CN1239991A - Process for making detergent composition by non-tower process - Google Patents
Process for making detergent composition by non-tower process Download PDFInfo
- Publication number
- CN1239991A CN1239991A CN97180293.9A CN97180293A CN1239991A CN 1239991 A CN1239991 A CN 1239991A CN 97180293 A CN97180293 A CN 97180293A CN 1239991 A CN1239991 A CN 1239991A
- Authority
- CN
- China
- Prior art keywords
- mixing tank
- agglomerate
- composition
- tensio
- active agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000000034 method Methods 0.000 title claims abstract description 105
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 239000003599 detergent Substances 0.000 title claims abstract description 52
- 230000008569 process Effects 0.000 title abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 104
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 239000013543 active substance Substances 0.000 claims description 38
- -1 non-ionic type Chemical group 0.000 claims description 29
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 20
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 17
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 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 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 230000036571 hydration Effects 0.000 claims description 5
- 238000006703 hydration reaction Methods 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims 2
- 150000004996 alkyl benzenes Chemical group 0.000 claims 1
- 238000005507 spraying Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 20
- 238000005406 washing Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 14
- 239000012747 synergistic agent Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- 238000005054 agglomeration Methods 0.000 description 11
- 230000002776 aggregation Effects 0.000 description 11
- 238000005342 ion exchange Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000000280 densification Methods 0.000 description 6
- 239000003595 mist Substances 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 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 5
- 229930182556 Polyacetal Natural products 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 229920006324 polyoxymethylene Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 150000003818 basic metals Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 235000011837 pasties Nutrition 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 230000021523 carboxylation Effects 0.000 description 3
- 238000006473 carboxylation reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 150000004646 arylidenes Chemical group 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- HXDRSFFFXJISME-UHFFFAOYSA-N butanedioic acid;2,3-dihydroxybutanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)C(O)C(O)C(O)=O HXDRSFFFXJISME-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 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 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound 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
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
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- 150000003900 succinic acid esters Chemical class 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 1
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- XSBRVRMMKVWXQZ-UHFFFAOYSA-M CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1.CC(C([O-])=O)N(C)C Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1.CC(C([O-])=O)N(C)C XSBRVRMMKVWXQZ-UHFFFAOYSA-M 0.000 description 1
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 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
- 150000007513 acids Chemical class 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
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- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- CQUHXBUZUBJWMR-UHFFFAOYSA-N dimethylazanium hexane-1-sulfonate Chemical compound C[NH2+]C.CCCCCCS([O-])(=O)=O CQUHXBUZUBJWMR-UHFFFAOYSA-N 0.000 description 1
- IYNJILVYWCLNBH-UHFFFAOYSA-N dimethylazanium;2-hydroxypropane-1-sulfonate Chemical compound C[NH2+]C.CC(O)CS([O-])(=O)=O IYNJILVYWCLNBH-UHFFFAOYSA-N 0.000 description 1
- JMUARGQPJWIZIP-UHFFFAOYSA-N dimethylazanium;hexanoate Chemical compound C[NH2+]C.CCCCCC([O-])=O JMUARGQPJWIZIP-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- QFCZQEFMGQVACW-UHFFFAOYSA-N ethyl(dihydroxy)azanium propane-1-sulfonate Chemical compound CC[NH+](O)O.CCCS([O-])(=O)=O QFCZQEFMGQVACW-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical class [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical compound CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229940045916 polymetaphosphate Drugs 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 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 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000004577 thatch Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 230000002087 whitening effect 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
- 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
- C11D11/0088—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 the liquefied ingredients being sprayed or adsorbed onto solid particles
-
- 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
-
- 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
- C11D11/02—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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A non-tower process for continuously preparing granular detergent composition having a density of at least about 600 g/l is provided. The process comprises the steps of: (a) dispersing a surfactant, and coating the surfactant with fine powder having a diameter from 0.1 to 500 microns, in a mixer, wherein first agglomerates are formed, and (b) spraying on finely atomized liquid to the first agglomerates in a mixer, wherein second agglomerates are formed. Optionally, the second agglomerates are further subjected to the step (c), thoroughly mixing the second agglomerates in a mixer.
Description
Invention field
The present invention relates generally to produce the non-tower method of granular detergent compositions.More specifically, The present invention be directed to a kind of successive method, this method comprises adding tensio-active agent and coat last material in a series of mixing tank produces detergent agglomerate.This method is produced the free-pouring cleaning composition of a kind of energy, and its density can be adjusted in the needed wide range of human consumer, and said composition can be sold on market.
Background of invention
Quite interested in detergent for washing clothes " densification ", that the use volume is little in detergent industry recently.In order to promote the production of these so-called low consumption washing composition, to produce high bulk density for example density be that washing composition more than the 600g/l has carried out many explorations.Because low consumption washing composition is saved resource, and can with to the human consumer more easily small packages sell, so at present it is in great demand.Yet the compactness extent that modern Betengent product need reach does not in fact also solve.In fact, many human consumers', particularly developing country human consumer still likes bigger consumption in their laundry processes separately.
The method of preparing washing agent particle or powder generally has two big classes.First kind method is included in the aqueous washing composition slurry of spraying drying in the spray-drying tower, produces very loose detergent particles (tower process of for example production low density cleaning composition).In second class methods, with various detergent ingredients dry blending, adopt binding agent then, tensio-active agent for example non-ionic type or anionic earlier, make their agglomeration, produce highdensity detergent composition (for example producing the agglomeration method of high density detergent).In above two kinds of methods, the important factor of the detergent particle granule density that control is produced is described coating of particles, porosity and size-grade distribution, the density of various raw materials, the shape of various raw materials and chemical constitution separately thereof.
For the method that improves detergent particles or powder density is provided, many trials in this area, have been carried out.Especially notice and adopt (post tower) behind the tower to handle compaction spray-dried granules.For example, a kind of process of attempting using an interruption is arranged, in this process, make the detergent powder densification of the spray-dired or granulation that contains tripoly phosphate sodium STPP and sodium sulfate, and make its nodularization in a Marumerizer .In this equipment, comprise that one is level, coarse rotating disk basically, it is positioned at one is the bottom of slick cylinder on vertical, the wall basically.Yet this method is the method for an interruption basically, thereby is not suitable for producing on a large scale detergent powder.Recently, for forming the continuation method that improves " behind the tower " drying or spray-dried detergent pellet density, other trials have been carried out.These methods need be pulverized or grind the particulate primary equipment usually and improve by the second set of pulverized particles density by nodulizing.Though these methods are handled " behind the tower " drying or spray-dired particle or made its densification, have reached the requirement that improves density, do not have encapsulation steps subsequently, the ability that makes their improve tensio-active agent effective content is restricted.In addition, from the viewpoint of economics (investment cost height) and complicated operation degree, it is disadvantageous adopting " behind the tower " processing or densification.And all above-mentioned methods are mainly at densification, or in other words, are at handling spray-dired particle.In the production of granulated detergent, the relative populations and the kind of the material of process spray drying treatment are restricted at present.For example in the cleaning composition of producing, obtain high-load tensio-active agent and be difficult to, this is the principal element that promotes to produce with more efficient methods washing composition.Therefore, need a kind of method that can not be subjected to the production cleaning composition of restriction that conventional spray drying technology adds.
Also there are many open source informations that carry out the method for cleaning composition agglomeration process for this purpose this area.For example mixed zeolite and/or lamellated silicate in mixing tank carry out the agglomerant trial of scrubbed component, so that make free-pouring agglomerate.Though these trials show, their method can be applied to produce detergent agglomerate, but they do not propose and can effectively pasty state, liquid be agglomerated into mechanism crisp, the free-pouring detergent agglomerate of energy with the exsiccant detergent raw material.
