A Matrix Acidizing System for Controlled Carbonate Well Stimulation using a Carboxylic Acid Salt with a Chelating Agent

2021 ◽  
Author(s):  
Albert Bokkers ◽  
Piter Brandenburg ◽  
Coert Van Lare ◽  
Cees Kooijman ◽  
Arjan Schutte
Keyword(s):  
Chelating Agent ◽  
Life Time ◽  
Nitrogen Atmosphere ◽  
Injection Rate ◽  
Sodium Gluconate ◽  
Matrix Acidizing ◽  
Well Stimulation ◽  
Stirred Reactor ◽  
Core Flood ◽  
Optimum Injection Rate

Abstract This work presents a matrix acidizing formulation which comprises a salt of monochloroacetic acid giving a delayed acidification and a chelating agent to prevent precipitation of a calcium salt. Results of dissolution capacity, core flood test and corrosion inhibition are presented and are compared to performance of 15 wt% emulsified HCl. Dissolution capacity tests were performed in a stirred reactor at atmospheric pressure using equimolar amounts of the crushed limestone and dolomites. Four different chelating agents were added to test the calcium ion sequestering power. Corrosion tests were executed using an autoclave reactor under nitrogen atmosphere at 10 barg. Core flood tests were performed to simulate carbonate matrix stimulation using limestone cores. It was found that the half-life time of the hydrolysis reaction is 77 min at a temperature of 100 °C. Sodium gluconate and the sodium salt of D-glucoheptonic acid were identified to successfully prevent the precipitation of the reaction product calcium glycolate at a temperature of 40 °C. Computed Tomography (CT) scans of the treated cores at optimum injection rate showed a single wormhole formed. At 150 °C an optimum injection rate of 1 ml/min was found which corresponds to a minimum PVBT of 6. In addition, no face dissolution was observed after coreflooding. Furthermore, the corrosion rates of different metallurgies (L80 and J55) were measured which are significantly less than data reported in literature for 15wt% emulsified HCl. The novelty of this formulation is that it slowly releases an organic acid in the well allowing deeper penetration in the formation and sodium gluconate prevents precipitation of the reaction product. The corrosivity of this formulation is relatively low saving maintenance costs to installations and pipe work. The active ingredient in the formulation is a solid, allowing onsite preparation of the acidizing fluid.

Comparison of Wormhole Profiles on Carbonate Rocks Using Emulsified and Single-Phase Retarded Acids

2022 ◽  
Author(s):  
Norah Aljuryyed ◽  
Abdullah Al Moajil ◽  
Sinan Caliskan ◽  
Saeed Alghamdi
Keyword(s):  
Organic Acids ◽  
Single Phase ◽  
Injection Rate ◽  
Flow Rates ◽  
Low Viscosity ◽  
Propagation Behavior ◽  
Additional Equipment ◽  
Acid Reaction ◽  
Optimum Injection Rate ◽  
Indiana Limestone

Abstract Acid retardation through emulsification is commonly used in reservoir stimulation operations, however, emulsified acid are viscous fluids, thus require additional equipment at field for preparation and pumping requirements. Mixture of HCl with organic acids and/or chemical retarders have been used developed to retard acid reaction with carbonate, however, lower dissolving power. Development of low viscosity and high dissolving retarded acid recipes (e.g., equivalent to 15-26 wt.% HCl) addresses the drawbacks of emulsified acids and HCl acid mixtures with weaker organic acids. The objective of this study is to compare wormhole profile generated as a result of injecting acids in Indian limestone cores using 28 wt.% emulsified acid and single-phase retarded acids at comparable dissolving power at 200 and 300°F. Coreflood analysis testing was conducted using Indiana limestone core plugs to assess the pore volume profile of retarded acid at temperatures of 200 and 300° F. This test is supported by Computed Tomography to evaluate the propagation behavior as a result of the fluid/rock reaction. Wider wormholes were observed with 28 wt.% emulsified acid at 200°F when compared to test results conducted at 300°F. The optimum injection rate was 1 cm3/min at 200 and 300°F based on wormhole profile and examined flow rates. Generally, face-dissolution and wider wormholes were observed with emulsified acids, especially at 200°F. Narrower wormholes were formed as a result of injecting retarded acids into Indiana limestone cores compared to 28 wt.% emulsified acid. Breakthrough was not achieved with retarded acid recipe at 300°F and flow rates of 1 and 3 cm3/min, suggesting higher flow rates (e.g., > 3 cm3/min) are required for the retarded acid to be more effective at 300°F.

