PALMFONATE 6918

Synonyms:
PALMFONATE 6918; SULPHONATED METHYL ESTERS; PALMFONATE 6918; PALMFONATE; PALMPHONATE; PALMPHONATE 6918;sulfonate d'ester méthylique; PALMFONATE 6918; SULPHONATED METHYL ESTERS; PALMFONATE 6918; PALMFONATE; PALMPHONATE; PALMPHONATE 6918; SULFONATE D'ESTER MÉTHYLİQUE; SULPHONATE D'ESTER MÉTHYLİQUE; SULFONATE ESTER MÉTHYLİQUE; PALMFONATE 6918; SEM; SULFONATED METHYL ESTERS; SULPHONATED METİL ESTER; PALMFONATE 6918; Sulphonated Methyl Esters;PALMFONATE 6918; SULPHONATED METHYL ESTERS; PALMFONATE 6918; PALMFONATE; PALMPHONATE; PALMPHONATE 6918;sulfonate d'ester méthylique; PALMFONATE 6918; SULPHONATED METHYL ESTERS; PALMFONATE 6918; PALMFONATE; PALMPHONATE; PALMPHONATE 6918; SULFONATE D'ESTER MÉTHYLİQUE; SULPHONATE D'ESTER MÉTHYLİQUE; SULFONATE ESTER MÉTHYLİQUE; PALMFONATE 6918; SEM; PALMFONATE 6918; SULPHONATED METHYL ESTERS; PALMFONATE 6918; PALMFONATE; PALMPHONATE; PALMPHONATE 6918;sulfonate d'ester méthylique; PALMFONATE 6918; SULPHONATED METHYL ESTERS; PALMFONATE 6918; PALMFONATE; PALMPHONATE; PALMPHONATE 6918; SULFONATE D'ESTER MÉTHYLİQUE; SULPHONATE D'ESTER MÉTHYLİQUE; SULFONATE ESTER MÉTHYLİQUE; MES; SEM; SULFONATED METHYL ESTERS; SULPHONATED METİL ESTER; Mes; Sulphonated Methyl Esters;MES; SULPHONATED METHYL ESTERS; PALMFONATE 6918; PALMFONATE; PALMPHONATE; PALMPHONATE 6918;sulfonate d'ester méthylique; MES; SULPHONATED METHYL ESTERS; PALMFONATE 6918; PALMFONATE; PALMPHONATE; PALMPHONATE 6918; SULFONATE D'ESTER MÉTHYLİQUE; SULPHONATE D'ESTER MÉTHYLİQUE; SULFONATE ESTER MÉTHYLİQUE; MES; SEM; SULFONATED METHYL ESTERS; SULPHONATED METİL ESTER; Mes; Sulphonated Methyl Esters; Palmfonate 6918; Palmfonate; Palmphonate; Palmphonate 6918; Sulfonate D'ester Méthylique; Sulphonate D'ester Méthylique; Sulfonate Ester Méthylique; Mes; Sem; Sulfonated Methyl Esters; Sulphonated Metil Ester;  mes; sulphonated methyl esters; palmfonate 6918; palmfonate; palmphonate; palmphonate 6918; sulfonate d'ester méthylique; Palmfonate 6918; Palmfonate; Palmphonate; Palmphonate 6918; Sulfonate D'ester Méthylique; Sulphonate D'ester Méthylique; Sulfonate Ester Méthylique; Mes; Sem; Sulfonated Methyl Esters; Sulphonated Metil Ester;  mes; sulphonated methyl esters; palmfonate 6918; palmfonate; palmphonate; palmphonate 6918; sulfonate d'ester méthylique; sulphonate d'ester méthylique; sulfonate ester méthylique; mes; sem; sulfonated methyl esters; sulphonated metil ester; PALMFONATE 6918; PALMONATE 6918; PALM FONATE 6918; PALMFONATE-6918; PALMFONATE/6918; PALMFONATE; PALMPHONATE-6918; SULFONATED METHYL ESTERS; SULPHONATED METİL ESTER; Mes; Sulphonated Methyl Esters; Palmfonate 6918; Palmfonate; Palmphonate; Palmphonate 6918; Sulfonate D'ester Méthylique; Sulphonate D'ester Méthylique; Sulfonate Ester Méthylique; Mes; Sem; Sulfonated Methyl Esters; Sulphonated Metil Ester;  mes; sulphonated methyl esters; palmfonate 6918; palmfonate; palmphonate; palmphonate 6918; sulfonate d'ester méthylique; Palmfonate 6918; Palmfonate; Palmphonate; Palmphonate 6918; Sulfonate D'ester Méthylique; Sulphonate D'ester Méthylique; Sulfonate Ester Méthylique; Mes; Sem; Sulfonated Methyl Esters; Sulphonated Metil Ester;  mes; sulphonated methyl esters; palmfonate 6918; palmfonate; palmphonate; palmphonate 6918; sulfonate d'ester méthylique; sulphonate d'ester méthylique; sulfonate ester méthylique; mes; sem; sulfonated methyl esters; sulphonated metil ester; PALMFONATE 6918; PALMONATE 6918; PALM FONATE 6918; PALMFONATE-6918; PALMFONATE/6918; PALMFONATE; PALMPHONATE-6918;  Palmfonate; Palmphonate; Palmphonate 6918

