WO1995029215A1 - Procede de fabrication de granules detersives coulantes - Google Patents
Procede de fabrication de granules detersives coulantes Download PDFInfo
- Publication number
- WO1995029215A1 WO1995029215A1 PCT/US1995/004798 US9504798W WO9529215A1 WO 1995029215 A1 WO1995029215 A1 WO 1995029215A1 US 9504798 W US9504798 W US 9504798W WO 9529215 A1 WO9529215 A1 WO 9529215A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- paste
- process according
- weight
- spray dried
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 34
- 239000003599 detergent Substances 0.000 title claims abstract description 20
- 239000008187 granular material Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 41
- 239000004094 surface-active agent Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 24
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 6
- 150000007513 acids Chemical class 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 29
- 239000007921 spray Substances 0.000 claims description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 22
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 235000011837 pasties Nutrition 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 3
- 229940091181 aconitic acid Drugs 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 235000003704 aspartic acid Nutrition 0.000 claims description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 3
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 229960002598 fumaric acid Drugs 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 claims description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 3
- 125000002348 vinylic group Chemical group 0.000 claims description 3
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical group 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- 229940018557 citraconic acid Drugs 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 28
- 239000000463 material Substances 0.000 description 24
- 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 22
- 125000000217 alkyl group Chemical group 0.000 description 22
- 239000011734 sodium Substances 0.000 description 22
- 229910052708 sodium Inorganic materials 0.000 description 21
- 238000005342 ion exchange Methods 0.000 description 17
- -1 alkyl sulphate Chemical compound 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000005469 granulation Methods 0.000 description 10
- 230000003179 granulation Effects 0.000 description 10
- 239000002736 nonionic surfactant Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 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
- 230000000694 effects Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 159000000001 potassium salts Chemical class 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229920013820 alkyl cellulose Polymers 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 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
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000014366 other mixer Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000015227 regulation of liquid surface tension Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000019351 sodium silicates Nutrition 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 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
- QSGNIOHURMPLSO-OLGQORCHSA-N (z)-2-methylbut-2-enedioic acid;2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O.OC(=O)C(/C)=C\C(O)=O QSGNIOHURMPLSO-OLGQORCHSA-N 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
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 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
- 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000388 Polyphosphate Chemical class 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 101000693619 Starmerella bombicola Lactone esterase Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 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
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes 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
- 150000001408 amides Chemical class 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
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 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
- UZABCLFSICXBCM-UHFFFAOYSA-N ethoxy hydrogen sulfate Chemical compound CCOOS(O)(=O)=O UZABCLFSICXBCM-UHFFFAOYSA-N 0.000 description 1
- LSJWUSSUFZMXQM-UHFFFAOYSA-N ethoxy(dimethyl)azanium;chloride Chemical compound [Cl-].CCO[NH+](C)C LSJWUSSUFZMXQM-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 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
- 239000010419 fine particle Substances 0.000 description 1
- 150000002222 fluorine compounds 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
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052739 hydrogen Chemical group 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 150000002689 maleic acids Chemical class 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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Chemical class 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
Definitions
- the present invention is concerned with a process for the manufacture of free & flowing detergent granules having a bulk density of at least 600 g/1 which comprises the addition of a spray dried powder comprising anionic polymer and cationic surfactant.
- Cationic surfactants are well-known detergent ingredients which are used, in particular, for imparting a soft feel to fabrics after they have been washed.
- the most commonly used cationic surfactants are commercially available as aqueous
- tl SHEET RULE 26 solutions typically with a surfactant activity of about 35% or 40%.
- Anionic polymers such as polycarboxylates are also well- known detergent ingredients. It has been found to be particularly beneficial to incorporate such polymers into surfactant pastes during the process of preparing high density detergent granules.
- EP508543 published on 12th April 1991 describes a process in which a surfactant paste is structured (or "conditioned") with various agents, including polycarboxylate, prior to an agglomeration step. The addition of the polymer enables higher surfactant activities to be achieved in this process whilst still providing free-flowing, high bulk density detergent granules with a rapid rate of dissolution.
- the present invention provides a process for incorporating aqueous solutions of cationic surfactants into free- flowing, high bulk density, high active detergent granules.
- the objective of the present invention is achieved by complexing anionic polymer with cationic surfactant in solution.
