Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C227/38—Separation; Purification; Stabilisation; Use of additives
  • C07C227/40—Separation; Purification
  • C07C227/42—Crystallisation
• • 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
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
  • C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
• • 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
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
  • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

• the invention relates to a process for the preparation of a powder containing one or more complexing agent salts of general formula I.
• aminopolyphosphonates, polycarboxylates or aminopolycarboxylates such as ethylenediaminetetraacetic acid (EDTA), which are frequently used as complexing agents, for example in detergents and cleaners, are only slightly biodegradable.
• EDTA ethylenediaminetetraacetic acid
• glycine-N, N-diacetic acid derivatives such as methylglycine-N, N-diacetic acid (MGDA) and its salts - e.g. the trialkali metal salts - which have beneficial toxicological properties and are readily biodegradable.
• MGDA methylglycine-N, N-diacetic acid
• salts e.g. the trialkali metal salts - which have beneficial toxicological properties and are readily biodegradable.
• the use of MGDA and related glycine-N, N-diacetic acid derivatives in detergents and their syntheses are e.g. in WO-A 94/029421 or US 5,849,950.
• For a cost-effective production of glycine-N, N-diacetic acid derivatives high demands are placed on the yield of the individual synthesis steps and purity of the isolated intermediates.
• MGDA is prepared in particular by reaction of iminodiacetonetril with acetaldehyde and hydrocyanic acid or of alpha-alanine nitrile with formaldehyde and hydrocyanic acid and alkaline hydrolysis of the intermediate methylglycinediacetonitrile (MGDN) with sodium hydroxide solution, the trisodium salt of the MGDA being obtained.
• MGDN is generally isolated as an intermediate and used as a pure substance in the subsequent hydrolysis step.
• the problem with the hydrolysis of alkylglycinnitrile-N, N-diacetonitriles is their thermal lability, especially in the alkaline medium.
• the object is achieved by a process for producing a powder comprising one or more complexing agent salts of the general formula
• n and m are each an integer from 0 to 5 and
• R '" is hydrogen or a Ci-Ci2-alkyl radical or a C 2 -C 2 -alkenyl radical, which may be additionally substituted with up to 5 hydroxyl groups, or one of the moieties
• M is independently of one another hydrogen, alkali metal, alkaline earth metal, ammonium or substituted ammonium in the corresponding stoichiometric amounts
• the sputtering step with the addition of crystalline particulate matter of the same or the same complexing agent salts, as contained in the aqueous solution, or one or more different complexing agent salts of the above formula I, with an upper limit for the average particle diameter of the crystalline particulate matter by at least the Factor 2 is smaller than the lower limit of the mean particle diameter of the powder obtained by the method,
• a spray is made available which in a continuous phase of an inert gas, in particular air, as a disperse phase liquid droplets of the aqueous starting solution containing the one or more complexing agent salts and next to another disperse solid Phase, containing the crystalline fine dust of one or more complexing agent salts.
• the crystalline fine dust offers crystallization nuclei during the drying process, during which the droplets of the aqueous solution crystallize out and grow up.
• the particle size in the drying zone can be increased and the granulometry of the powder obtained in the process can be positively influenced.
• the crystalline fine powder also has the effect of powdering the wet powder obtained in the spray-drying plant.
• the term powder is understood to mean a flowable solid which has mean particle sizes in the range from about 1 ⁇ m to about 10 mm; for the coarser particles from the range defined above, from about 100 ⁇ , the term "granules" is alternatively used.
• the powder containing one or more of the above complexing agent salts is prepared according to the invention in a spray-drying process.
• spray-drying method in the present case as a generic term all processes in which a liquid starting material which may be present as a solution or dispersion is atomized and dried with the aim of producing a solid.
• a spray-drying process is characterized by the atomization and drying steps. These can be carried out in the same apparatus or also in rear-connected areas of the same apparatus.
• the first process step of any spray-drying process is to atomize the liquid starting material into an inert gas, usually air, to give a spray, wherein the spray as the continuous phase is the inert gas, usually air, and as dis-continuous phases finely divided liquid droplets of the liquid starting material and additionally in addition, according to the method of the invention disperse solid phase formed from the crystalline particulate matter of the one or more complexing agent salts.
• the spray is characterized by a particular droplet size distribution and droplet size distribution width (Span).
• Span droplet size distribution width
• Spray drying in the strict sense, agglomerative spray drying, spray agglomeration and spray granulation.
• Spray drying in the narrower sense is the historically oldest spray drying process. It is carried out in spray towers.
