EP0772674A1 - Verfahren zur herstellung von tensidgranulaten - Google Patents
Verfahren zur herstellung von tensidgranulatenInfo
- Publication number
- EP0772674A1 EP0772674A1 EP95926892A EP95926892A EP0772674A1 EP 0772674 A1 EP0772674 A1 EP 0772674A1 EP 95926892 A EP95926892 A EP 95926892A EP 95926892 A EP95926892 A EP 95926892A EP 0772674 A1 EP0772674 A1 EP 0772674A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- granulation
- spray
- surfactant
- anionic
- 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.)
- Granted
Links
- 239000008187 granular material Substances 0.000 title claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 32
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000003380 propellant Substances 0.000 claims abstract description 6
- 239000010419 fine particle Substances 0.000 claims abstract description 3
- 238000005469 granulation Methods 0.000 claims description 23
- 230000003179 granulation Effects 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 9
- -1 fatty acid isethionates Chemical class 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 239000002280 amphoteric surfactant Substances 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000012432 intermediate storage Methods 0.000 claims description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 239000000126 substance Substances 0.000 abstract description 8
- 239000000428 dust Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 101000802895 Dendroaspis angusticeps Fasciculin-1 Proteins 0.000 description 5
- 101000802894 Dendroaspis angusticeps Fasciculin-2 Proteins 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 101000611023 Homo sapiens Tumor necrosis factor receptor superfamily member 6 Proteins 0.000 description 4
- 102100040403 Tumor necrosis factor receptor superfamily member 6 Human genes 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 241000273930 Brevoortia tyrannus Species 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N 1-Tetradecanol Natural products CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004165 Methyl ester of fatty acids Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000007257 deesterification reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940068917 polyethylene glycols Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical group OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
-
- 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
Definitions
- the invention relates to a process for the production of detergent granules with high bulk density and good dissolving behavior in water, the granulate size being controllable at least in such a way that dust-free or at least low-dust granules are produced.
- Surfactant granules can be produced, for example, by conventional drying techniques for surfactant-containing solutions and pastes, especially in the spray tower.
- European patent application EP-A-0 319819 discloses a process for the preparation of surfactant granules by spray drying, an anionic surfactant in its acid form and a highly concentrated aqueous alkaline component being acted upon separately with a gaseous medium, then combined in stoichiometric amounts, in neutralized with a multi-component nozzle and sprayed at a high propellant pressure in the drying tower.
- the products obtained are solid or pasty, solid products mostly being relatively dusty, having a relatively high water content and a low bulk density.
- Granulation is an alternative to spray drying of surfactant pastes.
- European patent application EP-A-0430 148 describes a process for producing fatty alcohol sulfate granules which are dispersible in cold water.
- a highly concentrated aqueous paste holsulfat fatty alcohols containing less than 14 wt .-% of water and less than 20 wt .-% is further additives, at temperatures between 10 and 45 C ⁇ so long me ⁇ mechanically processed until granules are formed .
- a surfactant preparation containing water as a liquid component and additionally organic polymer and Bu lder substances can contain, mixed with a finely divided solid and granulated in a high-speed mixer.
- the water content of the surfactant paste also represents a critical process parameter here. If the water content of the surfactant paste is too high, the solid is dispersed so that it can no longer act as a deagglomeration agent. On the other hand, if the solids content exceeds a certain value, the mass will not have the consistency required for granulation.
- the object of the invention was to develop a method which does not have the disadvantages of the above-mentioned methods.
- low-dust granules with increased bulk density should be produced, which nevertheless have good dissolving behavior in water.
- the invention accordingly relates to a process for the preparation of surfactant granules by spray drying, an anionic surfactant or more anionic surfactants in its / its acid form and a highly concentrated aqueous alkaline component being separately charged with a gaseous medium, combined, neutralized in a multi-component nozzle and at a high rate Propellant gas pressure are sprayed in the drying tower, the combination of the acidic and alkaline components in almost stoichiometric amounts and the solid, one-piece products obtained in a mechanisc working mixer are transferred in which the fine particles are agglomerated into granules having a bulk density of at least 400 g / l.
- the first process step, spray neutralization can be carried out, for example, according to the teaching of European patent application EP-A-0319819. At this point, reference is expressly made to the disclosure in European patent application EP-A-0319819.
- a preferred embodiment of the present invention provides that the acidic and alkaline reactant streams separately charged with a gaseous medium are brought together via a single multi-component nozzle, for example via a 2-component nozzle or a 3-component nozzle, and dry ⁇ nungsraum be sprayed. It is also possible to bring the gas-charged reactant streams together before the nozzle. It should be noted, however, that the distance between the location of the junction from the spraying device depends on the process conditions and the material systems used, but is preferably kept as small as possible in order to avoid clogging of the nozzle due to premature neutralization reactions.
