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WO2016053080A1 - Forme pulvérulente des sulfonates d'ester de méthyle (mes) et son procédé de production - Google Patents

Forme pulvérulente des sulfonates d'ester de méthyle (mes) et son procédé de production Download PDF

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Publication number
WO2016053080A1
WO2016053080A1 PCT/MY2015/000060 MY2015000060W WO2016053080A1 WO 2016053080 A1 WO2016053080 A1 WO 2016053080A1 MY 2015000060 W MY2015000060 W MY 2015000060W WO 2016053080 A1 WO2016053080 A1 WO 2016053080A1
Authority
WO
WIPO (PCT)
Prior art keywords
mes
slurry
spray drying
process according
free flowing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/MY2015/000060
Other languages
English (en)
Inventor
Zainab Idris
Zulina ABD MAURAD
Mohd Suria Affandi Yusoff
Zahariah Ismail
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Malaysian Palm Oil Board MPOB
Sime Darby Malaysia Bhd
Original Assignee
Malaysian Palm Oil Board MPOB
Sime Darby Malaysia Bhd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Malaysian Palm Oil Board MPOB, Sime Darby Malaysia Bhd filed Critical Malaysian Palm Oil Board MPOB
Publication of WO2016053080A1 publication Critical patent/WO2016053080A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides

Definitions

  • the present disclosure relates generally to a powder form of methyl ester sulphonates and processes for producing the powder form of methyl ester sulphonates.
  • Methyl ester sulphonates are versatile surfactants which have been extensively studied and formulated since 1950.
  • MES surfactants also referred to as a-sulfo fatty methyl ester surfactants, alkyl ester sulphonates surfactants and sulphonated fatty acid alkyl ester surfactants, represent a class of anionic surfactants used in a wide range of applications including powder and liquid laundry detergents and dish washing detergents.
  • MES Produced by the sulphonation of methyl esters, MES have been studied (Weil et al., 1953 (pg 48-59), Smith et al., 1967 (pg,405) Stein et al.,1975, (pg. 323-329) Okumura et al.,1976, (pg 224-237) Kapur et al., 1978 and Meffert, 1984 (pg. 549 ). Since the oil crisis of 1973, they have been viewed with more interest as surfactants obtained from natural raw materials. However, to date MES has been commonly used as an industrial surfactant as compared to LABSA (Linear Alkyl Benzene Sulfonic Acid).
  • LABSA Linear Alkyl Benzene Sulfonic Acid
  • Detergent powder as a final product is prepared either by mixing ground MES with builder/filler ingredients or spray drying the slurry as described in US Patent 5,948,747, US Patent 4,849,125, US Patent 6,528,474, US Patent 5,431,780, US Patent 5,527,489, US Patent 7,098,177, and US Patent 5,496,487.
  • US patent no. 5,536,430 describes the process of producing low-dust anionic surfactant concentrates in powder or granule form with improved solubility in aqueous media.
  • the present disclosure describes processes for producing a free flowing powder of methyl ester sulphonate. Accordingly, in one aspect, the present disclosure provides a process for producing a free flowing powder comprising methyl ester sulphonate the process comprising the steps of: i. preparing a slurry comprising methyl ester sulphonate; and, ii. spray drying the slurry to produce the free flowing powder.
  • the spray drying step is part of a closed-loop spray drying with dehumidifier process.
  • the slurry includes about 30% to about 50 % total solid content. In some embodiments, the slurry includes about 35% to about 45 % total solids content. In some embodiments, the slurry includes about 35 wt% to 65 wt% methyl ester sulphonate.
  • the slurry includes about 30 wt% to about 40 wt% of a solvent.
  • the solvent is methanol.
  • the spray drying step includes introducing the slurry via an atomizer at a temperature of about 100°C to 250°C.
  • the spray drying step includes introducing the slurry via an atomizer at a temperature of about 100°C to 200°C.
  • the spray drying step includes introducing the slurry via an atomizer at a pressure of about 50 psi.
  • the spray drying step includes introducing the slurry via an atomizer at a pressure of about 40 to 60 psi.
  • the spray drying step includes introducing the slurry via an atomizer at a pressure of about 45 to 55 psi.
  • the present disclosure provides a free flowing powder comprising methyl ester sulphonate.
  • the free flowing powder prepared from a process as herein described.
  • the free flowing powder includes a fill density of about 185 to 351 kg/m 3 . In some embodiments the free flowing powder has a particle size at d(0.5) of about 50 to 90 ⁇
  • the free flowing powder has a surface tension of about 33.35 to 34.56 dyn/cm 2 .
  • invention includes all aspects, embodiments and examples described herein.
  • methyl ester sulphonate in powder form that is free flowing with improved solubility, low surface tension, a fill density of about 185 to 351kg/m 3 , and a small particle size at d(0.5) of about 50 ⁇ to
  • MES MES slurry with significant amounts of water and methanol.
  • a process for preparation of a free flowing MES surfactant powder through a process of spray drying a MES preparation.
  • Spray drying may occur in a closed loop with dehumidification, wherein the MES preparation is sprayed co-current to the drying atmosphere in the spray dryer.
  • the spray drying process may be followed by one or more further separation processes, for example cyclones or scrubbers, to remove fine particles from the MES powder created by spray drying.
  • the spray dryer may be configured counter current with the drying atmosphere.
  • Methyl Ester Sulphonate (MES) powder which is prepared from anionic surfactant paste (MES paste) using a spray dry technique which includes spraying the paste in appropriate ratios of non-aqueous solution in a closed loop spray drying process with dehumidification.
  • MES paste anionic surfactant paste
  • a preparation of MES in the form of a slurry or paste is stored in a feed tank 1, which is in fluid communication with the suction inlet of a feed pump 2.
  • a peristaltic pump is used, though any pump suitable for handling MES slurry at the required rate may be used.
