EP0560802B2 - Process for the production of granular zeolites - Google Patents
Process for the production of granular zeolites Download PDFInfo
- Publication number
- EP0560802B2 EP0560802B2 EP91920221A EP91920221A EP0560802B2 EP 0560802 B2 EP0560802 B2 EP 0560802B2 EP 91920221 A EP91920221 A EP 91920221A EP 91920221 A EP91920221 A EP 91920221A EP 0560802 B2 EP0560802 B2 EP 0560802B2
- 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 72
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 70
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 64
- 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 64
- 239000008187 granular material Substances 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920001577 copolymer Polymers 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000005469 granulation Methods 0.000 claims abstract description 24
- 230000003179 granulation Effects 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 13
- 239000000470 constituent Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 31
- 239000002736 nonionic surfactant Substances 0.000 claims description 24
- 239000003599 detergent Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 12
- 150000001735 carboxylic acids Chemical class 0.000 claims description 11
- 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
- 238000001035 drying Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 229920005646 polycarboxylate Polymers 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
- -1 ethylene, propylene Chemical group 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
- 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
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000003138 primary alcohols Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007921 spray 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
- 239000004435 Oxo alcohol Substances 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
- 238000004364 calculation method Methods 0.000 description 3
- 238000007046 ethoxylation reaction Methods 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000007787 solid Substances 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
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 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
- 239000012459 cleaning agent Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 2
- 230000000694 effects Effects 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
- 239000010419 fine particle Substances 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
- 239000004615 ingredient Substances 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
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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 Polymers 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
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000001419 dependent effect 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
- 238000005516 engineering process Methods 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
- 239000012530 fluid 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
- 125000001165 hydrophobic group Chemical group 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
- 238000002360 preparation method Methods 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.
- European patent application 21 267 describes granules containing zeolites and Alkali silicates which have a particle size between 0.15 and 2 mm and a bulk density of 300 to Have 700 g / l. They are also suitable for adsorbing liquid detergent components, in particular of nonionic surfactants.
- a dry premix of zeolite and Alkali metal silicate (mixing ratio 1: 1 to 1: 8) sprayed with water and agglomerated in a granulator, whereupon the excess water to a residual content of less than 5 wt .-% Drying is removed.
- the main disadvantage is the high content of strongly alkaline-reacting alkali silicates, thus the 'use of these granules in neutral to weakly alkaline, for sensitive Textiles suitable detergents is severely restricted.
- European patent application 149 264 (Unilever) teaches that the adsorption of liquid detergent components, especially non-ionic ones Surfactants commercially available spray-dried zeolites or their mixtures with inorganic salts, such as Sodium sulfate.
- the bulk density of the relatively fine-particle spray products is in the range from 450 to 600 g / l, the particles having a size between 0.05 and 0.5 mm.
- German patent application 38 38 086 describes the production of zeolite and granules the sodium or potassium salts of polymeric or copolymeric carboxylic acids, the agglomeration or granulation with the addition of a granulating liquid and the agglomerate obtained up to Reaching a free-flowing granulate with a bulk density of 750 to 1000 g / l is dried.
- This is based on a homogeneous powdery mixture of zeolite and the salt of the (co) polymers Carboxylic acids and granulates them 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 not in dissolved form as part of the granulating liquid added because the amount of granulating liquid used is a critical factor and therefore exact must be dosed. Excessive amounts of granulating liquid lead to granules with a wide one Grain spectrum and an undesirably high coarse fraction (particle size above 2 mm in length) as well a lower bulk density.
- the invention relates to a method for producing granules from zeolite and sodium or Potassium salts of polymeric or copolymeric carboxylic acids, the granulation with the presence of zeolite and subsequent addition of a Granulation liquid takes place and the granules obtained until a free-flowing granulate is reached is dried with a bulk density of 750 to 1,000 g / l, which is characterized in that as Granulating liquid a mixture of water, surfactants and (co) polymeric carboxylates is used, wherein the content of surfactants in the granulating liquid is 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 is advantageously below 30%. Preferred zeolites if there are no particles larger than 30 ⁇ m, at least 80% consist of particles one Size of less than 10 microns and are in detergent quality.
- zeolite powder as such Spray-dried zeolite powder mixtures are also suitable (products from Degussa, trade name Wessalith), the small amounts of additives such as sodium sulfate, salts of nitrilotriacetic acid, sodium hydroxide, Contain 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, as an aqueous suspension and 95 to 70 wt .-%, based on the total amount Zeolite, presented 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 granulation stage can be reduced by these shares.
- the zeolite suspensions used contain usually about 1.5 to 3% by weight, based on the suspension, of stabilizers, including those Nonionic surfactants, anionic surfactants or polymeric polycarboxylates belong.
- the granules that after the process according to the invention are preferably 50 to 95% by weight, in particular 70 to 92% by weight, based on the dried granules, of water-containing zeolite.
