EP0560802B1 - Procede de fabrication de granulats de zeolite - Google Patents
Procede de fabrication de granulats de zeolite Download PDFInfo
- Publication number
- EP0560802B1 EP0560802B1 EP91920221A EP91920221A EP0560802B1 EP 0560802 B1 EP0560802 B1 EP 0560802B1 EP 91920221 A EP91920221 A EP 91920221A EP 91920221 A EP91920221 A EP 91920221A EP 0560802 B1 EP0560802 B1 EP 0560802B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- zeolite
- granules
- liquid
- water
- 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
- 239000010457 zeolite Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 72
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 63
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000008187 granular material Substances 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920001577 copolymer Polymers 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000005469 granulation Methods 0.000 claims abstract description 26
- 230000003179 granulation Effects 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 13
- 239000000470 constituent Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims description 29
- 239000002736 nonionic surfactant Substances 0.000 claims description 25
- 239000003599 detergent Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- 150000001735 carboxylic acids Chemical class 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 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 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 159000000001 potassium salts Chemical class 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000002156 adsorbate Substances 0.000 claims description 3
- 239000008240 homogeneous mixture Substances 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 36
- 229920002125 Sokalan® Polymers 0.000 description 20
- 150000002191 fatty alcohols Chemical class 0.000 description 18
- 238000002156 mixing Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 229920005646 polycarboxylate Polymers 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- -1 sodium sulfate Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000003760 tallow Substances 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 238000007046 ethoxylation reaction Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 150000003138 primary alcohols Chemical class 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940055577 oleyl alcohol Drugs 0.000 description 3
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 3
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000004482 other powder Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N 1-Tetradecanol Natural products CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Chemical class 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Chemical class 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
Definitions
- the invention relates to a process for the production of zeolite granules with a high bulk density, which have a pronounced adsorption capacity for liquid active substances, and the use of the zeolite granules as a preliminary product for the production of detergents and cleaning agents.
- European patent application 21 267 discloses granules containing zeolites and alkali silicates which have a particle size between 0.15 and 2 mm and a bulk density of 300 to 700 g / l. They are also suitable for adsorbing liquid detergent components, especially nonionic surfactants.
- a dry premix of zeolite and alkali metal silicate (mixing ratio 1: 1 to 1: 8) is sprayed with water in a granulator and agglomerated, whereupon the excess water is removed to a residual proportion of less than 5% by weight by drying .
- the main disadvantage is the high content of strongly alkaline-reacting alkali silicates, which severely limits the use of these granules in detergents which are neutral to weakly alkaline and suitable for sensitive textiles.
- bulk densities of over 700 g / l cannot be achieved.
- European patent application 149 264 Unilever teaches that commercially available spray-dried zeolites or mixtures thereof with inorganic salts, such as sodium sulfate, can be used for the adsorption of liquid detergent components, in particular nonionic surfactants.
- the bulk density of the relatively finely divided spray products is in the range from 450 to 600 g / l, the size of the particles being between 0.05 and 0.5 mm.
- German patent application 38 38 086 describes the production of granules from zeolite and the sodium or potassium salts of polymeric or copolymeric carboxylic acids, the agglomeration or granulation taking place with the addition of a granulating liquid and the agglomerate obtained until a free-flowing granulate is reached a bulk density of 750 to 1,000 g / l is dried.
- This is based on a homogeneous powdery mixture of zeolite and the salt of the (co) polymeric carboxylic acids and granulated in a further mixing and granulation step with the addition of water, which is preferably sprayed onto the powder mixture kept in motion.
- the polycarboxylates are presented in solid form and are not added in dissolved form as a constituent of the granulating liquid, since the amount of granulating liquid used is a critical factor and must therefore be metered exactly. Excessive amounts of granulating liquid lead to granules with a wide grain spectrum and an undesirably high coarse fraction (particle size above 2 mm length) as well as a lower bulk density.
- the invention relates to a process for the production of granules from zeolite and sodium or potassium salts of polymeric or copolymeric carboxylic acids, the granulation being carried out with the addition of a granulating liquid and the granules obtained until a free-flowing granulate having a bulk density of 750 to 1,000 is reached g / I is dried, which is characterized in that a mixture of water, surfactants and (co) polymeric carboxylates is used as the granulating liquid, the content of surfactants in the granulating liquid being at least 10% by weight.
- zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%.
