EP0349199B1 - Zweistufiges Trocknen von Waschmittelzusammensetzungen - Google Patents
Zweistufiges Trocknen von Waschmittelzusammensetzungen Download PDFInfo
- Publication number
- EP0349199B1 EP0349199B1 EP89306334A EP89306334A EP0349199B1 EP 0349199 B1 EP0349199 B1 EP 0349199B1 EP 89306334 A EP89306334 A EP 89306334A EP 89306334 A EP89306334 A EP 89306334A EP 0349199 B1 EP0349199 B1 EP 0349199B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- water
- slurry
- granules
- pyrophosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 57
- 239000003599 detergent Substances 0.000 title claims description 29
- 238000001035 drying Methods 0.000 title claims description 18
- 239000008187 granular material Substances 0.000 claims description 73
- 239000002002 slurry Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 39
- -1 alkali metal tripolyphosphate Chemical class 0.000 claims description 36
- 239000011734 sodium Substances 0.000 claims description 33
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 31
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 30
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 30
- 229910052708 sodium Inorganic materials 0.000 claims description 30
- 238000005342 ion exchange Methods 0.000 claims description 26
- 235000011180 diphosphates Nutrition 0.000 claims description 25
- 239000007921 spray Substances 0.000 claims description 21
- 238000001694 spray drying Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 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 17
- 238000000034 method Methods 0.000 claims description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 11
- 159000000011 group IA salts Chemical class 0.000 claims description 11
- 239000000344 soap Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Chemical group 0.000 claims description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 235000010216 calcium carbonate Nutrition 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 229910009112 xH2O Inorganic materials 0.000 claims description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 description 27
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 21
- 125000000217 alkyl group Chemical group 0.000 description 19
- 229940048084 pyrophosphate Drugs 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 16
- 150000001340 alkali metals Chemical class 0.000 description 10
- 229920000388 Polyphosphate Polymers 0.000 description 7
- 239000003093 cationic surfactant Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 229920005646 polycarboxylate Polymers 0.000 description 7
- 239000001205 polyphosphate Substances 0.000 description 7
- 235000011176 polyphosphates Nutrition 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- 159000000001 potassium salts Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003760 tallow Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 229930182556 Polyacetal Natural products 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 238000010981 drying operation Methods 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000007844 bleaching agent 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
- 239000007859 condensation product Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000004687 hexahydrates Chemical group 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000019820 disodium diphosphate Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 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
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- VJSWLXWONORKLD-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-trisulfonic acid Chemical compound OC1=C(S(O)(=O)=O)C(O)=C(S(O)(=O)=O)C(O)=C1S(O)(=O)=O VJSWLXWONORKLD-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- 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
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910015955 MxHy Inorganic materials 0.000 description 1
- SXKQTYJLWWQUKA-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.O.OB(O)O.OB(O)O.OB(O)O.OB(O)O Chemical compound O.O.O.O.O.O.O.O.O.O.OB(O)O.OB(O)O.OB(O)O.OB(O)O SXKQTYJLWWQUKA-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910001491 alkali aluminosilicate Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000005192 alkyl ethylene group Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 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
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004691 decahydrates Chemical class 0.000 description 1
- JIBFYZIQZVPIBC-UHFFFAOYSA-L dipotassium;2-(carboxymethoxy)propanedioate Chemical compound [K+].[K+].OC(=O)COC(C([O-])=O)C([O-])=O JIBFYZIQZVPIBC-UHFFFAOYSA-L 0.000 description 1
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
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- 125000005313 fatty acid group Chemical group 0.000 description 1
- 239000000945 filler Substances 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
- 150000004820 halides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 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
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- 150000004690 nonahydrates Chemical class 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
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts 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
- 229910021647 smectite Inorganic materials 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- VZWGHDYJGOMEKT-UHFFFAOYSA-J sodium pyrophosphate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O VZWGHDYJGOMEKT-UHFFFAOYSA-J 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- YIVJSMIYMAOVSJ-UHFFFAOYSA-M sodium;hydron;phosphonato phosphate Chemical compound [Na+].OP(O)(=O)OP(O)([O-])=O YIVJSMIYMAOVSJ-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001180 sulfating effect Effects 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
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- MLIKYFGFHUYZAL-UHFFFAOYSA-K trisodium;hydron;phosphonato phosphate Chemical compound [Na+].[Na+].[Na+].OP([O-])(=O)OP([O-])([O-])=O MLIKYFGFHUYZAL-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- 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
- C11D11/02—Preparation in the form of powder by spray drying
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
Definitions
- the present invention relates to a process for preparing granular detergent compositions by a two step drying operation that results in granules having a low level of reversion of polyphosphate builder (i.e., reversion of tripolyphosphate to pyrophosphate and orthophosphate, or reversion of pyrophosphate to orthophosphate) and/or improved solubility due to a low level of insoluble silicate formation.
