Chelating Agents as a Stimulation Fluid with a Negative Reaction Order: More Diluted Solutions React Faster with Carbonates

2021 ◽  
Author(s):  
Igor Ivanishin ◽  
Hamidreza Samouei
Keyword(s):  
Dissolution Rate ◽  
Reaction Rate ◽  
Chelating Agents ◽  
Reaction Order ◽  
Rotating Disk ◽  
Carbonate Reservoir ◽  
Reaction Behavior ◽  
Calcite Dissolution ◽  
Reservoir Rocks ◽  
Kinetics Of

Abstract Chelating agents are used to stimulate high-temperature carbonate reservoirs and remove mineral scales. For field applications, commercial chelates—EDTA, DTPA, GLDA, etc.—are commonly supplied as 3550 wt% (1.2-1.7 M) solutions and diluted two times in water. However, the dependence of the reaction rate on the concentration of chelate in solution has never been quantified. This paper focuses on determining the kinetics of calcite dissolution as a function of the dilution factor of commonly used chelates at acidic pH. Using a rotating disk apparatus, the kinetics of calcite marble dissolution in 0.10.25 M EDTA (pH=4.9-5.0), 0.1-0.25 M DTPA (pH=3.5-5.0), and 0.28-0.85 M GLDA (pH=3.7-5.0) solutions has been investigated. The dissolution of calcite in all chelates has a negative fractional-order that increases with temperature in the range -0.6 < n< -1.9. Thus, less concentrated chelate solutions react faster with calcite, and the effect of chelate dilution becomes less pronounced with a temperature increase. For example, three times dilution of pH=3.7 commercial GLDA solution—from commonly used 50 vol% (0.85 M) to 16.7 vol% (0.28 M)—increases calcite dissolution rate 8.4, 4.9, 2.7, and 2.0 times at 98.6, 116.6, 134.6, and 188.6°F, respectively. Dilution of pH=5.0 EDTA and pH=3.5 DTPA from 0.25 M to 0.1 M increases the dissolution rate of calcite 1.4-3.1 times at 98.6-188.6°F. Probable reasons for such an unusual reaction behavior are discussed in the paper. Presented results are integral for designing the stimulation operations in carbonate reservoir rocks and the removal of carbonate scales.

To the Problem of Reducing the Amount of Harmful Emissions when Refining Silver

2018 ◽  
Vol 284 ◽  
pp. 877-881
Author(s):  
Sergey E. Polygalov ◽  
S.A. Mastugin ◽  
E.A. Shadrina
Keyword(s):  
Nitric Acid ◽  
Nitrogen Oxides ◽  
Dissolution Rate ◽  
Rotating Disk ◽  
Oxidation Potential ◽  
Solution Temperature ◽  
Harmful Emissions ◽  
Environmentally Friendly Process ◽  
Silver Dissolution ◽  
Kinetics Of

The work is devoted to the study of the possibilities of minimizing the release of nitrogen oxides during the dissolution of silver in nitric acid solutions during refining of the gold and silver alloy. Using a rotating disk, the maximum concentration of nitric acid is determined, at which the oxidation potential of the system is insufficient for the oxidation of silver. It has been established that at a temperature of 363 K and a concentration of HNO3 = 50 g/l, the dissolution rate of silver does not exceed 0.00022∙10-5 mol/(cm2∙s), and such conditions can be considered as background for an environmentally friendly process. To initiate dissolution, hydrogen peroxide was used as an alternative oxidizing agent. As a criterion for the rational use of the oxidant and the ecological purity of the process, the excess pressure over the solution was evaluated. The influence of the initial and current composition of the solution, temperature, and conditions of oxidant supply to the reactor on the kinetics of the target process was studied. It is shown that at a silver dissolution rate of 2.7∙10-6 mol/(cm2∙s), no release of nitrogen oxides was observed.

scholarly journals REACTION KINETICS OF Cu ELECTRO-DEPOSITION ON THE SURFACE OF TiO2/GRAPHITE

