EP0508543B1 - Chemical structuring of surfactant pastes to form high active surfactant granules - Google Patents
Chemical structuring of surfactant pastes to form high active surfactant granules Download PDFInfo
- Publication number
- EP0508543B1 EP0508543B1 EP92200994A EP92200994A EP0508543B1 EP 0508543 B1 EP0508543 B1 EP 0508543B1 EP 92200994 A EP92200994 A EP 92200994A EP 92200994 A EP92200994 A EP 92200994A EP 0508543 B1 EP0508543 B1 EP 0508543B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- paste
- surfactant
- extruder
- process according
- alkyl
- 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
Links
- 239000004094 surface-active agent Substances 0.000 title claims description 68
- 239000000126 substance Substances 0.000 title claims description 22
- 239000008187 granular material Substances 0.000 title description 24
- 238000000034 method Methods 0.000 claims description 64
- 230000008569 process Effects 0.000 claims description 58
- 239000003599 detergent Substances 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 34
- 238000005469 granulation Methods 0.000 claims description 32
- 230000003179 granulation Effects 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 29
- 239000003945 anionic surfactant Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000003750 conditioning effect Effects 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002736 nonionic surfactant Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 description 37
- -1 alkyl sulfate acids Chemical class 0.000 description 29
- 239000011734 sodium Substances 0.000 description 29
- 229910052708 sodium Inorganic materials 0.000 description 27
- 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 26
- 125000000217 alkyl group Chemical group 0.000 description 26
- 239000002245 particle Substances 0.000 description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 23
- 150000003839 salts Chemical class 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 229910000323 aluminium silicate Inorganic materials 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 18
- 238000005342 ion exchange Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 13
- 238000005054 agglomeration Methods 0.000 description 12
- 230000002776 aggregation Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000003760 tallow Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000007859 condensation product Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 159000000001 potassium salts Chemical class 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 239000003093 cationic surfactant Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 5
- 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
- 230000000704 physical effect Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000008051 alkyl sulfates Chemical class 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920013820 alkyl cellulose Polymers 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 239000002563 ionic surfactant Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000002888 zwitterionic surfactant Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 150000001253 acrylic acids Chemical class 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 150000002689 maleic acids Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 235000014366 other mixer Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000007858 starting material 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 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
- 229920002153 Hydroxypropyl cellulose Polymers 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
- 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 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
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon 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
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000029087 digestion Effects 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000011552 falling film Substances 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
- 239000010408 film Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229960002598 fumaric acid Drugs 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
- 159000000011 group IA salts Chemical class 0.000 description 1
- 238000010438 heat treatment 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 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
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 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
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical class CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- LUIGSJYSMIUMPK-UHFFFAOYSA-N propane-1-sulfonoperoxoic acid Chemical class CCCS(=O)(=O)OO LUIGSJYSMIUMPK-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 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
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 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
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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 compositions comprising condensed detergent granules.
- Granular detergent compositions 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 is expensive.
- a good agglomeration process could be less expensive.
- Spray drying requires 30-40 wt. % of the water to be removed.
- the equipment used to produce spray dry is expensive.
- the granule obtained has good solubility but a low bulk density, so the packing volume is large.
- the flow properties of the granule obtained by spray drying are adversely affected by large surface irregularities, and thus the granulate has a poor appearance.
- EP-A-0 110 731 published August 13, 1984, discloses processes for making detergent powders by mixing surfactant solutions in a neat phase, with builder powders in order to form a solid without any evaporative drying. Processes for solid bars or blocks for milling are described, but there is no teaching of paste conditioning to directly form high active granules by agglomeration.
- EP-A-0 345 090 discloses a process for manufacturing particulate detergent compositions comprising contacting detergent acid with neutralizing agents and providing particulates by contacting the detergent acid with a particulate neutralizing agent or detergent salt with carrier in an absorption zone.
- EP-A-0 349 201 published on January 3, 1990
- EP-A-0 402 111 published on 12th December 1990, both disclose a process for preparing condensed detergent granules by mixing dry detergent builders and high active surfactant paste to form a uniform dough, which is subsequently granulated using fine dispersion to form uniform, free flowing particles.
- the dough is chilled to a temperature of -25°C to 20°C, prior to "cold" granulation.
- One problem associated with the processes of both EP-A-0 349 201 and EP-A-0 402 111 is that the dough is too viscous to be pumped, stored, transported or otherwise handled, especially in large, industrial quantities.
- EP-A-0 403 148 published on 19th December 1990, discloses an alternative granulation process wherein very high active pastes are mixed, with mechanical work input, above their solidification point. The pastes are then chilled, or allowed to cool to low temperatures at which the paste solidifies. The resulting solid is subsequently formed into granules by a suitable size reduction process e.g. by grinding or extrusion after the worked paste has been allowed to come to room temperature.
- EP-0 390 251 discloses a process for the continuous preparation of a granular detergent or composition comprising steps of treating, firstly, particulate starting material of detergent surfactant and builders in a high-spead mixer, secondly in a moderate-speed granulator/densifier and thirdly in a drying/cooling apparatus, with the addition of powder in the second or between the first and second step to reduce the amount of oversize particles.
- a second route is the in-situ neutralisation of the anionic surfactant acid with caustic solutions (e.g. 50% NaOH) or caustic powders (e.g. Na 2 CO 3 ) right before or in the course of the granulation step.
