EP1622864A1 - Procede de production de nitriles d'ammonium sous forme de granules - Google Patents

Procede de production de nitriles d'ammonium sous forme de granules

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Publication number
EP1622864A1
EP1622864A1 EP04729633A EP04729633A EP1622864A1 EP 1622864 A1 EP1622864 A1 EP 1622864A1 EP 04729633 A EP04729633 A EP 04729633A EP 04729633 A EP04729633 A EP 04729633A EP 1622864 A1 EP1622864 A1 EP 1622864A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
ammonium
granulated
acid
ammonium nitrile
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.)
Withdrawn
Application number
EP04729633A
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German (de)
English (en)
Inventor
Georg Borchers
Andreas Schottstedt
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.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
Clariant GmbH
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 Clariant Produkte Deutschland GmbH, Clariant GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of EP1622864A1 publication Critical patent/EP1622864A1/fr
Withdrawn legal-status Critical Current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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles

Definitions

  • the invention relates to a process for the production of bleach activator granules from one or more ammonium nitriles, wherein the ammonium nitrile is granulated together with a binder and, if appropriate, further additives in the presence of water in a pneumatically generated fluidized bed and dried at the same time.
  • the fluidized bed granules are characterized by a very uniform morphology, high abrasion resistance, good storage stability and high active substance contents.
  • Bleach activators are important components in compact detergents, stain removers and machine dishwashing detergents. Conventional bleach activators at 40 ° C to 60 ° C enable a bleaching result comparable to that of boilers by reacting with hydrogen peroxide donors (mostly perborates, percarbonates, persilicates and perphosphates) to release an organic peroxycarboxylic acid.
  • hydrogen peroxide donors mostly perborates, percarbonates, persilicates and perphosphates
  • the achievable bleaching result is determined by the type and reactivity of the peroxycarboxylic acid formed, the structure of the bond to be hydrolyzed, and the water solubility of the bleach activator.
  • bleach activators Many substances are known in the art as bleach activators. Usually these are reactive organic compounds with an O-acyl or N-acyl group, already in the washing powder mixture, favored by the residual moisture present, with the bleaching agent, e.g. Sodium perborate can react if both components are unprotected.
  • bleach activators are, for example, N, N, N ', N'-tetraacetylethylenediamine (TAED), nonanoylcaprolactamphenylsulfonate ester (APES), glucose pentaacetate (GPA), xylose tetraacetate (TAX), acyloxybenzenesulfonate (e.g.
  • nonanoyloxybenzene sulfonate (4-nonanoyloxybenzene sulfonate ( SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS)), diacetyldioxohexahydrotriazine (DADHT), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH) and nitrilotriacetate.
  • SBOBS sodium trimethylhexanoyloxybenzenesulfonate
  • DADHT diacetyldioxohexahydrotriazine
  • TAGU tetraacetylglucoluril
  • TACA tetraacetylcyanoic acid
  • ADMG di-
  • nitrile quats Ammonium nitriles
  • Compounds of this type develop their effects at low temperatures in the range from 10 ° C to 50 ° C.
  • the preparation of nitrile quats and their use as bleach activator in bleaching agents are described in EP-A-0 303 520, EP-A-0 464 880, EP-A-0 458 396, EP-A-0 897 974 and EP-A-0 790 244.
  • WO 98/23531, WO 00/58273 and WO 00/36061 describe that ammonium nitriles, in particular cyclic ammonium nitriles, are converted into a solid form for incorporation into solid detergents and cleaning agents by adding a carrier material with the largest possible surface area, for example silica an aqueous ammonium nitrile solution is stirred in or the aqueous solution is sprayed or mixed onto the carrier and the resulting mixture is dried in vacuo at elevated temperatures.
  • a carrier material with the largest possible surface area
  • silica an aqueous ammonium nitrile solution is stirred in or the aqueous solution is sprayed or mixed onto the carrier and the resulting mixture is dried in vacuo at elevated temperatures.
  • the granules or particles described in the documents have water contents of up to 20% by weight, preferably less than 1% by weight.
