EP0349200B1 - Verfahren zur Herstellung konzentrierter Granulatkörner von oberflächenaktiven Mitteln - Google Patents
Verfahren zur Herstellung konzentrierter Granulatkörner von oberflächenaktiven Mitteln Download PDFInfo
- Publication number
- EP0349200B1 EP0349200B1 EP89306335A EP89306335A EP0349200B1 EP 0349200 B1 EP0349200 B1 EP 0349200B1 EP 89306335 A EP89306335 A EP 89306335A EP 89306335 A EP89306335 A EP 89306335A EP 0349200 B1 EP0349200 B1 EP 0349200B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- paste
- surfactant
- granules
- process according
- granulation
- 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.)
- Expired - Lifetime
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- 239000004094 surface-active agent Substances 0.000 title claims description 82
- 239000008187 granular material Substances 0.000 title claims description 51
- 238000000034 method Methods 0.000 title claims description 35
- 230000008569 process Effects 0.000 title claims description 32
- 238000005469 granulation Methods 0.000 claims description 40
- 230000003179 granulation Effects 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 11
- 239000003945 anionic surfactant Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 239000002563 ionic surfactant Substances 0.000 claims description 3
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 29
- 125000000217 alkyl group Chemical group 0.000 description 21
- -1 alkyl sulfate acids Chemical class 0.000 description 18
- 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 15
- 239000011734 sodium Substances 0.000 description 15
- 229910052708 sodium Inorganic materials 0.000 description 15
- 239000002253 acid Substances 0.000 description 12
- 239000003599 detergent Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 235000013305 food Nutrition 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 159000000001 potassium salts Chemical class 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- ONLRKTIYOMZEJM-UHFFFAOYSA-N n-methylmethanamine oxide Chemical compound C[NH+](C)[O-] ONLRKTIYOMZEJM-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 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 2
- 230000007613 environmental effect Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000013020 final formulation Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- XYJLPCAKKYOLGU-UHFFFAOYSA-N 2-phosphonoethylphosphonic acid Chemical class OP(O)(=O)CCP(O)(O)=O XYJLPCAKKYOLGU-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical class OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- SXKQTYJLWWQUKA-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.O.OB(O)O.OB(O)O.OB(O)O.OB(O)O Chemical compound O.O.O.O.O.O.O.O.O.O.OB(O)O.OB(O)O.OB(O)O.OB(O)O SXKQTYJLWWQUKA-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000388 Polyphosphate Chemical class 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005192 alkyl ethylene group Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Chemical class 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
Definitions
- the present invention relates to a process for preparing concentrated (condensed) surfactant granules.
- Granular surfactant compositions are principally prepared by spray or drum drying.
- the surfactant components, plus perhaps salts and builders are mixed with as much as 35-50% water to form a slurry.
- the slurry obtained is heated and spray dried, which is expensive.
- Such spray drying requires 30-40 wt.% of the water to be removed.
- the spray drying equipment used is expensive.
- the granule obtained has good solubility but a low bulk density, so the packing volume is large.
- the particles also may be sticky, particularly when hot, and thus wall buildup is an additional problem.
- There are other known disadvantages in preparing granular materials by spray drying such as environmental concerns and heat sensitivity.
- An agglomeration process would be cleaner, as well as less expensive, both in terms of equipment and operating costs.
- a practical problem with the use of a surfactant acid form is that it requires immediate use after it is made, or cool temperature storage, for such highly reactive acids, such as the alkyl sulfate acids, are subject to degradation unless cooled. They also tend to undergo hydrolysis during storage, forming free sulfuric acid and alcohol. In practical terms, such prior art processes require close-coupling of surfactant acid production with granulation which requires an additional capital investment.
- GB 2 171 414 A published on 28th August 1986, describes a process for making granules, especially anti-foam granules.
- a liquid hydrocarbon is sprayed on to a core material to produce granules which are subsequently chilled prior to a classification step.
- the present invention relates to an economical process for making a dense, concentrated surfactant granule from a high active surfactant paste using fine dispersion cold granulation.