Therefore, this area also needs a kind of method (non-tower method) of continuous production high density detergent composition agglomerate, and its high-density is directly produced by the washing composition original composition, can preferably reach this density by regulating working condition.Yet needing a kind of (1) can adapt to the final densities of final product composition having and (2) and can adapt to several dissimilar detergent ingredients (particularly Ye Tai composition) in the adition process, more effective, more flexible and more economical method is so that produce washing composition on a large scale.
As follows at the reference that makes spray-dired particle densification: people's such as A Peier United States Patent (USP) 5,133,924 (Lever); People's such as rich holder loti United States Patent (USP) 5,160,657 (Lever); People's such as Johnson English Patent 1,517,713 (Unilever); European patent application 451,894 with Ke Disi.
As follows at the reference that adopts agglomeration method production washing composition: than people's such as treasure patent, publication number is WO93/23,523 (Henkel), people's such as Lu thatch United States Patent (USP) 4,992,079 (FMC Corp.); People's such as Bo Laxike United States Patent (USP) 4,427,417 (Korex); People's such as Bill's Si grade United States Patent (USP) 5,108,646 (Procter ﹠amp; Gamble); People's such as Ka Peixi United States Patent (USP) 5,366,652 (Procter; Gamble); People's such as Hollingworth european patent application 351,937 (Unilever); People's such as Si Watelin United States Patent (USP) 5,205,958; People's such as Da Erwodika patent, publication number are WO96/04,359 (Unilever).
For example, open application is WO93/23, and the method that 523 (Henkel) are narrated is comprising adopting the pre-agglomeration of slow-speed mixer and adopting the further agglomerant step of super mixer, to obtain highdensity cleaning composition, wherein diameter is lower than 25% (weight) greater than the particle of 2mm.United States Patent (USP) 4,427,417 (Korex) have narrated the successive agglomeration method, and this method has reduced the agglomerate of caking and oversized dimensions.
There is not a kind of prior art that all these advantages of the present invention and benefit can be provided.
Summary of the invention
The invention provides a kind of method of producing high-density granulated cleaning composition, satisfied the above-mentioned needs of this area.The present invention also provides a kind of method by agglomeration technique (for example non-tower method) production granular detergent compositions that can adapt to the final product composition having final densities, has satisfied the above-mentioned needs of this area.This method does not adopt conventional spray-drying tower, and this tower is restricted in the high Composition Aspects of production surfactant content at present.In addition, method of the present invention various cleaning composition that available present method is produced are all more effective, both economical and adaptability is stronger.And because present method does not adopt the common spray-drying tower that can give out particle and volatile organic compounds in atmosphere, it more can stand the check of environmental protection aspect.
Term used herein " agglomerate " means the employing binding agent, and for example tensio-active agent and/or inorganic solution/organic solvent and polymers soln make the particle that the raw material agglomeration is made.Term used herein " mean residence time " means to give a definition:
Mean residence time (h)=quality (kg)/flow (kg/h)
Except as otherwise noted, all percentage used herein are all represented with weight percentage.Except as otherwise noted, all ratios all are weight ratios." comprising " used herein means and can add other step and other composition that does not influence the result.This term contained term " by ... form " and " basically by ... composition ".
According to an aspect of the present invention, provide a kind of method for preparing granular detergent compositions, the density of said composition is at least about 600g/l.
This method may further comprise the steps:
(a) in mixing tank, disperse a kind of tensio-active agent, and be that the fine powder of 0.1-500 μ coats this tensio-active agent with diameter, wherein the operational condition of mixing tank comprises: (i) mean residence time about 2 is to about 50s, (ii) terminal velocity about 4 is to about 25m/s, (iii) energy state about 0.15 is made agglomerate therein to about 7kj/kg; With
(b) in mixing tank with the spray liquid of mistization to agglomerate, wherein the operational condition of mixing tank comprises: (i) mean residence time about 0.2 is to about 5s, (ii) terminal velocity about 10 to about 30m/s and (iii) energy state about 0.15 to about 5ki/kg.
The present invention also provides a kind of method for preparing granular detergent compositions, and the density of said composition is at least about 600g/l, and this method may further comprise the steps:
(a) in mixing tank, disperse a kind of tensio-active agent, and coat this tensio-active agent with the fine powder of diameter 0.1-500 μ, wherein the operational condition of mixing tank comprises: (i) mean residence time about 2 is to about 50s, (ii) terminal velocity about 4 is to about 25m/s, (iii) energy state about 0.15 is made first agglomerate therein to about 7kj/kg;
(b) in mixing tank with the spray liquid of mistization to first agglomerate, wherein the operational condition of mixing tank comprises: (i) mean residence time about 0.2 is to about 5s, (ii) last auspicious speed about 10 is to about 30m/s, (iii) energy state about 0.15 is made second agglomerate therein to about 5kj/kg; With
(c) thorough mixing second agglomerate in mixing tank, wherein the operational condition of mixing tank comprises: (i) mean residence time about 0.5 to about 15min and (ii) energy state about 0.15 to about 7ki/kg.
The present invention also provides the highdensity granular detergent compositions of being produced by the embodiment of any method as herein described, and its density is at least about 600g/l.
Therefore, the purpose of this invention is to provide a kind of method of continuous production cleaning composition, by energy input, the residence time and the terminal velocity condition in the control mixing tank, the density of regulating finished product neatly.Another object of the present invention provides a kind of scale operation of being convenient to, more effective, more flexible and more economical method.To those skilled in the art, by below reading to the detailed description of preferred embodiment and claims, these and other objects of the present invention, feature and attendant advantages are clearly.
To description of Preferred Embodiments
The present invention be directed to the method for the free-pouring granulated detergent agglomerate of production energy, the density of agglomerate is at least about 600g/l.This method is produced the granulous detergent agglomerate by tensio-active agent water-based and/or nonaqueous, and tensio-active agent coats with the fine powder of diameter 0.1-500 μ subsequently, so that obtain low-density particle.
Method first step (step (a))
In the first step of present method, the water-based that one or more are pulverous, pasty state and/or liquid and/or nonaqueous tensio-active agent, with diameter 0.1-500 μ, preferred about 1 fine powder to about 100 μ adds in first mixing tank, so that make agglomerate.(at length having narrated the definition of tensio-active agent and fine powder hereinafter) is except fine powder, can choose wantonly will be by what produce in the additional step " optional regulate process (being drying and/or cooling step) " after the method for the present invention, and diameter general about 0.1 to the internal recycle stream of about 300 μ powder adds in the mixing tank.The amount of described powder internal recycle stream can be finished product 0 to about 60% (weight).
In another embodiment of the invention, can be before above-mentioned step, tensio-active agent is added in a mixing tank or the premixer (for example Chang Gui screw extruder or other similar mixing tank) beginning, then the blended detergent materials is added in the mixing tank of first step described herein and carry out agglomeration.
In general, the mean residence time of preferred first mixing tank is about 2 to about 50s, the terminal velocity of first mixing tank is that about 4m/s is to about 25m/s, the energy of the first mixing tank per unit mass (energy state) is that about 0.15kj/kg is to about 7kj/kg, more preferably the mean residence time of first mixing tank is about 5 to about 30s, the terminal velocity of first mixing tank is that about 6m/s is to about 18m/s, the energy of the first mixing tank per unit mass (energy state) is that about 0.3kj/kg is to about 4kj/kg, more preferably the mean residence time of first mixing tank is about 5 to about 20s, the terminal velocity of first mixing tank is extremely about 18m/s of about 8m/s, and the energy of the first mixing tank per unit mass (energy state) is that about 0.3kj/kg is to about 4kj/kg.