  • the feed pump 2 delivers the MES slurry to a spray drying vessel 3 via an inlet manifold 4.
  • the inlet manifold combines the MES slurry stream with an atomisation gas delivered to the inlet manifold 4 by a gas compressor 5.
  • the combined MES slurry and atomisation gas stream moves through the inlet manifold 4 to the atomiser 6 which is located within the main chamber 7 of the spray dryer 3.
  • the atomiser 6 may be in the form of a spray nozzle, which converts the mixture of the MES slurry and atomisation gas into a spray within the main chamber 7.
  • the spray comes into contact with a drying gas, which removes the liquid content from the atomised droplets of slurry, leaving only dry granules of MES.
  • the drying gas can be introduced either co- current or counter-current to the direction of the spray ingress into the spray dryer.
  • the drying gas is air which is recycled within the system through a closed loop with dehumidification step 8.
  • the closed loop system may include cooling stages 16 and heating stages 9 to adjust the properties of the drying gas.
  • Granulated MES powder is collected by a collecting portion 10 of the spray dryer 3.
  • drying gas with entrained particles of MES are firstly transferred to a primary cyclone 11 and then a secondary cyclone 13.
  • entrained particles are separated from the drying gas and collected.
  • Any residual fine particles of MES are then removed by a scrubber down stream of the cyclones.
  • other suitable equipment for solid gas separation may be used in place of cyclones or scrubbers, such as bag filters.
  • the drying gas can be recycled into the spray dryer. Additional processing of the drying gas may be beneficial before recycling.
  • the gas is cooled 16, humidified 8 and heated 9 before being recycled into the spray dryer 3.
  • the anionic surfactant (MES) powder or granules which may also be present as compounds in admixture with other auxiliaries and/or useful materials suitable for use in detergents or cleaning products and which have apparent densities of at least 150g/l are produced by hot air drying of the water-containing preparation with superheated steam as the drying gas. Preferred apparent densities are about above 200g/l and are preferably at least about 350g/l.
  • the pourable and free flowing material is preferable in the form of a substantially dust-free material through the presence of dust-binding auxiliaries and/or useful materials and/or by regulation of the residual water content.
  • the anionic surfactant concentrate is in the form of porous carrier beads, with an absorbent porous inner structure.
  • Sulphonation of methyl ester (ME) in a pilot plant is performed in a falling film reactor at a rate of about 0.1 kmole per hour.
  • concentration of gaseous sulphur trioxide used is 7 vol.% in dry air, and the inlet gas temperature is typically 400°C.
  • the ME feedstock is continuously supplied at 40°C, and the flow rate of reactants is controlled to maintain a desirable mole ration in the range 1.25 to 1.30 moles of S0 3 per mole of ME.
  • the reactor is continuously cooled with a large flow of cooling water through an external jacket.
  • the gas-liquid reaction mixture is quench-cooled neat the reactor outlet by a large flow of recycled sulphonic acid, and then gas and liquid flows are separated in a high efficiency cyclone.
  • a stream of MESA is continuously discharged from the recycle system to the acid digester, where the mixture is held 80°C to 85°C for one hour.
  • Continuous acid bleaching is carried out in the next process system where the mass flow rate of inlet sulphonic acid is used to control the proportions of 99+% methanol and 50% hydrogen peroxide added.
  • the methanol addition to the mixture is 30 wt% and the bleaching temperature is held at 95 ⁇ 2°C with refluxing methanol.
  • the acid bleaching step requires 1 to 1.5 hours using 2 to 3+ wt.% hydrogen peroxide.
  • the excess methanol effectively limits the production of di-salt, and significantly reduces the viscosity of the mixture, which improves mixing and heat transfer during the initial exothermic reaction.
  • Bleached MESA is forwarded to the neutralizer where a controlled proportion of 50% sodium hydroxide is admixed with the inlet MESA mixture and a large recycle stream of neutralized paste.
  • the pH is controlled in a neutral range, typically 6.0 ⁇ lpH.
  • Neutralized MES paste is continuously discharges to a drying plant.
  • MES slurries were prepared according to example 1 ranging from 80 to 60% MES in methanol with a solid content from 30% to 40%.
  • the slurry produced according to the above method for use in the spray drying process of example 3 had the following characteristics:
  • the drying plant contains several steps, the first being the proprietary Turbo TubeTM Dryer (TTD) plant, where excess water and methanol are removed from the MES paste.
  • TTD pilot plant functions as a distinct processing system, and processes concentrated pastes at rate of about 60kg/hr.
