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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
  • C11D17/065—High-density particulate detergent compositions
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/06—Phosphates, including polyphosphates
  • C11D3/062—Special methods concerning phosphates
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—Salts
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—Salts
  • C11D7/12—Carbonates bicarbonates
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—Salts
  • C11D7/16—Phosphates including polyphosphates

Definitions

• the invention relates to homogeneous granules composed of sodium tripolyphosphate, sodium sulphate and sodium carbonate, useful as raw material in the formulation and detergent and washing agent manufacture processes.
• TPF sodium tripolyphosphate
• the properties of the final product depend directly on the properties of the constituent ingredients. It is necessary to use either so-called “intelligent raw materials", which are generally commercially expensive, or to resort to mixing and multi-stage agglomeration processes with raw materials with high surfactant absorption capacity (absorbency).
• the main ingredients are based on TPF, sodium carbonate and sodium sulphate.
• the Polish patent PL 118.429 describes the formation of a mixture made up of a Glauber salt (Na 2 SO 4 .10H 2 O), TPF and/or sodium carbonate by mixing the ingredients, which are then mixed with a concentration of detergent to give a concentrated detergent powder.
• said Polish patent does not describe the characteristics of the ingredients of the mixture and, furthermore, the aforementioned mixture can only be applied to the manufacture of detergent powders by pulverisation.
• a homogeneous granulate is described, with total fluidity and mobility (totally free-flowing), the mixture of said ingredients, that allows it to be used advantageously as a base raw material (builder) in both types of process avoiding the complexity and aforementioned problems for each process.
• This material is compatible with the current detergent manufacturing installations, and would not require additional equipment for the post-addition or specially designed agglomerates for this process.
• TPF is a chemical product with a variety of uses and applications, and is a key component in the formulation of detergents.
• TPF is of critical importance to select the product most suitable for technical and economic success.
• TPF is obtained by calcination of orthophosphate sodium salts.
• the procedure starts with the reaction of phosphoric acid and an alkaline compound of sodium, such as sodium carbonate and/or sodium hydroxide, to produce in a first instance an aqueous suspension of sodium orthophosphate with a molar proportion Na:P of 5:3, commonly denominated "ortho liquor".
• This suspension is dried and calcined in a rotary calcinator at a high enough temperature to form anhydrous TPF.
• the resulting TPF from this calcination process is an anhydrous crystalline product that can exist in two crystalline structures, designated as Phase I and Phase II, depending on the calcination temperature.
• Phase I and Phase II anhydrous crystalline product that can exist in two crystalline structures, designated as Phase I and Phase II, depending on the calcination temperature.
• a commercial TPF containing a ratio Phase II/Phase I of 20/70 is obtained in a rotary calcinator at a calcination temperature lying between 500 and 560°C.
• TPF.6H 2 O hexahydrated species
• TPF Clogging of TPF is well known in the detergent industry as is its tendency to form agglomerates (caking) in the aforementioned hydration reaction when coming into contact with water. This behaviour leads to problems related to its processing during the manufacture of the detergent, as well as during it use by the consumer. In this case, the compression can occur on the inside of the detergent packaging or in the dispenser of the washing machine when it comes into contact with the water of the wash.
• the TPF used in the manufacture of the homogeneous granules object of this invention avoids the aforementioned problems and is characterised by having a Phase I content, a pre-moistened water content and a pre-determined granulometry suitable for the required ends.
• An object of this invention constitutes some homogeneous granules, of total fluidity and mobility (totally free-flowing), that comprise TPF, sodium sulphate and sodium carbonate.
• This granules have some properties, such as apparent density, non-ionic surfactant absorption capacity (absorbency), granulometry, content of chemically bound water such as crystallisation water or hydration water and non-bound free water, which make them suitable for use as a raw material in the formulation of detergents produced by atomisation or by dry blending and/or agglomeration.
• An additional object of this invention constitutes a procedure for manufacturing the homogeneous granules object of this invention, that comprises using a liquid binder for hydrating/agglomerating the components, drying the resulting granules and separating the desired product fraction.
• An another additional object of this invention constitutes the use of the homogeneous granules object of this invention in the processes and formulations of detergent compositions.
• the invention provides homogeneous granules, of total fluidity and mobility (totally free-flowing), hereinafter the granules of the invention, that comprise:
• the granules of the invention have an apparent density lying between 600 and 1,000 grams/litre (g/L), preferably between 700 and 900 g/L, a particle size distribution of less than 1,500 micrometers ( ⁇ m), preferably with an average diameter lying between 150 and 800 ⁇ m, a chemically bound water content of between 0.2 and 10 % by weight, a non-bound free water content less than 1 % by weight, and a capacity for absorption of non-ionic surfactants (absorbency) of, at least, 20 %, preferably between 23 and 25 %.
