CN115916938A - 漂白催化剂 - Google Patents
漂白催化剂 Download PDFInfo
- Publication number
- CN115916938A CN115916938A CN202180040124.0A CN202180040124A CN115916938A CN 115916938 A CN115916938 A CN 115916938A CN 202180040124 A CN202180040124 A CN 202180040124A CN 115916938 A CN115916938 A CN 115916938A
- Authority
- CN
- China
- Prior art keywords
- acid
- catalyst
- metal oxide
- automatic dishwashing
- bleaching
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000004061 bleaching Methods 0.000 title description 21
- 238000004851 dishwashing Methods 0.000 claims abstract description 28
- 239000007844 bleaching agent Substances 0.000 claims abstract description 26
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims description 39
- 229910052802 copper Inorganic materials 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 description 12
- 239000003599 detergent Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229940088598 enzyme Drugs 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 241000894007 species Species 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
- GTXVUMKMNLRHKO-UHFFFAOYSA-N 2-[carboxymethyl(2-sulfoethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCS(O)(=O)=O GTXVUMKMNLRHKO-UHFFFAOYSA-N 0.000 description 4
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- 229910017985 Cu—Zr Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 108091005804 Peptidases Proteins 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004365 Protease Substances 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- -1 sulfide ions Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UWRLZJRHSWQCQV-YFKPBYRVSA-N (2s)-2-(2-sulfoethylamino)pentanedioic acid Chemical compound OC(=O)CC[C@@H](C(O)=O)NCCS(O)(=O)=O UWRLZJRHSWQCQV-YFKPBYRVSA-N 0.000 description 2
- HWXFTWCFFAXRMQ-JTQLQIEISA-N (2s)-2-[bis(carboxymethyl)amino]-3-phenylpropanoic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H](C(O)=O)CC1=CC=CC=C1 HWXFTWCFFAXRMQ-JTQLQIEISA-N 0.000 description 2
- DCCWEYXHEXDZQW-BYPYZUCNSA-N (2s)-2-[bis(carboxymethyl)amino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O DCCWEYXHEXDZQW-BYPYZUCNSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 2
