EP0848750B1 - Process for producing granulated precursors of low alkalinity detergents - Google Patents
Process for producing granulated precursors of low alkalinity detergents Download PDFInfo
- Publication number
- EP0848750B1 EP0848750B1 EP96930091A EP96930091A EP0848750B1 EP 0848750 B1 EP0848750 B1 EP 0848750B1 EP 96930091 A EP96930091 A EP 96930091A EP 96930091 A EP96930091 A EP 96930091A EP 0848750 B1 EP0848750 B1 EP 0848750B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- salts
- carbonate
- alkali metal
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 37
- 239000003599 detergent Substances 0.000 title claims description 21
- 239000002243 precursor Substances 0.000 title description 5
- 239000002253 acid Substances 0.000 claims description 46
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- 150000007513 acids Chemical class 0.000 claims description 20
- -1 alkali metal salts Chemical class 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 16
- 238000004851 dishwashing Methods 0.000 claims description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 239000000975 dye Substances 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 239000011872 intimate mixture Substances 0.000 claims 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims 1
- 230000001012 protector Effects 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 239000007844 bleaching agent Substances 0.000 description 13
- 239000008187 granular material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000012190 activator Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 229920001503 Glucan Polymers 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 235000019351 sodium silicates Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RWGBLAUNEKSPME-ARJAWSKDSA-N (z)-4-(2-methylprop-2-enoyloxy)-4-oxobut-2-enoic acid Chemical compound CC(=C)C(=O)OC(=O)\C=C/C(O)=O RWGBLAUNEKSPME-ARJAWSKDSA-N 0.000 description 1
- UBWFWCYQLDDVFQ-ARJAWSKDSA-N (z)-4-oxo-4-prop-2-enoyloxybut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OC(=O)C=C UBWFWCYQLDDVFQ-ARJAWSKDSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- SWGJRPGVODDXKM-LNKPDPKZSA-N C(C)(=O)OC=C.C(\C=C/C(=O)O)(=O)OC(=O)C=C Chemical compound C(C)(=O)OC=C.C(\C=C/C(=O)O)(=O)OC(=O)C=C SWGJRPGVODDXKM-LNKPDPKZSA-N 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 208000009043 Chemical Burns Diseases 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
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 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
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- ZDPZTMRJGAOYNT-UHFFFAOYSA-E O.O.C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] Chemical compound O.O.C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] ZDPZTMRJGAOYNT-UHFFFAOYSA-E 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 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 1
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- MFLMBWASGCAJGO-UHFFFAOYSA-L disodium;hydrogen peroxide;carbonate Chemical compound [Na+].[Na+].OO.[O-]C([O-])=O MFLMBWASGCAJGO-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 238000002156 mixing Methods 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 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
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000001993 wax 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
-
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the invention relates to a method for producing granular precursors lower alkaline cleaning agent, which is improved by Grain resistance and lower fine grain fractions and the in usual way to lower alkaline detergents for automatic dishwashing can be assembled.
- German patent application DE 42 32 170 Al the applicant becomes a weakly alkaline agent for the machine Dish washing described in which sodium citrate, Sodium bicarbonate, a bleach, a bleach activator and enzymes are contained in 1% by weight aqueous solution has a pH of about 8 to 10.
- aqueous solution has a pH of about 8 to 10.
- the means mentioned there are granular. However, detailed information on the manufacture is not included.
- the European application EP 414 197 (Beckiser) describes a machine dishwashing detergent claims which at least 25 wt .-% of a combination contains sodium carbonate and sodium hydrogen carbonate, is free of metasilicates, free of chlorine bleach and in 1 percent by weight aqueous solution has a mildly alkaline pH of less than 10.5 having.
- a further component can be a Acrylic acid-maleic acid copolymer may be present as the sodium salt.
- the preparation of the agents can only be seen as dry powders or granules can be formulated in a conventional manner.
- EP 530 635 (Benckiser) it is known a liquid or powdered, phosphate-free automatic dishwasher detergent, containing a builder system to manufacture, in which in 1 weight percent aqueous solution a pH of 5 to 9 is reached and that contains a builder system from the salt of a hydroxycarboxylic acid, or the mixture of a hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid or the mixture of a hydroxycarboxylic acid and the salt a hydroxy carboxylic acid and a polymer.
- This patent application too does not contain any specific information on the manufacture of the products.
- German patent application DE-A-42 28 786 describes a dishwashing detergent with a selected builder system that should be solid, low alkaline, phosphate and chlorine free and next to one organic water-soluble builder, alkali carbonate, bleach Contains oxygen base, surfactants and other common ingredients, wherein the builder component oxidation products of polyglucosans and / or their contains soluble salts.
- a mixed granulation process is used for production discloses, in which the builder component in admixture with at least another component mixed and granulated in the presence of a liquid becomes.
- Granulation processes are generally used in the manufacture of these products applied. It has been shown here that in technical The frame is difficult, stable, uniform granules with a low proportion of fines to obtain. This applies in particular to products based on Alkali metal salts of carbonic acid and of alkali metal salts of polycarboxylic acids. The reason for this is that the alkali metal salts mentioned, especially the sodium salts such as soda, sodium bicarbonate and sodium citrate, to name the most important raw materials in this class, comparatively are coarsely crystalline substances that are involved in a granulation process heavily baked to a firm grain. Especially citrate is difficult or not with the other ingredients soda and bicarbonate granulable.
- the granules break down, which causes individual components to separate as fine grains, collect on the bottom of the pack and thus along with problems of recipe constancy through segregation processes, even one that is not desired by the consumer Deliver the appearance of the product.
- the invention seeks to remedy this; it goes from two Realizations. Firstly, it was observed that in situ production the alkali metal salts of polycarboxylic acids from alkali carbonates Granules low in fine substances stable under mixing and granulating conditions can be obtained. Furthermore, the knowledge was gained that alkali carbonates, especially sodium carbonate in the presence of Large-scale water in a favorable manner in hydrogen carbonates and salts can be transferred from polycarboxylic acids when the alkali carbonates a proportion of the alkali metal salts of the polycarboxylic acids right at the start of the reaction admixed.
- the invention thus relates to a process for producing granular Pre-products of low alkaline detergents for mechanical Dishwashing, consisting of alkali metal salts of carbonic acid and organic Polycarboxylic acids, characterized in that a subset the salts of the polycarboxylic acids in the usual way, then in Presence of 2 to 12 wt .-% water, alkali carbonate in the presence of the alkali metal salts of the polycarboxylic acids with the free polycarboxylic acid their salts and essentially alkali hydrogen carbonate at temperatures implemented below 60 ° C.
- the invention furthermore relates to a granular precursor of a automatic dishwashing detergent, containing 20 to 70% by weight of trisodium citrate dihydrate, 20 to 60% by weight sodium bicarbonate, 0 to 10% by weight Sodium carbonate and 0 to 4% by weight nonionic surfactants in intimate admixture, produced by the method according to the invention.
- alkali metal salts of Carbonic acid and polycarboxylic acids are preferred carbon dioxide such as sodium carbonate (soda, anhydrous or in hydrated form) and sodium bicarbonate use. Even with the Salts of the polycarboxylic acids are preferred the sodium salts.
- a special one preferred polycarboxylic acid is citric acid, a particularly preferred one Salt is trisodium citrate, especially trisodium citrate dihydrate.
- polycarboxylic acids can also be used Example malic acid, tartaric acid, nitrogen-containing polycarboxylic acids, such as Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or triethylenetetraamine hexaacetic acid, methylglycinediacetic acid and the same.
- DE-A-42 28 can also be used 786 called oxidation products of polyglucosans.
- Copolymers of polymerizable acids if desired with esters and sulfonic acids copolymerized to use. So especially copolymers Based on acrylic acid-maleic anhydride, acrylic acid-maleic anhydride-vinyl acetate (saponified to vinyl alcohol), methacrylic acid-maleic anhydride and the same.
- the inventive method is carried out so that in a first Stage prepared the alkali metal salt of a polycarboxylic acid in a conventional manner becomes. This can be done by reacting the polycarboxylic acid, for example done with alkali lye, alkali bicarbonate or alkali carbonate. In A second stage is then in the presence of this amount of polycarboxylic acid salt the alkali carbonate, for example sodium carbonate, with the polycarboxylic acid, for example citric acid, to alkali hydrogen carbonate and implemented the salt of the polycarboxylic acid.