- caustic solutions e.g. 50% NaOH
- caustic powders e.g. Na 2 CO 3
- precautions are needed to ensure complete neutralisation of the acid to avoid undesirable effects on the rest of the surfactant matrix upon storage/or during the wash.
- the resulting particle is a highly dense granule which can be incorporated into granular detergents.
- the present invention brings solutions to the problems mentioned above and provides with a more flexible and versatile route to the processing of granular detergents.
- the present invention is based on an agglomeration/ granulation step that is completely uncoupled from the sulphation/sulphonation process.
- the present invention enables the increase in the ratio of paste to powder that can be formed into crisp granules. This is achieved by a chemical structuring of the paste by the addition of specific chemical structuring agents.
- the basis of the invention is the introduction of the anionic surfactant in an aqueous, highly concentrated solution of its salt, most preferably of its sodium salt.
- high active (low moisture) surfactant pastes are of a high viscosity but remain pumpable at temperatures at which the surfactants are stable. This guarantees the ability to transport and transfer the chemical from the manufacturing location to the granulation site and to be able to have adequate storage facilities prior to the formation of a particle. For those cases where both the sulphation/sulphonation is already immediately preceding the granulation step, it provides the possibility to install intermediate buffer tanks that simplifies the control of the whole unit. In the case of some anionic surfactants or mixtures of them where highly viscous liquid crystal phases occur, this technology requires that either lower viscous phases can be formed (e.g. neat phases) or that some viscosity modifiers are used (e.g. hydrotropes).
- the present invention also describes a process for carrying out the conditioning of the paste. It has been discovered that the addition of the chemical structuring agents, is critical to physical properties such as viscosity, melting point and stickiness which in turn determine the characteristics of the detergent granules made by mixing/granulation of the paste. It has been found that a very effective way to achieve this paste conditioning is to use an extruder.
- An important object of the present invention is to make a dense, concentrated detergent granular product by an agglomeration process as opposed to a spray-drying process.
- Other objects of the present invention will be apparent in view of the following.
- the present invention relates to an economical process for making a dense, concentrated detergent granular product, and particularly, compositions comprising very high active condensed detergent granules, wherein said process comprises high active paste agglomeration steps coupled with chemical treatment of the resultant paste.
- the present invention is particularly applicable to all neutralized AS aqueous pastes. It may prove applicable to a wide variety of surfactants.
- the present invention relates to a process for making a free flowing granular detergent comprising : mixing an effective amount of a chemical structuring agent and an effective amount of an aqueous surfactant paste having a detergency activity of at least 40%; rapidly forming a uniform stiff paste from said mix at a paste temperature of at least 20°C but excluding 20°C; granulating said paste upon mixing with a dry detergent powder wherein said surfactant paste is comprised of at least one anionic surfactant, and any other surfactants, if present, are selected from the group of anionic, nonionic, zwitterionic, ampholytic and cationic surfactants and mixtures thereof.
- said chemical structuring agent is added in a continuous process.
- the present invention is based on a process for producing high active surfactant pastes, having an agglomeration/ granulation step that is completely uncoupled from the sulphation/sulphonation process, and, additionally, a chemical conditioning of the pastes produced by said process to obtain high active granules.
- Conditioning of a paste means the modifying its physical characteristics to form higher active agglomerates which otherwise are not easily obtainable under normal operating conditions.
- the present invention is particularly applicable to all neutralized AS aqueous pastes. It may prove applicable to a wide variety of surfactants (e.g. Coco, Tallow, ... etc).
- high active (and, preferably, low moisture) surfactant pastes are of a high viscosity but remain pumpable at temperatures at which the surfactants are stable.
- anionic surfactants or mixtures comprising at least one anionic surfactant, where highly viscous liquid crystal phases occur requires that either lower viscous phases be formed or that some viscosity modifiers are used.
- Chemical structuring agents are organic and/or inorganic compounds that alter the physical structure and/or physical characteristics of the surfactant paste when added to the paste. It has been found that the addition to the surfactant paste reduces the stickiness of the paste, increases its viscosity and increases its softening point. This allows for more paste to be added during the agglomeration process thus leading to higher active agglomerates i.e. more than 50%.
- This method of treating the surfactant paste can be performed batchwise and continuous, preferably continuously.
- an extruder is used to condition the paste.
- the extruder is a versatile piece of equipment which enables two or more pastes to be mixed and/or the chemical structuring agents to be added to, and mixed with the viscous paste. Furthermore it enables moisture to be removed under vacuum, and it enables control of paste temperature.
- Conditioning of the paste means: a) increasing its apparent viscosity, b) increasing its effective melting point, c) increasing the "hardness" of the paste and d) decreasing the stickiness of the granules formed.
- the hardness/softness of the paste may be measured by a softness penetrometer according to ASTM D 217-IP50 or ISO 2137.
- Paste hardness measured in this way should be less than 2 cm, preferably less than 1 cm.
- This paste conditioning is achieved by adding of structurants (usually electolytes) to the high active detergent paste.
- a paste useful for this invention will consist of at least 40% by weight of salts of anionic surfactants, which has a viscosity of at least 10 Pa.s when measured at 70°C and a shear rate of 25s -1 .
