WO1997039100A1 - High density detergent-making process using a high active surfactant paste having improved stability - Google Patents
High density detergent-making process using a high active surfactant paste having improved stability Download PDFInfo
- Publication number
- WO1997039100A1 WO1997039100A1 PCT/US1997/006484 US9706484W WO9739100A1 WO 1997039100 A1 WO1997039100 A1 WO 1997039100A1 US 9706484 W US9706484 W US 9706484W WO 9739100 A1 WO9739100 A1 WO 9739100A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- surfactant paste
- surfactant
- detergent
- paste
- process according
- Prior art date
Links
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 63
- 230000008569 process Effects 0.000 title claims abstract description 62
- 239000003599 detergent Substances 0.000 claims abstract description 107
- 239000000203 mixture Substances 0.000 claims description 44
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 13
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000356 contaminant Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000006072 paste Substances 0.000 description 108
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- 239000011734 sodium Substances 0.000 description 21
- 125000000217 alkyl group Chemical group 0.000 description 18
- 229910052708 sodium Inorganic materials 0.000 description 18
- 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 16
- 150000003839 salts Chemical class 0.000 description 15
- 229910052770 Uranium Inorganic materials 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000012530 fluid Substances 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 150000004760 silicates Chemical class 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 6
- 150000007942 carboxylates Chemical class 0.000 description 6
- 239000003093 cationic surfactant Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 5
- 229920005646 polycarboxylate Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052739 hydrogen Chemical group 0.000 description 4
- 239000001257 hydrogen Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
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- 230000002708 enhancing effect Effects 0.000 description 3
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- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
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- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 2
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 2
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 229910001748 carbonate mineral Inorganic materials 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004851 dishwashing Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000013178 mathematical model Methods 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910021647 smectite Inorganic materials 0.000 description 2
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 2
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 235000011044 succinic acid Nutrition 0.000 description 2
- 230000001180 sulfating effect Effects 0.000 description 2
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 2
- VJSWLXWONORKLD-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-trisulfonic acid Chemical compound OC1=C(S(O)(=O)=O)C(O)=C(S(O)(=O)=O)C(O)=C1S(O)(=O)=O VJSWLXWONORKLD-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-UHFFFAOYSA-N 2-dodec-1-enylbutanedioic acid Chemical compound CCCCCCCCCCC=CC(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-UHFFFAOYSA-N 0.000 description 1
- GCVQVCAAUXFNGJ-UHFFFAOYSA-N 2-hexadecylbutanedioic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)CC(O)=O GCVQVCAAUXFNGJ-UHFFFAOYSA-N 0.000 description 1
- DXPLEDYRQHTBDJ-UHFFFAOYSA-N 2-pentadec-1-enylbutanedioic acid Chemical compound CCCCCCCCCCCCCC=CC(C(O)=O)CC(O)=O DXPLEDYRQHTBDJ-UHFFFAOYSA-N 0.000 description 1
- MWTDCUHMQIAYDT-UHFFFAOYSA-N 2-tetradecylbutanedioic acid Chemical compound CCCCCCCCCCCCCCC(C(O)=O)CC(O)=O MWTDCUHMQIAYDT-UHFFFAOYSA-N 0.000 description 1
- 238000006677 Appel reaction Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
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- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000012188 paraffin wax Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910001752 sacrofanite Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
Definitions
- the present invention is generally directed to a process for making high density detergent compositions from a high active surfactant paste and other detergent ingredients. More particularly, the invention is directed to a process for producing a high density detergent composition in the form of agglomerates in which the stability and shelf life of a high active surfactant paste is unexpectedly improved and maintained. This process is especially useful in the production of modern compact granular detergent compositions which typically require higher levels of active detersive surfactants.
- the first type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower to produce highly porous detergent granules.
- various detergent components are mixed after which they are agglomerated with a nonionic or anionic detergent paste that also serves as the binder for the agglomerated particle itself.
- the most important factors which govern the density of the resulting detergent granules are the density, porosity and surface area of the various starting materials and their respective chemical composition. These parameters, however, can only be varied within a limited range. Thus, a substantial bulk density increase can only be achieved by additional processing steps which lead to densification of the detergent granules or via build-up agglomeration processes.
- surfactant pastes are manufactured by a process in which fatty alcohol is sulfated, and thereafter, neutralized with an alkaline material (e.g. sodium hydroxide).
