1. School of Chemical Engineering and Technology, Southwest Petroleum University, China; nasimarafat06@gmail.com

*             Correspondence: nasimarafat06@gmail.com

Keywords: Ion recovery, salt lake, valuable ions in the brine

1. INTRODUCTION

Ion recovery in oilfields refers to the process of extracting and recovering ions from various fluids encountered during oil production operations. It is significant to manage and control the composition of these fluids to optimize production and minimize environmental impact [1]. The ions of interest in oilfield operations can include both desirable and undesirable species. It is an important process in oilfield operations, particularly in increased oil recovery techniques for example, water flooding and polymer flooding. These methods involve injecting water or polymers into the reservoir to displace oil and improve recovery rates [2]. During these processes, ions are often present in the injected fluids and can accumulate in the reservoir. This can lead to problems such as scaling, corrosion, and formation damage, which can negatively impact production and increase costs [3]. To address these issues, ion recovery systems can be used to remove excess ions from the injected fluids and minimize their impact on the reservoir. These systems typically use various technologies such as ion exchange, reverse osmosis, and electrocoagulation to selectively remove target ions from the fluid stream [4]. In addition to improving production and reducing costs, ion recovery can also have environmental benefits by reducing the amount of waste generated from oilfield operations. It is important to note that the specific ion recovery processes implemented in an oilfield depend on the nature of the ions present, the desired level of purification, the economics of the operation, and local environmental regulations [5]. Additionally, energy consumption, waste production, and overall process efficacy should be considered when selecting a technology. When primary oil recovery is no longer viable, secondary oil recovery is implemented to extract more crude oil from the reservoir using pressure maintenance techniques such as water inundation and gas injection [6].  Recovery of ions is a crucial aspect of oil field operations. By saturating ion-matched water, it is possible to reduce the ionic strength and modify the ionic composition of the formation water, thereby minimizing the difference between the effective concentration of monovalent and divalent ions at the surface of carbonate minerals. It is a mechanism that facilitates oil recovery [7]. Distillation of water is the process in which the oilfield is the separation of brine from oil and gas. This is typically done through a process known as water separation, which separates the brine from the hydrocarbons produced. Likewise, in the preprocessing Oil field brines typically contain various ions such as sodium (Na+), potassium (K+), calcium (Ca2+), and magnesium (Mg2+). Brine may require pretreatment measures such as filtration or pH adjustment to remove impurities and suspended solids. Evaporation is a common technique for concentrating saline solutions and recovering valuable ions. As water is drained from the heated brine, the ionic concentration increases. Finally, additional processing can yield salt crystals or solid precipitates containing valuable ions. Ion exchange processes can be used to remove certain ions from saline [8]. Ion exchange resins or membranes allow unwanted ions to be selectively bound and exchanged for desired ions, thus allowing the desired recovery of valuable ions. Brine is usually taken directly from salt lakes and processed for ion extraction. Similarly, evaporation by solar heat is a natural process that benefits salt lakes. Salt water flows into shallow channels or basins where it is exposed to sunlight and wind. The water evaporates over time, leaving behind a concentrated salt solution containing valuable ions that can be recovered. Precipitation is Depending on the composition of the brine, additional precipitation techniques can be used to facilitate crystallization of the valuable ions [9]. By manipulating variables such as temperature, pH, and concentration, specific ions can be precipitated out of brine as salts. The importance of ion recovery from brine is to reduce environmental hazards and help recover resources. Many ions in seawater can potentially be recovered through an extraction process [10]. The electrochemically switched ion exchange process, which combines electrochemistry and ion exchange, is an efficient and environmentally friendly method for recovering lithium from low-concentration brines. It is important to remember that most continental brine deposits are located at high altitudes. Recovery of ions from brine is crucial because brine, in the form of seawater, salt lakes, and geothermal water, contains vast quantities of valuable minerals [11]. Among the diversity of metallic and non-metallic elements recovered from saline at varying scales, Lithium (Li) has attracted a great deal of attention in recent years due to its exponentially increasing demand. The electrochemically switched ion exchange process is an efficient and environmentally favorable process that combines electrochemistry and ion-exchange, allowing for Li recovery from brines with low concentrations. Moreover, the importance of ion recovery from brines is to help recover valuable minerals such as lithium and magnesium from seawater, salt lakes and geothermal water [12].