- agents when added to the surfactant paste, result in a modification of the chemical and/or physical characteristics of the paste to form very high active agglomerates.
- These agents may be in a solid, liquid or solution form, depending on their specific chemical properties.
- agents useful in the present invention include 50% NaOH (aq), 50% KOH (aq), NaCl, phosphonate, silicate, silica, starch, polymers and copolymers, nonionic surfactant and urea.
- the agents above can be used independently or in combination with each other, in accordance with their compatability.
- One or various aqueous pastes of the salts of anionic surfactants is preferred for use in the present invention, preferably the sodium salt of the anionic surfactant.
- the anionic surfactant is preferably as concentrated as possible, (that is, with the lowest possible moisture content that allows it to flow in the manner of a liquid) so that it can be pumped at temperatures at which it remains stable. While granulation using various pure or mixed surfactants is known, for the present invention to be of practical use in industry and to result in particles of adequate physical properties to be incorporated into granular detergents, an anionic surfactant must be part of the paste in a concentration of above 40%, preferably from 40-95%.
- the moisture in the surfactant aqueous paste is as low as possible, while maintaining paste fluidity, since low moisture leads to a higher concentration of the surfactant in the finished particle.
- the paste contains between 5 and 40% water, more preferably between 5 and 30% water and most preferably between 5% and 20% water.
- high active surfactant pastes it is preferable to use high active surfactant pastes to minimize the total water level in the system during mixing, granulating and drying.
- Lower water levels allow for: (1) a higher active surfactant to builder ratio, e.g., 1:1; (2) higher levels of other liquids in the formula without causing dough or granular stickiness; (3) less cooling, due to higher allowable granulation temperatures; and (4) less granular drying to meet final moisture limits.
- Viscosity is a function, among others, of concentration and temperature, with a range in this application from about 10 Pa.s to 10,000 Pa.s
- the viscosity of the paste entering the system is from about 20 Pa.s to 100 Pa.s. and more preferably from 30 to 70 Pa.s.
- the viscosity of the paste of this invention is measured at a temperature of 70°C.
- the paste can be introduced into the mixer at an initial temperature between its softening point (generally in the range of 40-60°C) and its degradation point (depending on the chemical nature of the paste, e.g. alkyl sulphate pastes tend to degrade above 75-85°C).
- High temperatures reduce viscosity simplifying the pumping of the paste but result in lower active agglomerates.
- in-line moisture reduction steps e.g. flash drying
- the activity of the agglomerates is maintained high due to the elimination of moisture.
- the introduction of the paste into the mixer can be done in many ways, from simply pouring to high pressure pumping through small holes at the end of the pipe, before the entrance to the mixer. While all these ways are viable to manufacture agglomerates with good physical properties, it has been found that in a preferred embodiment of the present invention the extrusion of the paste results in a better distribution in the mixer which improves the yield of particles with the desired size.
- the use of high pumping pressures prior to the entrance in the mixer results in an increased activity in the final agglomerates.
- the activity of the aqueous surfactant paste is at least 40% and can go up to about 95%; preferred activities are : 50-80% and 65-75%.
- the balance of the paste is primarily water but can include a processing aid such as a nonionic surfactant. At the higher active concentrations, little or no builder is required for cold granulation of the paste.
- the resultant concentrated surfactant granules can be added to dry builders or powders or used in conventional agglomeration operations.
- the aqueous surfactant paste contains an organic surfactant selected from the group consisting of anionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof. Anionic surfactants are preferred.
- Nonionic surfactants are used as secondary surfactants or processing aids and are not included herein as an "active" surfactant.
- 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. 4,239,659, Murphy, issued Dec. 16, 1980.
- cationic surfactants are generally less compatible with the aluminosilicate materials herein, and thus are preferably used at low levels, if at all, in the present compositions. 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 about 10 to about 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 (C 8 -C 18 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 about 9 to about 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 C 11 -C 13 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.
- Suitable 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 about 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; watersoluble 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 acid salts are typically discussed and used, the acid neutralization cam be performed as part of the
- 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.
- Water-soluble nonionic surfactants are also useful as secondary surfactant in the compositions of the invention. Indeed, preferred processes use anionic/nonionic blends.
- a particularly preferred paste comprises a blend of nonionic and anionic surfactants having a ratio of from 0.01:1 to 1:1, more preferably 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 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 more 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.
- Particularly preferred surfactants herein include linear alkylbenzene sulfonates containing from 11 to 14 carbon atoms in the alkyl group; tallow alkyl sulfates; coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from 14 to 18 carbon atoms and wherein the average degree of ethoxylation is from 1 to 4; olefin or paraffin sulfonates containing from 14 to 16 carbon atoms; alkyldimethylamine oxides wherein the alkyl group contains from 11 to 16 carbon atoms; alkyldimethylammonio propane sulfonates and alkyldimethylammonio hydroxy propane sulfonates wherein the alkyl group contains from 14 to 18 carbon atoms; soaps of higher fatty acids containing from 12 to 18 carbon atoms; condensation products of C9-C15 alcohols with from 3 to 8 moles of
- Useful cationic surfactants include.
- Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R 4 R 5 R 6 R 7 N + X - , wherein R 4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R 5 , R 6 and R 7 are each C 1 to C 7 alkyl preferably methyl; X - is an anion, e.g. chloride.