The Feasibility of Fluorine Ammonium Compounds for Sandstone Formation Matrix Acidizing: Laboratory Study and Discussion

2013 ◽  
Vol 773 ◽  
pp. 628-633
Author(s):  
Fu Li ◽  
An Lin Wu ◽  
Min Min Xia ◽  
Hong Xian Liu ◽  
Ting Ting Zhang
Keyword(s):  
Acid System ◽  
Matrix Acidizing ◽  
Chemical Structures ◽  
Well Stimulation ◽  
Energy Needs ◽  
Ammonium Hydrogen ◽  
Lower Effect ◽  
Sandstone Formation ◽  
Great Possibility ◽  
Ammonium Compounds

As a preferred technology to enhance oilfield energy production, well stimulation has and will continue to have an important role in fulfilling the worlds future energy needs. Mud acid is a conventional acid system that reacts with most injurants and removes damages. However, fast reaction rate with minerals will lead to high leak-off velocity, great possibility of secondary and tertiary precipitation, lower effect of corrosion inhibitor in high temperature as well as short efficient operating range. Therefore, new kinds of acid system are required to cope with these problems above. This paper proposed three acid system with the similarity of fluorine ammonium compounds for sandstone acidizing ammonium hydrogen fluoride (AHF), ammonium fluotitanate (AFT), and ammonium fluoroborate system (AFB). Chemical structures, acidity test and solubility tests have proved the feasibility. Then, performance comparisons are conducted to prove the advantages over mud acid system.

Matrix Acidizing with Gelled Acid

2012 ◽  
Author(s):  
Issham Ismail ◽  
Wei Loon Kweh
Keyword(s):  
Xanthan Gum ◽  
Research Study ◽  
High Viscosity ◽  
Injection Rate ◽  
Formation Damage ◽  
Polymer Gel ◽  
Matrix Acidizing ◽  
Steel Core ◽  
Core Holder ◽  
Viscosity Polymer

Suatu uji kaji makmal telah dilakukan untuk membandingkan kecekapan asid gel dan asid lumpur konvensional dalam merawat kerosakan formasi yang disebabkan oleh lumpur dasar air. Suatu sistem pengasidan telah dibina untuk mengkaji kesan kadar alir dan kelikatan asid gel terhadap batu pasir Berea. Peralatan utama yang membentuk sistem pengasidan ialah pemegang teras, sel lumpur, injap, dan tiub 3 mm. Semua komponen ini diperbuat daripada keluli kalis karat. Bendalir perawat yang digunakan dalam uji kaji terdiri daripada asid lumpur (3% HF–12% HCl), asid hidroklorik, dan gel polimer (gam xanthan). Keputusan uji kaji menunjukkan bahawa polimer dengan kelikatan kurang daripada 73 cP memberikan kecekapan yang lebih baik berbanding kelikatan yang melebihi 73 cP. Ini terbukti apabila nisbah kebolehtelapan mencapai 3.5 pada kelikatan gel 73 cP berbanding 1.5 sahaja pada kelikatan 126 cP. Perbezaan nisbah kebolehtelapan yang ketara berlaku kerana polimer yang terlalu likat cenderung untuk memalam liang secara kekal. Asid gel berjaya merawat kerosakan formasi dengan lebih berkesan berbanding asid lumpur, terutama apabila gel polimer berkelikatan 73 cP dialirkan pada kadar alir 0.28 ml/saat, berbanding kadar alir yang lebih rendah. Kata kunci: Teknik lencongan; asid gel; pengasidan; gel polimer A laboratory investigation was conducted to compare the efficiency of gelled acid with conventional/plain mud acid in removing the formation damage induced by water-based mud. An acidizing system was developed to study the effect of flow/injection rate and gel viscosity on Berea sandstone. The main equipments used in this research study were stainless steel core holder, mud cells, valves, and 3 mm tubing. The treatment fluids used were mud acid (3% HF–12% HCl), hydrochloric acid, and polymer gel (xanthan gum). The experimental results revealed that polymer gel with viscosity lower than 73 cP gave better performance as compared to polymer gel with viscosity greater than 73 cP. At gel viscosity of 73 cP, the permeability ratio was 3.5 compared to 1.5 only at viscosity of 126 cP. This was due to the permanent plugging by the high viscosity polymer gel in the core after the injection. Gelled acid has shown tremendous improvement in removing formation damage, where polymer gel with viscosity of 73 cP was found to give better treatment at flow rate of 0.28 ml/s as compared to lower flow rates. Key words: Diversion technique; galled acid; acidizing; polymer gel