2. THE RECOVERY TECHNIQUE IONS

Common techniques for recovering ions from salt lakes (also called salt lakes or salt flats) depend on the ions of interest and the composition of the salt lake. Here are some techniques commonly used to recover ions from salt lakes:

2.1 Solar Evaporation

Salt lakes are often affected by solar evaporation, pouring salt water into large shallow ponds or valleys and allowing it to evaporate in the sun. As the water evaporates, the ion concentration increases and eventually the salt precipitates. The collected compounds are further refined to extract valuable ions such as lithium, potassium and sodium [13].

2.2 Ion exchange

Ion exchange is a technique for selectively extracting specific ions from a solution. Salt lake regeneration can use ion-exchange polymers or membranes to trap and bind specific ions. Trapped ions are released and recovered from the resin or membrane using appropriate regeneration techniques [14].

2.3 Precipitation and Crystallization

Specific ions can be obtained through precipitation and crystallization processes. By adjusting the temperature, pressure, and concentration of the brine in the salt lake, specific ions can be precipitated as solid crystals. The separated crystals are then processed to extract the desired ions [15].

2.4 Solvent Extraction

Solvent extraction utilises organic solvents to selectively extract ions from solution. Salt lake extraction uses a suitable solvent to extract the desired ions from a salt solution. The solvent phase containing the desired ions is then separated and treated to recover the desired ions [16].

2.5 Chemical Precipitation

Chemical precipitation involves the addition of certain compounds to the brine of a salt lake to induce precipitation of the desired ions. By precisely altering the pH, temperature, and concentration of the brine, specific ions can be precipitated as solid salts. Precipitated compounds can be processed to recover the desired ions [17].

2.6 Electrodialysis

Electrodialysis is a membrane-based separation method that uses an electric field to selectively transport ions through ion exchange membranes. Salt lake recovery uses electrodialysis to separate and concentrate specific ions from brine by selectively passing them through a membrane while retaining unwanted ions. The solution containing the desired ions can then be subjected to further processing for recovery [18].

3. BROMINE

Recovering bromine from salt lakes, also known as bromine brine deposits, requires extraction and washing of bromine compounds from the brine solution. Bromine-rich salinity basins, such as the Dead Sea and the Salton Sea, contain significant concentrations of dissolved bromine compounds. The chemical element bromine can be extracted from salt lakes [19].  Recovery of bromide ions from salt lakes usually requires a combination of techniques such as evaporation, chemical treatment and extraction. Here are some common techniques for recovering bromide ions from salt lakes:

3.1 Evaporation ponds

Evaporation ponds or reservoirs are used to collect bromine-rich brine from salt lakes or brine deposits. As the salt water is exposed to the sun and wind, the water evaporates more and more. As water evaporates, the concentration of dissolved compounds such as bromine increases.

3.2 Precipitation

When the brine reaches a sufficient concentration, it undergoes a chemical treatment to precipitate the bromine compounds. Bromide ions are oxidized upon addition of chemicals such as chlorine and hydrogen peroxide to produce bromine gas (Br₂) and bromine compounds such as sodium bromate (NaBrO₃) and potassium bromate (KBrO₃).

3.3 Friction and absorption

The bromine gas normally produced during the precipitation phase is captured by a process called purging. The gas is washed with water or another chemical solution to dissolve the bromine and produce a bromine-rich solution. This solution is then further processed to obtain the bromine-containing compound.

3.4 Solvent extraction

Solvent extraction techniques can be used to selectively extract bromide ions from the bromine-rich solution obtained in the previous step. Bromine is typically extracted from solution using organic solvents such as tributyl phosphate (TBP) or diethyl ether. Bromine is recovered by separating and working up the bromine-rich organic phase. Solvent extraction processes are primarily used to remove ingredients that adversely affect the potency of the final product. Removal of heavy aromatics from lubricants is an important application. The elimination of impurities enhances the product’s viscosity-temperature relationship, thereby expanding the temperature range over which satisfactory lubrication can be attained. Typical extraction solvents for lubricants are phenol and furfural.

3.5 Distillation

Another method of recovering bromine is distillation. The bromine-rich solution or organic phase undergoes controlled distillation to separate it from impurities or solvent. Purified bromine can be recovered in liquid form by distillation.