• the "absorption capacity” or “absorbency” defines the capacity of the particle for absorbing the liquid components of the formulation of a detergent composition. Values of high absorbency are necessary in free-flowing formulations of detergents that contain non-ionic surface-active agents characteristic of the dry blending and/or agglomeration processes of production. Values of above 10 % are generally desired, values greater than 15 % are considered very good, and values greater than 20 % are excellent or highly absorbent.
• TPF hydrolysis is characteristic of certain formulations based on TPF as a structural component (builder), especially in atomised detergent compositions and in those with production by means of agglomeration with ionic surface-active agents, resulting in a loss of effectiveness and detergent efficiency of the said compositions due to the presence of the species ortho- and pyrophosphates arising from reversion of TPF.
• builder structural component
• the granules of the invention have a TPF content lying between 40 and 80 % by dry weight of the granules.
• a characteristic of the invention is to specify their existence in granules as "true" TPF, that is to say, excluding other phosphate forms from, to give a TPF richness of at least 94 %. This point is particularly important as it means that in the application of the granules of the invention, TPF is also present at at least the same richness of 94 % in the detergent formulation.
• the manufacturing procedure for the granules of the invention comprises the stages of:
• the raw materials that constitute the composition of granules of the invention are TPF, sodium sulphate and sodium carbonate.
• the TPF used in the production of the granules of the invention are characterised by being mostly of type Phase I, with a Phase I content lying between 20 and 70% by weight with respect to the total amount of TPF, a Phase I content preferably lying between 40 and 55 %, a pre-moistened water content lying between 0.3 % and 1.5 % by weight, preferably between 0.5 and 1 %, and a granulometry with an average particle size less than 250 ⁇ m, preferably with a content of fine particles, that is to say, less than 150 ⁇ m, of at least 75 %.
• TPF used for producing the granules of the invention are considered critical in the first stage of the procedure (stage of hydration/agglomeration) for controlling the degree of agglomeration and the physical properties of the resulting granules with regards their apparent density and porosity/absorbency.
• the sodium carbonate used in producing the granules of the invention are characterised by having a minimum richness of sodium carbonate (Na 2 CO 3 ) of 99 % by weight, a particle size preferably lying between 9 and 100 mesh (Standard Tyler Mesh), and an apparent density of, at least, 500 g/L, and preferably greater than 800 g/L.
• the sodium sulphate used in the production of the granules of the invention is characterised by having a minimum richness of sodium sulphate (Na 2 SO 4 ) of 99 % by weight, a particle size preferably lying between 16 and 270 mesh (Stand Tyler Mesh), and an apparent density of, at least, 1,000 g/L, and preferably greater than 1,400 g/L.
• the appropriate mixture of TPF, sodium sulphate and sodium carbonate is fed to the hydration stage to give homogeneous moistened granules, by means of the agglomeration of the ingredients of the mixture by hydration with a liquid binder.
• the liquid binder used in the procedure of the invention is water.
• water refers to pure water or water containing small quantities, that is to say, less than 15 % by weight, of TPF, sodium sulphate and sodium carbonate in proportions identical to those of the granules of the invention.
• the temperature of the water is not critical although it preferably lies in the range 10 to 40°C. In general it is not necessary or practical to employ temperatures above 50°C or less than 5°C. Due to the heat generated by the hydration of TPF, sodium sulphate and sodium carbonate when forming the stable hydrated species, it is critical, according to the invention, that the raw feed materials for this hydration stage are at a temperature less than 60°C, preferably less than 40°C.
• the hydration process of the feed material is submitted to stirring while the liquid binder is added, which leads to a more uniform distribution and spread of the water in the feed, as well as the tendency for agglomeration to occur, especially with the most fine particles less than 150 ⁇ m.
• Stirring is preferably effected by rotation in a horizontal rotary hydrator with inner lifting and turning paddles.
• Pulverisation is the preferred method of the invention for adding the liquid binder and this can be carried out using conventional pulverisation systems with atomisation air nozzles or pneumatic pulverisers.
• the residence time in the hydrator is a critical parameter of the invention for obtaining the agglomeration of the feed material as well as for guaranteeing the chemical absorption of the water added and the TPF hydration, sodium sulphate and sodium carbonate.