The example of first step first mixing tank can be the mixing tank of oneself any type of knowing of those skilled in the art, as long as this mixing tank can keep the above-mentioned condition of first step.The L dige CB mixing tank that L dige company (Germany) makes can be an example.Obtain on the surface of agglomerate (first agglomerate), having the agglomerate of fine powder by first step.Second step (the step b)
The agglomerate (i.e. first agglomerate) that first step is made adds in second mixing tank.In second mixing tank with the spray liquid of mistization to agglomerate.If the optional fine powder of crossing that comprises from first step in adding the product of second step, the liquid that sprays mistization is to being effective with meticulous powder bonded to the agglomerate from first step.Can be with about 0-10%, more preferably from about the various powder detergent compositions and/or other detergent ingredients that use in first step of 2-5% adds in second mixing tank.
In general, the mean residence time of preferred second mixing tank is about 0.2 to about 5s, the terminal velocity of second mixing tank is that about 10m/s is to about 30m/s, the energy of the second mixing tank per unit mass (energy state) is that about 0.15kj/kg is to about 5kj/kg, more preferably the mean residence time of second mixing tank is about 0.2 to about 5s, the terminal velocity of second mixing tank is that about 10m/s is to about 30m/s, the energy of the second mixing tank per unit mass (energy state) is that about 0.15kj/kg is to about 5kj/kg, most preferably the mean residence time of second mixing tank is about 0.2 to about 5s, the terminal velocity of second mixing tank is extremely about 26m/s of about 15m/s, and the energy of the second mixing tank per unit mass (energy state) is that about 0.15kj/kg is to about 2kj/kg.
The example of second mixing tank can be the mixing tank of oneself any type of knowing of those skilled in the art, as long as this mixing tank can keep the above-mentioned condition of second step.The Flexomic Model that Schugi company (Holland) makes can be an example.By second step, make second agglomerate.Third step (step (c))
If second agglomerate is less than 600g/l, if or preferably adopt further agglomeration to satisfy the top condition of the made finished product of method of the present invention, will add in the 3rd mixing tank from the agglomerate (second agglomerate) of second step.Promptly thorough mixing second agglomerate and it is fully sheared in the 3rd mixing tank makes agglomerate become circle and just grows up.Can choose wantonly will about 0-10%, more preferably from about the various powder detergent compositions and/or other detergent ingredients that use in first step, second step of 2-5% is added in the third step.Can preferably use the agglomerate of the broken undesirable oversize of chopping mechanism of the 3rd mixing tank installation.Therefore this method comprises that the 3rd mixing tank with chopping mechanism is that effectively this method is an embodiment preferred of the present invention to the agglomerate amount that reduces oversize in the finished product.
In general, the mean residence time of preferred the 3rd mixing tank is about 0.5 to about 15min, the energy of the 3rd mixing tank per unit mass (energy state) is about 0.15 to about 7kj/kg, more preferably the mean residence time of the 3rd mixing tank is about 3 to about 6min, and the energy of the 3rd mixing tank per unit mass (energy state) is about 0.15 to about 4kj/kg.
The example of the 3rd mixing tank can be the mixing tank of any type known to those skilled in the art, as long as this mixing tank can keep the above-mentioned condition of third step.The L dige KM mixing tank that L dige company (Germany) produces can be an example.
By second step (or third step), make the made product that density is at least about 600g/l.Also can choose wantonly make made product through super-dry, cool off and/or grind.
Adopting (1) to be fit to inject the CB mixing tank of at least two kinds of liquid components; (2) the suitable Schugi mixing tank that injects at least two kinds of liquid components; (3) the KM mixing tank that is fit at least a liquid component of injection realizes under the situation of method of the present invention that this method can add 5 kinds of dissimilar liquid components during the course.Therefore, for liquid state, quite valuable, the detergent raw material than more difficult transportation of solid material and/or storage joins in the granulation process sometimes, the method for being recommended is useful to those skilled in the art.
Detergent raw material
In the made product of the present invention, the finished product total that the total amount of tensio-active agent makes with method of the present invention, be generally about 5% to about 60%, more preferably from about 12% to about 40%, more preferably from about 15 to about 35%, they are included in the liquid and washing composition added ingredients of following detergent materials, mistization again.The tensio-active agent that comprises in above-mentioned materials can for example add from one of first step of the present invention, second step and/or third step from arbitrary part of method of the present invention.Detergent surfactant (water-based/nonaqueous)
The consumption of the tensio-active agent of present method by the finished product total of method gained of the present invention, can be about 5% to about 60%, and more preferably from about 12% to about 40%, and more more preferably from about 15 to about 35%.
The tensio-active agent of present method that is used as the above-mentioned detergent raw material of first step is the raw material of Powdered, pasty state or liquid form.
The kind of tensio-active agent itself is preferably from anionic, non-ionic type, amphoteric ion type, amphoteric, cationic and compatible mixture.United States Patent (USP) 3 the Norris of on May 23rd, 1972 promulgation, the people's such as Lao Kelin of promulgation on December 30th, 664,961 and 1975 United States Patent (USP) 3,929, narrate the used detergent surfactant of the present invention in 678, be incorporated herein these two parts of patents as a reference.Used cats product also is included in the United States Patent (USP) 4 of the Cockerell of promulgation on September 16th, 1980,222,905 and at the luxuriant and rich with fragrance United States Patent (USP) 4,239 of the China ink of on December 16th, 1980 promulgation, described in 659 those are also introduced these two parts of patents as a reference at this.In tensio-active agent, anionic and non-ionic type are preferred, and anionic is most preferred.
The limiting examples of the preferred anionic surfactants tensio-active agent of Shi Yonging comprises conventional C in the present invention
11-C
18Alkylbenzene sulfonate (" LAS "); Have main chain, side chain and random C
10-C
20Alkyl sulfuric ester salt (" AS "); General formula is CH
3(CH
2)
x(CHOSO
3 -M
+) CH
3And CH
3(CH
2)
y(CHOSO
3 -M
+) CH
2CH
3C
10-C
18(2,3) alkyl sulfuric ester salt in addition, x and (y+1) be at least about 7 integer in the formula, preferably at least about 9, M is a water-soluble cationic, particularly sodium; Undersaturated sulfuric acid, for example oleyl alcohol sulfuric acid; And C
10-C
18Alkyl alkoxy sulfuric acid (" AE
xS "; EO1-7 oxyethyl group sulfuric acid particularly).
The anion surfactant that uses also comprises the water-soluble salt of 2-acyloxy-alkane-1-sulfonic acid, wherein contains about 2-9 carbon atom in acyl group, contains about 9 to about 23 carbon atoms in the alkane chain; The water-soluble salt of alkenes sulfonate wherein contains about 12-24 carbon atom; β-alkoxyl group alkyl sulfonate, wherein alkyl contains about 1-3 carbon atom, contains about 8-20 carbon atom in the alkane chain.
Other exemplary surfactants of using with pasty state in the present invention, the optional C that comprises
10-C
18Alkyl alkoxy carboxylate salt (particularly ethoxy carboxylate), C
10-C
18Glyceryl ether, C
10-C
18The poly-glycosides and the C of alkylpolyglycosides and corresponding sulphating
12-C
18α-sulfonated fatty acid ester.If desired, in total composition, also can comprise conventional non-ionic type and tensio-active agent amphoteric, for example comprise the C of the alkylethoxylate at so-called narrow peak
12-C
18Alkylethoxylate (" AE ") and C
6-C
12Alkyl phenolic alkoxy thing (particularly ethoxylate and blended oxyethyl group/propoxy-), C
10-C
18Amine oxide etc.Also can use C
10-C
18Many hydroxy fatty acids of N-alkyl acid amides.Typical example comprises C
12-C
18The N-methyl glucose amide.See WO9,206,154.Other sucrose deutero-tensio-active agent comprises many hydroxy fatty acids of N-alkoxyl group acid amides, for example C
10-C
18N-(3-methoxy-propyl) glucamide.Also can use the N-propyl group to N-hexyl C
12-C
18Glucamide reduces foam.Also can use C
10-C
20Conventional soap.Many if desired foams can use branched C
10-C
16Soap.The mixture of anionic and nonionic surface active agent is a particularly suitable.In the textbook of standard, listed other tensio-active agent commonly used.