- Carboxylic acids 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.
- copolymeric acids in in which one of the components has no acid function, in the interest of one is their proportion sufficient water solubility not more than 50 mole%, preferably less than 30 mole%.
- Copolymers of acrylic acid and methacrylic acid with maleic acid have proven particularly suitable. Copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight are particularly preferred. Contain maleic acid.
- the relative molecular weight of the homo- or copolymeric polycarboxylates is in generally 2,000 to 150,000, preferably 5,000 to 100,000.
- the polycarboxylates are preferred in the form of 30 to 50% by weight, in particular 35 to 45% by weight, aqueous solutions.
- this Solutions can, for the purpose of lowering the viscosity, water-soluble inorganic salts, for example Sodium sulfate, in amounts up to 10 wt .-%, based on the polycarboxylate added become.
- the polycarboxylates are partially combined in powder form presented with the finely divided zeolite. It is preferred to have a maximum of 50% by weight and in particular to use a maximum of 40% by weight of the polymeric carboxylates in powder form.
- the commercially available salts (co-) polymer Powdered carboxylic acids often contain 5 to 15% by weight of moisture. This proportion of water is also included in the calculation of the water balance.
- the mathematical is Proportion of the salts in the preparation of the compositions or in the composition of the finished granules obtain anhydrous salt.
- the granules according to the invention contain the salts of the polymeric or copolymeric carboxylic acids preferably in amounts of 2 to 12 wt .-% and especially in amounts from 4 to 10% by weight.
- the granulating liquid contains at least water as a liquid component, at least polymer or copolymeric carboxylates as a fixed component and anionic and / or nonionic surfactants.
- the granulating liquid contains a mixture of water and liquid as a liquid component nonionic surfactants.
- the granulating liquid advantageously consists of 5 to 30% by weight of (co) polymeric Carboxylate, 10 to 75 wt .-% 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 wt .-% of nonionic surfactants or 10 to 40 wt .-% 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 oil or oleyl alcohol, or on primary alcohols (oxo alcohols) branched with 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 9 -C 13 alkylbenzenesulfonates, in particular C 12 alkylbenzenesulfonate, and sulfonates based on oleochemicals such as the esters of ⁇ -sulfofatty acids, the sulfo group being in its salt form (mono salt), e.g. B. the ⁇ -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 content is included in the calculation of the introduced liquid components, or the amount of liquid introduced into the pelletizing stage can this proportion can be reduced.
- the moist, non-dried granules 100 parts by weight of zeolite are calculated as an anhydrous substance, or to a homogeneous mixture of zeolite and optionally in powder form submitted salt of the polymeric or copolymeric carboxylic acid granulating liquid in the amount admixed that preferably 15 to 45 parts by weight, in particular 18 to 40 parts by weight, based on the moist granules, are present in liquid components.
- the proportion of free, not in the form of water of crystallization or water bound in a similar way in the granulating liquid be small and solely dependent on the amount and concentration of the polymer or copolymeric carboxylate solution.
- 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 in free water.
- the granulation can be carried out batchwise or continuously in conventional mixing and granulating devices be performed.
- B. pelletizers which are arranged horizontally or consist of cylindrical containers inclined to the horizontal, one in the longitudinal axis with Mixing tools and conveyor blades equipped shaft rotates.
- the feeding of the granulating liquid can be done through the spray nozzle in the wall or on the high shaft.
- two consecutive mixers can be used first mixer the production of the dry or, if an aqueous zeolite suspension is used, wet premix and in the second mixer the granulation with the addition of surfactant and polycarboxylate Granulating liquid takes place.
- Continuous work is also possible in a mixer, wherein in a first mixing section either the powder streams and / or the powder streams and the zeolite suspension be combined and homogenized and the mixture after further transport in one subsequent mixing section treated with the surfactant and polycarboxylate-containing granulating liquid and is granulated.
- the granulating liquid is preferably sprayed onto the fluid in motion Sprayed mixture.
- the granulation is generally normal to moderately elevated temperatures, preferably at temperatures between 20 and 40 ° C and generally requires 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 also after the granules have been discharged from the mixer, for example in a vibratory conveyor, a free fall dryer or in a thin layer on a conveyor belt.
- a third mixing section e.g. B. a fluidized bed
- the drying is carried out until the water added in the granulation step to a level of less than 5% by weight, preferably less than 3% by weight, based in each case on the dried granules, is removed.
- the drying process still contains more water, originally with the zeolite or a non-anhydrous one inserted (co) polymeric salt were removed.
- Such "over-dried" granules can have application technology advantages, for example when added to detergents contain moisture-sensitive active ingredients.
- drainage of the zeolite should preferably be used not to be driven below a water content of 18% by weight, based on zeolite, in order to reduce the activity to avoid.