• the residence time is from, at least, 5 minute, and preferably between 5 and 10 minutes.
• the drying stage can be carried out by passing the previously obtained moistened granules through a jet of hot air, in a rotary horizontal drier with inner lifting and turning paddles.
• the temperature of the hot gases lies approximately between 80 and 250°C.
• the moistened granules are dried until reaching a free humidity weight of 1 % in the granules of the invention, and so the residence time in the drier is also critical, being at least 5 minutes, preferably between 5 and 20 minutes, depending on the desired degree of hydration in the dry granules.
• granules are obtained with a total water content of between 0.2 and 10 % by weight as crystallisation water, and less than 1 % by weight of free humidity.
• the dry granules from the previous stage are sieved to separate the desired granulometric fraction into the final product.
• the particle distribution obtained in the present invention is less than 1,500 ⁇ m, preferably with an average size lying between 150 and 800 ⁇ m.
• the manufacturing procedure for the granules of the invention can be carried out in batches or, preferably, continuously.
• the fraction of the large particles rejected by the sieve in the third stage are ground, preferably to give a size less than 1,500 ⁇ m, and recycled to be fed into the first stage (hydration/agglomeration).
• the granules of the invention are useful as raw material in the formulation and manufacturing processes of detergents and washing agents, in particular, in the treatment of mixtures and densifying powder detergents or atomised granules and in processes for manufacturing detergents by dry blending and/or agglomeration. Therefore, the invention provides a procedure for manufacturing powder detergents and washing agents and/or granules by dry blending and/or agglomeration that comprises the use of the homogeneous granules of the invention as raw material, as well as a procedure for manufacturing densified atomised detergents that comprises the use of the granules of the invention as a post-atomiser treatment (post-addition or post-tower).
• the analytical method followed is that corresponding to ISO 150, based on the absorption of an oil.
• the sample is mixed with an acid until saturation is reached at the end of the mixing, and the percentage weight of oil required is the value of the capacity of absorption or absorbency. No special prior treatment for the sample is required.
• the oil used is linseed oil and should comply with the ISO 150, with a specific weight of 0.93 grams/millilitre (g/mL).
• the equipment necessary is a watch glass (about 15 cm in diameter), a graduated micro-burette with a capacity going from 5 or 10 mL with divisions of 0.05 mL, accurate scales ( ⁇ 0.01 g), and a flexible spatula of stainless steel (approximately 10 cm long and 2 cm wide).
• This example illustrates a continuous procedure for manufacturing the granules of the invention and relates to the operating conditions, to the composition and to the properties of the final granules.
• the resulting granules of this Example have been obtained by feeding (1,818 kg/h) homogenised mixture of TPF, sodium sulphate and sodium carbonate (1,000 kg/h of TPF, 546 kg/h of sodium sulphate and 272 kg/h of sodium carbonate) into a horizontal rotary hydrator (approximately 4.6 m long and with a diameter of approximately 0.7 cm) equipped with 5 pulzerisation nozzles.
• the rotation speed was 20 rpm and the mixture was pulverised with water at 20-25°C, until a total content of 9 % by weight of the feed mixture was reached, with a residence time of 10 minutes.
• the granulated product leaving the hydrator was fed continuously into a horizontal rotary drier (approximately 5 m long and with a diameter of approximately 1 m) with a speed of rotation of 12 rpm.
• the drying was carried out in different operating conditions with input of hot gases between 80 and 250°C and residence times of between 5 and 15 minutes, to attain final water contents lying between 0.2 and 8 % by weight, and less than 1 % in free humidity.
• the drying conditions were as follows: Case Temperature of hot gases (°C) Residence time in drier (minutes) 1 225 12 2 180 10 3 150 5
• Homogeneous granules were obtained with composition of dry base of 55 % by weight TPF, 30 % by weight of sodium sulphate and 15 % by weight of sodium carbonate, with a granulometry less than 1,000 ⁇ m, a final capacity for absorption of non-ionic surface-active agents of 20 to 25 %, and total water contents lying between 0.2 and 8 % by weight, and less than 1% by weight of free humidity.

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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)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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• 1997
  • 1997-11-07 WO PCT/ES1997/000266 patent/WO1999024544A1/fr not_active Application Discontinuation
  • 1997-11-07 AU AU47828/97A patent/AU4782897A/en not_active Abandoned
  • 1997-11-07 EP EP97910458A patent/EP0974641A1/fr not_active Withdrawn

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