- ODAKQJVOEZMLOD-UHFFFAOYSA-N 3-[bis(carboxymethyl)amino]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)CN(CC(O)=O)CC(O)=O ODAKQJVOEZMLOD-UHFFFAOYSA-N 0.000 description 2
- UWRBFYBQPCJRRL-UHFFFAOYSA-N 3-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CC(O)=O)CC(O)=O UWRBFYBQPCJRRL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 235000003704 aspartic acid Nutrition 0.000 description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000004967 organic peroxy acids Chemical class 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- DIWZKTYQKVKILN-VKHMYHEASA-N (2s)-2-(dicarboxymethylamino)pentanedioic acid Chemical compound OC(=O)CC[C@@H](C(O)=O)NC(C(O)=O)C(O)=O DIWZKTYQKVKILN-VKHMYHEASA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- WLDGDTPNAKWAIR-UHFFFAOYSA-N 1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1 WLDGDTPNAKWAIR-UHFFFAOYSA-N 0.000 description 1
- XMIFEDVGGQMJQD-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)-2-hydroxybutanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(O)(C(O)=O)CC(O)=O XMIFEDVGGQMJQD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XMWLVXXYIYBETQ-UHFFFAOYSA-N 2-hydroxy-3-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)NCC(O)CS(O)(=O)=O XMWLVXXYIYBETQ-UHFFFAOYSA-N 0.000 description 1
- KOQQKLZTINXBAS-UHFFFAOYSA-N 2-hydroxy-3-prop-2-enoxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(O)COCC=C KOQQKLZTINXBAS-UHFFFAOYSA-N 0.000 description 1
- VSSGDAWBDKMCMI-UHFFFAOYSA-N 2-methyl-2-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)NC(C)(C)CS(O)(=O)=O VSSGDAWBDKMCMI-UHFFFAOYSA-N 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 1
- ZRKSKKQONQUFMR-UHFFFAOYSA-N 3-amino-2-methyl-3-oxoprop-1-ene-1-sulfonic acid Chemical compound NC(=O)C(C)=CS(O)(=O)=O ZRKSKKQONQUFMR-UHFFFAOYSA-N 0.000 description 1
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000669058 Fiorinia theae Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000018208 Hyperimmunoglobulinemia D with periodic fever Diseases 0.000 description 1
- 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 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 206010072219 Mevalonic aciduria Diseases 0.000 description 1