• the first spray towers were built by Niro in the 1930s. Although the types of spray towers are different, the principle is always the same: each droplet of the spray obtained in the spray tower should produce exactly one particle at a time. Since the residence time in the spray towers is limited, the droplets in the spray tower may only be very small in order to dry in the spray tower.
• the average particle size of spray powders, which is obtained by spray drying in the strict sense is often in the range of about 50 ⁇ to about 300 ⁇ .
• so-called agglomerative spray drying developed by spray tower manufacturers in the 1980's may be carried out to reduce the dust content in the spray powder.
• the fine fraction of the spray powder is separated in the spray tower and recycled into the area of the atomizer.
• There the particles come in contact with the still liquid spray and can agglomerate, i. two or more small particles combine to form a larger particle, the so-called agglomerate.
• a fluidized bed is integrated into the spray tower to increase the residence time.
• Such spray towers with integrated fluidized bed are known, for example, as Fluidized Spray Dryer (FSD) from Niro or Spray Bed Dryer (SBD) from Anhydro.
• the so-called spray agglomeration powder which is present in a mixer with moving internals is connected to larger particles, so-called agglomerates, by spraying binder liquid.
• a dryer In the spray agglomeration in a mixer, a dryer must be connected downstream, which may be in particular a fluidized bed. The spray agglomeration can be carried out both continuously and discontinuously.
• the so-called spray granulation the liquid starting material is sprayed into a fluidized bed. The drops of the spray are predominantly deposited on the granules already present in the fluidized bed and contribute to their further growth.
• the final product is often recovered via sieving or sifting from the wider fluid bed bed fraction. Coarse material is often ground and recycled together with the separated fines in the fluidized bed. The process is thus more complicated than the spray drying in the strict sense or the spray agglomeration. However, larger particles and narrower particle size distributions can be achieved.
• the spray-drying process according to the invention can preferably be carried out in each of the process variants described above, it being imperative that crystalline particulate matter of the same or the same complexing agent salts as contained in the aqueous starting solution or one or more different complexing agent salts of the above formula I are used in the sputtering step , with an upper limit for the average particle diameter of the crystalline particulate matter which is at least a factor of 2 smaller than the lower limit of the mean particle diameter of the powder obtained after the spray-drying process.
• the average particle diameters of the crystalline particulate matter and the powder obtained by the process of the present invention are usually determined by methods such as laser diffraction (e.g., Malvern) or optical methods (e.g., CamSizer).
• the mean particle diameters of the powders thus obtained are often in a range of about 50 to 300 ⁇ m.
• crystalline fine dust with an upper limit for the mean particle diameter of not more than 25 ⁇ m must be used in the atomization step.
• powders are obtained which frequently have an average particle diameter in the range from about 200 to 2000 ⁇ m.
• crystalline fine dust must be used for which the permissible upper limit for the mean particle diameter is at most 100 ⁇ m.
• the proportion by weight of the addition of crystalline fine dust in the spray-drying process according to the invention is in the range from about 0.1 to 20% by weight, based on the weight of the powder obtained by the process, preferably about 4 to 10 Wt .-%, based on the total weight of the obtained by the process powder.
• the one or more complexing agent salts correspond to the general formula
• R ' is hydrogen or one of the groupings
• n and m are each an integer from 0 to 5 and
• R '" is hydrogen or a Ci-Ci2-alkyl radical or a C 2 -C 2 -alkenyl radical, which may be additionally substituted with up to 5 hydroxyl groups, or one of the moieties
• M is independently hydrogen, alkali metal, alkaline earth metal, ammonium or substituted ammonium in the corresponding stoichiometric amounts. These are preferably derivatives of glycine-N, N-diacetic acid or derivatives of glutamine-N, N-diacetic acid. Also preferred are derivatives of ethylenediaminetriacetic acid or nitrilotriacetic acid.
• Alkali salts of methylglycine-N, N-diacetic acid are particularly preferred as derivatives of glycine-N, N-diacetic acid.
• the drying step of the spray-drying process is preferably carried out at a pressure in the range from about 0.1 bar absolute to 10 bar absolute, in particular at a pressure in the range from about 0.8 bar absolute to 2 bar absolute.
• the residence time in the drying step is preferably in a range of about 10 seconds to 1 hour.
• the invention also provides a formulation comprising the powder obtained according to the process described above or an aqueous solution thereof as a complexing agent for alkaline earth and heavy metal ions, in the amounts customary therefor, in addition to other conventional constituents of such formulations.