- An important object of the present invention is to make a dense and more concentrated surfactant granular product by an agglomeration process without an expensive drying step. Another object is to provide a more concentrated surfactant granule which can be stored and then admixed with other ingredients to provide a final end product. Another object of the process of this invention is to provide a formulated granule containing higher total surfactant levels than typically obtained via other means. Yet another object of the present invention is to prepare a very high active surfactant granule essential free of hydrated inorganic salts. Other objects of the present invention will be apparent in view of the following.
- the process of the present invention comprises fine dispersion mixing and cooling of a high active surfactant paste to provide a very concentrated surfactant granule.
- Most high active surfactant pastes are too tacky at normal mixing temperatures to successfully granulate using fine dispersion mixing. So the high active surfactant paste is cooled as needed to a granulation temperature while mixing. Large discrete particles (granules) are surprisingly formed right in the mixer. Thus “cold" granulation of a high surfactant past is achieved.
- the granulation temperature ranges from -65°C to 25°C using a critical fine dispersion mixing tip speed of from 5 m/sec. to 50 m/sec. Dry ice is a preferred cooling means.
- the preferred granules made according to the present invention are large, essentially pure surfactant granules. They preferably have a bulk density of from 0.4 to 1.1 g/cc, more preferably from 0.5 to 0.8 g/cc.
- the weight average particle size of the preferred particles of this invention are from 200 to 2,000 microns.
- the more preferred granules have a particle size range of from 300 to 1,200 microns. Yields of 25% to 85% in these ranges can be achieved.
- a second brief mixing increases yields of granular particles in these preferred ranges. Oversized and undersized particles can also be recycled.
- the more preferred granulation temperatures of the high active surfactant paste ranges from -40°C to 10°C, and most preferably from -30°C to 0°C. More details of the present invention are highlighted below.
- the resultant surfactant granules made by the process of the present invention can comprise a combination of all, or substantially all, of the ingredients of the total composition or they can be used as an intermediate.
- Such granules greatly reduce or even eliminate the need to admix additional materials for a final detergent formulation.
- the possibility of segregation of ingredients during shipping, handling or storage is greatly reduced, especially if only minor quantities of other materials of differing particle sizes or densities are to be included.
- the concentrated granule of this invention can be admixed with detergent granules produced by more conventional means to increase the total surfactant level in a final formulation.
- Cooling jackets or coils can be integrated around or into the mixer. Chipped dry ice or liquid CO2 can be added or injected into the uniform paste. The idea is to lower the high active surfactant paste temperature to a granulation temperature so that it can be finely dispersed or "granulated" into discrete particles.
- the paste temperature and the paste viscosity are important parameters of the high active surfactant pastes which can affect the parameters of the mixing and granulation step of the present invention.
- the viscosity is a function of surfactant concentration and its temperature.
- the high active surfactants of the present invention have viscosities which range from 10,000 cps to 10,000,000 cps; preferably, from 70,000 to 7,000,000 cps; and more preferably from 100,000 to 1,000,000 cps. These viscosities are measured at a temperature of about 50°C for the present invention.
- the high active surfactant paste can be introduced into the mixer at an initial temperature in the range of 5-70°C, preferably 20-30°C. Higher temperatures reduce their viscosities but a temperature greater than 70°C can lead to poor initial mixing due to increased product stickiness.
- the process of the present invention surprisingly forms large, but usable, granules, preferably in the 200 to 1200 micron range.
- Such large granules are preferred, particularly if the surfactant granule is to be admixed with other materials which have a tendency to be dusty. Particles of similar size are preferred to minimize segregation. No extra grinding step is required or desirable.
- larger particles are less dusty, which is important in many consumer applications, especially those which comprise porous, unitized dose pouch-like products.
- Such porous products are designed: (1) to avoid consumer contact with the product and (2) to reinforce the convenience and nonmessiness perceptions of a unitized pouch form. If desired, granules of insufficient size can be screened after drying and recycled to the fine dispersion mixer.
- fine dispersion mixing and/or “granulation,” as used herein are synonymous and mean mixing and granulating of a high active surfactant paste in a fine dispersion mixer using a blade tip speed of from 5 m/sec. to 50 m/sec.
- the total residence time of the mixing and granulation process is preferably in the order of from 0.1 to 10 minutes, more preferably 0.5-8 and most preferably 1-6 minutes.