Optimum Injection Rate of A New Chelate That Can Be Used To Stimulate Carbonate Reservoirs

SPE Journal ◽  
2011 ◽  
Vol 16 (04) ◽  
pp. 968-980 ◽  
Author(s):  
M.A.. A. Mahmoud ◽  
H.A.. A. Nasr-El-Din ◽  
C.A.. A. De Wolf ◽  
J.N.. N. LePage
Keyword(s):  
Acetic Acid ◽  
Ethylenediaminetetraacetic Acid ◽  
Injection Rate ◽  
Carbonate Reservoirs ◽  
Damkohler Number ◽  
Optimum Conditions ◽  
The Core ◽  
Damköhler Number ◽  
Optimum Injection Rate ◽  
Injection Rates

Summary Different chelating agents were used as alternatives for hydrochloric acid (HCl) in matrix acidizing to create wormholes in carbonate formations. Previous studies demonstrated the use of ethylenediaminetetraacetic acid (EDTA), hydroxy ethylenediaminetriacetic (HEDTA), and glutamic acid-N,N-diacetic acid (GLDA) as standalone stimulation fluids to stimulate carbonate reservoirs. The main problem of using EDTA and HEDTA is their low bio-degradability. GLDA was introduced as a standalone stimulation fluid for deep carbonate reservoirs where HCl can cause corrosion and face dissolution problems. In this study, calcite cores 1.5 in. in diameter and 6 or 20 in. in length were used to determine the optimum conditions where the GLDA can break through the core and form wormholes. GLDA solutions with pH values of 1.7, 3, and 3.8 were used. The optimum conditions of injection rate and pH were determined using coreflood experiments. Damköhler number was determined using the wormhole length and diameter from the CT scan 3D and 2D images. GLDA was compared with chelates that are used in the oil industry such as EDTA and HEDTA. GLDA also was used to stimulate parallel cores with different permeability ratios (up to 6.25). GLDA was found to be very effective in creating wormholes at pH = 1.7, 3, and 3.8; at different injection rates; and at temperatures up to 300°F. Increasing the temperature increased the reaction rate and less volume of GLDA was required to break through the core and form wormholes. Unlike HCl, in GLDA there was no face dissolution or washout in the cores even at low injection rates (0.5 cm3/min). An optimum injection rate and Damköhler number were found at which the pore volume (PV) required to create wormholes was the minimum. GLDA at pH 1.7 and 3 created wormholes with a small number of PV (at 1 cm3/min, GLDA at pH 1.7 required 1.5 PV at 300°F, and at pH 3 it required 1.8 PV). Compared with acetic acid, the volume of GLDA at pH 3 required to create wormholes was less than that required with acetic acid at the same conditions. GLDA was found to be effective in stimulating parallel cores up to 6.25 permeability contrast (final permeability/initial permeability).

Evaluation of a New Environmentally Friendly Chelating Agent for High-Temperature Applications

SPE Journal ◽  
2011 ◽  
Vol 16 (03) ◽  
pp. 559-574 ◽  
Author(s):  
M.A.. A. Mahmoud ◽  
H.A.. A. Nasr-El-Din ◽  
C.A.. A. De Wolf ◽  
J.N.. N. LePage ◽  
J.H.. H. Bemelaar
Keyword(s):  
Carbonate Rocks ◽  
Chelating Agents ◽  
Oil And Gas ◽  
Environmentally Friendly ◽  
Chelating Agent ◽  
Reaction Rates ◽  
Acid Dissolution ◽  
Matrix Acidizing ◽  
Good Ability ◽  
Wide Range

Summary Matrix acidizing is used in carbonate formations to create wormholes that connect the formation to the wellbore. Hydrochloric acid (HCl), organic acids, or mixtures of these acids are typically used in matrix-acidizing treatments of carbonate reservoirs. However, the use of these acids in deep wells has some major drawbacks, including high and uncontrolled reaction rates and corrosion to well tubulars, especially those made of chromium-based tubulars (Cr-13 and duplex steel); and these problems become severe at high temperatures. To overcome problems associated with strong acids, chelating agents were introduced and used in the field. However, major concerns with most of these chemicals are their limited dissolving power and negative environmental impact. L-glutamic acid diacetic acid (GLDA), a newly developed environmentally friendly chelate, was examined as a replacement for acid treatments in deep oil and gas wells. The solubility of calcium carbonate (CaCO3) in the new chelate was measured over a wide range of parameters. Coreflood tests were conducted using long Indiana limestone cores 1.5 in. in diameter and 20 in. in length, which allowed better understanding of the propagation of this chemical in carbonate rocks. The cores were X-ray scanned before and after the injection of chelate solutions into the cores. The concentration of calcium (Ca) and chelate was measured in the core effluent samples. To the best of our knowledge, this is the first study to examine the fate and propagation of chelating agents in coreflood studies. GLDA has a very good ability to dissolve Ca from carbonate rocks over a wide pH range by a combination of acid dissolution and chelation. The addition of 5 wt% sodium chloride (NaCl) did not affect the GLDA performance at pH = 13 but significantly accelerated the reaction at pH = 1.7. Compared with other chelating agents, GLDA dissolved more Ca than ethanoldiglycinic acid (EDG) but less than hydroxyethyl ethylenediamine triacetic acid (HEDTA) at high pH values. GLDA of pH = 1.7 was able to form wormholes at 2 and 3 cm3/min. GLDA was found to be thermally stable at temperatures up to 350°F.

Phase-formation kinetics of xerogel and electrical properties of sol-gel-derived BaxSr1−xTiO3 thin films

1997 ◽  
Vol 12 (5) ◽  
pp. 1327-1334 ◽  
Author(s):  
Soo-Ik Jang ◽  
Byung-Cheul Choi ◽  
Hyun M. Jang
Keyword(s):  
Perovskite Phase ◽  
Sol Gel ◽  
Chelating Agent ◽  
Life Time ◽  
Titanium Isopropoxide ◽  
Hydrolysis Rate ◽  
Relative Dielectric Permittivity ◽  
Strontium Chloride ◽  
Heating Rates ◽  
Enolic Form

Chemically homogeneous BaxSr1−xTiO3 (BST with x = 0.6) multicomponent sol was synthesized using barium oxide, strontium chloride, and Ti-alkoxide (titanium isopropoxide) as starting materials. Acetylacetone (AcAc) was introduced as a chelating agent to reduce a rapid hydrolysis rate of Ti-alkoxide. Analysis of Fourier transform infrared spectroscopy (FTIR) spectra indicated that the stabilization of BST sols was achieved by the chelation of Ti-alkoxide with the enolic form of AcAc. The effective activation energy associated with the formation of perovskite phase from the xerogel was estimated by the differential thermal analysis (DTA) experiment using various heating rates. It is approximately 400 kJ/mol with the Avrami exponent (reaction order) of n = 1, suggesting that the growth of perovskite BST is diffusion-controlled. The calculated half-life time suggests that the minimum temperature for the crystallization which is practically accessible to a real processing is approximately 600 °C. The BST thin film fabricated on the “Pt(150 nm)/Ti(100 nm)/SiO2(100 nm)/Si” substrate exhibited the relative dielectric permittivity of 310 and can be represented by an equivalent circuit consisting of a resistive component originated from the bulk perovskite grain and a parallel RC component resulting from the presence of the grain boundary.

Quantifying the Effect of Multiphase Flow on Matrix Acidizing in Oil-Bearing Carbonate Formations

2021 ◽  
pp. 1-12
Author(s):  
Mohamed Elsafih ◽  
Mashhad Fahes
Keyword(s):  
High Pressure ◽  
Multiphase Flow ◽  
Injection Rate ◽  
Low Permeability ◽  
Matrix Acidizing ◽  
Permeability Heterogeneity ◽  
Acid Injection ◽  
Water Saturated ◽  
Carbonate Formations ◽  
The Impact

Summary It is common to inject acidic stimulation fluids into oil-bearing carbonate formations to enhance well productivity. This process of matrix acidizing is designed to maximize the propagation of wormholes into the formation by optimizing the injection parameters, including acid-injection rate and volume. Previous studies have suggested that saturation conditions, permeability, heterogeneity, temperature, and pressure can significantly affect the design of matrix-acidizing treatments. However, laboratory studies’ results are inconsistent in their conclusions and are mostly limited to water-saturated cores. In this work, we designed a systematic experimental study to evaluate the impact of multiphase flow on the acidizing process when injecting 15 wt% hydrochloric acid (HCl) into crude-oil-saturated Indiana Limestone cores. The results reveal the following: Contrary to published literature for water-saturated cores, acidizing in partially oil-saturatedhigh-permeability cores at high pressure requires less acid volume than in low-permeability cores; lower-pressure acid injection results in more efficient wormhole propagation in low-permeability cores compared to high-pressure acid injection; acidizing in low- and high-permeability cores at low pressure leads to similar efficiency; and wormholing is more effective in partially oil-saturated cores, resulting in multiple parallel branches as compared to inefficient leakoff in water-saturatedcores.

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