EP0555622A1 - Verfahren zur Herstellung von Detergenskörnchen durch Neutralisation von Sulfonsäuren - Google Patents
Verfahren zur Herstellung von Detergenskörnchen durch Neutralisation von Sulfonsäuren Download PDFInfo
- Publication number
- EP0555622A1 EP0555622A1 EP92870026A EP92870026A EP0555622A1 EP 0555622 A1 EP0555622 A1 EP 0555622A1 EP 92870026 A EP92870026 A EP 92870026A EP 92870026 A EP92870026 A EP 92870026A EP 0555622 A1 EP0555622 A1 EP 0555622A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent
- anionic surfactant
- neutralisation
- neutralising agent
- agglomerate
- 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
- 239000003599 detergent Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 238000006386 neutralization reaction Methods 0.000 title claims abstract description 19
- 239000008187 granular material Substances 0.000 title description 9
- 150000007513 acids Chemical class 0.000 title description 6
- 239000002245 particle Substances 0.000 claims abstract description 41
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims description 25
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 9
- 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 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 description 21
- 125000000217 alkyl group Chemical group 0.000 description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000004615 ingredient Substances 0.000 description 12
- -1 optical brighteners Chemical compound 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil 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
- 238000009826 distribution Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000005192 alkyl ethylene group Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 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
- 229920001577 copolymer Polymers 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 238000000915 furnace ionisation nonthermal excitation spectrometry Methods 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 235000012771 pancakes Nutrition 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
-
- 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
Definitions
- the present invention relates to a process for dry neutralisation of sulphonic acids and to detergent compositions made by this process.
- Granular detergents have so far been principally prepared by spray drying.
- the detergent components such as surfactants and builders, are mixed with as much as 35-50% water to form a slurry.
- the slurry obtained is heated and spray dried which requires high energy input and expensive equipment. An efficient method of processing detergents without slurrying in water and then subsequently drying would be less expensive.
- the detergent granules made by the invention have a bulk density greater than 650 g/l.
- Japanese Pat. No. 60 072 999 discloses a batch process whereby a detergent sulphonic acid, sodium carbonate, water and other optional ingredients are brought together in a high shear mixer followed by cooling to 40°C or below and pulverising with zeolite powder and granulating.
- EP A 0 420 317 published April 3, 1991, discloses a continuous process whereby a detergent sulphonic acid, particulate inorganic material, water and other optional ingredients are brought together in a high speed mixer/densifier. Material is subsequently treated in a moderate speed granulator/densifier. Addition of fine powders in the second step, or between the first and second step, is described as beneficial for the agglomeration process.
- the present invention relates to a process for making a detergent particle by neutralisation of the acid form of an anionic surfactant in a high shear mixer by a stoichiometric excess of finely divided particulate neutralising agent having an average particle size of less than 5 ⁇ m.
- the present invention also encompasses free-flowing detergent compositions made with the process.
- a stream of dry powder ingredients is fed into a high shear mixer where it is mixed with a liquid or paste stream of anionic surfactant acid and, optionally, other liquid binders.
- the powder stream comprises a particulate neutralising agent, typically an alkali inorganic salt, and neutralisation starts in the high shear mixer and continues during subsequent processing. It is a characteristic of the invention that the particulate neutralising agent in the powder stream is in the form of a finely ground powder.
- the powder stream contains a particulate neutralising agent.
- Preferred neutralising agents include any of the salts of carbonate or bicarbonate or mixtures thereof. Especially suitable is calcium or sodium carbonate.
- the neutralising agent should be present in a stoichiometric excess over the anionic surfactant acid. Preferably at least five times as much neutralising agent should be present than is required for stoichiometric neutralisation.
- the powder stream may also contain any other suitable detergent powders.
- Preferred powders are those which are active in the detergency process. This includes zeolites, sodium tripolyphosphate, silica, silicates, polymers including copolymers of maleic and acrylic acid, carboxymethyl cellulose, optical brighteners, ethylene diamine tetra acetic acid and inorganic salts such as sulphates.