- Preferred zeolites have no particles larger than 30 ⁇ m, consist of at least 80% particles smaller than 10 ⁇ m and are detergent grade.
- zeolite powder mixtures products from Degussa, trade name Wessalith
- additives such as sodium sulfate, salts of nitrilotriacetic acid, sodium hydroxide, carboxymethyl cellulose, (co) polymeric carboxylates or nonionic surfactants
- part of the zeolite is in the form of a 45 to 55% by weight aqueous suspension used.
- zeolite based on the total amount of zeolite, are introduced as an aqueous suspension and 95 to 70% by weight, based on the total amount of zeolite, as a powder.
- This water content and the water content of the powdered zeolite are included in the calculation of the water balance; the amount of water to be introduced into the pelletizing stage can be reduced by these proportions.
- the zeolite suspensions used usually contain about 1.5 to 3% by weight, based on the suspension, of stabilizers, which also include nonionic surfactants, anionic surfactants or polymeric polycarboxylates.
- the proportion of these active ingredients introduced via the suspension is so small that the effect according to the invention can only be achieved by using additional amounts of surfactants and (co) polymeric carboxylates.
- the granules which are produced by the process according to the invention preferably contain 50 to 95% by weight, in particular 70 to 92% by weight, based on the dried granules, of water-containing zeolite.
- Suitable water-soluble salts of the homopolymeric and / or copolymeric carboxylic acids contained in the granules, of which the sodium salts are preferred are polyacrylic acid, polymethacrylic acid and polymaleic acid, copolymers of acrylic acid or methacrylic acid with maleic acid or vinyl ethers such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters such as vinyl acetate or Vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
- the proportion thereof in the interest of sufficient water solubility is not more than 50 mol%, preferably less than 30 mol%.
- Copolymers of acrylic acid and methacrylic acid with maleic acid have proven to be particularly suitable. Copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid are particularly preferred.
- the relative molecular weight of the homo- or copolymeric polycarboxylates is generally 2,000 to 150,000, preferably 5,000 to 100,000.
- the polycarboxylates are preferably in the form of 30 to 50% by weight, in particular 35 to 45% by weight aqueous solutions used.
- water-soluble inorganic salts for example sodium sulfate, can be added to these solutions in amounts of up to 10% by weight, based on the polycarboxylate used.
- the polycarboxylates are initially presented in powder form together with the finely divided zeolite. It is preferred to use a maximum of 50% by weight and in particular a maximum of 40% by weight of the polymeric carboxylates in powder form.
- the commercially available salts of (co) polymeric carboxylic acids in powder form often contain 5 to 15% by weight of moisture. This proportion of water is also included in the calculation of the water balance.
- the proportion of salts in the preparation of the compositions or in the composition of the finished granules is based on anhydrous salt.
- the granules according to the invention preferably contain the salts of the polymeric or copolymeric carboxylic acids in amounts of 2 to 12% by weight and in particular in amounts of 4 to 10% by weight.
- the granulating liquid contains at least water as a liquid component, at least polymeric or copolymeric carboxylates as a solid component and anionic and / or nonionic surfactants.
- the granulating liquid preferably contains a mixture of water and liquid nonionic surfactants as the liquid constituent.
- the granulating liquid advantageously consists of 5 to 30% by weight of (co) polymeric carboxylate, 10 to 75% by weight of anionic and / or nonionic surfactants and 7 to 70% by weight of water.
- the granulating liquid consists of 10 to 25% by weight of (co) polymeric carboxylate, 10 to 65% by weight of nonionic surfactants or 10 to 40% by weight of anionic surfactants and 10 to 68% by weight of water.
- the liquid nonionic surfactants used are preferably ethoxylated and / or propoxylated fatty alcohols, with preference for the ethoxylated fatty alcohols, in particular addition products of 2 to 7 moles of ethylene oxide (EO) with linear primary alcohols, such as, for. B. on coconut oil, tallow or oleyl alcohol, or on primary alcohols (oxo alcohols) branched methyl in the 2-position.
- EO ethylene oxide
- C 12 -C 14 alcohols with 3 EO or 4 EO C 13 -C 15 alcohols with 3, 5 or 7 EO
- C 12 -C 18 alcohols with 2, 3, 5 or 7 EO and mixtures this, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
- Preferred ethoxylated fatty alcohols are also those with a narrow homolog distribution (narrow range ethoxylates, nre).
- the water-soluble anionic surfactants are alkali metal salts, sodium or potassium salts, from the class of the sulfonates and sulfates.