- aqueous slurry comprising the tripolyphosphate, pyrophosphate and/or silicate, other neutral or alkaline salt, water, and optional detergent surfactant
- the slurry is spray dried in a spray drying tower in a manner such that the granule temperature does not exceed 90°C.
- the granule temperature refers to the bulk granule temperature.
- the partially dried granules are then placed in a secondary dryer to complete the drying operation.
- the granule temperature does not exceed 90°C to minimize polyphosphate reversion in compositions containing tripolyphosphate and/or pyrophosphate, and to minimize formation of silicate insolubles in compositions containing silicate.
- Granules prepared by the gentle two stage drying process herein also exhibit improved physical properties, such as better flow characteristics and lower caking grades, versus corresponding spray dried granules containing the same water content. Alternatively, granules exhibiting similar physical properties can be obtained at higher moisture levels when prepared by the present process.
- US-A-3 629 951 and US-A-3 629 955 both published on December 28th, 1971, disclose a means for spray drying large volumes of a synthetic detergent slurry using uniformly spaced atomizing nozzles positioned at at least two different levels, the lower level being in a region having a temperature above 88°C (190°F).
- One of the benefits claimed. is reduced phosphate reversion. No secondary drying stage is suggested.
- GB-A-1 237 084 published on 30th June 1971, discloses a soap drying process. Soap slurries are passed through a spray-cooling or spray-drying tower and subsequently through a fluidised bed.
- Spray-drying processes in general using aqueous crutcher mix slurries are commonly known in the state of the art. Such aqueous slurries often contain from about 25% to 50% by weight of water to allow the slurry to be pumped to the top of spray drying towers. Processes for spray drying large volumes of such slurries in spray drying towers typically utilize inlet air temperatures greater than about 200°C, and often in the range of 300°C to 375°C, in order to remove excess water in the short time (generally about 30 seconds) that the granules remain in the spray drying tower. Crisp, free flowing granules generally contain little free water.
- the amount of free water in the granules varies depending upon the drying conditions (e.g., time, temperature, and air flow) encountered by any particular granule. Some of the granules are over-dried and not only lose all free water, but also bound water or water of hydration. It has been found that when the granule temperature exceeds about 90°C during drying, excessive amounts of tripolyphosphate and pyrophosphate in the granules revert to the lower polyphosphates. It is desirable to minimize the amount of reversion of tripolyphosphate and pyrophosphate, particularly to orthophosphates which can complex with hardness ions and form insoluble deposits on laundered fabrics. Moreover, when the granule temperature exceeds about 90°C, the formation of silicate insolubles increases.
- This invention relates to a process for preparing a granular detergent composition comprising the steps of
- the invention also relates to a process for preparing a granular detergent composition comprising the steps of:
- the granular detergent compositions herein are prepared by a process that first requires the preparation of an aqueous crutcher mix slurry comprising alkali metal tripolyphosphate and/or pyrophosphate, or silicate, together with other water-soluble neutral or alkaline salt, and detergent surfactant.
- aqueous crutcher mix slurry comprising alkali metal tripolyphosphate and/or pyrophosphate, or silicate, together with other water-soluble neutral or alkaline salt, and detergent surfactant.
- the crutcher mix slurry contains from 5% to 50%, preferably from 5% to 40%, more preferably from 10% to 30%, by weight, of a detergent surfactant selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof.
- the surfactant preferably represents from 5% to 60%, more preferably from 10% to 50%, most preferably from 15% to 40%, by weight of the finished composition.
- surfactants useful herein are listed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, and in U.S. Pat. No. 3,919,678, Laughlin, et al, issued Dec. 30, 1975.
- Useful cationic surfactants also include those described in U.S. Pat. No. 4,222,905, Cockrell, issued Sept. 16, 1980, and in U.S. Pat. No. 4,239,659, Murphy, issued Dec. 16, 1980.
- 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.
- anionic synthetic surfactants are preferred herein and the amount of soap in the slurry is limited to less than 2% by weight.
- Useful anionic synthetic surfactants include the water-soluble salts, preferably the alkali metal, ammonium and substituted ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms and sulfonic acid or sulfuric acid ester group.
- alkyl the alkyl portion of acyl groups.
- these 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 alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain 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 alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C11 ⁇ 13LAS.
- anionic surfactants suitable for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates, containing from 1 to 10 units of ethylene oxide per molecule and from 8 to 12 carbon atoms in the alkyl group; and sodium or potassium salts of alkyl ethylene oxide ether sulfates, containing from 1 to 10 units of ethylene oxide per molecule and from 10 to 20 carbon atoms in the alkyl group.