  • EP 1 122 300 describes bleaching agents which contain an ammonium nitrile as a bleach activator, optionally in a mixture with other bleach activators, for example alkanoyloxybenzenesulfonic acid or tetraacetylethylene diamine, and an inorganic peroxide and an alkali metal carbonate.
  • an ammonium nitrile as a bleach activator
  • other bleach activators for example alkanoyloxybenzenesulfonic acid or tetraacetylethylene diamine
  • an inorganic peroxide and an alkali metal carbonate for example alkanoyloxybenzenesulfonic acid or tetraacetylethylene diamine, and an inorganic peroxide and an alkali metal carbonate.
  • the invention relates to a process for the production of granulated ammonium nitriles, characterized in that an ammonium nitrile is granulated together with a binder and optionally a further additive in the presence of water in a pneumatically generated fluidized bed and dried at the same time.
  • R 1, R 2, R 3 are identical or different and are linear or branched C ⁇ -C24 alkyl groups, C 2 -C 24 alkenyl or C ⁇ -C - C alkoxy-C ⁇ -4 -Alkyl deficit, substituted or unsubstituted benzyl, or wherein R 1 and R 2 together with the nitrogen atom to which they are attached form a ring with 4 to 6 carbon atoms, the -C-C 5 alkyl, CrCs-alkoxy , D- to Cs-alkanoyl, phenyl, amino, ammonium, cyano, cyanamino, chlorine or bromine can be substituted and in addition to the nitrogen atom instead of carbon atoms one or two oxygen or nitrogen atoms, a group N- R 6 or a group R 3 -NR 6 can contain, wherein R 6 is hydrogen, d- to C 5 - Is alkyl, C 2 - to C 5 -alkenyl,
  • R 1 , R 2 and R 3 represent a linear or branched, saturated or unsaturated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms or substituted or unsubstituted benzyl and
  • A represents any charge-balancing ion, for example chloride, Bromide, iodide, fluoride, sulfate, hydrogen sulfate, carbonate, hydrogen carbonate, phosphate, mono- and di-hydrogen phosphate, pyrophosphate, metaphosphate, nitrate, methyl sulfate, phosphonate, methyl phosphonate, methane disulfonate, methyl sulfonate,
  • chloride Bromide, iodide, fluoride, sulfate, hydrogen sulfate, carbonate, hydrogen carbonate, phosphate, mono- and di-hydrogen phosphate, pyrophosphate, metaphosphate, nitrate,
  • the charge-balancing anion can be any, preferably chloride or methosulfate or a mixture of different anions, for example chloride or methosulfate and cumene sulfonate and / or lauryl sulfate and / or fatty acid alkyl carboxylates.
  • the ammonium nitriles are mixed together with further (second) bleach activators.
  • These other bleach activators are solid and naturally have a different structure than the ammonium nitriles.
  • SBOBS nonanoyloxybenzenesulfonate
  • STHOBS sodium trimethyl hexanoyloxybenzenesulfonate
  • DADHT diacetyldioxohexahydrotriazine
  • TAGU tetraacetylglucoluril
  • TACA Tetraacetylcyanoic acid
  • ADMG di-N-acetyldimethylglyoxin
  • PAH 1-phenyl-3-acetylhydantoin
  • NTA nitrilotriacetate
  • the preferred co-bleach activator is TAED.
  • the mixture of ammonium nitrile and further bleach activators, based on the finished, dry, uncoated granules is generally 25 to 70% by weight, preferably 30 to 60% by weight, in particular 45 to 55% by weight.
  • the proportion by weight of ammonium nitrile alone, based on the finished, dry, uncoated granules is generally 1 to 50% by weight, preferably 10 to 40% by weight, particularly preferably 15 to 35% by weight.
  • Suitable binders are cellulose and starch and their ethers or esters, for example carboxymethyl cellulose (CMC), methyl cellulose (MC) or hydroxyethyl cellulose (HEC) and the corresponding starch derivatives, but also film-forming polymers, for example polyacrylic acids or their salts.
  • Powdery anionic components in particular alkanesulfonates, are also particularly suitable as binders in the sense of this invention.