PALMFONATE 6918

PALMFONATE 6918 SS SULPHONATED METHYL ESTERS

PALMFONATE Methyl Ester Sulfonate (or MES) is an anionic surfactant, which is the active cleaning ingredient in laundry detergents.

The primary use of PALMFONATE is to replace the current surfactant workhorse Linear Alkyl Benzene Sulfonate in detergent formulations. It is made from renewable natural resources, which gives it excellent biodegradability; better tolerance to calcium hardness during the washing process and superior detergency.

Available in dry powder, flakes and paste. The powder quality of PALMFONATE allows direct addition to detergent formulas in the post-addition stage in the manufacturing process.

 
PALMFONATE Sulfonated Methyl Esters (or Methyl Ester Sulfonates or MES) is the anionic surfactant brand of KLK OLEO, which is the active cleaning ingredient in laundry detergents.

The primary use of PALMFONATE is to replace the current surfactant workhorse Linear Alkyl Benzene Sulfonate in detergent formulations. Palmfonate is made from renewable natural resources, which gives it excellent biodegradability; better tolerance to calcium hardness during the washing process and superior detergency.

Available in dry powder, flakes and paste. The powder quality of PALMFONATE allows direct addition to detergent formulas in the post-addition stage in the manufacturing process.

Methyl ester sulfonates (PALMFONATE 6918) have been considered as an alternative green surfactant for the detergent market. Of great interest is research on the purification of methyl ester sulfonates (PALMFONATE 6918) with various C12, C14, C16 and C16–18 carbon chains derived from palm methyl ester. These PALMFONATE 6918 powders were repeatedly crystallized with ethanol and the purity of PALMFONATE 6918 increased to a maximum of 99% active content and 96% crystallinity index without changing the structure. These high active content crystallized PALMFONATE 6918 have a moisture content of 1.0% to 2.3% and have kept their di-salt content in the 5% range. The crystallized PALMFONATE 6918 C16 and C16–18 achieved excellent flow characteristics. Morphology, structure and crystallinity analyzes showed that PALMFONATE 6918 crystals had good solubility properties, a stable crystal structure (polymorphic β) and a triclinic lateral structure when they have a high active content. The fragility of PALMFONATE 6918 crystals changed from a β sub-cell to a β sub-cell. The high brittleness crystal has the potential to facilitate powder production, which leads to lower production cost and improves efficiency.
Keywords: methyl ester sulfonates; purification; crystallization of the solvent; oleochemicals
1. Introduction
Methyl esters without further modification are used as a substitute for diesel or biodiesel. However, due to the high content of palmitic acid and therefore the higher pour point, methyl esters derived from palm oil or palm stearin are not suitable for the winter season. The palm olein must be used or the palm methyl ester must be fractionated to obtain the more liquid methyl ester. With the rapid growth of palm biodiesel, whose production had increased by a factor of 2.8 from 2016 to 2017, this will lead to overcapacity of the saturated methyl ester [1]. Therefore, there is a need to increase the consumption of saturated methyl ester and one of the alternatives is to channel saturated methyl ester as starting materials to produce methyl ester sulfonates (PALMFONATE 6918).
PALMFONATE 6918 production technology is available worldwide; however, there are only a few producers of this surfactant in the world, such as Malaysian Palm Oil Board (MPOB), Chemithon Corporation (USA), Lion Corporation (Japan), KLK Oleomas (Malaysia), Stephan Company ( United States), Wilmar International Ltd. (Indonesia), Guangzhou Keylink Chemical Co., Ltd. (China), Guangzhou Lonkey Industrial Co Ltd. (China) and Sinopec Jinling Petrochemical Co., Ltd. (China) [2,3]. Palm-based PALMFONATE 6918 production technology involves the sulfonation of a palm oil-based methyl ester with sulfur trioxide / air, followed by digestion, bleaching and neutralization to producing PALMFONATE 6918 C12 and C14 and further steps through the turbo tube drying and scaling system process to produce PALMFONATE 6918 C16 and C16–18 secs, as summarized in Figure 1 [4].