- Preferred surfactants of the sulfonate type are C g- C 13 -alkylbenzenesulfonates, in particular C 12 -alkylbenzenesulfonate, and sulfonates on a oleochemical basis, such as the esters of ⁇ -sulfofatty acids, the sulfo group being in its salt form (mono salt), e.g. B. the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids into consideration.
- Suitable surfactants of the sulfate type are, for example, the optionally ethoxylated sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols such as. B.
- the solid, water-soluble anionic surfactants can be incorporated in the liquid constituents of the granulating liquid in powder form or in paste form.
- the wet fraction is included in the calculation of the liquid constituents, or the amount of liquid introduced into the granulation stage can be reduced by this fraction.
- granulating liquid is added to 100 parts by weight of zeolite, calculated as an anhydrous substance, or to a homogeneous mixture of zeolite and optionally powdered salt of the polymeric or copolymeric carboxylic acids, preferably in an amount of 15 up to 45 parts by weight, in particular 18 to 40 parts by weight, based on the moist granules, of liquid constituents are present.
- the proportion of free water not added as water of crystallization or in a comparable form in the granulating liquid can be very small and solely depends on the amount and concentration of the polymeric or copolymeric carboxylate solution used.
- the granulating liquid preferably contains at least 2 parts by weight, for example 5 to 35 parts by weight and in particular 5 to 25 parts by weight, based on the moist granules, of free water.
- the granulation can be carried out batchwise or continuously in conventional mixing and granulating devices.
- B. pelletizers which consist of a horizontally arranged or inclined to the horizontal, cylindrical container, rotates in the longitudinal axis of a shaft equipped with mixing tools and conveyor blades.
- the granulation liquid can be supplied through the spray nozzle attached to the wall or on the high shaft. If continuous work is carried out, two consecutive mixers can be used, the first mixer producing the dry or, if an aqueous zeolite suspension is used, the wet premix and in the second mixer the granulation with the addition of the surfactant and polycarboxylate-containing granulation liquid he follows.
- Continuous operation is also possible in a mixer, with either the powder streams and / or the powder streams and the zeolite suspension being combined and homogenized in a first mixing section, and the mixture being transported with the surfactant and polycarboxylate in a subsequent mixing section in a subsequent mixing section
- Granulating liquid is treated and granulated.
- the granulating liquid is preferably sprayed onto the mixture kept in motion by means of nozzles. It is possible to spray a mixture of all components of the granulating liquid or individual components in succession, in particular the surfactant-containing components before and after the addition of the polycarboxylate solution.
- the granulation is generally carried out at normal to moderately elevated temperatures, preferably at temperatures between 20 and 40 ° C. and generally requires a time of 5 to 15 minutes.
- the drying can be carried out by introducing hot gases in a third mixing section, e.g. B. a fluidized bed, or after the discharge of the granules from the mixer, for example in a vibratory conveyor, a free-fall dryer or in a thin layer on a conveyor belt. Drying in a fluidized bed is preferred, the temperature of the granules preferably being between 60 and 85 ° C. and in particular between 65 to 80 ° C. The drying is carried out until the water added in the granulation stage is removed to a level of less than 5% by weight, preferably less than 3% by weight, based in each case on the dried granules.
- a third mixing section e.g. B. a fluidized bed
- water components that were originally introduced with the zeolite or a (co) polymeric salt which is not used anhydrous can be removed during drying.
- Such "over-dried" granules can have application advantages, for example when added to detergents that contain moisture-sensitive active ingredients.
- the dewatering of the zeolite should preferably not be driven below a water content of 18% by weight, based on zeolite, in order to avoid a reduction in activity.
- the water content of the granules is expediently in a range in which the water-binding capacity of the zeolite is largely saturated, ie in which the zeolite has a total water content of 19 to 22% by weight.
- the granules preferably have a bulk density of 780 to 980 g / l, in particular from 800 to 950 g / l. Due to their dense packing and their small pore volume, their absorption capacity for liquid or pasty detergent components, especially nonionic surfactants and foam inhibitors, e.g. paraffin oil or silicone oil, is somewhat reduced compared to specifically lighter carrier grains, but is still 15 to a maximum of 20% by weight without any noteworthy impairment the flowability of the granules. In view of the high packing density and the possibly already contained content of non-ionic surfactants in the granules, this surprisingly high adsorption capacity is completely sufficient for the usual fields of application, in particular for use as a mixture component in detergents and cleaning agents.