• the formulations may in particular be detergent and cleaner formulations.
• Another object of the invention is also the use of a powder obtained by the above process for the production of press agglomerates, and a use of the press agglomerates for use in solid detergents.
• the above cleaning agents may be provided in particular for automatic dishwashers.
• these may be tabs for dishwashers.
• the spray-drying process according to the invention can also be carried out with mixtures of one or more complexing agent salts and other substances.
• Further substances are to be understood as meaning, in particular, auxiliaries and additives customarily used in the washing and cleaning industry.
• auxiliaries and additives customarily used in the washing and cleaning industry.
• surfactants, polymers, inorganic salts, and / or citrates can be used.
• inorganic salts such as carbonates, sulfates, phosphates, silicates
• organic salts such as citrates
• Polymers such as polycarboxylates or sulfonated polymers or phosphonates.
• Such mixtures make the production process for the production of detergents and cleaners easier.
• the powders obtained by the above process can also be used in particular in blends with customary auxiliaries and additives.
• a methylglycine-N, N-diacetic acid trisodium salt powder having a degree of crystallinity of> 30% and comprising a first crystalline modification with the following d values in angstroms at the diffraction angles 2-theta in ° can be obtained by the process according to the invention:
• FIGS. 2 to 4 X-ray diffractograms for each powder obtained according to embodiments 2 to 4 (according to the invention).
• the X-ray powder diffractometer measurements were carried out on a D8 Advance® diffractometer from Bruker AXS (Karlsruhe). Measured was in reflection with Cu-K a radiation with a variable aperture setting on the primary and secondary side. The measuring range was 2 ° to 80 ° 2-theta, the step size 0.01 ° and the measuring time per angular step 3.6 seconds.
• the degree of crystallinity was determined in a known manner by determining, as usual, the area ratio of the crystalline phase and the amorphous phase, and from this the crystallinity degree, KG, as the ratio of the area of the crystalline phase, l c , to the total area calculated from the area of the amorphous phase, l a , and the area of the crystalline phase, l c ,
• the determination of the degree of crystallinity can be carried out in particular using a software program, for example the software program TOPAS® from Bruker AXS.
• an amorphous sample is first measured and the line course is fitted with the aid of six individual lines in a profile fit. Thereafter, the line positions of these lines and their half-widths are fixed and these values are stored as "amorphous phase".
• the area fraction of the crystalline phase and the area fraction of the amorphous phase are determined and from this the crystallinity degree KG is calculated according to the formula given above.
• the amorphous phase is used as defined above.
• the underground is fitted as a polynomial of the first degree.
• the program TOPAS® calculates the optimal fit between the measured diffractogram and the theoretical diffractogram consisting of amorphous and crystalline phase. embodiments
• EMBODIMENT 1 (Comparative) Conventional Spray Drying Without Addition of Crystalline Fine Dust
• a mass flow of 60 kg / h of an aqueous solution of Na3-MGDA with a solids content of 40% was carried out in a plate heat exchanger evaporator (heating surface). 1, 7 m 2 ) to a solids content of 59% and deposited in a separating vessel.
• the evaporation took place at a wall temperature of 152 ° C. (steam heating) and at a pressure of 2.5 bar abs in the separator.
• the evaporated solution was metered at a temperature of about 128 ° C with a gear wheel pump in the downstream piston diaphragm pump and sprayed with a single-fluid nozzle in a spray tower.
• the spray tower had a diameter of 800 mm and a length of 12 m.
• the spray tower was operated with an air volume of 1400 kg / h and a gas inlet temperature of 160 ° C.
• the product outlet temperature was 127 ° C. and the solids content of the dry product was 94.1%.
• the product was deposited via a 2-point discharge (directly at the spray tower and at the downstream filter).
• the product thus prepared was a free-flowing powder.
• the bulk density was 529 kg / m 3 .
• the X-ray structure analysis shows that the product is amorphous.
• the storage behavior of this sample was evaluated in the desiccator test. For this purpose, a sample of 3 g is stored in an open weighing dish in a desiccator at 20 ° C and a relative humidity of 76% over a period of 144 hours. Subsequently, the mass increase of the sample is determined and the flowability of the sample is evaluated. The mass increase was 27.1% and the sample was annealed, i. she was wet and no longer pourable.
• Exemplary embodiment 2 (according to the invention) Spray tower with addition of crystalline fine dust
• a mass flow of 75 kg / h of an aqueous solution of Na3-MGDA with a solids content of 40% was evaporated in a plate heat exchanger evaporator (heating surface 1.7 m 2 ) to a solids content of 60% and deposited in a separating vessel.