- the solution is then spray dried and mixed with high active surfactant pastes, preferably in a twin screw extruder, prior to agglomeration resulting in high active surfactant agglomerates of desirable properties.
- the present invention provides a process for the manufacture of free flowing detergent granules having a bulk density of at least 600 g/1, comprising the steps of: a) neutralising anionic surfactant acid or acids in an excess of alkali to form a paste, and optionally mixing other surfactants with the paste, to give a total surfactant level in the paste of at least 40% by weight; b) mixing said paste with one or more powders to form a granular product; and c) optionally drying the granular product. wherein at least one of the powders in step b) is spray dried and comprises anionic polymer and cationic surfactant.
- step b) comprises the steps of: b) (i) mixing said paste with at least one spray dried powder comprising anionic polymer and cationic surfactant to form a homogeneous pasty mixture; and subsequently b) (ii) mixing the homogeneous pasty mixture with additional powders in a high shear mixer to form the granular product.
- the spray dried powder which is added in step (b) preferably comprises:
- the spray-dried powder comprises less than 10% by weight, preferably less than 5% by weight, (on anhydrous basis) of inorganic components. If however inorganic components are present, the spray dried component should comprise less than 5% by weight (on anhydrous basis) of aluminosilicate, carbonate and tripolyphosphate. It is also preferred that the spray dried powder comprises less than 10%, more preferably less than 1% by weight of anionic surfactant.
- a useful anionic polymer (II) is one which comprises carboxylate functional groups.
- Such a polymer may be selected from the group consisting of water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as acrylic acid, maleic acid, vinylic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, methylenemalonic acid, aspartic acid and mixtures thereof.
- hydrophobically modified polycarboxylates partially esterfied with long chain alcohols
- anionic polymer (II) is a copolymer of maleic and acrylic acid having a molecular weight of from 2 000 to 100 000.
- a useful cationic surfactant (I) is a quaternary ammonium salt such as ditallow dimethyl ammonium chloride or coco dimethyl ethoxy ammonium chloride.
- One or various aqueous pastes of the salts of anionic surfactants, and optionally nonionic surfactants are preferred for use in the present invention, preferably comprising the sodium salt of the anionic surfactant.
- the anionic surfactant, or anionic / nonionic surfactant mix 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.
- a surfactant must be part of the paste in a concentration of preferably from 40% to 95%, more preferably from 60% to 85% by weight.
- the moisture in the surfactant aqueous paste is as low as possible, while maintaining paste fluidity, since low moisture leads to a higher concentration of the surfactant in the finished particle.
- the paste contains between 0 and 40% water, more preferably between 5 and 30% water and most preferably between 5% and 20% water.
- high active surfactant pastes it is preferable to use high active surfactant pastes to minimize the total water level in the system during mixing, granulating and drying.
- Lower water levels allow for: (1) a higher active surfactant to builder ratio, e.g., 1:1; (2) higher levels of other liquids in the formula without causing dough or granular stickiness; and (3) less granular drying to meet final moisture limits.
- Viscosity is a function, among others, of concentration and temperature, with a range in this application up to about 10,000 Pas.
- the viscosity of the paste entering the system is from about 1 Pas to about 100 Pas. and more preferably from about 10 Pas to about 70 Pas.
- the viscosity of the paste of this invention is measured at a temperature of 70°C and a shear rate of 25 s-***.
- the paste can be introduced into the mixer at an initial temperature between its softening point (generally in the range of 20-60°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
- R t 26 the paste but result in lower active agglomerates.
- the use of in-line cooling steps are preferred ways to increase agglomerate activity.
- the use of in-line moisture reduction steps e.g. flash drying, however, require the use of higher temperatures (above 100°C) .
- 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 parste results in a better distribution in the mixer which improves the yield of particles with the desired size.
- the use of high pumping pressures prior to the entrance in the mixer results in an increased activity in the final agglomerates.
- the activity of the aqueous surfactant paste is at least 40% and can go up to about 95%; preferred activities are 60% to 85%, most preferred are 70% to 85%. At the higher active concentrations, little or no builder is required for cold granulation of the paste.
- the resultant high active 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, nonionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof. Anionic surfactants, and mixtures of anionic and nonionic surfactants are preferred. Surfactants useful herein are listed in U.S.
- Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
- Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
- Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- Useful anionic surfactants also include the water- soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-Cie 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 LAS.
- Suitable 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-l-
- the acid salts are typically discussed and used, the acid neutralization cam be performed as part of the fine dispersion mixing step.
- Water-soluble nonionic surfactants are also useful as surfactants 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 4:1.
- 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 2 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 2 to 25 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
- Nonionics are polyhydroxy fatty acid amides, such as tallow N-methyl glucose amide, and alkyl poly glucoside.
- Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water- soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
- Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
- Preferred cationic surfactants are water soluble quartenary ammonium salts containing one or two long alkyl groups containing from 10 to 14 carbon atoms and 2 or 3 short alkyl groups each of which contain no more than 2 carbon atoms and optionally have ethoxy groups.
- Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4R5RgR7N + X ⁇ , wherein R4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R5 is C ⁇ _ to C20 / R 6 anci R 7 are each C]_ to C7 alkyl preferably methyl; X ⁇ is an anion, e.g. chloride.
- trimethyl ammonium compounds examples include C12-1 alkyl trimethyl ammonium chloride, C12-14 alkyl dimethyl ethoxy ammonium chloride and cocalkyl trimethyl ammonium methosulfate.
- Other useful cationic surfactants are described in US Pat No. 4,222,905, Cockrell, issued Sept 16, 1990 and in US Pat No 4,239,659, Murphy, issued Dec. 16, 1980.
- Useful organic polymers may also 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, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000.
- Polymeric polycarboxyate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as acrylic acid, maleic acid, vinylic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid methylenemalonic acid, and aspartic acid. ⁇
- the spray dried powder comprising the cationic surfactant and anionic polymer may be prepared by any conventional method, such as spray drying using pressure nozzle, two- fluid nozzle or spinning disc atomiser.
- the spinning disc atomiser and the two fluid nozzle are preferred.
- the spray dried powder is preferably mixed with the high active surfactant paste to form a uniform pasty mixture.
- the high active paste may also be thickened or "structured". Suitable thickening or structuring agents are fatty acids, fatty acid soaps, silicates and polymers. It is preferred that the mixing of this processing step is carried out in an extruder.
- the extruder fulfills 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.
- Additional ports in the barrel may allow other ingredients, including the spray dried powder to be added directly into the barrel.
- 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 Baker, (CP series) ; Werner and Pfleiderer, (Continua Series) ; Wenger, (TF Series); Leistritz, (ZSE Series); and Buss, (LR Series) .
- high shear mixing means mixing and/or granulation of the above pasty mixture with powders in a high shear mixer at a blade tip speed of from about 5m/sec. to about 50 ml 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.
- the ratio of pasty mixture to powder should be chosen in order to maintain discrete particles at all stages of the process. These particles may be sticky but must be substantially free flowing so that the mixing and granulation steps can be carried out simultaneously, or immediately sequentially without causing blockage of the mixer/granulator.
- Suitable apparatus includes, for example, falling film sulphonating reactors, digestion tanks, esterification reactors, etc.
- mixing/ agglomeration any of a number of mixers/agglomerators can be used.
- the process of the invention is continuously carried out.
- mixers of the Fukae R FS-G series manufactured by Fukae Powtech Kogyo Co., Japan 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 inlcude Diosna R V series ex Dierks & S ⁇ hne, Germany; and the Pharma Matrix R ex T K Fielder Ltd., England.
- Other mixers believed to be suitable for use in the process of the invention are the Fuji R VG-C series ex Fuji Sangyo Co., Japan; and the Roto R ex Zanchetta & Co srl, Italy.
- Other preferred suitable equipment can include Eirich R , series RV, manufactured by Gustau Eirich Hardheim, Germany; L ⁇ dige R , series CB and KM in series for continuous mixing/agglomeration, manufactured by L ⁇ dige Machinenbau GmbH, Paderborn Germany; Drais R T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth R RT 25 series, manufactured by Winkworth Machinery Ltd., Bershire, England.
- the Littleford Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two examples of suitable mixers. Any other mixer with fine dispersion mixing and granulation capability and having a residence time in the order of 0.1 to 10 minutes can be used.