  • the amount of binder, based on the finished granules can be 1 to 45% by weight, preferably 5 to 30% by weight.
  • the granules according to the invention additionally contain further additives, preferably acid additives, which reduce the hygroscopicity and sensitivity to hydrolysis of the ammonium nitrile.
  • acidic additives are suitable sulfuric acid, sodium hydrogen sulfate, phosphoric acid, sodium hydrogen phosphate, phosphonic acids and their salts, carboxylic acids or their salts such as citric acid, in anhydrous or hydrated form, glycolic acid, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, maleic acid, maleic anhydride or lactic acid , but also acidic polymers.
  • Particularly suitable acidic additives are polyacrylic acid, polymaleic acid or copolymers of acrylic acid and maleic acid (Sokalan ® types).
  • the amount of acidic additive is such that the proportion of the acidic additive in the finished granulate is approximately 0 to 30% by weight, preferably 1 to 20% by weight, in particular 10 to 18% by weight.
  • the process according to the invention can in principle be carried out by metering all components separately or together in solid form into the fluidized bed apparatus and adding water for the granulation. Another possibility is that all components are entered into the fluidized bed apparatus separately or together in the form of aqueous solutions or suspensions. In practice, various variants of these methods are preferred, as described below. Since the ammonium nitriles are hygroscopic and therefore difficult to isolate in solid form, it is advisable to use these ammonium nitriles in the invention
  • an aqueous spray slurry is made
  • Ammonium nitrile, another bleach activator, binders and acidic additive produced at room temperature, in a stirred tank with stirring with a (mobile) Ultra-Turrax, optionally heated to a temperature of 25 ° C to 85 ° C, using a suitable pump (e.g. peristaltic pump ) pumped to the nozzle and sprayed into the fluidized bed from below.
  • a suitable pump e.g. peristaltic pump
  • a spray slurry can be granulated in this way, each containing 25 to 30% by weight, preferably 27.8% by weight of ammonium nitrile, Na-cumene sulfonate and TAED, and 15 to 20% by weight, preferably 16.7% by weight.
  • Sokalan CP45 contains, calculated as the active ingredient content of the respective components in the final granulate.
  • only part of the second sheet metal catalyst is metered into the spray slurry, comprising ammonium nitrile, binder and acidic additive, as described above, while the rest of this second catalyst is added separately in solid form.
  • the dust content of the finished granules, as they occur in the process according to the invention, can also be returned to the fluidized bed as a solid. In principle, this recycling of the dust components is possible in all variants of the method according to the invention.
  • Such an additional solids feed for example of dusty fine fractions of the finished granules or of powdery ones
  • Formulation components for example TAED, can also be advantageous in order to increase the germ concentration in the fluidized bed.
  • the addition takes place either before the atomization of the ammonium nitrile solution or preferably simultaneously with this.
  • the solid can also be added together with the ammonium nitrile solution, the mixing of these liquid components preferably taking place either before the atomization or directly in the nozzle.
  • Ground germ material is preferably metered in, preferably with a grain size ⁇ 1250 ⁇ m.
  • the finished granulate is advantageously discharged from the fluidized bed by classifying the size of the granules.
  • This classification can be carried out via a central tube with an opposite air flow (classifier air), which is regulated in such a way that only particles of a certain particle size are discharged from the fluidized bed and smaller particles are retained in the fluidized bed.
  • the particles discharged from the gas stream above the fluidized bed are separated (e.g. filter or cyclone), fine dust entrained by the gas, if necessary, can be removed in a downstream separator, e.g. Wet scrubbers are separated. The separated dust is fed back into the fluidized bed in the area of the spray nozzle, where it is wetted again.
  • Granules preferred according to the invention have a d50 value between 0.4 and 2.5 mm.
  • the grain fraction that is greater than 1.4 mm is returned. This coarse fraction can either be added as a solid component to the fluidized bed after grinding or it is dissolved again and sprayed into the fluidized bed.
  • the air flowing in from below is composed of the heated or unheated classifier air and the heated soil air.