- the more preferred mixing and granulation tip speeds are 10-40 m/sec. and 15-35 m/sec.
- the Littleford® Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart® Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two examples of suitable mixers. Any other mixer with fine dispersion mixing and granulation capability and which preferably has a residence time in the order of 0.1 to 10 minutes can be used.
- the "turbine-type" impeller mixer, having several blades on an axis of rotation, is preferred.
- the invention can be practiced as a batch or a continuous process.
- the mixer must finely disperse the paste and, if desired, the other ingredients. When the contents of the mixer are cooled, the mixing must be conducted at said fine dispersion tip speed in order to granulate the surfactant into discrete particles. Care must be taken not to use too low or too high of a tip speed at the granulation step. While not being bound to a theory, "too high a shear" is believed to prevent granulation because of a wide variety of stresses, e.g., a broader particle size distribution caused by the higher tip speeds with a higher level of fines generated. Also, too high of a tip speed increases the temperature of the material and additional cooling is required.
- the work input required for fine dispersion mixing in the practice of the present invention varies with: (1) the type of fine dispersion mixer used, (2) the mixer loading level, (3) the viscosity of the paste material, and (4) the amount and the type of dry solids used, if any.
- the corresponding Incremental Work varied from 0.93 to 6.05 Joules per gram (0.4 BTU's to 2.6 BTU's per pound) of paste material.
- the No Load Work for the Cuisinart® food processor is about 0.21 kJ (0.2 BTU's) per second.
- the Cuisinart® food processor has a single 19.7 cm flat horizontal propeller and is operated at 1800 rpm, which is a tip speed of about 18.55 m/sec.
- the Total Work required to mix and granulate the surfactant paste of the present invention can vary from 7.0 to 70 Joules per gram (3 BTU's to 30 BTU's per pound) of material depending on viscosity, load, etc.
- a preferred range is from 11.6 to 46.5 Joules gram (5 BTU's to 20 BTU's per pound). (These BTU ranges in kilogram of material are, respectively, from 6.6 to 66, and from 11 to 44 BTU/Kg).
- Some benefits of fine dispersion mixing and granulation include: (1) a lower level of granulated fines; (2) a more uniform granular particle size distribution; and (3) a higher density granule than a granular product made with standard agglomeration-type mixers, such as pan-type mixers.
- the activity of the aqueous surfactant paste is at least 50% and can go up to 98%; preferred activities are: 60-80% and 65-75%.
- the balance of the paste is primarily water but can include a processing aid such as mineral oil.
- the resultant concentrated surfactant granules can be added to dry detergency builders or conventionally agglomerated with binders with these builders or other materials to yield desired finished formula compositions.
- moisture or solvent (hereinafter referred to as “moisture”) content of the high active surfactant should not exceed 50%.
- the total moisture can range from 2% to 50%, but is preferably from 10% to 40%, and more preferably from 15% to 30%.
- the lower granulation temperatures are used for the higher moisture-containing pastes. Conversely, the higher granulation temperatures can be used for lower moisture pastes.
- Paste compositions which have lower moisture contents of below 5%, e.g., 1% to 4%, can contain an effective amount of an organic liquid solvent or processing aid.
- organic liquid solvent or processing aid examples are selected from suitable organic liquid, including mineral oil, glycerin, short chain alcohols, and the like, and mixtures thereof.
- the processing aid preferably can be used at a level of "0.5% to 20%," more preferably 1-10%; most preferably 2-5% by weight of the paste.
- the desired moisture content of the surfactant granules of this invention can be adjusted by adding other desired dry ingredients prior to cooling and granulation. Thus, additional “drying" is unnecessary in low moisture formulations.
- drying the discrete granules can be accomplished in a standard fluid bed dryer. The idea here is to provide a free flowing granule with a desired moisture content of 0.5-10%, preferably 1-5%.
- the aqueous surfactant paste contains an organic surfactant selected from the group consisting of anionic, zwitterionic, ampholytic, nonionic and cationic surfactants, and mixtures thereof.
- Anionic surfactants are preferred.
- Surfactants useful herein are listed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, and in U.S. Pat. No. 3,919,678, Laughlin et al., issued Dec. 30, 1975.