- an alkaline material e.g. sodium hydroxide
- the resulting high active surfactant pastes are extremely sensitive to their environment, for example., high temperature zones or "hot spots" in the equipment (pipes, valves, storage tanks and the like) to which it is exposed as well as any contaminants having a pH of less than 7 which make their way into the paste.
- additional ingredients such as carbonates which are included so as to maintain the storage and transport stability of the surfactant paste before it is processed has the effect of increasing the viscoelasticity of the high active surfactant paste, therefore rendering it very difficult to process.
- the difficulty in processing arises due to a change in the viscoelasticity of the surfactant paste which requires relatively expensive high-pressure pumps, larger pipe lines and shorter transport distances to be implemented into the detergent-making process. As a consequence, it would be desirable to have a process in which the storage stability of the paste is maintained without sacrificing its processability.
- Patent No. 5,045,238 Procter & Gamble
- Van Zorn et al EP 504,986 (Shell).
- the following references are directed to densifying spray-dried granules: Appel et al, U.S. Patent No. 5,133,924 (Lever); Bortolotti et al, U.S. Patent No. 5,160,657 (Lever); Johnson et al, British patent No. 1,517,713
- the present invention meets the needs identified above by providing a process for making detergent agglomerates from a high active surfactant paste and a detergent builder.
- the surfactant paste is stable, pumpable, and transportable over an extended period of time so as to facilitate multi- location, large-scale manufacture of modern compact detergent products.
- the high active surfactant paste can be manufactured in one facility, and thereafter, stored and transported to a remote facility for further processing into the finished detergent agglomerates.
- the term "contaminants” means any foreign substance with which the surfactant paste comes into contact while being stored and transported prior to the inputting and agglomerating steps in the process. Examples of such contaminants include, but are not limited to, multi-colored residue of sulfuric acid, sodium sulfate, fatty alcohol, iron, chromium, and nickel.
- the term “stable” means that the surfactant paste substantially retains its formulation which contains a neutralized surfactant and has not significantly reverted via hydrolysis back to its alcohol form.
- the term "processable” means that the surfactant paste retains desirable rheological properties so as to allow it to be used in the current process which typically means that it will have a viscosity as detailed hereinafter with respect to the Power Law Model.
- agglomerates refers to particles formed by agglomerating detergent granules or particles which typically have a smaller mean particle size than the formed agglomerates. All percentages and ratios used herein are expressed as percentages by weight (anhydrous basis) unless otherwise indicated. All documents are incorporated herein by reference. All viscosities referenced herein are measured at 70°C ( ⁇ 5°C) and at shear rates of about 10 to 100 sec'l unless indicated otherwise.
- a process for producing detergent agglomerates comprises the steps of : (a) providing a non-linear viscoelastic surfactant paste including, by weight of the surfactant paste, from about 70% to 95% of a detersive surfactant, from about 5% to about 30% of water, and an excess amount of an alkali metal hydroxide such that the pH of the surfactant paste is at least about 10; (b) regulating the temperature of the surfactant paste within a range from about 50°C to about 80°C so that the surfactant paste is processable and stable for at least 48 hours; (c) charging the surfactant paste into a high speed mixer/densifier; (d) inputting from about 1% to about 70% by weight of a detergency builder into the high speed mixer/densifier; and (e) agglomerating the surfactant paste and the builder by treating the surfactant paste and the builder initially in the high speed mixer/densifier and
- another process for producing detergent agglomerates comprises the steps of: (a) providing a non-linear viscoelastic surfactant paste including, by weight of the surfactant paste, from about 70% to 80% of a mixture of C 14.15 alkyl sulfate surfactant and Cj2-13 linear alkylbenzene sulfonate surfactant, from about 15% to about 20% of water, from about 2% to about 8% of polyethylene glycol and from about 0.5% to about 1% of sodium hydroxide such that the pH of the surfactant paste is at least about 1 1 ; (b) regulating the temperature of the surfactant paste within a range from about 65 °C to about 70°C so that the surfactant paste is processable and stable for at least 120 hours; (c) charging from about 1% to about 50% by weight of the surfactant paste into a high speed mixer/densifier; (d) inputting from about 1% to about 70% by weight of
- an object of the invention to provide a process for producing an agglomerated detergent composition from a high active surfactant paste which is sufficiently stable during transportation and storage for sufficiently extended periods of time so as to enable large-scale commercial manufacture of modern compact detergent compositions. It is also an object of the invention to provide such a process which is inexpensive and can be easily incorporated into large-scale production facilities for low dosage or compact detergents.