- nonionic surfactants and foam inhibitors e.g. paraffin oil or silicone oil
- the granules obtained by the process according to the invention are distinguished by a grain spectrum in which the fine fraction (particle diameter smaller than 0.1 mm) is generally below 10% and the coarse fraction (particle diameter larger than 2 mm) is generally up to 40%.
- the content of fine fractions is preferably less than 7% and is in particular 0 to 5%, while the content of coarse fractions is preferably 2 to 32%.
- the coarse and fine particles are sieved.
- the coarse fractions are ground and mixed into the product, while the fine fractions or the dust are returned to the granulation.
- the granules disintegrate quickly and completely in cold water and do not leave any residues in the washing-up devices of washing machines, i. H. they have a very good induction ability. This advantageous property is also noticeable after impregnation with nonionic surfactants and in a mixture with other powder detergent components.
- the granules contain 2 to 25% by weight of surfactants and in particular 4 to 20% by weight of anionic and / or nonionic surfactants.
- Particularly advantageous granules contain 75 to 90% by weight of zeolite which has been placed in an aqueous suspension in powder form or as a mixture of 94 to 73% by weight of powder and 6 to 27% by weight, in each case based on zeolite, 2 up to 10% by weight sodium salt of a copolymer of acrylic acid and maleic acid and 4 to 20% by weight liquid nonionic surfactants.
- the granules contain zeolite as above, 3 to 8% by weight sodium salt of a copolymer of acrylic acid and maleic acid and 6 to 11% by weight anionic surfactants, in particular alkylbenzenesulfonate and fatty alcohol sulfate.
- the granules can be impregnated with liquid detergent constituents which cannot be incorporated into conventional powdered or granular detergents and cleaning agents in other ways or only with a loss of activity.
- liquid detergent constituents which cannot be incorporated into conventional powdered or granular detergents and cleaning agents in other ways or only with a loss of activity.
- foam inhibitors in particular paraffin hydrocarbons, silicones, silicone resins and bis-acyl-alkylenediamines derived from long-chain fatty acids, and mixtures thereof.
- Further adsorbable active ingredients are fatty acid alkylolamides and cationic plasticizers, such as quaternary ammonium salts containing long-chain fatty residues, and also fat-dissolving solvents such as terpenes.
- the granules are preferably used as carrier grains for liquid nonionic surfactants and foam inhibitors.
- Those components which are present in liquid form at room temperature or at the processing temperature between 25 ° C. and about 80 ° C., preferably up to 75 ° C., are considered to be “liquid”. It can be advantageous to heat components that are already liquid at room temperature, but have an undesirably high viscosity, before the impregnation of the carrier grains.
- Suitable nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic radical and 3 to 20 glycol ether groups. These include ethoxylation products of alcohols, vicinal diols, amines, thioalcohols, fatty acid amides and fatty acids. Block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronic (from BASF / Wyandotte), are also suitable. Furthermore, alkyl glycosides or alkyl polyglycosides and mixtures thereof with the ethoxylation products mentioned can be used.
- Preferred nonionic surfactants which can be adsorbed on the granules and together with these are in the form of a free-flowing mixture, are derived from alcohols with 12 to 18 carbon atoms which are saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical ) could be.
- Their reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation, the number of EO or PO groups given below corresponding to a statistical mean.
- Examples of preferred ethoxylated fatty alcohols are C 12 -C 18 coconut alcohols with 3 to 12 EO, C 16 -C, 8-tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chains and ethoxylation products obtainable from other native fatty alcohol mixtures EO distribution. From the series of ethoxylated oxo alcohols, for example those of the composition C 12 -C15 with 5 to 10 EO and C 14 -C15 with 6 to 12 EO are suitable.
- alkoxylates which contain EO groups and PO groups, for example C 12 -C 18 alcohols of the formula R- (PO) a- (EO) b or R- (EO) b - (PO) c , where a is from 1 to 3, b is from 5 to 20 and c is from 1 to 10, where b is to be greater than c.
- the liquid, optionally heated additives, in particular the application of the nonionic surfactants and the foam inhibitors, can be applied to the granules by mixing, preferably spraying, the carrier material expediently using suitable mixing devices Movement is kept. Further treatment of the granular adsorbate is not necessary. However, leaving the product to rest for several hours at high contents of applied liquid material can be expedient, since its diffusion into the interior of the grain takes some time. The treatment of the granules with the liquid additives leads to a further increase in the bulk density, which can rise to values of over 1,000 g / l.
- the grains can optionally be dusted with a finely divided powder as powdering agent or coated on the surface.
- a finely divided powder as powdering agent or coated on the surface.
- Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be present in proportions of 0.03 to 3, preferably 0.05 to 2% by weight, based on that with additive loaded adsorbent.
- finely powdered zeolites, silica airgel (Aerosil ( R )), colorless or colored pigments such as titanium dioxide are suitable. In general, however, such an aftertreatment is superfluous, especially since it does not improve the solution properties.
- the detergent additives can be combined and mixed in a known manner with the granular or pulverulent detergent, for example a tower spray powder and its mixtures with other powder components, such as persalts, enzyme granules, bleach activators or defoamers.
- the detergents generally contain 10 to 40% by weight of the additive according to the invention.
- the granulation was carried out in a mixing granulator consisting of a horizontally arranged cylindrical mixer with a rotating shaft (ploughshare mixer, Lödige type) equipped with mixing elements rotating in the central axis with a capacity of 130 l and a connected one with a speed of 1 200 to 1 Knife mill operated at 500 revolutions / minute.
- the pulverulent constituents and, if appropriate, the aqueous zeolite suspension were placed in the mixing granulator and processed to form a homogeneous mixture.
- the granulating liquid was sprayed in over the course of 1 to 5 minutes by means of nozzles and the mixture was granulated for a further 1 to 3 minutes with constant mixing.
- the granules leaving the mixer were dried in a fluidized bed with hot, flowing dry gases (70 ° C.).
- the fine fraction particle diameter smaller than 0.1 mm
- the coarse fraction particle diameter larger than 2 mm
- the zeolite powder used was finely crystalline, spray-dried zeolite of the NaA type, which contained 20% by weight of bound water.
- the aqueous zeolite suspension was 48% by weight.
- the sodium salt of the acrylic acid-maleic acid copolymer used (Sokalan ( R ) CP5 from BASF / Germany) had a relative molecular weight of approximately 70,000 and was used as a 40% by weight solution; the quantities refer to anhydrous substance.
- zeolite 100 parts by weight of zeolite, based on anhydrous substance, with 49.5 parts by weight of a granulating liquid consisting of 20% by weight of Sokalan CP5, 14% by weight of C 12 -C 18 fatty alcohol with 5 EO and 66 wt .-% H 2 0, sprayed.
- the granules obtained after drying contained 88.1% by weight of anhydrous zeolite, which had been presented as a powder, 7% by weight of Sokalan CP5 and 4.9% by weight of C 12 -C 18 fatty alcohol with 5 EO.
- the bulk density before sieving was 810 g / l; the gross share was 17.3%.
- zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 44.2 parts by weight of a granulating liquid consisting of 19.8% by weight of Sokalan CP5, 50.6% by weight of C 12 -C 18 - Fatty alcohol with 5 EO and 29.6 wt .-% water, sprayed.
- the granules obtained after drying contained 80.1% by weight of water-containing zeolite, which had been presented as a powder, 5.6% by weight of Sokalan CP5 and 14.3% by weight of C 12 -C 18 fatty alcohol with 5 EO.
- the bulk density before sieving was 900 g / l; the gross share was 5%.
- zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 42.5 parts by weight of a granulating liquid consisting of 13.3% by weight of Sokalan CP5, 62.1% by weight of C 12 -C 18 - Sprayed fatty alcohol with 7 EO and 24.6 wt .-% water.
- the granules obtained after drying contained 79.6% by weight of water-containing zeolite, which had been presented as a powder, 3.6% by weight of Sokalan CP5 and 16.8% by weight of C 12 -C 18 fatty alcohol with 7 EO.
- the bulk density before screening was 850 g / l; the gross share was 13.9%.
- zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 39 parts by weight of a granulating liquid consisting of 8.9% by weight of Sokalan CP5, 73.3% by weight of C 12 -C 18 fatty alcohol 7 EO and 17.8 wt .-% water, sprayed.
- the granules obtained after drying contained 79.6% by weight of water-containing zeolite, which had been presented as a powder, 2.2% by weight of Sokalan CP5 and 18.2% by weight of C12-C18 fatty alcohol with 7 EO.
- the bulk weight was 870 g / l; the gross share was 2.9%.
- zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 47.5 parts by weight of a granulating liquid consisting of 22.7% by weight of Sokalan CP5, 20.5% by weight of sodium dodecylbenzenesulfonate and 56.8% by weight .-% water, sprayed.
- the granules obtained after drying contained 85.9% by weight of water-containing zeolite, which had been presented as a powder, 7.4% by weight of Sokalan CP5 and 6.7% by weight of sodium dodecylbenzenesulfonate.
- the bulk density before sieving was 860 g / l; the gross share was 30.2%.
- zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 44 parts by weight of a granulating liquid consisting of 11.25% by weight of Sokalan CP5, 35.75% by weight of sodium dodecylbenzenesulfonate and 53% by weight of water , sprayed.
- the granules obtained after drying contained 85.8% by weight of water-containing zeolite, which had been presented as a powder, 3.4% by weight of Sokalan CP5 and 10.8% by weight of sodium dodecylbenzenesulfonate.
- the bulk weight was 770 g / l; the gross share was 29.8%.
- zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 46.4 parts by weight of a granulating liquid consisting of 20.25% by weight of Sokalan CP5, 48.7% by weight of C 12 -C 18 - Fatty alcohol with 7 EO and 31.05 wt .-% water, sprayed.
- the granules obtained after drying contained 79.6% by weight of water-containing zeolite, 74.4% by weight as powder and 5.2% by weight as suspension, 6% by weight of Sokalan CP5 and 14 , 4 wt .-% C 12 -C 18 fatty alcohol with 7 EO.
- the bulk density before sieving was 940 g / l; the gross share was 31.1%.
- zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 42.0 parts by weight of a granulating liquid consisting of 29.5% by weight of Sokalan CP5, 22.9% by weight of C 12 -C 18 - Fatty alcohol with 5 EO and 47.6 wt .-% water, sprayed.
- the granules obtained after drying contained 76.5% by weight of water-containing zeolite, 73.1% by weight as powder and 13.4% by weight as suspension, 7.6% by weight of Sokalan CP5 and 5.9% by weight of C12-C18 fatty alcohol with 5 EO.
- the bulk density before sieving was 830 g / l; the gross share was 17.5%.
- zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 41.0 parts by weight of a granulating liquid consisting of 19.5% by weight of Sokalan CP5, 31.3% by weight of C 12 -C 18 - Fatty alcohol with 7 EO and 49.2 wt .-% water, sprayed.
- the granules obtained after drying contained 85.5% by weight of water-containing zeolite, 62.5% by weight as powder and 23% by weight as suspension 5.5% by weight of Sokalan CP5 and 8.8% by weight of C12-C18 fatty alcohol with 7 EO.
- the bulk density before sieving was 840 g / l; the gross share was 24.5%.
- the granules treated with the nonionic surfactant were free-flowing and had a perfect rinsing ability, both as unblended powder and mixed with a powdered household detergent in a ratio of 1: 4.
Landscapes
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Cosmetics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Claims (10)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4038609 | 1990-12-04 | ||
DE4038609A DE4038609A1 (de) | 1990-12-04 | 1990-12-04 | Verfahren zur herstellung von zeolith-granulaten |
PCT/EP1991/002209 WO1992010559A1 (fr) | 1990-12-04 | 1991-11-25 | Procede de fabrication de granulats de zeolite |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0560802A1 EP0560802A1 (fr) | 1993-09-22 |
EP0560802B1 true EP0560802B1 (fr) | 1995-05-10 |
EP0560802B2 EP0560802B2 (fr) | 2002-08-28 |
Family
ID=6419545
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91920221A Expired - Lifetime EP0560802B2 (fr) | 1990-12-04 | 1991-11-25 | Procede de fabrication de granulats de zeolite |
Country Status (8)
Country | Link |
---|---|
US (1) | US5399287A (fr) |
EP (1) | EP0560802B2 (fr) |
JP (1) | JP3167721B2 (fr) |
KR (1) | KR0181978B1 (fr) |
AT (1) | ATE122382T1 (fr) |
DE (2) | DE4038609A1 (fr) |
ES (1) | ES2071345T5 (fr) |
WO (1) | WO1992010559A1 (fr) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19549411C2 (de) * | 1994-02-11 | 1999-05-12 | Degussa | Zeolithgranulate |
DE19504043C2 (de) * | 1994-02-11 | 1998-07-09 | Degussa | Zeolithgranulate |
DE19515256A1 (de) * | 1995-04-26 | 1996-10-31 | Degussa | Zeolithgranulat, Verfahren zu seiner Herstellung und Verwendung |
PL185641B1 (pl) * | 1995-09-04 | 2003-06-30 | Unilever Nv | Sposób wytwarzania nierozpyłowo suszonej, rozdrobnionej detergentowej kompozycji lub jej składnika |