- Examples of such trimethyl ammonium compounds include C 12-14 alkyl trimethyl ammonium chloride and cocalkyl trimethyl ammonium methosulfate.
- Specific preferred surfactants for use herein include: sodium linear C 11 -C 13 alkylbenzene sulfonate; ⁇ -olefin sulphonates; triethanolammonium C 11 -C 13 alkylbenzene sulfonate; alkyl sulfates, (tallow, coconut, palm, synthetic origins, e.g.
- surfactant means non-nonionic surfactants, unless otherwise specified).
- the extruder fulfils the functions of pumping and mixing the viscous surfactant paste on a continuous basis.
- a basic extruder consists of a barrel with a smooth inner cylindrical surface. Mounted within this barrel is the extruder screw. There is an inlet port for the high active paste which, when the screw is rotated, causes the paste to be moved along the length of the barrel.
- the detailed design of the extruder allows various functions to be carried out. Firstly additional ports in the barrel may allow other ingredients, including the chemical structuring agents to be added directly into the barrel. Secondly a vacuum pump and a seal around the shaft of the screw allows a vacuum to be drawn which enables the moisture level to be reduced. Thirdly means for heating or cooling may be installed in the wall of the barrel for temperature control.
- a preferred extruder is the twin screw extruder. This type of extruder has two screws mounted in parallel within the same barrel, which are made to rotate either in the same direction (co-rotation) or in opposite directions (counter-rotation).
- the co-rotating twin screw extruder is the most preferred piece of equipment for use in this invention.
- An extruder is particularly useful in this invention because the paste can be effectively cooled by adding liquid nitrogen or solid carbon dioxide into the barrel (this may be considered surprising, because normally an extruder heats its contents as a result of the mechanical energy input to overcome viscous shear forces) and at the same time pumps the increasingly viscous (colder) paste out of the extruder and into the mixer/agglomerator were granulation takes place.
- Suitable twin screw extruders for use in the present invention include those supplied by : APV Baker, (CP series); Werner and Pfleiderer, (Continua Series); Wenger, (TF Series); Leistritz, (ZSE Series); and Buss, (LR Series).
- the extruder allows moisture and temperature reduction. Moisture may be removed under vacuum, preferably between O mmHg (gauge) and -55 mmHg (gauge), (0 - 7.3 kPa below atmospheric pressure).
- Temperature may be reduced by the addition of solid carbon dioxide or liquid nitrogen directly into the extruder barrel.
- liquid nitrogen is used at up to 30% by weight of the paste.
- the preferred embodiment of the process of the present invention involves introduction of the anionic surfactant in via pastes as described above, it is possible to have a certain amount via the powder stream, for example in the form of blown powder. In these embodiments, it is necessary that the stickiness and moisture of the powder stream be kept at low levels, thus preventing increased "loading" of the anionic surfactant and, thus, the production of agglomerates with too high of a concentration of surfactant.
- the liquid stream of a preferred agglomeration process can also be used to introduce other surfactants and/or polymers. This can be done by premixing the surfactant into one liquid stream or, alternatively by introducing various streams in the agglomerator.
- fine dispersion mixing and/or granulation means mixing and/or granulation of the above mixture in a fine dispersion mixer at a blade tip speed of from 5m/sec. to 50 m/sec., unless otherwise specified.
- the total residence time of the mixing and granulation process is preferably in the order of from 0.1 to 10 minutes, more preferably 0.1-5 and most preferably 0.2-4 minutes.
- the more preferred mixing and granulation tip speeds are 10-45 m/sec. and 15-40 m/sec.
- the ratio of paste to powder should be chosen in order to maintain visible, discrete particles at all stages of the process. These particles may be sticky at higher temperatures but must be substantially free flowing so that the mixing and granulation steps can be carried out simultaneously, or immediately sequentially without causing blockage of the mixer/granulator.
- Suitable apparatus includes, for example, falling film sulphonating reactors, digestion tanks, esterification reactors, etc.
- any of a number of mixers/agglomerators can be used.
- the process of the invention is continuously carried out.
- mixers of the Fukae R FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are especially preferred.
- this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
- the stirrer and cutter may be operated independently of one another and at separately variable speeds.
- the vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
- mixers found to be suitable for use in the process of the invention inlcude Diosna R V series ex Dierks & Söhne, Germany; and the Pharma Matrix R ex T K Fielder Ltd., England.
- Other mixers believed to be suitable for use in the process of the invention are the Fuji R VG-C series ex Fuji Sangyo Co., Japan; and the Roto R ex Zanchetta & Co srl, Italy.
- Other preferred suitable equipment can include Eirich R , series RV, manufactured by Gustau Eirich Hardheim, Germany; Lödige R , series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lödige Machinenbau GmbH, Paderborn Germany; Drais R T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth R RT 25 series, manufactured by Winkworth Machinery Ltd., Bershire, England.
- 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 having 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.
- Preferred operating temperatures should also be as low as possible since this leads to a higher surfactant concentration in the finished particle.
- the temperature during the agglomeration is less than 100°C, more preferably between 20 and 90°C, and most preferably between 20 and 80°C, but excluding 20°C.