- the "turbine-type" impeller mixer, having several blades on an axis of rotation, is preferred.
- the invention can be practiced as a batch or a continuous process. Operating Temperatures
- Preferred operating temperatures should also be as low as possible since this leads to a higher surfactant concentration in the finished particle.
- the temperature during the agglomeration is less than 100°C, more preferably between 10 and 90°C, and most preferably between 25 and 80°C.
- Lower operating temperatures useful in the process of the present invention may be achieved by a variety of methods known in the art such as nitrogen cooling, cool water jacketing of the equipment, addition of solid CO2, and the like; with a preferred method being solid CO2, and the most preferred method being nitrogen cooling.
- powders are suitable for use in the granulation step of the present process.
- Prefered powders for use in the process and compositions of the present invention are compatible detergency builder or combination of builders or powder.
- the detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula Na z [ (A10 2 ) z * (Si0 2 ) y ] *xH 2 0 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 ⁇
- 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.
- 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 CaC ⁇ 3 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/galIon.
- 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, incorporated herein by reference.
- Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite MAP and Zeolite X.
- the crystalline aluminosilicate ion exchange material has the formula
- 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.
- 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, citrates, silicas and polyhyroxysulfonates.
- alkali metal especially sodium, salts of the above.
- inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
- polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-l, 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, incorporated herein by reference.
- nonphosphorus, inorganic .builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of Si ⁇ 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
- Highly preferred materials within the silicate class are crystalline layered sodium silicates of general formula :
- NaMSi ⁇ 2 ⁇ + ⁇ -yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.
- Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A- 3417649 and DE-A-3742043.
- x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the ⁇ and ⁇ forms of Na2Si2 ⁇ s. These materials are available from Hoechst AG FRG as respectively NaSKS-11 and NaSKS-6.
- the most preferred material is ⁇ -Na2Si2 ⁇ 5, (NaSKS-6) .
- Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.
- the compositions made by the process of the present invention does not require excess carbonate for processing, and preferably does not contain over 2% finely divided calcium carbonate as disclosed in U.S. Pat. No. 4,196,093, Clarke et al., issued Apr.l, 1980, and is .preferably free of the latter.
- composition was prepared by mixing a 40% active solution of the sodium salt of the copolymer and a 40% active solution of fatty alkyldimethylhydroxethylamoniumchloride to give a well mixed slurry.
- the slurry was then processed through a continuous spray dryer with concurrent air inlet and a rotatin ⁇ disc (15000 rpm) at the top of the tower. After the exit from the bottom of the tower, the product is further dried and cooled in a fluid bed dryer and fluid bed cooler in series. After classification (removal of fines and oversize particles) by vibrating screens, the resulting spray dried powder had an apparent bulk density of 250 g/1.
- An aqueous surfactant paste was prepared comprising :
- aqueous surfactant paste and the powder compound described in example one were intimately mixed in a twin screw extruder (manufactured by Werner & Pfleiderer, C170) .
- the resulting viscous paste was extruded (at a temperature of 60°C) directly into a Loedige CB30 (trade name) high speed mixer containing a mixture of 2 part zeolite A to 1 part finely divided light carbonate.
- the mixer operates on a continuous basis and discharges directly into a Loedige KM 3000 (trade name) continuous ploughshare- ixer.
- the resulting agglomerates were transferred to a fluid bed drier, cooled in a fluid bed cooler and then' classified through mesh sieves to remove oversize and fine particles.
- the agglomerates formed have an anionic surfactant content of 40% by weight, a polymer level of 14%, a cationic surfactant level of 7% and an equilibrium relative humidity level of 10% at room temperature.
- the granules have an apparent bulk density of 680 g/1 and have excellent flow and handling properties.
- This powder had a bulk density of 300 g/L.
- This powder was then incorporated into a free flowing, high density particle, by the same process as described in example 1 (b) , (except that the composition of the powder mixture entering the high speed mixer was: Zeolite A, 42%; light sodium carbonate 58%) to give a free flowing granular product having an anionic surfactant content of 40%, a polymer content of 7%, a cationic surfactant level of 7%, and an equilibrium relative humidity level of 10% at room temperature.
- the granules have an apparent bulk density of 700 g/1 and have excellent flow and handling properties.