- Useful cationic surfactants also include those described in U.S. Pat. No. 4,222,905, Cockrell, issued Sept. 16, 1980, and in U.S. Pat. No. 4,239,659, Murphy, issued Dec. 16, 1980.
- the following are representative examples of surfactants useful in the present compositions.
- Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
- Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
- Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383.
- Especially valuable are linear straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C11-C13 LAS.
- anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
- Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
- the preferred anionic surfactant pastes are mixtures of linear or branched alkylbenzene sulfonates having an alkyl of 10-16 carbon atoms and alkyl sulfates having an alkyl of 10-18 carbon atoms. These pastes are usually produced by reacting a liquid organic material with sulfur trioxide to produce a sulfonic or sulfuric acid and then neutralizing the acid to produce a salt of that acid.
- the salt is the surfactant paste discussed throughout this document.
- the sodium salt is preferred due to end performance benefits and cost of NaOH vs. other neutralizing agents, but is not required as other agents such as KOH may be used.
- the neutralization can be performed as part of the fine dispersion mixing step, but preneutralization of the acid in conjunction with the acid production is preferred.
- Nonionic surfactants are also useful as surfactant in the compositions of the invention.
- Many final detergent compositions include nonionics or nonionic/anionic surfactant blends. Inclusion of nonionics in many applications is difficult, particularly if a spray-dry process is used, because of potential degradation and environmental concerns.
- a nonionic granule can thus be admixed with a spray-dry granule to produce a preferred final formulation.
- Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
- Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 4 to 25 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 4 to 25 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
- Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
- Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from 8 to 18 carbon atoms.
- the high active surfactant paste formulation must be solid at about room temperature unless the granules are kept cool until mixed with other detergent solids.
- LAS and AS as used herein mean, respectively, “sodium lauryl benzene sulfonate” and “alkyl sulfate.”
- C45 mean C14 and C15 alkyl, unless otherwise specified.
- the surfactant granules of the present invention can be made with some detergency builder and/or inorganic, water-soluble salts. So, the surfactant paste can contain such materials at a ratio of salt/builder to surfactant active of from 0:1 to 1:1 on a dry weight basis. Any compatible detergency builder or combination of builders or water-soluble salts can be used in the process to produce desired end products or intermediates. However, in most cases the inclusion of such solid material is unnecessary and not desired.
- the present invention is aimed at making a purer, denser surfactant granule.
- the granular detergents of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature.
- the builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
- neutral water-soluble salts include the alkali metal, ammonium or substituted ammonium chorides, fluorides and sulfates.
- the alkali metal, and especially sodium, salts of the above are preferred.
- Sodium sulfate is typically used in detergent granules and is a particularly preferred salt.
- water-soluble salts include the compounds commonly known as detergent builder materials.
- Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, and polyhydroxysulfonates.
- alkali metal especially sodium, salts of the above.
- inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from 6 to 21, and orthophosphate.
- polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
- Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148.
- nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SiO2 to alkali metal oxide of from 0.5 to 4.0, preferably from 1.0 to 2.4.
- the compositions made by the process of the present invention does not require excess carbonate for processing, and preferably does not contain over 2% finely divided calcium carbonate as disclosed In U.S. Pat. No. 4,196,093, Clarke et al., issued Apr. 1, 1980, and is preferably free of the latter.
- compositions of the present invention can be included in the compositions of the present invention to produce desired end product laundry products, but are not necessary, and are included here to show the breadth of this invention.
- ingredients commonly used in detergent compositions can be included in the compositions of the present invention to produce desired end product laundry products, but are not necessary, and are included here to show the breadth of this invention.
- These include flow aids, color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, chelating agents and perfumes.
- LAS and AS as used herein mean, respectively, “sodium lauryl benzene sulfonate” and “alkyl sulfate.”
- C45 mean C14 and C15 alkyl, unless otherwise specified.
- a Cuisinart® food processor, Model #DCX-Plus with 19.7 cm metal blades operating at 1800 rpm is used for all examples.
- the tip speed is 18.55 m/sec.