- Other useful anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
- Nonionic surfactants are also useful in the compositions of the invention. However, because of their volatility, such nonionics are generally not present in amounts greater than 10% by weight of the crutcher mix slurry. Preferably, these nonionics represent less than 5% by weight of the slurry. Most preferably, these nonionics are not present in the slurry.
- Nonionic surfactants herein include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
- Preferred nonionic surfactants 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 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 4 to 8 moles of ethylene oxide per mole of alcohol.
- Semi-polar nonionic surfactants useful herein include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
- Ampholytic surfactants include aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from 8 to 18 carbon atoms.
- Cationic surfactants can also be included in laundry compositions of the present invention.
- Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methyl sulfate and hydroxide. Tertiary amines can have characteristics similar to cationic surfactants at washing solution pH values less than 8.5. A more complete disclosure of these and other cationic surfactants useful herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
- Cationic surfactants are often used in detergent compositions to provide fabric softening and/or antistatic benefits.
- Antistatic agents which provide some softening benefit and which are preferred herein are the quaternary ammonium salts described in U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3, 1976. Such materials will normally be present in an amount from 1% to 10% by weight of the detergent composition.
- Particularly preferred surfactants herein are anionic surfactants selected from the group consisting of the alkali metal salts of C11 ⁇ 13 alkylbenzene sulfonates, C12 ⁇ 18 alkyl sulfates, C12 ⁇ 18 alkyl linear polyethoxy sulfates containing up to 4 ethylene oxide units, and mixtures thereof.
- the crutcher mix slurry further contain from 5% to 55%, preferably from 10% to 40%, more preferably from 15% to 30% of an alkali metal tripolyphosphate or pyrophosphate detergent builder material.
- Tripolyphosphates herein may be Form I or Form II, anhydrous or hydrated.
- commercially available anhydrous tripolyphosphates typically contain small amounts (e.g., 2-3% by weight) of hydrated material, which aids hydration in the crutcher slurry.
- commercially available tripolyphosphates generally also contain 4% to 12% by weight of a mixture of pyrophosphate and orthophosphate. Of course, the amount of orthophosphate is preferably minimized, as described previously.
- a particularly preferred material is sodium tripolyphosphate, some of which (e.g., 40-50%) preferably is present in its hexahydrate form in the crutcher mix slurry.
- the pyrophosphate salts useful herein can be obtained commercially or can be formed by neutralization of the corresponding pyrophosphoric acids or acid salts.
- the preferred material herein is sodium or potassium pyrophosphate.
- tetrasodium pyrophosphate Na4P2O7 and its decahydrate Na4P2O7.10H2O tetrapotassium pyrophosphate K4P2O7, sodium acid pyrophosphate or "acid pyro" Na2H2P2O7 and its hexahydrate Na2H2P2O7.6H2O, and pyrophosphoric acid H4P2O7.
- Monosodium pyrophosphate and trisodium pyrophosphate also exist, the latter as the anhydrous form or the mono- or nona-hydrate.
- the generic formula for the anhydrous forms of these compounds can be expressed as M x H y P2O7, where M is alkali metal and x and y are integers having the sum of 4.
- the crutcher mix slurry contains from 1% to 50%, preferably from 3% to 30%, more preferably from 5% to 20%, by weight of an alkali metal silicate having a molar ratio of SiO2 to alkali metal oxide of from 1.6 to 3.2, preferably from 1.6 to 2.4.
- an alkali metal silicate having a molar ratio of SiO2 to alkali metal oxide of from 1.6 to 3.2, preferably from 1.6 to 2.4.
- Sodium silicate particularly having a molar ratio of from 1.6 to 2.2, is preferred.
- the alkali metal silicates can be purchased in either liquid or granular form. Silicate solutions or slurries can conveniently be used to avoid having to dissolve the dried form in the aqueous crutcher mix slurry of the components herein.
- the slurry also contains up to 50%, preferably from 5% to 40%, more preferably from 10% to 30%, by weight of a finely divided water-insoluble aluminosilicate ion exchange material of the formula Na z [(AlO2) z .(SiO2) y ].xH2O wherein z and y are at least 6, the molar ratio of z to y is from 1.0 to 0.5 and x is from 10 to 264.
- Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zAlO2.ySiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2 and y is 1, said material having a magnesium ion exchange capacity of at least 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate.
- the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from 10% to 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from 18% to 22% water in their crystal matrix.
- the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from 0.1 microns to 10 microns. Amorphous materials are often smaller, e.g., down to less than 0.01 microns.
- Preferred ion exchange materials have a particle size diameter of from 0.2 microns to 4 microns.