- Other suitable ingredients, including additional surfactants, that may be handled as solids are described later.
- the average particle size of the neutralising agent should be less than 5 ⁇ m. The definitions for average particle size are given below.
- the high specific surface area of the particulate neutralising agent improves the efficiency of the neutralisation reaction.
- a narrow range of particle size distribution is preferred, as well as a small average particle size.
- Preferably 90% of the particles by volume have an equivalent particle size of less than 10 ⁇ m.
- the particle size of any given particle is taken to be the diameter of a spherical particle occupying the same volume as the given particle.
- the average (or median) particle size is taken to be the particle size which has 50% of the particles by volume smaller than that particle size.
- Any type of mill suitable for grinding the particulate neutralising agent to the desired particle size may be used.
- a pan-cake jet mill provided by Trade Microniser, Kent, England and an air classifier mill, supplied by Hosokawa Micron have been found to be particularly suitable.
- Useful anionic surfactant acids include organic sulphuric reaction products having in their molecular structure an alkyl group containing from about 9 to about 20 carbon atoms and a sulphonic acid.
- Examples of this group of synthetic surfactants are the alkyl benzene sulphonic acids in which the alkyl group contains from about 9 to about 15 carbon atoms in straight or branched chain configuration.
- Especially suitable anionic surfactant acids are linear alkyl benzene sulphonates in which the alkyl group contains from about 11 to about 13 carbon atoms.
- Other useful surfactant acids include alpha sulphonated fatty acid methyl esters, olefin sulphonates and beta alkyloxy alkane sulphonates. Mixtures of the above may also be used.
- liquids may be sprayed into the high shear mixer including amino polyphosphates, diethylene triamine penta acetic acid and additional anionic surfactants (as neutralised salts), nonionic, cationic, ampholytic and zwitterionic surfactants.
- Especially suitable amino polyphosphonates include diethylene triamine penta methylene phosphonic acid and ethylene diamine tetra methylene phosphonic acid.
- Especially suitable additional anionic surfactants are water-soluble salts of the higher fatty acids.
- 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 about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- Examples of 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
- anionic surfactants herein are the sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
- Water-soluble nonionic surfactants are also useful as secondary surfactant in the compositions of the invention.
- a particularly preferred paste comprises a blend of nonionic and anionic surfactants having a ratio of from about 0.01:1 to about 1:1, more preferably about 0.05:1.
- Nonionics can be used up to an equal amount of the primary organic surfactant.
- 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 about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 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 more of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 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 about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 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 about 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 about 8 to 18 carbon atoms.
- Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4R5R6R7N+X ⁇ , wherein R4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R5, R6 and R7 are each C1 to C7 alkyl preferably methyl; X ⁇ is an anion, e.g. chloride.
- Examples of such trimethyl ammonium compounds include C12 ⁇ 14 alkyl trimethyl ammonium chloride and cocalkyl trimethyl ammonium methosulfate.
- liquid ingredients anionic surfactant acids and binders
- powder ingredients are limited by the stickiness of the powder produced.
- a ratio from 1:1 to 1:4 is preferred. Most preferred is from 1:2 to 1:3.
- a preferred high shear mixer is the Loedige R CB series manufactured by Loedige Maschinenbau GmbH, Paderhorn, Germany. Operated at speed range from 500 to 2000 rpm and preferably cooled to maintain the temperature below 40°C. The residence time is from 5 to 30 seconds, preferably about 10 seconds. The resulting granules should be further processed to give finished agglomerates as described below.
- Other suitable high shear mixers are believed to be Zig-Zag Blenders manufactured by P K Niro, Denmark.
- the Eirich R batch mixers manufactured by Gustau Eirich, Hardheim, Germany. In this type of batch mixer the agglomerates may be formed directly with a mixing time of about 1 minute without the need for further processing.
- the powder stream may be fed to the high shear mixer by any suitable powder handling and conveying system.
- anionic surfactant acid and any other liquid binders will normally be pumped into the high shear mixers through conventional nozzles including spray nozzles.
- the granules made by the process described hereinabove are suitable for further processing into detergent agglomerates.