- the first-mentioned variant of combining the reactant streams in the nozzle is to be preferred, since in this case the neutralization takes place essentially in the nozzle or directly when it emerges from the nozzle.
- the combined acidic and alkaline reactant streams it is also possible for the combined acidic and alkaline reactant streams to be sprayed into the drying chamber via a plurality of multi-component nozzles. This is particularly preferred when products are to be produced from different types of anionic surfactants and thus different, combined acidic and alkaline reactant streams are to be sprayed.
- the starting materials are introduced, for example using piston pumps, in almost stoichiometric metered amounts into one or two non-modified commercial nozzle (s) or one or two spray tube (s).
- the gaseous medium (propellant) is mixed in directly in front of the nozzle. This means that the gaseous medium is mixed into the reactant streams before they meet in front of or in the nozzle.
- the flow rate of the reactant streams or the pressure at which the reaction mixture is sprayed into the drying room can be found in European patent application EP-A-0319819.
- almost stoichiometric amounts mean that the ratio of the number of acidic groups to alkaline groups is preferably in the range from 1.1: 1 to 0.8: 1 and in particular from 1: 1 to 0.9 : 1 lies.
- the anionic surfactants in their acid form can be carboxylic acids, sulfuric acid semesters and sulfonic acids, preferably fatty acids, alkylarylsulfonic acids, ⁇ -sulfofatty acid esters and the sulfuric acid semiesters of optionally alkoxylated, especially ethoxylated alcohols and fatty alcohols and / or sulfosuccinic acid.
- fatty acid esters in particular fatty acid methyl esters, can also be used, in which case the ester group is not saponified, but instead is saponified.
- Suitable anionic surfactants in their acid form are therefore in particular either an anionic surfactant in its acid form or a mixture of the group of anionic surfactants in their acid form, optionally in combination with nonionic, amphoteric and / or cationic surfactants.
- Preferred anionic surfactants in their acid form are C ⁇ -C ⁇ alkylsulfonic acids, Cg-Ci3-alkylbenzenesulfonic acid, usually called dodecylbenzenesulfonic acid, and ⁇ -sulfofatty acid methyl ester in its acid form.
- Particularly preferred alkylsulfonic acids are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, e.g.
- esters of ⁇ -sulfofatty acids which, by sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 10 to 20 C atoms in the fatty acid molecule, for example the ⁇ -sulfonated methyl esters of the hydrogenated coconut oil, , Palm kernel or tallow fatty acids, as well as those caused by the ester cleavage available ⁇ -sulfo fatty acids (diacids) used.
- diacids ⁇ -sulfofatty acids
- alkanesulfonic acids which are obtainable from Ci2-Ci8-alkanes by sulfochlorination or sulfoxidation.
- ingredients can be used, which are preferably derived from the group of ingredients that are usually used in spray-dried washing or cleaning agents.
- nonionic surfactants but also builder substances such as phosphates and zeolites or polycarboxylic acids or their salts and polymeric polycarboxylates, and also inorganic salts such as carbonates, bicarbonates, silicates, sulfates and bisulfates are suitable.
- Solid substances can be blown into the spray drying room, for example, while liquid components can additionally be introduced into the spray drying room in combination with one of the reactant streams.
- anionic surfactant and / or nonionic, surfactant pastes are also introduced into the spray drying room in addition to the reactant streams.
- an anionic surfactant in its acid form or a mixture of anionic surfactants in its acidic form is used in combination with anionic, nonionic, amphoteric and / or cationic surfactants.
- Suitable anionic surfactants which can be introduced into the process in paste form in particular, are all salts which are concordant with the acid forms mentioned above.
- Nonionic surfactants preferably used in combination with these anionic surfactants in acid form are derived from liquid alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 40 moles of ethylene oxide per mole of alcohol, in which the alcohol residue may be linear or methyl-branched in the 2-position, or may contain linear and methyl-branched residues in the mixture, as is usually present in oxo alcohol residues.
- linear residues from alcohols of native origin with 12 to 18 carbon atoms are preferred, such as from coconut, tallow or oleyl alcohol.
- the degrees of ethoxylation given represent statistical mean values, which can be an integer or a fractional number for a special product.
- Alcohol ethoxylates with a narrow homolog distribution are also suitable.
- alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
- the preferred ethoxylated alcohols include, for example, Cg-Cn-oxo alcohol with 7 EO, Ci3 ⁇ Ci5-0xoalcohol with 3 EO, 5 EO or 7 EO and in particular Ci2-C j 4-alcohol with 3 EO or 4 EO, Ci2- Ci8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of Ci2-Ci4 alcohol with 3 EO and C ⁇ 2-Ci8 alcohol with 5 EO.