- particle size diameter herein represents the average particle size diameter 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 CaCO3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
- the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least 3.26 mmolCa++/litre/minute/gram/litre (2 grains Ca++/gallon/minute/gram/gallon) of aluminosilicate (anhydrous basis), and generally lies with the range of from 3.26 mmolCa++/litre/minute/gram/litre (2 grains/gallon/minute/gram/gallon) to 9.78 mmolCa++/litre/minute/gram/litre (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 6.52 mmolCa++/litre/minute/gram/litre (4 grains/gallon/minute/gram/gallon).
- the amorphous aluminosilicate ion exchange materials usually have a Mg++ exchange capacity of at least about 50 mg eq. CaCO 2/g (12 mg Mg++/g) and a Mg++ exchange rate of at least 2.72 mmol/litre/minute/gram/litre (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. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
- Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X.
- the crystalline aluminosilicate ion exchange material has the formula Na12[(AlO2)12.(SiO2)12].xH2O wherein x is from 20 to 30, especially about 27.
- the crutcher mix slurry herein also contains from 5% to 65%, preferably from 10% to 50%, more preferably from 15% to 40%, by weight, of a water-soluble neutral or alkaline salt other than the tripolyphosphate, and pyrophosphate described above in compositions containing these ingredients, or other than the alkali metal silicate and aluminosilicate materials described above in compositions containing these ingredients.
- a water-soluble neutral or alkaline salt other than the tripolyphosphate, and pyrophosphate described above in compositions containing these ingredients, or other than the alkali metal silicate and aluminosilicate materials described above in compositions containing these ingredients.
- Other neutral or alkaline salts herein are described in U.S. Patent 4,379,080, Murphy, issued April 5, 1987.
- Such neutral or alkaline salts have a pH in solution of about seven or greater, and can be either organic or inorganic in nature. While some of the salts are inert, many of them also function
- neutral water-soluble salts include the alkali metal, ammonium or substituted ammonium chlorides and sulfates.
- the alkali metal, and especially sodium, salts of the above are preferred.
- Sodium sulfate and sodium carbonate are typically found in detergent granules and are preferred salts herein.
- the water-soluble salts herein preferably include the compounds commonly known as detergent builder materials.
- Such builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
- Preferred are the alkali metal, especially sodium, salts of the above.
- inorganic phosphate builders are polymeric metaphosphate having a degree of polymerization of from 6 to 21.
- 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. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176; and 3,400,148.
- nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, and tetraborate decahydrate.
- Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
- polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Salts of nitrilotriacetic acid, such as sodium nitrilotriacetate, are particularly preferred.
- Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
- Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, phloroglucinol trisulfonate, and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
- polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al.
- These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution and converted to the corresponding salt.
- Preferred polycarboxylate builders herein are described in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987.
- the neutral or alkaline salt of the present invention is preferably selected from the alkali metal polycarboxylates, carbonates, sulfates, and silicates (in compositions containing tripolyphosphates and/or pyrophosphates), and mixtures thereof.
- the crutcher mix slurry herein also contains from 25% to 50%, preferably from 30% to 45%, more preferably from 30% to 40%, by weight, of water.
- the aqueous crutcher mix slurry is spray dried in a spray drying tower at an inlet air temperature of at least 200 o C in a manner so that the bulk granule temperature does not exceed 90°C to obtain base granules containing from 5% to 25% water. If there is more than 5% alkali metal tripolyphosphate in the slurry, the base granules preferably contain from 8% to about 20% by weight of water. Otherwise, the base granules preferably contain from 7% to 15% by weight of water.
- the air inlet temperature is preferably at least 230 o C, more preferably at least 260°C. It is also preferred that the granule temperature not be allowed to exceed 85°C, and more preferably not exceed 80°C, to minimize reversion of polyphosphates when present in the granules and also to minimize formation of silicate insolubles when silicate is present.
- the resulting base granules which are generally free flowing agglomerates, are then further dried in a secondary dryer in a manner so that the granule temperature again does not exceed 90 o C to obtain granules containing from 2% to 20%, preferably from 2% to 8%, water.
- the granule temperature does not exceed 85°C. More preferably, it does not exceed 80°C.
- the granules should contain at least 4% water, and preferably contain from 8% to 16% water, after drying in the secondary dryer.
- the drying should be accomplished so that no more than 5% by weight of each of the tripolyphosphate and pyrophosphate is reverted to lower phosphates during the drying in the spray tower and in the secondary dryer.
- Any secondary dryer capable of drying the granules at the required temperature and moisture levels can be used in the practice of this invention.