- the viscosities of LAS and AS are measured using Brookfield HAT Serial No. 74002 as follows: For 60% and 70%, at 0.5 rpm with spindle T-A at 50°C; For 74% AS, at 0.5 rpm with spindle T-E at 50°C; For 50% AS, at 2.5 rpm with spindle T-A at 50°C.
- the granulation temperature for each high active surfactant paste is determined on a case by case basis.
- the viscosity of the paste is 800,000 cps (see note below on viscosity measurement technique).
- the paste temperature was first 25°C. The paste temperature drops from 25°C to -50°C and surfactant granules are formed.
- Example 2 is similar to Example 1, except that a 60% active (vs. 70%) C13LAS is used.
- the paste viscosity is 350,000 cps.
- the temperature at granulation is -20°C.
- Example 3 is similar to Example 1, except that 10% sodium sulfate is added to the 70% active C13LAS.
- the builder salt to surfactant active ratio is 0.16.
- the temperature at granulation is -35°C.
- Example 4 is similar to Example 3, except 93% active C13LAS is used and 35% sodium carbonate monohydrate is added to the surfactant paste.
- the paste viscosity is >1,000,000 cps.
- the builder salt to surfactant active ratio is 0.54.
- the temperature at granulation is 4°C.
- Example 5 is similar to Example 1, except a 1:1 blend of C13LAS and C45AS is used. Both pastes have an activity level of 70%. The viscosity of the C45LAS is >7,000,000 cps. The temperature at granulation is -5°C.
- Example 6 is similar to Example 1, except 74% active C45AS (vs. 70% active C13LAS) is used.
- the viscosity of the paste is >7,000,000 cps.
- the temperature at granulation is 23°C.
- the yield of these granules in the 200-2,000 micron particle size range is 42%.
- the granules are set under ambient conditions and placed back in the mixer and mixed for about 15 seconds.
- the final yield is 85%; moisture is 14%.
- Example 7 is similar to Example 6, except 50% active (vs. 74%) C45AS is used.
- the viscosity of the paste is 25,000 cps.
- the temperature at granulation is -5°C.
- Example 8 is similar to Example 6, except 7.7% mineral oil is added as a processing aid.
- the temperature at granulation is -2°C.
- Example 9 is similar to Example 1, except 87% active Barlox 12 (C12 ⁇ 16 dimethyl amine oxide) is used instead of 70% C13LAS.
- the viscosity of the paste is 1,000,000 cps.
- the temperature at granulation is -60°C.
- Example 10 is similar to Example 9, except 37% sodium carbonate monohydrate is added to the 87% active Barlox 12.
- the builder salt to surfactant active ratio is 0.65.
- the temperature at granulation is -40°C.
- Example 11 is similar to Example 1, except 70% Amphoterge K is used instead of 70% C13LAS.
- the viscosity of the paste is about 500,000 cps.
- the temperature at granulation is -52°C.
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Claims (9)
- Verfahren zur Herstellung kondensierter Tensidgranulate, umfassend:A. Mischen einer Tensidpaste mit einer Waschwirkungsaktivität von mindestens 50 %;B. Kühlen der Paste auf eine Granulierungstemperatur von -65°C bis 25°C;C. Granulieren der gekühlten Paste zu diskreten Tensidgranulaten unter Anwendung eines Feindispersionsmischens mit einer Spitzengeschwindigkeit von 5-50 m/s; undwobei das Tensid aus der anionische, zwitterionische, ampholytische, nichtionische und kationische Tenside und Mischungen davon umfassenden Gruppe gewählt wird; und
wobei das Mischen und Granulieren bei einer Mischerverweilzeit von 0.1 bis 10 Minuten durchgeführt werden. - Verfahren nach Anspruch 1, wobei die Tensidpaste eine Waschwirkungsaktivität bis zu 98 % aufweist; und wobei die Paste eine Viskosität von 10 000 bis 10 000 000 cps bei 50°C besitzt; und wobei die Tensidpaste aus Schritt A eine Temperatur von 5°C bis 70°C besitzt.
- Verfahren nach Anspruch 2, wobei die kondensierten Granulate eine Tensid-Waschwirkungsaktivität von mindestens 50 % aufweisen.
- Verfahren nach Anspruch 1, wobei die Granulierungstemperatur der Paste -40°C bis 10°C beträgt.