- This implementation takes place in the present of small amounts of water, namely 2 to 12% by weight, preferably 3 to 8 wt .-% water instead.
- the salt of the polycarboxylic acid be placed in a mixer, granulator or the like and then in the presence of the amount of water, the other ingredients be added continuously or in portions.
- the gentle driving style preferred, this is especially true if the reaction is of simplicity half not in a separate reactor, but rather as a solid reaction in a disperse phase with a high solids content in a mixer is carried out with simultaneous granulation.
- the job of the mixer is to mix the reaction intimately Allow residues to run off completely and build up a granular grain possibly by adding other granulation aids such as Surfactants, polycarboxylate solutions. Mixers were therefore used for Granulations are suitable and in which residence times of 1 to 10 have min set.
- Suitable mixers are e.g. B. Eirich (R) mixers of the R or RV series, manufactured by machine factory Gustav Eirich, Hardheim, Germany, the Fukae (R) FS-G mixers, manufactured by Fukal Powtech Kogyo Co., Japan the Lödige (R) FM, KM and CB mixer, manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany or the Drais (R) series T or KT, manufactured by Drais Maschinene GmbH, Mannheim, Germany.
- R B. Eirich (R) mixers of the R or RV series, manufactured by machine factory Gustav Eirich, Hardheim, Germany
- the Fukae (R) FS-G mixers manufactured by Fukal Powtech Kogyo Co.
- Japan the Lödige (R) FM, KM and CB mixer manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany or the Drais (R) series T or KT, manufactured by Drais Maschinene GmbH, Mannheim, Germany.
- Alkaline carbonate soda used and sodium tricitrate-2-hydrate as the polycarboxylic acid salt as Alkaline carbonate soda used and sodium tricitrate-2-hydrate as the polycarboxylic acid salt.
- the acid is then worked with citric acid and it sodium bicarbonate is mixed intimately with sodium tricitrate dihydrate and, if desired, small amounts of soda.
- the weight amount of polycarboxylic acid sodium salts used in the reaction quasi presented as a buffer can be freely determined by the expert, based on the amount of soda, it is 10 to 500% by weight, preferably 50 up to 150 wt .-%, based on alkali carbonate.
- the process according to the invention is controlled so that the residual content of Alkali carbonate less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight.
- Low alkali carbonate levels with a simultaneously high amount of hydrogen carbonate can be achieved by 50 to 150% by weight, based on alkali carbonate, of polycarboxylic acid salts, specifies and works in mild temperature conditions. Higher Content of alkali carbonate, with less hydrogen carbonate, reached one, either by working at higher temperatures or with smaller amounts of the salts of the polycarboxylic acids starts.
- the person skilled in the art within the scope of the invention Process in a post-drying step from alkali hydrogen carbonate To produce alkali carbonate. This happens especially when the Temperature at or above the decomposition point of the sodium hydrogen carbonate is increased.
- the amount of alkali carbonate Loads of the amount of alkali hydrogen carbonate can be increased, for example at temperatures from 50 to 150 ° C, especially 100 ° C to 150 ° C.
- Surfactants can also be used as further constituents in the process according to the invention.
- the total content of surfactants in the compositions is generally between 0.5% by weight and 8% by weight and can preferably be 0.8 to 5% by weight.
- Usual surfactants for cleaning agents belong to the groups of anionic, nonionic and / or zwitterionic surfactants, the use of anionic and / or nonionic surfactants being preferred.
- Particularly suitable anionic surfactants are sulfonates and sulfates and soaps made from preferably natural fatty acids or fatty acid mixtures.
- surfactants of the sulfonate type used are C 9-13- alkylbenzosulfonates, olefin sulfonates, esters and alpha-sulfofatty acids or alpha-sulfofatty acid disalts.
- Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, ie from C 12-18 fatty alcohols or from C 10-20 oxo alcohols, and those of secondary alcohols of this chain length.
- the sulfuric acid monoesters of the alcohols reacted with 1 to 6 mol of ethylene oxide (EO) are also suitable.
- Addition products of preferably 2 to 20 moles of EO to 1 mole of an aliphatic compound with essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and alkanesulfonamides are of particular interest as nonionic surfactants.
- nonionic surfactants polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule, which are not or not completely water-soluble, are also important, especially when they are used together with water-soluble nonionic or anionic surfactants.
- nonionic surfactants made from alkyl polyglycosides of the general formula RO- (G) x can be used, in which R denotes a primary, straight-chain or branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, G for a glycose unit is with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10.
- the dishwashing detergents contain the invention not more than 10 wt .-% water-soluble organic complexing agents or co-builders from the group of synthetic polymeric polycarboxylates, among which the salts of polymerization products unsaturated Carboxylic acids are understood and include, for example, polyacrylates, Polymethacrylates, polymaleinates or copolymers of acrylic acid with maleic acid or maleic anhydride. Such substances are completely absent in the agents according to the invention.
- the solid dishwashing detergents produced by the process according to the invention can also contain up to 10% by weight of further alkalizing agents.
- alkali silicates include in particular the alkali silicates.
- Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio Na 2 O: SiO 2 of 1: 1.5 to 1: 2.5.
- Such amorphous alkali silicates are commercially available, for example, under the trade name Portil (R).
- Portil (R) Compounds made from alkali silicates and soda, as are commercially available, can also be used.
- the process products of the process according to the invention are in particular as granular intermediate products for the production of cleaning agents for. the machine dishwashing. As a rule, they do not contain any oxidizing agents and also not in machine dishwashing detergents, some sensitive small quantities. To get out of the products machine dishwashing detergent, you can use these remaining Ingredients are mixed or granulated into the end products. These remaining ingredients primarily include bleach and Bleach activators.
- bleaching agents which can be used are, for example, peroxycarbonate (Na 2 CO 3 .1.5 H 2 O 2 ) or persic acid salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid.
- Suitable bleach activators for these oxidizing agents are, in particular, the N-acyl or O-acyl compounds which form with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines such as N, N, N ', N'-tetraacetylethylene diamine.
- the salary of the then ready-made dishwasher detergent on oxidizing agent Oxygen base is preferably about 5 wt% to 15 wt%, especially in combination with 1% by weight to 10% by weight, in particular 2% by weight up to 5% by weight of a bleach activator.
- the precursors according to the invention can also be used and bleach activators still others, usually only in each case small amounts of active ingredients are given. These substances will preferably in amounts of 5 to 10 wt .-%, based on the final manufactured Detergent.
- These small components include for example foam inhibitors and enzymes of the protease type, Amylases, lipases and / or cellulases and not bound as water of crystallization or in a similar solid form associated with the components Water.
- the enzymes can be adsorbed onto carriers in the usual way and / or be embedded in coating substances and are preferably in Quantities of not more than 5% by weight in total, in particular 2 to 4% by weight used.
- Suitable non-surfactant-like and preferably used Foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica. It is also possible foam-inhibiting use of long-chain soaps. Can also be suitable Mixtures of different foam inhibitors, for example those made from Silicones and paraffins or waxes. These foam inhibitors are preferred to a granular, water-soluble or dispersible carrier substance bound.
- inorganic transition metal salts e.g. B. manganese salts such as manganese sulfate, potassium hexafluorotianate and the like, inorganic transition metal complexes, nitrogen-containing heterocycles such as benzotriazole or isocyanuric acid, natural amino acids such as cystine, histidine, methionine, reversible organic redox systems such as quinone / hydroquinone and / or reversible inorganic redox systems such as Fe 2+ / Fe 3+ .
- inorganic transition metal salts e.g. B.
- manganese salts such as manganese sulfate, potassium hexafluorotianate and the like
- inorganic transition metal complexes nitrogen-containing heterocycles such as benzotriazole or isocyanuric acid
- natural amino acids such as cystine, histidine, methionine
- reversible organic redox systems such as quinone / hydroquinon
- the preliminary products produced by the process according to the invention can further be processed into tablets.
- the preliminary products with the other constituents mentioned are mixed with one another in a mixer and as a mixture using conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range of 200. 10 5 Pa to 1 500. 10 5 Pa pressed.