- This further processing includes the continuing neutralisation of the anionic surfactant acid by the particulate neutralising agent. This may be achieved by further mixing in a moderate speed granulator.
- Suitable mixers include the Loedige R KM mixers.
- Residence time is from 1 to 10 minutes, preferably about 5 minutes, with cooling if necessary.
- Additional liquid or powder streams may optionally be added to the moderate speed granulator, or between the two mixers. Any suitable detergent ingredient may be used, including any of those previously described above.
- the resulting particles may then be dried in one or more cooling or drying steps.
- Suitable equipment includes commercially available fluid bed driers and air lifts.
- Fine particles may be removed from the final powder stream and may be recycled into the process via the high shear mixer. Any commercially available air separation equipment, in combination, if necessary with suitable filters may be used. Suitable techniques will be familiar to the man skilled in the art. If fines removal and recycling is effectively carried out, then there will be little or no finely ground particulate neutralising agent detectable in the finished composition. However if the fines removal and recycling operation are not carried out, or are not carried out effectively, then there may some finely ground particulate neutralising agent present in the finished composition.
- the resulting agglomerates should have a bulk density greater than 650 g/l and should be crisp particles of low porosity.
- the agglomerates may be mixed with other powder ingredients to give a free-flowing granular detergent composition. Alternatively the agglomerates themselves may be used as the finished composition.
- a detergent composition made according to the present invention should comprise from 50% to 100% by weight of the agglomerates, preferably from 80% to 100%.
- detergent ingredients may be sprayed on to the granular detergent, for example, nonionic surfactants, perfumes, or added as dry powders to the agglomerates, for example, bleach and bleach activators, enzymes, polymers including polyethylene glycol
- the detergent agglomerate was prepared by dry neutralization of C11-C13 linear alkyl benzene sulphonate with sodium carbonate.
- the sodium carbonate (light soda ash ex ICI) was prepared to 5 different particle sizes as defined in samples A to E.
- agglomerates and finished compositions made according to the invention from sample A (the most finely ground carbonate) give significant benefits in cleaning performance and physical characteristics, when compared to the agglomerates and finished compositions made from samples B-E (carbonates with particle size outside of the present claimed range).
- samples B-E carbonates with particle size outside of the present claimed range.
- the above results also show that the finished detergent composition made according to the present invention from sample A show a cleaning performance comparable to an identical composition made by a conventional spray-dry process.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Priority Applications (15)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1992620773 DE69220773T2 (de) | 1992-02-14 | 1992-02-14 | Verfahren zur Herstellung von Detergenskörnchen durch Neutralisation von Sulfonsäuren |
ES92870026T ES2104884T3 (es) | 1992-02-14 | 1992-02-14 | Procedimiento para elaborar granulos de detergente por neutralizacion de acidos sulfonicos. |
EP19920870026 EP0555622B1 (de) | 1992-02-14 | 1992-02-14 | Verfahren zur Herstellung von Detergenskörnchen durch Neutralisation von Sulfonsäuren |