2015 ◽  
Vol 8 (2) ◽  
pp. 116
Author(s):  
Fitria Rahmawati ◽  
Wanodya Anggit Mawasthi ◽  
Patiha
Keyword(s):  
Equilibrium Constant ◽  
Rate Constant ◽  
Reaction Rate ◽  
Reaction Order ◽  
Electrode Reaction ◽  
Deposition Process ◽  
Anodic Reaction ◽  
Electro Deposition ◽  
First Order ◽  
Kinetics Of

Research on the kinetics of electrode reaction during copper electro-deposition on the surface of TiO2/graphite has been conducted. The aims of this research are to determine the ratio of anodic reaction rate to cathodic reaction rate , the ratio of anodic rate constant to cathodic rate constant , the equilibrium constant when the reaction reach equilibrium condition and to study the polarization in the electro-deposition reaction. Copper was deposited electrochemically from CuSO4 solution at various concentration i.e. 0.1 M; 0.2 M; 0.3 M; 0.4 M; 0.5 M. In every 5 minutes during electro-deposition process, the pH changes in anode cell was recorded and the change of Cu2+ concentration was also analyzed by spectrophotometric method. The result shows that the reaction order of Cu2+ reduction is first order and the oxidation of H2O in anodic cell is zero order. The ratio of anodic rate constant to cathodic rate constant, is 4.589´10-3 ± 0.071´10‑3. It indicates that the reaction rate  in cathode is larger than the reaction rate in anode and it allowed polarization.  The electrochemical cell reached equilibrium after 25 minutes with the equilibrium constant is 8.188´10-10 ± 1.628´10-10.

Measuring the Reaction Rate of Lactic Acid With Calcite and Dolomite by Use of the Rotating-Disk Apparatus

SPE Journal ◽  
2014 ◽  
Vol 19 (06) ◽  
pp. 1192-1202 ◽  
Author(s):  
Ahmed I. Rabie ◽  
Daniel C. Shedd ◽  
Hisham A. Nasr-El-Din
Keyword(s):  
Mass Transfer ◽  
Lactic Acid ◽  
Concentration Gradient ◽  
Reaction Rate ◽  
Surface Reaction ◽  
Rotating Disk ◽  
Acid Fracturing ◽  
Rate Of Reaction ◽  
Indiana Limestone ◽  
Kinetics Of

Summary Lactic acid has been examined in various laboratories and applied in the oil field for acid fracturing and drilling-fluid-filter-cake removal, and as an iron-control agent during acid treatments. However, the reaction of lactic acid with calcite has not been addressed before. Determination of the reaction rate and the acid-diffusion properties is a critical step for successful treatments in matrix acidizing and acid fracturing. Therefore, the objective of this work is to conduct a detailed study on the reaction of lactic acid with calcite. Mass transfer and reaction kinetics are reported for the lactic acid/calcite system by use of the rotating-disk apparatus. Disk samples were cut from Indiana limestone or Silurian dolomite and were used in the reaction-rate experiments. The effect of lactic acid concentration (1, 5, and 10 wt%), temperature (80–250°F), disk rotational speed (100–1,800 rev/min), and different inorganic salts on the reaction rate was investigated. The diffusion coefficient of 5 wt% lactic acid was determined at low disk rotational speeds and reported at 80, 200, and 250°F. A model that accounts for the effect of the kinetics of the surface reactions and the transport of reactants and products was developed. The activation energy and the rate constant at 80, 150, and 250°F for the reaction of lactic acid with Indiana limestone were reported. Reaction experiments of lactic acid with dolomite at 150°F over disk rotational speeds of 100–1,800 rev/min, and at 1,500 rev/min over a temperature range of 80–250°F, were conducted and the results were compared with those obtained for the calcite reaction. At 80°F, the reaction of lactic acid with calcite was controlled by mass transfer at low disk rotational speeds (up to 500 rev/min) and was surface reaction limited at higher speeds. At higher temperatures (150, 200, and 250°F), both mass transfer and surface reaction influence the overall calcite dissolution. The kinetics of the surface reaction were influenced by both forward and backward reactions. At 80°F, the surface reaction contributes to 28% of the overall resistance. This dependence becomes much less (13 and 10%) at higher temperatures (150 and 250°F, respectively). The reaction of lactic acid with dolomite at 150°F was mainly controlled by mass transfer up to 1,000 rev/min and by the kinetics of the surface reaction after 1,000 rev/min. At 80 and 150°F, the rate of reaction of lactic acid with calcite was an order of magnitude higher than that with dolomite. At temperatures of 200 and 250°F, the rate of reaction of lactic acid with calcite is twice the rate of reaction with dolomite. The presence of Ca2+, Mg2+, and SO42− ions reduced the reaction rate, which is most likely because of the reduction in the concentration gradient of the products. The reduction in the concentration gradient will cause a reduction in the rate of diffusion of the generated calcium away from the surface, and hence a lower rate of dissolution.