- the water content of the granules is expediently in a range in which the water binding capacity of the zeolite is largely saturated, d. H. where 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 tight packing and their small pore volume, their absorption capacity is for liquid or pasty detergent ingredients, especially nonionic surfactants and foam inhibitors, for example paraffin oil or silicone oil, something compared to specifically lighter carrier grains reduced, but is still 15 to a maximum of 20 wt .-% without significant impairment the flowability of the granules. This in view of the high packing density and if necessary already contained in the granules of nonionic surfactants still surprisingly high Adsorption capacity is sufficient for the usual areas of application, in particular for use as Compound component in detergents and cleaning agents, completely from.
- the granules obtained by the process according to the invention are distinguished by a grain spectrum in which the fine fraction (particle diameter less than 0.1 mm) generally less than 10% and the Coarse fraction (particle diameter greater than 2 mm) is generally up to 40%.
- the Fines content less than 7% and is in particular 0 to 5%, while the content of Coarse fractions are preferably 2 to 32%.
- the coarse and fine particles are sieved.
- the rough shares are ground and mixed into the product, while the fines or dust in the Granulation can be attributed.
- the granules disintegrate regardless of their high packing density and their high Content of water-insoluble components in cold water quickly and completely and leave in no residue is left in the washing-up devices of washing machines, d. H. they have a very good one Ein HughesFC. This advantageous property is also evident after impregnation with nonionic Surfactants and in a mixture with other powder detergent components are noticeable.
- 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, in powder form or as a mixture of 94 to 73 % By weight of powder and 6 to 27% by weight, based in each case on zeolite, of an aqueous suspension 2 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 of anionic surfactants, in particular alkylbenzenesulfonate and fatty alcohol sulfate.
- the granules can be impregnated with liquid detergent ingredients that are on others Because of no or only loss of effectiveness in conventional powder or granular detergents and cleaning agents can be incorporated.
- liquid detergent ingredients that are on others Because of no or only loss of effectiveness in conventional powder or granular detergents and cleaning agents can be incorporated.
- foam inhibitors especially paraffin hydrocarbons, Silicones, silicone resins and bis-acyl-alkylenediamines derived from long-chain fatty acids as well as their mixtures.
- Other adsorbable active ingredients are fatty acid alkylolamides and cationic Plasticizers, such as long-chain fatty quaternary ammonium salts, and also fat-dissolving solvents like terpenes.
- the granules are preferred as carrier grains for liquid nonionic Surfactants and foam inhibitors used.
- Those components that are considered “liquid” are those Room temperature or at the processing temperature between 25 ° C and about 80 ° C, preferably up to 75 ° C, in liquid form. It can be advantageous to use components that already exist, for example are liquid at room temperature but have an undesirably high viscosity before impregnation to heat the carrier grains.
- Suitable nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic residue and 3 to 20 glycol ether groups. These include ethoxylation products of alcohols, vicinal diols, amines, thio alcohols, fatty acid amides and fatty acids. Block polymers also come from ethylene oxide and propylene oxide, which are sold under the name Pluronic (BASF / Wyandotte) are customary in the trade. Furthermore, alkyl glycosides or alkyl polyglycosides and their Mixtures with the ethoxylation products mentioned can be used.
- Preferred nonionic surfactants which can be adsorbed on the granules and with them together as a free-flowing mixture are derived from alcohols with 12 to 18 carbon atoms, which saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical).
- Your Reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or in water dispersible mixtures of compounds with different degrees of alkoxylation, the following specified number of EO or PO groups corresponds to a statistical mean.
- Examples of preferred ethoxylated fatty alcohols are C 12 -C 18 coco alcohols with 3 to 12 EO, C 16 -C 18 tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO available from other native fatty alcohol mixtures -Distribution. From the series of ethoxylated oxo alcohols, for example those of the composition C 12 -C 15 with 5 to 10 EO and C 14 -C 15 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 application of the liquid, optionally heated additives, in particular the application of the nonionic surfactants and the foam inhibitors on the granules can be added by mixing, preferably Spraying take place, the carrier material expediently by suitable mixing devices in Movement is kept. Further treatment of the granular adsorbate is not necessary. However, leaving the product to rest for several hours at high levels of applied liquid material may be useful, 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 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 mixed with the granular or powder detergent, for example a tower spray powder and its mixtures with other powder components, such as persalt, enzyme granules, Bleach activators or defoamers containing granules, combined in a known manner and be mixed.
- the detergents contain general 10 to 40 wt .-% of the additive according to the invention.
- the granulation was carried out in a mixing granulator consisting of a horizontally arranged one cylindrical mixer with a rotating shaft rotating in the central axis and equipped with mixing elements (Ploughshare mixer, type Lödige) with a capacity of 130 l and a connected Knife mill operated at a speed of 1,200 to 1,500 revolutions / minute.