Molecules 25 02629 g001 550 Figure 1. Schematic diagram of the pilot plant of the methyl estersulfonate process (PALMFONATE 6918) at the Malaysian Palm Oil Board (MPOB).
The mechanism of formation of PALMFONATE 6918 has been carefully studied and is believed to occur through several stages of the process, as in Figure 2 [5,6,7]. The first step is to react the sulfur trioxide with a saturated fatty methyl ester and rapidly produce the mono-adduct (I). The mono-adduct binds to an intermediate which activates the carbon in the alpha position of the carboxylic group; it will then be sulfonated with a second molecule of sulfur trioxide. Then the di-adduct reorganizes to form a dark-colored fatty methyl ester sulfonic acid (PALMFONATE 6918A) and releases a sulfur (II) trioxide molecule. The rearrangement of the di-adduct is a limiting step and the process continues until all the esters have been sulfonated (III). In the presence of an alkali, the fatty acid methyl ester sulfonic acid will form PALMFONATE 6918 (V), but the di-adduct will hydrolyze to a di-salt (VI).
Molecules 02629 g002 550Figure 2. Reaction of methyl ester sulfonates (V) and intermediates, such as di-salt (VI).
The research results confirmed the superior properties of PALMFONATE 6918 based on palm terPALMFONATE 6918 in detergency, biodegradation [8], synergy with soap [9] and tolerance to different water hardness compared to THE ACE. In addition, the production cost of PALMFONATE 6918 is comparatively lower than that of LAS [10]. These research activities and extensive tests have confirmed that PALMFONATE 6918 and its cleaning products are environmentally friendly [11]. PALMFONATE 6918 and cleaning products formulated from palm are readily biodegradable [12].
One of the major applications of PALMFONATE 6918 was in the detergents segment; however, Grand View Research has reported that the personal care segment is expected to emerge for over 34% of the PALMFONATE 6918 market volume share by 2025 [13]. Application flexibility largely depends on the quality of PALMFONATE 6918; in particular, the composition and physical form of the product. In Malaysia, PALMFONATE 6918 C16 and C16–18 are currently available on the market under the brand names Mizulan and Palmfonate, with an active content of about 86% and the Lly genera used in detergents. PALMFONATE 6918 C12 and C14 based on palm oil are not commercially available; however, MPOB had the ability to produce the intermediate cut with active contents of 68% and 83%, respectively, but contained a substantial amount of water, methanol, di-salt and other impurities. These impurities present in PALMFONATE 6918 C12 and C14 are irritating to the eye according to the SkinEthicTM HCE model [14]. Successful use of PALMFONATE 6918 as an active ingredient in personal care could be achieved if the PALMFONATE 6918 C12 and C14 products were non-irritating. The objective of this preliminary study was to study the feasibility of using the crystallization process with ethanol as a solvent, to produce PALMFONATE 6918 powder crystallized from various carbons with an active content of 97% to 99% and analyze their properties for knowledge.
2. Results and discussion
2.1. PALMFONATE 6918 crystallized powder