- Suitable secondary dryers include rotary drum dryers, pneumatic conveying dryers, air lift dryers, conveyor and tray-type dryers, and the like.
- a fluid bed dryer is particularly preferred.
- the resulting granular detergent compositions can be used as is as finished detergent compositions or as detergent additive compositions.
- the granules are preferably admixed with or agglomerated with other optional ingredients to provide finished detergent compositions.
- compositions of the present invention can be included in the compositions of the present invention.
- auxiliary detergent surfactant and builder materials bleaching agents and bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil suspending agents, soil release agents, fillers, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes.
- bleaching agents and bleach activators suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil suspending agents, soil release agents, fillers, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes.
- Bleaching agents and activators are also described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,
- typical laundry wash water solutions comprise from 0.1% to 2% by weight of the composition. Fabrics to be laundered are agitated in these solutions to effect cleaning, stain removal, and optional fabric care benefits.
- the pH of a 0.1% by weight aqueous solution of this composition will be in the range of from 7.0 to 11.0, preferably from 8.0 to 11.0, and most preferably from 9.0 to 10.5.
- a crutcher slurry is prepared containing the following components.
- Component Wt. % Sodium C13 linear alkylbenzene sulfonate 7.5 Sodium C14 ⁇ 15 alkyl sulfate 7.5 Sodium tripolyphosphate (anhydrous) 32.8 Sodium silicate (1.6 ratio) 4.6 Sodium polyacrylate (MW 4500) 0.9 Polyethylene glycol (MW 8000) 0.4 Sodium sulfate and minors 9.8 Water 36.5
- the crutcher slurry is held approximately 5-10 minutes so that 30-80% of the tripolyphosphate hydrates to the hexahydrate form.
- the slurry is spray dried by atomizing with swirl nozzles at 35-84 kg/cm2 pressure into a counter-current spray drying tower having an inlet air temperature of about 332°C.
- a slip stream sample of partially dried granules having a temperature of less than about 55°C and containing about 18.8% water is captured from within the spray tower and continuously fed to a fluidized bed, having a cross-sectional area of 0.14 m2. Fluid bed air is heated to about 165°C and pumped through a perforated distribution plate at sufficient rate to fluidize the bed of granules.
- Dried granules are continuously withdrawn from the bed at about 72.7 kg/hr. and contain 10.4% water.
- the temperature of the sample is about 88°C.
- Less than about 3% of the tripolyphosphate has reverted to pyrophosphate and orthophosphate during the drying process. This compares to about 15% reversion in a sample taken from the bottom of the spray tower at the same time and having a temperature of about 104°C.
- the black-fabric solubility grade for the above fluid bed sample is 9.5 (on a 0-10 scale, where 10 equals no insolubles) versus a grade of 7.5 for the totally spray dried sample taken from the bottom of the spray drying tower. Further, the cake grade for the fluid bed sample is 1.5 (kg force to break a 6.35 cm diameter x 6.35 cm long cylindrical plug formed under a 9.1 kg weight for one minute) versus a grade of 3.3 for the totally spray dried sample.
- a crutcher slurry is prepared containing the following components.
- Component Wt. % Sodium C12 linear alkylbenzene sulfonate 3.3 Sodium tallowalkyl sulfate 5.3 Sodium C14 ⁇ 15 alkyl sulfate 5.3 Sodium toluene sulfonate 0.8 Sodium tripolyphosphate 4.5 Tetrasodium pyrophosphate 18.2 Sodium silicate (1.6 ratio) 4.5 Sodium polyacrylate (MW 4500) 1.0 Sodium sulfate and minors 24.6 Water 32.5
- the slurry is dried in two stages as described in Example I to provide a composition of the present invention.
- a crutcher slurry is prepared containing the following components.
- Component Wt. % Sodium C13 linear alkylbenzene sulfonate 7.3 Sodium C14 ⁇ 15 alkyl sulfate 7.3 Tallow fatty acid 0.7 Sodium Zeolite A (hydrated, avg. dia. 3 microns) 17.9 Sodium silicate (1.6 ratio) 1.4 Sodium carbonate 3.7 Sodium polyacrylate (MW 4500) 1.1 Polyethene glycol (MW 8000) 1.1 Sodium sulfate and minors 26.1 Water 33.4
- the slurry is spray dried by atomizing with swirl nozzles at 77 kg/cm2 pressure into a counter-current spray drying tower having an inlet air temperature of about 254°C.
- a sample of partially dried granules having a temperature of less than about 55°C and containing about 18.8% water is captured from within the spray tower and charged to a batch fluidized bed having a cross-sectional area of 0.14 m2. Fluid bed air is heated to about 163°C and pumped through a perforated distribution plate at sufficient rate to fluidize the bed of partially dried granules.