- Verfahren nach Anspruch 1, wobei die Spitzengeschwindigkeit 10-40 m/s und die Verweilzeit 0.5-8 Minuten betragen.
- Verfahren nach Anspruch 1, wobei die Paste eine Waschwirkungsaktivität von 60-80 % aufweist; und wobei die Paste eine Viskosität von 70 000 bis 7 000 000 cps besitzt; wobei die Paste bei einer anfänglichen Temperatur von 20-30°C eingesetzt wird und wobei die Granulierungstemperatur -30°C bis 0°C beträgt, und wobei die aus der Paste gebildeten, diskreten Tensidgranulate eine durchschnittliche Teilchengröße von 200 Mikron bis 2000 Mikron aufweisen und wobei die diskreten Tensidgranulate eine Schüttdichte von 0,4 bis 1,1 g/cm³ besitzen.
- Verfahren nach Anspruch 1, wobei die Waschwirkungsaktivität der Paste 65-75% beträgt; und wobei die Dichte der Granulate 0,5 bis 0,7 g/cm³ beträgt.
- Verfahren nach Anspruch 1, wobei die Tensidpaste ein aus anorganischen Salzen oder Buildern oder Mischungen davon gewähltes Material mit einem Verhältnis von Salz/Builder zu Pasten-Wirkstoff von 0:1 bis 1:1 enthält.
- Verfahren nach Anspruch 1, wobei die Feuchtigkeit der diskreten Granulate durch Trocknen in einem Wirbelbettrockner auf einen Feuchtigkeitsgehalt von 1-8 % verringert wird.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/213,575 US4925585A (en) | 1988-06-29 | 1988-06-29 | Detergent granules from cold dough using fine dispersion granulation |
US213575 | 1988-06-29 | ||
US288759 | 1988-12-22 | ||
US07/288,759 US5080848A (en) | 1988-12-22 | 1988-12-22 | Process for making concentrated surfactant granules |
Publications (3)
Publication Number | Publication Date |
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EP0349200A2 EP0349200A2 (de) | 1990-01-03 |
EP0349200A3 EP0349200A3 (en) | 1990-06-20 |
EP0349200B1 true EP0349200B1 (de) | 1995-09-27 |
Family
ID=26908207
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP89306335A Expired - Lifetime EP0349200B1 (de) | 1988-06-29 | 1989-06-23 | Verfahren zur Herstellung konzentrierter Granulatkörner von oberflächenaktiven Mitteln |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0349200B1 (de) |
JP (1) | JP2845953B2 (de) |
AR (1) | AR245773A1 (de) |
AU (1) | AU624155B2 (de) |
BR (1) | BR8903195A (de) |
CA (1) | CA1322705C (de) |
DE (1) | DE68924373T2 (de) |
DK (1) | DK323989A (de) |
ES (1) | ES2076963T3 (de) |
IE (1) | IE892100L (de) |
MX (1) | MX165307B (de) |
NZ (1) | NZ229756A (de) |
TR (1) | TR24383A (de) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4925585A (en) * | 1988-06-29 | 1990-05-15 | The Procter & Gamble Company | Detergent granules from cold dough using fine dispersion granulation |
US5045238A (en) * | 1989-06-09 | 1991-09-03 | The Procter & Gamble Company | High active detergent particles which are dispersible in cold water |
CA2017921C (en) * | 1989-06-09 | 1995-05-16 | John Michael Jolicoeur | Formation of detergent granules by deagglomeration of detergent dough |
KR0170424B1 (ko) * | 1990-07-05 | 1999-01-15 | 호르스트 헤를레,요한 글라슬 | 세제 및 청정제용 표면 활성제 과립의 제조방법 |
US5494599A (en) * | 1991-04-12 | 1996-02-27 | The Procter & Gamble Company | Agglomeration of high active pastes to form surfactant granules useful in detergent compositions |
EP0560001B1 (de) * | 1992-03-10 | 1999-05-19 | The Procter & Gamble Company | Hochaktive Tensidpasten |
US5486303A (en) * | 1993-08-27 | 1996-01-23 | The Procter & Gamble Company | Process for making high density detergent agglomerates using an anhydrous powder additive |