  • the soil air temperature is preferably between 85 and 95 ° C, preferably between 90 and 93 ° C.
  • the fluidized air cools down due to heat losses and the heat of vaporization of the constituents of the solvent. This sets the temperature of the layer mass in the fluidized bed to 50 to 70 ° C., preferably 60 to 63 ° C.
  • the air outlet temperature is preferably between 55 ° C and 65 ° C.
  • the water content of the products can be set within wide limits.
  • drying takes place simultaneously with the granulation in the fluidized bed.
  • the drying means that the water content of the granules is ⁇ 2% by weight and the bleach activator content is> 50% by weight, based on uncoated co-granules.
  • Round fluidized bed apparatuses which are preferably used have base plates with dimensions of at least 0.4 m.
  • fluidized bed apparatuses are preferred which have a base plate with a diameter between 0.4 m and 3 m, for example 1, 2 m or 2.5 m.
  • the fluidized bed apparatus can have a rectangular shape.
  • a perforated base plate or a conid ur plate, a wire mesh or a combination base made of a perforated plate with a grid can be used as the base plate.
  • the granules obtained according to the invention are directly suitable for use in detergents and cleaning agents.
  • they can be provided with a coating shell by methods known per se.
  • the granulate is coated with a film-forming substance in an additional step, which can significantly influence the product properties.
  • All film-forming substances such as waxes, silicones, fatty acids, fatty alcohols, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, anionic and cationic polymers, polyethylene glycols and polyalkylene glycols are suitable as coating agents.
  • C 8 -C 3 fatty acids for example: lauric, myristic, stearic acid), dicarboxylic acids, for example glutaric acid, adipic acid or their anhydrides are suitable; Phosphonic acids, optionally phosphonic acids mixed with other common coating agents, in particular fatty acids, for example stearic acid, C 8 -C 3 - ⁇ fatty alcohols; Polyalkenyl glycols (eg polyethylene glycols with a molecular weight of 1000 to 50,000 g / mol); Nonionics (eg Cs-C 3 ⁇ - fatty alcohol polyalkoxylates with 1 to 100 moles of EO); Anionics (eg alkanesulfonates, alkylbenzenesulfonates, ⁇ -olefinsulfonates, alkyl sulfates, alkyl ether sulfates with C 3 -C 3 ⁇ hydrocarbon residues); Polymers (eg polyvinyl alcohols); W
  • further substances which do not soften or melt in this temperature range can be present in dissolved or suspended form, for example: polymers (for example homo-, co- or graft copolymers of unsaturated carboxylic acids and / or Sulfonic acids and their alkali salts, cellulose ether, starch, starch ether, polyvinylpyrrolidone); Organic substances (eg mono- or polyvalent carboxylic acids, hydroxycarboxylic acids or ether carboxylic acids with 3 to 8 carbon atoms and their salts); dyes; Inorganic substances (e.g. silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates).
  • polymers for example homo-, co- or graft copolymers of unsaturated carboxylic acids and / or Sulfonic acids and their alkali salts, cellulose ether, starch, starch ether, polyvinylpyrrolidone
  • Organic substances eg mono- or polyvalent carboxylic
  • the content of the coating substance can be 1 to 30% by weight, preferably 5 to 15% by weight, based on the coated activator granules.
  • Mixers mechanically induced fluidized bed
  • fluidized bed apparatus pneumatically induced fluidized bed
  • mixers e.g. Ploughshare mixers (continuous and batch-wise)
  • ring bed mixers or Schugi mixers possible.
  • the tempering can take place in a granulate preheater and / or in the mixer directly and / or in a fluid bed downstream of the mixer.
  • Granulate coolers or fluid bed coolers can be used to cool the coated granules.
  • the tempering is carried out using the hot gas used for the fluidization.
  • the granulate coated by the fluidized bed process can be similar to the
  • the tempering consists of a heat treatment at a temperature of 30 to 100 ° C, but at or below the melting or softening temperature of the respective coating substance. It is preferred to work at a temperature just below the melting or softening temperature.