DE19844522A1 (de) | 1998-09-29 | 2000-03-30 | Henkel Kgaa | Granulationsverfahren |
KR100750190B1 (ko) * | 2004-06-16 | 2007-08-31 | 요업기술원 | 골 수복에 효과적인 골 충전재 및 그의 제조 방법 |
GB0811302D0 (en) * | 2008-06-20 | 2008-07-30 | Dow Corning | Shampoo compositions |
JP5705525B2 (ja) * | 2010-12-16 | 2015-04-22 | 花王株式会社 | ゼオライト複合粒子群 |
RU2615506C1 (ru) * | 2015-10-13 | 2017-04-05 | Александр Адольфович Ламберов | Способ гранулирования цеолита в качестве компонента синтетических моющих средств |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2652488C3 (de) * | 1976-11-18 | 1983-03-10 | Kali-Chemie Ag, 3000 Hannover | Verfahren zur Herstellung von Granulaten aus Zeolithen und sauerstoffabgebenden Verbindungen |
DE3316513A1 (de) * | 1983-05-06 | 1984-11-08 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | Abriebfeste granulate auf basis von alkalialuminiumsilikat |
GB8329880D0 (en) * | 1983-11-09 | 1983-12-14 | Unilever Plc | Particulate adjuncts |
US4552681A (en) * | 1983-12-10 | 1985-11-12 | Henkel Kommanditgesellschaft Auf Aktien | Granular, free-flowing detergent component and method for its production |
DE3444960A1 (de) * | 1984-12-10 | 1986-06-12 | Henkel KGaA, 4000 Düsseldorf | Koerniges adsorptionsmittel |
GB8526999D0 (en) * | 1985-11-01 | 1985-12-04 | Unilever Plc | Detergent compositions |
DE3545947A1 (de) * | 1985-12-23 | 1987-07-02 | Henkel Kgaa | Phosphatfreies, granulares waschmittel |
DE3614779A1 (de) * | 1986-05-02 | 1987-11-05 | Henkel Kgaa | Granulares, phosphatfreies wasserenthaertungsmittel |
DE3838086A1 (de) * | 1988-11-10 | 1990-05-17 | Henkel Kgaa | Verfahren zur herstellung zeolithhaltiger granulate hoher dichte |
CA2017921C (fr) * | 1989-06-09 | 1995-05-16 | John Michael Jolicoeur | Preparation de granules detergentes par voie de separation d'une pate detergente |
US5024782A (en) * | 1989-06-16 | 1991-06-18 | The Clorox Company | Zeolite agglomeration process and product |
US5205958A (en) * | 1989-06-16 | 1993-04-27 | The Clorox Company | Zeolite agglomeration process and product |
-
1990
- 1990-12-04 DE DE4038609A patent/DE4038609A1/de not_active Withdrawn
-
1991
- 1991-11-25 JP JP50030992A patent/JP3167721B2/ja not_active Expired - Lifetime
- 1991-11-25 US US08/070,442 patent/US5399287A/en not_active Expired - Lifetime
- 1991-11-25 KR KR1019930701683A patent/KR0181978B1/ko not_active IP Right Cessation
- 1991-11-25 EP EP91920221A patent/EP0560802B2/fr not_active Expired - Lifetime
- 1991-11-25 WO PCT/EP1991/002209 patent/WO1992010559A1/fr active IP Right Grant
- 1991-11-25 DE DE59105474T patent/DE59105474D1/de not_active Expired - Lifetime
- 1991-11-25 ES ES91920221T patent/ES2071345T5/es not_active Expired - Lifetime
- 1991-11-25 AT AT91920221T patent/ATE122382T1/de not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
JPH06503109A (ja) | 1994-04-07 |
EP0560802A1 (fr) | 1993-09-22 |
WO1992010559A1 (fr) | 1992-06-25 |
DE4038609A1 (de) | 1992-06-11 |
US5399287A (en) | 1995-03-21 |
ATE122382T1 (de) | 1995-05-15 |
ES2071345T3 (es) | 1995-06-16 |
KR930703424A (ko) | 1993-11-30 |
KR0181978B1 (ko) | 1999-04-15 |
ES2071345T5 (es) | 2003-03-16 |
EP0560802B2 (fr) | 2002-08-28 |
DE59105474D1 (de) | 1995-06-14 |
JP3167721B2 (ja) | 2001-05-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0184794B1 (fr) | Produit adsorbant granulé | |
EP0536110B1 (fr) | Procede pour fabriquer des granules tensio-actifs | |
EP0337330B1 (fr) | Procédé pour augmenter la densité des détergents séchés par pulvérisation et contenant peu de phosphate | |
EP0368137B1 (fr) | Méthode de préparation de granules en zéolite de haute densité | |
EP0344629A1 (fr) | Composition adsorbente granulaire avec une capacité de dégagement ameliorée | |
EP0150386A1 (fr) | Régulateur de mousse pour l'utilisation dans des composés tensio-actifs | |
WO1993015180A1 (fr) | Procede pour fabriquer des produits solides de lavage et de nettoyage de densite apparente elevee et presentant une vitesse de dissolution amelioree | |
EP0560802B1 (fr) | Procede de fabrication de granulats de zeolite | |
EP0605436B1 (fr) | Procede de preparation de granules de zeolithe | |
EP0425519A1 (fr) | Additif d'agent de lavage a dispersibilite amelioree | |
EP0473622B1 (fr) | Additif granulaire sans phosphates contenant des agents tensio-actifs non ioniques pour produit a lessive | |
WO1994014946A1 (fr) | Produits granules de lavage et/ou de nettoyage | |