- alcohols are preferred which have more than 10 EO per molecule of alcohol, for example 11 EO, 14 EO, 20 EO, 25 EO, 30 EO or also 40 E0 such as tallow fatty alcohol with 40 E0.
- nonionic surfactants which can be used are alkylglycosides of the general formula R- 0- (G) x , in which R is a primary straight-chain or aliphatic radical which is methyl-branched in the 2-position and has 8 to 22, preferably 12 to 18, atoms, G is a symbol , which stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligo erization x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4.
- R is a primary straight-chain or aliphatic radical which is methyl-branched in the 2-position and has 8 to 22, preferably 12 to 18, atoms
- G is a symbol , which stands for a glycose unit with 5 or 6 carbon atoms
- the degree of oligo erization x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4.
- the neutralization or saponification reaction is preferably carried out with concentrated aqueous alkaline solutions, for example solutions of hydroxides, carbonates or hypochlorites of sodium or potassium, in particular with a concentrated aqueous sodium hydroxide solution and / or potassium hydroxide solution, concentrations around 45 to 55% by weight are particularly preferred. A further dilution of the reactant streams with water is not necessary.
- Suitable gaseous medium are, in particular, gases such as air or nitrogen which are inert to the starting and end materials.
- gases such as air or nitrogen which are inert to the starting and end materials.
- water vapor is also suitable here, in particular if one of the reactant streams or the reactant streams is to be heated before the merging.
- Such solid products can now be transferred to any of the known mechanically operating mixers or granulators, with the aid of which the powders are granulated and at the same time recompacted to bulk densities of at least 400 g / 1, preferably of about 420 to 650 g / 1 can.
- Such mixers are, for example, ploughshare mixers or annular layer mixers, such as those sold by the companies Lödige, Imcatec or Drais, but also mixer types from Schugi (Flexomi ⁇ (R)) or Niro (ZigZag mixer ( R ) or HEC granulator ( R )). Both batch and continuous mixer types can be used, with the continuously operating mixer types being preferred.
- this granulation is carried out at a temperature at which the solid product softens and can thus be shaped.
- a temperature at which the solid product softens and can thus be shaped In the lower temperature range, granules with an only slightly increased bulk density are formed; however, this increases at higher temperatures. If the temperatures are too high, however, the mixture to be granulated is softened to a great extent and the mixer becomes blocked by pasty caking on walls and tools. With a given chemical composition, the preferred temperature range also shifts downward with increasing water content.
- drying or moistening, cooling or heating the spray-neutralized product before or during the granulation can be advantageous.
- the spray-neutralized powders are subjected to a treatment in a fluidized bed before the granulation, and the powders can be dried and / or cooled.
- cooling or initially drying and then cooling of the products is carried out, preferably such Product temperatures are set which have proven to be advantageous in the granulation, so that direct further processing of the product is made possible.
- the powdery products produced in the spray chamber are even further processed directly, that is to say without intermediate storage and without treatment in the fluidized bed, in the mechanically working mixer.
- the granulation in the mixer is carried out at product temperatures between 30 and 80 ° C., preferably between 40 and 70 ° C.
- solid and / or liquid additional components in this process stage, it is not necessary.
- the granulation of the dusty products succeeded without the addition of liquid components, which usually had to be added as a granulating liquid.
- advantageous low-dust granules with controllable particle size and high bulk density are obtained, which also show very good flow behavior, so that granulation of the spray-dried powder without the addition of liquid components is a preferred embodiment.
- the applicant assumes that the relatively high water content of the sprayed and dusty products from the first process stage serves as a "liquid reserve", which enables granulation. It is precisely the parameter that leads to the manifold disadvantages of the powdery products in the first process stage that results in particularly advantageous products after the second process stage.
- additives can of course be added at this point, as is customary in conventional granulation, even at these temperatures liquid to pasty additives such as nonionic surfactants (see above), but also anionic surfactant pastes (see above).
- nonionic surfactants see above
- anionic surfactant pastes see above.
- liquid components are added during the granulation and the proportion of the added liquid components exceeds 5% by weight, to further solids
- Add usual ingredients of washing or cleaning agents are also peroxy bleaching agents, such as perborate and percarbonate, but also conventional graying inhibitors and substances which prevent the fabric from being soiled again.
- Enzymes can also be granulated at this stage; however, it is preferred to add these to the end product in granular form.