Crystallized PALMFONATE 6918 powder of different carbon chain lengths (C12, C14, C16 and C16–18) with an active content of 97% to 99% had been obtained by grinding, crystallization and drying processes. These processes were to remove the moisture content and increase the active content while maintaining the di-salt content. Four solvents, such as methanol, ethanol, isopropyl alcohol (IPA) and hexane, were selected to determine the solubility of PALMFONATE 6918, as in Figure 3. Ethanol was the second polar solvent of highest solubility having a solubility of 6.3 to 2.5 mg / ml with PALMFONATE 6918.. PALMFONATE 6918 C12 has the highest solvent solubility rates compared to other carbon chain lengths. The shorter the carbon chain of PALMFONATE 6918, the higher the solubility rate of the solvent. If the carbon chain of PALMFONATE 6918 is large, the critical micellar concentration (CMC) and solubility should decrease [15,16]. Methanol should not be used as a solvent in the purification of PALMFONATE 6918 as it may increase the (undesirable) di-salt content and is extremely toxic [17]. Ethanol is the most suitable solvent for the crystallization process of PALMFONATE 6918. In addition, ethanol can be made from a renewable fuel from sugar crops, starches or cellulosic biomass [18] . In this study, PALMFONATE 6918 was not dissolved in Hexane. The overall cost-benefit ratio using a co-solvent (ethanol and water) with a solvent of low toxicity in the repeated crystallization of PALMFONATE 6918 is high. The crystallization process of the solvent can increase the stability of the product, which can have a positive influence on reducing manufacturing costs. However, the cost of removing the solvent used must be taken into consideration.
Molecules 02629 g003 550 Figure 3. Solubility of PALMFONATE 6918 in solvents.
The dried crystallized PALMFONATE 6918 powder produced by repeated crystallization from ethanol has an active content of PALMFONATE 6918 C12: 98.96%, PALMFONATE 6918 C14: 97.76%, PALMFONATE 6918 C16: 99.32% and PALMFONATE 6918 C16– 18: 99.18%. The active content of PALMFONATE 6918 C14, C16 and C16–18 has an increment of 15% to 19% while PALMFONATE 6918 C12 has the highest active increment of 45%. The moisture content of PALMFONATE 6918 was dried at 1.0% to 2.3%, while the di-salt content was kept below 5%, which is desirable. A higher di-salt content leads to lower surface activity of PALMFONATE 6918 and lower hardness, because the Krafft point of di-salt is higher than that of PALMFONATE 6918 [19]. Crystallization can also be considered as a technique to obtain solid products, because PALMFONATE 6918 C12 and C14 after repeated crystallization becomes a solid powder from a paste. Further specifications of PALMFONATE 6918 are shown in Table 1.
Table 1. Specifications of PALMFONATE 6918 crystallized powder with high active content.
Table
2.2. Structural conformation of crystallized PALMFONATE 6918 powder
The infrared spectrum of PALMFONATE 6918 before and after repeated crystallization is shown in Figure 4; Figure 5, respectively. Both infrared have the same band pattern, except for PALMFONATE 6918 after repeated crystallization, which has an intensity less than 3611–3420 cm - 1 (stretch -OH) and 1640–1600 cm - 1 (region of H - O flexion - H) compared to the infrared of PALMFONATE 6918 before crystallization. This is due to a lower moisture content in the high active PALMFONATE 6918 after repeated crystallization and is in agreement with the study by Hongping et al. [20]. Typical peaks for the methyl group (C - H) at 2958–2849 cm - 1 and the carbonyl group (C = O) at 1724–1716 cm - 1 were observed in both infrared. The presence of the stretching vibration of the sulfonate group (S = O) at the strong peak 1222–1051 cm - 1 and the stretching (S - O) at the peak 857–719 cm - 1 indicates that the two compounds are of methyl ester sulfonate [21,22]. Crystallization does not affect the structure of PALMFONATE 6918, but on the contrary increased the active content and reduced the moisture content.
Molecules 25 02629 g004 550 Infrared of PALMFONATE 6918 before crystallization.
Molecules 25 02629 g005 550 Infrared of PALMFONATE 6918 after repeated crystallization.