- a sample of dried granules is withdrawn from the bed and contains 8.8% water.
- the temperature of the sample is about 47°C.
- the black-fabric solubility grade for the fluid bed sample is 9.0 (on a 0-10 scale, where 10 equals no insolubles) versus a grade of 7.5 for a sample taken at the exit of the spray tower during the same time period.
- a crutcher slurry is prepared containing the following components.
- Component Wt. % Sodium C13 linear alkylbenzene sulfonate 9.5 Sodium C14 ⁇ 15 alkyl polyethoxy (2.25) sulfate 4.1 Tallow fatty acid 0.1 Sodium silicate (2.4 ratio) 13.2 Sodium carbonate 13.8 Sodium sulfate 23.7 Minors 0.6 Water 35.0
- the slurry is spray dried by atomizing with swirl nozzles at 28-84 kg/cm2 pressure into a counter-current spray drying tower having an inlet air temperature of about 343°C.
- a 13.6 kg sample of partially dried granules having a temperature of less than about 55°C and containing about 9.2% water is captured from within the spray tower and charged to a batch fluidized bed having a cross-sectional area of 0.14 m2.
- the fluid bed inlet air is heated to about 152°C and pumped through a perforated distribution plate at sufficient rate to thoroughly fluidize the bed of partially dried granules.
- a sample of dried granules is withdrawn from the bed and contains 5.6% water.
- the temperature of the sample is about 84°C.
- the black-fabric solubility grade for the fluid bed sample is 7.0 (on a 0-10 scale, where 10 equals no insolubles) versus a grade of 3.5 for a sample taken at the exit of the spray tower during the same time period and having a temperature of 123°C.
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Claims (11)
- Verfahren zur Herstellung einer granulatförmigen Waschmittelzusammensetzung, umfassend die Schritte(a) Bildung einer wäßrigen Aufschlämmung, umfassend, bezogen auf Gewicht:(1) ein Waschmitteltensid;(2) 5 bis 55%, vorzugsweise 15 bis 30%, eines Alkalimetalltripolyphosphats oder -pyrophosphats oder Mischungen davon;(3) 5 bis 65% eines wasserlöslichen, neutralen oder alkalischen Salzes, welches von dem Tripolyphosphat und Pyrophosphat in (2) verschieden ist; und(4) 25 bis 50%, vorzugsweise 30 bis 45% Wasser;(b) Spühtrocknen der wäßrigen Aufschlämmung in einem Sprühturm bei einer Einlaß- Lufttemperatur von mindestends 200 °C, um Basisgranulate zu erhalten, welche 5 bis 25 Gew.-% Wasser umfassen; und(c) Trocknen der Basisgranulate in einem zweiten Trockner, um Granulate zu erhalten, welche 2 bis 20 Gew.-% Wasser, jedoch mindestens 4 Gew.-% Wasser umfassen, wenn die Aufschlämmung mehr als 5 Gew.-% Tripolyphosphat umfaßt, wobei nicht mehr als 5 Gew.-% jedes des in der Aufschlämmung vorliegenden Tripolyphosphats und Pyrophosphats während (b) und (c) zu Pyrophosphat, Orthophosphat und Mischungen davon umgewandelt wird,dadurch gekennzeichnet, daß die wäßrige Aufschlämmung 5 bis 50 Gew.-% eines Waschmitteltensids, vorzusgweise 10 bis 30% eines anionischen Tensids umfaßt; und daß die Menge an Seife in der Aufschlämmung auf weniger als 2 Gew.-% begrenzt ist, und daß die Granulattemperatur zu jeder Zeit während den Schritten (b) und (c) 90 °C nicht überschreitet.
- Verfahren nach Anspruch 1, wobei das anionische Tensid aus der C₁₁₋₁₃-Alkylbenzolsulfonate, C₁₂₋₁₈-Alkylsulfate, C₁₂₋₁₆-Alkylsulfate, welche im Durchschnitt mit bis zu 4 Ethylenoxideinheiten ethoxyliert sind, und Mischungen davon umfassenden Gruppe gewählt wird.
- Verfahren nach Anspruch 1 oder 2, wobei die Einlaß-Lufttemperatur des Turms mindestens 230 °C, vorzugsweise mindestens 260 °C beträgt, die Temperatur der Basisgranulate 85 °C nicht überschreitet und die Basisgranulate 8 bis 20 Gew.-% Wasser umfassen.
- Verfahren nach mindestend einem der vorangehenden Ansprüche, wobei die Basisgranulate in einem zweiten Trockner, vorzugsweise einem Wirbelbetttrockner, getrocknet werden, während die Granulattemperatur 85 °C nicht überschreitet, um Granulate zu erhalten, welche 8 bis 16 Gew.-% Wasser umfassen.