- water and aqueous solutions are less preferred: on the one hand, the water - as stated above - is not required as a granulating liquid and, on the other hand, a subsequent drying would have to be connected in most cases, but this is not preferred.
- Such drying of the granules and thus a concentration of the granules following the second process stage can, in principle, be carried out, for example, in a so-called long-term dryer, for example in a fluidized bed or a vacuum dryer. Just like drying, cooling the granules, as is known from the prior art, is also possible.
- customary processing steps such as sieving and, if appropriate, recycling fine and coarse-grained fractions into the mixer can follow.
- finely divided solids for example zeolites, in particular zeolite A and / or zeolite P, silicates, silicas, sulfates, calcium stearates and mixtures thereof, are advantageously added at the end of the granulation step in order to improve the storage stability of the granules.
- soaps, alkyl sulfates and / or fatty acid isethionates are also added as solid additional components in the granulation stage. It has been shown that the dissolution behavior of the granular end products produced according to the invention in water, which in themselves have good values, by adding these solids, for example in amounts of 0.5 to 15% by weight, preferably in amounts of 1 to 10 wt .-%, can still be increased.
- the products obtained according to the invention, which are quickly soluble in water, are low-dust granules.
- the grain sizes or certain grain size ranges can be controlled via the process parameters of the mechanically operating mixers or granulators used. Bulk weights between 400 and 600 g / l and particle size ranges are preferably set, less than 5% by weight having a particle diameter below 0.1 mm and at least 85% by weight having a maximum particle diameter of 1.6 mm.
- surfactant granules having the following composition are produced which contain more than 40% by weight, preferably 50 to 95% by weight and in particular 80 to 90% by weight, of anionic surfactants, preferably C8-C22- Have alkyl sulfates, in particular C12-Ci ⁇ -alkyl sulfates, Cjs-Cis-alkyl sulfates or cuts with higher proportions of C12 and d j4.
- Example 1 analogously to the disclosure of EP-A-0 319 819, half-sulfuric acid (FAS1 and FAS2) were spray-neutralized with 50% by weight sodium hydroxide solution via a multi-component nozzle.
- the spray-neutralized products FAS1 and FAS2 obtained had the composition given below (Table 1).
- the spray-neutralized, relatively dusty products were transferred directly, ie without intermediate storage, to the mixers specified below.
- granules with a bulk density of at least 400 g / l were produced which had good dissolving behavior in water.
- Baten B B mean 1 2 1.5 1.5 ⁇ 0.5
- Example 1 Spout diameter of radially symmetrical stainless steel bunkers after 24-hour storage according to the Jenike shear test (AW Jenike, Gravity Flow of Bulk Solids, Bulletin of the University of Utah No. 108, Vol. 52 (No.29), October 1961 and AW Jenike, Storage and Flow of Solids, Bulletin of the University of Utah No. 123, Vol. 53 (No.26), November 1964)
- Example 1 was repeated with the FAS 2 type. The composition, bulk density and grain size distribution were in the same size range as for FAS 1.
- Examples 2 and 3 show the effects of the residence time on the particle size distribution and the bulk density.
- Examples 4 and 5 show the effects of the granulation temperature on the bulk density.
- the improved flow properties of the products 2 to 6 produced according to the invention can be read off from the value of the required outlet diameter of a bunker: for a further processing of a relatively dusty, only spray-neutralized product according to Example 1 after storage in a bunker, this would have to have an outlet diameter of 3 , 1 m, while for products according to one of the examples 2 to 6 outlet diameters of less than 1 m are sufficient.