• the evaporation took place at a wall temperature of 156 ° C. (steam heating) and at a pressure of 2.5 bar abs in the separator.
• the evaporated solution was metered at a temperature of about 130 ° C with a gear wheel pump in the downstream piston diaphragm pump and sprayed with a single-fluid nozzle in a spray tower.
• the spray tower had a diameter of 800 mm and a length of 12 m.
• the spray tower was operated with an air volume of 1400 kg / h and a gas inlet temperature of 202 ° C.
• a mass flow of 4 kg / h of crystalline fine dust Na3-MGDA was injected by means of an injector.
• the product outlet temperature was 99 ° C and the solids content of the dry product 90.2%.
• the product was deposited via a 2-point discharge (directly at the spray tower and at the downstream filter).
• the product thus prepared was a free-flowing powder.
• the bulk density was 568 kg / m 3 .
• the X-ray structure analysis shows that the product is crystalline.
• the storage behavior of this sample was evaluated in the desiccator test. For this purpose, a sample of 3 g is stored in an open weighing dish in a desiccator at 20 ° C and a relative humidity of 76% over a period of 144 hours. Subsequently, the mass increase of the sample is determined and the flowability of the sample is evaluated. The mass increase was 20.4% and the sample was baked only slightly and could be brought by light tapping back into the free-flowing state.
• Embodiment 3 (According to the Invention) Agglomerating Spray Drying in a Spray Tower with Integrated Fluidized Spray Drives (FSD)
• 500 g of a 41% Na3-MGDA aqueous solution having a total solids content of 46% by weight was diluted with 150 g of deionized water.
• the solution was then stirred in a glass flask with stirrer at room temperature and then fed into a spray dryer with integrated fluidized bed on a laboratory scale, under supply of drying air at 130 ° C, a supply air temperature of the fluidized bed of 1 10 ° C and atomized via a two-fluid nozzle.
• the liquid droplets were dried, forming the granulation nuclei in the bed.
• the bed temperature was then lowered to initiate the granulation phase, with the granulation cores being agglomerated with feed solution.
• the resulting granules were continuously withdrawn from the spray dryer.
• the granulation of the solution was carried out in a range for the bed temperature between 64 ° C and 74 ° C.
• the product had a residual moisture content of 6.5% by weight, a high bulk density of 700 kg / m 3 and was very free flowing.
• the product After 144 hours in an eksiccator at 20 ° C and 76% relative humidity, the product remained free-flowing and the X-ray diffraction pattern (Figure 3) shows a crystalline content of 70%.
• Exemplary embodiment 4 (according to the invention) spray granulation with the addition of crystalline fine dust
• Aqueous Na3-MGDA solution having a solids content of 48.8% was spray granulated on a continuous laboratory spray fluidized bed.
• the conical fluidized bed with a diameter of 150 mm at the bottom and 300 mm at the top had internal hose filters and a pneumatic atomizing nozzle, which was sprayed into the fluidized bed from below.
• the fluidized bed was operated with 55 Nm 3 / h of nitrogen inlet temperature of 140 ° C and a fluidized bed temperature of 79 ° C.
• Na3-MGDA - spray granules from previous experiments was filled as a template. Over a period of 1, 92 hours, a total of 6.03 kg of solution was sprayed.
• the pneumatic atomizing nozzle was operated with 4.7 Nm 3 / h of nitrogen at room temperature and at a pressure of 3.3 bar (absolute). Solid was released via a screw from the Fluidized bed discharged so that the fluidized bed height remained constant. The discharged solid was sifted out every 30 minutes. In the particle size range of 355 to 1250 ⁇ were 46.8% of the discharged particles. The bulk density of this fraction was 778 kg / m 3 and its water content was 1 1, 8 mass%. The screened fine fraction of less than 355 ⁇ m was returned to the fluidized bed every 30 minutes.
• the product thus produced was a free-flowing granulate.
• the X-ray structure analysis shows that the product contains crystals of the above-defined first modification and is 71% crystalline.
• the storage behavior of this sample was evaluated in the desiccator test. For this purpose, a sample of 3 g is stored in an open weighing dish in a desiccator at 20 ° C and a relative humidity of 76% over a period of 144 hours. Subsequently, the mass increase of the sample is determined and the flowability of the sample is evaluated. The mass increase was 25.8% and the sample was baked only slightly and could be brought by light tapping back into the free-flowing state.

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