- mixing elements Ploughshare mixer, type Lödige
- the pulverulent constituents and optionally the aqueous zeolite suspension were mixed granulators submitted and processed into a homogeneous mixture. After mixing, this is about 10 seconds took 1 minute, the granulating liquid was sprayed in the course of 1 to 5 minutes by means of nozzles sprayed in and the mixture was granulated for a further 1 to 3 minutes with constant mixing.
- Granules leaving the mixer were placed in a fluidized bed with hot, flowing dry gases (70 ° C.) dried.
- the fine fraction particle diameter less 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% by weight H 2 O, sprayed.
- the granules obtained after drying contained 88.1% by weight of anhydrous zeolite, which had been introduced 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 C 12 -C 18 fatty alcohol with 7 EO.
- the bulk density was 870 g / l; the gross share was 2.9%.
- zeolite based on anhydrous substance
- 47.5 parts by weight of one Granulating liquid consisting of 22.7% by weight Sokalan CP5, 20.5% by weight sodium dodecylbenzenesulfonate and 56.8 wt% water.
- the granules obtained after drying contained 85.9% by weight water-containing zeolite, which had been presented as a powder, 7.4% by weight of Sokalan CP5 and 6.7% by weight Dodecylbenzenesulfonate.
- the bulk density before sieving was 860 g / l; the bulk was 30.2%.
- zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 44 parts by weight of one Granulating liquid consisting of 11.25% by weight Sokalan CP5, 35.75% by weight sodium dodecylbenzenesulfonate and 53% by weight water.
- the granules obtained after drying contained 85.8% by weight water-containing zeolite, which was presented as a powder, 3.4 wt .-% Sokalan CP5 and 10.8 wt .-% Dodecylbenzenesulfonate.
- the bulk density 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 C 12 -C 18 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 wt .-% C 12 -C 18 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 indicated perfect induction, both as unblended powder and mixed with a powdered household detergent in a ratio of 1: 4.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Zeolith-Granulaten mit hohem Schüttgewicht, die ein ausgeprägtes Adsorptionsvermögen für flüssige Wirkstoffe besitzen.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.
Aus der deutschen Patentanmeldung 33 16 513 (Benckiser) sind bereits Granulate bekannt, die durch Sprühtrocknung von wäßrigen Aufschlämmungen hergestellt wurden und feinpulvrige Zeolithe und Salze von (co-)polymeren Carbonsäuren enthalten. Sie weisen ein Schüttgewicht von lediglich 560 bis 610 g/l auf. Granulate, die Zeolithe, Salze (co-)polymerer Carbonsäuren und zusätzlich geringe Mengen an Alkalimetallsilikaten enthalten und als Trägermaterial für flüssige Waschmittelbestandteile, insbesondere für nichtionische Tenside dienen, werden in der deutschen Patentanmeldung 34 44 960 beschrieben. Das Schüttgewicht dieser durch Sprühtrocknung hergestellten Granulate beträgt maximal 700 g/l und liegt vorzugsweise zwischen 500 und 650 g/l.From the German patent application 33 16 513 (Benckiser) granules are already known, which by Spray drying of aqueous slurries were made and fine powder zeolites and salts contain of (co) polymeric carboxylic acids. They have a bulk density of only 560 to 610 g / l. Granules, the zeolites, salts of (co) polymeric carboxylic acids and additionally small amounts of alkali metal silicates contain and as a carrier material for liquid detergent components, especially for nonionic Serving surfactants are described in German patent application 34 44 960. The bulk weight these granules produced by spray drying are at most 700 g / l and are preferably between 500 and 650 g / l.