  • the exact temperature during tempering or the temperature difference to the melting point of the coating substance depends on the coating amount, the tempering time and the properties desired for the coated bleach activator granulate and must be determined for the respective system in preliminary tests.
  • the storage stability and hygroscopicity, as well as the compatibility with other detergent components, in particular strongly alkaline components, can be further improved and the reaction kinetics can be influenced in a targeted manner in this way
  • the granules according to the invention can also contain other suitable additives, such as anionic and nonionic surfactants which contribute to a faster dissolution of the granules according to the invention, and bleach stabilizers such as, for example, phosphonates and polyphosphonates.
  • suitable additives such as anionic and nonionic surfactants which contribute to a faster dissolution of the granules according to the invention, and bleach stabilizers such as, for example, phosphonates and polyphosphonates.
  • Preferred anionic surfactants are alkali metal salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl ether sulfates, alkyl amide sulfates and ether sulfates, alkyl aryl polyether sulfates, monoglyceride sulfates, alkyl amide sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinate, sulfate sulfate, alkyl amide sulfate sulfates, alkyl amide sulfate sulfates, Alkylamidopolypeptidates, alkylisethionates, alkyl taurates, alkylpolyglycol ether carboxylic acids or fatty acids, such as oleic acid, Ricinoleic acid, palmitic acid, stearic acid, copraic acid salt or hydrogenated co
  • Preferred nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerolized fatty acid esters, polyethyloxylated esters of fatty acids and of sorbitol, polyethoxylated or polyglycerolated fatty amides.
  • suitable additives are complexing agents and transition metal complexes, e.g. Metal complexes containing iron, cobalt or manganese as described in EP-A-0 458 397 and EP-A-0 458 398.
  • additives are substances which react in the wash liquor with the peroxycarboxylic acid released from the activator to form reactive intermediates, such as dioxiranes or oxaziridines, and can thus increase the reactivity.
  • Corresponding compounds are ketones and sulfonimines corresponding to US-A-3 822 114 and EP-A-O 446 982.
  • the amount of the additive depends in particular on its type.
  • acidifying additives and organic activators for increasing the performance of the peracid are used in amounts of 0 to 20% by weight, in particular in amounts of 1 to 10% by weight, based on the total weight. added, however, metal complexes in concentrations in the ppm range.
  • the granules produced according to the invention are distinguished by very good storage stability in powder detergent, cleaning and disinfectant formulations. They are ideal for use in
  • Heavy duty detergents stain removal salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
  • the granules according to the invention are used in combination with a hydrogen peroxide source.
  • a hydrogen peroxide source examples include perborate monohydrate, perborate tetrahydrate, percarbonates, alkali persulfates, persilicates and percitrates, sodium being the preferred alkali metal, and hydrogen peroxide adducts with urea or amine oxides.
  • peroxycarboxylic acids for example dodecanediperic acid or phthalimidopercarboxylic acids, which can optionally be substituted on the aromatic, can be present.
  • bleach stabilizers such as, for example, phosphonates, borates, or metaborates and metasilicates
  • magnesium salts such as magnesium sulfate
  • the formulation may have further detergent components, such as surfactants of nonionic, anionic, cationic or amphoteric nature, organic and inorganic builders and co-builders, enzymes, bleach activators, bleach catalysts, salts, optical brighteners, graying inhibitors, foam inhibitors, sequestering agents and Fragrances and dyes.
  • surfactants of nonionic, anionic, cationic or amphoteric nature organic and inorganic builders and co-builders, enzymes, bleach activators, bleach catalysts, salts, optical brighteners, graying inhibitors, foam inhibitors, sequestering agents and Fragrances and dyes.
  • Preferred nonionic surfactants are fatty alcohol oxyethylates with approx. 1 to approx. 25 mol ethylene oxide.
  • the alkyl chain of the aliphatic alcohols can be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms.
  • the condensation products of alcohols which contain an alkyl chain of 10 to 20 carbons with 2 to 18 mol of ethylene oxide per mol of alcohol are particularly preferred.
  • the alkyl chain can be saturated or unsaturated.
  • the alcohol ethoxylates can have a narrow homolog distribution of the ethylene oxide ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates").