US5723433A (en) * | 1993-09-24 | 1998-03-03 | The Chemithon Corporation | Sovent removal process |
US6058623A (en) * | 1993-09-24 | 2000-05-09 | The Chemithon Corporation | Apparatus and process for removing volatile components from a composition |
HU219203B (en) * | 1993-11-24 | 2001-03-28 | Unilever Nv | Particulate detergent composition and process for producing thereof |
FR2721616A1 (fr) | 1994-06-22 | 1995-12-29 | Hoechst France | Compositions de tensioactifs anioniques en poudre, en perles ou en granulés, leur procédé de préparation et leur utilisation dans les produits de nettoyage et d'entretien. |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0220024A2 (de) * | 1985-10-09 | 1987-04-29 | The Procter & Gamble Company | Granulierte Reinigungsmittel mit Löslichkeit |
EP0349201A2 (de) * | 1988-06-29 | 1990-01-03 | The Procter & Gamble Company | Reinigungsmittelgranulat aus einer kalten Paste durch Feindispersionsgranulierung |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4115308A (en) * | 1976-12-27 | 1978-09-19 | The Procter & Gamble Company | High-shear process for preparing silicate-containing paste-form detergent compositions |
IN160448B (de) * | 1982-12-07 | 1987-07-11 | Albright & Wilson | |
JPS6072998A (ja) * | 1983-09-30 | 1985-04-25 | 花王株式会社 | 粉末物性に優れた界面活性剤粉体組成物の製造法 |
GB8505062D0 (en) * | 1985-02-27 | 1985-03-27 | Unilever Plc | Processing granulated solids |
-
1989
- 1989-06-23 DE DE1989624373 patent/DE68924373T2/de not_active Expired - Fee Related
- 1989-06-23 EP EP89306335A patent/EP0349200B1/de not_active Expired - Lifetime
- 1989-06-23 ES ES89306335T patent/ES2076963T3/es not_active Expired - Lifetime
- 1989-06-28 IE IE210089A patent/IE892100L/xx unknown
- 1989-06-28 TR TR51789A patent/TR24383A/xx unknown
- 1989-06-28 CA CA000604216A patent/CA1322705C/en not_active Expired - Fee Related
- 1989-06-28 AU AU37135/89A patent/AU624155B2/en not_active Ceased
- 1989-06-28 NZ NZ22975689A patent/NZ229756A/en unknown
- 1989-06-29 MX MX1665589A patent/MX165307B/es unknown
- 1989-06-29 BR BR898903195A patent/BR8903195A/pt not_active Application Discontinuation
- 1989-06-29 JP JP1168233A patent/JP2845953B2/ja not_active Expired - Lifetime
- 1989-06-29 DK DK323989A patent/DK323989A/da not_active Application Discontinuation
- 1989-06-29 AR AR89314293A patent/AR245773A1/es active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0220024A2 (de) * | 1985-10-09 | 1987-04-29 | The Procter & Gamble Company | Granulierte Reinigungsmittel mit Löslichkeit |
EP0349201A2 (de) * | 1988-06-29 | 1990-01-03 | The Procter & Gamble Company | Reinigungsmittelgranulat aus einer kalten Paste durch Feindispersionsgranulierung |
Also Published As
Publication number | Publication date |
---|---|
TR24383A (tr) | 1991-09-23 |
JP2845953B2 (ja) | 1999-01-13 |
NZ229756A (en) | 1992-04-28 |
AU3713589A (en) | 1990-01-04 |
MX165307B (es) | 1992-11-04 |
BR8903195A (pt) | 1990-02-13 |
DK323989A (da) | 1989-12-30 |
IE892100L (en) | 1989-12-29 |
DE68924373T2 (de) | 1996-05-15 |
EP0349200A3 (en) | 1990-06-20 |
EP0349200A2 (de) | 1990-01-03 |
DE68924373D1 (de) | 1995-11-02 |
AR245773A1 (es) | 1994-02-28 |
JPH0481500A (ja) | 1992-03-16 |
DK323989D0 (da) | 1989-06-29 |
CA1322705C (en) | 1993-10-05 |
AU624155B2 (en) | 1992-06-04 |
ES2076963T3 (es) | 1995-11-16 |
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