Aus der europäischen Patentanmeldung 21 267 (PQ) sind Granulate mit einem Gehalt an Zeolithen und Alkalisilikaten bekannt, die eine Teilchengröße zwischen 0,15 und 2 mm und ein Schüttgewicht von 300 bis 700 g/l aufweisen. Sie eignen sich ebenfalls zum Adsorbieren flüssiger Waschmittelbestandteile, insbesondere von nichtionischen Tensiden. Zu ihrer Herstellung wird ein trockenes Vorgemisch aus Zeolith und Alkalimetallsilikat (Mischungsverhältnis 1:1 bis 1:8) in einem Granulator mit Wasser besprüht und agglomeriert, worauf das überschüssige Wasser bis auf einen Restanteil von weniger als 5 Gew.-% durch Trocknung entfernt wird. Nachteilig ist vor allem der hohe Gehalt an stark alkalisch reagierenden Alkalisilikaten, wodurch der' Einsatz dieser Granulate in neutral bis schwach alkalisch reagierenden, für empfindliche Textilien geeigneten Waschmitteln stark einschränkt ist. Außerdem lassen sich nach den Lehren dieses Dokumentes keine Schüttgewichte von über 700 g/l erzielen. Die europäische Patentanmeldung 149 264 (Unilever) lehrt, daß man zur Adsorption flüssiger Waschmittelbestandteile, insbesondere von nichtionischen Tensiden handelsübliche sprühgetrocknete Zeolithe bzw. deren Gemische mit anorganischen Salzen, wie Natriumsulfat, verwenden kann. Das Schüttgewicht der relativ feinteiligen Sprühprodukte liegt im Bereich von 450 bis 600 g/l, wobei die Teilchen eine Größe zwischen 0,05 und 0,5 mm aufweisen.European patent application 21 267 (PQ) describes granules containing zeolites and Alkali silicates are known which have a particle size between 0.15 and 2 mm and a bulk density of 300 to Have 700 g / l. They are also suitable for adsorbing liquid detergent components, in particular of nonionic surfactants. A dry premix of zeolite and Alkali metal silicate (mixing ratio 1: 1 to 1: 8) sprayed with water and agglomerated in a granulator, whereupon the excess water to a residual content of less than 5 wt .-% Drying is removed. The main disadvantage is the high content of strongly alkaline-reacting alkali silicates, thus the 'use of these granules in neutral to weakly alkaline, for sensitive Textiles suitable detergents is severely restricted. In addition, according to the teachings of this Do not achieve a bulk density of more than 700 g / l in the document. European patent application 149 264 (Unilever) teaches that the adsorption of liquid detergent components, especially non-ionic ones Surfactants commercially available spray-dried zeolites or their mixtures with inorganic salts, such as Sodium sulfate. The bulk density of the relatively fine-particle spray products is in the range from 450 to 600 g / l, the particles having a size between 0.05 and 0.5 mm.
Die deutsche Patentanmeldung 38 38 086 beschreibt die Herstellung von Granulaten aus Zeolith und den Natrium- oder Kalium-Salzen polymerer bzw. copolymerer Carbonsäuren, wobei die Agglomerierung bzw. Granulierung unter Zusatz einer Granulierflüssigkeit erfolgt und das erhaltene Agglomerat bis zum Erreichen eines gut rieselfähigen Granulates mit einem Schüttgewicht von 750 bis 1 000 g/l getrocknet wird. Dabei geht man von einer homogenen pulvrigen Mischung aus Zeolith und dem Salz der (co-)polymeren Carbonsäuren aus und granuliert diese in einer weiteren Misch- und Granulationsstufe unter Zusatz von Wasser, das vorzugsweise auf das in Bewegung gehaltene Pulvergemisch aufgesprüht wird. Die Polycarboxylate werden in fester Form vorgelegt und nicht in gelöster Form als Bestandteil der Granulierflüssigkeit zugesetzt, da die Einsatzmenge der Granulierflüssigkeit einen kritischen Faktor darstellt und daher exakt dosierbar sein muß. Zu hohe Mengen an Granulierflüssigkeit führen zu Granulaten mit einem breiten Kornspektrum und einem unerwünscht hohen Grobanteil (Teilchengröße oberhalb 2 mm Länge) sowie zu einem niedrigeren Schüttgewicht.German patent application 38 38 086 describes the production of zeolite and granules the sodium or potassium salts of polymeric or copolymeric carboxylic acids, the agglomeration or granulation with the addition of a granulating liquid and the agglomerate obtained up to Reaching a free-flowing granulate with a bulk density of 750 to 1000 g / l is dried. This is based on a homogeneous powdery mixture of zeolite and the salt of the (co) polymers Carboxylic acids and granulates them 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 not in dissolved form as part of the granulating liquid added because the amount of granulating liquid used is a critical factor and therefore exact must be dosed. Excessive amounts of granulating liquid lead to granules with a wide one Grain spectrum and an undesirably high coarse fraction (particle size above 2 mm in length) as well a lower bulk density.
Es wurde nun gefunden, daß die Menge an Granulierflüssigkeit einen wesentlich geringeren kritischen Faktor darstellt, so daß die (co-)polymeren Carboxylate als gelöster Bestandteil der Granulierflüssigkeit eingesetzt werden können, wenn bestimmte Verfahrensschritte eingehalten werden.It has now been found that the amount of granulating liquid is much less critical Represents factor, so that the (co) polymeric carboxylates as a dissolved component of the granulating liquid can be used if certain procedural steps are followed.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Granulaten aus Zeolith und Natriumoder Kaliumsalzen polymerer bzw. copolymerer Carbonsäuren, wobei die Granulierung unter vorlage von zeolith und anschließendem Zusatz einer Granulierflüssigkeit erfolgt und das erhaltene Granulat bis zum Erreichen eines gut rieselfähigen Granulats mit einem Schüttgewicht von 750 bis 1 000 g/l getrocknet wird, das dadurch gekennzeichnet ist, daß als Granulierflüssigkeit eine Mischung aus Wasser, Tensiden und (co-)polymeren Carboxylaten verwendet wird, wobei der Gehalt an Tensiden in der Granulierflüssigkeit mindestens 10 Gew.-% beträgt.The invention relates to a method for producing granules from zeolite and sodium or Potassium salts of polymeric or copolymeric carboxylic acids, the granulation with the presence of zeolite and subsequent addition of a Granulation liquid takes place and the granules obtained until a free-flowing granulate is reached is dried with a bulk density of 750 to 1,000 g / l, which is characterized in that as Granulating liquid a mixture of water, surfactants and (co) polymeric carboxylates is used, wherein the content of surfactants in the granulating liquid is at least 10% by weight.