- UDPYEFRYPGXIAL-UHFFFAOYSA-N NC(=O)C(C)=CCS(O)(=O)=O Chemical compound NC(=O)C(C)=CCS(O)(=O)=O UDPYEFRYPGXIAL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 108700020962 Peroxidase Proteins 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XEWDPEHESOQHLI-UHFFFAOYSA-J [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(=N)C([O-])=O.[O-]C(=O)CC(=N)C([O-])=O Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(=N)C([O-])=O.[O-]C(=O)CC(=N)C([O-])=O XEWDPEHESOQHLI-UHFFFAOYSA-J 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000010987 cubic zirconia Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 238000001303 quality assessment method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000009895 reductive bleaching Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- DTXLBRAVKYTGFE-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)-3-hydroxybutanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)C(O)C(C([O-])=O)NC(C([O-])=O)CC([O-])=O DTXLBRAVKYTGFE-UHFFFAOYSA-J 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0091—Dishwashing tablets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3953—Inorganic bleaching agents
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/20—Water-insoluble oxides
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Detergent Compositions (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种适用于自动餐具洗涤的漂白催化剂,其包含混合金属氧化物。
Description
本发明涉及催化剂,特别是漂白催化剂、其制备方法及其在自动餐具洗涤方法中的用途。
氧漂白剂由于其从基材上除去污渍的能力而众所周知。传统上,基材经受过氧化氢处理。后者可以是无机或有机过氧化物。然而,这些体系通常必须在实现活化所需的60℃以上的温度下活化。遗憾的是,高温是耗能的并且可以使酶失活。
优选的方法是使用与有机活化剂化合物偶联的无机过氧化物。这些体系用于许多商业洗涤剂,并且通常基于四乙酰基乙二胺(TAED)与过硼酸钠或过碳酸钠的组合。
因此,漂白(或氧化)催化剂用于污渍去除领域。这样的催化剂导致使用过氧化合物(包括过氧化氢或过氧化氢加合物)的漂白活性物质的进一步活化。
目前用于自动餐具洗涤的商业配方中的催化剂技术基于均相锰催化剂。已知基于三氮杂环壬烷配体(例如1,4,7-三甲基-1,4,7-三氮杂环壬烷(TACN))的锰催化剂在衣物洗涤剂产品和餐具洗涤产品中的污渍漂白中和在例如木浆或原棉中的纤维素基材的处理中是活性催化剂。其中,尽管其价格高,但MnTACN被认为是漂白活性的工业基准。尽管过去对均相催化剂的进一步实质性努力已经揭示了其它稳定和活性的分子结构,但只有少数已经商业化。尽管非均相催化剂被用于许多不相关的工业氧化方法中,但是迄今为止该技术还没有成功地用于消费者自动餐具洗地(ADW)和去污方面。
贵金属或有毒金属已用作非均相氧化催化剂并用于工业过程中。然而,诸如餐具洗涤的领域需要更便宜和更良性的替代物。对于可用作洗涤剂漂白组合物中的漂白催化剂的金属,金属化合物必须不会通过非漂白途径过度促进过氧化物分解,并且必须是水解和氧化稳定的。此外,由于过多的食物污垢(例如含有反应性官能团如硫离子、硫醇、各种氨基酸等的污垢)以及具有潜在配位部分的洗涤剂成分(例如酶、反应性氧化剂、表面活性剂、腐蚀抑制剂、聚合物等),餐具洗涤机中催化活性位点的抑制是主要关注的问题。
因此,需要开发基于丰富且良性的金属的成本有效的非均相催化剂,其在自动餐具洗涤机中提供显著的漂白性能,并且其可以不复杂且经济有效的方法大规模生产。
本发明解决了这些问题。
在本发明的第一方面,提供了一种用于自动餐具洗涤的非均相漂白催化剂,其包含混合金属氧化物。
优选地,金属氧化物的一种或多种是过渡金属。