- the present process is used in the production of low dosage detergents, whereby the resulting detergent agglomerates can be used as a detergent or as a detergent additive.
- the process can be used to form "high active" (i.e. high surfactant level) detergent agglomerates which are used as an admix for purposes of enhancing the active levels in granular low dosage detergents, and thereby, allow for more compact detergents.
- the process produces free flowing, high density detergent agglomerates, preferably having a density of at least 650 g/1.
- the process produces high density detergent agglomerates from a highly active and viscoelastic surfactant paste having a relatively low water content.
- processing and storing certain highly viscoelastic, high active surfactant pastes has been a problem, especially in light of their sensitivity to temperature variations and contaminants which are acidic in nature. While not intending to be bound by theory, it is believed that such temperature variations and acidic contaminants cause the autocatalytic hydrolysis reaction of the surfactant paste which effectively reverts the surfactant paste to an aqueous alcohol solution that cannot be reprocessed.
- a non-linear viscoelastic surfactant paste is provided which is characteristic of many highly active, highly viscoelastic pastes used in producing high density detergent agglomerates.
- the phrase "nonlinear viscoelastic” means that the paste has a nonlinear fluid velocity profile and exhibits viscoelastic fluid behavior, i.e. it can be stretched during flow such as chewing gum or the like. Until now, such nonlinear viscoelastic surfactant pastes have been very difficult to process and keep stable.
- the surfactant paste comprises, by weight of the surfactant paste, from about 70% to about 95%, more preferably from about 70% to about 85%, and most preferably from about 70% to about 75%, of a detersive surfactant.
- the surfactant paste is a mixture of C 14.15 alkyl sulfate (“AS”) and C 12.13 linear alkylbenzene sulfonate (“LAS”) surfactants in a weight ratio of from about 1 :1 to about 5:1 (AS:LAS).
- AS:LAS C 14.15 alkyl sulfate
- LAS linear alkylbenzene sulfonate
- Another preferred embodiment herein contemplates a surfactant paste mixture having a weight ratio of C 14.15 alkyl sulfate to C 12- 13 linear alk lbenzene sulfonate of about 3:1.
- Other optional surfactant systems include pure AS or pure LAS surfactants in the paste as well as alkyl ethoxy sulfate (“AES”) systems in which AES is the sole or one of the surfactants in the paste.
- the surfactant paste also includes from about 5% to about 30%, more preferably from about 15% to about 25%, and most preferably from about 15% to about 20%, by weight of the paste, of water. Additionally, the paste includes from about 0.1% to about 10%, more preferably from about 1% to about 8%, and most preferably from about 2% to about 8%, by weight of the paste, of polyethylene glycol.
- the surfactant paste also contains from about 0.01% to about 5%, more preferably from about 0.1% to about 1%, and most preferably from about 0.5% to about 1%, by weight of the paste, of an alkali metal hydroxide which preferably is sodium hydroxide. Also included in the surfactant paste are minor ingredients such as unreacted alcohols, sulfates and the like, although it is preferable to keep these amounts to a minimum.
- the surfactant paste is regulated within a temperature range of from about 50°C to about 80°C, more preferably from about 60°C to about 75°C, and most preferably from about 65°C to about 70°C.
- the regulating step maintains or renders the surfactant paste stable for at least 48 hours, more preferably for at least 72 hours, and most preferably for at least 170 hours. In this way, the likelihood of the surfactant paste undergoing the undesirable hydrolysis reaction and/or being difficult to transport and process due to unbearable rheological properties, such as high viscosity, is eliminated.
- the surfactant paste be substantially free of materials which produces a gas when reacted with an acid.
- materials include carbonates, percarbonates, perborates or any other material which produces a gas upon contact with an acidic material.
- the surfactant paste includes such a gas-producing material, it will react with any acidic contaminant material to produce a gas that propagates through the remaining surfactant paste, thereby creating a "channel" or "path” through which the acidic contaminant can traverse the paste. This facilitates the hydrolysis reaction of the entire surfactant paste as opposed to only a small isolated hydrolysis incident which would not otherwise affect the overall surfactant paste composition.
- it is preferable in the current process to maintain the surfactant paste substantially free of contaminant materials having a pH of less than about 7.
- the surfactant paste is charged into a high speed mixer/densifier (e.g. L ⁇ dige Recycler CB 30) which typically operates in 300 ⁇ m to about 2500 m range.
- a high speed mixer/densifier e.g. L ⁇ dige Recycler CB 30
- from about 25% to about 65%, more preferably 30% to about 60%, and most preferably from about 35% to about 55%, by weight of the surfactant paste is used in the process to make the agglomerates.
- from about 1% to about 70%, more preferably from about 5% to about 70% and, most preferably from about 50% to about 70%, by weight of a detergency builder is inputted into the high speed mixer/densifier.
- aluminosilicate builder is the preferred.
- the surfactant paste and the builder are agglomerated by treating the paste and the builder initially in the high speed mixer/densifier and subsequently in a moderate speed mixer/densifier (e.g. L ⁇ dige Recycler KM 300 "Ploughshare" having a large central shaft operating in the 100 ⁇ m to 300 ⁇ m range) so as to form detergent agglomerates.
- a moderate speed mixer/densifier e.g. L ⁇ dige Recycler KM 300 "Ploughshare" having a large central shaft operating in the 100 ⁇ m to 300 ⁇ m range
- Other equipment suitable for use as the high speed mixer/densifier or moderate speed mixer/densifier are described in Capeci, U.S. Patent 5,366,652, the disclosure of which is inco ⁇ orated herein by reference.
- ⁇ conventional detergent ingredients as described hereinafter can also be inputted into the high speed mixer/densifier and/or moderate speed mixer/densifier to make a fully formulated detergent agglomerate.
- the surfactant paste, builder and other optional starting detergent materials are sent to a moderate speed mixer/densifier for further build-up agglomeration resulting in agglomerates having a density of at least 650 g/1 and, more preferably from about 700 g/1 to about 900 g/1.
- the mean residence time of the surfactant paste and other starting detergent materials in the high speed mixer/densifier e.g.
- L ⁇ dige Recycler CB 30 mixer/densifier is from about 1 to 30 seconds while the residence time in low or moderate speed mixer/densifier (e.g. L ⁇ dige Recycler KM 300 "Ploughshare" mixer/densifier) is from about 0.25 to 10 minutes.
- low or moderate speed mixer/densifier e.g. L ⁇ dige Recycler KM 300 "Ploughshare” mixer/densifier
- a certain amount of the agglomerates exiting the moderate speed mixer/densifier will be below the predetermined particle size range and optionally, can be separated and recycled back to the high speed mixer/densifier for further build-up agglomeration.
- these so-called undersized agglomerates or "fines" will comprise from about 5% to about 30% by weight of the detergent agglomerates.
- the particle porosity of the resulting detergent agglomerates produced according to the process of the invention is preferably in a range from about 5% to about 20%, more preferably at about 10%.
- the combination of the above-referenced porosity and particle size results in agglomerates having density values of 650 g/1 and higher.
- Such a feature is especially useful in the production of low dosage laundry detergents as well as other granular compositions such as dishwashing compositions.
- the process can comprise the steps of spraying an additional binder in the mixer/densifier(s) used in the agglomeration step to facilitate production of the desired detergent agglomerates.
- a binder is added for pu ⁇ oses of enhancing agglomeration by providing a "binding" or "sticking" agent for the detergent components.
- the binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyacrylates, citric acid and mixtures thereof.
- Other suitable binder materials including those listed herein are described in Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble Co.), the disclosure of which is inco ⁇ orated herein by reference.
- Another optional step contemplated by the present process includes conditioning the detergent agglomerates by drying the detergent agglomerates after the moderate speed mixer/densifier.
- Yet another optional step involves adding a coating agent (e.g. aluminosilicates, carbonates, sulfates, or any other dry powdered material) to the detergent agglomerate before or after they exit the moderate speed mixer/densifier for pu ⁇ oses of enhancing the flowability of the agglomerates (i.e. reduce caking). This furthers enhances the condition of the detergent agglomerates for use as an additive or to place them in shippable or packagable form.
- a coating agent e.g. aluminosilicates, carbonates, sulfates, or any other dry powdered material
- the viscoelastic surfactant paste used herein has viscoelastic fluid properties which can be described by a commonly used mathematical model that accounts for the shear thinning nature of the paste.
- Rate Index Rate Index (dimensionless).
- the rate index n varies from 0 to 1. The closer n is to 0, the more shear thinning the fluid. The closer n is to 1, the closer it is to simple Newtonian behavior, i.e. constant viscosity behavior. K can be inte ⁇ reted as the apparent viscosity at a shear rate of I sec' 1 In this context, the viscoelastic surfactant paste used in the process has a consistency K at
- the surfactant paste has a shear index n of from about 0.05 to about 0.25, more preferably from about 0.08 to about 0.20 and most preferably from about 0.10 to about 0.15.
- the surfactant in the paste can be selected from anionic, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
- Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, both of which are inco ⁇ orated herein by reference.
- Useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Mu ⁇ hy, issued December 16, 1980, both of which are also inco ⁇ orated herein by reference.
- surfactants anionics and nonionic are preferred and anionics are most preferred.
- the following are representative examples of detergent surfactants useful in the present surfactant paste.
- Water-soluble salts of the higher fatty acids i.e., "soaps" are useful anionic surfactants in the compositions herein.
- This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms.
- Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
- Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- Additional anionic surfactants which suitable for use herein include the water- soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C Intel .
- anionic surfactants suitable for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
- suitable anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about I to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-l -sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
- Preferred anionic surfactants are C, 0 . disturb linear alkylbenzene sulfonate and C. Q , deliberately alkyl sulfate.
- low moisture (less than about 25% water) alkyl sulfate paste can be the sole ingredient in the surfactant paste.
- Most preferred are C .tician .
- a preferred embodiment of the present invention is wherein the surfactant paste comprises from about 20% to about 40% of a mixture of sodium C , n . , linear alkylbenzene sulfonate and sodium C . - .
- alkyl sulfate in a weight ratio of about 2:1 to 1:2.
- Another preferred embodiment of the detergent composition includes a mixture of C j _ i g alkyl sulfate and C i Q-18 allcv ' ethoxy sulfate in a weight ratio of about 80:20.
- Water-soluble nonionic surfactants are also useful in the instant invention. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from about 3 to 12 moles of ethylene oxide per mole of alkyl phenol. Included are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol.
- nonionics suitable for use herein are semi-polar nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from abut 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
- Preferred nonionic surfactants are of the formula R (OG-.H.) OH, wherein R is a
- n is from 3 to about 80.
- Particularly preferred are condensation products of C . ⁇ -C . - alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C. ⁇ -C. , alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
- nonionic surfactants include polyhydroxy fatty acid amides of the formula
- Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
- Cationic surfactants can also be included in the present invention.
- Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds.
- Suitable anions are halides, methyl sulfate and hydroxide.
- Tertiary amines can have characteristics similar to cationic surfactants at washing solution pH values less than about 8.5.
- a more complete disclosure of these and other cationic surfactants useful herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, inco ⁇ orated herein by reference.
- Cationic surfactants are often used in detergent compositions to provide fabric softening and/or antistatic benefits.
- Antistatic agents which provide some softening benefit and which are preferred herein are the quaternary ammonium salts described in U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3, 1976, the disclosure of which is inco ⁇ orated herein by reference.
- Detergency Builder The present process includes the step of inputting a detergent builder into the high speed mixer/densifier to coagglomerate with the surfactant paste.
- the builder also assists in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces.
- Builders can operate via a variety of mechanisms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering a surface more favorable to the precipitation of hardness ions than are the surfaces of articles to be cleaned.
- Builder level can vary widely depending upon end use and physical form of the composition.
- Built detergents typically comprise at least about 1% builder.
- Liquid formulations typically comprise about 5% to about 50%, more typically 5% to 35% of builder.
- Granular formulations typically comprise from about 10% to about 80%, more typically 15% to 50% builder by weight of the detergent composition.
- Lower or higher levels of builders are not excluded. For example, certain detergent additive or high-sur
- Suitable builders herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; silicates including water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amo ⁇ hous-solid or non-structured-liquid types; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; aluminosilicates; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
- borates e.g., for pH-buffering pu ⁇ oses
- sulfates especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or builder-containing detergent compositions.