  • nonionic surfactants of this type are Tergitol TM 15-S-9 (condensation product of a C11-C15 linear secondary alcohol with 9 mol of ethylene oxide), Tergitol TM 24-L-NMW (condensation product of a C 1 -C 4 -linearene primary alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution).
  • Genapol TM brands from Clariant GmbH also fall under this product class.
  • nonionic surfactants such as polyethylene, polypropylene, polybutylene and polypentylene oxide adducts of fatty alcohols with 8-22 carbon atoms and Alkylphenols with 6 to 12 carbon atoms in the alkyl chain, addition products of ethylene oxide with a hydrophobic base, formed from the condensation of propylene oxide with propylene glycol or addition products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.
  • Semipolar nonionic surfactants for example amine oxides, can also be used.
  • Particularly suitable amine oxides are C 0 -C 8 -alkyldimethylamine oxides and C 8 -C-
  • Suitable anionic surfactants are in particular straight-chain and branched alkyl sulfates, sulfonates, carboxylates, phosphates, alkyl ester sulfonates, arylalkyl sulfonates, alkyl ether sulfates and mixtures of the compounds mentioned. Some of the types of anionic surfactants in question are described below.
  • Alkyl ester sulfonates are linear esters of C 8 -C 2 o-carboxylic acids (ie fatty acids) which are sulfonated by SO 3 , as described in "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting materials are natural fat derivatives, such as tallow or palm oil fatty acid.
  • Alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, in which R is preferably a C 1 -C 2 -hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C atoms, particularly preferably a C 1 -C 8 -alkyl group or hydroxyalkyl radical.
  • M is hydrogen or a cation, for example an alkali metal cation (for example sodium, potassium, lithium) or ammonium or substituted ammonium, for example a methyl, dimethyl and trimethylammonium cation or a quaternary ammonium cation such as tetramethylammonium and dimethylpiperidinium cation and quaternary
  • alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.
  • Alkyl chains with C 1 -C 6 are preferred for low washing temperatures (eg below approx. 50 ° C) and alkyl chains with Ci6-C 18 preferred for higher washing temperatures (eg above approx. 50 ° C).
  • Alkyl ether sulfates are water-soluble salts or acids of the formula
  • RO (A) m SO 3 M in which R is an unsubstituted C 0 -C 2 alkyl or hydroxyalkyl radical with 10 to 24 C atoms, preferably a C 2 -C 2 o alkyl or hydroxyalkyl radical, particularly preferably a C 2 -Ci 8 alkyl or hydroxyalkyl.
  • A is an ethoxy or propoxy unit
  • m is a number greater than 0, typically between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3
  • M is a hydrogen atom or a cation such as e.g. a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation.
  • substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like.
  • Examples include C 2 -C 8 alkyl polyethoxylate (1, 0) sulfate, Ci 2 -C 8 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 alkyl polyethoxylate (3, 0) sulfate, Ci 2 -Ci 8 alkyl polyethoxylate (4.0) sulfate, the cation being sodium or potassium.
  • anionic surfactants which are useful for use in detergents and cleaning agents are C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in British Patent GB 1, 082,179, alkyl glycerol sulfates, fatty acyl glycerol sulfates acylglycerol sulfates, alkylphenol ether sulfates, linear or branched alkyl benzene sulfonates, primary and secondary paraffin sulfonates, alkyl phosphates, alkyl ether phosphates, isethionates, such as acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoester of sulfosuccinates (especially saturated and unsatur
  • Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids can also be used. Further examples are described in "Surface Active Agents and Detergents” (Vol. I and II, Schwartz, Perry and Berch). A large number of such surfactants are also described in US Pat. No. 3,929,678 claimed.
  • amphoteric surfactants which can be used in the formulations of the present invention are, in particular, those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be linear or branched and in which one of the aliphatic Contains substituents between 8 to 18 carbon atoms and an anionic, water-soluble group, such as Contains carboxy, sulfonate, sulfate, phosphate or phosphonate.