- Lower operating temperatures useful in the process of the present invention may be achieved by a variety of methods known in the art such as nitrogen cooling, cool water jacketing of the equipment, addition of solid CO 2 , and the like; with a preferred method being solid CO 2 , and the most preferred method being nitrogen cooling.
- a highly attractive option in a preferred embodiment of the present invention to further increase the concentration of surfactant in the final particle is accomplished by the addition to a liquid stream containing the anionic surfactant and/or other surfactant, of other elements that result in increases in viscosity and/or melting point and/or decrease the stickiness of the paste.
- the addition of these elements can be done in line as the paste is pumped into the agglomerator.
- Example of these elements can be various powders, described in more detail herein.
- the present invention produces granules of high density for use in detergent compositions.
- a preferred composition of the final agglomerate for incorporation into granular detergents has a high surfactant concentration.
- the particles/agglomerates made by the present invention are more suitable for a variety of different formulations.
- These high surfactants containing particle agglomerates require fewer finishing techniques to reach the final agglomerates, thus freeing up large amounts of processing aids (inorganic powders, etc.) that can be used in other processing steps of the overall detergent manufacturing process (spray drying, dusting off, etc).
- the granules made according to the present invention are large, low dust and free flowing, and preferably have a bulk density of from 0.4 to 1.2 g/cc, more preferably from 0.6 to 0.8 g/cc.
- the weight average particle size of the particles of this invention are from 200 to 1000 microns.
- the preferred granules so formed have a particle size range of from 200 to 2000 microns.
- the more preferred granulation temperatures range from 20°C to 60°C, and most preferably from 20°C to 50°C, but excluding 20°C.
- the desired moisture content of the free flowing granules of this invention can be adjusted to levels adequate for the intended application by drying in conventional powder drying equipment such as fluid bed dryers. If a hot air fluid bed dryer is used, care must be exercised to avoid degradation of heat sensitive components of the granules. It is also advantageous to have a cooling step prior to large scale storage. This step can also be done in a conventional fluid bed operated with cool air. The drying/cooling of the agglomerates can also be done in any other equipment suitable for powder drying such as rotary dryers, etc.
- the final moisture of the agglomerates needs to be maintained below levels at which the agglomerates can be stored and transported in bulk.
- the exact moisture level depends on the composition of the agglomerate but is typically achieved at levels of 1-8% free water (i.e. water not associated to any crystalline species in the agglomerate) and most typically at 2-4%.
- Any compatible detergency builder or combination of builders or powder can be used in the process and compositions of the present invention.
- the detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula Na z [(AlO 2 ) z ⁇ (SiO 2 ) y ] ⁇ xH 2 O wherein z and y are at least about 6, the molar ratio of z to y is from 1.0 to 0.4 and z is from 10 to 264.
- Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zAlO 2 ⁇ ySiO 2 ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from 1 to 10 microns is preferred.
- the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from 10% to 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from 18% to 22% water in their crystal matrix.
- the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from 0.1 micron to 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron.
- Preferred ion exchange materials have a particle size diameter of from 0.2 micron to 4 microns.
- particle size diameter herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
- the crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg equivalent of CaCO 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
- the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from 2 grains/gallon/minute/gram/gallon to 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness.
- Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
- the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange of at least about 50 mg eq. CaCO 3 /g (12 mg Mg ++ /g) and a Mg ++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
- Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
- the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
- a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976, incorporated herein by reference.
- Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X.
- the crystalline aluminosilicate ion exchange material has the formula Na 12 [(AlO 2 ) 12 (SiO2) 12 ] ⁇ xH 2 O wherein x is from 20 to 30, especially about 27 and has a particle size generally less than about 5 microns.
- 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 examples include the alkali metal, ammonium or substituted ammonium chlorides, 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.
- Citric acid and, in general, any other organic or inorganic acid may be incorporated into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
- 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 polyhyroxysulfonates.
- 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 SiO 2 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.
- powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate, etc. and process acids such as starch, can be used in preferred embodiments of the present invention.
- organic polymers are also useful as builders to improve detergency. Included among such polymers may be mentioned sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate), polyacrylamides, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000.
- Polymeric polycarboxyate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
- compositions of the present invention can be included in the compositions of the present 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.
- the detergent granules of the present invention are particularly useful in a pouched through-the-wash product.
- Materials like sodium perborate tetrahydrate and monohydrate can be included as part of the granular detergent compositions of this invention.
- Pouched through-the-wash products are disclosed in the art, e.g., those disclosed in commonly assigned U.S. Pat. No. 4,740,326, Hortel et al., issued April 26, 1988.
- Another useful pouch has at least one of its walls constructed of a finely apertured polymeric film.
- LAS and “AS” as used herein mean, respectively, “sodium lauryl benzene sulfonate” and “alkyl sulfate.”
- MES means sodium methyl ester sulphonate.
- C 45 mean C 14 and C 15 alkyl, unless otherwise specified.
- TAS means Tallow alkyl sulphate.
- This Example describes the process in batch mode in a pilot plant scale high shear mixer, an Eirich® RV02.
- the powders to be used are in this particular case a 2:1 ratio of Zeolite A to finely divided carbonate or Zeolite A to finely divided citrate.
- the surfactant is an aqueous paste of C 45 AS with a detergent activity of 78% and a water content of 13%.