- Builder mixtures sometimes termed “builder systems” can be used and typically comprise two or more conventional builders, optionally complemented by chelants, pH- buffers or fillers, though these latter materials are generally accounted for separately when describing quantities of materials herein.
- preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from about 60: 1 to about 1 :80.
- Certain preferred laundry detergents have said ratio in the range 0.90: 1.0 to 4.0: 1.0, more preferably from 0.95:1.0 to 3.0:1.0.
- P-containing detergent builders often preferred where permitted by legislation include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.
- Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6: 1 to 3.2: 1, including, particularly for automatic dishwashing purposes, solid hydrous 2-ratio silicates marketed by PQ Corp.
- BRITESIL® e.g., BRITESIL H20
- layered silicates e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck.
- NaSKS-6 sometimes abbreviated "SKS-6"
- SKS-6 is a crystalline layered aluminum-free ⁇ -Na2Si ⁇ 5 mo ⁇ hology silicate marketed by Hoechst and is preferred especially in granular laundry compositions. See preparative methods in German DE-A-3,417,649 and DE-A-3, 742,043.
- layered silicates such as those having the general formula NaMSi x ⁇ 2 ⁇ + ⁇ H2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2. and y is a number from 0 to 20, preferably 0, can also or alternately be used herein.
- Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS- 1 1 , as the ⁇ , ⁇ and ⁇ layer-silicate forms.
- Other silicates may also be useful, such as magnesium silicate, which can serve as a crispening agent in granules, as a stabilizing agent for bleaches, and as a component of suds control systems.
- crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM2O.ySiO2.zMO wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,71 1, Sakaguchi et al, June 27, 1995.
- Suitable carbonate builders include alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2C ⁇ 3.CaC ⁇ 3 when anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially forms having high surface areas relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars.
- Aluminosilicate builders are especially useful in granular detergents, but can also be inco ⁇ orated in liquids, pastes or gels.
- Suitable for the present purposes are those having empirical formula: [M z (Al ⁇ 2) z (Si ⁇ 2) v ]*xH2 ⁇ wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
- Aluminosilicates can be crystalline or amo ⁇ hous, naturally-occurring or synthetically derived. An aluminosilicate production method is in U.S. 3,985,669, Krummel, et al,
- the aluminosilicate has a particle size of 0.1-10 microns in diameter.
- Suitable organic detergent builders include polycarboxylate compounds, including water-soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates.
- Carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
- Polycarboxylate builders include the ether polycarboxylates, such as oxydisuccinate, see Berg, U.S. 3,128,287, April 7, 1964, and Lamberti et al, U.S.
- Suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy benzene-2, 4, 6- trisulphonic acid; carboxymethyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
- Citrates e.g., citric acid and soluble salts thereof are important carboxylate builders e.g., for heavy duty liquid detergents, due to availability from renewable resources and biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicates. Oxydisuccinates are also especially useful in such compositions and combinations.
- alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
- Phosphonate builders such as ethane- l-hydroxy-l,l-diphosphonate and other known phosphonates, e.g., those of U.S. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable antiscaling properties.
- detersive surfactants or their short-chain homologs also have a builder action. For unambiguous formula accounting pu ⁇ oses, when they have surfactant capability, these materials are summed up as detersive surfactants.
- Preferred types for builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986.
- Succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
- Succinate builders also include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.
- Lauryl-succinates are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
- Fatty acids e.g., C12-C18 monocarboxylic acids, can also be inco ⁇ orated into the compositions as surfactant/builder materials alone or in combination with the aforementioned builders, especially citrate and/or the succinate builders, to provide additional builder activity.
- Other suitable polycarboxylates are disclosed in U.S.
- Waters of hydration or anions other than carbonate may be added provided that the overall charge is balanced or neutral.
- the charge or valence effects of such anions should be added to the right side of the above equation.
- a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more preferably, sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium and potassium being highly preferred.
- Nonlimiting examples of noncarbonate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures thereof.