有利地,混合金属氧化物是金属氧化物载体上的金属氧化物。因此,催化剂可以包含在过渡金属氧化物载体如氧化锆载体上的过渡金属氧化物,优选如铜、锰、铁和/或锌等第一行过渡金属氧化物。
不受理论束缚,氧化锆(也称为二氧化锆或ZrO2)被认为作为载体是特别有益的,因为它可以使非均相漂白可能需要的短寿命自由基物质稳定化。
过渡金属氧化物优选以相对于金属氧化物载体为1至50mol%、例如1至45mol%、1至35mol%、1至25mol%、1.5至22.5mol%、优选2至20mol%、例如2.5至15mol%的量存在。
在特别优选的选择中,催化剂包括在氧化锆载体上的铜氧化物。这是因为,不受理论的束缚,Cu(OH)2的形成可用作漂白过程中的活性物质。
优选地,铜表面积大于0,例如大于0.01m2/g且小于4m2/g,例如小于3m2/g或2m2/g,优选小于1m2/g。令人惊奇地发现,金属表面积的减少可产生良好的漂白性能。
催化剂优选经过煅烧。据信,合适前体的煅烧既用于产生混合金属氧化物形式,又产生无定形的高表面积材料。煅烧优选在空气或其它含氧气氛下,在至少200℃,例如250℃、300℃、350℃、400℃、450℃或甚至至少500℃的温度下进行。
本发明人还惊奇地发现,用酸处理过(如用硝酸(HNO3)、硫酸(H2SO4)、盐酸(HCl)或其它强酸洗涤)的催化剂的催化性能得到改善。不希望受理论束缚,据信酸处理降低铜的表面浓度并除去将H2O2分解成H2O并因此降低漂白活性的大CuO颗粒。
有利地,催化剂可以具有与均相参考催化剂Mn(TACN)相当的漂白活性。
在本发明的第二方面中,提供了包含如本文所述的非均相催化剂的自动餐具洗涤组合物。
当存在于自动餐具洗涤组合物中时,该组合物可以是任何形式,例如粉末、片剂、凝胶或容纳在水溶性袋中。优选地,产品是单位剂量或单剂形式。最终产品可包含多种组合物。例如,组合物作为整体可以分为两种以上的固体、液体、凝胶或糊剂形式的组合物和至少一种固体、液体、凝胶或糊剂形式的另外的组合物。
自动餐具洗涤组合物优选包含一种或多种漂白剂、漂白活化剂、助洗剂、表面活性剂和/或酶。
漂白剂优选选自氧释放性漂白剂、氯释放性漂白剂及其两种以上的混合物。更优选地,漂白剂是或包含氧释放性漂白剂。
漂白剂可包括活性漂白物质本身或该物质的前体。优选地,漂白剂选自无机过氧化物、有机过酸及其两种以上的混合物。术语“无机过氧化物”和“有机过酸”包括其盐和衍生物。无机过氧化物包括过碳酸盐、过硼酸盐、过硫酸盐、过氧化氢及其衍生物和盐。这些无机过氧化物的钠盐和钾盐是合适的,特别是钠盐。过碳酸钠是特别优选的。
在自动餐具洗涤组合物的情况下,优选使阴离子表面活性剂的量最小化,因此,组合物优选包含不超过2重量%、不超过1重量%的阴离子表面活性剂,或不含阴离子表面活性剂。反而,非离子表面活性剂对于自动餐具洗涤产品而言是特别优选的。
助洗剂有利地选自甲基甘氨酸二乙酸(MGDA)、N,N-二羧基甲基谷氨酸(GLDA)、柠檬酸盐及其两种以上的组合。应当理解,术语MGDA、GLDA和柠檬酸盐包括游离酸及其盐、酯和衍生物。优选地,柠檬酸盐是柠檬酸三钠。
其他无磷助洗剂包括琥珀酸盐类化合物。术语“琥珀酸盐类化合物”和“琥珀酸类化合物”在本文中可互换使用。
特别合适的助洗剂包括:例如,天冬氨酸-N-单乙酸(ASMA)、天冬氨酸-N,N-二乙酸(ASDA)、天冬氨酸-N-单丙酸(ASMP)、亚氨基二琥珀酸(IDA)、N-(2-磺甲基)天冬氨酸(SMAS)、N-(2-磺甲基)谷氨酸(SMGL)、N-(2-磺乙基)谷氨酸(SEGL)、N-甲基亚氨基二乙酸(MIDA)、α-丙氨酸-N,N-二乙酸(α-ALDA)、β-丙氨酸-N,N-二乙酸(β-ALDA)、丝氨酸-N,N-二乙酸(SEDA)、异丝氨酸-N,N-二乙酸(ISDA)、苯丙氨酸-N,N-二乙酸(PHDA)、邻氨基苯甲酸-N,N-二乙酸(ANDA)、磺胺酸-N,N-二乙酸(SLDA)、牛磺酸-N,N-二乙酸(TUDA)和磺甲基-N,N-二乙酸(SMDA)及其碱金属盐或铵盐。
合适的助洗剂包括:例如,天冬氨酸-N-单乙酸(ASMA)、天冬氨酸-N,N-二乙酸(ASDA)、天冬氨酸-N-单丙酸(ASMP)、亚氨基二琥珀酸(IDA)、N-(2-磺甲基)天冬氨酸(SMAS)、N-(2-磺甲基)谷氨酸(SMGL)、N-(2-磺乙基)谷氨酸(SEGL)、N-甲基亚氨基二乙酸(MIDA)、α-丙氨酸-N,N-二乙酸(α-ALDA)、β-丙氨酸-N,N-二乙酸(β-ALDA)、丝氨酸-N,N-二乙酸(SEDA)、异丝氨酸-N,N-二乙酸(ISDA)、苯丙氨酸-N,N-二乙酸(PHDA)、邻氨基苯甲酸-N,N-二乙酸(ANDA)、磺胺酸-N,N-二乙酸(SLDA)、牛磺酸-N,N-二乙酸(TUDA)和磺甲基-N,N-二乙酸(SMDA)及其碱金属盐或铵盐。
其他琥珀酸酯化合物具有下式:
其中R和R1彼此独立地表示H或OH;R2、R3、R4、R5彼此独立地表示阳离子、氢、碱金属离子和铵离子,具有通式R6R7R8R9N+的铵离子,R6、R7、R8、R9彼此独立地表示氢、具有1至12个C原子的烷基或羟基取代的具有2至3个C原子的烷基。