Crystallization Kinetics of CaOx in Artificial Urine and in Saline System

2014 ◽  
Vol 881-883 ◽  
pp. 708-711
Author(s):  
Lan Qing Deng ◽  
Jun Fa Xue ◽  
Li Kuan ◽  
Jian Ming Ouyang
Keyword(s):  
Reaction Time ◽  
Calcium Oxalate ◽  
Crystallization Kinetics ◽  
Rate Constant ◽  
Reaction Rate ◽  
Reaction Order ◽  
Reaction Rate Constant ◽  
Artificial Urine ◽  
Kinetics Of

The crystallization kinetics of calcium oxalate (CaOx) was comparatively studied by detecting the change of free Ca2+ ions concentration with the reaction time in artificial urine and in saline system. The dynamics equations of CaOx crystallization was r=kcα, and the average reaction order (α) was 3.3 regardless of the relative suprasaturation degree (RS) of CaOx in the range of RS=10.58~17.53. The average reaction rate constant (κ) was (0.97±0.1)×109 in artificial urine and κ=(3.1±1.8)×109 in saline system, due to the presence of inhibitors to CaOx crystallization in artificial urine.

Anomalous Acid Reaction Rates in Carbonate Reservoir Rocks

SPE Journal ◽  
2006 ◽  
Vol 11 (04) ◽  
pp. 488-496 ◽  
Author(s):  
Kevin C. Taylor ◽  
Hisham A. Nasr-El-Din ◽  
Sudhir Mehta
Keyword(s):  
Saudi Arabia ◽  
Rotating Disk ◽  
Reaction Rates ◽  
Carbonate Reservoir ◽  
Reservoir Rock ◽  
Acid Dissolution ◽  
Gas Reservoir ◽  
Dissolution Rates ◽  
Reservoir Rocks ◽  
Acid Reaction