- a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm up to 40 mm.
- the granular detergent precursors produced by the process according to the invention are stable granules, they show a low proportion of fines and can be used in particular with the other components mentioned build up in a favorable way. To homogeneous, non-segregating Granulate detergents further.
- a particular advantage of the process according to the invention is that only very small amounts of carbon dioxide are produced in the neutralization and granulation step. It is shown, for example, by the surprisingly high bulk densities (bulk weights over 900 g / l can be produced), which in turn shows that the process products are not inflated by CO 2 .
- Example No. 1 2nd 3rd kg kg kg C 8 / C 10 alkyl polyglycoside, DP approx. 1.4 35% aqueous solution 0.17 0.17 0.17 C 12 C 14 fatty alcohol, 4 E0 0.08 0.08 0.08 C 12 C 14 fatty alcohol, 10 E0 butyl ether 0.03 0.03 0.03 Trisodium citrate 2 H20 (TNC) 2.48 2.48 2.48 Soda calc.
- Example No. 3 differs from Example 1 only in that bicarbonate was initially introduced. According to the two possible parallel reactions, a favored formation of CO 2 is to be expected: 1.5 Na 2 CO 3 + ZS-H 3 -ZS-Na 3 +1.5 NaHCO 3 3 NaHCO 3 + ZS-H 3 -ZS-Na 3 + 3H 2 O + 3CO 2
- the granules thus obtained were dried in a fluidized bed dryer.
- the percentages are based on the batch quantity and surprisingly despite those present in the neutralization step in Example 3 high amounts of bicarbonate low.
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Description
Die Erfindung betrifft ein Verfahren zur Herstellung granularer Vorprodukte niederalkalischer Reinigungsmittel, die sich durch eine verbesserte Kornbeständigkeit und geringerer Feinkornanteile auszeichnen und die in üblicher Weise zu niederalkalischen Reinigern für das maschinelle Geschirrspülen konfektioniert werden können. The invention relates to a method for producing granular precursors lower alkaline cleaning agent, which is improved by Grain resistance and lower fine grain fractions and the in usual way to lower alkaline detergents for automatic dishwashing can be assembled.
Aus der japanischen Anmeldung JP-A-1-146998 (Matsushita Electric Industrial Co.) ist ein Reinigungsmittel für den Einsatz in Geschirrspülgeräten bekannt, das 1 bis 30 Gew.-% einer Peroxyverbindung sowie 10 bis 30 Gew.-% Oxosäuresalze und/oder Aminopolycarbonsäuresalze enthält und phosphatfrei ist. Als Vorteil dieser Zusammensetzung wird ausgelobt, daß niedriger pH-Wert mit Abwesenheit von Chlorverbindungen kombiniert sind. Über Herstellung und Kornaufbau dieser Mittel ist in der japanischen Anmeldung nichts beschrieben. In der deutschen Patentanmeldung DE 42 32 170 Al der Anmelderin wird ein schwach alkalisches Mittel für das maschinelle Geschirreinigen beschrieben, bei dem als wesentliche Komponente Natriumcitrat, Natriumhydrogencarbonat, ein Bleichmittel, ein Bleichmittelaktivator und Enzyme enthalten sind und das in 1-gewichtsprozentiger wäßriger Lösung einen pH-Wert von etwa 8 bis 10 aufweist. Die dort genannten Mittel sind granular. Detaillierte Angaben zur Herstellung sind jedoch nicht enthalten. From Japanese application JP-A-1-146998 (Matsushita Electric Industrial Co.) is a cleaning agent for use in dishwashers known, the 1 to 30 wt .-% of a peroxy compound and 10 to 30 % By weight contains oxo acid salts and / or aminopolycarboxylic acid salts and is phosphate-free is. The advantage of this composition is that low pH combined with the absence of chlorine compounds. About the production and grain structure of these agents is in the Japanese application nothing described. In German patent application DE 42 32 170 Al the applicant becomes a weakly alkaline agent for the machine Dish washing described in which sodium citrate, Sodium bicarbonate, a bleach, a bleach activator and enzymes are contained in 1% by weight aqueous solution has a pH of about 8 to 10. The means mentioned there are granular. However, detailed information on the manufacture is not included.
In der europäischen Anmeldung EP 414 197 (Beckiser) wird ein Maschinengeschirrspülmittel beansprucht, welches mindestens 25 Gew.-% einer Kombination aus Natriumcarbonat und Natriumhydrogencarbonat enthält, frei ist von Metasilikaten, frei ist von Chlorbleichmitteln und in 1-gewichtsprozentiger wäßriger Lösung einen mildalkalischen pH-Wert von weniger 10,5 aufweist. Als weitere Komponente kann hier ein Acrylsäuremaleinsäurecopolymer als Natriumsalz vorhanden sein. Über die Herstellung der Mittel ist nur zu entnehmen, daß sie als trockene Pulver oder Granulate in herkömmlicher Weise formuliert werden. The European application EP 414 197 (Beckiser) describes a machine dishwashing detergent claims which at least 25 wt .-% of a combination contains sodium carbonate and sodium hydrogen carbonate, is free of metasilicates, free of chlorine bleach and in 1 percent by weight aqueous solution has a mildly alkaline pH of less than 10.5 having. A further component can be a Acrylic acid-maleic acid copolymer may be present as the sodium salt. About the The preparation of the agents can only be seen as dry powders or granules can be formulated in a conventional manner.
Aus der europäischen Patentanmeldung EP 530 635 (Benckiser) ist bekannt, ein flüssiges oder pulverförmiges, phosphatfreies maschinelles Geschirrspülmittel, enthaltend ein Buildersystem, herzustellen, bei dem in 1-gewichtsprozentiger wäßriger Lösung ein pH-Wert von 5 bis 9 erreicht wird und das ein Buildersystem enthält aus dem Salz einer Hydroxycarbonsäure, oder dem Gemisch aus einer Hydroxycarbonsäure und dem Salz einer Hydroxycarbonsäure oder dem Gemisch aus einer Hydroxycarbonsäure und dem Salz einer Hydroxycarbonsäure und einem Polymer. Auch diese Patentanmeldung enthält keine dezidierten Angaben zur Herstellung der Produkte. From European patent application EP 530 635 (Benckiser) it is known a liquid or powdered, phosphate-free automatic dishwasher detergent, containing a builder system to manufacture, in which in 1 weight percent aqueous solution a pH of 5 to 9 is reached and that contains a builder system from the salt of a hydroxycarboxylic acid, or the mixture of a hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid or the mixture of a hydroxycarboxylic acid and the salt a hydroxy carboxylic acid and a polymer. This patent application too does not contain any specific information on the manufacture of the products.
In der deutschen Patentanmeldung DE-A-42 28 786 der Anmelderin schließlich ist ein Geschirrspülmittel mit ausgewähltem Buildersystem beschrieben, das fest, niederalkalisch, phosphat- und chlorfrei sein soll und neben einem organischen wasserlöslichen Builder, Alkalicarbonat, Bleichmittel auf Sauerstoffbasis, Tenside und andere übliche Bestandteile enthält, wobei die Builderkomponente Oxidationsprodukte von Polyglucosanen und/oder deren lösliche Salze enthält. Zur Herstellung wird ein Mischgranulationsverfahren offenbart, bei dem die Builderkomponente in Abmischung mit wenigstens einer weiteren Komponente in Gegenwart einer Flüssigkeit gemischt und granuliert wird. Finally, in the applicant's German patent application DE-A-42 28 786 describes a dishwashing detergent with a selected builder system that should be solid, low alkaline, phosphate and chlorine free and next to one organic water-soluble builder, alkali carbonate, bleach Contains oxygen base, surfactants and other common ingredients, wherein the builder component oxidation products of polyglucosans and / or their contains soluble salts. A mixed granulation process is used for production discloses, in which the builder component in admixture with at least another component mixed and granulated in the presence of a liquid becomes.
Niederalkalische Reiniger für das maschinelle Geschirrspülen der vorgenannten Art haben in den letzten Jahren kontinuierlich am Markt Bedeutung gewonnen. Grund dafür ist, daß die Produkte bei hohem Leistungsniveau ohne Verätzungsgefahren gehandhabt werden können. Low-alkaline machine dishwashing detergents for the aforesaid Art have been of importance on the market in recent years won. The reason for this is that the products with a high level of performance without Chemical burns can be handled.
Bei der Herstellung dieser Produkte werden im allgemeinen Granulationsverfahren angewendet. Hierbei hat es sich gezeigt, daß es im technischen Rahmen schwierig ist, stabile, gleichförmige Granulate mit geringem Feinstoffanteil zu erhalten. Dies gilt insbesondere für Produkte auf Basis der Alkalimetallsalze der Kohlensäure und von Alkalimetallsalzen von Polycarbonsäuren. Grund dafür ist, daß die genannten Alkalimetallsalze, insbesondere die Natriumsalze, wie Soda, Natriumbicarbonat und Natriumcitrat, um die wichtigsten Rohstoffe dieser Klasse zu nennen, vergleichsweise grobkristalline Substanzen sind, die sich bei einem Granulationsprozeß schwer zu einem festen Korn verbacken lassen. Insbesondere Citrat ist nur schwer oder nicht mit den übrigen Bestandteilen Soda und Bicarbonat granulierbar. So daß bei dem Granulationsprozeß dieser Bestandteile im eigentlichen Sinne überhaupt keine homogenen Granulate aus Citrat, Soda und Bicarbonat entstehen, sondern mehr oder weniger in homogene Mischungen, deren Homogenität vor allem von der Kornverteilung der einsetzten Rohstoffe abhängt. Dies ist jedoch äußerst ungünstig für die Produkthomogenität. Aus wirtschaftlichen Gesichtspunkten, insbesondere aus Kostengründen müssen jedoch Rohstoffe unterschiedlichster Kornverteilung verarbeitbar sein. Granulation processes are generally used in the manufacture of these products applied. It has been shown here that in technical The frame is difficult, stable, uniform granules with a low proportion of fines to obtain. This applies in particular to products based on Alkali metal salts of carbonic acid and of alkali metal salts of polycarboxylic acids. The reason for this is that the alkali metal salts mentioned, especially the sodium salts such as soda, sodium bicarbonate and sodium citrate, to name the most important raw materials in this class, comparatively are coarsely crystalline substances that are involved in a granulation process heavily baked to a firm grain. Especially citrate is difficult or not with the other ingredients soda and bicarbonate granulable. So that in the granulation process of these components in the strictest sense no homogeneous granules from citrate, soda and bicarbonate, but more or less in homogeneous mixtures, whose homogeneity mainly depends on the grain distribution of the used Raw materials depends. However, this is extremely unfavorable for product homogeneity. From an economic point of view, especially for cost reasons However, raw materials with different grain sizes must be processable be.
Insbesondere bei langem Transport und Rütteln zerfallen daher die Granulatkörner, was dazu führt, daß einzelne Bestandteile als Feinkorn, entmischt, sich am Packungsboden sammeln und somit neben Problemen der Rezepturkonstanz durch Entmischungsvorgänge, auch ein vom Verbraucher nicht gewünschtes Erscheinungsbild des Produktes liefern. Especially during long transport and shaking, the granules break down, which causes individual components to separate as fine grains, collect on the bottom of the pack and thus along with problems of recipe constancy through segregation processes, even one that is not desired by the consumer Deliver the appearance of the product.
Die Erfindung will an diesem Punkt Abhilfe schaffen; sie geht von zwei Erkenntnissen aus. Zum einen wurde beobachtet, daß bei der in situ Herstellung der Alkalimetallsalze von Polycarbonsäuren aus Alkalicarbonaten unter mischenden und granulierenden Bedingungen stabile feinstoffarme Granulate erhalten werden können. Weiterhin wurde die Erkenntnis gewonnen, daß sich Alkalicarbonate, insbesondere Natriumcarbonat in Gegenwart von Wasser großtechnisch in günstiger Weise in Hydrogencarbonate und Salzen von Polycarbonsäuren überführen lassen, wenn man den Alkalicarbonaten gleich zu Beginn der Reaktion einen Anteil an den Alkalisalzen der Polycarbonsäuren beimischt. The invention seeks to remedy this; it goes from two Realizations. Firstly, it was observed that in situ production the alkali metal salts of polycarboxylic acids from alkali carbonates Granules low in fine substances stable under mixing and granulating conditions can be obtained. Furthermore, the knowledge was gained that alkali carbonates, especially sodium carbonate in the presence of Large-scale water in a favorable manner in hydrogen carbonates and salts can be transferred from polycarboxylic acids when the alkali carbonates a proportion of the alkali metal salts of the polycarboxylic acids right at the start of the reaction admixed.
Die großen Vorteile des erfindungsgemäßen Verfahrens werden wissenschaftlich nicht voll verstanden, doch kann spekuliert werden, daß das bessere Granulationsverhalten auf die Ausbildung kleinerer, eventuell miteinander verwachsener Kristalle zurückzuführen ist und daß der Effekt der Polycarbonsäurealkalimetallsalze auf die Reaktion von Alkalicarbonaten mit den Säuren im weitesten Sinne analog einer Pufferwirkung verstanden werden kann. The great advantages of the method according to the invention become scientific not fully understood, but it can be speculated that the better Granulation behavior on the formation of smaller, possibly with each other overgrown crystals and that the effect of the polycarboxylic acid alkali metal salts on the reaction of alkali carbonates with the Acids in the broadest sense can be understood as a buffer effect can.
Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung granularer Vorprodukte niederalkalischer Reinigungsmittel für das maschinelle Geschirrspülen, bestehend aus Alkalimetallsalzen der Kohlensäure und organischer Polycarbonsäuren, dadurch gekennzeichnet, daß man eine Teilmenge der Salze der Polycarbonsäuren in üblicher Weise herstellt, so dann in Gegenwart von 2 bis 12 Gew.-% Wasser, Alkalicarbonat in Gegenwart der Alkalimetallsalze der Polycarbonsäuren mit der freien Polycarbonsäure zu deren Salzen und im wesentlichen Alkalihydrogencarbonat bei Temperaturen unterhalb von 60 °C umsetzt. The invention thus relates to a process for producing granular Pre-products of low alkaline detergents for mechanical Dishwashing, consisting of alkali metal salts of carbonic acid and organic Polycarboxylic acids, characterized in that a subset the salts of the polycarboxylic acids in the usual way, then in Presence of 2 to 12 wt .-% water, alkali carbonate in the presence of the alkali metal salts of the polycarboxylic acids with the free polycarboxylic acid their salts and essentially alkali hydrogen carbonate at temperatures implemented below 60 ° C.
Weiterhin ist Gegenstand der Erfindung ein granulares Vorprodukt eines maschinellen Geschirrspülmittels, enthaltend 20 bis 70 Gew.-% Trinatriumcitratdihydrat, 20 bis 60 Gew.-% Natriumhydrogencarbonat, 0 bis 10 Gew.-% Natriumcarbonat sowie 0 bis 4 Gew.-% nichtionische Tenside in inniger Abmischung, hergestellt nach dem erfindungsgemäßen Verfahren. The invention furthermore relates to a granular precursor of a automatic dishwashing detergent, containing 20 to 70% by weight of trisodium citrate dihydrate, 20 to 60% by weight sodium bicarbonate, 0 to 10% by weight Sodium carbonate and 0 to 4% by weight nonionic surfactants in intimate admixture, produced by the method according to the invention.
Im Rahmen des erfindungsgemäßen Verfahrens werden Alkalimetallsalze der Kohlensäure und von Polycarbonsäuren eingesetzt. Bevorzugt finden die Natriumsalze der Kohlensäure wie Natriumcarbonat (Soda, wasserfrei oder in hydratisierter Form) und Natriumhydrogencarbonat Verwendung. Auch bei den Salzen der Polycarbonsäuren sind die Natriumsalze bevorzugt. Eine besonders bevorzugte Polycarbonsäure ist die Citronensäure, ein besonders bevorzugtes Salz ist Trinatriumcitrat, insbesondere Trinatriumcitratdihydrat. Eingesetzt werden können jedoch auch andere Polycarbonsäuren, zum Beispiel Äpfelsäure, Weinsäure, stickstoffhaltige Polycarbonsäuren, wie Ethylendiamintetraessigsäure, Nitrilotriessigsäure, Diethylentriaminpentaessigsäure oder Triethylentetraaminhexaessigsäure, Methylglycindiessigsäure und dergleichen. Eingesetzt werden können auch die in der DE-A-42 28 786 genannten Oxidationsprodukte von Polyglucosanen. Es ist auch möglich Copolymere polymerisierbare Säuren, gewünschtenfalls mit Estern und Sulfonsäuren copolymerisiert, einzusetzen. So insbesondere Copolymere auf Basis Acrylsäure-Maleinsäureanhydrid, Acrylsäure-Maleinsäureanhydrid-Vinylacetat (verseift zu Vinylalkohol), Methacrylsäure-Maleinsäureanhydrid und dergleichen. In the process of the invention, alkali metal salts of Carbonic acid and polycarboxylic acids. The sodium salts are preferred carbon dioxide such as sodium carbonate (soda, anhydrous or in hydrated form) and sodium bicarbonate use. Even with the Salts of the polycarboxylic acids are preferred the sodium salts. A special one preferred polycarboxylic acid is citric acid, a particularly preferred one Salt is trisodium citrate, especially trisodium citrate dihydrate. However, other polycarboxylic acids can also be used Example malic acid, tartaric acid, nitrogen-containing polycarboxylic acids, such as Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or triethylenetetraamine hexaacetic acid, methylglycinediacetic acid and the same. DE-A-42 28 can also be used 786 called oxidation products of polyglucosans. It is also possible Copolymers of polymerizable acids, if desired with esters and sulfonic acids copolymerized to use. So especially copolymers Based on acrylic acid-maleic anhydride, acrylic acid-maleic anhydride-vinyl acetate (saponified to vinyl alcohol), methacrylic acid-maleic anhydride and the same.
Vom Mengengerüst her bewegen sich die granularen Vorprodukte im Rahmen der
folgenden Zusammensetzung:
Der Fachmann kann dabei die Rezepturbestandteile so wählen, daß Mittel entstehen, die in 1-gewichtsprozentiger Lösung einen pH-Wert zwischen 7 und 11, insbesondere 8 und 10 und insbesondere 8 bis 9, aufweisen. The person skilled in the art can choose the recipe components so that means arise, which in 1% by weight solution have a pH between 7 and 11, in particular 8 and 10 and in particular 8 to 9.
Das erfindungsgemäße Verfahren wird so durchgeführt, daß in einer ersten Stufe das Alkalimetallsalz einer Polycarbonsäure in üblicher Weise hergestellt wird. Dies kann durch Umsetzen der Polycarbonsäure, zum Beispiel mit Alkalilauge, Alkalihydrogencarbonat oder Alkalicarbonat geschehen. In einer zweiten Stufe wird dann in Gegenwart dieser Polycarbonsäuresalzmenge das Alkalicarbonat, also beispielsweise Natriumcarbonat, mit der Polycarbonsäure, also zum Beispiel Citronensäure, zu Alkalihydrogencarbonat und dem Salz der Polycarbonsäure umgesetzt. Diese Umsetzung findet in Gegenwart von geringen Wassermengen, nämlich 2 bis 12 Gew.-% vorzugsweise 3 bis 8 Gew.-% Wasser statt. The inventive method is carried out so that in a first Stage prepared the alkali metal salt of a polycarboxylic acid in a conventional manner becomes. This can be done by reacting the polycarboxylic acid, for example done with alkali lye, alkali bicarbonate or alkali carbonate. In A second stage is then in the presence of this amount of polycarboxylic acid salt the alkali carbonate, for example sodium carbonate, with the polycarboxylic acid, for example citric acid, to alkali hydrogen carbonate and implemented the salt of the polycarboxylic acid. This implementation takes place in the present of small amounts of water, namely 2 to 12% by weight, preferably 3 to 8 wt .-% water instead.
Für die Ausführung der Erfindung stehendem Verfahrenstechniker eine Reihe von Alternativen zur Verfügung. So kann beispielsweise das Salz der Polycarbonsäure in einem Mischer, Granulator oder dergleichen vorgelegt werden und sodann können in Gegenwart der Wassermenge die anderen Bestandteile kontinuierlich oder portionsweise zugegeben werden. A number of process engineers for the implementation of the invention of alternatives available. For example, the salt of the polycarboxylic acid be placed in a mixer, granulator or the like and then in the presence of the amount of water, the other ingredients be added continuously or in portions.
Nach einer weiteren Ausführungsform kann auch in einem kontinuierlichen Mischer gearbeitet werden, in dem der vorgelegten Menge an Polycarbonsäuresalz die anderen Substanzen und das Wasser kontinuierlich zugegeben werden. According to a further embodiment can also be in a continuous Mixers are worked in the amount presented Polycarboxylic acid salt the other substances and the water continuously be added.
Weiterhin kann auch in der Weise gearbeitet werden, daß alle Feststoffe in einem Granulationsmischer vorgelegt werden und sodann durch Zugabe von Wasser die Reaktion gestartet wird. It is also possible to work in such a way that all solids in be submitted to a granulation mixer and then by adding Water the reaction is started.
Im Rahmen des erfindungsgemäßen Verfahrens kann es bevorzugt sein, die Reaktion unter so schonenden Bedingungen zu führen, daß ein Großteil des Alkalicarbonats in Hydrogencarbonat und das Natriumsalz der Polycarbonsäure überführt wird. Arbeitet man unter drastischen Bedingungen, also zum Beispiel unter Erwärmen oder aber in Gegenwart von nur geringen Mengen an Polycarbonsäuresalz, so ensteht anstelle von Hydrogencarbonat in substantiellem Umfang Alkalicarbonat und freies C02. In the context of the method according to the invention, it can be preferred that To carry out the reaction under such gentle conditions that a large part of the Alkali carbonate in bicarbonate and the sodium salt of polycarboxylic acid is transferred. If you work under drastic conditions, that is to say Example with heating or in the presence of only small amounts Polycarboxylic acid salt, so instead of bicarbonate in substantial Scope of alkali carbonate and free C02.
Im Rahmen des erfindungsgemäßen Verfahrens ist die schonende Fahrweise bevorzugt, dies gilt insbesondere dann, wenn die Reaktion der Einfachheit halber nicht in einem gesonderten Reaktor, sondern quasi als Feststoffreaktion in disperser Phase mit hohem Feststoffanteil in einem Mischer unter gleichzeitigem Granulieren durchgeführt wird. In the context of the method according to the invention, the gentle driving style preferred, this is especially true if the reaction is of simplicity half not in a separate reactor, but rather as a solid reaction in a disperse phase with a high solids content in a mixer is carried out with simultaneous granulation.
Der Mischer hat die Aufgabe, die Reaktion durch inniges Vermischen der Reststoffe vollständig ablaufen zu lassen und ein granulares Korn aufzubauen unter Umständen durch Zugabe weiterer Granulationshilfsmittel wie Tenside, Polycarboxylat-Lösungen. Verwendet wurden daher Mischer die zur Granulations geeignet sind und in denen sich Verweilzeiten von 1 bis 10 min einstellen lassen. The job of the mixer is to mix the reaction intimately Allow residues to run off completely and build up a granular grain possibly by adding other granulation aids such as Surfactants, polycarboxylate solutions. Mixers were therefore used for Granulations are suitable and in which residence times of 1 to 10 have min set.
Geeignete Mischer sind z. B. Eirich(R) Mischer der Serien R oder RV, hergestellt durch Maschinenfabrik Gustav Eirich, Hardheim, Deutschland, die Fukae(R) FS-G Mischer, hergestellt durch Fukal Powtech Kogyo Co., Japan die Lödige(R) FM, KM und CB Mischer, hergestellt durch Lödige Maschinenbau GmbH, Paderborn, Deutschland oder die Drais(R) Serien T oder K-T, hergestellt durch Drais Werke GmbH, Mannheim, Deutschland. Suitable mixers are e.g. B. Eirich (R) mixers of the R or RV series, manufactured by machine factory Gustav Eirich, Hardheim, Germany, the Fukae (R) FS-G mixers, manufactured by Fukal Powtech Kogyo Co., Japan the Lödige (R) FM, KM and CB mixer, manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany or the Drais (R) series T or KT, manufactured by Drais Werke GmbH, Mannheim, Germany.
In einer besonders bevorzugten Ausführungsform des Verfahrens werden als Alkalicarbonate Soda eingesetzt und als Polycarbonsäuresalz Natriumtricitrat-2-hydrat. Als Säure wird dann mit Citronensäure gearbeitet und es wird Natriumhydrogencarbonat in inniger Abmischung mit Natriumtricitratdihydrat und gewünschtenfalls geringen Mengen Soda erhalten. In a particularly preferred embodiment of the method, as Alkaline carbonate soda used and sodium tricitrate-2-hydrate as the polycarboxylic acid salt. The acid is then worked with citric acid and it sodium bicarbonate is mixed intimately with sodium tricitrate dihydrate and, if desired, small amounts of soda.
Die Gewichts-Menge an Polycarbonsäurenatriumsalzen, das in die Reaktion quasi als Puffer vorgelegt wird, kann vom Fachmann frei bestimmt werden, bezogen auf die Sodamenge beträgt sie 10 bis 500 Gew.-%, vorzugsweise 50 bis 150 Gew.-%, bezogen auf Alkalicarbonat. The weight amount of polycarboxylic acid sodium salts used in the reaction quasi presented as a buffer, can be freely determined by the expert, based on the amount of soda, it is 10 to 500% by weight, preferably 50 up to 150 wt .-%, based on alkali carbonate.
Das erfindungsgemäße Verfahren wird so gesteuert, daß der Restgehalt an Alkalicarbonat weniger als 20 Gew.%, vorzugsweise weniger als 10 Gew.-% und insbesondere weniger als 5 Gew.-%, beträgt. Geringe Alkalicarbonatgehalte bei gleichzeitig hoher Menge an Hydrogencarbonat erreicht man, indem man 50 bis 150 Gew.-%, bezogen auf Alkalicarbonat an Polycarbonsäuresalzen, vorgibt und bei schonenden Temperaturbedingungen arbeitet. Höhere Gehalte an Alkalicarbonat, bei gleichzeitig weniger Hydrogencarbonat, erreicht man, indem man entweder bei höheren Temperaturen arbeitet oder mit geringeren Mengen der Salze der Polycarbonsäuren startet. The process according to the invention is controlled so that the residual content of Alkali carbonate less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight. Low alkali carbonate levels with a simultaneously high amount of hydrogen carbonate can be achieved by 50 to 150% by weight, based on alkali carbonate, of polycarboxylic acid salts, specifies and works in mild temperature conditions. Higher Content of alkali carbonate, with less hydrogen carbonate, reached one, either by working at higher temperatures or with smaller amounts of the salts of the polycarboxylic acids starts.
Es ist für den Fachmann jedoch auch möglich, im Rahmen des erfindungsgemäßen Verfahrens in einem Nachtrocknungsschritt aus Alkalihydrogencarbonat Alkalicarbonat zu erzeugen. Dies geschieht insbesondere dann, wenn die Temperatur auf oder über den Zersetzungspunkt des Natriumhydrogencarbonats erhöht wird. So kann beispielsweise in einem nachfolgenden Trockenschritt, zum Beispiel in einem Wirbelschichttrockner die Menge an Alkalicarbonat zu Lasten der Menge an Alkalihydrogencarbonat erhöht werden, so zum Beispiel bei Temperaturen von 50 bis 150 °C, besonders 100 °C bis 150 °C. However, it is also possible for the person skilled in the art, within the scope of the invention Process in a post-drying step from alkali hydrogen carbonate To produce alkali carbonate. This happens especially when the Temperature at or above the decomposition point of the sodium hydrogen carbonate is increased. For example, in a subsequent drying step, for example in a fluidized bed dryer, the amount of alkali carbonate Loads of the amount of alkali hydrogen carbonate can be increased, for example at temperatures from 50 to 150 ° C, especially 100 ° C to 150 ° C.
Als weitere Bestandteile können in dem erfindungsgemäßen Verfahren auch Tenside miteingesetzt werden. Der Gesamtgehalt der Mittel an Tensiden liegt im allgemeinen zwischen 0,5 Gew.-% und 8 Gew.-% und kann vorzugsweise 0,8 bis 5 Gew.-% betragen. Übliche Tenside für Reinigungsmittel zählen zu den Gruppen der anionischen, der nichtionischen und/oder der zwitterionischen Tenside, wobei der Einsatz von anionischen und/oder nichtionischen Tensiden bevorzugt ist. Als Aniontenside kommen insbesondere Sulfonate und Sulfate sowie Seifen aus vorzugsweise natürlichen Fettsäuren beziehungsweise Fettsäuregemischen in Betracht. Als Tenside vom Sulfonattyp werden beispielsweise C9-13-Alkylbenzosulfonate, Olefinsulfonate, Ester und Alpha-Sulfofettsäuren oder Alpha-Sulfofettsäure-Disalze eingesetzt. Geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester aus primären Alkoholen natürlichen oder synthetischen Ursprungs, d. h. aus C12-18-Fettalkoholen oder aus C10-20-Oxoalkoholen, und die diejenigen sekundärer Alkohole dieser Kettenlänge. Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid (EO) umgesetzten Alkohole kommen in Betracht. Surfactants can also be used as further constituents in the process according to the invention. The total content of surfactants in the compositions is generally between 0.5% by weight and 8% by weight and can preferably be 0.8 to 5% by weight. Usual surfactants for cleaning agents belong to the groups of anionic, nonionic and / or zwitterionic surfactants, the use of anionic and / or nonionic surfactants being preferred. Particularly suitable anionic surfactants are sulfonates and sulfates and soaps made from preferably natural fatty acids or fatty acid mixtures. Examples of surfactants of the sulfonate type used are C 9-13- alkylbenzosulfonates, olefin sulfonates, esters and alpha-sulfofatty acids or alpha-sulfofatty acid disalts. Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, ie from C 12-18 fatty alcohols or from C 10-20 oxo alcohols, and those of secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols reacted with 1 to 6 mol of ethylene oxide (EO) are also suitable.
Als nichtionische Tenside sind vor allem Anlagerungsprodukte von vorzugsweise 2 bis 20 Mol EO an 1 Mol einer aliphatischen Verbindung mit im wesentlichen 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alkohole, Carbonsäuren, Fettamine, Carbonsäureamide und Alkansulfonamide von Interesse. Wichtig sind neben den wasserlöslichen Niotensiden aber auch nicht beziehungsweise nicht vollständig wasserlösliche Polyglykolether mit 2 bis 7 Ethylenglykoletherresten im Molekül, insbesondere dann, wenn sie zusammen mit wasserlöslichen nichtionischen oder anionischen Tensiden eingesetzt werden. Außerdem können als nichtionische Tenside aus Alkylpolyglykoside der allgemeinen Formel R-O-(G)x eingesetzt werden, in der R einen primären, geradkettigen oder verzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet, G für eine Glykose-Einheit mit 5 oder 6 C-Atomen steht und der Oligomerisierungsgrad x zwischen 1 und 10 liegt. Addition products of preferably 2 to 20 moles of EO to 1 mole of an aliphatic compound with essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and alkanesulfonamides are of particular interest as nonionic surfactants. In addition to the water-soluble nonionic surfactants, polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule, which are not or not completely water-soluble, are also important, especially when they are used together with water-soluble nonionic or anionic surfactants. In addition, nonionic surfactants made from alkyl polyglycosides of the general formula RO- (G) x can be used, in which R denotes a primary, straight-chain or branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, G for a glycose unit is with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10.
In einer bevorzugten Ausführungsform enthalten die Geschirreinigungsmittel der Erfindung nicht mehr als 10 Gew.-% wasserlösliche organische Komplexbildner bzw. Co-Builder aus der Gruppe der synthetischen polymeren Polycarboxylate, unter denen die Salze von Polymerisationsprodukten ungesättigter Carbonsäuren verstanden werden und zu denen beispielsweise Polyacrylate, Polymethacrylate, Polymaleinate oder Copolymere der Acrylsäure mit Maleinsäure bzw. Maleinsäureanhydrid gehören. Derartige Substanzen fehlen in den erfindungsgemäßen Mitteln vorzugsweise ganz. In a preferred embodiment, the dishwashing detergents contain the invention not more than 10 wt .-% water-soluble organic complexing agents or co-builders from the group of synthetic polymeric polycarboxylates, among which the salts of polymerization products unsaturated Carboxylic acids are understood and include, for example, polyacrylates, Polymethacrylates, polymaleinates or copolymers of acrylic acid with maleic acid or maleic anhydride. Such substances are completely absent in the agents according to the invention.
Die nach dem erfindungsgemäßen Verfahren hergestellten festen Geschirrspülmittel können noch bis zu 10 Gew.-% weitere Alkalisierungsmittel enthalten. Zu diesen zählen insbesondere die Alkalisilikate. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate mit einem molaren Verhältnis Na2O : SiO2 von 1 : 1,5 bis 1 : 2,5. Derartige amorphe Alkalisilikate sind beispielsweise unter dem Handelsnamen Portil (R) im Handel erhältlich. Eingesetzt werden können auch Compounds aus Alkalisilikaten und Soda, wie sie im Handel erhältlich sind. The solid dishwashing detergents produced by the process according to the invention can also contain up to 10% by weight of further alkalizing agents. These include in particular the alkali silicates. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio Na 2 O: SiO 2 of 1: 1.5 to 1: 2.5. Such amorphous alkali silicates are commercially available, for example, under the trade name Portil (R). Compounds made from alkali silicates and soda, as are commercially available, can also be used.
Die Verfahrensprodukte des erfindungsgemäßen Verfahrens sind insbesondere als granulare Vorprodukte für die Erzeugung von Reinigungsmitteln für. das maschinelle Geschirrspülen. Sie enthalten in der Regel keine Oxidationsmittel und auch nicht die in maschinellen Geschirrspülmitteln vorhanden, teils empfindlichen mengenmäßig kleinen Bestandteile. Um aus den Produkten maschinelle Geschirrspülmittel herzustellen, können sie mit diesen restlichen Bestandteilen zu den Endprodukten gemischt oder granuliert werden. Zu diesen restlichen Bestandteilen zählen in erster Linie Bleichmittel und Bleichaktivatoren. The process products of the process according to the invention are in particular as granular intermediate products for the production of cleaning agents for. the machine dishwashing. As a rule, they do not contain any oxidizing agents and also not in machine dishwashing detergents, some sensitive small quantities. To get out of the products machine dishwashing detergent, you can use these remaining Ingredients are mixed or granulated into the end products. These remaining ingredients primarily include bleach and Bleach activators.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborat-Tetrahydrat und das Natriumperborat-Monohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxycarbonat (Na2CO3 . 1,5 H2O2) oder persaure Salze organischer Säuren, wie Perbenzoate oder Salze der Diperdodecandisäure. Geeignete Bleichaktivatoren für diese Oxidationsmittel sind insbesondere die mit H2O2 organische Persäuren bildenden N-Acyl bzw. O-Acyl-Verbindungen, vorzugsweise N,N'-tetraacylierte Diamine wie N,N,N',N'-Tetraacetylethylendiamin. Among the compounds which serve as bleaching agents and supply H 2 O 2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, peroxycarbonate (Na 2 CO 3 .1.5 H 2 O 2 ) or persic acid salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid. Suitable bleach activators for these oxidizing agents are, in particular, the N-acyl or O-acyl compounds which form with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines such as N, N, N ', N'-tetraacetylethylene diamine.
Üblicherweise werden die Vorprodukte mit den Bleichmitteln und sonstigen Bestandteilen in Mengen von etwa 7 : 3 bis 9 : 1 gemischt. Der Gehalt der dann fertig konfektionierten Geschirrspülmittel an Oxidationsmittel auf Sauerstoffbasis beträgt vorzugsweise etwa 5 Gew.-% bis 15 Gew.-%, insbesondere in Kombination mit 1 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew.-% bis 5 Gew.-%, eines Bleichaktivators. Usually the preliminary products with the bleaching agents and others Ingredients mixed in amounts of about 7: 3 to 9: 1. The salary of the then ready-made dishwasher detergent on oxidizing agent Oxygen base is preferably about 5 wt% to 15 wt%, especially in combination with 1% by weight to 10% by weight, in particular 2% by weight up to 5% by weight of a bleach activator.
Zu den erfindungsgemäßen Vorprodukten können außer den erwähnten Bleichmitteln und Bleichaktivatoren noch weitere, üblicherweise jeweils nur in kleinen Mengen vorliegende, Wirkstoffe gegeben werden. Diese Stoffe werden vorzugsweise in Mengen von 5 bis 10 Gew.-%, bezogen auf das endgültig hergestellte Reinigungsmittel, eingesetzt. Zu diesen Kleikomponenten gehören beispielsweise Schauminhibitoren und Enzyme von der Art der Proteasen, Amylasen, Lipasen und/oder Cellulasen sowie nicht als Kristallwasser gebundenes oder in ähnlich fester Form mit den Bestandteilen assoziertes Wasser. Die Enzyme können in üblicher Weise an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein und werden vorzugsweise in Mengen von insgesamt nicht über 5 Gew.-%, insbesondere 2 bis 4 Gew.-% eingesetzt. Geeignete nicht-tensidartige und bevorzugt eingesetzte Schauminhibitoren sind Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure. Möglich ist auch der schauminhibierende Einsatz langkettiger Seifen. Geeignet können auch Gemische verschiedener Schauminhibitoren sein, zum Beispiel solche aus Silikonen und Paraffinen oder Wachsen. Bevorzugt sind diese Schauminhibitoren an eine granulare, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden. In addition to the bleaching agents mentioned, the precursors according to the invention can also be used and bleach activators still others, usually only in each case small amounts of active ingredients are given. These substances will preferably in amounts of 5 to 10 wt .-%, based on the final manufactured Detergent. These small components include for example foam inhibitors and enzymes of the protease type, Amylases, lipases and / or cellulases and not bound as water of crystallization or in a similar solid form associated with the components Water. The enzymes can be adsorbed onto carriers in the usual way and / or be embedded in coating substances and are preferably in Quantities of not more than 5% by weight in total, in particular 2 to 4% by weight used. Suitable non-surfactant-like and preferably used Foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica. It is also possible foam-inhibiting use of long-chain soaps. Can also be suitable Mixtures of different foam inhibitors, for example those made from Silicones and paraffins or waxes. These foam inhibitors are preferred to a granular, water-soluble or dispersible carrier substance bound.
Weitere hier einsetzbare Substanzen sind Silberschutzmittel, dies sind insbesondere anorganische Übergangsmetallsalze, z. B. Mangansalze wie Mangansulfat, Kaliumhexafluorotianat und dergleichen, anorganische Übergangsmetallkomplexe, stickstoffhaltige Heterocyclen wie Benzotriazol oder Isocyanursäure, natürliche Aminosäuren wie Cystin, Histidin, Methionin, reversible organische Redoxsysteme wie Chinon/Hydrochinon und/oder reversible anorganische Redoxsysteme wie Fe2+/Fe3+. Other substances that can be used here are silver protection agents. These are, in particular, inorganic transition metal salts, e.g. B. manganese salts such as manganese sulfate, potassium hexafluorotianate and the like, inorganic transition metal complexes, nitrogen-containing heterocycles such as benzotriazole or isocyanuric acid, natural amino acids such as cystine, histidine, methionine, reversible organic redox systems such as quinone / hydroquinone and / or reversible inorganic redox systems such as Fe 2+ / Fe 3+ .
Die nach dem erfindungsgemäßen Verfahren hergestellten Vorprodukte können weiterhin zu Tabletten weiterverarbeitet werden. Dazu werden die Vorprodukte mit den genannten weiteren Bestandteilen in einem Mischer miteinander vermischt und als Gemisch mittels herkömmlichen Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßdrucken im Bereich von 200 . 105 Pa bis 1 500 . 105 Pa verpreßt. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeiten von normalerweise über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 15 g bis 40 g, insbesondere von 20 g bis 30 g, bei einem Durchmesser von 35 mm bis 40 mm auf. The preliminary products produced by the process according to the invention can further be processed into tablets. For this purpose, the preliminary products with the other constituents mentioned are mixed with one another in a mixer and as a mixture using conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range of 200. 10 5 Pa to 1 500. 10 5 Pa pressed. In this way, break-resistant tablets are obtained which, under application conditions, dissolve sufficiently quickly, with bending strengths of normally more than 150 N. Preferably, a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm up to 40 mm.
Die nach dem erfindungsgemäßen Verfahren hergestellten granularen Reinigungsmittelvorprodukte sind stabile Granulate, sie zeigen geringen Feinstoffanteil und lassen sich insbesondere mit den genannten weiteren Bestandteilen in günstiger Weise aufbauen. Zu homogenen, nichtentmischenden Reinigungsmitteln weiter granulieren. The granular detergent precursors produced by the process according to the invention are stable granules, they show a low proportion of fines and can be used in particular with the other components mentioned build up in a favorable way. To homogeneous, non-segregating Granulate detergents further.
Ein besonderer Vorteil des erfindungsgemäßen Verfahrens liegt darin, daß bei dem Neutralisations- und Granulierungsschritt nur sehr geringe Mengen an Kohlendioxid entstehen. Es zeigt sich z.B. durch die überraschend hohen Schüttgewichte (es können Schüttgewichte über 900 g/l erzeugt werden) dies wiederum zeigt, daß die Verfahrensprodukte nicht durch CO2 aufgebläht sind. A particular advantage of the process according to the invention is that only very small amounts of carbon dioxide are produced in the neutralization and granulation step. It is shown, for example, by the surprisingly high bulk densities (bulk weights over 900 g / l can be produced), which in turn shows that the process products are not inflated by CO 2 .
In einem Drais Mischer PMH 12,5 Tex wurden die folgenden Ansatzmengen zu
einem granularen Vorprodukt verabeitet:
Die so erhaltenen Granulate wurden in einem Wirbelschichtrockner getrocknet. The granules thus obtained were dried in a fluidized bed dryer.
Während der Granulation entstanden die folgenden Mengen CO2:
Die prozentualen Angaben sind auf die Ansatzmenge bezogen und überraschenderweise trotz der in Beispiel 3 im Neutralisationsschritt anwesenden hohen Bicarbonatmengen niedrig. The percentages are based on the batch quantity and surprisingly despite those present in the neutralization step in Example 3 high amounts of bicarbonate low.
Claims (13)
- A process for the production of granular compounds of low-alkali machine dishwashing detergents consisting of alkali metal salts of carbonic acid and organic polycarboxylic acids, characterized in that a partial amount of the salts of the polycarboxylic acids is prepared in the usual way, after which alkali metal carbonate is reacted with the free polycarboxylic acid in the presence of the alkali metal salts of the polycarboxylic acids to form the salts of the free polycarboxylic acid and, essentially, alkali metal hydrogen carbonate, the reaction being carried out in the presence of 2 to 12% by weight of water at temperatures below 60°C.
- A process as claimed in claim 1, characterized in that the components are granulated during the reaction.
- A process as claimed in claims 1 and 2, characterized in that the reaction is carried out in a mixer suitable for granulation over residence times of 1 to 10 mins.
- A process as claimed in claims 1 to 3, characterized in that the quantity of salts of the polycarboxylic acids initially introduced is between 10 and 500% by weight and preferably between 50 and 150% by weight of the quantity of alkali metal carbonate.
- A process as claimed in claims 1 to 4, characterized in that the polycarboxylic acid or polycarboxylic acid sodium salt used is in particular trisodium citrate and in that the alkali metal carbonate is soda.
- A process as claimed in claims 1 to 5, characterized in that all but 20% by weight (based on the total), preferably all but 10% by weight and more preferably all but 5% by weight of the soda is reacted to the polycarboxylic acid salt and sodium hydrogen carbonate.
- A process as claimed in claims 1 to 6, characterized in that the sodium hydrogen carbonate is subsequently converted at least partly into sodium carbonate by heating.
- A process as claimed in claim 7, characterized in that the heat treatment is carried out in a fluidized bed dryer.
- A process as claimed in claims 1 to 8, characterized in that surfactants, more especially nonionic surfactants, such as alkyl polyglycosides and/or alkoxylation products of long-chain alcohols with 2 to 10 moles of ethylene oxide per mole of alcohol, are used as further components.
- A process as claimed in claims 1 to 9, characterized in that the mixtures are made up into the end product in known manner by addition of peroxy compounds and other components typically encountered in machine dishwashing detergents, such as silver protectors, dyes, fragrances and the like.
- A process as claimed in claims 1 to 9, characterized in that the mixtures are pressed in known manner with other components of machine dishwashing detergents to form shapes, particularly tablets.
- A process as claimed in claims 1 to 11, characterized in that the ratio of soda, sodium hydrogen carbonate and salts of polycarboxylic acids is selected so that a 1% solution of the detergents has a pH value of 7 to 11 and preferably 8 to 10.
- Granular compounds of a machine dishwashing detergent containing 20 to 70% by weight of trisodium citrate dihydrate, 20 to 60% by weight of sodium hydrogen carbonate, up to 10% by weight of sodium carbonate and 0 to 4% by weight of nonionic surfactants in the form of an intimate mixture prepared by the process claimed in claims 1 to 12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19532304 | 1995-09-01 | ||
| DE19532304A DE19532304A1 (en) | 1995-09-01 | 1995-09-01 | Process for the production of granular intermediate products of low alkaline cleaning agents |
| PCT/EP1996/003730 WO1997009411A1 (en) | 1995-09-01 | 1996-08-23 | Process for producing granulated precursors of low alkalinity detergents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0848750A1 EP0848750A1 (en) | 1998-06-24 |
| EP0848750B1 true EP0848750B1 (en) | 1999-11-10 |
Family
ID=7771024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96930091A Expired - Lifetime EP0848750B1 (en) | 1995-09-01 | 1996-08-23 | Process for producing granulated precursors of low alkalinity detergents |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0848750B1 (en) |
| DE (2) | DE19532304A1 (en) |
| ES (1) | ES2140894T3 (en) |
| WO (1) | WO1997009411A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998014548A2 (en) * | 1996-10-02 | 1998-04-09 | Herbert Schmitz | Method for producing a detergent, specially a powder detergent for dish washing machines |
| US6124253A (en) * | 1997-09-16 | 2000-09-26 | Church & Dwight Co., Inc. | Aqueous composition for low-temperature metal-cleaning and method of use |
| DE102008028229A1 (en) * | 2008-06-16 | 2009-12-17 | Fit Gmbh | Composition, useful for preparing detergents or in tablet mixture for preparing detergent-molded body for dishwasher, comprises particles comprising alkali metal salt of citric acid and surfactant on their surface layer |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK166548B1 (en) * | 1991-03-15 | 1993-06-07 | Cleantabs As | PHOSPHATE-FREE MACHINE DISHWASH |
| US5256327A (en) * | 1991-08-01 | 1993-10-26 | Shaklee Corporation | Method of preparing a sequestering agent for a non-phosphate cleaning composition |
| EP0626996A1 (en) * | 1992-02-20 | 1994-12-07 | Henkel Kommanditgesellschaft auf Aktien | Process for producing low-alkaline dishwasher rinsing agents without active chlorine, silicates and phosphates, in the form of heavy granulates |
| DE4232170C2 (en) * | 1992-09-25 | 1999-09-16 | Henkel Kgaa | Weakly alkaline dish detergent |
| WO1995012654A1 (en) * | 1993-11-03 | 1995-05-11 | The Procter & Gamble Company | Control of calcium carbonate precipitation in automatic dishwashing |
-
1995
- 1995-09-01 DE DE19532304A patent/DE19532304A1/en not_active Withdrawn
-
1996
- 1996-08-23 EP EP96930091A patent/EP0848750B1/en not_active Expired - Lifetime
- 1996-08-23 WO PCT/EP1996/003730 patent/WO1997009411A1/en active IP Right Grant
- 1996-08-23 DE DE59603641T patent/DE59603641D1/en not_active Expired - Fee Related
- 1996-08-23 ES ES96930091T patent/ES2140894T3/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE59603641D1 (en) | 1999-12-16 |
| WO1997009411A1 (en) | 1997-03-13 |
| ES2140894T3 (en) | 2000-03-01 |
| DE19532304A1 (en) | 1997-03-06 |
| EP0848750A1 (en) | 1998-06-24 |
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