EP0804535B1 (fr) | Detergents et nettoyants de blanchiment sous forme de granulats | |
DE2418294B2 (de) | Pulverfoermiges bis koerniges, nichtionische waschaktivsubstanzen enthaltendes waschmittel | |
EP0633923B1 (fr) | Additif granulaire sans phosphate contenant des tensioactifs non ioniques pour produits de lavage et detergents | |
EP0874684B1 (fr) | Procede de production d'un additif granule | |
EP0880580A1 (fr) | Procede pour la preparation de detergents ou de nettoyants granulaires et constituants utilises a cet effet | |
WO2000071654A1 (fr) | Procede de preparation de granulat de tensio-actifs | |
WO2000071657A1 (fr) | Procede de preparation de granulat de tensio-actifs | |
WO1997023595A1 (fr) | Procede pour produire des agents de lavage et/ou de nettoyage et dispositif correspondant |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19930526 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB IT LI NL |
|
17Q | First examination report despatched |
Effective date: 19940321 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES FR GB IT LI NL |
|
REF | Corresponds to: |
Ref document number: 122382 Country of ref document: AT Date of ref document: 19950515 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 59105474 Country of ref document: DE Date of ref document: 19950614 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2071345 Country of ref document: ES Kind code of ref document: T3 |
|
ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19950814 |
|
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
26 | Opposition filed |
Opponent name: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER N.V. Effective date: 19960205 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER N.V. |
|
PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN |
|
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER N.V. Effective date: 19960205 |
|
PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER N.V. |
|
APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
APAE | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOS REFNO |
|
APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
APAE | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOS REFNO |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form |
Effective date: 20020828 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): AT BE CH DE ES FR GB IT LI NL |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: AEN Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM |
|
NLR2 | Nl: decision of opposition | ||
GBTA | Gb: translation of amended ep patent filed (gb section 77(6)(b)/1977) | ||
NLR3 | Nl: receipt of modified translations in the netherlands language after an opposition procedure | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: DC2A Date of ref document: 20021126 Kind code of ref document: T5 |
|
ET3 | Fr: translation filed ** decision concerning opposition | ||
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20051106 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20051129 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20060117 Year of fee payment: 15 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061130 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061130 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070601 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20070601 |
|
BERE | Be: lapsed |
Owner name: *HENKEL K.G.A.A. Effective date: 20061130 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20101110 Year of fee payment: 20 Ref country code: FR Payment date: 20101123 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20101117 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20101124 Year of fee payment: 20 Ref country code: IT Payment date: 20101113 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20101217 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59105474 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59105474 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20111124 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK07 Ref document number: 122382 Country of ref document: AT Kind code of ref document: T Effective date: 20111125 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20111124 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20111126 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20130718 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20111126 |