Summary It is generally assumed that the reaction of acid with limestone reservoir rock is much more rapid than acid reaction with dolomite reservoir rock. This work is the first to show this assumption to be false in some cases, because of mineral impurities commonly found in these rocks. Trace amounts of clay impurities in limestone reservoir rocks were found to reduce the acid dissolution rate by up to a factor of 25, to make the acid reactivity of these rocks similar to that of fully dolomitized rock. A rotating disk instrument was used to measure dissolution rates of reservoir rock from a deep, dolomitic gas reservoir in Saudi Arabia (275°F, 7,500 psi). More than 60 experiments were made at temperatures of 23 and 85°C and HCl concentration of 1.0 M (3.6 wt%). Eight distinctly different rock types that varied in composition from 0 to 100% dolomite were used in this study. In addition, the mineralogy of each rock disk was examined before and after each rotating disk experiment with an environmental scanning electron microscope (ESEM) using secondary and backscattered electron imaging and energy dispersive X-ray (EDS) spectroscopy. Acid reactivity was correlated with the detailed mineralogy of the reservoir rock. It was also shown that bulk anhydrite in the rock samples was converted to anhydrite fines by the acid at 85°C, a potential source of formation damage. Introduction A study of acid reaction rates and reaction coefficients of a dolomitic reservoir rock was recently reported by Taylor et al. (2004a). In that work, it was found that reaction rates depended on mineralogy and the presence of trace components such as clays. This paper examines in detail the relationship between acid reactivity and mineralogy of a deep, dolomitic gas reservoir rock. An accurate knowledge of acid reaction rates of deep gas reservoirs can contribute to the success of matrix and acid fracture treatments. Many studies of acid stimulation treatments of Formation K, a deep, dolomitic gas reservoir in Saudi Arabia, have been published (Nasr-El-Din et al. 2001, 2002a, 2002b; Bartko et al. 2003). It is generally assumed that the reaction of acid with limestone reservoir rock is much more rapid than acid reaction with dolomite reservoir rock during acidizing treatments. However, much of the reported data were obtained with pure limestones, dolomites, and marbles. These include calcite marble (CaCO3) (Lund et al. 1975; de Rozieres 1994; Frenier and Hill 2002), dolomite marble [CaMg(CO3)2] (Lund et al. 1973; Herman and White 1985), Indiana limestone (Mumallah 1991), St. Maximin and Lavoux limestones (Alkattan et al. 1998), Haute Vallée de l'Aude dolomite (Gautelier et al. 1999), Bellefonte dolomite (Herman and White 1985), San Andres dolomite (Anderson 1991), Kasota dolomite (Anderson 1991), and Khuff dolomite reservoir cores (Nasr-El-Din et al. 2002b). The effects of common acid additives on calcite and dolomite dissolution rates were reported in detail (Frenier and Hill 2002; Taylor et al. (2004b; Al-Mohammed et al. 2006). The effects of impurities such as clays on rock dissolution have not been reported.

Study on the Kinetics of Immersion of Photocatalyst in Bamboo

2012 ◽  
Vol 271-272 ◽  
pp. 218-221
Author(s):  
Xu Zhang ◽  
Zhong Feng Zhang ◽  
Kai Huang
Keyword(s):  
Reaction Rate ◽  
Reaction Order ◽  
Reaction Rate Constant ◽  
Exponential Factor ◽  
First Order ◽  
Higher Temperature ◽  
Three Stages ◽  
Increasing Temperature ◽  
Kinetics Of ◽  
Stable Stage

In order to improve the anti-mildew property of modified bamboo with photocatalyst, it used TiO2 which is one of the typical photocatalyst as the main study object to discussed the kinetics of immersion of photocatalyst in bamboo. The results show that immersion of TiO2 in bamboo can be divided into three stages, starting with the rapid immersion, the slow immersion in the middle stage, and the stable immersion in the later stage. In the stable stage, only little TiO2 immerse bamboo. The immersion rate is faster at higher temperature to take less time to reach equilibrium. By establishing the kinetic models, the reaction of immersion of photocatalyst can be regarded as the first order reaction with reaction order of 0.97, the reaction rate constant increases with increasing temperature, the activation energy is 5663.133J/mol, and the pre-exponential factor is 20.47h-1.

scholarly journals The influence of the catalyst on the kinetics of ethyl metacrylate synthesis

2007 ◽  
Vol 9 (1) ◽  
pp. 7-9
Author(s):  
Mirosław Grzesik ◽  
Teresa Witczak
Keyword(s):  
Liquid Phase ◽  
Integral Method ◽  
Reaction Rate ◽  
Reaction Order ◽  
Equilibrium Constants ◽  
Chemical Compounds ◽  
Rate Equations ◽  
Reaction Rate Constants ◽  
Kinetic Relations ◽  
Kinetics Of

The influence of the catalyst on the kinetics of ethyl metacrylate synthesis The synthesis of ethyl metacrylate in the liquid phase was studied. Tungstophosphoric and molybdophosphoric acids, which belong to heteropolyacids group, were used as a catalyst. The chemical compounds from this group are often utilized in the catalysis with regard to their activity and selectivity. The rate equations, reaction rate constants and equilibrium constants have been determined. The reaction order and the kinetic parameters of the kinetic relations were determined by the integral method. All rate equations are formulated with activities taking the non ideal effects of the compounds into consideration. It was found that the kinetics of the esterification of the presented reactions was non-elementary

Reaction of In-Situ-Gelled Acids With Calcite: Reaction-Rate Study

SPE Journal ◽  
2011 ◽  
Vol 16 (04) ◽  
pp. 981-992 ◽  
Author(s):  
Ahmed I. Rabie ◽  
Ahmed M. Gomaa ◽  
Hisham A. Nasr-El-Din
Keyword(s):  
Mass Transfer ◽  
Rotational Speed ◽  
Reaction Rate ◽  
Rotating Disk ◽  
Effect Of Temperature ◽  
Kinetics Parameters ◽  
Calcite Dissolution ◽  
Rock Samples ◽  
Rate Of Dissolution

Summary In-situ-gelled acids have been used extensively in matrix acidizing and acid fracturing for acid diversion and reducing the leakoff rate, respectively. A few studies investigated the rate of dissolution of calcite in polymer-based acids, yet none has addressed in detail the in-situ-gelled acids. Therefore, the aim of this work is to examine the mass transfer and the kinetics of the reaction of 5 wt% HCl in-situ-gelled acids with calcite and determine the effect of Fe crosslinker on the rate of calcite dissolution. The rate of reaction of 5 wt% HCl in-situ-gelled acid was measured using the rotating-disk apparatus. Rock samples of 1.5in. diameter and 1-in. length were used. The effect of temperature (100-250°F) and disk-rotational speed (100-1,800 rev/min) was investigated using Pink Desert limestone rock samples. Calcium concentration was measured in the collected samples and was used to determine the acid-reaction rate. Experimental results showed that the rate of calcite dissolution at 150°F was controlled mainly by the rate of mass transfer of the acid to the surface up to a disk rotational speed of 1,000 rev/min and by the rate of the surface reaction above this value. On the basis of the results obtained, the diffusion coefficient of 5 wt% HCl in in-situ-gelled acid at 150°F; the activation energy; and the reaction rate constant at 150, 200, and 250°F were determined for the first time. A power-law kinetic model was used to determine the kinetics parameters. The presence of Fe3+ crosslinker had a significant effect on the rate of dissolution in comparison with reactions with gelled acid (no crosslinker) at the same condition. The reaction rate decreased by a factor of 2.2 and by a factor of 1.4 when the reaction was conducted at 100 and 1,500 rev/min, respectively. A gel layer, formed on the surface, acted as a barrier between the acid and the rock, which reduced the rate of calcite dissolution.

STUDYING THE KINETIC CHARACTERISTICS OF THE EXTRACTION OF ANTHOCYANINS FROM THE SQUEEZE OF KRASNOSTOP ZOLOTOVSKY

2020 ◽  
Author(s):  
M.A. Egyan ◽  
Keyword(s):  
Reaction Rate ◽  
Sugar Content ◽  
Extraction Process ◽  
Efficiency Coefficient ◽  
Kinetic Characteristics ◽  
Reaction Rate Constants ◽  
Solids Content ◽  
Kinetics Of ◽  
Process Speed

The article shows studies characterizing the quality of the squeeze: the mechanical composition of the squeeze is determined, the structural moisture of each component is determined, the sugar content in the formed process of sedimentation of the juice and its acidity are determined refractometrically. The kinetics of anthocyanins extraction was determined in two ways, the solids content in the extract was calculated, and the reaction rate constants of the extraction process and the efficiency coefficient of ultrasonic amplification of the extraction process speed were calculated.

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