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Industrial Application of Gemini Quaternary Ammonium Salt Surfactants

Gemini quaternary ammonium salt surfactants, also known as cationic Gemini surfactants, are a new type of surfactant that connects two or more single chain cationic surfactants through linking groups. The special double N-terminal molecular structure of Gemini quaternary ammonium salt surfactants endows them with unique physicochemical properties. Compared with traditional single chain quaternary ammonium salts, they have superior surface/interface activity, antibacterial and bactericidal properties, and unique rheological behavior, as well as good wettability and strong emulsifying ability.

Gemini quaternary ammonium salt surfactants currently have great application value and have received widespread attention in fields such as sterilization and disinfection, oil fields, metal corrosion inhibition, textile printing and dyeing, sewage treatment, and new materials.

 

Application in the field of sterilization and disinfection

Due to the presence of two positively charged hydrophilic groups and two hydrophobic chains in the Gemini Quaternary Ammonium Salt surfactant molecules, it has stronger bactericidal ability compared to traditional single chain quaternary ammonium salts (1231 and 1227), as well as low toxicity, wide biological activity, and good water solubility.
Application areas: ① It has great application value in sterilization and anti-corrosion of personal care products, cosmetics, and paper industry; ② Can be used as an efficient bactericide for industrial cooling circulating water, reducing pipeline blockage and equipment corrosion; ③ As a substitute for corrosion inhibitors (1227) in tertiary oil recovery in oil fields, it reduces the corrosion of bacteria (such as sulfate reducing bacteria, iron bacteria, and saprophytic bacteria) on oil pipelines and solves the problem of bacterial resistance.

The sterilization and disinfection mechanism of Gemini Quaternary Ammonium Salt Surfactants: ① Gemini Quaternary Ammonium Salt Surfactants have two hydrophobic chains in their molecular structure, which facilitates their hydrophobic groups to penetrate into the lipid layer of bacterial cells, and their hydrophilic groups to penetrate into the protein layer, leading to enzyme inactivation and protein denaturation; ② The molecular structure contains two N-terminal groups, and under induction, the positive charge density of the dicycloquaternary ammonium salt head group increases, making it easier for surfactants to adsorb onto bacterial surfaces, changing the permeability of bacterial cell walls and causing them to rupture, achieving the effect of killing bacteria.

 

Application in tertiary oil recovery

Used as a clean fracturing fluid for oil fields

Fracturing fluid is a working fluid used for fracturing and transforming oil and gas reservoirs. Its main function is to transfer high pressure from the surface to the formation to form fractures and transport proppants. Traditional fracturing agents such as guar gum and hydroxyethyl cellulose can leave residues in fractures that can damage the formation, resulting in reduced permeability and productivity. Gemini quaternary ammonium salt surfactants have good application prospects in viscoelastic surfactant fracturing fluids (VES) due to their unique rheological properties and low damage.

Chemical depressurization and injection increase in water injection wells

After long-term water injection, the chemical depressurization and enhancement of water injection wells can lead to severe reservoir blockage due to liquid resistance effect, water lock damage, clay migration, formation scaling, and extensive bacterial growth. This problem is particularly prominent in the near wellbore area, resulting in high water injection pressure and insufficient water injection volume.

Chemical depressurization and injection enhancement mainly involves injecting depressurization and injection enhancement agents containing quaternary ammonium salts into water wells to reduce oil-water interfacial tension, reduce Jamin effect, and increase oil flow capacity; Changing the wettability of the rock surface to make the reservoir more hydrophilic and exert capillary force; Inhibit clay swelling and reduce damage to the formation; Inhibit the growth of microorganisms and reduce damage to the wellbore and formation; Improve the permeability of injected water to achieve the goal of reducing pressure and increasing injection in low-permeability oil fields. And the technology of reducing pressure and increasing injection has a certain oil displacement effect.

Used in tertiary oil recovery

Compared with traditional single chain quaternary ammonium salts, the efficient chemical oil displacement agent Gemini Quaternary Ammonium Salt has better surface activity and lower critical micelle concentration. It can form flexible linear micelles and entangle with each other to form a network structure at extremely low concentrations. The solution viscosity is greatly increased and has shear thinning characteristics. Its special rheological properties can effectively change the oil-water flow ratio, expand the affected volume, and improve oil displacement efficiency. Injecting a solution system containing such binary quaternary ammonium salts into the formation can not only greatly reduce the interfacial tension between oil and water (up to 10-3 mN/m), change the rheological and emulsifying properties of oil, but also improve the wettability of the formation surface (occurrence of wetting reversal), reduce the adhesion force of oil to the formation surface, and greatly improve the oil washing ability; It can also form relatively stable oil-water emulsions, making flow and extraction easier.

Fluid energy-saving and drag reducing agent

With the growth of the global economy, humanity is facing an increasingly profound energy crisis. How to reduce the flow friction resistance during long-distance pipeline fluid transportation and reduce the power consumption of pump stations is an important part of the development of energy-saving and drag reduction technologies.

Adding fluid chemical drag reducers can significantly reduce the resistance of the flow process and lower pump consumption, a phenomenon known as the Toms effect. The most commonly used drag reducers currently are polymers and surfactants. Polymers are prone to chain breakage under mechanical shear of pumps, which weakens their drag reduction performance and is not suitable for closed-loop systems. Surfactant micelles have self-assembly properties and can spontaneously recover to a sheared structure after high-speed shearing. They have good reversibility and are suitable for both cyclic and non cyclic fluid transport systems. Compared with traditional surfactants, Gemini surfactants have superior surface activity and self-assembly properties, and have great application value in fluid drag reduction systems.

Application in the field of metal corrosion inhibition

Metal corrosion can alter the mechanical and physicochemical properties of metal materials, causing significant economic losses to industrial production and living facilities. Gemini quaternary ammonium salt surfactants exhibit more outstanding performance in metal corrosion resistance compared to traditional single chain quaternary ammonium salts, with high efficiency and non-toxic characteristics. It can form a dense adsorption film on the surface of metals through the strong electrostatic attraction of its double N-terminal group, significantly reducing the corrosion behavior of metals in chemical media. At present, it has a wide range of applications in the fields of petrochemicals, transportation, steel, and machinery.

The mechanism of metal corrosion inhibition by surfactants: Metal surfaces generally carry negative charges. Gemini quaternary ammonium salt surfactants dissolve in water and dissociate into cations with two charges. Gemini quaternary ammonium salt surfactant ions are adsorbed on the metal surface by electrostatic attraction, and hydrophobic groups can form a dense hydrophobic film on the metal surface, which can effectively isolate water or other corrosion-resistant substances from contact with the metal, thereby achieving efficient metal corrosion inhibition.

 

Application in the textile printing and dyeing industry

Can be used as an alkali reduction promoter and cationic dye dyeing retarder for polyester fabrics

Gemini quaternary ammonium salts have a significant promoting effect on the alkali reduction treatment of polyester fabrics. The strength loss of the treated fabrics is relatively small, and the drape, breathability, and moisture retention of the fabrics can be effectively improved. The crystallinity and glass transition temperature of the fibers treated with cationic dyes are lower, and the internal structure of the fibers is relatively loose, resulting in a faster adsorption rate. The Gemini quaternary ammonium salt added to the dye first enters the interior of the fiber and binds with the sulfonic acid anion. After the cationic dye enters, it is replaced, thereby slowing down the dye adsorption rate and achieving a slow dyeing effect. Wang Rongxiang et al. applied twin quaternary ammonium salts (m-n-m type) to polyester fabric alkali reduction accelerators and retarders, and found that this type of twin quaternary ammonium salts has a significant promoting effect on the alkali reduction treatment of polyester fabrics. After finishing, the fabric performance is good, and the performance is significantly better than traditional single chain quaternary ammonium salts.

Can be used to improve nylon printing dots

Nylon is prone to producing pitting on the surface during acid dye printing, manifested as local aggregation on the fabric surface. By adding appropriate dicot quaternary ammonium salts, anionic dyes and dicot quaternary ammonium salts form a spatial network structure on the fabric surface, making it difficult for the dyes to move during the printing stage lifting or drying process, and preventing the generation of textile dots. The stable interaction between Gemini quaternary ammonium salts and acidic dyes is beneficial for reducing the production of printed dots. Studies have shown that the use of hydroxyl containing quaternary ammonium salts in combination with other additives can eliminate the pitting caused by dyes during nylon printing.

Low salt technology in the dyeing process of cotton and linen fabrics

The use of a large amount of inorganic salts in the dyeing process of cotton fabrics poses great difficulties for wastewater treatment, and salt free/low salt/alternative alkali dyeing has become a research hotspot. By modifying cotton fibers with a small amount of quaternary ammonium salts and then using reactive dyes for delayed dyeing, the amount of inorganic salts can be greatly reduced, which is beneficial for reducing costs, minimizing salt pollution to the environment, and improving product quality. Jia Lihua et al. used ester based quaternary ammonium salts as additives to dye linen fabrics with reactive dyes. The dye uptake and fixation rate of reactive yellow M-3RE reached over 85%. The dyeing performance of linen fabrics treated with this type of quaternary ammonium salt was superior to that of traditional quaternary ammonium salt CTAB, with an increase of nearly 10% in coloring rate and fixation rate, respectively.