- Preferred builders of this type in their simplest forms are selected from the group consisting of Na 2 Ca(C0 3 )2, K 2 Ca(C0 3 ) 2 , Na 2 Ca 2 (C0 3 )3, NaKCa(C0 3 ) 2 , NaKCa 2 (C0 3 )3,
- An especially preferred material for the builder described herein is Na2Ca(C ⁇ 3)2 in any of its crystalline modifications.
- Suitable builders of the above-defined type are further illustrated by, and include, the natural or synthetic forms of any one or combinations of the following minerals: aceaite, Andersonite, AshcroftineY, Beyerite, Borcarite, Burbankite, Butschliite, Cancrinite, Carbocemaite, Carletonite, Davyne, DonnayiteY, Fairchildite, Ferrisurite, Franzinite, Gaudefroyite, Gaylussite, Girvasite, Gregoryite, Jouravskite, KamphaugiteY, Kettnerite, Khanneshite, LepersonniteGd, Liottite, MckelveyiteY, Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite, Schrocking
- the starting or entering detergent components in the present process can also include any-number of additional ingredients.
- additional ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes.
- additional ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes.
- Chelating agents are also described in U.S. Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, inco ⁇ orated herein by reference.
- Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both inco ⁇ orated herein by reference.
- Suitable smectite clays for use herein are described in U.S.
- a falling film S0 3 reactor is used to prepare the acid form of C 14 ., 5 alkyl sulfate and C 123 linear alkylbenzene sulfonate.
- the acid is fed to a high active neutralization system which consists of a recycle loop containing a heat exchanger for cooling, a recircuiation pump suitable for highly viscous fluids, and a high shear mixer with which the reactants are introduced.
- Surfactant paste exiting the high active neutralization system is transported and stored in jacketed, temperature-controlled 316L stainless steel storage vessels at a temperature of 71°C.
- the surfactant paste remains stable and maintains a pH above 10 for at least five days (120 hours).
- the temperature of the paste is maintained between 65°C to about 70°C by the circulation of glycol solution through the vessel jacketing.
- Two feed streams of various detergent starting ingredients are continuously fed, at a rate of 2800 kg/hr, into a Lodige CB-30 mixer/densifier, one of which comprises the surfactant paste and the other stream containing the detergent builder which is aluminosilicate.
- the surfactant paste, aluminosilicate and optional co-builder sodium carbonate are agglomerated to form detergent agglomerates.
- the detergent agglomerates from the L ⁇ dige CB-30 mixer/densifier are continuously fed into a L ⁇ dige KM-600 mixer/densifier for further agglomeration.
- the resulting detergent agglomerates are then fed to optional conditioning apparatus including a fluid bed dryer and a fluid bed cooler.
- the detergent agglomerates exiting the fluid bed cooler are screened, after which adjunct detergent ingredients are admixed therewith to result in a fully formulated detergent product having a uniform particle size distribution.
- the composition of the detergent agglomerates exiting the fluid bed cooler is set forth in Table II below:
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Abstract
Description
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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AT97921254T ATE209247T1 (en) | 1996-04-17 | 1997-04-16 | METHOD FOR PRODUCING HIGH DENSITY DETERGENT USING A HIGHLY EFFECTIVE SURFACTANT PASTE WITH IMPROVED STABILITY |
DE69709726T DE69709726T3 (en) | 1996-04-17 | 1997-04-16 | PROCESS FOR PREPARING HIGH DENSITY DETERGENT USING A HIGH-ACTIVE TENSID PASTE WITH IMPROVED STABILITY |
CA002251844A CA2251844C (en) | 1996-04-17 | 1997-04-16 | High density detergent-making process using a high active surfactant paste having improved stability |
BR9708702A BR9708702A (en) | 1996-04-17 | 1997-04-16 | Process for the production of high-density detergent using a very active surface tension paste with improved stability |
JP09537386A JP3080998B2 (en) | 1996-04-17 | 1997-04-16 | Method for producing high-density detergents using highly active surfactant pastes with improved stability |