  • the drying plant comprises a feed tank and supply system, a preheater, the proprietary dryer (TTD), the separation vessel, product discharge device (typically a plodder), the vacuum system and overhead condenser.
  • the properties of the dried product are pass to chilled belt for flake formation.
  • the condition of chilled belt where the activate belt roller matching with press speed to belt speed (-40%) and cooling water on press, tempered water ( ⁇ 50°C).
  • the produced flakes can then be further processed to a powdered form by mechanical means.
  • the spray drying process was developed to convert the paste of example 1 (total solids content of approx 40 wt%) into a free flowing powder by a single processing step.
  • the slurry/paste was sprayed using a spray drying unit in a closed loop system with dehumidification.
  • the slurry was pumped at a mass flow rate of approximately 0.03 kg/hr from a storage vessel to the atomizing device, located in the air disperser at the top of the spray drying chamber.
  • the drying air was drawn from the atmosphere via a filter by a supply blower fan and is passed through the air heater which was heated at range of 100 - 250 °C to the air disperser.
  • the anionic surfactant is dried in the drying chamber, followed by separation of the particles in the primary and secondary cyclone and scrubber to remove fine particles.
  • the paste was sprayed according to the following parameters: Inlet Temperature: 100° - 250°C
  • Atomizer Pressure for Air flow 50 psi
  • Mass flow rate 0.03 kg hr
  • the MES powder obtained a dry matter content of 94% to 100%.
  • the powder had the following characteristics:
  • the surface tension of the MES powder (1% active substance) was measured with the Wilhelmy plate at 25°C, and using RO water as solvent.
  • the RO water surface tension was 71.486 ⁇ 0.014mN/m.
  • the MES powder had a surface tension at 33.35 to 34.56 mN/m.
  • the detection of the CMC by increasing the concentration method was done using a series of surface tension measurements on the same sample. The concentration was increased automatically by an liquid disperse unit.
  • the Wilhelmy plate (PT11) was used according to DIN 53914. Measurements were carried out at room temperature, 25°C.
  • the CMC of MES exhibited at 0.158-0.279 ppm.
  • the measurement of interfacial tension was done using Wilhelmy plate PT 11, according to DIN 53914. The measurements were done in three steps. First was the buoyancy of the probe in the liquid with the lower density (oil) was measured. After that, the surface of the liquid with higher density (MES 1% solution) was detected. The third step was measurement of interfacial tensions between the two immiscible liquids.Table 2 shows interfacial tension of 1% active concentration of MES powder against palm olein. From the results obtained, the MES powder has ability to lowered interfacial tension at 0.336 mN/m.
  • Bulk density is the mass of powder divided by its total volume under various loads. The densification of the sample was achieved by the application of both normal (fill density) and sheer stresses. The fill density was found at 185-351 kg/m and bulk density at 356kg/m 3 at 5 kPa.
  • MES is an anionic surfactant. Therefore when it dissolves in water it would release negative ions.
  • Conductivity was used to measure the solubility of MES of various concentrations at fixed temperatures. Conductivity was affected by temperature: the warmer the water, the higher the conductivity. For this reason, conductivity was reported as at 25°C. Conductivity was measured in Siemens and ohms. The higher the Siemens, the more conductive the liquid. The higher conductivity showed the higher soluble anions present in the solution.
  • the conductivity of MES powder solution with concentrations of 0.1 ppm, 0.2ppm, 0.3ppm, 0.4ppm, 0.5ppm, 0.6ppm, 0.7ppm, 0.8ppm, 0.9ppm and 1.0 ppm was measured using Metier Toledo Conductivity Meter. The measurements were done at 25°C using I LAB ® 73X Series probe.
  • MES powder had good conductivity.
  • the highest solubility was indicated at 0.8 ppm at 8.8 ⁇ s/cm which was the process of producing MES due to the smaller particle size of the powder.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un procédé de production d'une poudre s'écoulant librement comprenant un sulfonate d'ester de méthyle, le procédé comprenant les étapes suivantes : préparation d'une suspension épaisse comprenant un sulfonate d'ester de méthyle ; et, séchage par pulvérisation de la suspension épaisse pour obtenir la poudre s'écoulant librement.
PCT/MY2015/000060 2014-09-29 2015-07-16 Forme pulvérulente des sulfonates d'ester de méthyle (mes) et son procédé de production Ceased WO2016053080A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI2014702864 2014-09-29
MYPI2014702864A MY187405A (en) 2014-09-29 2014-09-29 Powder form of methyl ester sulphonates (mes) and process for producing the same