Bei der Herstellung der Granulate geht man zweckmäßigerweise von sprühgetrocknetem, feinpulvrigem Zeolith, der im allgemeinen einen Wassergehalt von 17 bis 25 Gew.-% aufweist, aus. Geeignete Zeolithe sind solche vom Zeolith A-Typ. Brauchbar sind ferner Gemische aus Zeolith NaA und NaX, wobei der Anteil des Zeoliths NaX in derartigen Gemischen zweckmäßigerweise unter 30 % liegt. Bevorzugte Zeolithe weisen keine Teilchen mit einer Größe über 30 µm auf, bestehen zu wenigstens 80 % aus Teilchen einer Größe von weniger als 10 µm und liegen in Waschmittel-Qualität vor. Außer Zeolith-Pulver als solchem eignen sich auch sprühgetrocknete Zeolith-Pulvermischungen (Produkte der Firma Degussa, Handelsname Wessalith), die geringe Mengen an Zusatzstoffen wie Natriumsulfat, Salzen der Nitrilotriessigsäure, Natriumhydroxid, Carboxymethylcellulose, (co-)polymere Carboxylate oder nichtionischen Tensiden enthalten. In einer bevorzugten Ausführungsform wird ein Teil des Zeoliths in Form einer 45 bis 55 Gew.-%igen wäßrigen Suspension eingesetzt. Insbesondere werden 5 bis 30 Gew.-% an Zeolith, bezogen auf die Gesamtmenge Zeolith, als wäßrige Suspension und 95 bis 70 Gew.-%, bezogen auf die Gesamtmenge Zeolith, als Pulver vorgelegt. Dieser Wasseranteil sowie der Wassergehalt des pulverförmigen Zeoliths werden in die Berechnung der Wasserbilanz eingebracht; die in die Granulierstufe einzubringende Wassermenge kann um diese Anteile reduziert werden. Die eingesetzten Zeolith-Suspensionen enthalten zwar üblicherweise etwa 1,5 bis 3 Gew.-%, bezogen auf die Suspension, an Stabilisatoren, zu denen auch Niotenside, Aniontenside oder polymere Polycarboxylate gehören. Jedoch ist der Anteil dieser über die Suspension eingebrachten Wirkstoffe so gering, daß der erfindungsgemäße Effekt erst durch den Einsatz zusätzlicher Mengen an Tensiden und (co-)polymeren Carboxylaten erreicht wird. Die Granulate, die nach dem erfindungsgemäßen Verfahren hergestellt werden, enthalten vorzugsweise 50 bis 95 Gew.%, insbesondere 70 bis 92 Gew.-%, bezogen auf das getrocknete Granulat, an wasserhaltigem Zeolith.In the production of the granules, it is expedient to start with spray-dried, finely powdered Zeolite, which generally has a water content of 17 to 25% by weight. Suitable 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 is advantageously below 30%. Preferred zeolites if there are no particles larger than 30 µm, at least 80% consist of particles one Size of less than 10 microns and are in detergent quality. Except for zeolite powder as such Spray-dried zeolite powder mixtures are also suitable (products from Degussa, trade name Wessalith), the small amounts of additives such as sodium sulfate, salts of nitrilotriacetic acid, sodium hydroxide, Contain carboxymethyl cellulose, (co) polymeric carboxylates or nonionic surfactants. In In a preferred embodiment, part of the zeolite is in the form of a 45 to 55% by weight aqueous suspension used. In particular, 5 to 30 wt .-% of zeolite, based on the Total amount of zeolite, as an aqueous suspension and 95 to 70 wt .-%, based on the total amount Zeolite, presented 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 granulation stage can be reduced by these shares. The zeolite suspensions used contain usually about 1.5 to 3% by weight, based on the suspension, of stabilizers, including those Nonionic surfactants, anionic surfactants or polymeric polycarboxylates belong. However, the proportion of these is over Active ingredients introduced into the suspension are so low that the effect according to the invention can only be achieved through use additional amounts of surfactants and (co) polymeric carboxylates is achieved. The granules that after the process according to the invention are preferably 50 to 95% by weight, in particular 70 to 92% by weight, based on the dried granules, of water-containing zeolite.
Geeignete wasserlösliche Salze der in den Granulaten enthaltenen homopolymeren und/oder copolymeren Carbonsäuren, von denen die Natriumsalze bevorzugt werden, sind Polyacrylsäure, Polymethacrylsäure und Polymaleinsäure, Copolymere der Acrylsäure oder Methacrylsäure mit Maleinsäure oder Vinylethern wie Vinylmethylether bzw. Vinylethylether, ferner mit Vinylestern wie Vinylacetat oder Vinylpropionat, Acrylamid, Methacrylamid sowie mit Ethylen, Propylen oder Styrol. In solchen copolymeren Säuren, in denen eine der Komponenten keine Säurefunktion aufweist, beträgt deren Anteil im Interesse einer ausreichenden Wasserlöslichkeit nicht mehr als 50 Mol-%, vorzugsweise weniger als 30 Mol-%. Als besonders geeignet haben sich Copolymere der Acrylsäure bzw. Methacrylsäure mit Maleinsäure erwiesen. Insbesondere werden Copolymerisate bevorzugt, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Die relative Molekülmasse der homo- bzw. copolymeren Polycarboxylate beträgt im allgemeinen 2 000 bis 150 000, vorzugsweise 5 000 bis 100 000. Vorzugsweise werden die Polycarboxylate in Form 30 bis 50 Gew.-%iger, insbesondere 35 bis 45 Gew.-%iger wäßriger Lösungen eingesetzt. Diesen Lösungen können zum Zwecke der Viskositätserniedrigung wasserlösliche, anorganische Salze, beispielsweise Natriumsulfat, in Mengen bis zu 10 Gew.-%, bezogen auf eingesetztes Polycarboxylat, zugesetzt werden. In einer weiteren Ausführungsform werden die Polycarboxylate teilweise in pulvriger Form zusammen mit dem feinteiligen Zeolith vorgelegt. Dabei ist es bevorzugt, maximal 50 Gew.-% und insbesondere maximal 40 Gew.-% der polymeren Carboxylate in Pulverform einzusetzen. Die handelsüblichen Salze (co-)polymerer Carbonsäuren in pulvriger Form enthalten vielfach Feuchtigkeitsanteile von 5 bis 15 Gew.-%. Dieser Wasseranteil wird ebenfalls in die Berechnung der Wasserbilanz eingebracht. Rechnerisch ist der Anteil der Salze bei der Herstellung der Mittel bzw. bei der Zusammensetzung der fertigen Granulate auf wasserfreies Salz zu beziehen. Die erfindungsgemäßen Granulate enthalten die Salze der polymeren bzw. copolymeren Carbonsäuren vorzugsweise in Mengen von 2 bis 12 Gew.-% und insbesondere in Mengen von 4 bis 10 Gew.-%.Suitable water-soluble salts of the homopolymers and / or copolymers contained in the granules Carboxylic acids, 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. In such copolymeric acids, in in which one of the components has no acid function, in the interest of one is their proportion sufficient water solubility not more than 50 mole%, preferably less than 30 mole%. As Copolymers of acrylic acid and methacrylic acid with maleic acid have proven particularly suitable. Copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight are particularly preferred. Contain maleic acid. The relative molecular weight of the homo- or copolymeric polycarboxylates is in generally 2,000 to 150,000, preferably 5,000 to 100,000. The polycarboxylates are preferred in the form of 30 to 50% by weight, in particular 35 to 45% by weight, aqueous solutions. this Solutions can, for the purpose of lowering the viscosity, water-soluble inorganic salts, for example Sodium sulfate, in amounts up to 10 wt .-%, based on the polycarboxylate added become. In a further embodiment, the polycarboxylates are partially combined in powder form presented with the finely divided zeolite. It is preferred to have a maximum of 50% by weight and in particular to use a maximum of 40% by weight of the polymeric carboxylates in powder form. The commercially available salts (co-) polymer Powdered carboxylic acids often contain 5 to 15% by weight of moisture. This proportion of water is also included in the calculation of the water balance. The mathematical is Proportion of the salts in the preparation of the compositions or in the composition of the finished granules obtain anhydrous salt. The granules according to the invention contain the salts of the polymeric or copolymeric carboxylic acids preferably in amounts of 2 to 12 wt .-% and especially in amounts from 4 to 10% by weight.
Die Granulierflüssigkeit enthält zumindest Wasser als flüssigen Bestandteil, zumindest polymere oder copolymere Carboxylate als festen Bestandteil sowie anionische und/oder nichtionische Tenside. Vorzugsweise enthält die Granulierflüssigkeit als flüssigen Bestandteil eine Mischung aus Wasser und flüssigen nichtionischen Tensiden. Mit Vorteil besteht die Granulierflüssigkeit zu 5 bis 30 Gew.-% aus (co-)polymerem Carboxylat, zu 10 bis 75 Gew.-% aus anionischen und/oder nichtionischen Tensiden und zu 7 bis 70 Gew.-% aus Wasser. Insbesondere besteht die Granulierflüssigkeit zu 10 bis 25 Gew.-% aus (co-)polymerem Carboxylat, zu 10 bis 65 Gew.-% aus Niotensiden oder zu 10 bis 40 Gew.-% aus Aniontensiden und zu 10 bis 68 Gew.-% aus Wasser.The granulating liquid contains at least water as a liquid component, at least polymer or copolymeric carboxylates as a fixed component and anionic and / or nonionic surfactants. Preferably The granulating liquid contains a mixture of water and liquid as a liquid component nonionic surfactants. The granulating liquid advantageously consists of 5 to 30% by weight of (co) polymeric Carboxylate, 10 to 75 wt .-% of anionic and / or nonionic surfactants and 7 to 70 % By weight of water. In particular, the granulating liquid consists of 10 to 25% by weight of (co) polymeric Carboxylate, 10 to 65 wt .-% of nonionic surfactants or 10 to 40 wt .-% of anionic surfactants and 10 to 68% by weight of water.