- Verfahren nach den Anspüchen 1, 2 oder 3, wobei die Basisgranulate in einem zweiten Trockner, vorzugsweise einem Wirbelbetttrockner, getrocknet werden, während die Granulattemperatur 85 °C nicht überschreitet, um Granulate zu erhalten, welche 2 bis 8 Gew.-% Wasser umfassen, und wobei nicht mehr als 2 Gew.-% von jeweils in der Aufschlämmung vorliegendem Tripolyphosphat und Pyrophosphat während den Schritten (b) und (c) in Pyrophosphat, Orthophosphat und Mischungen davon umgewandelt werden.
- Verfahren zur Herstellung einer granulatförmigen Waschmittelzusammensetzung, umfassend die Schritte(a) Bildung einer wäßrigen Aufschlämmung, umfassend, bezogen auf Gewicht:(1) ein Waschmitteltensid;(2) 1 bis 50%, vorzugsweise 3 bis 30%, eines Alkalimetallsilicats mit einem Molverhältnis von SiO₂ zu Alkalimetalloxid von 1,6 bis 3,2, vorzugsweise Natriumsilicat mit einem Molverhältnis von SiO₂ zu Natriumoxid von 1,6 bis 2,4;(3) 5 bis 65% eines wasserlöslichen, neutralen oder alkalischen Salzes, welches von dem Silicat in (2) und Aluminosilicat verschieden ist; und(4) 25 bis 50%, vorzugsweise 30 bis 45% Wasser;(b) Spühtrocknen der wäßrigen Aufschlämmung in einem Sprühturm bei einer Einlaß-Lufttemperatur von mindestens 200 °C, um Basisgranulate zu erhalten, welche 5 bis 25 Gew.-% Wasser umfassen; und(c) Trocknen der Basisgranulate in einem zweiten Trockner, um Granulate zu erhalten, welche 2 bis 20 Gew.-% Wasser umfassen,dadurch gekennzeichnet, daß die wäßrige Aufschlämmung 5 bis 50 Gew.-% eines Waschmitteltensids, vorzugsweise 10 bis 30% eines anionischen Tensids umfaßt, und daß die Menge an Seife in der Aufschlämmung auf weniger als 2 Gew.-% begrenzt ist, und daß die Granulattemperatur zu jeder Zeit während den Schritten (b) und (c) 90 °C nicht überschreitet.
- Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die Aufschlämmung 5 bis 50% eines fein verteilten Aluminosilicat-Ionenaustauschermaterials umfaßt, welches aus der(i) kristallines Aluminosilicatmaterial der Formel:
Naz [ (AℓO₂) z (SiO₂) y ] .xH₂O
worin z und y mindestens 6 sind, das Molverhältnis von z zu y 1,0 bis 0,5 beträgt und x 10 bis 264 ist, wobei dieses Material einen Teilchengrößendurchmesser von 0,1 Mikrometer bis 10 Mikrometer besitzt, eine Kalziumionen-Austauschkapazität von mindestens 200 mg CaCO₃ eq. /g und eine Kalziumlonen-Austauschgeschwindigkeit von mindestens 3,26 mMol Ca⁺⁺/Liter/Minute/Gramm/Liter (2 grains Ca⁺⁺ /gallon/minute/gram/gallon) aufweist;(ii) amorphes hydratisiertes Aluminosilicatmaterial der empirischen Formel:
Mz (zAlO₂ . ySiO₂)
worin M Natrium, Kalium, Ammonium oder substituiertes Ammonium ist, z 0,5 bis 2 ist und y 1 ist, wobei das Material eine Magnesium-Austauschkapazität von midestens 50 Milligrammäquivalenten an CaCO₃-Härte pro Gramm wasserfreies Aluminomsilicat und eine Mg⁺⁺-Austauschgeschwindigkeit von mindestens 2,72 mMol/Liter/Minute/Gramm/Liter (1 grain/gallon/minute/gram/gallon) aufweist; und(iii) Mischungen davonumfassenden Gruppe gewählt wird. - Verfahren nach den Ansprüchen 6 oder 7, wobei das anionische synthetische Tensid aus der C₁₁₋₁₃-Alkylbenzolsulfonate, C₁₂₋₁₈ Alkylsulfate, C₁₂₋₁₆-Alkylsulfate, welche im Durchschnitt mit bis zu 4 Ethylenoxideinheiten ethoxyliert sind, und Mischungen davon umfassenden Gruppe gewählt wird.