  • Preferred amphoteric surfactants are monocarboxylates and dicarboxylates such as cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (or also referred to as cocoamphodiacetate) and cocoamphoacetate.
  • amphoteric surfactants are alkyldimethylbetaines, alkylamidobetaines and alkyldipolyethoxybetaines with an alkyl radical which may be linear or branched with. 8 to 22 carbon atoms, preferably with 8 to 18 carbon atoms and particularly preferably with 12 to 18 carbon atoms. These compounds are marketed, for example, by Clariant GmbH under the trade names Genagen ® GAB and LAB.
  • cationic surfactants are quaternary ammonium compounds, ester quats, ether quats, hydroxyethyl quats, ethoxylated quats, in particular quaternized fatty acid alkanolamine ester salts and dialkylaminopropylamine ester salts.
  • Suitable organic and inorganic builders are neutral or, in particular, alkaline salts which can precipitate or bind calcium ions in a complex manner.
  • Suitable and in particular ecologically harmless builder substances such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g, are preferably used.
  • alkali phosphates which can be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples include trisodium phosphate, tetranate diphosphate, dinate dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and mixtures of sodium and potassium salts.
  • Usable organic builders are, for example, the carboxylic acids preferably used in the form of their sodium salts, such as citric acid, nitriloacetate (NTA) and ethylenediaminetetraacetic acid, provided that such use is not objectionable for ecological reasons, and phosphonic and polyphosphonic acids.
  • polymeric carboxylates and their salts can also be used. These include, for example, the salts of homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those made from 50% to 10% maleic acid, and also polyaspartic acid and also polyvinylpyrrolidone and urethanes.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid, in particular water-soluble polyacrylates are also suitable, for example with about 1% of a Polyallylethers of the Subrose are cross-linked and have a relative molecular mass above one million. Examples of these are the polymers available under the name Carbopol 940 and 941.
  • Enzymes from the class of proteases, lipases, amylases, pullinases, cutinases, and cellulases or mixtures thereof can be used.
  • the enzymes can be adsorbed on carrier substances and / or embedded in coating substances.
  • the detergent formulations can also contain the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from EP 446 982 and EP 453 003 as so-called bleaching catalysts.
  • Sodium sulfate, sodium carbonate or sodium silicate (water glass), for example, are used as salts or adjusting agents.
  • Further constituents of the detergent formulation can be optical brighteners, for example derivatives of diaminostilbenedisulfonic acid or its alkali metal salts and foam inhibitors such as fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed silica.
  • foam inhibitors such as fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed silica.
  • Mixtures of different foam inhibitors can also advantageously be used, e.g. those made of silicone oil, paraffin oil or waxes.
  • Foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • the salts of polyphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylene-phosphonic acid (EDTMP) and diethylenetriaminepentamethylenephosphonic acid (DTPMP) can be added.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • ETMP ethylenediaminetetramethylene-phosphonic acid
  • DTPMP diethylenetriaminepentamethylenephosphonic acid
  • Typical individual examples of other additives are sodium borate, cellulose and starch and their ethers or esters, sucrose, polydextrose and polymer additives.
  • the first step 486.1 g of a 40% aqueous sodium cumene sulfonate solution were mixed with 259.3 g of a 45% aqueous Sokalan C45 solution at room temperature. Then 422.7 g of a 55.6% strength aqueous ammonium nitrile solution were gradually added, the active content of the solution being approximately 46%.
  • the mixed solution was intensively homogenized during the addition with an Ultra-Turrax.
  • a batch fluidized laboratory fluidized bed of the type GPCG 1.1 from Glatt with an inflow diameter of D 150 mm was used for laboratory tests, the spray nozzle spraying from below into the fluidized bed.
  • a vortex mass is required, onto which the active ingredient solution can be sprayed.
  • the suitable vortex mass is usually not yet available, so that it usually has to be started with a carrier material.
  • the process is very complex must be operated for a long period of time until the original starter material is safely replaced and only the actual target product is contained in the fluidized bed.
  • the recipe examined here showed that it could be spray dried very well in a fluidized bed apparatus. This made it possible to dispense with the use of a carrier and to produce a spray-dried powder with the desired target composition as a fluidized bed. A lengthy exchange process was no longer necessary.
