (Figure 3)
basedon
based onmicroreaction
microreactiontechnology
technologywas
wascreated usingthe
createdusing thelatest
the latestcontinuous
latest continuousflow
continuous flowmicroreac-
flow microre-
microre-
tion technology
action technology[7].[7].
TheThe
multifactor dynamic
multifactor simulation
dynamic corrosion
simulation test of
corrosion carbonate
test rocks
of carbonate
carbonate
action
under technology
different [7]. The
hydrochemicalmultifactor dynamic
conditions, simulation
temperature corrosion
conditions, test
pressureof conditions,
rocks under different hydrochemical conditions, temperature conditions, pressure condi-
rocks
and under differentconditions
hydrodynamic hydrochemical conditions, temperature conditions, pressure condi-
was realized.
tions, and hydrodynamic conditions was realized.
tions, and hydrodynamic conditions was realized.
Figure3.3.Self-made
Figure Self-made YDYR-2
YDYR-2 rock
rock hydrodynamic
hydrodynamic pressure
pressure dissolution
dissolution test
test equipment
equipment[7].
[7].
Figure 3. Self-made YDYR-2 rock hydrodynamic pressure dissolution test equipment [7].
Thereaction
The reactionchamber
chamberininthe the dissolution
dissolution reaction
reaction system
system cancan simultaneously
simultaneously holdhold
four
fourThe
cylindrical reaction
cylindrical
samples chamber
samples in the
Φ13
withinwithin Φ13
mm dissolution
×mm reaction
× 25 mm.
25 mm. system
Between
Between the can
the upper
upper simultaneously
covercover andmain
and the hold
the main
body
four a cylindrical
isbody coversamples
is a design
cover design within
for an for Φ13seat
inletanfilter
inlet mmthat
filter ×seat
25forms
mm.
that Between
forms theumbrella-shaped
four upper cover
four umbrella-shaped andstructures
the on
structures mainthe
body
upper is and
on the aupper
cover
lowerdesign
and lower
sidesfor an inlet
sides
through filtera seat
through thatdesign.
forms
three-degree
a three-degree four
design. umbrella-shaped
Furthermore,
Furthermore, structures
an outlet
an outlet filter
filter seat
on the cover
seat
cover upper isand
is designed lower
designed sides
between
between through
the abody
the main
main three-degree
body design.
andlower
and the the lowerFurthermore,
cover, cover, and an
and 316L outlet
316L filter
stainless
stainless steel
seat cover
steel is
filters designed
were between
installed in the the main
inlet and body
outletand the
filter lower
seats to cover,
filter and
liquid 316L stainless
impurities
filters were installed in the inlet and outlet filter seats to filter liquid impurities and rock and
steel
rockfilters
residues weredamaged
residues
damaged installed indissolution.
by the inlet and outlet filter seats to filter liquid impurities and
by dissolution.
rock residues damaged by dissolution.
Materials 2023, 16, 1828 6 of 22
2.2.2. CT Scanning Equipment

As a nondestructive testing technology, CT can transmit an object through an X-ray
beam and obtain the internal three-dimensional structural characteristics of the object under
nondestructive testing conditions, such as the distribution of pores and material composition.
Micronano focus CT 3D scanning technology was used to study the microstructure
characterization of rock samples to quantitatively analyze the internal structural characteris-
tics of rock samples before and after dissolution. The diondo d2 high-resolution all-around
micronano focus CT detection system was used for CT scanning. For the detection range,
the specimen was rotated at 360◦ and irradiated. The collected 2D projection images were
reconstructed using computer data to obtain 3D CT volume data. Subsequently, the data
were visually analyzed to form a 3D perspective view.
2.2.3. NMR Equipment

The NMR equipment is the MacroMR12-150H-I MRI Analyzer produced by Numai
Electronic Technology Co., Ltd, Shanghai, China. It can realize the simulation study under
various conditions. The pore size distribution, porosity, pore connectivity, and some
physical properties of rocks can be obtained by measuring the relaxation characteristics
of hydrogen protons contained in the fluid of internal rock pores. Then, the internal
microstructure of rocks can be analyzed qualitatively or quantitatively. Unfortunately, it
cannot achieve DWI and DTI detection and analysis of the related topic.
2.3. Test Plan

The test was divided into two parts. The first was a carbonated water dissolution
test of limestone. The second was a CT scanning of rock salt samples before and after
dissolution to investigate the influence of dissolution on the physical and mechanical
properties of rock salt, particularly the changes in the microscopic results of rock salt before
and after dissolution.
2.3.1. Orthogonal Dissolution Test Scheme

By using the orthogonal design software Latin, an orthogonal experimental design
method, and an orthogonal table the experimental simulation scheme was determined;
some representative points are selected from the comprehensive test for experiments based
on the orthogonality. These representative points are uniformly dispersed, neat, and
comparable. As the main method of analytical factor design, the orthogonal test design
is efficient, fast, and economical. It can significantly reduce workload while determining
the best combination level for various factors. Five influencing factors were chosen: pH,
hydrodynamic pressure, temperature, current speed, and duration, and each was uniformly
set at four levels (Table 3).
Table 3. Research level of orthogonal numerical simulation experimental parameters.
Dissolution Conditions
Level
pH Value Pressure (MPa) Temperature (◦ C) Current Speed (mL·min−1 ) Duration (d)
1 4.6 2 25 15 3
2 5.4 4 45 35 7
3 6.2 6 65 55 14
4 7.0 8 85 75 21
Using orthogonal table L16(45) for scheme design, 16 groups of simulation test schemes
were obtained to carry out the dissolution test of 64 rock samples under 16 groups of
working conditions, and the final values of each factor level are shown in Table 4.
Materials 2023, 16, 1828 7 of 22
Table 4. Orthogonal numerical simulation experimental schemes.
Experimental Dissolution Conditions Parameters

Scheme pH Value Pressure (MPa) Temperature (◦ C) Current Speed (mL·min−1 ) Duration (d)
1 4.6 2 25 15 3
2 4.6 4 45 35 7
3 4.6 6 65 55 14
4 4.6 8 85 75 21
5 5.4 2 45 55 21
6 5.4 4 25 75 14
7 5.4 6 85 15 7
8 5.4 8 65 35 3
9 6.2 2 65 75 7
10 6.2 4 85 55 3
11 6.2 6 25 35 21
12 6.2 8 45 15 14
13 7.0 2 85 35 14
14 7.0 4 65 15 21
15 7.0 6 45 75 3
16 7.0 8 25 55 7
2.3.2. CT Scanning Test Scheme

Because of the restrictions of the test setup, rock samples No. 4 (5-4,6-4,7-4,8-4) from
groups 5 to 8 of the 16 groups of the dissolution test are chosen. These will be referred to as
5#, 6#, 7#, and 8#, respectively, from now on. Two CT tests before and after dissolution are
conducted. The scanning conditions of rock samples are as follows: one layer is scanned
every 0.008 mm from top to bottom, and 1400 layers are scanned continuously. The internal
mesostructural damage changes and macro-dissolution damage of the specimen at the
same position before and after dissolution were compared by measuring the composi-
tion characteristics of the internal structure before rock salt dissolution. This was for CT
macroscopic image analysis and a thorough understanding of the rock microstructure.
2.3.3. NMR Test Scheme

Four rock samples (5#, 6#, 7#, and 8#) selected in the CT test were tested by NMR,
wherein the internal porosity and permeability of the rock samples were quantitatively
analyzed. These could then be compared with the CT scanning results.
2.4. Test Steps

2.4.1. Initial CT Scans of Carbonate Rocks
Four rock samples (5#–8#) were scanned by CT before dissolution; the CT machine
was debugged, the scanning interval was determined, and the number of scanning layers
was chosen. The procedure corresponded with that of the first batch of rock salt samples
and the test results were recorded and analyzed.
2.4.2. Dissolution of Carbonate Rocks