- Verfahren nach den Ansprüchen 6, 7 oder 8, wobei die Aufschlämmung 5 bis 40%, vorzugsweise 10 bis 30% Gew.-% Aluminosilicat-Ionenaustauschermaterial der Formel
Na₁₂ [ (AlO₂)₁₂ · (SiO₂)₁₂] · xH₂O
umfaßt, worin x 20 bis 30 ist. - Verfahren nach den Ansprüchen 6, 7, 8 oder 9, wobei die Aufschlämmung bei einer Turmeinlaß-Lufttemperatur von mindestens 260 °C sprühgetrocknet wird, während die Granlulattemperatur 85 °C nicht überschreitet, um Basisgranulate zu erhalten, welche 7 bis 15 Gew.-% Wasser umfassen.
- Verfahren nach den Ansprüchen 6, 7, 8, 9 oder 10, wobei die Basisgranulate in einem zweiten Trockner, vorzugsweise einem Wirbelbetttrockner, getrocknet werden, während die Granulattemperatur 85 °C nicht überschreitet, um Granulate zu erhalten, welche 2 bis 8 Gew.-% Wasser umfassen.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US21280588A | 1988-06-29 | 1988-06-29 | |
US212805 | 1988-06-29 |
Publications (2)
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EP0349199A1 EP0349199A1 (de) | 1990-01-03 |
EP0349199B1 true EP0349199B1 (de) | 1995-03-08 |
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EP89306334A Expired - Lifetime EP0349199B1 (de) | 1988-06-29 | 1989-06-23 | Zweistufiges Trocknen von Waschmittelzusammensetzungen |
Country Status (3)
Country | Link |
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EP (1) | EP0349199B1 (de) |
DE (1) | DE68921512T2 (de) |
ES (1) | ES2068894T3 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2318584A (en) * | 1996-10-25 | 1998-04-29 | Procter & Gamble | Process for preparing detergent compositions by spray drying |
EP1754776A1 (de) | 2005-08-19 | 2007-02-21 | The Procter and Gamble Company | Verfahren zur Herstellung einer festförmigen Waschmittelzusammensetzung, enthaltend mindestens zwei Trocknungsstufen |
EP1754777B1 (de) | 2005-08-19 | 2010-10-20 | The Procter & Gamble Company | Festförmige Waschmittelzusammensetzung enthaltend Alkylbenzolsulphonat, Carbonat-Salz und Carboxylat-Polymer |
EP1754780B1 (de) | 2005-08-19 | 2010-04-21 | The Procter and Gamble Company | Festförmige Waschmittelzusammensetzung enthaltend Alkylbenzolsulphonat und ein hydratbarer Stoff |
EP1754781B1 (de) | 2005-08-19 | 2013-04-03 | The Procter and Gamble Company | Festförmige Waschmittelzusammensetzung enthaltend anionisches Tensid und eine Calcium-Vergrösserung-Technologie |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3629955A (en) * | 1970-07-31 | 1971-12-28 | Procter & Gamble | Multilevel spray-drying apparatus |
US3629951A (en) * | 1970-07-31 | 1971-12-28 | Procter & Gamble | Multilevel spray-drying method |
US4019998A (en) * | 1974-09-27 | 1977-04-26 | The Procter & Gamble Company | Process for preparing a pyrophosphate-silicate detergent product |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1481514A (fr) * | 1965-05-28 | 1967-05-19 | Knapsack Ag | Procédé de préparation de détersifs contenant du tripolyphosphate de sodium |
GB1237084A (en) * | 1967-10-02 | 1971-06-30 | Unilever Ltd | Soap drying process |
US4116852A (en) * | 1975-02-14 | 1978-09-26 | The Procter & Gamble Company | Builders and built detergent compositions |
GR79391B (de) * | 1982-11-08 | 1984-10-22 | Procter & Gamble |
-
1989
- 1989-06-23 EP EP89306334A patent/EP0349199B1/de not_active Expired - Lifetime
- 1989-06-23 ES ES89306334T patent/ES2068894T3/es not_active Expired - Lifetime
- 1989-06-23 DE DE1989621512 patent/DE68921512T2/de not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3629955A (en) * | 1970-07-31 | 1971-12-28 | Procter & Gamble | Multilevel spray-drying apparatus |
US3629951A (en) * | 1970-07-31 | 1971-12-28 | Procter & Gamble | Multilevel spray-drying method |
US4019998A (en) * | 1974-09-27 | 1977-04-26 | The Procter & Gamble Company | Process for preparing a pyrophosphate-silicate detergent product |
Also Published As
Publication number | Publication date |
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ES2068894T3 (es) | 1995-05-01 |
DE68921512T2 (de) | 1995-11-09 |
DE68921512D1 (de) | 1995-04-13 |
EP0349199A1 (de) | 1990-01-03 |
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