  • the gas volume flow for swirling the bed material was approximately 33 m 3 / h.
  • the supply air temperature was limited to approx. 95 ° C, which ensured a sufficient distance from the softening and sintering effects of the product starting at approx. 110 ° C.
  • a spray rate of approx. 12-19 g / min solution corresponding to approx. 8-10 g / min solids
  • a temperature in the fluidized bed of approx. 62-63 ° C. was established, this temperature level being able to be kept stable.
  • an exhaust air temperature of approx. 56 - 57 ° C was reached.
  • the first step 347.2 g of a 40% aqueous sodium cumene sulfonate solution were mixed with 185.2 g of a 45% aqueous Sokalan C45 solution at room temperature. 284.6 g of a 59% strength aqueous ammonium nitrile solution were then added in stages, the active content of the solution being approximately 49%.
  • the mixed solution was intensively homogenized during the addition with an Ultra-Turrax.
  • a batch fluidized laboratory fluidized bed of the type GPCG 1.1 from Glatt with an inflow diameter of D 150 mm was used for laboratory tests, the spray nozzle spraying onto the fluidized bed from above.
  • the TAED amount of 139 g required to complete the recipe was presented in the laboratory fluidized bed together with 495.7 g of fluidized bed material from preliminary tests (granules and comminuted coarse material).
  • the material was swirled with a gas volume flow of approx. 22-31 m 3 / h, the gas inlet temperature being approx. 90-95 ° C.
  • 810 g of the spray slurry were sprayed into the fluidized bed at a metering rate of 14-22 g / min.
  • a temperature in the fluidized bed of approximately 63-71 ° C. was established.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Glanulating (AREA)

Abstract

L'invention concerne un procédé de production de nitriles d'ammonium sous forme de granulés, lequel consiste à granuler du nitrile d'ammonium avec un liant et, éventuellement, avec un autre additif, dans un lit fluidisé produit pneumatiquement, et à faire sécher simultanément les granulés obtenus.
EP04729633A 2003-05-02 2004-04-27 Procede de production de nitriles d'ammonium sous forme de granules Withdrawn EP1622864A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10320796 2003-05-02
PCT/EP2004/004426 WO2004096756A1 (fr) 2003-05-02 2004-04-27 Procede de production de nitriles d'ammonium sous forme de granules

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EP1622864A1 true EP1622864A1 (fr) 2006-02-08

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US (1) US20090131298A1 (fr)
EP (1) EP1622864A1 (fr)
JP (1) JP2007509188A (fr)
BR (1) BRPI0409840A (fr)
WO (1) WO2004096756A1 (fr)

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DE102016015660A1 (de) * 2016-12-31 2018-07-05 Weylchem Wiesbaden Gmbh Granulate, deren Verwendung und Wasch- und Reinigungsmittel enthaltend diese

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DE19750424A1 (de) * 1997-11-14 1999-05-20 Henkel Kgaa Verbessertes Verfahren zum Herstellen von Tensidgranulaten mit einem hohen Schüttgewicht
DE10038180A1 (de) * 2000-08-04 2002-02-14 Reckitt Benckiser Nv Verwendung eines neuartigen Bleichaktivator-Compounds in Geschirrspülmittelzusammensetzungen
US20030166484A1 (en) * 2000-09-28 2003-09-04 Kingma Arend Jouke Coated, granular n-alkylammonium acetonitrile salts and use thereof as bleach activators
DE10159386A1 (de) * 2001-12-04 2003-06-12 Henkel Kgaa Verfahren zur Herstellung von Bleichaktivatorgranulaten
DE10161766A1 (de) * 2001-12-15 2003-06-26 Clariant Gmbh Bleichaktivator-Co-Granulate

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See references of WO2004096756A1 *

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BRPI0409840A (pt) 2006-05-09
US20090131298A1 (en) 2009-05-21
JP2007509188A (ja) 2007-04-12
WO2004096756A1 (fr) 2004-11-11

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