Also can adopt cationic surfactant as detergent surfactant of the present invention, suitable quaternary ammonium surfactant is selected from-C
6-C
16, preferred C
6-C
10N-alkyl or alkylene quaternary ammonium surfactant, wherein Sheng Xia N position is replaced by methyl, hydroxyethyl or hydroxypropyl.Also can adopt amphoterics as detergent surfactant of the present invention, comprising the aliphatic derivatives of heterocyclic secondary and tertiary amine; Zwitterionics is comprising the derivative of aliphatic quaternary ammonium, Phosphonium, sulfonium compound; The water-soluble salt of α-sulfonated fatty acid ester; Sulfated alkyl ether; The water-soluble salt of alkene sulfonate; β-alkoxyl group alkyl sulfonate; General formula is R (R
1)
2N
+R
2COO
-Trimethyl-glycine, R is C in the formula
6-C
18Alkyl, preferred C
10-C
16Alkyl or C
10-C
16Amidoalkyl, each R
1Be generally C
1-C
3Alkyl, preferable methyl, and R
2Be C
1-C
5Alkyl, preferred C
1-C
3Alkylidene group, more preferably C
1-C
2Alkylidene group.The example of suitable trimethyl-glycine comprises coconut amido propyl-dimethyl trimethyl-glycine; The hexadecyldimethyl benzyl ammonium trimethyl-glycine; C
12-14Amido propyl betaine; C
8-14Amido hexyl diethyl betaines; 4 (C
14-16Acyl group methylamino-diethyl ammonium)-1-carboxylic butane; C
16-18The amido dimethyl betaine; C
12-16Amido pentane diethyl betaines; And C
12-16Acyl group methylamino-dimethyl betaine.Preferred trimethyl-glycine is C
12-18Dimethyl-ammonium hexanoate and C
10-18Amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine; With general formula be R (R
1)
2N
+R
2SO
3 -The sulfonation trimethyl-glycine, R is C in the formula
6-C
18Alkyl, preferred C
10-C
16Alkyl, more preferably C
12-C
13Alkyl, each R
1Be generally C
1-C
3Alkyl, preferable methyl, R
2Be C
1-C
6Alkyl, preferred C
1-C
3Alkylidene group or preferred hydroxy alkylidene.The example of suitable sulfonation trimethyl-glycine comprises C
12-C
14Dimethylammonium-2-hydroxypropyl sulfonate, C
12-C
14Amino third ammonium-2-hydroxypropyl sulfonation trimethyl-glycine, C
12-C
14Dihydroxy ethyl ammonium propane sulfonate, and C
16-C
18Dimethylammonium hexane sulfonate, and preferred C
12-C
14Amido third ammonium-2-hydroxypropyl sulfonation trimethyl-glycine.Fine powder
The fine powder amount that present method is used in first step can be about 94%-30% of first step raw material total amount, preferred 86%-54%.The powder internal recycle stream that the fine powder raw material of present method preferably produces from ground SODA ASH LIGHT 99.2, pulverous tripoly phosphate sodium STPP (STPP), hydration tri-polyphosphate, ground sodium sulfate, aluminosilicate, crystalline layered silicate, nitrilotriacetic acid(NTA) salt (NTA), phosphoric acid salt, precipitated silicate, polymkeric substance, carbonate, Citrate trianion, pulverous tensio-active agent (for example pulverous alkyl sulfonic acid) and method of the present invention, wherein the mean diameter of powder is 0.1-500 μ, preferred 1-300 μ, more preferably 5-100 μ.Adopting under the situation of hydration STPP as fine powder of the present invention, it is preferred that hydration levels is not less than 50% STPP.Preferably calcium ion-exchanged capacity and the high aluminosilicate ion exchange material of exchange velocity are used as washing synergistic agent of the present invention.Though do not expect to be subjected to theoretical constraint, be sure of that this high calcium ion exchange rate and capacity are the functions of producing the correlation factors of aluminosilicate ion exchange material method.Thus, the used aluminosilicate ion exchange material of the present invention is preferably pressed people's such as section Kiel United States Patent (USP) 4,605,509 (Procter ﹠amp; Gamble) produce, be incorporated herein its disclosure as a reference.
Preferred aluminosilicate ion exchange material is " sodium " type, because the exchange velocity of the aluminosilicate of potassium type and Hydrogen and capacity are not as the height of sodium type.In addition, preferred aluminosilicate ion exchange material is over-drying form, is beneficial to produce frangible detergent agglomerate described herein.The aluminosilicate ion exchange material that the present invention uses preferably has the particle diameter as washing synergistic agent best results.Term used herein " particle diameter " is meant uses conventional method of analysis, and for example measurement microscope and scanning electronic microscope (SEM) are measured the median size of specifying aluminosilicate ion exchange material.The preferred particle diameter of aluminosilicate is extremely about 10 μ of about 0.1 μ, and more preferably from about 0.5 μ is to about 9 μ.Most preferably particle diameter is that about 1 μ is to about 8 μ.
The general formula of preferred aluminosilicate ion exchange material is Na
z[(AlO
2)
z(Si0
2)
y] xH
2O, z and y are integers in the formula, are at least 6, and z is about 1 to about 5 to the molecule ratio of y, and x is about 10 to about 264.More preferably the general formula of aluminosilicate is Na
12[(AlO
2)
12(SiO
2)
12] xH
2O, x is about 20 to about 30, preferred about 27 in the formula.These preferred aluminosilicates can have been bought on market, for example trade mark zeolite A, zeolite B and X zeolite.Adopt another kind of scheme, natural or with the aluminosilicate ion exchange material of the present invention that is applicable to of synthetic method preparation, can be incorporated herein its disclosure as a reference by people's such as Crewe Mel United States Patent (USP) 3,985,669 described preparations.
The feature of the aluminosilicate that the present invention is used also is their loading capacity, presses butt and calculates, and is at least about 200meg CaCO
3Hardness/g is preferably about 300-352megCaCO
3Hardness/g.In addition, the feature of this aluminosilicate ion exchange material is that also they are at least about 2grains (grain) Ca to the exchange velocity of calcium ion
++/ gallon/min/-g/ gallon.2grains Ca more preferably from about
++/ gallon/min/-g/ gallon is to about 6grains Ca
++/ gallon/min/-g/ gallon.The liquid of mistization
The amount of liquid of present method mistization can be finished product total amount that method of the present invention obtains about 1% to about 10% (active group), preferred 2% to about 6% (active group).The mist liquid that present method is used can be selected from liquid silicate; Anionic or cationic tensio-active agent, these tensio-active agents are liquid, water-based or nonaqueous polymers solns; Water and composition thereof.Other optional example of the mist liquid that the present invention uses can be carboxymethylcellulose sodium solution, polyoxyethylene glycol (PEG) and dimethylene triamine pentamethyl-phosphonic acids (DETMP).
Can be used as the preferred embodiment of the anionic surfactant solution of mist liquid in the present invention, be the active HLAS of about 88-97%, the active NaLAS of about 30-50%, about 28% active A E3S solution, the active liquid silicate of about 40-50% etc.
Also can adopt cationic surfactant as mist liquid of the present invention, suitable quaternary ammonium surfactant is selected from single C
6-C
16, preferred C
6-C
10N-alkyl or alkenyl quaternary ammonium surfactant, wherein Sheng Xia N position is replaced by methyl, hydroxyethyl or hydroxypropyl.
Can be in the present invention as preferred embodiment water-based or nonaqueous polymers soln of the mist liquid polyamines that is modification, comprising the polyamine main chain that is equivalent to following formula:
The general formula of its modified polyamine is V
(n-1)W
mY
nZ, or be equivalent to the polyamine main chain of following formula:
The general formula of its modified polyamine is V
(n-k+1)W
mY
nY '
kZ, k is less than or equal to n in the formula, and before modification, the molecular weight of described polyamine main chain is greater than about 200 dalton (dalton), wherein:
(i) the V unit is the terminal units with following formula:
Or
Or
(ii) the W unit is the skeleton unit with following formula:
Or
Or
(iii) the Y unit is the cladon with following formula:
Or
Or
With
(iv) the Z unit is the end-blocking unit with following formula:
Or
Wherein connect basic R unit on the main chain and be selected from C
2-C
12Alkylidene group, C
4-C
12Alkylene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-,-(CH
2) CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) (CH
2)
w-,-C (O) (R
4)
rC (O)-,-CH
2CH (OR
2) CH
2-and composition thereof, R wherein
1Be C
2-C
6Alkylidene group and composition thereof; R
2Be hydrogen ,-(R
1O)
xB, and composition thereof; R
3Be C
1-C
18Alkyl, C
7-C
12Aralkyl, C
7-C
12Alkyl substituting aromatic base, C
6-C
12Aryl and composition thereof; R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkylene group, C
8-C
12Aryl alkylene, C
6-C
10Arylidene and composition thereof; R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-and composition thereof; R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene; The E unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, C
7-C
22Aralkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
xB ,-C (O) R
3And composition thereof; Oxide compound; B is hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q-(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M and composition thereof; M is hydrogen or the water-soluble cationic that satisfies the q.s of charge balance; X is a water soluble anion; The m value is 4 to about 400; The n value is 0 to about 200; The p value is 1-6; The q value is 0-6; The r value is 0 or 1; The w value is 0 or 1; The x value is 1-100; The y value is 0-100; The z value is 0 or 1.An example of most preferred polymine is that to have molecular weight be 1800 polymine, again by oxyethylation with its modification, reach residual about 7 oxyethylene of each nitrogen degree (PEI1800, E7).For above-mentioned polymers soln, preferably with aniorfic surfactant NaLAS coordinate solution in advance for example.
Can be used as the water-based of mist liquid of the present invention or other preferred examples of nonaqueous polymers soln, is polymeric multi-carboxylate dispersion agent, and dispersion agent can preferably adopt the monomer of acid type by suitable polymerization of unsaturated monomers or copolymerization.Can polymerization prepare suitable multi-carboxylate polymer's unsaturated acids monomer, comprise vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.In the multi-carboxylate polymer that the present invention uses, do not contain carboxylate radical, for example monomer segmental existence such as vinyl methyl ether, vinylbenzene, ethene also suit, but press the weight calculating of polymkeric substance, and these segments must not surpass about 40%.
Molecular weight is the homopolymerization multi-carboxylate more than 4,000, narrated below for example, and be preferred.Shi Yi homopolymerization multi-carboxylate can be prepared by vinylformic acid especially.These used acrylic acid based polymers of the present invention are water-soluble salts of polymeric acrylic acid.Press acid type and calculate, preferably the molecular-weight average of this base polymer is 4,000-10, and more than 000, preferably 4,000-7, more than 000 and most preferably 4,000-5 is more than 000.The water-soluble salt of this class acrylate copolymer comprises for example ammonium salt of basic metal, ammonium and replacement.
Also can use copolymerization multi-carboxylate, for example vinylformic acid/maleic copolymer.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.Calculate with acid type, preferably the molecular-weight average of this analog copolymer is about 2,000-100,000, more preferably from about 5,000-75,000, most preferably from about 7,000-65,000.Acrylate was generally about 30: 1 to about 1: 1 maleate segmental ratio in this analog copolymer, more preferably from about 10: 1 to 2: 1.The water-soluble salt of this class vinylformic acid/maleic acid can comprise for example ammonium salt of basic metal, ammonium and replacement.Preferably make for example LAS coordination in advance of above-mentioned polymers soln and anion surfactant.The washing composition auxiliary ingredients
The detergent raw material of present method can comprise other washing composition batching, and/or can in some follow-up steps of present method any other batching be added in the cleaning composition.These auxiliary ingredients comprise decontamination synergistic agent, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, suds booster or defoamer, anti-tarnishing agent and sanitas, soil-suspending agent, soil releasing agent, sterilant, pH regulator agent, no synergistic agent alkali source, sequestrant, smectic clays, enzyme, enzyme stabilizers and spices.See the people's such as little Baskerville of promulgation on February 3rd, 1976 United States Patent (USP) 3,936,537, be hereby incorporated by.
Other synergistic agent generally can be selected from various water miscible basic metal, ammonium or replace phosphoric acid salt, poly-phosphate, phosphonate, polyphosphonate, carbonate, borate, polyhydroxy sulfonate, polyacetic acid salt, carboxylate salt and the multi-carboxylate of ammonium.Above-mentioned an alkali metal salt, particularly sodium salt are preferred.That preferred use is phosphoric acid salt, carbonate, C in the present invention
10-C
18Lipid acid, multi-carboxylate and composition thereof.Two succinates of tripoly phosphate sodium STPP, tetrasodium pyrophosphate, Citrate trianion, tartrate monosuccinic acid salt and tartrate and composition thereof (seeing below) more preferably.
Compare with unbodied water glass, laminar crystal sodium silicate obviously increases the loading capacity of calcium, magnesium.In addition, lamina sodium silicate is better than commutativity to calcium ion to magnesium ion, to guaranteeing that it is necessary removing all " hardness " from washing water basically.Yet these lamellated crystalline sodium disilicates are generally expensive than unbodied silicate and other synergistic agent.Therefore in order to prepare a kind of economically viable detergent for washing clothes, must determine to use the ratio of laminar crystal sodium silicate carefully.In the people's such as section Kiel that this paper is incorporated herein by reference previously United States Patent (USP) 4,605,509, these laminar crystal sodium silicates have been discussed.
The specific examples of inorganic phosphate synergistic agent is that tri-polyphosphate, pyrophosphate salt, the polymerization degree of sodium and potassium is polymetaphosphate and the orthophosphoric acid salt of about 6-21.The example of polyphosphonate synergistic agent is the sodium salt of ethylidene diphosphonic acid and sylvite, ethane 1-hydroxyl-1, the sodium salt of 1-di 2 ethylhexyl phosphonic acid and sylvite and ethane 1,1, the sodium salt of 2-tri methylene phosphonic acid and sylvite.In United States Patent (USP) 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176; With 3,400, other phosphorous synergist compound is disclosed in 148, be incorporated herein all these patents as a reference.
The example of the inorganic synergistic agent of phosphorated is not ten hydration tetraborates, SiO
2To the weight ratio of alkalimetal oxide is about 0.5 to about 4.0 silicate, preferred about 1.0 to about 2.4.The water miscible not phosphorated organic synergistic agent of Shi Yonging in the present invention comprises various basic metal, ammonium and replaces polyacetic acid salt, carboxylate salt, multi-carboxylate and the polyhydroxy sulfonate of ammonium.The example of polyacetic acid salt and multi-carboxylate's synergistic agent is the ammonium salt of sodium, potassium, lithium, ammonium and the replacement of ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), oxo disuccinic acid, mellitic acid, benzene polycarboxylic acid and citric acid.
In the United States Patent (USP) 3,308,067 of the Deere of on March 7th, 1967 promulgation, narrated polymeric multi-carboxylate synergistic agent.Be incorporated herein its disclosure as a reference.This class material comprises aliphatic carboxylic acid, for example the homopolymer of toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid and the water-soluble salt of multipolymer.Some is used as water-soluble anionic polymer hereinafter described in these materials, but just with the non-soap anionic surfactant thorough mixing time.
Other suitable multi-carboxylate that the present invention uses is the United States Patent (USP) 4 the people such as Crutchfield of promulgation on March 13rd, 1979,144, in 226 and at the people's such as Crutchfield of on March 27th, 1979 promulgation United States Patent (USP) 4,246, polyacetal carboxylation described in 495 is incorporated herein these two parts of patents as a reference.These polyacetal carboxylations can be by adding preparation together with hydrated glyoxylate and polymerization starter under polymerizing condition, be connected on the stable end group with the polyacetal carboxylic acid ester of chemical process then gained, make the polyacetal carboxylation that rapid depolymerization not take place in basic solution, the polyacetal carboxylic acid ester changes into corresponding salt simultaneously, and adds in the cleaning composition.The carboxylate salt enhancer composition that particularly preferred multi-carboxylate's synergistic agent is an ether, United States Patent (USP) 4 comprising the people such as Bush that issue on May 5th, 1987,663, the mixture of the two succinates of tartrate monosuccinic acid salt described in 071 and tartrate is incorporated herein its disclosure as a reference.
Having narrated SYNTHETIC OPTICAL WHITNER and activator in the United States Patent (USP) 4,412,934 of the Qiu Dengren of November 1 nineteen eighty-three promulgation and in the Hartmann's of promulgation on November 20th, 1984 the United States Patent (USP) 4,483,781, be incorporated herein these two parts of patents as a reference.In people's such as Bush United States Patent (USP) 4,663,071, walk to 18 hurdles, 68 row from 17 hurdles 54 and also narrated some sequestrants, be hereby incorporated by.The foam modifying agent also is an optional ingredients, at the people's such as Ba Tuolita of on January 20th, 1976 promulgation United States Patent (USP) 3,933, the Gao Er top grade people's who issues with on January 23rd, 1979 in 672 United States Patent (USP) 4, existing narration is incorporated herein these two parts of patents as a reference in 136,045.
Be fit to the smectic clays used in the present invention, walk to existing narration in 7 hurdles, 24 row, be hereby incorporated by on 6 hurdles 3 of the people's such as Plutarch of promulgation on August 9th, 1988 United States Patent (USP) 4,762,645.Other washing synergistic agent that is fit to use in the present invention walks to existing enumerating in 16 hurdles, 16 row and the United States Patent (USP) 4,663,071 the people such as Bush of promulgation on May 5th, 1987 on patent 13 hurdles 54 of Baskerville, is incorporated herein these two parts of patents as a reference.
Optional processing step
Present method can be chosen wantonly in one or more mixing tanks in first, second and/or the 3rd mixing tank of the present invention and comprise the step of spraying auxiliary binder.The purpose that adds tackiness agent is to provide " bonding " or " adhesion " agent to strengthen nodulizing to detergent ingredients.Tackiness agent is preferably from water, aniorfic surfactant, nonionic surface active agent, liquid silicate, polyoxyethylene glycol, polyvinylpyrrolidone, polyacrylic ester, citric acid and composition thereof.The jointing material that other is suitable comprises these that this paper lists, at people's such as Bill's Si grade United States Patent (USP) 5,108,646 (Procter ﹠amp; Gamble company) existing narration is incorporated herein its disclosure as a reference in.
Other optional step that present method is considered comprises that the employing screening plant sifts out the detergent agglomerate of oversize, and screening plant can adopt and include but not limited to sieve for reaching the various forms of routines that the granularity requirements of finished product washing composition is selected.Other optional step comprises utilizes aforesaid equipment to make agglomerate adjust detergent agglomerate through additional desiccation.
Another optional step of present method is the made detergent agglomerate of the whole bag of tricks finishing that sprays and/or mix other conventional detergent ingredients by comprising.For example finishing step comprises on by the agglomerate of finishing sprays spices, whitening agent and enzyme, makes detergent composition more completely, and these technology and composition are well-known in this area.
Another optional step of present method is the manufacturing processed that tensio-active agent is stuck with paste body, for example before process of the present invention, adopts forcing machine to add and sticks with paste the body hardened material, makes aqueous aniorfic surfactant stick with paste body and hardens.Co-applications PCT/US 9,6/1 5960 (on October 4th, 1996 submitted to) discloses the detailed content that tensio-active agent is stuck with paste the system making method.
For the present invention is more readily understood, can stipulate that these embodiment are illustrative with reference to the following examples, scope of the present invention is not limited.
EXAMPLE Example 1:
Be an embodiment who makes the high-density agglomerate below, comprising adopting earlier L digeCB mixing tank (CB-30), then adopting Schugi FX-160 mixing tank.
(step 1) utilizes the cylindricality utensil (pintools) of CB-30 mixing tank that the aqueous CFAS of 250-270kg/h (coconut Fatty Alcohol(C12-C14 and C12-C18) sulfuric acid tensio-active agent) is stuck with paste body (C
12-C
18, active ingredient 71.5%) disperse with the internal recycle of the Powdered STPP of 220kg/h (mean particle size 40-75 μ), 160-200kg/h ground SODA ASH LIGHT 99.2 (mean particle size 15 μ), 80-120kg/h ground sodium sulfate (mean particle size 15 μ) and 200kg/h powder stream.Tensio-active agent is stuck with paste body and is added down at about 40-52 ℃, and powder at room temperature adds.The operational condition of CB-30 mixing tank is as follows:
Mean residence time: 10-18s
Terminal velocity: 7.5-14m/s
Energy state: 0.5-4kj/kg
Mixer speed: 550-900rpm
Jacket temperature: 30 ℃
(step 2) will add from the agglomerate of CB-30 mixing tank in the Schugi FX-160 mixing tank.Under about 50-60 ℃ in the Schugi mixing tank with 30kg/h HLAS (C
11-C
18The acid presoma of alkylbenzene sulfonate, active ingredient 94-97%) is dispersed into the liquid of mistization.In the Schugi mixing tank, add 20-80kg/h SODA ASH LIGHT 99.2 (the about 10-20 μ of mean particle size).The operational condition of Schugi mixing tank is as follows:
Mean residence time: 0.2-5s
Terminal velocity: 16-26m/s
Energy state: 0.15-2kj/kg
Mixer speed: 2000-3200rpm
The particulate density that makes from step 2 is about 600g/l, can choose wantonly to make it through optional drying, cooling, screening and/or attrition process.Embodiment 2:
Be an embodiment who makes the high-density agglomerate below, comprising adopt earlier L digeCB mixing tank (CB-30), then adopt Schugi FX-160 mixing tank, adopt L dige KM mixing tank (KM-600) then.
(step 1) adopts the cylindricality utensil of CB-30 mixing tank with about 50 ℃ 15kg/h-30kg/h HLAS (C
11-C
18The acid presoma of alkylbenzene sulfonate, active ingredient 95%) and the aqueous CFAS of 250-270kg/h (coconut Fatty Alcohol(C12-C14 and C12-C18) sulfuric acid tensio-active agent) paste body (C
12-C
18, active ingredient 70%), disperse with the internal recycle of the Powdered STPP of 220kg/h (mean particle size 40-75 μ), 160-200kg/h ground SODA ASH LIGHT 99.2 (mean particle size 15 μ), 80-120kg/h ground sodium sulfate (mean particle size 15 μ) and 200kg/h powder stream.Tensio-active agent is stuck with paste body and is added down at about 45-52 ℃, and powder at room temperature adds.The operational condition of CB-30 mixing tank is as follows:
Mean residence time: 10-18s
Terminal velocity: 7.5-14m/s
Energy state: 0.5-4kj/kg
Mixer speed: 550-900rpm
Jacket temperature: 30 ℃
(step 2) will add from the agglomerate of CB-30 mixing tank in the Schugi FX-160 mixing tank.Under about 30-40 ℃ in the Schugi mixing tank with 35kg/h neutral AE
3S liquid (active ingredient 28%) is dispersed into the liquid of mistization.The operational condition that adds 20-80kg/h SODA ASH LIGHT 99.2 Schugi mixing tank in the Schugi mixing tank is as follows:
Mean residence time: 0.2-5s
Terminal velocity: 16-26m/s
Energy state: 0.15-2kj/kg
Mixer speed: 2000-3200rpm
(step 3) will add further agglomeration in the KM-600 mixing tank from the agglomerate of Schugi mixing tank, make agglomerate become circle and grow up.Also in the KM mixing tank, add 60kg/h ground SODA ASH LIGHT 99.2 (mean particle size 15 μ), can adopt the hybrid element of profile of tooth scraper plate (Serrated plows) as the KM mixing tank.Can adopt the chopping mechanism of KM mixing tank to reduce the agglomerate amount of oversize.The operational condition of KM mixing tank is as follows:
Mean residence time: 3-6min
Energy state: 0.15-2kj/kg
Mixer speed: 100-150rpm
Jacket temperature: 30-40 ℃
The particulate density that makes from step 3 is about 700g/l, can choose wantonly to make it through optional cooling, drying, screening and/or attrition process.
Now at length narrated the present invention,, obviously can make various changes and do not exceed scope of the present invention, should not think that the present invention is only limited in the content described in the specification sheets for those skilled in the art.
Claims (11)
1. non-tower method for preparing granular detergent compositions, the density of said composition is at least about 600g/l, comprising following steps:
(a) in mixing tank, disperse and with the fine powder clad surface promoting agent of diameter 0.1-500 μ, wherein the operational condition of mixing tank comprises: (i) mean residence time about 2 is to about 50s, (ii) terminal velocity about 4 is to about 25m/s, (iii) energy state about 0.15 is made agglomerate therein to 7kj/kg; With
(b) in mixing tank with the spray liquid of mistization to agglomerate, wherein the operational condition of mixing tank comprises: (i) mean residence time about 0.2 is to about 5s, (ii) terminal velocity about 10 to about 30m/s and (iii) energy state about 0.15 to about 5ki/kg.
2. non-tower method for preparing granular detergent compositions, the density of said composition is at least about 600g/l, comprising following steps:
(a) in mixing tank, disperse and with the fine powder clad surface promoting agent of diameter 0.1 to 500 μ, wherein the operational condition of mixing tank comprises: (i) mean residence time about 2 is to about 50s, (ii) terminal velocity about 4 is to about 25m/s, (iii) energy state about 0.15 is made first agglomerate therein to about 7kj/kg;
(b) in mixing tank with the spray liquid of mistization to first agglomerate, wherein the operational condition of mixing tank comprises: (i) mean residence time about 0.2 is to about 5s, (ii) terminal velocity about 10 is to about 30m/s, (iii) energy state about 0.1 5 is made second agglomerate therein to about 5kj/kg; With
(c) thorough mixing second agglomerate in mixing tank, wherein the operational condition of mixing tank comprises: (i) mean residence time about 0.5 to about 1 5min and (ii) energy state about 0.15 to about 7kj/kg.
3. according to the method for claim 1 or 2, wherein said tensio-active agent is selected from anionic, non-ionic type, cationic, amphoteric ion type and tensio-active agent amphoteric and composition thereof.
4. according to the method for claim 1 or 2, wherein said tensio-active agent is selected from alkylbenzene sulfonate, alkyl alkoxy sulfuric acid, alkylethoxylate, alkyl sulfuric ester salt, coconut Fatty Alcohol(C12-C14 and C12-C18) sulfuric acid and composition thereof.
5. according to the method for claim 2, wherein meticulous powder forms in step (a), wherein this meticulous powder is added in the step (b).
6. according to the method for claim 1 or 2, wherein water-based or nonaqueous polymers soln disperse in step (a) with described tensio-active agent.
7. according to the method for claim 1 or 2, wherein fine powder is selected from SODA ASH LIGHT 99.2, Powdered tripoly phosphate sodium STPP, hydration tri-polyphosphate, sodium sulfate, aluminosilicate, crystalline layered silicate, phosphoric acid salt, precipitated silicate, polymkeric substance, carbonate, Citrate trianion, nitrilotriacetic acid(NTA) salt, Powdered tensio-active agent and composition thereof.
8. according to the method for claim 1 or 2, wherein the liquid of mistization is selected from the polymers soln of liquid silicate, aniorfic surfactant, cationic surfactant, water-based, nonaqueous polymers soln, water and composition thereof.
9. according to the method for claim 1, wherein this method is a kind of successive method, wherein make the product that makes from step (b) again through overcooling and/or drying step, wherein produce powder internal recycle stream, wherein also this powder internal recycle stream is added in step (a) in this step.
10. according to the method for claim 2, wherein this method is a kind of successive method, wherein make the product that makes from step (c) again through overcooling and/or drying step, wherein produce powder internal recycle stream, wherein also this powder internal recycle stream is added in step (a) in this step.
11. granular detergent compositions according to the method preparation of claim 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| WOPCT/US96/15881 | 1996-10-04 | ||
| PCT/US1996/015881 WO1998014549A1 (en) | 1996-10-04 | 1996-10-04 | Process for making a low density detergent composition by non-tower process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1239991A true CN1239991A (en) | 1999-12-29 |
| CN1133739C CN1133739C (en) | 2004-01-07 |
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| CNB971802963A Expired - Fee Related CN1156562C (en) | 1996-10-04 | 1997-06-05 | Process for making detergent composition by non-tower process |
| CNB971802785A Expired - Fee Related CN1133738C (en) | 1996-10-04 | 1997-06-05 | Process for making detergent compsn. by non-tower process |
| CN97180294.7A Pending CN1239992A (en) | 1996-10-04 | 1997-06-05 | Process for making detergent composition by non-tower process |
| CNB971802971A Expired - Fee Related CN1156563C (en) | 1996-10-04 | 1997-06-05 | Process for making detergent composition by non-tower process |
| CNB971802807A Expired - Fee Related CN1156561C (en) | 1996-10-04 | 1997-06-05 | Process for making detergent compsn. by non-tower process |
| CNB971802793A Expired - Fee Related CN1156560C (en) | 1996-10-04 | 1997-06-05 | Process for making detergent compsn. by non-tower process |
| CNB971802939A Expired - Fee Related CN1133739C (en) | 1996-10-04 | 1997-06-05 | Process for making detergent composition by non-tower process |
| CN97180298.XA Pending CN1239995A (en) | 1996-10-04 | 1997-06-05 | Process for making detergent composition by non-tower process |
Family Applications Before (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB971802963A Expired - Fee Related CN1156562C (en) | 1996-10-04 | 1997-06-05 | Process for making detergent composition by non-tower process |
| CNB971802785A Expired - Fee Related CN1133738C (en) | 1996-10-04 | 1997-06-05 | Process for making detergent compsn. by non-tower process |
| CN97180294.7A Pending CN1239992A (en) | 1996-10-04 | 1997-06-05 | Process for making detergent composition by non-tower process |
| CNB971802971A Expired - Fee Related CN1156563C (en) | 1996-10-04 | 1997-06-05 | Process for making detergent composition by non-tower process |
| CNB971802807A Expired - Fee Related CN1156561C (en) | 1996-10-04 | 1997-06-05 | Process for making detergent compsn. by non-tower process |
| CNB971802793A Expired - Fee Related CN1156560C (en) | 1996-10-04 | 1997-06-05 | Process for making detergent compsn. by non-tower process |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97180298.XA Pending CN1239995A (en) | 1996-10-04 | 1997-06-05 | Process for making detergent composition by non-tower process |
Country Status (12)
| Country | Link |
|---|---|
| EP (9) | EP0929645A1 (en) |
| JP (9) | JP3305327B2 (en) |
| CN (8) | CN1156562C (en) |
| AR (6) | AR010507A1 (en) |
| AT (5) | ATE238409T1 (en) |
| AU (9) | AU7388196A (en) |
| BR (7) | BR9612732A (en) |
| CA (9) | CA2267291C (en) |
| DE (5) | DE69726439T2 (en) |
| ES (5) | ES2212109T3 (en) |
| MX (2) | MX219077B (en) |
| WO (9) | WO1998014549A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996031510A1 (en) * | 1995-04-03 | 1996-10-10 | Novartis Ag | Pyrazole derivatives and processes for the preparation thereof |
| GB9526097D0 (en) * | 1995-12-20 | 1996-02-21 | Unilever Plc | Process |
| GB9712580D0 (en) * | 1997-06-16 | 1997-08-20 | Unilever Plc | Production of detergent granulates |
| GB9712583D0 (en) | 1997-06-16 | 1997-08-20 | Unilever Plc | Production of detergent granulates |
| GB9713748D0 (en) * | 1997-06-27 | 1997-09-03 | Unilever Plc | Production of detergent granulates |
| US6258773B1 (en) | 1997-07-14 | 2001-07-10 | The Procter & Gamble Company | Process for making a low density detergent composition by controlling agglomeration via particle size |
| CN1218027C (en) | 1997-07-14 | 2005-09-07 | 普罗格特-甘布尔公司 | Process for making low density detergent composition by controlled agglomeration in fluid bed dryer |
| WO1999003965A1 (en) | 1997-07-15 | 1999-01-28 | The Procter & Gamble Company | Process for making high-active detergent agglomerates by multi-stage surfactant paste injection |
| US6440342B1 (en) | 1998-07-08 | 2002-08-27 | The Procter & Gamble Company | Process for making a low density detergent composition by controlling nozzle height in a fluid bed dryer |
| DE69932827T2 (en) | 1998-08-20 | 2007-03-15 | The Procter & Gamble Company, Cincinnati | METHOD FOR PRODUCING DETERGENTS USING A MEDIUM-FAST MIXER / COMPRESSOR |
| US6794354B1 (en) * | 1998-09-18 | 2004-09-21 | The Procter & Gamble Company | Continuous process for making detergent composition |
| JP2002528600A (en) * | 1998-10-26 | 2002-09-03 | ザ、プロクター、エンド、ギャンブル、カンパニー | Method for producing a granular detergent composition having improved appearance and solubility |
| GB9825558D0 (en) * | 1998-11-20 | 1999-01-13 | Unilever Plc | Granular detergent components and particulate detergent compositions containing them |
| GB9913546D0 (en) | 1999-06-10 | 1999-08-11 | Unilever Plc | Granular detergent component containing zeolite map and laundry detergent compositions containing it |
| EP1187904B1 (en) * | 1999-06-21 | 2004-08-11 | The Procter & Gamble Company | Process for making a granular detergent composition |
| US6894018B1 (en) | 1999-06-21 | 2005-05-17 | The Procter & Gamble Company | Process for making granular detergent in a fluidized bed granulator having recycling of improperly sized particles |
| GB0009877D0 (en) † | 2000-04-20 | 2000-06-07 | Unilever Plc | Granular detergent component and process for its preparation |
| EP2123742A1 (en) | 2008-05-14 | 2009-11-25 | The Procter and Gamble Company | A solid laundry detergent composition comprising light density silicate salt |
| WO2011061045A1 (en) | 2009-11-20 | 2011-05-26 | Unilever Nv | Detergent granule and its manufacture |
| WO2015154277A1 (en) | 2014-04-10 | 2015-10-15 | The Procter & Gamble Company | Composite detergent granules and laundry compositions comprising the same |
| US11377628B2 (en) * | 2018-01-26 | 2022-07-05 | Ecolab Usa Inc. | Solidifying liquid anionic surfactants |
| EP3743494A1 (en) | 2018-01-26 | 2020-12-02 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier |
| CA3089629A1 (en) | 2018-01-26 | 2019-08-01 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier |
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| US3625902A (en) * | 1968-10-11 | 1971-12-07 | Stauffer Chemical Co | Method of preparing agglomerated detergent composition |
| US4169806A (en) * | 1978-08-09 | 1979-10-02 | The Procter & Gamble Company | Agglomeration process for making granular detergents |
| US4992079A (en) * | 1986-11-07 | 1991-02-12 | Fmc Corporation | Process for preparing a nonphosphate laundry detergent |
| GB2209172A (en) * | 1987-08-28 | 1989-05-04 | Unilever Plc | Preparation of solid particulate components for detergents |
| KR0170424B1 (en) * | 1990-07-05 | 1999-01-15 | 호르스트 헤를레,요한 글라슬 | Process for making washing and cleaning active tensile granulates |
| ES2071494T3 (en) * | 1990-11-14 | 1995-06-16 | Procter & Gamble | PROCEDURE FOR THE PREPARATION OF COMPOSITIONS FOR NON-PHOSPHATE DISHWASHERS WITH OXYGEN BLEACHING SYSTEMS. |
| KR100276030B1 (en) * | 1992-06-15 | 2000-12-15 | 데이비드 엠 모이어 | Manufacturing method of granulated detergent and granulated detergent obtained in such a manner |
| CA2173108A1 (en) * | 1993-10-15 | 1995-04-20 | Scott William Capeci | Continuous process for making high density detergent granules |
| GB9322530D0 (en) * | 1993-11-02 | 1993-12-22 | Unilever Plc | Process for the production of a detergent composition |
| EP0663439B1 (en) * | 1994-01-17 | 2000-08-16 | The Procter & Gamble Company | Process for preparing detergent granules |
| US5516448A (en) * | 1994-09-20 | 1996-05-14 | The Procter & Gamble Company | Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate |
| US5489392A (en) * | 1994-09-20 | 1996-02-06 | The Procter & Gamble Company | Process for making a high density detergent composition in a single mixer/densifier with selected recycle streams for improved agglomerate properties |
| US5554587A (en) * | 1995-08-15 | 1996-09-10 | The Procter & Gamble Company | Process for making high density detergent composition using conditioned air |
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1996
- 1996-10-04 WO PCT/US1996/015881 patent/WO1998014549A1/en not_active Application Discontinuation
- 1996-10-04 AU AU73881/96A patent/AU7388196A/en not_active Abandoned
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- 1997-06-05 EP EP97928871A patent/EP0929648B1/en not_active Expired - Lifetime
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- 1997-06-05 EP EP97931057A patent/EP0929652A1/en not_active Ceased
- 1997-06-05 CN CNB971802963A patent/CN1156562C/en not_active Expired - Fee Related
- 1997-06-05 WO PCT/US1997/009792 patent/WO1998014554A1/en not_active Application Discontinuation
- 1997-06-05 AU AU34782/97A patent/AU3478297A/en not_active Abandoned
- 1997-06-05 DE DE69726439T patent/DE69726439T2/en not_active Expired - Fee Related
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- 1997-06-05 AT AT97931058T patent/ATE238409T1/en not_active IP Right Cessation
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- 1997-06-05 AU AU33785/97A patent/AU3378597A/en not_active Abandoned
- 1997-06-05 ES ES97928872T patent/ES2212109T3/en not_active Expired - Lifetime
- 1997-06-05 CN CNB971802785A patent/CN1133738C/en not_active Expired - Fee Related
- 1997-06-05 CN CN97180294.7A patent/CN1239992A/en active Pending
- 1997-06-05 AU AU34783/97A patent/AU3478397A/en not_active Abandoned
- 1997-06-05 BR BR9712492-3A patent/BR9712492A/en not_active IP Right Cessation
- 1997-06-05 AU AU33031/97A patent/AU3303197A/en not_active Abandoned
- 1997-06-05 WO PCT/US1997/009790 patent/WO1998014552A1/en active IP Right Grant
- 1997-06-05 WO PCT/US1997/009796 patent/WO1998014558A1/en active Application Filing
- 1997-06-05 CN CNB971802971A patent/CN1156563C/en not_active Expired - Fee Related
- 1997-06-05 JP JP51649698A patent/JP3299987B2/en not_active Expired - Fee Related
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- 1997-06-05 EP EP97931056A patent/EP0929651B1/en not_active Expired - Lifetime
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