- a 50% solution of NaOH (0.6 kg) is added to the paste (3 kg) in the mixer (the Eirich® RV 02) before starting the granulation.
- the paste solidifies and is ground by the mixer at 2500 rpm.
- the process is stopped and the powders (1.050 kg) are added.
- the mixer is operated until granulation takes place.
- the process is then stopped and the agglomerates are dried in a fluid bed and classified through mesh sieves.
- the agglomerates made have a detergent activity of 60% and a density of 600 g/L. They show excellent physical properties.
- This Example describes the process in batch mode in a lab scale high shear mixer (food processor).
- the powders to be used are in this particular case a 2:1 ratio of Zeolite A to finely divided sodium carbonate.
- the surfactant is an aqueous paste of C45 AS with detergent activity of 72% and a water content of 24%.
- silica powder 40 g
- silica powder 40 g
- the paste 400 g
- the paste stiffens.
- the process is stopped and the powders (105 g) are added to the paste (335 g).
- the mixer is operated until granulation takes place.
- the process is then stopped and the agglomerates are dried in a fluid bed and classified through mesh sieves.
- the agglomerates made have a detergent activity of 55-60% and a density of 650 g/L. they show excellent physical properties.
- This example describes the process of paste conditioning in continuous mode in a pilot plant twin screw extruder, Werner and Pfleiderer® C58 with a barrel in six sections, followed by immediate granulation of the paste exiting the extruder in a lab scale high shear mixer.
- the surfactant is an aqueous paste of sodium linear alkyl benzene sulphonate (NaLAS) with a detergent activity of 78% and a water content of 18%.
- NaLAS sodium linear alkyl benzene sulphonate
- the paste is introduced into the extruder at a temperature of 70°C and at a flow rate of 150 kg/hr.
- the paste exiting the extruder is agglomerated in the lab scale high shear mixer with a ratio of 2:1 by weight of zeolite A to finely divided carbonate powders.
- the paste is added to the bed of powders until agglomerates of average particle size between 400 and 800 ⁇ m are obtained.
- the agglomerates are then dried in a fluid bed and analysed for LAS content (described herein as activity).
- the paste is simply pumped through the extruder which is operated between 100 and 120 rpm.
- the paste exiting the extruder is still at 70°C and the activity of the resulting agglomerates is 32%.
- Agglomerates are made using the same equipment and weight ratios as described in comparative example 3.
- a solid powder of a copolymer of maleic and acrylic acids is added to the paste at the inlet of the extruder. Without any cooling, the paste temperature exiting the extruder is 68°C and the activity of the resulting agglomerates is 38%.
- Agglomerates are made using the same equipment and weight ratios as described in comparative example 3. However in this example the NaLAS is replaced by a surfactant paste containing 60% by weight of sodium alkyl sulphate with a carbon chain length of C14-C15 and containing 25% water. The inlet temperature is again 70°C. The paste is simply pumped through the extruder and exits at a temperature of 70°C. The activity of the resulting agglomerates is 36%.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP91870060 | 1991-04-12 | ||
EP91870060 | 1991-04-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0508543A1 EP0508543A1 (en) | 1992-10-14 |
EP0508543B1 true EP0508543B1 (en) | 1997-08-06 |
Family
ID=8209015
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92200994A Expired - Lifetime EP0508543B1 (en) | 1991-04-12 | 1992-04-07 | Chemical structuring of surfactant pastes to form high active surfactant granules |
Country Status (20)
Country | Link |
---|---|
EP (1) | EP0508543B1 (hu) |
JP (1) | JP3225041B2 (hu) |
CN (1) | CN1042746C (hu) |
AU (1) | AU1870092A (hu) |
BR (1) | BR9205890A (hu) |
CA (1) | CA2108166C (hu) |
CZ (1) | CZ213793A3 (hu) |
DE (1) | DE69221357T2 (hu) |
EG (1) | EG20046A (hu) |
ES (1) | ES2104809T3 (hu) |
FI (1) | FI934463A0 (hu) |
HU (1) | HUT66724A (hu) |
IE (1) | IE921162A1 (hu) |
MX (1) | MX9201721A (hu) |
NO (1) | NO933641L (hu) |
PT (1) | PT100371A (hu) |
SK (1) | SK108493A3 (hu) |
TR (1) | TR26814A (hu) |
TW (1) | TW200524B (hu) |
WO (1) | WO1992018602A1 (hu) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7186677B2 (en) | 2001-12-21 | 2007-03-06 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Method for the production of surfactant granulates containing builders |
Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE172240T1 (de) * | 1992-07-15 | 1998-10-15 | Procter & Gamble | Waschmittelzusammensetzungen |
EP0618289B1 (en) * | 1993-03-30 | 1998-08-19 | The Procter & Gamble Company | High active granular detergents comprising chelants and polymers, and processes for their preparation |
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 |
EP0663439B1 (en) * | 1994-01-17 | 2000-08-16 | The Procter & Gamble Company | Process for preparing detergent granules |
US5703037A (en) * | 1994-04-20 | 1997-12-30 | The Procter & Gamble Company | Process for the manufacture of free-flowing detergent granules |