3.6 Crystallization

Pure bromine compounds can also be obtained by crystallization processes. To induce the formation of solid bromine compounds, bromine-rich solutions are subjected to controlled cooling or chemical reactions. These crystals are separated, dried and further processed to obtain the purified bromine compound. Crystallization of the wax from the lubricating oil fraction is required for the lubricant to be fit for use. The oil is first mixed with a solvent (often a mixture of benzene and methyl ethyl ketone) and then cooled to about 20°C (5°F). Benzene keeps the oil in solution and fluid at low temperatures, and methyl ethyl ketone acts as a precipitant for the wax. The wax crystals are deposited through a rotating filter onto a specially woven fabric that is draped over a perforated cylindrical cylinder. Maintaining a vacuum inside the drum allows the oil to flow through the holes. After rinsing with a solvent to remove any traces of oil, use a metal scraper to remove wax crystals from the fabric. The solvent is then separated from the oil and recycled.

3.7 Purification and Refining

Recovered bromine or bromine compounds may undergo additional refining and purification processes to improve quality and remove residual impurities. Techniques such as filtration, chemical treatment, and additional distillation can be used to achieve higher levels of purity. Purification is the removal of impurities or impurities from a substance or material. This can be achieved by filtration, distillation, crystallization, chromatography, chemical reactions, etc. Cleaning is essential to ensure final product quality, safety and regulatory compliance. Refining is the process of improving the quality and integrity of a substance by removing impurities, purifying unwanted components, and enhancing desirable properties. Refining is primarily associated with petroleum refining in the oil and gas industry, where crude oil is refined to produce gasoline, diesel, aviation fuel, and various petrochemicals.

3.8 Steaming-out and air blow-out technique

Steaming was the earliest method of obtaining bromine in the chemical industry. Acidified brine was fed to a packed column were chlorine counter currently oxidized bromide ions. Free bromine was introduced into the condenser using different volatile liquids consisting of water and bromine. The condensed vapor was then discharged as final product. Low handling complexity and minimal raw material consumption made this method suitable for large-scale production of bromine. The higher the salt concentration, the less steam is required. This technology is used in areas such as bittern, well bittern, oil and gas bittern to produce higher yields. However, considering the economics of bromine extraction, the required liquid temperature was very high and the hydrolysis of free bromine and the reaction of bromine with excess chlorine affected the rate of oxidation and blowdown. With increasing demand, the air blowout method has become more and more popular. The air sparging technique used air as the carrier for free bromine and the desorption process was performed in a packed column. After acidification and oxidation, the free bromine in the brine was blown into an absorption tower where absorbents such as sulfite solution and caustic soda were used to absorb the free bromine recovered during the desorption process. The goal of bromine enrichment was thus achieved. Various absorbents were used, including caustic soda (NaOH) and soda ash (Na₂CO₃) solutions, sulfur dioxide (SO₂), and iron (Fe). This technique is the most popular method of bromine extraction due to its simple procedure and operation. However, this method requires large-scale equipment and a lot of energy consumption, and is also greatly affected by temperature. Bromine recovery techniques vary depending on the composition of the brine, the bromine concentration, and the desired end product. Environmental considerations and regulations also play an important role in ensuring the safe and responsible extraction of bromine from salt lakes.

4. POTASSIUM

Potassium extraction from salt lakes, also called potash extraction, is an important technique for extracting potassium compounds, mainly potassium chloride. Potassium-rich salt lakes, such as the Dead Sea and the Great Salt Lake, contain high concentrations of dissolved potassium compounds in salt water. Potassium chloride extracted from salt lakes is widely used in agriculture as a potassium fertilizer. It is also used in various industrial applications such as chemical manufacturing, water treatment and food processing. Recovering potassium ions from salt lakes usually requires a combination of techniques such as evaporation, precipitation, and chemical treatment. Here are some common techniques for extracting potassium ions from salt lakes.

4.1 Evaporation ponds

Evaporation ponds or reservoirs are filled with potassium-rich brine from potassium-rich salt lakes or brine deposits. As the salt water is exposed to the sun and wind, the water evaporates more and more. The concentration of dissolved compounds such as potassium increases as water evaporates.

4.2 Precipitation

Once the saltwater concentration reaches a sufficient level, a chemical treatment is used to precipitate the potassium compounds. This can be achieved by adding compounds such as sodium carbonate (Na₂CO₃) or sodium hydroxide (NaOH) to the brine. These compounds react with potassium ions to form insoluble potassium carbonate (K₂CO₃) or potassium hydroxide (KOH) precipitates.