EP97921254A EP0898614B2 (en) | 1996-04-17 | 1997-04-16 | High density detergent-making process using a high active surfactant paste having improved stability |
Applications Claiming Priority (2)
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US1568596P | 1996-04-17 | 1996-04-17 | |
US60/015,685 | 1996-04-17 |
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WO1997039100A1 true WO1997039100A1 (en) | 1997-10-23 |
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PCT/US1997/006484 WO1997039100A1 (en) | 1996-04-17 | 1997-04-16 | High density detergent-making process using a high active surfactant paste having improved stability |
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EP (1) | EP0898614B2 (en) |
JP (1) | JP3080998B2 (en) |
CN (1) | CN1221448A (en) |
AR (1) | AR006684A1 (en) |
AT (1) | ATE209247T1 (en) |
BR (1) | BR9708702A (en) |
CA (1) | CA2251844C (en) |
DE (1) | DE69709726T3 (en) |
ES (1) | ES2163760T5 (en) |
WO (1) | WO1997039100A1 (en) |
Cited By (3)
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JP2002530516A (en) * | 1998-11-25 | 2002-09-17 | ザ、プロクター、エンド、ギャンブル、カンパニー | Manufacturing method of cleaning composition |
WO2004053050A1 (en) * | 2002-12-07 | 2004-06-24 | Unilever Plc | Detergent compositions |
WO2022078916A1 (en) | 2020-10-13 | 2022-04-21 | Unilever Ip Holdings B.V. | Composition |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0438320A2 (en) * | 1990-01-19 | 1991-07-24 | Unilever Plc | Detergent compositions and process for preparing them |
WO1995006109A1 (en) * | 1993-08-27 | 1995-03-02 | The Procter & Gamble Company | Process for making high density detergent agglomerates |
WO1996027655A1 (en) * | 1995-03-07 | 1996-09-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
Family Cites Families (1)
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GB8415492D0 (en) † | 1984-06-18 | 1984-07-25 | Unilever Plc | Manufacture of alcohol sulphate |
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- 1997-04-16 DE DE69709726T patent/DE69709726T3/en not_active Expired - Lifetime
- 1997-04-16 CA CA002251844A patent/CA2251844C/en not_active Expired - Fee Related
- 1997-04-16 WO PCT/US1997/006484 patent/WO1997039100A1/en active IP Right Grant
- 1997-04-16 BR BR9708702A patent/BR9708702A/en unknown
- 1997-04-16 AT AT97921254T patent/ATE209247T1/en not_active IP Right Cessation
- 1997-04-16 EP EP97921254A patent/EP0898614B2/en not_active Expired - Lifetime
- 1997-04-16 JP JP09537386A patent/JP3080998B2/en not_active Expired - Fee Related
- 1997-04-16 ES ES97921254T patent/ES2163760T5/en not_active Expired - Lifetime
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0438320A2 (en) * | 1990-01-19 | 1991-07-24 | Unilever Plc | Detergent compositions and process for preparing them |
WO1995006109A1 (en) * | 1993-08-27 | 1995-03-02 | The Procter & Gamble Company | Process for making high density detergent agglomerates |
WO1996027655A1 (en) * | 1995-03-07 | 1996-09-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002530516A (en) * | 1998-11-25 | 2002-09-17 | ザ、プロクター、エンド、ギャンブル、カンパニー | Manufacturing method of cleaning composition |
WO2004053050A1 (en) * | 2002-12-07 | 2004-06-24 | Unilever Plc | Detergent compositions |
US7208461B2 (en) | 2002-12-07 | 2007-04-24 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Detergent compositions |
CN1324122C (en) * | 2002-12-07 | 2007-07-04 | 荷兰联合利华有限公司 | Detergent compositions |
WO2022078916A1 (en) | 2020-10-13 | 2022-04-21 | Unilever Ip Holdings B.V. | Composition |
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JP3080998B2 (en) | 2000-08-28 |
ES2163760T3 (en) | 2002-02-01 |
AR006684A1 (en) | 1999-09-08 |
EP0898614A1 (en) | 1999-03-03 |
CA2251844C (en) | 2003-01-14 |
ES2163760T5 (en) | 2005-12-01 |
DE69709726T3 (en) | 2006-03-16 |
EP0898614B2 (en) | 2005-06-15 |
DE69709726D1 (en) | 2002-02-21 |
EP0898614B1 (en) | 2001-11-21 |
CN1221448A (en) | 1999-06-30 |
DE69709726T2 (en) | 2002-07-18 |
CA2251844A1 (en) | 1997-10-23 |
JPH11507988A (en) | 1999-07-13 |
BR9708702A (en) | 1999-08-03 |
ATE209247T1 (en) | 2001-12-15 |
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