CA 2130007 CA2130007C (en) | 1992-02-14 | 1993-01-27 | Process for making detergent granules by neutralisation of sulphonic acids |
US08/284,591 US5486317A (en) | 1992-02-14 | 1993-01-27 | Process for making detergent granules by neutralization of sulphonic acids |
AU35955/93A AU3595593A (en) | 1992-02-14 | 1993-01-27 | Process for making detergent granules by neutralisation of sulphonic acids |
JP51410093A JP3295083B2 (ja) | 1992-02-14 | 1993-01-27 | スルホン酸の中和による洗剤粒状物の製法 |
PCT/US1993/000736 WO1993016154A1 (en) | 1992-02-14 | 1993-01-27 | Process for making detergent granules by neutralisation of sulphonic acids |
TR00093/93A TR26854A (tr) | 1992-02-14 | 1993-01-28 | Sülfonik asitlerin nötralizasyonuyla deterjan zerrelerinin yapilmasi icin islem. |
PH45691A PH31576A (en) | 1992-02-14 | 1993-02-08 | Process for making detergent granules by neutralization of sulphonic acids. |
MYPI9300204 MY130067A (en) | 1992-02-14 | 1993-02-10 | Process for making detergent granules by neutralisation of sulphonic acids |
EG20893D EG20243A (en) | 1992-02-14 | 1993-02-11 | Process for making detergent granules by neutralization of sulfonic acids |
MX9300770A MX9300770A (es) | 1992-02-14 | 1993-02-12 | Procedimiento para hacer granulos detergentes por neutralizacion de acidos sulfonicos. |
MA23088A MA22796A1 (fr) | 1992-02-14 | 1993-02-12 | Procede pour la fabrication de granules detergents par neutralisation d'acides sulfoniques. |
CN93101600A CN1054632C (zh) | 1992-02-14 | 1993-02-13 | 磺酸中和制造颗粒洗涤剂的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19920870026 EP0555622B1 (de) | 1992-02-14 | 1992-02-14 | Verfahren zur Herstellung von Detergenskörnchen durch Neutralisation von Sulfonsäuren |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0555622A1 true EP0555622A1 (de) | 1993-08-18 |
EP0555622B1 EP0555622B1 (de) | 1997-07-09 |
Family
ID=8212240
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19920870026 Expired - Lifetime EP0555622B1 (de) | 1992-02-14 | 1992-02-14 | Verfahren zur Herstellung von Detergenskörnchen durch Neutralisation von Sulfonsäuren |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0555622B1 (de) |
JP (1) | JP3295083B2 (de) |
CN (1) | CN1054632C (de) |
AU (1) | AU3595593A (de) |
CA (1) | CA2130007C (de) |
DE (1) | DE69220773T2 (de) |
EG (1) | EG20243A (de) |
ES (1) | ES2104884T3 (de) |
MA (1) | MA22796A1 (de) |
MX (1) | MX9300770A (de) |
MY (1) | MY130067A (de) |
PH (1) | PH31576A (de) |
TR (1) | TR26854A (de) |
WO (1) | WO1993016154A1 (de) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0623593A2 (de) * | 1993-05-05 | 1994-11-09 | Süd-Chemie Ag | Verfahren zur Neutralisation der Säureform von anionischen Tensiden, danach erhaltene Agglomerate und Waschmittel |
WO1996006917A1 (en) * | 1994-08-26 | 1996-03-07 | Unilever Plc | Production of anionic surfactant granules by in situ neutralisation |
WO1997032003A1 (en) * | 1996-02-29 | 1997-09-04 | The Procter & Gamble Company | Process for manufacture of high density detergent granules |
EP0853117A1 (de) * | 1997-01-13 | 1998-07-15 | Henkel Kommanditgesellschaft auf Aktien | Granulares Waschmittel mit verbessertem Fettauswaschvermögen |
WO1999000475A1 (en) * | 1997-06-27 | 1999-01-07 | Unilever Plc | Production of detergent granulates |
WO1999014308A1 (en) * | 1997-09-12 | 1999-03-25 | Izabella Bogacka | Method of obtaining everyday hygiene agents |
EP0936269A1 (de) * | 1996-09-06 | 1999-08-18 | Kao Corporation | Waschmittelteilchen, verfahren zu ihrer herstellung, sowie waschmittel mit hohem schüttgewicht |