ES2152286T3 (es) * | 1994-04-20 | 2001-02-01 | Procter & Gamble | Procedimiento de fabricacion de granulos de detergente que fluyen libremente. |
US5565137A (en) * | 1994-05-20 | 1996-10-15 | The Proctor & Gamble Co. | Process for making a high density detergent composition from starting detergent ingredients |
EP0688862A1 (en) * | 1994-06-24 | 1995-12-27 | The Procter & Gamble Company | Structured detergent pastes and a method for manufacturing detergent particles from such pastes |
GB9417354D0 (en) | 1994-08-26 | 1994-10-19 | Unilever Plc | Detergent particles and process for their production |
GB9417356D0 (en) * | 1994-08-26 | 1994-10-19 | Unilever Plc | Detergent particles and process for their production |
US5489392A (en) * | 1994-09-20 | 1996-02-06 | The Procter & Gamble Company | Process for making a high density detergent composition in a single mixer/densifier with selected recycle streams for improved agglomerate properties |
US5516448A (en) * | 1994-09-20 | 1996-05-14 | The Procter & Gamble Company | Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate |
WO1996025482A1 (en) * | 1995-02-13 | 1996-08-22 | The Procter & Gamble Company | Process for producing detergent agglomerates in which particle size is controlled |
US5574005A (en) * | 1995-03-07 | 1996-11-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
AUPN535095A0 (en) * | 1995-09-12 | 1995-10-05 | Procter & Gamble Company, The | Compositions comprising hydrophilic silica particulates |
US6159927A (en) * | 1995-09-12 | 2000-12-12 | The Procter & Gamble Company | Compositions comprising hydrophilic silica particulates |
US6172033B1 (en) | 1996-07-04 | 2001-01-09 | The Procter & Gamble Company | Process for conditioning of surfactant pastes to form high active surfactant agglomerates |
ATE264384T1 (de) * | 1996-07-04 | 2004-04-15 | Procter & Gamble | Verfahren zur konditionierung von tensidpasten zwecks bildung hochaktiver tensidgranulate |
GB9618877D0 (en) * | 1996-09-10 | 1996-10-23 | Unilever Plc | Process for preparing high bulk density detergent compositions |
GB9618876D0 (en) * | 1996-09-10 | 1996-10-23 | Unilever Plc | Process for preparing high bulk density detergent compositions |
GB9618875D0 (en) * | 1996-09-10 | 1996-10-23 | Unilever Plc | Process for preparing high bulk density detergent compositions |
US6281188B1 (en) * | 1996-10-04 | 2001-08-28 | The Procter & Gamble Company | Process for making a low density detergent composition |
GB9726824D0 (en) * | 1997-12-19 | 1998-02-18 | Manro Performance Chemicals Lt | Method of manufacturing particles |
DE19822942A1 (de) * | 1998-05-22 | 1999-11-25 | Henkel Kgaa | Granulation von Aniontensidsäuren |
DE19822943A1 (de) * | 1998-05-22 | 1999-11-25 | Henkel Kgaa | Verfahren zur Herstellung von Wasch- und Reinigungsmitteln |
DE19844523A1 (de) | 1998-09-29 | 2000-03-30 | Henkel Kgaa | Granulationsverfahren |
DE19844522A1 (de) | 1998-09-29 | 2000-03-30 | Henkel Kgaa | Granulationsverfahren |
DE10232304B4 (de) * | 2002-07-17 | 2005-10-27 | Henkel Kgaa | Neutralisation im Mischer |
GB0323273D0 (en) * | 2003-10-04 | 2003-11-05 | Unilever Plc | Process for making a detergent composition |
ES2753025T3 (es) * | 2012-07-09 | 2020-04-07 | Unilever Nv | Proceso para la producción de un gránulo de detergente, gránulo de detergente y composición de detergente que comprende dicho gránulo |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6072999A (ja) * | 1983-09-30 | 1985-04-25 | 花王株式会社 | 超濃縮粉末洗剤の製法 |
JPS61118500A (ja) * | 1984-11-14 | 1986-06-05 | ライオン株式会社 | 濃縮型洗剤組成物の製造方法 |
US4933100A (en) * | 1988-01-19 | 1990-06-12 | Colgate-Palmolive Co. | Built synthetic organic detergent composition patties and processes for washing laundry therewith |
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 |
US4925585A (en) * | 1988-06-29 | 1990-05-15 | The Procter & Gamble Company | Detergent granules from cold dough using fine dispersion granulation |
GB8907187D0 (en) * | 1989-03-30 | 1989-05-10 | Unilever Plc | Detergent compositions and process for preparing them |
CA2017922C (en) * | 1989-06-09 | 1995-07-11 | Frank Joseph Mueller | Formation of discrete, high active detergent granules using a continuous neutralization system |
US5045238A (en) * | 1989-06-09 | 1991-09-03 | The Procter & Gamble Company | High active detergent particles which are dispersible in cold water |
-
1992
- 1992-04-07 EP EP92200994A patent/EP0508543B1/en not_active Expired - Lifetime
- 1992-04-07 DE DE69221357T patent/DE69221357T2/de not_active Expired - Fee Related
- 1992-04-07 ES ES92200994T patent/ES2104809T3/es not_active Expired - Lifetime
- 1992-04-09 AU AU18700/92A patent/AU1870092A/en not_active Abandoned
- 1992-04-09 BR BR9205890A patent/BR9205890A/pt not_active Application Discontinuation
- 1992-04-09 CZ CS932137A patent/CZ213793A3/cs unknown
- 1992-04-09 CA CA002108166A patent/CA2108166C/en not_active Expired - Fee Related
- 1992-04-09 WO PCT/US1992/002879 patent/WO1992018602A1/en not_active Application Discontinuation
- 1992-04-09 HU HU9302874A patent/HUT66724A/hu unknown
- 1992-04-09 JP JP51026592A patent/JP3225041B2/ja not_active Expired - Fee Related