实例包括亚氨基琥珀酸四钠。亚氨基二琥珀酸(IDS)和(羟基)亚氨基二琥珀酸(HIDS)及其碱金属盐或铵盐是特别优选的琥珀酸盐类助洗剂盐。无磷共助洗剂还可以包含或作为另选包含具有羧基的非聚合有机分子。作为含有羧基的有机分子的助洗剂化合物包括柠檬酸、富马酸、酒石酸、马来酸、乳酸及其盐。特别地,可以使用这些有机化合物的碱金属或碱土金属盐,尤其是钠盐。
然而,最优选地,助洗剂是羧酸盐如柠檬酸盐,和/或氨基羧酸盐如甲基甘氨酸二乙酸。
组合物可包括一种或多种聚合物。聚合物旨在改善自动餐具洗涤组合物的清洁性能。例如,可以使用磺化聚合物。优选的实例包括CH2=CR1CR2R3-O-C4H3R4-SO3X与任何合适的其他单体单元的共聚物,其中R1、R2、R3、R4独立地为1至6个碳的烷基或氢,X为氢或碱,所述其他单体单元包括改性的丙烯酸、富马酸、马来酸、衣康酸、乌头酸、中康酸、柠康酸和亚甲基丙二酸或它们的盐,马来酸酐、丙烯酰胺、烯烃、乙烯基甲基醚、苯乙烯和它们的任何混合物。用于掺入磺化聚合物(共聚物)中的其它合适的磺化单体是2-丙烯酰氨基-2-甲基-1-丙磺酸、2-甲基丙烯酰氨基-2-甲基-1-丙磺酸、3-甲基丙烯酰氨基-2-羟基-丙磺酸、烯丙基磺酸、甲代烯丙基磺酸、2-羟基-3-(2-丙烯氧基)丙磺酸、2-甲基-2-丙烯-1-磺酸、苯乙烯磺酸、乙烯基磺酸、3-磺基丙基丙烯酸酯、3-磺基丙基甲基丙烯酸酯、磺基甲基丙烯酰胺、磺基甲基甲基丙烯酰胺及其水溶性盐。
还优选的是包含丙烯酸的聚合物或共聚物,包括丙烯酸与马来酸和/或2-丙烯酰胺基-2-甲基-1-丙磺酸的共聚物。
所述组合物可包含一种或多种酶。优选的是,一种或多种酶选自蛋白酶、脂肪酶、淀粉酶、纤维素酶和过氧化物酶,最优选的是蛋白酶和淀粉酶。最优选的是,在本发明的组合物中包括蛋白酶和/或淀粉酶,因为这些酶在餐具洗涤剂组合物中特别有效。可以使用多于一种的物质。
组合物还可包含一种或多种漂白活化剂。如果需要活化漂白剂来活化漂白剂,则可以包括任何合适的漂白活化剂,例如TAED。漂白活化剂优选以1重量%至15重量%、例如2重量%至12重量%、3重量%至11重量%或甚至4重量%至8重量%的量存在。
在本发明的第三方面,提供了如本文所述的催化剂或包含此类催化剂的自动餐具洗涤组合物在自动餐具洗涤过程中的用途。
催化剂可以存在于在餐具洗涤循环中完全消耗的自动餐具洗涤组合物中,或者保留在机器中而用于两个以上餐具洗涤循环。例如,催化剂可以固定在自动餐具洗涤机中。
优选地,催化剂和/或组合物用于处理可漂白的污渍。
在本发明的第四方面,提供了制备适用于自动餐具洗涤的非均相混合金属氧化物催化剂(优选为本文所述的催化剂)的方法,其包括(a)沉淀两种以上金属盐。
优选地,沉淀步骤形成混合金属草酸盐。该方法可以使用金属盐,优选相应的硝酸盐作为起始材料。有机溶剂如醇、优选乙醇可用作沉淀用溶剂。沉淀可以在空气或其它含氧气氛下进行。所得沉淀物可通过过滤收集和/或在高温(例如大于50℃、60℃、70℃、80℃、90℃或甚至100℃)下干燥。
有利地,对沉淀物进行煅烧以形成混合金属氧化物。煅烧优选在气流如空气或其它含氧气氛下进行。该流速优选大于20mL/min,例如30mL/min或甚至40mL/min。
优选地,混合金属氧化物用酸处理,如硝酸(HNO3)、硫酸(H2SO4)、盐酸(HCl)或其它强酸。该步骤可以包括在酸中搅拌例如1至5小时,或2至3小时。然后,可以将混合金属氧化物在水中洗涤直至返回中性pH。
本发明在以下非限制性实施例中进行描述。
实施例
沉淀物制备
在室温下,在空气中将Cu(NO3)2·3H2O(0.01mol)和ZrO(NO3)2水合物(0.01mol)分别溶解在无水乙醇(100mL)中。溶解后,将两种溶液在400mL烧杯中混合并在室温下在空气中搅拌。随后将草酸二水合物(3.03g,0.024mol,固体)加入到该溶液中,导致金属草酸盐立即沉淀。该沉淀由溶液外观的视觉变化证明,同时形成浅蓝色不透明混合物。将溶液在室温下在空气中再搅拌2小时。然后通过过滤收集草酸盐凝胶。随后将该滤饼在110℃下在静态空气烘箱中干燥16小时。干燥后,使用研钵和研杵将剩余固体粉碎成蓝色细粉。
成功地重复该工序以合成Cu-Zr、Mn-Zr、Fe-Zr和Zn-Zr草酸盐前体。
煅烧
随后在流动空气下煅烧草酸盐前体以产生所需的活性材料。为了制备CuOx/ZrOy催化剂,将Cu-Zr草酸盐加入到CoorsTM高氧化铝燃烧舟中并在CarboliteTM管式炉中煅烧。管式炉以10℃/min的加热速率从室温加热到550℃。一旦达到550℃,将炉温保持2小时。在处理期间,空气以50mL/min的速率通过催化剂。一旦炉冷却至室温,收集粉末状催化剂。Cu-Zr草酸盐前体的分解由颜色变为深绿色和质量损失证明。
酸处理
随后通过用浓HNO3洗涤材料实现表面金属的去除。在室温下,将相应的金属氧化物(0.2g)在HNO3(70重量%,200mL)中搅拌2小时。收集催化剂并通过离心和倾析酸性溶液与酸分离。加入去离子水,振摇使催化剂重新悬浮,然后再次离心并倾析。
该过程再重复3次,直到离心后水的pH为7。在静态空气炉中,在110℃下干燥16小时。收集干燥粉末形式的催化剂。
分析和结果
茶渍漂白评价