Publications (1)

Publication Number Publication Date
WO2016053080A1 true WO2016053080A1 (fr) 2016-04-07

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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4438025A (en) 1981-12-30 1984-03-20 Lion Corporation Detergent compositions
US4849125A (en) 1985-12-23 1989-07-18 Wolfgang Seiter Process for preparing a phosphate-reduced granular detergent
WO1993005013A1 (fr) * 1991-09-03 1993-03-18 The Procter & Gamble Company Procede d'amelioration de la couleur de tensioactifs sulfates ou sulfones sans decoloration
DE4310671A1 (de) * 1993-04-01 1994-10-06 Henkel Kgaa alpha-Sulfofettsäurealkylester enthaltendes Granulat
US5431780A (en) 1990-09-28 1995-07-11 Henkel Kommanditgesellschaft Auf Aktien Process for spray-drying materials and mixtures thereof using superheated steam
US5496487A (en) 1994-08-26 1996-03-05 The Procter & Gamble Company Agglomeration process for making a detergent composition utilizing existing spray drying towers for conditioning detergent agglomerates
US5527489A (en) 1990-10-03 1996-06-18 The Procter & Gamble Company Process for preparing high density detergent compositions containing particulate pH sensitive surfactant
US5536430A (en) 1992-02-12 1996-07-16 Henkel Kommanditgesellschaft Auf Aktien Process of producing low-dust anionic surfactant concentrates in powder or granule form with improved solubility in aqueous media
US5587500A (en) 1993-09-17 1996-12-24 The Chemithon Corporation Sulfonation of fatty acid esters
US5723433A (en) 1993-09-24 1998-03-03 The Chemithon Corporation Sovent removal process
US5723533A (en) 1992-10-30 1998-03-03 Bridgestone Corporation Soluble anionic polymerization initiators and products therefrom
US5948747A (en) 1995-01-12 1999-09-07 Henkel Kommanditgesellschaft Auf Aktien Spray-dried detergent or a component therefor
US6058623A (en) 1993-09-24 2000-05-09 The Chemithon Corporation Apparatus and process for removing volatile components from a composition
US6528474B1 (en) 1999-08-04 2003-03-04 Henkel Kommanditgesellschaft Auf Aktien Method of manufacturing a detergent with soluble builder
US7098177B1 (en) 1998-10-16 2006-08-29 Kao Corporation Process for producing detergent particles

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4438025A (en) 1981-12-30 1984-03-20 Lion Corporation Detergent compositions
US4849125A (en) 1985-12-23 1989-07-18 Wolfgang Seiter Process for preparing a phosphate-reduced granular detergent
US5431780A (en) 1990-09-28 1995-07-11 Henkel Kommanditgesellschaft Auf Aktien Process for spray-drying materials and mixtures thereof using superheated steam
US5527489A (en) 1990-10-03 1996-06-18 The Procter & Gamble Company Process for preparing high density detergent compositions containing particulate pH sensitive surfactant
WO1993005013A1 (fr) * 1991-09-03 1993-03-18 The Procter & Gamble Company Procede d'amelioration de la couleur de tensioactifs sulfates ou sulfones sans decoloration
US5536430A (en) 1992-02-12 1996-07-16 Henkel Kommanditgesellschaft Auf Aktien Process of producing low-dust anionic surfactant concentrates in powder or granule form with improved solubility in aqueous media
US5723533A (en) 1992-10-30 1998-03-03 Bridgestone Corporation Soluble anionic polymerization initiators and products therefrom
DE4310671A1 (de) * 1993-04-01 1994-10-06 Henkel Kgaa alpha-Sulfofettsäurealkylester enthaltendes Granulat
US5587500A (en) 1993-09-17 1996-12-24 The Chemithon Corporation Sulfonation of fatty acid esters
US5723433A (en) 1993-09-24 1998-03-03 The Chemithon Corporation Sovent removal process
US6058623A (en) 1993-09-24 2000-05-09 The Chemithon Corporation Apparatus and process for removing volatile components from a composition
US5496487A (en) 1994-08-26 1996-03-05 The Procter & Gamble Company Agglomeration process for making a detergent composition utilizing existing spray drying towers for conditioning detergent agglomerates
US5948747A (en) 1995-01-12 1999-09-07 Henkel Kommanditgesellschaft Auf Aktien Spray-dried detergent or a component therefor
US7098177B1 (en) 1998-10-16 2006-08-29 Kao Corporation Process for producing detergent particles
US6528474B1 (en) 1999-08-04 2003-03-04 Henkel Kommanditgesellschaft Auf Aktien Method of manufacturing a detergent with soluble builder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PARTHIBAN SIWAYANAN: "Detergency Stability and Particle Characterization of Phophate-Free Spray Dried Detergent Powders Incorporated with Palm C16 Methyl Ester Sulfonate (C16MES)", JOURNAL OF OLEO SCIENCE, vol. 63, no. 6, 15 May 2014 (2014-05-15), pages 585 - 592, XP002748187 *

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