- 1992-04-09 SK SK1084-93A patent/SK108493A3/sk unknown
- 1992-04-10 TR TR00344/92A patent/TR26814A/xx unknown
- 1992-04-10 IE IE116292A patent/IE921162A1/en not_active Application Discontinuation
- 1992-04-10 PT PT100371A patent/PT100371A/pt not_active Application Discontinuation
- 1992-04-11 CN CN92103408A patent/CN1042746C/zh not_active Expired - Fee Related
- 1992-04-11 EG EG18692A patent/EG20046A/xx active
- 1992-04-13 MX MX9201721A patent/MX9201721A/es unknown
- 1992-05-06 TW TW081103529A patent/TW200524B/zh active
-
1993
- 1993-10-11 NO NO933641A patent/NO933641L/no unknown
- 1993-10-11 FI FI934463A patent/FI934463A0/fi not_active Application Discontinuation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7186677B2 (en) | 2001-12-21 | 2007-03-06 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Method for the production of surfactant granulates containing builders |
Also Published As
Publication number | Publication date |
---|---|
CZ213793A3 (en) | 1994-10-19 |
WO1992018602A1 (en) | 1992-10-29 |
DE69221357D1 (de) | 1997-09-11 |
TW200524B (hu) | 1993-02-21 |
ES2104809T3 (es) | 1997-10-16 |
CN1042746C (zh) | 1999-03-31 |
DE69221357T2 (de) | 1998-03-12 |
TR26814A (tr) | 1994-08-09 |
MX9201721A (es) | 1992-10-01 |
CA2108166C (en) | 1998-08-04 |
FI934463A (fi) | 1993-10-11 |
JPH06506719A (ja) | 1994-07-28 |
BR9205890A (pt) | 1994-09-27 |
HU9302874D0 (en) | 1994-01-28 |
CA2108166A1 (en) | 1992-10-13 |
PT100371A (pt) | 1993-07-30 |
EG20046A (en) | 1997-08-31 |
JP3225041B2 (ja) | 2001-11-05 |
CN1066881A (zh) | 1992-12-09 |
NO933641L (no) | 1993-12-13 |
FI934463A0 (fi) | 1993-10-11 |
AU1870092A (en) | 1992-11-17 |
SK108493A3 (en) | 1994-12-07 |
EP0508543A1 (en) | 1992-10-14 |
NO933641D0 (no) | 1993-10-11 |
IE921162A1 (en) | 1992-10-21 |
HUT66724A (en) | 1994-12-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0508543B1 (en) | Chemical structuring of surfactant pastes to form high active surfactant granules | |
EP0510746A2 (en) | Process for preparing condensed detergent granules | |
EP0656825B2 (en) | Process for making compact detergent compositions | |
US5663136A (en) | Process for making compact detergent compositions | |
US5712242A (en) | High active granular detergents comprising chelants and polymers, and processes for their preparation | |
US5494599A (en) | Agglomeration of high active pastes to form surfactant granules useful in detergent compositions | |
EP0578871B1 (en) | Process and compositions for compact detergents | |
US5529710A (en) | Production of detergent granules with excellent white appearance | |
US5451354A (en) | Chemical structuring of surfactant pastes to form high active surfactant granules | |
EP0560001B1 (en) | High active detergent pastes | |
EP0578872B1 (en) | Detergent compositions | |
EP0618289B1 (en) | High active granular detergents comprising chelants and polymers, and processes for their preparation | |
US5703037A (en) | Process for the manufacture of free-flowing detergent granules | |
US5529722A (en) | High active detergent pastes | |
EP0816486B1 (en) | Process for conditioning of surfactant pastes to form high active surfactant agglomerates | |
AU1878592A (en) | Agglomeration of high active pastes to form surfactant granules useful in detergent compositions | |
US6172033B1 (en) | Process for conditioning of surfactant pastes to form high active surfactant agglomerates | |
EP0678573B1 (en) | Process for the manufacture of free-flowing detergent granules |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL PT SE |
|
17P | Request for examination filed |
Effective date: 19930308 |
|
17Q | First examination report despatched |
Effective date: 19930408 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
RBV | Designated contracting states (corrected) |
Designated state(s): DE ES FR GB IT NL |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE ES FR GB IT NL |
|
REF | Corresponds to: |
Ref document number: 69221357 Country of ref document: DE Date of ref document: 19970911 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2104809 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20060324 Year of fee payment: 15 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20071101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20071101 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20070404 Year of fee payment: 16 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20081231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080430 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20090414 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20090418 Year of fee payment: 18 Ref country code: DE Payment date: 20090430 Year of fee payment: 18 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100407 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20110708 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110628 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20110328 Year of fee payment: 20 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100408 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20120406 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20120406 |