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Abstract
La présente invention concerne un procédé de fabrication de granules détersives coulantes présentant une masse volumique apparente d'au moins 600 g/l. Ce procédé se décompose en plusieurs opérations: a) neutralisation du ou des acides tensioactifs anioniques dans un excédent d'alcali pour former une pâte, et mélange facultatif à la pâte d'autres agents tensioactifs pour obtenir une teneur pondérale totale d'au moins 40 % d'agents tensioactifs dans la pâte; b) mélange de ladite pâte avec une ou plusieurs poudres permettant de former un produit granulaire; et c) séchage facultatif du produit granulaire. Selon ce procédé, au moins l'une des poudres de l'opération b) est séchée par pulvérisation et comporte un polymère anionique et un agent tensioactif cationique.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX9604965A MX9604965A (es) | 1995-04-20 | 1995-04-20 | Procedimiento para la manufactura de granulos de detergente de libre flujo. |
US08/722,089 US5703037A (en) | 1994-04-20 | 1995-04-20 | Process for the manufacture of free-flowing detergent granules |
CA002187516A CA2187516C (fr) | 1994-04-20 | 1995-04-20 | Procede de fabrication de granules detersives coulantes |
AU23892/95A AU2389295A (en) | 1994-04-20 | 1995-04-20 | Process for the manufacture of free-flowing detergent granules |
BR9507325A BR9507325A (pt) | 1994-04-20 | 1995-04-20 | Processo para a fabrição de grânulos detergentes com livre escoamento |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94201090.1 | 1994-04-20 | ||
EP94201090A EP0678573B1 (fr) | 1994-04-20 | 1994-04-20 | Procédé de préparation de granules s'écoulant librement |
Publications (1)
Publication Number | Publication Date |
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WO1995029215A1 true WO1995029215A1 (fr) | 1995-11-02 |
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ID=8216814
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1995/004798 WO1995029215A1 (fr) | 1994-04-20 | 1995-04-20 | Procede de fabrication de granules detersives coulantes |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0678573B1 (fr) |
JP (1) | JP2763403B2 (fr) |
CN (1) | CN1078246C (fr) |
AT (1) | ATE197811T1 (fr) |
AU (1) | AU2389295A (fr) |
BR (1) | BR9507325A (fr) |
CA (1) | CA2187516C (fr) |
DE (1) | DE69426356T2 (fr) |
ES (1) | ES2152286T3 (fr) |
PE (1) | PE4996A1 (fr) |
PH (1) | PH31632A (fr) |
WO (1) | WO1995029215A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0881279A2 (fr) † | 1997-05-26 | 1998-12-02 | Henkel Kommanditgesellschaft auf Aktien | Procédé de préparation de granules contenant un tensioactif cationique |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0745662B1 (fr) * | 1994-12-15 | 2004-06-16 | Nippon Shokubai Co., Ltd. | Adjuvant pour detergent, son procede de fabrication et composition detergente le contenant |
DE19844523A1 (de) | 1998-09-29 | 2000-03-30 | Henkel Kgaa | Granulationsverfahren |
DE10163603B4 (de) | 2001-12-21 | 2006-05-04 | Henkel Kgaa | Verfahren zur Herstellung builderhaltiger Tensidgranulate |
DE102008059447A1 (de) * | 2008-11-27 | 2010-06-02 | Henkel Ag & Co. Kgaa | Wasch- und Reinigungsmittel enthaltend Proteasen aus Bacillus pumilus |
DE102012217877A1 (de) | 2012-10-01 | 2013-08-14 | Henkel Ag & Co. Kgaa | Nontower-Verfahren |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4704221A (en) * | 1986-10-22 | 1987-11-03 | The Procter & Gamble Company | Granular detergents which contain high levels of anionic surfactant that forms a middle-phase, surface treated with a water soluble cationic surfactant |
EP0438320A2 (fr) * | 1990-01-19 | 1991-07-24 | Unilever Plc | Compositions détergentes et leur procédÀ© de préparation |