在剧烈搅拌下,在50℃,将过碳酸钠(1.5g)、TAED(0.45g)和MGDA(0.2g)加入到自来水(1.8L,5°dH,89ppm CaCO3)中。茶杯根据IKW程序(Recommendations for the qualityassessment of the cleaning performance of dishwasher detergents(B部分,2015更新),德国化妆品、洗漱用品、香水和洗涤剂协会,“Industrieverband Koerperpflege-undWaschmittel”,IKW,工作组自动洗餐具洗涤剂手册第142卷第06/1633-48页)预先沾污和评价。将预先沾污的茶杯半浸入洗涤溶液中并加入催化剂(3mg)。8分钟后,将杯子从烧杯中取出并在新鲜自来水中漂洗三次以除去任何漂白溶液残余物并在洗涤后停止继续在杯子中的漂白,使用1至10等级目测评价漂白性能,其中1为没有可见的漂白活性,10为完全漂白的表面。
测试具有50%至1%铜摩尔比的一系列铜催化剂对酸处理之前的杯子表面上茶渍的漂白性能。
将ZrO2载体材料与50mol%和10mol%铜催化剂一起在酸处理后再测试漂白性能。
结果示于表1中。
表1
催化剂组合物 | 漂白性能评分 |
无催化剂 | 2 |
锰(TACN) | 6 |
<![CDATA[ZrO<sub>2</sub>]]> | 2 |
<![CDATA[50mol%Cu<sub>x</sub>/ZrO<sub>y</sub>]]> | 2 |
<![CDATA[30mol%Cu<sub>x</sub>/ZrO<sub>y</sub>]]> | 2 |
<![CDATA[10mol%Cu<sub>x</sub>/ZrO<sub>y</sub>]]> | 3 |
<![CDATA[5mol%Cu<sub>x</sub>/ZrO<sub>y</sub>]]> | 4 |
<![CDATA[2.5mol%Cu<sub>x</sub>/ZrO<sub>y</sub>]]> | 3 |
<![CDATA[1mol%Cu<sub>x</sub>/ZrO<sub>y</sub>]]> | 2 |
<![CDATA[ZrO<sub>2</sub> AT]]> | 2 |
<![CDATA[50mol%Cu<sub>x</sub>/ZrO<sub>y</sub> AT]]> | 4 |
<![CDATA[10mol%Cu<sub>x</sub>/ZrO<sub>y</sub> AT]]> | 5 |
漂白活性在低铜浓度下降低。预计这是由于催化剂上促进漂白的活性位点的数目减少造成的。
铜表面积分析
使用ChemBET Pulsar Quantachrome进行铜表面积分析。催化剂(约100mg)装载到两侧用石英棉堵塞的玻璃管中。然后进行程序降温以将铜氧化物还原成铜金属。使氢气(150mL/min)流过该催化剂,同时以10℃/min将其加热至140℃。然后开始分析样品,同时以1℃/min将其进一步加热至280℃。当温度达到所需温度时,在冷却前保持10分钟。选择低温和缓慢升温速率以减少铜颗粒在表面上的烧结。
冷却后,将气体切换为氦气(150mL/min)并将样品加热至65℃。开始分析并向气流中引入N2O(113μL)的规则脉冲。当铜将N2O还原成N2时,记录产生的N2量。当N2峰保持恒定尺寸时,将N2O转换为N2,然后使用4个规则的N2脉冲(113μL)进行校准。实验期间产生的N2的总体积用于计算铜表面积。
表2
催化剂组合物 | 铜表面积(m2/g) |
<![CDATA[10mol%Cu<sub>x</sub>/ZrO<sub>y</sub>]]> | 4.6 |
<![CDATA[10mol%Cu<sub>x</sub>/ZrO<sub>y</sub> AT]]> | 0.2 |
<![CDATA[50mol%Cu<sub>x</sub>/ZrO<sub>y</sub>]]> | 6.4 |
<![CDATA[50mol%Cu<sub>x</sub>/ZrO<sub>y</sub> AT]]> | 0.4 |
X射线粉末衍射(XRPD)分析
使用X射线粉末衍射来确定酸处理前和酸处理后催化剂中存在的体相。衍射图如图1所示。
用菱形表示的峰与立方氧化锆的ICDD数据库00-027-0997匹配,用圆圈表示的峰与单斜Cu(II)O的ICDD数据库01-089-5895匹配,所述单斜Cu(II)O仅存在于50mol%CuOx/ZrO2酸处理前的催化剂中。这表明在该材料中存在大CuO颗粒,其可导致H2O2分解成H2O和O2。
显然,这些物质在酸处理后不再存在,用三角形表示的峰现在存在于50mol%CuOx酸处理后的样品中。这些峰与正交晶CuZrO3的ICDD数据库00-043-0953匹配,表明酸处理还导致在催化剂中形成更紧密混合的Cu-Zr相。
X射线光电子能谱(XPS)分析
使用X射线光电子能谱来确定以下催化剂的表面物质:(a)50mol%CuOx/ZrO2和(b)10mol%CuOx/ZrO2。分析如图2所示。
酸处理后,随着酸处理成功地从催化剂表面除去铜,铜峰的强度降低。在结合能(BE)=934eV处观察到的主峰表示CuO,而对于酸处理前的50mol%CuOx/ZrO2,在BE 944和941eV处存在2个峰,这表示存在Cu(II)O。对于10mol%CuOx/ZrO2,相同的峰现在更加扩散,这表明存在Cu(II)O(OH)2。