4.3 Separation of solids and liquids

Precipitated potassium compounds are then separated from the brine by sedimentation, centrifugation or filtration. At this stage, solid potassium compounds are extracted from the remaining salt solution.

4.4 Dissolution

Dissolve the isolated solid potassium compound in water or other solvent to produce a potassium-rich solution. In this phase potassium ions can be extracted from the solid precipitate.

4.5 Ion exchange

Potassium ions in potassium-rich solutions can be selectively captured and recovered using ion-exchange techniques. This is done by passing the solution through an ion exchange resin or membrane, which binds the potassium ions in the solution and exchanges them for other ions. The potassium-rich resin or membrane is then treated to provide a potassium solution in concentrated form.

4.6 Crystallization

Potassium ions can be further concentrated by a crystallization process to obtain a purer potassium compound. Crystalline potassium compounds such as potassium chloride (KCl) and potassium sulfate (K₂SO₄) can be precipitated from potassium-rich solutions by manipulating temperature, pressure, and chemical conditions. These particles can be separated and purified to obtain purified potassium compounds.

4.7 Drying and packaging

Potassium compounds, whether in solution or solid form, are usually dried to remove excess water. The dried potassium product is then packaged and prepared for distribution to potassium-using industries such as agriculture, fertilizer production, and chemical production.It is important to note that potassium ion recovery techniques may vary depending on salinity, potassium concentration, and desired end product. Additionally, environmental considerations and regulations play an important role in ensuring that potassium extraction from salt lakes is sustainable and responsible.

5. LITHIUM

Extraction of lithium compounds from salt lakes, also called lithium brine deposits, is a common practice. Lithium-rich salt lakes and brines contain dissolved lithium compounds at high concentrations, making them a valuable source of lithium. The methods and technologies used to recover lithium vary depending on the characteristics of the salt lake, the desired end product, and the economics of recovery. Additionally, environmentally sustainable practices are essential to minimize impacts on the surrounding salt lake ecosystem [19]. Recovery of lithium from brine is a complex process that requires separation of magnesium and lithium ions. Effective separation of Mg²⁺ and Li⁺ is essential to achieve high lithium recovery efficiency and product purity. Various techniques and materials are used in the field of lithium extraction from brine [20]. Separation of Li⁺ from the simulated brine reduces the Mg²⁺ /Li⁺ mass ratio to less than 6, which is the recommended value for Li recovery. The raw and refined brines were concentrated to enrich in lithium using the direct contact MD method. A nine-step simulated countercurrent process demonstrated high Li/Mg selectivity, high lithium recovery and efficient lithium extraction with water. This process therefore represents an important advance for the sustainable recovery of lithium from magnesium-rich brines [21]. There are several techniques for selectively isolating lithium from salt-lake brine, including the precipitation method, solvent extraction method, and adsorption technique. Lithium, which is the lightest among alkali metals, is used as the positive electrode material for lithium batteries due to its advantages such as high energy storage density and low self-discharge rate [22]. In recent years, demand due to environmental changes such as global warming and the carbon cycle has led to a boom in the new energy industry centering on lithium, and expansion of the lithium market is required. However, over 60% of the world’s lithium resources have been identified in salt lakes, and the selective extraction of Li(I) from brackish water is of great economic and environmental importance. In the figure 02 we can see the materials for lithium recovery from saltlake and when it comes to figure 01 we can see another recovery techniques. Lithium ions are typically recovered from salt lakes using a combination of evaporation, precipitation and extraction techniques. Here are some common techniques for recovering lithium ions from salt lakes.

Figure 01: Materials for lithium recovery from salt lake brine

Figure 02: Lithium recovery from salt lake brine by H2TiO3

5.1 Evaporation ponds

Salt lakes and brine sediments containing lithium-rich brine flow into huge evaporation ponds and reservoirs. Salt water is exposed to the sun and atmosphere, causing the water to slowly volatilize. As the water evaporates, dissolved compounds such as lithium become more concentrated.

5.2 Precipitation

When the brine concentration reaches a sufficient level, a chemical process precipitates lithium compound. This can be achieved by adding sodium carbonate (Na₂CO₃) or lime (CaO) to the brine. These react with lithium ions to form an insoluble precipitate of lithium carbonate (Li₂CO₃) or lithium hydroxide (LiOH).

5.3 Solid-Liquid separation

The precipitated lithium compounds are then separated from the brine using techniques such as sedimentation, centrifugation and filtration. This step separates the remaining salt solution from the solid lithium compound.

5.4 Solvent extraction

The separated solid lithium compounds are dissolved in water or other solvent and solvent extraction produces a lithium-rich solution. This solution is then treated with an organic solvent such as kerosene or butanol to selectively separate the lithium ions. The organic solvent phase containing lithium ions is separated from the aqueous phase and the ions are further purified.

5.5 Ion exchange

Ion-exchange technology can be used to selectively capture and recover lithium ions from lithium-rich solutions. The solution is passed through an ion exchange resin or membrane, preferentially binding lithium ions and exchanging them with other ions present in the solution. The lithium-rich resin or lithium membrane is then treated to release a concentrated lithium solution.

5.6 Crystallization

A crystallization process can be used to further concentrate the lithium ions and obtain a higher purity lithium compound. Lithium-rich solutions can be crystallized into lithium compounds such as lithium carbonate (Li₂CO₃) by manipulating temperature, pressure, and chemical conditions. These crystals can be separated and processed to obtain purified lithium compounds.

5.7 Drying and packing

The resulting lithium compound, whether a solution or a solid, is typically dried to remove excess moisture prior to packaging. Lithium products are then packaged and ready for distribution to lithium-using industries such as the battery industry, ceramics, glass, and lubricants. It is important to note that the specific techniques used to recover lithium ions may vary depending on the brine composition, lithium concentration, and desired end product. Furthermore, environmental considerations and regulations play an important role in ensuring the responsible and sustainable extraction of lithium from salt lakes.

6. BORON

There are several methods for extracting boron ions from brine. Solvent extraction is one of the most efficient techniques. Compared to traditional techniques, solvent extraction offers a simple, robust and highly productive process. In solvent extraction, the choice of extractant is critical [23]. Boron extractants are classified into aliphatic alcohols, aromatic alcohols, and mixed alcohols based on their structure and boron recovery mechanism. Boron is widely distributed in the hydrosphere and lithosphere of the earth, but its concentration is extremely low. Boron occurs naturally as undissociated orthoborates, polysorbates, transition metal complexes, and partially dissociated borate anions as fluoroborate complexes. Boron and boron compounds are widely used in over 300 industries [24].  Boron ions can be recovered from salt lakes using techniques to separate and extract boron compounds from brine. Here are some common techniques for recovering boron ions from salt lakes.

6.1 Ion exchange

In ion exchange, brine is passed through a special resin or membrane that selectively binds boron ions and exchanges them with other ions present in the brine. The boron-rich resin or membrane is then treated to provide a boron solution in concentrated form.

6.2 Membrane Filtration

Boron ions can be separated from brine by membrane filtration techniques such as reverse osmosis and nanofiltration. These processes use a semi-permeable membrane that allows water and smaller ions to pass through while retaining the larger boron ions.

6.3 Precipitation

During precipitation, certain chemicals are added to the brine to promote the formation of boron compounds, which are separated and recovered. For example, calcium or magnesium salts can be added to the brine to precipitate boron as boron minerals. Precipitated boron compounds are separated and processed further.

6.4 Solvent extraction

Solvent extraction uses an organic solvent to selectively extract boron ions from brine. Boron ions migrate from the aqueous phase to the organic phase when the brine and solvent are mixed. The boron-containing organic phase is then separated and treated to recover the elements.

6.5 Electrolysis

Electrolysis is a process that uses an electric current to transport boron ions to specific electrodes where they can be selectively captured and collected. Boron is often obtained from concentrated salt solutions using this method.

6.6 Evaporation and crystallization

Evaporation is a common technique in boron recovery. Under controlled conditions, the brine evaporates, evaporating water leaving a concentrated boron-rich solution. Additional crystallization methods can then be used to obtain pure boron compounds.

5. CONCLUSION

Ion recovery in oilfields is an important process that benefits both the environment and oilfield operations. By implementing efficient ion capture technology, companies can increase production efficiency, ensure high quality oil production, conserve resources and reduce costs, thereby improving the profitability and sustainability of oil field operations. In oilfields, ion recovery is the process of getting useful ions out of the product water that is made when oil is drilled and made. This is done to reduce the damage that dumping garbage has on the environment and to make it possible to use water for more things. In short, ion capture in oilfields is an important step in reducing the water’s effect on the environment and getting the most out of the resources. Using methods like membrane filtering, ion exchange, and evaporation/ crystallization, it is possible to collect and reuse useful ions while releasing less pollution into the environment.

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