US6056905A (en) * | 1997-06-16 | 2000-05-02 | Lever Brothers Company Division Of Conopco, Inc. | Production of detergent granulates |
WO2000032738A1 (de) * | 1998-12-01 | 2000-06-08 | Henkel Kommanditgesellschaft Auf Aktien | Granulationsverfahren |
US6207635B1 (en) | 1995-05-31 | 2001-03-27 | The Procter & Gamble Company | Process for manufacture of high density detergent granules |
US6274544B1 (en) | 1997-06-16 | 2001-08-14 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
WO2002024854A1 (en) * | 2000-09-25 | 2002-03-28 | Unilever Plc | Production of anionic surfactant granules by in situ neutralisation |
WO2002024855A1 (en) * | 2000-09-25 | 2002-03-28 | Unilever Plc | Production of anionic surfactant granules by in situ neutralisation |
US6369015B1 (en) | 1998-11-20 | 2002-04-09 | Unilever Home & Personal Care, Usa Division Of Conopco, Inc. | Particulate laundry detergent compositions containing anionic surfactant granules |
US6468957B1 (en) | 1998-09-29 | 2002-10-22 | Henkel Kommanditgesellschaft Auf Aktien | Granulation method |
US6514930B2 (en) | 2000-09-25 | 2003-02-04 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Production of anionic surfactant granules by in situ neutralisation |
WO2003054131A1 (de) * | 2001-12-21 | 2003-07-03 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur herstellung builderhaltiger tensidgranulate |
CN1116400C (zh) * | 1996-02-29 | 2003-07-30 | 普罗格特-甘布尔公司 | 制备洗涤剂附聚物的方法 |
DE10232304A1 (de) * | 2002-07-17 | 2004-02-05 | Henkel Kgaa | Neutralisation im Mischer |
WO2004053046A1 (de) * | 2002-12-12 | 2004-06-24 | Henkel Kommanditgesellschaft Auf Aktien | Trockenneutralisationsverfahren |
US7053038B2 (en) | 2001-08-13 | 2006-05-30 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Process for the production of detergent granules |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5573697A (en) * | 1995-05-31 | 1996-11-12 | Riddick; Eric F. | Process for making high active, high density detergent granules |
DE10160319B4 (de) * | 2001-12-07 | 2008-05-15 | Henkel Kgaa | Tensidgranulate und Verfahren zur Herstellung von Tensidgranulaten |
CN103773618B (zh) * | 2014-02-12 | 2015-04-01 | 浙江赞宇科技股份有限公司 | 一种连续化制备粉状洗衣粉粒子的工艺及装置 |
CN109913319B (zh) * | 2014-05-23 | 2022-03-01 | 宝洁公司 | 用于形成洗涤剂颗粒的两步中和法,以及包含所述洗涤剂颗粒的产品 |
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GB1404317A (en) * | 1971-10-23 | 1975-08-28 | Bell Chemicals Pty Ltd | Manufacture of detergent powders |
EP0420317A1 (de) * | 1989-09-29 | 1991-04-03 | Unilever N.V. | Verfahren zur Herstellung von Detergenszubereitungen mit hoher Schüttdichte |
EP0352135B1 (de) * | 1988-07-21 | 1994-09-28 | Unilever Plc | Waschmittelzusammensetzungen und Verfahren zu deren Herstellung |
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US4515707A (en) * | 1983-06-27 | 1985-05-07 | The Chemithon Corporation | Intermediate product for use in producing a detergent bar and method for producing same |
US4970017A (en) * | 1985-04-25 | 1990-11-13 | Lion Corporation | Process for production of granular detergent composition having high bulk density |
US4721580A (en) * | 1987-01-07 | 1988-01-26 | The Procter & Gamble Company | Anionic end-capped oligomeric esters as soil release agents in detergent compositions |
US4919847A (en) * | 1988-06-03 | 1990-04-24 | Colgate Palmolive Co. | Process for manufacturing particulate detergent composition directly from in situ produced anionic detergent salt |
AU612504B2 (en) * | 1988-07-21 | 1991-07-11 | Unilever Plc | Detergent compositions and process for preparing them |
JPH02273655A (ja) * | 1989-04-14 | 1990-11-08 | Teika Corp | 長鎖有機スルホン酸金属塩の製造方法 |
CA2017921C (en) * | 1989-06-09 | 1995-05-16 | John Michael Jolicoeur | Formation of detergent granules by deagglomeration of detergent dough |
GB9001285D0 (en) * | 1990-01-19 | 1990-03-21 | Unilever Plc | Detergent compositions and process for preparing them |
-
1992
- 1992-02-14 DE DE1992620773 patent/DE69220773T2/de not_active Expired - Fee Related
- 1992-02-14 ES ES92870026T patent/ES2104884T3/es not_active Expired - Lifetime
- 1992-02-14 EP EP19920870026 patent/EP0555622B1/de not_active Expired - Lifetime
-
1993
- 1993-01-27 WO PCT/US1993/000736 patent/WO1993016154A1/en active Application Filing
- 1993-01-27 JP JP51410093A patent/JP3295083B2/ja not_active Expired - Fee Related
- 1993-01-27 AU AU35955/93A patent/AU3595593A/en not_active Abandoned
- 1993-01-27 CA CA 2130007 patent/CA2130007C/en not_active Expired - Fee Related
- 1993-01-28 TR TR00093/93A patent/TR26854A/xx unknown
- 1993-02-08 PH PH45691A patent/PH31576A/en unknown
- 1993-02-10 MY MYPI9300204 patent/MY130067A/en unknown
- 1993-02-11 EG EG20893D patent/EG20243A/xx active
- 1993-02-12 MA MA23088A patent/MA22796A1/fr unknown
- 1993-02-12 MX MX9300770A patent/MX9300770A/es not_active IP Right Cessation
- 1993-02-13 CN CN93101600A patent/CN1054632C/zh not_active Expired - Fee Related
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GB1404317A (en) * | 1971-10-23 | 1975-08-28 | Bell Chemicals Pty Ltd | Manufacture of detergent powders |
EP0352135B1 (de) * | 1988-07-21 | 1994-09-28 | Unilever Plc | Waschmittelzusammensetzungen und Verfahren zu deren Herstellung |
EP0420317A1 (de) * | 1989-09-29 | 1991-04-03 | Unilever N.V. | Verfahren zur Herstellung von Detergenszubereitungen mit hoher Schüttdichte |
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Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0623593A3 (de) * | 1993-05-05 | 1998-05-27 | Süd-Chemie Ag | Verfahren zur Neutralisation der Säureform von anionischen Tensiden, danach erhaltene Agglomerate und Waschmittel |
EP0623593A2 (de) * | 1993-05-05 | 1994-11-09 | Süd-Chemie Ag | Verfahren zur Neutralisation der Säureform von anionischen Tensiden, danach erhaltene Agglomerate und Waschmittel |
AU702856B2 (en) * | 1994-08-26 | 1999-03-04 | Unilever Plc | Production of anionic surfactant granules by in situ neutralisation |
WO1996006917A1 (en) * | 1994-08-26 | 1996-03-07 | Unilever Plc | Production of anionic surfactant granules by in situ neutralisation |
US5641741A (en) * | 1994-08-26 | 1997-06-24 | Lever Brothers Company, Division Of Conopco, Inc. | Production of anionic surfactant granules by in situ neutralization |
USRE37949E1 (en) | 1994-08-26 | 2002-12-31 | Lever Brothers Company, Division Of Conopco, Inc. | Production of anionic surfactant granules by in situ neutralization |
US6207635B1 (en) | 1995-05-31 | 2001-03-27 | The Procter & Gamble Company | Process for manufacture of high density detergent granules |
WO1997032003A1 (en) * | 1996-02-29 | 1997-09-04 | The Procter & Gamble Company | Process for manufacture of high density detergent granules |
CN1116400C (zh) * | 1996-02-29 | 2003-07-30 | 普罗格特-甘布尔公司 | 制备洗涤剂附聚物的方法 |
US6992055B1 (en) * | 1996-09-06 | 2006-01-31 | Kao Corporation | Process for preparing detergent compositions having high bulk density |
EP0936269A1 (de) * | 1996-09-06 | 1999-08-18 | Kao Corporation | Waschmittelteilchen, verfahren zu ihrer herstellung, sowie waschmittel mit hohem schüttgewicht |
EP0936269A4 (de) * | 1996-09-06 | 2001-01-10 | Kao Corp | Waschmittelteilchen, verfahren zu ihrer herstellung, sowie waschmittel mit hohem schüttgewicht |
EP0853117A1 (de) * | 1997-01-13 | 1998-07-15 | Henkel Kommanditgesellschaft auf Aktien | Granulares Waschmittel mit verbessertem Fettauswaschvermögen |
US6056905A (en) * | 1997-06-16 | 2000-05-02 | Lever Brothers Company Division Of Conopco, Inc. | Production of detergent granulates |
US6274544B1 (en) | 1997-06-16 | 2001-08-14 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US6429184B1 (en) | 1997-06-16 | 2002-08-06 | Lever & Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US6133223A (en) * | 1997-06-27 | 2000-10-17 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
WO1999000475A1 (en) * | 1997-06-27 | 1999-01-07 | Unilever Plc | Production of detergent granulates |
WO1999014308A1 (en) * | 1997-09-12 | 1999-03-25 | Izabella Bogacka | Method of obtaining everyday hygiene agents |
US6468957B1 (en) | 1998-09-29 | 2002-10-22 | Henkel Kommanditgesellschaft Auf Aktien | Granulation method |
US6369015B1 (en) | 1998-11-20 | 2002-04-09 | Unilever Home & Personal Care, Usa Division Of Conopco, Inc. | Particulate laundry detergent compositions containing anionic surfactant granules |
WO2000032738A1 (de) * | 1998-12-01 | 2000-06-08 | Henkel Kommanditgesellschaft Auf Aktien | Granulationsverfahren |
WO2002024854A1 (en) * | 2000-09-25 | 2002-03-28 | Unilever Plc | Production of anionic surfactant granules by in situ neutralisation |
US6518234B2 (en) | 2000-09-25 | 2003-02-11 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Production of anionic surfactant granules by in situ neutralisation |
US6518233B2 (en) | 2000-09-25 | 2003-02-11 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Production of anionic surfactant granules by in situ neutralization |
US6514930B2 (en) | 2000-09-25 | 2003-02-04 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Production of anionic surfactant granules by in situ neutralisation |
WO2002024855A1 (en) * | 2000-09-25 | 2002-03-28 | Unilever Plc | Production of anionic surfactant granules by in situ neutralisation |
US7053038B2 (en) | 2001-08-13 | 2006-05-30 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Process for the production of detergent granules |
WO2003054131A1 (de) * | 2001-12-21 | 2003-07-03 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur herstellung builderhaltiger tensidgranulate |
DE10163603B4 (de) * | 2001-12-21 | 2006-05-04 | Henkel Kgaa | Verfahren zur Herstellung builderhaltiger Tensidgranulate |
US7186677B2 (en) | 2001-12-21 | 2007-03-06 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Method for the production of surfactant granulates containing builders |
DE10232304A1 (de) * | 2002-07-17 | 2004-02-05 | Henkel Kgaa | Neutralisation im Mischer |
DE10232304B4 (de) * | 2002-07-17 | 2005-10-27 | Henkel Kgaa | Neutralisation im Mischer |
WO2004053046A1 (de) * | 2002-12-12 | 2004-06-24 | Henkel Kommanditgesellschaft Auf Aktien | Trockenneutralisationsverfahren |
Also Published As
Publication number | Publication date |
---|---|
MX9300770A (es) | 1993-09-30 |
TR26854A (tr) | 1994-08-19 |
CN1054632C (zh) | 2000-07-19 |
MY130067A (en) | 2007-05-31 |
JPH07503750A (ja) | 1995-04-20 |
WO1993016154A1 (en) | 1993-08-19 |
CA2130007C (en) | 1998-08-25 |
PH31576A (en) | 1998-11-03 |
EP0555622B1 (de) | 1997-07-09 |
CN1075332A (zh) | 1993-08-18 |
EG20243A (en) | 1998-05-31 |
ES2104884T3 (es) | 1997-10-16 |
JP3295083B2 (ja) | 2002-06-24 |
AU3595593A (en) | 1993-09-03 |
MA22796A1 (fr) | 1993-10-01 |
DE69220773T2 (de) | 1998-02-12 |
DE69220773D1 (de) | 1997-08-14 |
CA2130007A1 (en) | 1993-08-15 |
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