总之,铜催化剂的表征已经确定了表面上的CuO和Cu(OH)2物质。酸处理似乎除去较大的CuO颗粒并增加OH物质的存在,得到更具活性的漂白催化剂。这表明Cu(OH)2可以是用于漂白的活性物质和/或CuO的去除可以降低导致H2O2分解的竞争反应。
结果总结
结果表明,混合金属氧化物是用于从固体表面除去茶垢的活性漂白催化剂,并且用浓酸处理这些催化剂的处理进一步增加高和低铜浓度催化剂的漂白活性。
因此,已经开发了一种新的非均相漂白催化剂,其使用丰富的过渡金属,并揭示了其与目前在ADW配方中使用的MnTACN和均相催化剂接近的技术性能。
本发明由权利要求限定。
Claims (14)
1.一种用于自动餐具洗涤的非均相漂白催化剂,其包含混合金属氧化物。
2.根据权利要求1所述的催化剂,其中,所述金属氧化物的一种或多种是过渡金属。
3.根据权利要求1或2所述的催化剂,其包含在氧化锆载体上的过渡金属氧化物,优选铜、锰、铁和/或锌。
4.根据权利要求3所述的催化剂,其中,所述过渡金属氧化物以1至50mol%、优选2至20mol%的量存在。
5.根据前述权利要求中任一项所述的催化剂,其包含在氧化锆载体上的铜氧化物。
6.根据权利要求5所述的催化剂,其中,铜表面积小于1m2/g。
7.根据前述权利要求中任一项所述的催化剂,其经过煅烧。
8.根据前述权利要求中任一项所述的催化剂,其经过酸处理。
9.一种自动餐具洗涤组合物,其包含权利要求1至8中任一项所述的催化剂。
10.一种制备适用于自动餐具洗涤的非均相混合金属氧化物催化剂的方法,其包括:(a)沉淀两种以上金属盐。
11.根据权利要求10所述的方法,其中,所述沉淀形成混合金属草酸盐。
12.根据权利要求10或11所述的方法,其中,将所述沉淀物煅烧以形成混合金属氧化物。
13.根据权利要求10至12中任一项所述的方法,其中,用酸处理所述混合金属氧化物。
14.权利要求1至8中任一项所述的催化剂或权利要求9所述的组合物在自动餐具洗涤过程中的用途。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2008512.2 | 2020-06-05 | ||
GBGB2008512.2A GB202008512D0 (en) | 2020-06-05 | 2020-06-05 | Catalyst |
PCT/EP2021/063471 WO2021244861A1 (en) | 2020-06-05 | 2021-05-20 | Bleach catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115916938A true CN115916938A (zh) | 2023-04-04 |
CN115916938B CN115916938B (zh) | 2024-05-28 |
Family
ID=71615999
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202180040124.0A Active CN115916938B (zh) | 2020-06-05 | 2021-05-20 | 漂白催化剂 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20230119694A1 (zh) |
EP (1) | EP4162019B1 (zh) |
CN (1) | CN115916938B (zh) |
GB (1) | GB202008512D0 (zh) |
WO (1) | WO2021244861A1 (zh) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2009143533A (ru) * | 2007-04-25 | 2011-05-27 | Рекитт Бенкизер Н.В. (Nl) | Композиция |
US20140053877A1 (en) * | 2012-08-24 | 2014-02-27 | The Procter & Gamble Company | Dishwashing method |
US20140303059A1 (en) * | 2010-12-21 | 2014-10-09 | Reckitt Benckiser N.V. | Bleach Catalyst Particle |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2572364A (en) * | 1948-03-31 | 1951-10-23 | Ibm | Automatic grinding machine |
WO2008132456A1 (en) * | 2007-04-25 | 2008-11-06 | Reckitt Benckiser N.V. | Composition |
EP2520166A1 (en) * | 2011-05-04 | 2012-11-07 | Taminco | New bisaminopropylamides and uses thereof in agricultural and detergent compositions |