After the initial CT scan of the four sets of rock samples, they were sequentially
placed in the sample bin with the other 12 sets of rock samples in the marked direction of
infiltration. The dissolution test was repeated according to the direction below.
The CO2 gas inlet was set using the gas mass flow controller and the water current
speed using the peristaltic pump. At the gas–liquid micro-mixer, the gas–liquid mixing in
real time was completed. Using the first pH meter, the solvent’s pH level was continuously
monitored in the solvent container. Further, the rock sample was kept in the reactor, and
the oil bath thermostat’s temperature was adjusted to the predetermined test temperature.
Then, the high-pressure constant-current infusion pump’s flow rate was set in accordance
with the demands of the test’s four test circumstances. To create a sample warehouse with
real time was completed. Using the first pH meter, the solvent’s pH level was continu-
ously monitored in the solvent container. Further, the rock sample was kept in the reactor,
and the oil bath thermostat’s temperature was adjusted to the predetermined test temper-
Materials 2023, 16, 1828 ature. Then, the high-pressure constant-current infusion pump’s flow rate was set8in of 22
ac-
cordance with the demands of the test’s four test circumstances. To create a sample ware-
house with a specific pressure and flow rate of carbonic acid water flowing at a fixed tem-
a perature, the backand
specific pressure pressure valve’s
flow rate pressure
of carbonic value
acid wasflowing
water graduallyat amodified. Followingthe
fixed temperature, the
reaction,
back the valve’s
pressure gas–liquid separator’s
pressure value wasseparated
graduallygasmodified.
is immediately
Followingreleased throughthe
the reaction, the
gas–liquid
back pressureseparator’s
valve andseparated
into the gas is immediately
atmosphere. Through released
a steadythrough the back
flow valve, the pressure
separated
valve and
liquid is into the atmosphere.
released into the waste Through
liquidacollection
steady flow valve,The
bottle. thepHseparated liquid is released
of the solution is contin-
into the waste
uously liquidby
monitored collection
the secondbottle.
pHThe pH in
meter of the solution is continuously
bottle. After the test, themonitored
solution wasby
the second pH meter in the bottle. After the test, the solution was collected
collected both before and after dissolution in a high-density polyethylene plastic bottle. both before and
after
The dissolution
rock sample inshould
a high-density
be takenpolyethylene plasticrinsed
out of the reactor, bottle.with
The rock sample
deionized should
water, be
dried,
taken out of
weighed the reactor,
again (W2), and rinsed with deionized
its volume should bewater, dried,(Figure
calculated weighed 4). again (W2), and its
volume should be calculated (Figure 4).
Figure 4. Flow chart of the dissolution test [7].

Figure 4. Flow chart of the dissolution test [7].
2.4.3. Second CT Scanning of Carbonate Rocks
2.4.3. Second CT
Following Scanning the
dissolution, of Carbonate Rocks underwent a second CT scan utilizing the
samples (5#–8#)
identical procedures
Following as the first,
dissolution, the and test results
samples (5#–8#)were again documented
underwent a second CTand
scanexamined.
utilizing the
identical procedures as the first, and test results were again documented and examined.
2.4.4. The NMR of Carbonate Rocks
After
2.4.4. Thethe
NMRsecond CT scan, NMR
of Carbonate Rockstests were performed on the rock samples (5#, 6#, 7#,
and 8#), wherein the test data were recorded and analyzed.
After the second CT scan, NMR tests were performed on the rock samples (5#, 6#, 7#,
3. Resultswherein
and 8#), the test data were recorded and analyzed.
and Discussion
3.1. Analysis of Dissolution Results and Influencing Factors
3. Results and Discussion
The dissolution amount is the weight difference (W1−W2) between the rock sample
3.1. Analysis of Dissolution Results and Influencing Factors
before and after dissolution. The dissolution amount to mass before the test ratio is the
The dissolution
unit mass dissolutionamount,
amount and is the
theweight difference
dissolution rate =(W1−W2) between
dissolution amount the rock sample
(mg)/weight
before and after dissolution. The dissolution amount to mass before
before dissolution (g). Table 5 shows the average dissolution rate of the 16 groups the test ratio is of
the
unit mass dissolution
test conditions. amount, and the dissolution rate = dissolution amount (mg)/weight
before dissolution
In working (g). Table
condition 4, the5 dissolution
shows the average dissolution
rate is 364.43 rate ofinthe
mg/g, while 16 groups
working of test
condition
conditions.
16, it is 3.69 mg/g. There are numerous variations in the dissolution rates.
Materials 2023, 16, 1828 9 of 22
Table 5. Orthogonal test results.
Test Batch Test Specimen Dissolution Rate Test Batch Test Specimen Dissolution Rate
Number Number (mg·g−1 ) Number Number (mg·g−1 )
1–1 12.17 9–1 24.51
1–2 14.67 9–2 22.06
1 1–3 12.08 9 9–3 22.00
1–4 12.22 9–4 22.28
Average value 12.78 Average value 22.71
2–1 65.69 10–1 12.25
2–2 95.12 10–2 12.32
2 2–3 65.38 10 10–3 14.74
2–4 93.14 10–4 12.29
3–1 155.34 11–1 19.75
3–2 200.00 11–2 24.45
3 3–3 141.49 11 11–3 22.00
2–4 202.93 11–4 22.06
4–1 344.66 12–1 22.17
4–2 373.17 12–2 24.51
4 4–3 373.13 12 12–3 24.57
4–4 366.75 12–4 24.57
5–1 108.37 13–1 9.85
5–2 105.65 13–2 14.67
5 5–3 105.13 13 13–3 12.17
5–4 103.96 13–4 12.17
6–1 32.02 14–1 12.25
6–2 31.71 14–2 19.85
6 6–3 26.57 14 14–3 17.16
6–4 34.40 14–4 17.16
7–1 59.11 15–1 9.51
7–2 59.11 15–2 9.50
7 7–3 54.19 15 15–3 7.82
7–4 56.23 15–4 9.40
8–1 29.27 16–1 4.90
8–2 27.30 16–2 2.46
8 8–3 22.11 16 16–3 4.90
8–4 26.89 16–4 2.47
An evaluation of each factor’s primary and secondary influence on the test indexes
using range analysis of orthogonal test results shows that the greater the range, the greater
the influence of the factor’s level change on the test index. Thus, the range is the most
important factor. Table 5 shows the average value and range of each level of each factor.
Conversely, Table 6 shows the range analysis results for the dissolution rate. Figure 5 shows
the sensitivity analysis chart of the dissolution rate. The graph shows that the influence
factor pH is the most significant and that the temperature, current speed, and pressure are
all similar. Consequently, the sensitivity of each factor to the dissolution rate was pH >
time > temperature > current speed > pressure, implying that pH was an important factor
in the dissolution rate of specimens.
Conversely, Table 6 shows the range analysis results for the dissolution rate. Figure 5
shows the sensitivity analysis chart of the dissolution rate. The graph shows that the in-
fluence factor pH is the most significant and that the temperature, current speed, and
pressure are all similar. Consequently, the sensitivity of each factor to the dissolution rate
Materials 2023, 16, 1828 was pH > time > temperature > current speed > pressure, implying that pH was an10im- of 22
portant factor in the dissolution rate of specimens.
Table 6. Extreme range analysis of dissolution rate of specimens (mg·g–1).

Table 6. Extreme range analysis of dissolution rate of specimens (mg·g−1 ).
Level pH Value Pressure (MPa) Temperature (°C) Current Speed (mL·
min–1) Duration (d)
Level pH Value Pressure (MPa) Temperature (◦ C) Current Speed (mL·min−1 )Duration (d)
1 157.938 38.373 17.422 27.623 15.310
2 1 55.123157.938 38.373
35.105 17.422
54.670 27.623
35.117 15.310
40.835
2 55.123 35.105 54.670 35.117 40.835
3 20.410 65.787 60.115 74.282 60.523
3 20.410 65.787 60.115 74.282 60.523
4 4 10.41510.415 104.620
104.620 111.678
111.678 106.862
106.862 127.218
127.218
Range
Range 147.523147.523 69.515
69.515 94.256
94.256 79.239
79.239 111.908
111.908
Figure 5. Sensitivity analysis of dissolution rate.

Figure 5. Sensitivity analysis of dissolution rate.
Table 7 shows the variance analysis table of the sample dissolution rate. It can be
Table from
observed 7 shows
the the variance
table that theanalysis
solutiontable
pH of
hadthethe
sample dissolution
greatest rate.rate
contribution It can
to be
the
observed from the table that the solution pH had the greatest contribution rate to
sample dissolution rate, which was 42.36%, followed by time, which was 21.37%. Hence, the sam-
ple
thedissolution
pH value hadrate, which wasimpact
a significant 42.36%,onfollowed
the rate by time, which
of sample was 21.37%. Hence, the
dissolution.
pH value had a significant impact on the rate of sample dissolution.
Table 7. Variance analysis of dissolution rate of the specimen (mg·g−1 ).
Table 7. Variance analysis of dissolution rate of the specimen (mg·g–1).
Deviation Degree of F Critical Contribution Rate
Factor FF Compar-
Comparison Contribution Rate
Factor Deviation Quadratic
QuadraticSum
SumDegreeFreedom
of Freedom F CriticalValue
Value (%)
ison (%)
pH Value 54,551.244 3 2.118 3.290 42.36
pH Value 54,551.244 3 2.118 3.290 42.36
Pressure (MPa) 12,432.704 3 0.483 3.290 9.65
Pressure (MPa) ◦
Temperature ( C) 12,432.704
18,032.225 33 0.483
0.700 3.290
3.290 9.65
14.00
Temperature
Current Speed (mL·min−1 ) 18,032.225
(°C) 16,255.007 33 0.700
0.631 3.290
3.290 14.00
12.62
Duration
Current Speed (d) 27,516.741 3 1.068 3.290 21.37
Deviation 16,255.007
128,787.92 315 0.631
- 3.290 - 12.62-
(mL·min )−1
Duration (d) 27,516.741 3 1.068 3.290 21.37

Deviation 3.2. Analysis of CT Scan Test
128,787.92 15Results - - -
To determine the controlling effect of the pore structure on the evolution of corroded
pores, the internal pores of the four groups of rock samples were compared and analyzed
before and after dissolution. The pore structure characteristics, such as porosity, pore size
distribution, pore number, and pore volume, were quantitatively evaluated.
Materials 2023, 16, 1828 11 of 22
3.2.1. Spatial Distribution Characteristics of Pores

The gray scale is indicated by the light and dark degrees of the CT image, while the
change in material density shows the change in the gray value in the image. The bright
white area with the larger grayscale is the high-density area, mostly made of rock salt
particles and cement. The small gray scale is a low-density area with pores, holes, cracks,
and other parts on the sample’s cross-section. CT scanning parameters should be consistent
with the cross-section, allowing the comparison of internal mesostructural damage and
macro-dissolution damage of rock salt at the same position before and after dissolution.
The scanning layer thickness was 0.008 mm in the experiment, and three scanning layers of
150, 750, and 1350 were chosen for comparison. Moreover, the spatial distribution of pores
and fractures and the mineral distribution characteristics were qualitatively analyzed.
The salt samples’ water inflow and infiltration directions are 150–750–1350 horizons.
Figure 6 depicts a cross-sectional view of the CT scanning of the four groups of samples
before and after the dissolution of the three horizons. The CT scan images before rock
salt dissolution in different zones had different light and dark ranges, indicating that the
density distribution was uneven. Furthermore, the rock salt observed was a medium with
nonuniform initial damage, primarily micropores and microcracks.
There are many abnormally low-density areas in the three horizons in the initial scan-
ning image of sample 5#. The density of the sample was unevenly distributed, indicating a
concentrated area of pores and cracks, which was essentially a microcrack development
zone with an extremely fragile structure. After salt dissolution, the abnormally low-density
areas grew extensively, a few pores enlarged, and fractures began to penetrate, indicat-
ing that the particles, arrangement forms, and fracture structures in the rock salt layers
were extremely uneven. The presence of low-density areas and dissolution increased the
dispersion of the rock salt’s internal structure, characterized by dissolution. Some rock
salt-soluble substances were removed from the solution, allowing fractures to form. One
hundred fifty horizons performed well, porosity varied greatly, and the density of different
areas increased unevenly in the other horizons.
The gray scale distribution of three horizons in the initial scanning image of rock
sample 7# was relatively uniform, with only a few abnormally low-density areas; the closer
to the edge of the image before salt dissolution, the greater the grayscale, which means
the greater the density of this area. The initial rock salt edge density was high, the density
of the central area was low, and the structure was fragile. When the image’s brightness
was compared before and after dissolution, the grayscale of the edge area of each horizon
increased noticeably. However, the grayscale of the other areas did not. That is, the initial
rock salt’s edge density was high, the density of the central area was low, and the structure
was fragile. When the image’s brightness was compared before and after dissolution, the
grayscale of the edge area of each horizon increased noticeably. In contrast, the grayscale of
the other areas did not.
The gray scale distribution of the three horizons was relatively uniform in the initial
scanning images of rock samples 6# and 8#, with only a few abnormally low-density areas,
scattered pores, and little damage to the internal structure. There was no obvious change
in the overall grayscale of the image before and after the dissolution of the rock salt, and
only the local area of the rock salt was abnormal. Hence, the grayscale increased.
Materials 2023, 16, 1828Materials 2023, 16, x FOR PEER REVIEW 12 of 22 12 of
Figure 6.view
Figure 6. Cross-sectional Cross-sectional
of CT scan.view of CT scan.
3.2.2. Quantitative Characterization of Pore Structure

There are many abnormally low-density areas in the three horizons in the initial sca
1. ning image of sample 5#. The density of the sample was unevenly distributed, indicatin
Porosity change
a concentrated area of pores and cracks, which was essentially a microcrack developme
The ratio ofzone
porewith
volume to total volume
an extremely obtainedAfter
fragile structure. fromsalt
CT dissolution,
scanning images of rock low-de
the abnormally
samples, including closed pores and connected pores, was defined as porosity.
sity areas grew extensively, a few pores enlarged, and fractures began to The initial
penetrate, ind
porosities of thecating
four rock samples were 0.189%, 0.023%, 0.029%, and 0.115%, respectively.
that the particles, arrangement forms, and fracture structures in the rock salt laye
Porosities were compared before
were extremely and after
uneven. Thedissolution
presence ofunder four different
low-density areas andtest conditions.
dissolution increased t
After dissolution, porosity was greater than before dissolution, increasing by
dispersion of the rock salt’s internal structure, characterized by dissolution.0.140%, Some ro
0.038%, 0.042%, salt-soluble
and 0.126%,substances
respectivelywere(Figure
removed 7). from
The initial porosity
the solution, of carbonate
allowing rock
fractures to form. O
significantly affected the increase in dissolution-induced porosity. Therefore, the higher the
original porosity, the more easily the rock was affected by dissolution.
The ratio of pore volume to total volume obtained from CT scanning images of rock
samples, including closed pores and connected pores, was defined as porosity. The initial
porosities of the four rock samples were 0.189%, 0.023%, 0.029%, and 0.115%, respectively.
Porosities were compared before and after dissolution under four different test condi-
tions. After dissolution, porosity was greater than before dissolution, increasing by
Materials 2023, 16, 1828 0.140%, 0.038%, 0.042%, and 0.126%, respectively (Figure 7). The initial porosity of car- 13 of 22
bonate rock significantly affected the increase in dissolution-induced porosity. Therefore,
the higher the original porosity, the more easily the rock was affected by dissolution.
Figure7. 7.
Figure Porosity
Porosity comparison
comparison before
before and afterand after dissolution.
dissolution.
Materials 2023, 16, x FOR PEER REVIEW 14 of 23

Figure
Figure8 shows the change
8 shows in the porosity
the change in the distribution of the rock samples
porosity distribution of thebefore
rockand
samples before and
after dissolution under different test conditions. The initial porosity of the different rock
after dissolution under different test conditions. The initial porosity of the different rock
samples (before dissolution) varied due to the heterogeneity of rock samples. The flow of
samples (before dissolution) varied due to the heterogeneity of rock samples. The flow of
thedissolution
the dissolution liquid
liquid was from
was from the topthe topbottom.
to the to the The
bottom. The
porosity porosity showed
distribution distribution showed
thatdissolution
that dissolution could
could improve
improve overalloverall
porosity.porosity. Furthermore,
Furthermore, the change inthe change
porosity ranin porosity ran
throughout
throughout thethe entire
entire sample,
sample, indicating
indicating that the that thecorroded
sample sampleincorroded in three
three directions of directions of
the
therectangular
rectangular coordinate system.
coordinate Since the
system. porosity
Since of the upper
the porosity of part was greater
the upper partthan
was greater than
that
thatofofthe
thelower
lower part, particularly
part, at theattop
particularly theoftop
the of
sample, it reacted
the sample, with the with
it reacted carbonic
the carbonic acid
acid solution entering the reactor, causing it to erode faster than the rest of the rock sample.
solution entering the reactor, causing it to erode faster than the rest of the rock sample.
(a) (b)
(c) (d)
Figure
Figure8. 8.
Changes of porosity
Changes distribution
of porosity of carbonate
distribution ofsamples before
carbonate and afterbefore
samples dissolution:
and (a)
after dissolution:
sample 5#, (b) sample 6#, (c) sample 7#, and (d) sample 8#.
(a) sample 5#, (b) sample 6#, (c) sample 7#, and (d) sample 8#.
2. Pore number and volume change
The number and volume of pores in carbonate samples were determined before and
after dissolution under various test conditions. In the four groups of rock samples, the
number of pores ranged from 2716 to 19,683. The number of pores decreased by 5429, 95,
331, and 4406, but the pore volume increased by 1.63 mm3, 0.53 mm3, 0.58 mm3, and 1.88
Materials 2023, 16, 1828 14 of 22
2. Pore number and volume change

The number and volume of pores in carbonate samples were determined before and
after dissolution under various test conditions. In the four groups of rock samples, the
number of pores ranged from 2716 to 19,683. The number of pores decreased by 5429,
95, 331, and 4406, but the pore volume increased by 1.63 mm3 , 0.53 mm3 , 0.58 mm3 , and
1.88 mm3 , respectively, after dissolution. The reduction in pore number and the increase in
pore volume indicated that some pores merged to form larger ones.
Following the overall characterization of pores, the number and volume percentage
of pores were statistically classified from the perspective of single pore volume to deeply
analyze the pore structure and distribution of the four groups of the rock samples. Figure 9
Materials 2023, 16, x FOR PEER REVIEWshows that as pore volume increased, the number of pores and the percentage 15ofof pore
23
volume increased at first and then decreased. Before dissolution, the percentage distri-
bution of pore volume had the characteristics of the right deviation under different test
conditions. However, after dissolution, the percentage distribution of pore volume has
characteristics of left of
the characteristics deviation, and most
left deviation, andof the of
most kurtosis valuesvalues
the kurtosis decreased, indicating
decreased, that
indicating
thethat
distribution peak was flatter than before dissolution. When the pore volume of
the distribution peak was flatter than before dissolution. When the pore volume of a a single
pore exceeded
single 0.0001 mm
pore exceeded
3, the percentage
0.0001 of pore volume
mm3 , the percentage of poreincreased significantly,
volume increased reach-
significantly,
ing the highest values of 48.6%, 37.5%, 41.9%, and 59.3%, and increasing by 11.7%,
reaching the highest values of 48.6%, 37.5%, 41.9%, and 59.3%, and increasing by 11.7%, 10.7%,
19.3%,
10.7%, and 37.5%,
19.3%, andrespectively, exceeding
37.5%, respectively, that before
exceeding thatdissolution.
before dissolution.
(a) (b)
(c) (d)
Figure
Figure 9. 9. Relationship
Relationship between
between porequantity
pore quantityandandthe
thecorresponding
correspondingvolume
volumepercentage
percentage for
for differ-
different
entpore
porevolumes:
volumes:(a) sample5#,
(a)sample 5#,(b) sample6#,
(b)sample 6#,(c) sample7#,
(c)sample 7#,and
and(d) sample8#.
(d)sample 8#.
3. 3. Change
Change
in in pore
pore size
size distribution
distribution
Each
Each pore
pore size
size ofof rock
rock samples
samples was
was extracted
extracted and
and characterized
characterized bybyCTCT scanning
scanning to to
quantitatively
quantitatively analyze
analyze thethe pore
pore size
size characteristics
characteristics of of rock
rock samples,
samples, and
and thethe average
average pore
pore
size
size of of carbonate
carbonate samples
samples before
before and
and after
after dissolution
dissolution under
under different
different test
test conditions
conditions was
was
obtained.
obtained. The
The average
average porepore diameter
diameter increased
increased byby 0.027
0.027 mm,
mm, 0.013
0.013 mm,
mm, 0.013
0.013 mm,
mm, and
and
0.034 mm from 0.075 mm, 0.077 mm, 0.065 mm, and 0.082 mm before dissolution, resulting
in a 1.36, 1.17, 1.2, and 1.41-fold increase in the initial state of the average aperture ratio.
To thoroughly examine the pore size characteristics of the four groups of rock sam-
ples, the pore number and pore size percentage were statistically classified from the angle
Materials 2023, 16, 1828 15 of 22
0.034 mm from 0.075 mm, 0.077 mm, 0.065 mm, and 0.082 mm before dissolution, resulting
in a 1.36, 1.17, 1.2, and 1.41-fold increase in the initial state of the average aperture ratio.
To thoroughly examine the pore size characteristics of the four groups of rock samples,
the pore number and pore size percentage were statistically classified from the angle of
a single pore diameter after the overall description of the average. Figure 10 shows the
pore size distribution (PSD) before and after dissolution. Before dissolution, the PSD of
carbonate rocks in four test conditions was logarithmic right, with many pore diameters
less than 0.05 mm and a pore size percentage greater than 40%. Regardless of the changes
in test conditions after dissolution, the PSD remained right but shifted slightly to16
Materials 2023, 16, x FOR PEER REVIEW theof left,
23
indicating that the pore diameter increased. When the pore diameter was greater than
0.15 mm, the number after the dissolution was above that before dissolution. The PSD curve
was flatter than before dissolution, indicating a decrease in the number. The increased PSD
PSD skewness after dissolution confirmed the increase in the overall aperture. Further-
skewness after dissolution confirmed the increase in the overall aperture. Furthermore,
more, the reduced PSD kurtosis indicated increased aperture ratios scattered around the
the reduced PSD kurtosis indicated increased aperture ratios scattered around the median
median value before dissolution.
value before dissolution.
Compared with the change law of dissolution results, there was no direct correlation
Compared with the change law of dissolution results, there was no direct correlation
between pore size change and dissolution rate. Hence, heterogeneity and numerous un-
between pore size change and dissolution rate. Hence, heterogeneity and numerous
stable carbonate minerals were the key factors for the pore size increase.
unstable carbonate minerals were the key factors for the pore size increase.
(a) (b)
(c) (d)
10.Relationship
Figure10.
Figure Relationship between
between pore number and and the
the corresponding
correspondingpore
porepercentage
percentagefor
fordifferent
different
porediameters:
pore diameters:(a) sample 5#;
(a) sample 5#; (b) sample 6#; (c) sample
6#; (c) sample7#; (d)sample
7#;(d) sample8#.
8#.
3.3.
3.3.Analysis
Analysis of
of NMR
NMR Test
Test Results
Results
TT22 spectrum
spectrum analysis was
analysis conducted on
was conducted on the
the rock
rock samples
samples (5#,
(5#, 6#,
6#,7#,
7#,and
and8#),
8#),and
and
NMR
NMR test results were obtained, including T22 spectrum curve, total atlas area, number ofof
test results were obtained, including T spectrum curve, total atlas area, number
wave
wavepeaks,
peaks,and
andcorresponding
corresponding peak
peak area. The starting
area. The starting and
and ending
endingpoints
pointsof ofpeaks
peakswere
were
also
alsoacquired.
acquired.
3.3.1. T2 Spectrum Analysis

The T2 distribution is related to pore size, while the number and size of each sample
peak value can be clearly and intuitively seen. The T2 spectrum ranging from small to large
represents micropores, small pores, mesoporous pores, large pores, and cracks, respec-
tively. According to research results [66], the three spectral peaks corresponding to the T2
Materials 2023, 16, 1828 16 of 22
3.3.1. T2 Spectrum Analysis

The T2 distribution is related to pore size, while the number and size of each sample
peak value can be clearly and intuitively seen. The T2 spectrum ranging from small to large
represents micropores, small pores, mesoporous pores, large pores, and cracks, respectively.
According to research results [66], the three spectral peaks corresponding to the T2 spectrum
of 0.5–2.5 ms, 20–50 ms, and greater than 100 ms, represent adsorption pore, seepage pore,
and fracture, respectively, for physical property analysis. The larger the spectral peak, the
more developed the pore fissure.
Figure 11 shows the T2 spectrum of four groups of rock samples. It is obvious that
two peaks appear in rock samples 5# and 6#, while three peaks appear in rock17samples
Materials 2023, 16, x FOR PEER REVIEW of 23 7#
and 8#. The first and second peak wave of sample 5# appeared at 0.005 ms and 2.582 ms,
while the end time was 2.382 ms and 148.202 ms, respectively. Additionally, the adsorption
space
whileandtheseepage
end time space developed
was 2.382 ms andwhile connectivity
148.202 between
ms, respectively. the two types
Additionally, of pores was
the adsorp-
good.
tion space and seepage space developed while connectivity between the two types The
Meanwhile, the adsorption capacity and seepage conditions were strong. of first
andpores was good. Meanwhile, the adsorption capacity and seepage conditions were strong. time
second peak wave of sample 6# appeared at 0.005 ms and 4.199 ms, while the end
wasThe0.766
firstmsandand 27.050
second peakms, respectively.
wave of sample 6#Inappeared
addition,atthe adsorption
0.005 ms and 4.199space
ms,and
whileseepage
the end
space time was
developed 0.766connectivity
while ms and 27.050 ms, respectively.
between In addition,
the two types thewas
of pores adsorption space
weak. Meanwhile,
theand seepage space
adsorption developed
capacity while connectivity
and seepage between
conditions were the two
strong. Thetypes
first,of pores was
second, and third
peak waves of rock sample 7# appeared at 0.005 ms, 3.293 ms, and 283.309The
weak. Meanwhile, the adsorption capacity and seepage conditions were strong. ms,first,
while the
endsecond,
time was and3.037
third ms,
peak57.709
wavesms,of and
rock 690.551
sample ms,
7# appeared at 0.005
respectively. ms, 3.293 the
Meanwhile, ms,adsorption
and
283.309 ms, while the end time was 3.037 ms, 57.709 ms, and 690.551 ms, respectively.
space and seepage space developed with a few crack spaces. Additionally, connectivity
Meanwhile, the adsorption space and seepage space developed with a few crack spaces.
between the three types of pores was weak while the adsorption capacity and seepage
Additionally, connectivity between the three types of pores was weak while the adsorp-
conditions
tion capacitywereand
strong.
seepageThe first, second,
conditions were and third
strong. Thepeak
first,wave
second,ofand
rockthird
sample
peak8# appeared
wave
at 0.005
of rockms, 3.571
sample 8# ms, and 60.802
appeared at 0.005ms,
ms, while theand
3.571 ms, end timems,
60.802 was 1.868
while thems,
end56.072
time wasms, and
307.211 ms,56.072
1.868 ms, respectively.
ms, and Meanwhile, the adsorption
307.211 ms, respectively. space and
Meanwhile, seepage space
the adsorption spacedeveloped
and
with a small
seepage part
space of fracture
developed withspace.
a smallIn addition,
part connectivity
of fracture between
space. In addition, the threebe-
connectivity types of
pores
tweenwas theweak
threewhile thepores
types of seepage condition
was weak while was strong.condition was strong.
the seepage
(a) (b)
(c) (d)
Figure 11. T2 spectrum of carbonate samples after dissolution under different test conditions: (a)
Figure 11. T2 spectrum of carbonate samples after dissolution under different test conditions:
sample 5#; (b) sample 6#; (c) sample 7#; (d) sample 8#.
(a) sample 5#; (b) sample 6#; (c) sample 7#; (d) sample 8#.
3.3.2. Pore Structure Analysis
Table 8 shows the NMR test results of four rock samples, including the time point of
wave crest, the area of each peak, and the peak proportion.
Materials 2023, 16, 1828 17 of 22
Materials 2023, 16, x FOR PEER REVIEW 18 of 23
3.3.2. Pore Structure Analysis

Table 8.Table 8 shows
Magnetic the NMR
resonance test
data of results of
carbonate four rock samples, including the time point of
rocks.
wave crest, the area of each peak, and the peak proportion.
Rock Sam- Total Spectral Peak Point Peak Proportion
Wave Peaks Peak Area
ple Area Time
Table 8. Magnetic resonance data of carbonate rocks. (%)
1 0.369 1012.26 0.48
5#Rock 2106.97
Total Spectral 2 Wave Peak Point 1094.71
34.489 Peak Area
Peak Proportion
0.52
Sample Area Peaks Time (%)
1 0.289 583.43 0.54
6# 1075.75
5# 2106.97 2 1 0.369
11.098 1012.26
492.32 0.560.48
2 34.489 1094.71 0.52
1 1 0.289
0.289
1034.44
583.43
0.650.54
7# 6# 1075.75
1601.11 2 2 12.034
11.098 512.41
492.32 0.320.56
3 1 460.592
0.289 53.66
1034.44 0.030.65
7# 1601.11 1 2 12.034
0.227 512.41
946.82 0.530.32
3 460.592 53.66 0.03
8# 1792.93 2 6.295 546.39 0.30
1 0.227 946.82 0.53
8# 1792.93 3 2 174.263
6.295 299.72
546.39 0.170.30
3 174.263 299.72 0.17
The total spectrum area can quantitatively show the difference of total porosity be-
tween different samples, which is consistent with the porosity distribution extracted by
The total spectrum area can quantitatively show the difference of total porosity be-
CT analysis. The value of rock sample 5# is the largest and that of rock sample 6# is the
tween different samples, which is consistent with the porosity distribution extracted by CT
smallest.
analysis. The value of rock sample 5# is the largest and that of rock sample 6# is the smallest.
Figure
Figure1212can clearly
can clearlyand
anddirectly show
directly show the pore
the diameter
pore diameterproportion
proportionofof
each sample
each sample
which
whichisismainly
mainlycomposed
composedof ofadsorption
adsorption pore,
pore, seepage pore, and
seepage pore, andfracture.
fracture.The
Thedistribution
distribu-
tion pattern
pattern of of differentrock
different rockpore
poresizes
sizesisis essentially
essentially consistent
consistent with
with that
thatobtained
obtainedbybyCT CT
scanning. After dissolution, pore diameter increases, and dispersed
scanning. After dissolution, pore diameter increases, and dispersed pore pore sizes near
sizes nearthe
the
median
median value
valueincrease.
increase.
Figure 12.12.
Figure Proportion
Proportion ofof
thethe aperture
aperture distribution
distribution after
after dissolution
dissolution under
under different
different testconditions.
test conditions.
4. 4. Summary
Summary andand Conclusions
Conclusions
InIn thisstudy,
this study,self-developed
self-developed carbonate
carbonate dissolution
dissolutiontest
testequipment
equipmentwas
wasused
usedtoto
perform
per-
dynamic dissolution and CT tests on carbonate rocks under thermal–hydraulic–chemical
form dynamic dissolution and CT tests on carbonate rocks under thermal–hydraulic–
coupling conditions and to investigate the dissolution effect and micro-development law
chemical coupling conditions and to investigate the dissolution effect and micro-develop-
of carbonate rocks under complex conditions. The main conclusions are as follows:
ment law of carbonate rocks under complex conditions. The main conclusions are as fol-
lows: The highest dissolution rate can be achieved under working condition 4 (when the
1.
five influence factors of the test are set at pH 4.6, 8 MPa, 85 ◦ C, 75 mL·min−1 , and
1. The highest dissolution rate can be achieved under working condition 4 (when the
five influence factors of the test are set at pH 4.6, 8 MPa, 85 °C, 75 mL·min−1, and 21
days). The rate is 364.43 mg/g. The lowest dissolution rate can be attained under
Materials 2023, 16, 1828 18 of 22
21 days). The rate is 364.43 mg/g. The lowest dissolution rate can be attained under
working condition 16 (when five influence factors of the test are set at pH 7.0, 8 MPa,
25 ◦ C, 55 mL·min−1 , and 7 days). The lowest rate is 3.69 mg/g. The dissolution
rate is proportional to the flow velocity, temperature, and hydrodynamic pressure
and inversely proportional to the pH. Furthermore, the sensitivity, significance, and
contribution rate of each influencing factor to each parameter were determined using
range analysis and variance analysis. The most influential factor in the dissolution
effect is pH, followed by time, temperature, current speed, and hydrodynamic pres-
sure. Moreover, pH has the greatest contribution rate to the erosion rate of rock
samples, accounting for 42.36%, followed by time, temperature, current speed, and
hydrodynamic pressure.
2. Carbonate rocks have a complex pore space system with different pore compositions
at the same facilities. The initial porosity of the four rock samples (5#–8#) was 0.189%,
0.023%, 0.029%, and 0.115%, and an increase of 0.140%, 0.038%, 0.042%, and 0.126%,
respectively, was observed after the dissolution. The dissolution can improve overall
porosity, and the initial porosity of carbonate rock significantly affected the increase in
the dissolution-induced porosity. The change in porosity runs throughout the entire
sample; the porosity of the upper part is greater than that of the lower part [67].
3. The total number of pores decreases, while the volume of pores increases after rock
dissolution. The number and percentage distribution of pores before and after disso-
lution increase and decrease as the single pore volume increases [68]. The percentage
distribution of pore volume before dissolution has the characteristics of right devi-
ation. Moreover, the percentage distribution of pore volume after dissolution has
the characteristics of left deviation, and the peak distribution is flatter than before
dissolution. When the single pore volume exceeds 0.0001 mm3 , the pore volume
percentage significantly increases. After dissolution, the average pore size of rock
samples increased with the same distribution trend. The corresponding pore size
decreased as the single pore size increased before and after dissolution. The PSD
of carbonate rocks is logarithmic right deviation before dissolution and slightly left
deviation after dissolution. The increased PSD skewness confirms the increase in
overall pore size, and the decreased PSD kurtosis shows more aperture ratios scattered
around the median before dissolution [69].
The dissolution of carbonate rocks is controlled by karst thermal–hydro–chemical
factors, followed by groundwater pH value, reaction time, temperature, groundwater runoff
change, and hydrodynamic pressure. The micropore structure can regulate the quality of
dissolved pore formation. Furthermore, rock salt is an uneven medium with initial damage,
primarily micropores and microcracks. When acid fluid migrates and reacts in the internal
pores of rocks, minerals on the pores’ edges dissolve, causing changes in the pore space.
Furthermore, some pores merge to form larger pores during the dissolution process. As
pore volume increases, the number and percentage of pores increase and decrease. The
altered pores alter the fluid migration process in the rock, exacerbating the formation of
dissolution pores. Moreover, most dissolved pores are the result of initial pore enlargement
rather than the formation of a new pore system. Heterogeneity, the presence of unstable
minerals, and a large initial pore size result in the formation of large pores and a new pore
system, which are also key factors in pore size increase. This study provides a foundation
for predicting the dissolution effect and the evolution law of dissolved pores in carbonate
rocks under multifactor coupling conditions. It has important guiding implications for
engineering design and construction in karst areas.
Different mesostructure evaluation methods have their respective advantages and
disadvantages. Pore structure characteristics of rock samples are observed using CT, and are
roughly consistent with the change of carbonate rock porosity in NMR. The characterization
of the overall distribution of pores is also consistent [34,70,71]. The porosity of the rock
sample is larger than that before corrosion, and corrosion preferentially affects the large
pore size. However, the CT scan field of view is too small and limited by the number of
Materials 2023, 16, 1828 19 of 22
rock samples [72]. For the further identification of carbonate rocks, the NMR experiment
can be combined with the CT scanning experiment technology. The DWI method makes
it possible to study 3D fluid flow, directly understand the connectivity of pore space, and
contribute dynamic value to standard imaging techniques [37]. Additionally, by taking µCT
technology as reference visualization technology, a fine description of the scale and spatial
development and distribution characteristics of pores and fissures should be conducted, to
establish the NMR identification method of core pores and fractures in carbonate reservoirs
to obtain more perfect pore structure data and provide assurance for the safety evaluation
of karst geological disasters [73,74].
Author Contributions: Conceptualization, J.M. and S.C.; Formal analysis, J.M., Z.C. and J.Z.; Funding
acquisition, S.C. and J.W.; Methodology, J.M. and J.W.; Project administration, S.C.; Resources, S.C.
and J.W.; Supervision, S.C.; Writing—Original draft, J.M.; Writing—review and editing, J.M., Z.C.
and J.Z. All authors have read and agreed to the published version of the manuscript.
Funding: This study was supported by the National Natural Science Foundation of China (Grant no.
51974187), the Natural Science Foundation of Liaoning Province (Grant no. 2019-MS-242), and Liaon-
ing Provincial Education Department focusing on tackling key problems (Grant no. LZGD2020004).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data used to support the findings of this study are available from
the corresponding author upon request.
Conflicts of Interest: The authors declare no conflict of interest.
References
1. Morse, J.W.; Arvidson, R.S.; Lüttge, A. Calcium Carbonate Formation and Dissolution. Chem. Rev. 2007, 107, 342–381. [CrossRef]
[PubMed]
2. Burdige, D.J.; Hu, X.; Zimmerman, R.C. The Widespread Occurrence of Coupled Carbonate Dissolution/Reprecipitation in
Surface Sediments on the Bahamas Bank. Am. J. Sci. 2010, 310, 492–521. [CrossRef]
3. Lunstrum, A.; Berelson, W. CaCO3 dissolution in carbonate-poor shelf sands increases with ocean acidification and porewater
residence time. Geochim. Cosmochim. Acta 2022, 329, 168–184. [CrossRef]
4. Cai, W.J.; Feely, R.A.; Testa, J.M.; Li, M.; Evans, W.; Alin, S.R.; Xu, Y.Y.; Pelletier, G.; Ahmed, A.; Greeley, D.J.; et al. Natural and
Anthropogenic Drivers of Acidification in Large Estuaries. Annu. Rev. Mar. Sci. 2021, 13, 23–55. [CrossRef] [PubMed]
5. Araújo, R.E.B.; La Bruna, V.; Rustichelli, A.; Bezerra, F.H.R.; Xavier, M.M.; Audra, P.; Barbosa, J.A.; Antonino, A.C.D. Structural
and Sedimentary Discontinuities Control the Generation of Karst Dissolution Cavities in a Carbonate Sequence, Potiguar Basin,
Brazil. Mar. Pet. Geol. 2021, 123, 104753. [CrossRef]
6. Zhang, C. Carbonate Rock Dissolution Rates in Different Landuses and Their Carbon Sink Effect. Chin. Sci. Bull. 2011, 56,
3759–3765. [CrossRef]
7. Meng, J.Z.; Chen, S.L.; Wang, J.X.; Chen, Z.; Zhang, J.Y. Development and application of carbonate dissolution test equipment
under thermal–hydraulic–chemical coupling condition. Materials 2022, 15, 7383. [CrossRef]
8. Sjöberg, E.L.; Rickard, D.T. Temperature dependence of calcite dissolution kinetics between 1 and 62 ◦ C at pH 2.7 to 8.4 in aqueous
solutions. Geochim. Cosmochim. Acta 1984, 48, 485–493. [CrossRef]
9. Amrhein, C.; Jurinak, J.J.; Moore, W.M. Kinetics of Calcite Dissolution as Affected by Carbon Dioxide Partial Pressure. Soil Sci.
Soc. Am. J. 1985, 49, 1393–1398. [CrossRef]
10. Buhmann, D.; Dreybrodt, W. Calcite dissolution kinetics in the system H2 O–CO2 –CaCO3 with participation of foreign ions. Chem.
Geol. 1987, 64, 89–102. [CrossRef]
11. Ma, K.; Liu, G. Three-dimensional discontinuous deformation analysis of failure mechanisms and movement characteristics of
slope rockfalls. Rock Mech. Rock Eng. 2022, 55, 275–296. [CrossRef]
12. Plummer, L.N.; Parkhurst, D.L.; Wigley, T.M.L. The kinetics of calcite dissolution in CO2 –water systems at 5 to 60 ◦ C and 0.0 to
1.0 atm CO2 . Am. J. Sci. 1978, 278, 179–216. [CrossRef]
13. Plummer, L.N.; Parkhurst, D.L.; Wigley, T.M.L. Critical review of the kinetics of calcite dissolution and precipitation. In Chemical
Modeling in Aqueous Systems; Amer Chemical Society: Washington, DC, USA, 1979; Volume 93, pp. 537–573.
14. Liu, L.H.; Ma, Y.S.; Liu, B.; Wang, C.L. Hydrothermal dissolution of Ordovician carbonates rocks and its dissolution mechanism
in Tarim Basin, China. Carbonates Evaporites 2017, 32, 525–537. [CrossRef]
15. Bai, Y.; Liu, Q.; Gu, Z.; Lu, Y.; Sheng, Z. The Dissolution Mechanism and Karst Development of Carbonate Rocks in Karst Rocky
Desertification Area of Zhenfeng–Guanling–Huajiang County, Guizhou, China. Carbonates Evaporites 2019, 34, 45–51. [CrossRef]
Materials 2023, 16, 1828 20 of 22
16. Zhang, K.N.; Zhu, K.F.; He, Y.; Zhang, Y.Y. Experimental study on karst development characteristics of calcrete and analysis of its
dissolution mechanism. Carbonates Evaporites 2022, 37, 41. [CrossRef]
17. Alkattan, M.; Oelkers, E.H.; Dandurand, J.L.; Schott, J. An experimental study of calcite and limestone dissolution rates as a
function of pH from −1 to 3 and temperature from 25 to 80 ◦ C. Chem. Geol. 1998, 151, 199–214. [CrossRef]
18. Pokrovsky, O.S.; Golubev, S.V.; Schott, J. Dissolution Kinetics of Calcite, Dolomite and Magnesite at 25 ◦ C and 0 to 50 Atm PCO2 .
Chem. Geol. 2005, 217, 239–255. [CrossRef]
19. Sjöberg, E.L.; Rickard, D. The Influence of Experimental Design on the Rate of Calcite Dissolution. Geochim. Cosmochim. Acta 1983,
47, 2281–2285. [CrossRef]
20. Liu, Q.; Lu, Y.; Zhang, F. Laboratory Simulation Experiment on Dissolution of Limestone under Hydrodynamic Pressure.
Carbonates Evaporites 2013, 28, 3–11. [CrossRef]
21. Mousavi Maddah, S.M.; Hafezi Moghaddas, N.; Ghafoori, M. Solubility Variations of Tirgan Limestone in Northeast of Iran with
Change of PH and Temperature. Carbonates Evaporites 2020, 35, 9. [CrossRef]
22. Fan, M.; Jiang, X.Q.; Liu, W.X.; Zhang, J.Y.; Chen, H.Y. Dissolution of carbonate rocks in CO2 solution under the different
temperatures. Acta Sedimentol. Sin. 2007, 25, 825–830.
23. Gao, J.W. Experimental Simulation of Dissolution of Carbonate Rocks in Acid Solution. Liaoning Chem. Ind. 2016, 45, 254–256.
24. Shao, D.M. Influence of temperature on dissolution rate in Ordovician carbonate rock in different water flow rate. Coal Geol.
Explor. 2012, 40, 62–65.
25. Rosenbauer, R.J.; Koksalan, T.; Palandri, J.L. Experimental Investigation of CO2 –Brine–Rock Interactions at Elevated Temperature
and Pressure: Implications for CO2 Sequestration in Deep-Saline Aquifers. Fuel Process. Technol. 2005, 86, 1581–1597. [CrossRef]
26. Yang, Y.K.; Liu, B.; Qin, S.; Luo, P.; Zhang, D.M.; Zhou, M.H.; Shi, K.B.; Tian, Y.J. Re-recognition of deep carbonate dissolution
based on the observation of in-situ simulation experiment. Acta Sci. Nat. Univ. Pekin. 2014, 50, 316–322.
27. Shou, J.F.; She, M.; Shen, A.J. Experimental study of carbonate dissolution modification effect under deep conditions. Bull. Mineral.
Petrol. Geochem. 2016, 35, 860–867.
28. Zhao, Y.J.; Wang, F.G.; Li, C.S.; Wu, F.S.; Cao, Y.Q. Carbonate Karst Erosion Experiment Research of Guizhou Huangguoshu
Tunnel. Coal Technol. 2016, 35, 310–312.
29. Zhou, J.W.; Yang, X.G.; Fu, W.X.; Xu, J.; Li, H.T.; Zhou, H.W.; Liu, J.F. Experimental test and fracture damage mechanical
characteristics of brittle rock under uniaxial cyclic loading and unloading conditions. Chin. J. Rock Mech. Eng. 2010, 29, 1172–1183.
30. De Boever, E.; Varloteaux, C.; Nader, F.H.; Foubert, A.; Békri, S.; Youssef, S.; Rosenberg, E. Quantification and Prediction of the 3D
Pore Network Evolution in Carbonate Reservoir Rocks. Oil Gas Sci. Technol. Rev. IFP Energ. Nouv. 2012, 67, 161–178. [CrossRef]
31. Hidajat, I.; Mohanty, K.K.; Flaum, M.; Hirasaki, G. Study of Vuggy Carbonates Using X-ray CT Scanner and NMR. In Proceedings
of the SPE Annual Technical Conference and Exhibition, San Antonio, TX, USA, 29 September 2002.
32. Zhang, F.; Sui, X.; Duan, C.; Deng, H.; Gao, S.; Li, Y. NMR Experimental Study on Carbonate Reservoirs with High Porosity and
Low Permeability. Well Logging Technol. 2018, 42, 497–502+529.
33. Jora, M.Z.; Nunes de Souza, R.; Lucas-Oliveira, E.; Speglich, C.; Bonagamba, T.J.; Sabadini, E. Static Acid Dissolution of Carbonate
Outcrops Investigated by 1 H NMR and X-ray Tomography. J. Pet. Sci. Eng. 2021, 207, 109124. [CrossRef]
34. Zhang, T.; Ni, X.; Huang, L.; Zhou, J.; Yu, Z.; Zhou, H.; Yi, Y.; Kang, T.; Zhang, C. Experimental Research Based on NMR and SIP
for Pore Evolution during Dissolution of Dolomite Reservoirs. J. China Univ. Pet. (Ed. Nat. Sci.) 2022, 46, 70–79.
35. Xiao, L. Application of NMR Log Data to Formation Pore Structure Evaluation. Xinjiang Pet. Geol. 2008, 29, 260–263.
36. Fheed, A. The Impact of Fossils on Diagenetically Controlled Reservoir Quality: The Zechstein Brońsko Reef (Upper Permian, W
Poland). ASGP 2019, 89, 47–81. [CrossRef]
37. Fheed, A.; Kłodowski, K.; Krzyżak, A. Fracture Orientation and Fluid Flow Direction Recognition in Carbonates Using Diffusion-
Weighted Nuclear Magnetic Resonance Imaging: An Example from Permian. J. Appl. Geophys. 2020, 174, 103964. [CrossRef]
38. Fheed, A.; Świerczewska, A.; Strzelecki, P.J.; Radzik-Hotloś, N.; Gebus-Czupyt, B. Influence of Substrate Morphology on Reef
Diagenesis: Examples from the Zechstein Limestone Formation (SE Wolsztyn Ridge, W Poland). Mar. Pet. Geol. 2022, 136, 105442.
[CrossRef]
39. Matenoglou, G.; Kelessidis, V.C.; Garcia, A.P.; Heidari, Z.; Fardis, M.; Karayanni, M.; Maris, T.G. Evaluation of the Wettability and
the Petrophysical Properties in Carbonate Reservoirs by Advanced NMR and MRI Techniques. In Proceedings of the Abu Dhabi
International Petroleum Exhibition & Conference, Abu Dhabi, United Arab Emirates, 7–10 November 2016.
40. Krzyżak, A.T.; Mazur, W.; Fheed, A.; W˛eglarz, W.P. Prospects and Challenges for the Spatial Quantification of the Diffusion of
Fluids Containing 1 H in the Pore System of Rock Cores. JGR Solid Earth 2022, 127, e2021JB023299. [CrossRef]
41. Kingsley, P.B. Introduction to Diffusion Tensor Imaging Mathematics: Part II. Anisotropy, Diffusion-Weighting Factors, and
Gradient Encoding Schemes. Concepts Magn. Reson. 2006, 28A, 123–154. [CrossRef]
42. Fheed, A.; Krzyżak, A.; Świerczewska, A. Exploring a Carbonate Reef Reservoir—Nuclear Magnetic Resonance and Computed
Microtomography Confronted with Narrow Channel and Fracture Porosity. J. Appl. Geophys. 2018, 151, 343–358. [CrossRef]
43. Hounsfield, G.N. Computerized transverse axial scanning (tomography): Part I. Description of system. Br. J. Radiol. 1973, 46,
1016–1022. [CrossRef]
44. Raynaud, S.; Fabre, D.; Mazerolle, F.; Geraud, Y.; Latière, H.J. Analysis of the Internal Structure of Rocks and Characterization of
Mechanical Deformation by a Non-Destructive Method: X-ray Tomodensitometry. Tectonophysics 1989, 159, 149–159. [CrossRef]
Materials 2023, 16, 1828 21 of 22
45. Ding, W.H.; Wu, Y.Q.; Pu, Y.B.; Cui, Z.X.; Cao, G.Z. History and present situation of X-ray computerized tomography (CT) of
rocks. Seismol. Geol. 2003, 25, 467–476.
46. Berg, S.; Ott, H.; Klapp, S.A.; Schwing, A.; Neiteler, R.; Brussee, N.; Makurat, A.; Leu, L.; Enzmann, F.; Schwarz, J.O.; et al.
Real-Time 3D Imaging of Haines Jumps in Porous Media Flow. Proc. Natl. Acad. Sci. USA 2013, 110, 3755–3759. [CrossRef]
[PubMed]
47. Wildenschild, D.; Sheppard, A.P. X-ray Imaging and Analysis Techniques for Quantifying Pore-Scale Structure and Processes in
Subsurface Porous Medium Systems. Adv. Water Resour. 2013, 51, 217–246. [CrossRef]
48. Blunt, M.J.; Bijeljic, B.; Dong, H.; Gharbi, O.; Iglauer, S.; Mostaghimi, P.; Paluszny, A.; Pentland, C. Pore-scale imaging and
modelling. Adv. Water Resour. 2013, 51, 197–216. [CrossRef]
49. Luquot, L.; Gouze, P. Experimental determination of porosity and permeability changes induced by injection of CO2 into
carbonate rocks. Chem. Geol. 2009, 265, 148–159. [CrossRef]
50. Garing, C.; Luquot, L.; Pezard, P.A.; Gouze, P. Electrical and flow properties of highly heterogeneous carbonate rocks. AAPG Bull.
2014, 98, 49–66. [CrossRef]
51. Bird, M.B.; Butler, S.L.; Hawkes, C.D.; Kotzer, T. Numerical modeling of fluid and electrical currents through geometries based on
synchrotron X-ray tomographic images of reservoir rocks using Avizo and COMSOL. Comput. Geosci. 2014, 73, 6–16. [CrossRef]
52. Bultreys, T.; Van Hoorebeke, L.; Cnudde, V. Multi-Scale, Micro-Computed Tomography-Based Pore Network Models to Simulate
Drainage in Heterogeneous Rocks. Adv. Water Resour. 2015, 78, 36–49. [CrossRef]
53. Cnudde, V.; Boone, M.N. High-Resolution X-ray Computed Tomography in Geosciences: A Review of the Current Technology
and Applications. Earth-Sci. Rev. 2013, 123, 1–17. [CrossRef]
54. Rabbani, A.; Ayatollahi, S.; Kharrat, R.; Dashti, N. Estimation of 3-D pore network coordination number of rocks from watershed
segmentation of a single 2-D image. Adv. Water Resour. 2016, 94, 264–277. [CrossRef]
55. Dong, H.; Touati, M.; Blunt, M. Pore Network Modeling: Analysis of Pore Size Distribution of Arabian Core Samples. In
Proceedings of the SPE Middle East Oil and Gas Show and Conference, Manama, Bahrain, 11–14 March 2007.
56. Freire-Gormaly, M.; Ellis, J.S.; MacLean, H.L.; Bazylak, A. Pore Structure Characterization of Indiana Limestone and Pink
Dolomite from Pore Network Reconstructions. Oil Gas Sci. Technol. Rev. IFP Energ. Nouv. 2016, 71, 33. [CrossRef]
57. Noiriel, C.; Gouze, P.; Madé, B. 3D analysis of geometry and flow changes in a limestone fracture during dissolution. J. Hydrol.
2013, 486, 211–223. [CrossRef]
58. Rötting, T.S.; Luquot, L.; Carrera, J.; Casalinuovo, D.J. Changes in porosity, permeability, water retention curve and reactive
surface area during carbonate rock dissolution. Chem. Geol. 2015, 403, 86–98. [CrossRef]
59. Krebs, M.; Lungwitz, B.; Souza, A.; Pépin, A.; Montoya, S.; Schlicht, P.; Boyd, A.; Vidoto, E.; Polli, R.; Bonagamba, T. The
First Visualization of Acid Treatments on Carbonates with 3D Nuclear-Magnetic-Resonance Imaging. SPE J. 2015, 20, 678–688.
[CrossRef]
60. Yao, Y.; Liu, D.; Cai, Y.; Li, J. Advanced characterization of pores and fractures in coals by nuclear magnetic resonance and X-ray
computed tomography. Sci. China Earth Sci. 2010, 53, 854–862. [CrossRef]
61. Fredd, C.N.; Fogler, H.S. Optimum conditions for wormhole formation in carbonate porous media: Influence of transport and
reaction. SPE J. 1999, 4, 196–205. [CrossRef]
62. Fredd, C.N.; Fogler, H.S. Alternative stimulation fluids and their impact on carbonate acidizing. SPE J. 1998, 3, 34–41. [CrossRef]
63. Fredd, C.N.; Fogler, H.S. Influence of Transport and Reaction on Wormhole Formation in Porous Media. AIChE J. 1998, 44,
1933–1949. [CrossRef]
64. Golfier, F.; Bazin, B.; Zarcone, C.; Lernorm, R.; Lasseux, D.; Quintard, M. Acidizing carbonate reservoirs: Numerical modelling of
wormhole propagation and comparison to experiments. In Proceedings of the SPE 68922, SPE European Formation Damage
Conference, The Hague, The Netherlands, 21–22 May 2001.
65. Tansey, J.; Balhoff, M.T. Pore Network Modeling of Reactive Transport and Dissolution in Porous Media. Transp. Porous Media
2016, 113, 303–327. [CrossRef]
66. Guo, G.; Xing, L.; Li, H. Quantitative Characterization of Different Coal Rank Reservoirs Permeability Based on NMR and X-CT
Technology. Geol. Surv. China 2020, 7, 103–108. (In Chinese)
67. Oliveira, M.F.S.; Lima, I.; Borghi, L.; Lopes, R.T. X-ray Microtomography Application in Pore Space Reservoir Rock. Appl. Radiat.
Isot. 2012, 70, 1376–1378. [CrossRef] [PubMed]
68. Chen, Y.J.; Su, X.F.; Wang, J.J.; Song, Y.; Wang, M.F.; Lang, Y.F. Multi-scale fine characterization of coal pore-fracture structure
based on X-ray micro-CT scanning: A case study of Mabidong Block, southern Qinshui Basin. Pet. Geol. Recovery Effic. 2019, 26,
66–72.
69. Andriamihaja, S.; Padmanabhan, E.; Ben-Awuah, J.; Sokkalingam, R. Static Dissolution-Induced 3D Pore Network Modification
and Its Impact on Critical Pore Attributes of Carbonate Rocks. Pet. Explor. Dev. 2019, 46, 374–383. [CrossRef]
70. Xu, Z.; Guo, S. Application of NMR and X-CT Technology in the Pore Structure Study of Shale Gas Reservoirs. Adv. Earth Sci.
2014, 29, 624–631.
71. Li, N.; Wang, K.; Zhang, G.; Wu, H.; Zhao, L.; Wu, L.; Feng, Q.; Feng, Z. Prediction of gas production in carbonates based on CT
analysis and nuclear magnetic resonance (NMR) logging. Pet. Explor. Dev. 2015, 42, 167–174. [CrossRef]
72. Tian, H.; Wang, G.; Feng, Q.; Li, C.; Tian, M. Review and Prospective of Complex Pore Structure of Carbonate Reservoir. Sci.
Technol. Eng. 2020, 20, 11825–11833.
Materials 2023, 16, 1828 22 of 22
73. Jiang, S. Study on the Characteristics of the Micro-Pore Structure and the Comprehensive Reservoir Evaluation Method for the
Low Permeability Carbonate Reservoir in One Typical Oil Field. Master’s Thesis, University of Chinese Academy of Sciences,
Langfang, China, 2015.
74. Huang, J.; Xu, K.; Guo, S.; Guo, H. Comprehensive Study on Pore Structures of Shale Reservoirs Based on SEM, NMR and X-CT.
Geoscience 2015, 29, 198–205.
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Academic Editor: Vit Smilauer

Materials 2023, 16, 1828. https://doi.org/10.3390/ma16051828 https://www.mdpi.com/journal/materials

2. Test Equipment and Experimental Methodology

cite, with a small amount of quartz.

2.2.2. CT Scanning Equipment

2.2.3. NMR Equipment

2.3. Test Plan

2.3.1. Orthogonal Dissolution Test Scheme

Table 3. Research level of orthogonal numerical simulation experimental parameters.

Table 4. Orthogonal numerical simulation experimental schemes.

Experimental Dissolution Conditions Parameters

2.3.2. CT Scanning Test Scheme

2.3.3. NMR Test Scheme

2.4. Test Steps

2.4.2. Dissolution of Carbonate Rocks

Figure 4. Flow chart of the dissolution test [7].

Table 5. Orthogonal test results.

Table 6. Extreme range analysis of dissolution rate of specimens (mg·g–1).

Figure 5. Sensitivity analysis of dissolution rate.

Duration (d) 27,516.741 3 1.068 3.290 21.37

3.2.1. Spatial Distribution Characteristics of Pores

3.2.2. Quantitative Characterization of Pore Structure

Materials 2023, 16, x FOR PEER REVIEW 14 of 23

2. Pore number and volume change

3.3.1. T2 Spectrum Analysis

3.3.1. T2 Spectrum Analysis

Materials 2023, 16, x FOR PEER REVIEW 18 of 23

3.3.2. Pore Structure Analysis

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