Landscapes
- 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)
- Detergent Compositions (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Compounds Of Unknown Constitution (AREA)
- Materials For Medical Uses (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4425968 | 1994-07-25 | ||
DE4425968A DE4425968A1 (de) | 1994-07-25 | 1994-07-25 | Verfahren zur Herstellung von Tensidgranulaten |
PCT/EP1995/002777 WO1996003488A1 (de) | 1994-07-25 | 1995-07-14 | Verfahren zur herstellung von tensidgranulaten |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0772674A1 true EP0772674A1 (de) | 1997-05-14 |
EP0772674B1 EP0772674B1 (de) | 1998-06-24 |
Family
ID=6523862
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95926892A Expired - Lifetime EP0772674B1 (de) | 1994-07-25 | 1995-07-14 | Verfahren zur herstellung von tensidgranulaten |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0772674B1 (de) |
AT (1) | ATE167700T1 (de) |
DE (2) | DE4425968A1 (de) |
DK (1) | DK0772674T3 (de) |
ES (1) | ES2117433T3 (de) |
WO (1) | WO1996003488A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6468957B1 (en) | 1998-09-29 | 2002-10-22 | Henkel Kommanditgesellschaft Auf Aktien | Granulation method |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19617085A1 (de) * | 1996-04-29 | 1997-10-30 | Bayer Ag | Verfahren zur Herstellung von feinstteiligen Kristallisationsprodukten |
DE19820943A1 (de) | 1998-05-11 | 1999-11-18 | Henkel Kgaa | Alkylsulfat-Granulate |
DE19844522A1 (de) | 1998-09-29 | 2000-03-30 | Henkel Kgaa | Granulationsverfahren |
DE19855380A1 (de) * | 1998-12-01 | 2000-06-08 | Henkel Kgaa | Granulationsverfahren |
DE19910789A1 (de) * | 1999-03-11 | 2000-09-14 | Henkel Kgaa | Granulationsverfahren |
DE10003124A1 (de) | 2000-01-26 | 2001-08-09 | Cognis Deutschland Gmbh | Verfahren zur Herstellung von Tensidgranulaten |
DE10163603B4 (de) | 2001-12-21 | 2006-05-04 | Henkel Kgaa | Verfahren zur Herstellung builderhaltiger Tensidgranulate |
DE102004005761A1 (de) * | 2004-02-05 | 2005-06-02 | Henkel Kgaa | Neutralisationsverfahren |
EP2138566A1 (de) | 2008-06-25 | 2009-12-30 | The Procter and Gamble Company | Sprühtrockenverfahren |
EP2138565A1 (de) * | 2008-06-25 | 2009-12-30 | The Procter and Gamble Company | Sprühtrockenverfahren |
US7811980B1 (en) | 2009-06-09 | 2010-10-12 | The Procter & Gamble Company | Spray-drying process |
EP2341123A1 (de) * | 2009-12-18 | 2011-07-06 | The Procter & Gamble Company | Sprühtrockenverfahren |
EP2338969B1 (de) * | 2009-12-18 | 2017-07-26 | The Procter & Gamble Company | Sprühtrockenverfahren |
EP2338968A1 (de) * | 2009-12-18 | 2011-06-29 | The Procter & Gamble Company | Sprühtrockenverfahren |
ES2390219T3 (es) * | 2009-12-18 | 2012-11-07 | The Procter & Gamble Company | Procedimiento de secado por pulverización |
EP2341124B1 (de) * | 2009-12-18 | 2017-07-26 | The Procter & Gamble Company | Sprühtrockenverfahren |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH555888A (it) * | 1966-03-18 | 1974-11-15 | Micol Anstalt | Procedimento e dispositivo per la produzione di detergenti sintetici in forma granulare. |
ZA72295B (en) * | 1971-02-01 | 1973-09-26 | Colgate Palmolive Co | Method for neutralization of detergent acid |
DE3741401A1 (de) * | 1987-12-07 | 1989-06-15 | Henkel Kgaa | Verfahren zur herstellung von festen oder pastenfoermigen produkten |
CA2143869C (en) * | 1992-09-08 | 2000-02-29 | Unilever Plc | Detergent composition and process for its production |
JPH06166898A (ja) * | 1992-12-01 | 1994-06-14 | Lion Corp | 高嵩密度洗剤組成物の製造方法 |
DE4304062A1 (de) * | 1993-02-11 | 1994-08-18 | Henkel Kgaa | Verfahren zur Herstellung von Tensidgranulaten |
-
1994
- 1994-07-25 DE DE4425968A patent/DE4425968A1/de not_active Withdrawn
-
1995
- 1995-07-14 AT AT95926892T patent/ATE167700T1/de not_active IP Right Cessation
- 1995-07-14 WO PCT/EP1995/002777 patent/WO1996003488A1/de active IP Right Grant
- 1995-07-14 EP EP95926892A patent/EP0772674B1/de not_active Expired - Lifetime
- 1995-07-14 DK DK95926892T patent/DK0772674T3/da active
- 1995-07-14 ES ES95926892T patent/ES2117433T3/es not_active Expired - Lifetime
- 1995-07-14 DE DE59502656T patent/DE59502656D1/de not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9603488A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6468957B1 (en) | 1998-09-29 | 2002-10-22 | Henkel Kommanditgesellschaft Auf Aktien | Granulation method |
Also Published As
Publication number | Publication date |
---|---|
ES2117433T3 (es) | 1998-08-01 |
WO1996003488A1 (de) | 1996-02-08 |
DK0772674T3 (da) | 1999-04-06 |
DE59502656D1 (de) | 1998-07-30 |
ATE167700T1 (de) | 1998-07-15 |
EP0772674B1 (de) | 1998-06-24 |
DE4425968A1 (de) | 1996-02-01 |
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