US5066425A (en) * | 1990-07-16 | 1991-11-19 | The Procter & Gamble Company | Formation of high active detergent particles |
EP0352135B1 (fr) * | 1988-07-21 | 1994-09-28 | Unilever Plc | Compositions détergentes et procédé pour leur préparation |
EP0402112B1 (fr) * | 1989-06-09 | 1996-08-14 | The Procter & Gamble Company | Formation de granules de détergent discrets à haute activité utilisant un système de neutralisation continu |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3521498A1 (de) * | 1984-06-20 | 1986-01-16 | Lion Corp., Tokio/Tokyo | Additiv fuer waschmittel-granulat |
JPS6272799A (ja) * | 1985-09-26 | 1987-04-03 | ライオン株式会社 | 粒状洗剤用添加剤 |
JPS62146998A (ja) * | 1985-12-19 | 1987-06-30 | ライオン株式会社 | 粒状洗剤用添加剤およびその製造方法 |
EP0508543B1 (fr) * | 1991-04-12 | 1997-08-06 | The Procter & Gamble Company | Structuration chimique de pâtes tensio-actives pour former des granulés tensio-actifs avec haute activité |
-
1994
- 1994-04-20 ES ES94201090T patent/ES2152286T3/es not_active Expired - Lifetime
- 1994-04-20 EP EP94201090A patent/EP0678573B1/fr not_active Expired - Lifetime
- 1994-04-20 DE DE69426356T patent/DE69426356T2/de not_active Expired - Fee Related
- 1994-04-20 AT AT94201090T patent/ATE197811T1/de not_active IP Right Cessation
-
1995
- 1995-04-20 CA CA002187516A patent/CA2187516C/fr not_active Expired - Fee Related
- 1995-04-20 WO PCT/US1995/004798 patent/WO1995029215A1/fr active Application Filing
- 1995-04-20 PH PH50365A patent/PH31632A/en unknown
- 1995-04-20 PE PE1995266823A patent/PE4996A1/es not_active Application Discontinuation
- 1995-04-20 JP JP7527733A patent/JP2763403B2/ja not_active Expired - Fee Related
- 1995-04-20 CN CN95193542A patent/CN1078246C/zh not_active Expired - Fee Related
- 1995-04-20 AU AU23892/95A patent/AU2389295A/en not_active Abandoned
- 1995-04-20 BR BR9507325A patent/BR9507325A/pt not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4704221A (en) * | 1986-10-22 | 1987-11-03 | The Procter & Gamble Company | Granular detergents which contain high levels of anionic surfactant that forms a middle-phase, surface treated with a water soluble cationic surfactant |
EP0352135B1 (fr) * | 1988-07-21 | 1994-09-28 | Unilever Plc | Compositions détergentes et procédé pour leur préparation |
EP0402112B1 (fr) * | 1989-06-09 | 1996-08-14 | The Procter & Gamble Company | Formation de granules de détergent discrets à haute activité utilisant un système de neutralisation continu |
EP0438320A2 (fr) * | 1990-01-19 | 1991-07-24 | Unilever Plc | Compositions détergentes et leur procédÀ© de préparation |
US5066425A (en) * | 1990-07-16 | 1991-11-19 | The Procter & Gamble Company | Formation of high active detergent particles |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0881279A2 (fr) † | 1997-05-26 | 1998-12-02 | Henkel Kommanditgesellschaft auf Aktien | Procédé de préparation de granules contenant un tensioactif cationique |
EP0881279B2 (fr) † | 1997-05-26 | 2007-04-18 | Cognis IP Management GmbH | Granules contenant un tensioactif cationique |
Also Published As
Publication number | Publication date |
---|---|
EP0678573A1 (fr) | 1995-10-25 |
DE69426356D1 (de) | 2001-01-04 |
CN1150449A (zh) | 1997-05-21 |
ATE197811T1 (de) | 2000-12-15 |
JPH09512299A (ja) | 1997-12-09 |
PE4996A1 (es) | 1996-04-01 |
EP0678573B1 (fr) | 2000-11-29 |
JP2763403B2 (ja) | 1998-06-11 |
PH31632A (en) | 1999-01-12 |
CA2187516C (fr) | 2000-02-15 |
CN1078246C (zh) | 2002-01-23 |
CA2187516A1 (fr) | 1995-11-02 |
AU2389295A (en) | 1995-11-16 |
ES2152286T3 (es) | 2001-02-01 |
DE69426356T2 (de) | 2001-06-21 |
BR9507325A (pt) | 1997-09-30 |
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