-
2020
- 2020-06-05 GB GBGB2008512.2A patent/GB202008512D0/en not_active Ceased
-
2021
- 2021-05-20 CN CN202180040124.0A patent/CN115916938B/zh active Active
- 2021-05-20 WO PCT/EP2021/063471 patent/WO2021244861A1/en active Application Filing
- 2021-05-20 US US18/000,142 patent/US20230119694A1/en active Pending
- 2021-05-20 EP EP21727838.1A patent/EP4162019B1/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2009143533A (ru) * | 2007-04-25 | 2011-05-27 | Рекитт Бенкизер Н.В. (Nl) | Композиция |
US20140303059A1 (en) * | 2010-12-21 | 2014-10-09 | Reckitt Benckiser N.V. | Bleach Catalyst Particle |
US20140053877A1 (en) * | 2012-08-24 | 2014-02-27 | The Procter & Gamble Company | Dishwashing method |
Also Published As
Publication number | Publication date |
---|---|
WO2021244861A1 (en) | 2021-12-09 |
CN115916938B (zh) | 2024-05-28 |
EP4162019A1 (en) | 2023-04-12 |
EP4162019B1 (en) | 2023-10-25 |
GB202008512D0 (en) | 2020-07-22 |
US20230119694A1 (en) | 2023-04-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
RU2668822C2 (ru) | Твердое посудомоечное средство с улучшенной эффективностью протеазы | |
EP0509787B1 (en) | Concentrated detergent powder compositions | |
AU2020202620B2 (en) | Automatic washing machine and method | |
AU662577B2 (en) | Bleach activation | |
EP1948770B1 (en) | Composition | |
JP4049881B2 (ja) | 漂白活性金属錯体 | |
US8927478B2 (en) | Use of manganese oxalates as bleach catalysts | |
JPH05263098A (ja) | 漂白活性体 | |
WO2016041681A1 (en) | Detergent composition | |
US20170114302A1 (en) | Dishwashing liquid having bleaching catalyst and protease | |
JP2005105275A (ja) | ラクタム配位子を有する遷移金属錯体を漂白触媒として使用する方法 | |
JP2002302698A (ja) | オキシム配位子を有する遷移金属錯体を漂白触媒として使用する方法 | |
US20110146723A1 (en) | Bleach Catalyst Mixtures Consisting Of Manganese Salts And Oxalic Acid Or The Salts Thereof | |
CN109312267B (zh) | 包含漂白催化剂颗粒的可倾倒洗涤剂悬浮液 | |
CN115916938B (zh) | 漂白催化剂 | |
WO2001045842A1 (en) | Bleach catalysts | |
JPH11140037A (ja) | 漂白活性化剤としての金属錯体 | |
EP3810743B1 (en) | Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid | |
WO2019233696A1 (en) | Composition | |
CA2310899A1 (en) | Production of a combination of active substances active as bleach catalysts |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |