CA2260008C - Process for conditioning of surfactant pastes to form high active surfactant agglomerates - Google Patents
Process for conditioning of surfactant pastes to form high active surfactant agglomerates Download PDFInfo
- Publication number
- CA2260008C CA2260008C CA002260008A CA2260008A CA2260008C CA 2260008 C CA2260008 C CA 2260008C CA 002260008 A CA002260008 A CA 002260008A CA 2260008 A CA2260008 A CA 2260008A CA 2260008 C CA2260008 C CA 2260008C
- Authority
- CA
- Canada
- Prior art keywords
- paste
- surfactant
- powder
- alkyl
- sodium
- 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 - Fee Related
Links
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000003750 conditioning effect Effects 0.000 title abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 52
- -1 alkyl sulphate Chemical compound 0.000 claims abstract description 48
- 239000003599 detergent Substances 0.000 claims abstract description 25
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims description 37
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 27
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- 239000000344 soap Substances 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000004614 Process Aid Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000001143 conditioned effect Effects 0.000 abstract description 3
- 230000015227 regulation of liquid surface tension Effects 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 37
- 239000011734 sodium Substances 0.000 description 27
- 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 25
- 239000000463 material Substances 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 19
- 238000005342 ion exchange Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 13
- 238000005469 granulation Methods 0.000 description 12
- 230000003179 granulation Effects 0.000 description 12
- 239000007859 condensation product Substances 0.000 description 9
- 239000003760 tallow Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008187 granular material Substances 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
- 239000002253 acid Substances 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000002736 nonionic surfactant Substances 0.000 description 7
- 159000000001 potassium salts Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 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
- 239000003093 cationic surfactant Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 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
- 239000007864 aqueous solution Substances 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
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 159000000000 sodium salts Chemical class 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
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 229920013820 alkyl cellulose Polymers 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 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
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002563 ionic surfactant Substances 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
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000002689 soil 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
- 239000002888 zwitterionic surfactant Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000388 Polyphosphate Chemical class 0.000 description 1
- 239000004115 Sodium Silicate Substances 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
- 235000010724 Wisteria floribunda Nutrition 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
- 229940091181 aconitic acid Drugs 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000012190 activator 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
- 239000002585 base Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 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
- 238000010924 continuous production Methods 0.000 description 1
- 239000013256 coordination polymer Substances 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
- 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
- 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
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 235000013305 food Nutrition 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
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000012149 noodles Nutrition 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
- 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
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000010452 phosphate 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
- 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
- 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
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 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
- 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
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000375 suspending agent 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- 239000004034 viscosity adjusting agent 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
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- 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
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- 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
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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Abstract
The invention provides an effective process for conditioning pastes comprisi ng at least 40 % by weight of anionic surfactant. The paste is conditioned by mixing alkyl sulphate powder with the surfactant paste in a ratio of at leas t 1 part powder to 100 parts paste. This conditioning step increases the viscosity of the surfactant paste. The conditioned paste is processed into agglomerates by granulating with builder powders wherein the ratio of high viscosity paste to builder powder is from 9:1 to 1:5. This process enables detergent agglomerates with high surfactant activity to be formed.
Description
- WO 98/01529 _ - PCT/IJS97/11282 PROCESS FOR CONDITIONING OF SURFACTANT PASTES TO FORM HIGH
ACTIVE SURFACTANT AGGLOMERATES
The invention relates to a process for making a granular detergent component or composition.
Manufacturing processes are known wherein granular detergent products are made by forming a neutral or alkaline paste comprising at least 40% by weight of anionic surfactant; and mixing the high viscosity paste so-formed with builder powders wherein the ratio of high viscosity paste to builder powder is from 9:1 to 1:5 to form the granular detergent component or composition. Such processes are commonly called agglomeration processes EP-A-0 663 439, published on 19th July 1995, and EP-A-0 508 543, published on 14th Oct., 1992, both describe enhanced embodiments of agglomeration processes which includes a process of surfactant paste conditioning in, for example, a twin-screw extruder, followed by granulation in a high shear mixer.
EP-A-0 508 543 mentions the possibility to add anionic surfactant into the process via a powder stream. However it is not specified whether this powder stream is added into the extruder, or into the high-shear mixer. Neither of these publications describes the use of dry alkyl sulphate powder in the conditioning step.
The object of the present invention is to provide an effective process for conditioning pastes comprising at least 40% by weight of anionic surfactant. The conditioning agent disrupts surfactant crystallinity, and also increases the viscoelasticity of the paste. The crystalline disruption improves rate of surfactant solubility, whilst the viscoelasticity increase "conditions" the paste enabling agglomerates with high surfactant activity to be formed. The paste is processed into agglomerates by granulating with builder powders wherein the ratio of high viscosity paste to builder powder is from 9:1 to 1:5.
Summary of the Invention The object is achieved by mixing a first powder with the surfactant paste in a ratio of at least 1 part powder to 100 parts paste, the first powder comprising at least 80o by weight of alkyl sulphate, and whereby the mixing step increases the viscosity of the surfactant paste.
In one particular embodiment there is provided a process for making a granular detergent component or composition comprising the steps of: (i) forming a neutral or alkaline paste comprising at least 40o by weight of anionic surfactant;
(ii) mixing a first powder with the surfactant paste at a temperature less then 100°C, in a ratio of at least 1 part powder to 100 parts paste, and whereby the mixing step increases the viscosity of the surfactant paste, from about 5,000 cps to 10,000,000 cps; (iii) forming the granular detergent component or composition at a temperature from about 25°C to about 60°C, by mixing the high viscosity paste so-formed with builder powders selected from the group consisting of carbonate, aluminosilicate, silicate, and mixtures thereof, wherein the ratio of high viscosity paste to builder powder is from 9:1 to 1:5, having a bulk density of from about 0.4 to about 1.2 g/cc, characterised in that the first powder 2a comprises at least 80o by weight of alkyl sulphate wherein the alkyl sulphate, comprises less than 5o by weight of water.
In a preferred embodiment of the invention, alkyl sulphate powder, comprising less than 5o by weight of water, is mixed with other surfactants in the paste in an extruder. In an even more preferred embodiment of the invention the paste and alkyl sulphate powder mixture is carried out sequentially in a high-shear mixer granulator having a tool tip-speed of from 5 to 50 m/sec, and a medium speed agglomerator.
Most preferred builder powders are carbonate, aluminosilicate and silicate.
Detailed Description of the Invention The present invention concerns conditioning of anionic surfactant in an aqueous, highly concentrated solution of - WO 98/01529 _ - PCT/US97/11282 its salt, preferably its sodium salt. These high active, low moisture surfactant pastes are of a high viscosity but remain pumpable at temperatures at which the surfactants are stable. In other processes, anionic surfactants or mixtures comprising at least one anionic surfactant, where highly viscous liquid crystal phases occur, requires that either lower viscous crystal phases be formed or that some viscosity modifiers are used. This requires expensive additives, and prevents high surfactant activities from being achieved.
Conditioning of a paste means the modifying of its physical characteristics to form higher active, less sticky agglomerates which are not easily obtainable under normal operating conditions. Conditioning of the paste as defined herein, means: a) increasing its apparent viscosity, b) increasing its effective melting point, c) increasing the "hardness" of the paste. The hardness/softness of the paste may be measured by a softness penetrometer according to ASTM D 217-IP50 or ISO 2137. The hardness of conditioned paste measured in this way should be less than 2cm, preferably less than lcm.
Chemical conditioning agents are compounds that alter the physical structure and/or physical characteristics of the surfactant paste when added to the paste. In the present invention the chemical conditioning agent is alkyl sulphate in powdered form. 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, preferably between 40% and 60%, more preferably greater than 50%. This method of treating the surfactant paste can be performed batchwise and continuous, preferably continuously.
ACTIVE SURFACTANT AGGLOMERATES
The invention relates to a process for making a granular detergent component or composition.
Manufacturing processes are known wherein granular detergent products are made by forming a neutral or alkaline paste comprising at least 40% by weight of anionic surfactant; and mixing the high viscosity paste so-formed with builder powders wherein the ratio of high viscosity paste to builder powder is from 9:1 to 1:5 to form the granular detergent component or composition. Such processes are commonly called agglomeration processes EP-A-0 663 439, published on 19th July 1995, and EP-A-0 508 543, published on 14th Oct., 1992, both describe enhanced embodiments of agglomeration processes which includes a process of surfactant paste conditioning in, for example, a twin-screw extruder, followed by granulation in a high shear mixer.
EP-A-0 508 543 mentions the possibility to add anionic surfactant into the process via a powder stream. However it is not specified whether this powder stream is added into the extruder, or into the high-shear mixer. Neither of these publications describes the use of dry alkyl sulphate powder in the conditioning step.
The object of the present invention is to provide an effective process for conditioning pastes comprising at least 40% by weight of anionic surfactant. The conditioning agent disrupts surfactant crystallinity, and also increases the viscoelasticity of the paste. The crystalline disruption improves rate of surfactant solubility, whilst the viscoelasticity increase "conditions" the paste enabling agglomerates with high surfactant activity to be formed. The paste is processed into agglomerates by granulating with builder powders wherein the ratio of high viscosity paste to builder powder is from 9:1 to 1:5.
Summary of the Invention The object is achieved by mixing a first powder with the surfactant paste in a ratio of at least 1 part powder to 100 parts paste, the first powder comprising at least 80o by weight of alkyl sulphate, and whereby the mixing step increases the viscosity of the surfactant paste.
In one particular embodiment there is provided a process for making a granular detergent component or composition comprising the steps of: (i) forming a neutral or alkaline paste comprising at least 40o by weight of anionic surfactant;
(ii) mixing a first powder with the surfactant paste at a temperature less then 100°C, in a ratio of at least 1 part powder to 100 parts paste, and whereby the mixing step increases the viscosity of the surfactant paste, from about 5,000 cps to 10,000,000 cps; (iii) forming the granular detergent component or composition at a temperature from about 25°C to about 60°C, by mixing the high viscosity paste so-formed with builder powders selected from the group consisting of carbonate, aluminosilicate, silicate, and mixtures thereof, wherein the ratio of high viscosity paste to builder powder is from 9:1 to 1:5, having a bulk density of from about 0.4 to about 1.2 g/cc, characterised in that the first powder 2a comprises at least 80o by weight of alkyl sulphate wherein the alkyl sulphate, comprises less than 5o by weight of water.
In a preferred embodiment of the invention, alkyl sulphate powder, comprising less than 5o by weight of water, is mixed with other surfactants in the paste in an extruder. In an even more preferred embodiment of the invention the paste and alkyl sulphate powder mixture is carried out sequentially in a high-shear mixer granulator having a tool tip-speed of from 5 to 50 m/sec, and a medium speed agglomerator.
Most preferred builder powders are carbonate, aluminosilicate and silicate.
Detailed Description of the Invention The present invention concerns conditioning of anionic surfactant in an aqueous, highly concentrated solution of - WO 98/01529 _ - PCT/US97/11282 its salt, preferably its sodium salt. These high active, low moisture surfactant pastes are of a high viscosity but remain pumpable at temperatures at which the surfactants are stable. In other processes, anionic surfactants or mixtures comprising at least one anionic surfactant, where highly viscous liquid crystal phases occur, requires that either lower viscous crystal phases be formed or that some viscosity modifiers are used. This requires expensive additives, and prevents high surfactant activities from being achieved.
Conditioning of a paste means the modifying of its physical characteristics to form higher active, less sticky agglomerates which are not easily obtainable under normal operating conditions. Conditioning of the paste as defined herein, means: a) increasing its apparent viscosity, b) increasing its effective melting point, c) increasing the "hardness" of the paste. The hardness/softness of the paste may be measured by a softness penetrometer according to ASTM D 217-IP50 or ISO 2137. The hardness of conditioned paste measured in this way should be less than 2cm, preferably less than lcm.
Chemical conditioning agents are compounds that alter the physical structure and/or physical characteristics of the surfactant paste when added to the paste. In the present invention the chemical conditioning agent is alkyl sulphate in powdered form. 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, preferably between 40% and 60%, more preferably greater than 50%. This method of treating the surfactant paste can be performed batchwise and continuous, preferably continuously.
Alkyl sulphate powder is defined herein as any free-flowing powder, flakes, noodles or needles which comprises at least 80o by weight of alkyl sulphate. Useful powders are commercially available from Albright & Wilson, Hickson Manro and Sidobre Sinnova. Alternatively suitable powders may be prepared by sulphating an alcohol, followed by neutralisation with, for example aqueous sodium hydroxide, then drying in a suitable spray drying tower, wiped film evaporator or suitable dryer. Dry neutralisation methods may also be used, neutralising alkyl sulphuric acid with, for example powdered sodium carbonate.
In a preferred embodiment of the invention an extruder is used to condition the paste. The extruder is a versatile piece of equipment which enables two or more pastes and the alkyl sulphate powder to be mixed .
Process aids may also be used. Preferred process aids which may be mixed with the surfactant paste are starch, soap, fatty acids and polymers. Process aids and surfactant paste may be mixed prior to the extruder in, for example, a high shear mixer; or in the extruder itself.
The Pastes 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. In a preferred embodiment, 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 WO 98/01529 _ - PCT/CTS97/11282 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°s, preferably from 40-95%.
It is preferred that 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.
Preferably the paste contains between 5 and 40% water, more preferably between 5 and 30% water and most preferably between 5% and 20% water.
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.
Two important parameters of the surfactant pastes which can affect the mixing and granulation step are the paste temperature and viscosity. Viscosity is a function, among others, of concentration and temperature, with a range in this application from about 5,000 cps to 10,000,000 cps. Preferably, the viscosity of the paste entering the system is from about 20,000 to about 100,000 cps. and more preferably from about 30,000 to about 70,000 cps. 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 - WO 98/01529 _ - PCT/US97/11282 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 the present invention, 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.
By combining both effects, and introducing the paste through holes (extrusion) small enough to allow the desired flow rate but that keep the pumping pressure to a maximum feasible in the system, highly advantageous results are achieved.
Hicrh Active Surfactant Paste 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°s. 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.
However, 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, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. 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 WO 98/01529 . PCT/US97/11282 sulfonic acid or sulfuric acid ester group. (Included in the term "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; 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 about 11 to 13, abbreviated as C11-C13 ~S-Other 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 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.
Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; watersoluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety. Although the acid salts are typically discussed and used, the acid neutralization cam be performed as part of the fine dispersion mixing step.
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 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 I8 carbon atoms.
Particularly preferred surfactants herein include linear alkylbenzene sulfonates containing from about 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 about 14 to 18 carbon atoms and wherein the average degree of ethoxylation is from about 1 to 4; olefin or paraffin sulfonates containing from about 14 to 16 carbon atoms;
alkyldimethylamine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethylammonio propane sulfonates and alkyldimethylammonio hydroxy propane sulfonates wherein the alkyl group contains from about 14 to 18 carbon atoms; soaps of higher fatty acids containing from about 12 to 18 carbon atoms; condensation products of C9-C15 alcohols with from about 3 to 8 moles of ethylene oxide, and mixtures thereof.
Useful cationic surfactants include. Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4R5R6R~N+X-, wherein R4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R5, R6 and R~ are each C1 to C~ 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.
Specific preferred surfactants for use herein include:
sodium linear C11-C13 alkylbenzene sulfonate; a-olefin sulphonates; triethanolammonium C11-C13 alkylbenzene sulfonate; alkyl sulfates, (tallow, coconut, palm, synthetic origins, e.g. C45, etc.); sodium alkyl sulfates;
MES; sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol with about 4 moles of ethylene oxide; the condensation product of a coconut fatty alcohol with about 6 moles of ethylene oxide; the condensation product of tallow fatty alcohol with about 11 moles of ethylene oxide;
the condensation of a fatty alcohol containing fram about 14 to about 15 carbon atoms with about 7 moles of ethylene oxide; the condensation product of a C12-C13 fatty alcohol with about 3 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkylammonio)-2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-coconutalkylammonio)-propane-1-sulfonate; 6- (N-dodecylbenzyl-N,N-dimethylammonio) hexanoate;
dodecyldimethylamine oxide; coconutalkyldimethylamine oxide; and the water-soluble sodium and potassium salts of coconut and tallow fatty acids.
(As used herein, the term "surfactant" means non-nonionic surfactants, unless otherwise specified. The ratio of the surfactant active (excluding the nonionic(s)) to dry detergent builder or powder ranges from 0.005 to 19:1, preferably from 0.05 to 10:1, and more preferably from 0.1:1 to 5:1. Even more preferred said surfactant active to builder ratios are 0.15:1 to 1:1; and 0.2:1 to 0.5:1) .
The Extruder 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 alkyl sulphate powder to be added directly into the barrel.
Secondly means for heating or cooling may be installed in the wall of the barrel for temperature control. Thirdly, careful design of the extruder screw promotes mixing of the paste both with itself and with other additives.
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.
Suitable twin screw extruders for use in the present invention include those supplied by . APV Bakes, (CP
series); Werner and Pfleiderer, (Continua Series); Wenger, (TF Series); Leistritz, (ZSE Series); and Buss, (LR
Series ) .
The Fine Dispersion Mixing and Granulation The term "fine dispersion mixing and/or granulation,"
as used herein, means mixing and/or granulation of the above mixture in a fine dispersion mixer at a blade tip speed of from about 5m/sec. to about 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 about 10-45 m/sec. and about 15-40 m/sec.
Any apparatus, plants or units suitable for the processing of surfactants can be used for carrying out the process according to the invention. Suitable apparatus includes, for example, falling film sulphonating reactors, digestion tanks, esterification reactors, etc. For mixing/
agglomeration any of a number of mixers/agglomerators can be used. In one preferred embodiment, the process of the invention is continuously carried out. Especially preferred are mixers of the FukaeR FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; 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.
Other similar mixers found to be suitable for use in the process of the invention include DiosnaR V series ex Dierks & Sohne, Germany; and the Pharma MatrixR ex T K
Fielder Ltd., England. Other mixers believed to~be suitable for use in the process of the invention are the FujiR VG-C series ex Fuji Sangyo Co., Japan; and the RotoR
ex Zanchetta ~ Co srl, Italy.
Other preferred suitable equipment can include EirichR, series RV, manufactured by Gustau Eirich Hardheim, Germany; LodigeR, series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lodige Machinenbau GmbH, Paderborn Germany; DraisR T160 series, manufactured by Drais Werke GmbH, Mannheim Germany;
and WinkworthR 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 (29.7 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.
Operating' Temperatures Preferred operating temperatures should also be as low as possible since this leads to a higher surfactant concentration in the finished particle. Preferably the temperature during the agglomeration is less than 100°C, more preferably between 25 and 90°C, and most preferably between 30 and 80°C.
Final AQCxlomerate Composition 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.
By increasing the concentration of surfactant, 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 about 0.4 to about 1.2 g/cc, more preferably from about 0.6 to about 0.8 g/cc. The weight average particle size of the particles of this invention are from about 200 to about 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 about 25°C to about 60°C, and most preferably from about 30°C to about 50°C.
Dryinct 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.
For detergent applications, 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%.
Deterctency Builders and Powders 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 f ormu 1 a Naz C (A102 ) z ~ C Si02 ) y7 ~ xH20 wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formula Mz(zA102~ySi02) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.
The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 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 about 18% to about 22% water in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 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 about 0.2 micron to about 4 microns. The term "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 CaC03 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 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 about 2 grains/gallon/minute/gram/gallon to about 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.
CaC03/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.
Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X and Zeolite P.
In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Nal2 [ (A102) 12 (Si02) 12] Wi20 wherein x is from about 20 to about 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.
Examples of neutral water-soluble salts 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.
Other useful 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, Preferred are the alkali metal, especially sodium, salts of the above.
Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of 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.
Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of Si02 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 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 2s finely divided calcium carbonate as disclosed in U.S. Pat. No. 4,196,093, Clarke et al., issued Apr.l, 1980, and is preferably free of the latter.
As mentioned above powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate, etc. and process aids such as starch, soap or fatty acid can be used in preferred embodiments of the present invention.
Polymers Also useful are various organic polymers, some of which also may function 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 malefic 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 malefic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
Optionals Other ingredients commonly used in detergent compositions 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, perfumes, soap and fatty acid.
EXAMPLES
In the following examples all percantages are by weight unless otherwise stated:
AS/AE3S paste is a 78o aqueous solution of alkyl sulphate and alkyl ether sulphate (with 3 EO groups per molecule) comprising 4 parts of alkyl sulphate to 1 part of alkyl ether sulphate.
LAS paste is a 78% active aqueous solution of sodium linear alkyl benzene sulphonate AS powder comprises 95% active powder Polyacrylate powder comprises co-polymer of acrylic and maliec acid Silicate powder comprises 80o sodium silicate and is produced by spray-drying Ex. 1 Ex. 2 Comparative Ex. 3 AS/AE3S Paste 16 32 38 LAS paste 20 - -Alkyl sulphate powder 4 18 -Polyacrylate polymer - 7 17 Sodium carbonate 20 20 12 Zeolite A 29 15 22 Silicate powder 1 -Water / Misc. minors 10 8 11 In each of examples 1 to 3 the AE3S/AS paste, and the LAS
paste when present, were fed into a continuous twin-screw extruder. The alkyl sulphate powder, or the polyacrylate polymer, and silicate when present, were added directly to into the barrel of the extruder through an inlet port. The mixture was then extruded through a die directly into a high shear mixer (Loedige~ CB) where is mixed with powder streams comprising the sodium carbonate and the zeolite.
The resulting product was then passed to a medium shear mixer (Loedige° KM) resulting in a free-flowing detergent product in the form of agglomerates.
The bulk density of the product from each of the examples was between 680 and 700 g/1.
AS/NI paste is a 95% aqueous solution of alkyl sulphate and alcohol ethoxylate (with 3 EO groups per molecule) comprising 2 parts of alkyl sulphate to 1 part of alcohol ethoxylate.
LAS/NI paste is a 95°s active aqueous solution of sodium linear alkyl benzene sulphonate and alcohol ethoxylate (with 3 EO groups per molecule) comprising 2 parts of LAS
to 1 part of alcohol ethoxylate.
Ex. 4 Ex. 5 Comparative Ex. 6 AS/NI Paste 30 - 30 LAS/NI paste - 30 -Alkyl sulphate powder 20 20 -Zeolite MAP 35 35 55 Sodium citrate 5 5 5 Water / Misc. minors 10 10 10 In each of examples 4 and 5 the AS/NI paste, or the LAS/NI
paste, was fed into a continuous twin-screw extruder. The alkyl sulphate powder was added directly to into the barrel of the extruder through an inlet port. The mixture was then extruded through a die directly into a high shear mixer (Loedige° CB) where is mixed with powder streams comprising the sodium citrate and the zeolite. The resulting product WO 98/01529 - PCT/L1S97l11282 was then passed to a medium shear mixer (Loedige~ KM) resulting in a free-flowing detergent product in the form of agglomerates.
In comparative example 6 the AS/NI paste was fed diectly into the high shear mixer.
The bulk density of the product from each of the examples was between 680 and 700 g/1.
In a preferred embodiment of the invention an extruder is used to condition the paste. The extruder is a versatile piece of equipment which enables two or more pastes and the alkyl sulphate powder to be mixed .
Process aids may also be used. Preferred process aids which may be mixed with the surfactant paste are starch, soap, fatty acids and polymers. Process aids and surfactant paste may be mixed prior to the extruder in, for example, a high shear mixer; or in the extruder itself.
The Pastes 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. In a preferred embodiment, 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 WO 98/01529 _ - PCT/CTS97/11282 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°s, preferably from 40-95%.
It is preferred that 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.
Preferably the paste contains between 5 and 40% water, more preferably between 5 and 30% water and most preferably between 5% and 20% water.
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.
Two important parameters of the surfactant pastes which can affect the mixing and granulation step are the paste temperature and viscosity. Viscosity is a function, among others, of concentration and temperature, with a range in this application from about 5,000 cps to 10,000,000 cps. Preferably, the viscosity of the paste entering the system is from about 20,000 to about 100,000 cps. and more preferably from about 30,000 to about 70,000 cps. 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 - WO 98/01529 _ - PCT/US97/11282 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 the present invention, 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.
By combining both effects, and introducing the paste through holes (extrusion) small enough to allow the desired flow rate but that keep the pumping pressure to a maximum feasible in the system, highly advantageous results are achieved.
Hicrh Active Surfactant Paste 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°s. 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.
However, 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, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. 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 WO 98/01529 . PCT/US97/11282 sulfonic acid or sulfuric acid ester group. (Included in the term "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; 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 about 11 to 13, abbreviated as C11-C13 ~S-Other 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 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.
Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; watersoluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety. Although the acid salts are typically discussed and used, the acid neutralization cam be performed as part of the fine dispersion mixing step.
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 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 I8 carbon atoms.
Particularly preferred surfactants herein include linear alkylbenzene sulfonates containing from about 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 about 14 to 18 carbon atoms and wherein the average degree of ethoxylation is from about 1 to 4; olefin or paraffin sulfonates containing from about 14 to 16 carbon atoms;
alkyldimethylamine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethylammonio propane sulfonates and alkyldimethylammonio hydroxy propane sulfonates wherein the alkyl group contains from about 14 to 18 carbon atoms; soaps of higher fatty acids containing from about 12 to 18 carbon atoms; condensation products of C9-C15 alcohols with from about 3 to 8 moles of ethylene oxide, and mixtures thereof.
Useful cationic surfactants include. Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4R5R6R~N+X-, wherein R4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R5, R6 and R~ are each C1 to C~ 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.
Specific preferred surfactants for use herein include:
sodium linear C11-C13 alkylbenzene sulfonate; a-olefin sulphonates; triethanolammonium C11-C13 alkylbenzene sulfonate; alkyl sulfates, (tallow, coconut, palm, synthetic origins, e.g. C45, etc.); sodium alkyl sulfates;
MES; sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol with about 4 moles of ethylene oxide; the condensation product of a coconut fatty alcohol with about 6 moles of ethylene oxide; the condensation product of tallow fatty alcohol with about 11 moles of ethylene oxide;
the condensation of a fatty alcohol containing fram about 14 to about 15 carbon atoms with about 7 moles of ethylene oxide; the condensation product of a C12-C13 fatty alcohol with about 3 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkylammonio)-2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-coconutalkylammonio)-propane-1-sulfonate; 6- (N-dodecylbenzyl-N,N-dimethylammonio) hexanoate;
dodecyldimethylamine oxide; coconutalkyldimethylamine oxide; and the water-soluble sodium and potassium salts of coconut and tallow fatty acids.
(As used herein, the term "surfactant" means non-nonionic surfactants, unless otherwise specified. The ratio of the surfactant active (excluding the nonionic(s)) to dry detergent builder or powder ranges from 0.005 to 19:1, preferably from 0.05 to 10:1, and more preferably from 0.1:1 to 5:1. Even more preferred said surfactant active to builder ratios are 0.15:1 to 1:1; and 0.2:1 to 0.5:1) .
The Extruder 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 alkyl sulphate powder to be added directly into the barrel.
Secondly means for heating or cooling may be installed in the wall of the barrel for temperature control. Thirdly, careful design of the extruder screw promotes mixing of the paste both with itself and with other additives.
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.
Suitable twin screw extruders for use in the present invention include those supplied by . APV Bakes, (CP
series); Werner and Pfleiderer, (Continua Series); Wenger, (TF Series); Leistritz, (ZSE Series); and Buss, (LR
Series ) .
The Fine Dispersion Mixing and Granulation The term "fine dispersion mixing and/or granulation,"
as used herein, means mixing and/or granulation of the above mixture in a fine dispersion mixer at a blade tip speed of from about 5m/sec. to about 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 about 10-45 m/sec. and about 15-40 m/sec.
Any apparatus, plants or units suitable for the processing of surfactants can be used for carrying out the process according to the invention. Suitable apparatus includes, for example, falling film sulphonating reactors, digestion tanks, esterification reactors, etc. For mixing/
agglomeration any of a number of mixers/agglomerators can be used. In one preferred embodiment, the process of the invention is continuously carried out. Especially preferred are mixers of the FukaeR FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; 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.
Other similar mixers found to be suitable for use in the process of the invention include DiosnaR V series ex Dierks & Sohne, Germany; and the Pharma MatrixR ex T K
Fielder Ltd., England. Other mixers believed to~be suitable for use in the process of the invention are the FujiR VG-C series ex Fuji Sangyo Co., Japan; and the RotoR
ex Zanchetta ~ Co srl, Italy.
Other preferred suitable equipment can include EirichR, series RV, manufactured by Gustau Eirich Hardheim, Germany; LodigeR, series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lodige Machinenbau GmbH, Paderborn Germany; DraisR T160 series, manufactured by Drais Werke GmbH, Mannheim Germany;
and WinkworthR 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 (29.7 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.
Operating' Temperatures Preferred operating temperatures should also be as low as possible since this leads to a higher surfactant concentration in the finished particle. Preferably the temperature during the agglomeration is less than 100°C, more preferably between 25 and 90°C, and most preferably between 30 and 80°C.
Final AQCxlomerate Composition 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.
By increasing the concentration of surfactant, 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 about 0.4 to about 1.2 g/cc, more preferably from about 0.6 to about 0.8 g/cc. The weight average particle size of the particles of this invention are from about 200 to about 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 about 25°C to about 60°C, and most preferably from about 30°C to about 50°C.
Dryinct 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.
For detergent applications, 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%.
Deterctency Builders and Powders 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 f ormu 1 a Naz C (A102 ) z ~ C Si02 ) y7 ~ xH20 wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formula Mz(zA102~ySi02) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.
The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 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 about 18% to about 22% water in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 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 about 0.2 micron to about 4 microns. The term "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 CaC03 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 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 about 2 grains/gallon/minute/gram/gallon to about 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.
CaC03/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.
Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X and Zeolite P.
In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Nal2 [ (A102) 12 (Si02) 12] Wi20 wherein x is from about 20 to about 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.
Examples of neutral water-soluble salts 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.
Other useful 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, Preferred are the alkali metal, especially sodium, salts of the above.
Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of 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.
Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of Si02 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 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 2s finely divided calcium carbonate as disclosed in U.S. Pat. No. 4,196,093, Clarke et al., issued Apr.l, 1980, and is preferably free of the latter.
As mentioned above powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate, etc. and process aids such as starch, soap or fatty acid can be used in preferred embodiments of the present invention.
Polymers Also useful are various organic polymers, some of which also may function 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 malefic 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 malefic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
Optionals Other ingredients commonly used in detergent compositions 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, perfumes, soap and fatty acid.
EXAMPLES
In the following examples all percantages are by weight unless otherwise stated:
AS/AE3S paste is a 78o aqueous solution of alkyl sulphate and alkyl ether sulphate (with 3 EO groups per molecule) comprising 4 parts of alkyl sulphate to 1 part of alkyl ether sulphate.
LAS paste is a 78% active aqueous solution of sodium linear alkyl benzene sulphonate AS powder comprises 95% active powder Polyacrylate powder comprises co-polymer of acrylic and maliec acid Silicate powder comprises 80o sodium silicate and is produced by spray-drying Ex. 1 Ex. 2 Comparative Ex. 3 AS/AE3S Paste 16 32 38 LAS paste 20 - -Alkyl sulphate powder 4 18 -Polyacrylate polymer - 7 17 Sodium carbonate 20 20 12 Zeolite A 29 15 22 Silicate powder 1 -Water / Misc. minors 10 8 11 In each of examples 1 to 3 the AE3S/AS paste, and the LAS
paste when present, were fed into a continuous twin-screw extruder. The alkyl sulphate powder, or the polyacrylate polymer, and silicate when present, were added directly to into the barrel of the extruder through an inlet port. The mixture was then extruded through a die directly into a high shear mixer (Loedige~ CB) where is mixed with powder streams comprising the sodium carbonate and the zeolite.
The resulting product was then passed to a medium shear mixer (Loedige° KM) resulting in a free-flowing detergent product in the form of agglomerates.
The bulk density of the product from each of the examples was between 680 and 700 g/1.
AS/NI paste is a 95% aqueous solution of alkyl sulphate and alcohol ethoxylate (with 3 EO groups per molecule) comprising 2 parts of alkyl sulphate to 1 part of alcohol ethoxylate.
LAS/NI paste is a 95°s active aqueous solution of sodium linear alkyl benzene sulphonate and alcohol ethoxylate (with 3 EO groups per molecule) comprising 2 parts of LAS
to 1 part of alcohol ethoxylate.
Ex. 4 Ex. 5 Comparative Ex. 6 AS/NI Paste 30 - 30 LAS/NI paste - 30 -Alkyl sulphate powder 20 20 -Zeolite MAP 35 35 55 Sodium citrate 5 5 5 Water / Misc. minors 10 10 10 In each of examples 4 and 5 the AS/NI paste, or the LAS/NI
paste, was fed into a continuous twin-screw extruder. The alkyl sulphate powder was added directly to into the barrel of the extruder through an inlet port. The mixture was then extruded through a die directly into a high shear mixer (Loedige° CB) where is mixed with powder streams comprising the sodium citrate and the zeolite. The resulting product WO 98/01529 - PCT/L1S97l11282 was then passed to a medium shear mixer (Loedige~ KM) resulting in a free-flowing detergent product in the form of agglomerates.
In comparative example 6 the AS/NI paste was fed diectly into the high shear mixer.
The bulk density of the product from each of the examples was between 680 and 700 g/1.
Claims (6)
1. A process for making a granular detergent component or composition comprising the steps of:
(i) forming a neutral or alkaline paste comprising at least 40% by weight of anionic surfactant;
(ii) mixing a first powder with the surfactant paste at a temperature less then 100°C, in a ratio of at least 1 part powder to 100 parts paste, and whereby the mixing step increases the viscosity of the surfactant paste, from about 5,000 cps to 10,000,000 cps;
(iii) forming the granular detergent component or composition at a temperature from about 25°C to about 60°C, by mixing the high viscosity paste so-formed with builder powders selected from the group consisting of carbonate, aluminosilicate, silicate, and mixtures thereof, wherein the ratio of high viscosity paste to builder powder is from 9:1 to 1:5, having a bulk density of from about 0.4 to about 1.2 g/cc, characterised in that the first powder comprises at least 80% by weight of alkyl sulphate, wherein the alkyl sulphate, comprises less than 5% by weight of water.
(i) forming a neutral or alkaline paste comprising at least 40% by weight of anionic surfactant;
(ii) mixing a first powder with the surfactant paste at a temperature less then 100°C, in a ratio of at least 1 part powder to 100 parts paste, and whereby the mixing step increases the viscosity of the surfactant paste, from about 5,000 cps to 10,000,000 cps;
(iii) forming the granular detergent component or composition at a temperature from about 25°C to about 60°C, by mixing the high viscosity paste so-formed with builder powders selected from the group consisting of carbonate, aluminosilicate, silicate, and mixtures thereof, wherein the ratio of high viscosity paste to builder powder is from 9:1 to 1:5, having a bulk density of from about 0.4 to about 1.2 g/cc, characterised in that the first powder comprises at least 80% by weight of alkyl sulphate, wherein the alkyl sulphate, comprises less than 5% by weight of water.
2. A process according to claim 1 wherein the granular detergent component or composition has a bulk density of at least 0.6 g/cc and comprises anionic surfactant at a level of between 40% and 60% by weight of the component or composition.
3. A process according to claim 1 wherein the surfactant paste is mixed with a process aid selected from the group consisting of starch, soap, fatty acid, polymer, or mixtures thereof.
4. A process according to claim 3 wherein the surfactant paste and process aid are mixed either between steps (i) and (ii), or in step (ii).
5. A process according to any one of claims 1, 2, 3 or 4 wherein step (ii) is carried out in an extruder.
6. A process according to any one of claims 1, 2, 3, 4 or 5 wherein step (iii) is carried out sequentially in a high-shear mixer granulator having a tool tip-speed of from 5 to 50 m/sec, and a medium speed agglomerator.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96201855A EP0816486B1 (en) | 1996-07-04 | 1996-07-04 | Process for conditioning of surfactant pastes to form high active surfactant agglomerates |
EP96201855.2 | 1996-07-04 | ||
PCT/US1997/011282 WO1998001529A1 (en) | 1996-07-04 | 1997-06-27 | Process for conditioning of surfactant pastes to form high active surfactant agglomerates |
Publications (2)
Publication Number | Publication Date |
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CA2260008A1 CA2260008A1 (en) | 1998-01-15 |
CA2260008C true CA2260008C (en) | 2002-05-21 |
Family
ID=8224141
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002260008A Expired - Fee Related CA2260008C (en) | 1996-07-04 | 1997-06-27 | Process for conditioning of surfactant pastes to form high active surfactant agglomerates |
Country Status (10)
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EP (1) | EP0816486B1 (en) |
JP (1) | JPH11514034A (en) |
CN (1) | CN1228115A (en) |
AR (1) | AR008771A1 (en) |
AT (1) | ATE264384T1 (en) |
AU (1) | AU3644297A (en) |
BR (1) | BR9710197A (en) |
CA (1) | CA2260008C (en) |
DE (1) | DE69632187T2 (en) |
WO (1) | WO1998001529A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US6172033B1 (en) | 1996-07-04 | 2001-01-09 | The Procter & Gamble Company | Process for conditioning of surfactant pastes to form high active surfactant agglomerates |
DE19722767A1 (en) * | 1997-06-02 | 1998-12-03 | Henkel Kgaa | Detergents or cleaning agents with increased cleaning performance |
DE19911570A1 (en) * | 1999-03-16 | 2000-09-28 | Henkel Kgaa | Anionic surfactant granules |
EP1505147B1 (en) * | 2003-08-06 | 2008-04-02 | Kao Corporation | Process for producing granular anionic surfactant |
JP4319133B2 (en) * | 2003-12-26 | 2009-08-26 | 花王株式会社 | Method for producing granular anionic surfactant |
CN1883784B (en) * | 2005-06-21 | 2010-10-13 | 花王株式会社 | Process for preparing granular anionic surfactant |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU612504B2 (en) * | 1988-07-21 | 1991-07-11 | Unilever Plc | Detergent compositions and process for preparing them |
US5494599A (en) * | 1991-04-12 | 1996-02-27 | The Procter & Gamble Company | Agglomeration of high active pastes to form surfactant granules useful in detergent compositions |
EP0508543B1 (en) * | 1991-04-12 | 1997-08-06 | The Procter & Gamble Company | Chemical structuring of surfactant pastes to form high active surfactant granules |
DE4203031A1 (en) * | 1992-02-04 | 1993-08-05 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF SOLID DETERGENT AND CLEANING AGENT WITH HIGH SHOCK WEIGHT AND IMPROVED SOLUTION SPEED |
ES2131524T3 (en) * | 1992-03-10 | 1999-08-01 | Procter & Gamble | VERY ACTIVE DETERGENT PASTES. |
US5529722A (en) * | 1992-03-10 | 1996-06-25 | The Procter & Gamble Company | High active detergent pastes |
ES2179054T5 (en) * | 1992-06-15 | 2006-06-16 | THE PROCTER & GAMBLE COMPANY | PROCEDURE TO PREPARE COMPACT DETERGENT COMPOSITIONS. |
US5529710A (en) * | 1992-07-15 | 1996-06-25 | The Procter & Gamble Company | Production of detergent granules with excellent white appearance |
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 |
-
1996
- 1996-07-04 EP EP96201855A patent/EP0816486B1/en not_active Expired - Lifetime
- 1996-07-04 AT AT96201855T patent/ATE264384T1/en not_active IP Right Cessation
- 1996-07-04 DE DE69632187T patent/DE69632187T2/en not_active Expired - Fee Related
-
1997
- 1997-06-27 CN CN97197366.0A patent/CN1228115A/en active Pending
- 1997-06-27 WO PCT/US1997/011282 patent/WO1998001529A1/en active Application Filing
- 1997-06-27 BR BR9710197A patent/BR9710197A/en not_active Application Discontinuation
- 1997-06-27 AU AU36442/97A patent/AU3644297A/en not_active Abandoned
- 1997-06-27 CA CA002260008A patent/CA2260008C/en not_active Expired - Fee Related
- 1997-06-27 JP JP10505242A patent/JPH11514034A/en active Pending
- 1997-07-03 AR ARP970102993A patent/AR008771A1/en not_active Application Discontinuation
Also Published As
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WO1998001529A1 (en) | 1998-01-15 |
AR008771A1 (en) | 2000-02-23 |
JPH11514034A (en) | 1999-11-30 |
ATE264384T1 (en) | 2004-04-15 |
CN1228115A (en) | 1999-09-08 |
BR9710197A (en) | 1999-08-10 |
DE69632187T2 (en) | 2005-03-17 |
EP0816486B1 (en) | 2004-04-14 |
DE69632187D1 (en) | 2004-05-19 |
CA2260008A1 (en) | 1998-01-15 |
AU3644297A (en) | 1998-02-02 |
EP0816486A1 (en) | 1998-01-07 |
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