Als flüssige nichtionische Tenside werden vorzugsweise ethoxylierte und/oder propoxylierte Fettalkohole mit Bevorzugung der ethoxylierten Fettalkohole eingesetzt, insbesondere Anlagerungsprodukte von 2 bis 7 Mol Ethylenoxid (EO) an lineare primäre Alkohole, wie z. B. an Kokos-, Talgfett- oder Oleylalkohol, oder an in 2-Stellung methylverzweigte primäre Alkohole (Oxoalkohole). Insbesondere werden C12-C14-Alkohole mit 3 EO oder 4 EO, C13-C15-Alkohole mit 3, 5 oder 7 EO, C12-C18-Alkohole mit 2, 3, 5 oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-C14-Alkohol mit 3 EO und C12-C18-Alkohol mit 5 EO eingesetzt. Bevorzugte ethoxylierte Fettalkohole sind weiterhin solche mit einer eingeengten Homologenverteilung (narrow range ethoxylates, nre).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 oil or oleyl alcohol, or on primary alcohols (oxo alcohols) branched with methyl in the 2-position. In particular, 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).
Die wasserlöslichen anionischen Tenside sind Alkalimetallsalze, Natrium- oder Kalium-Salze, aus der Klasse der Sulfonate und der Sulfate. Als Tenside vom Sulfonat-Typ kommen vorzugsweise C9-C13-Alkylbenzolsulfonate, insbesondere C12-Alkylbenzolsulfonat, und Sulfonate auf fettchemischer Basis wie die Ester von α-Sulfofettsäuren, wobei die Sulfogruppe in ihrer Salz-Form vorliegt (Monosalz), z. B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren in Betracht. Geeignet sind außerdem auch die biologisch gut abbaubaren Alkansulfonate, die aus C12-C18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxydation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Die Sulfonatgruppe ist über die gesamte Kohlenstoffkette statistisch verteilt, wobei die sekundären Alkansulfonate überwiegen. Geeignete Tenside vom Sulfat-Typ sind beispielsweise die gegebenenfalls ethoxylierten Schwefelsäuremonoester aus primären Alkoholen natürlichen und synthetischen Ursprungs, d. h. aus Fettalkoholen, wie z. B. Kokosfettalkohol, Talgfettalkohol, Oleylalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol, oder den C10-C20-Oxoalkoholen, sowie die Schwefelsäuremonoester sekundärer Alkohole dieser Kettenlänge, wobei die Schwefelsäuremonoester der primären Alkohole auf fettchemischer Basis bevorzugt sind. Die festen, wasserlöslichen Aniontenside können in Pulverform oder in Pastenform in die flüssigen Bestandteile der Granulierflüssigkeit eingearbeitet werden.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 9 -C 13 alkylbenzenesulfonates, in particular C 12 alkylbenzenesulfonate, and sulfonates based on oleochemicals such as the esters of α-sulfofatty acids, the sulfo group being in its salt form (mono salt), e.g. B. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids into consideration. Also suitable are the readily biodegradable alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating. 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. coconut fatty alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, as well as the sulfuric acid monoesters of secondary alcohols of this chain length, the sulfuric acid monoesters of the primary alcohols based on oleochemicals being preferred. The solid, water-soluble anionic surfactants can be incorporated in the liquid constituents of the granulating liquid in powder form or in paste form.
Dabei wird im Falle des Einsatzes wäßriger Tensidpasten der Nasseranteil in die Berechnung der flüssigen Bestandteile eingebracht, bzw. die in die Granulierstufe eingebrachte Flüssigkeitsmenge kann um diesen Anteil reduziert werden.If aqueous surfactant pastes are used, the wet content is included in the calculation of the introduced liquid components, or the amount of liquid introduced into the pelletizing stage can this proportion can be reduced.
Zur Herstellung der feuchten, nicht getrockneten Granulate wird zu 100 Gew.-Teilen Zeolith, berechnet als wasserfreie Substanz, oder zu einer homogenen Mischung aus Zeolith und gegebenenfalls in Pulverform vorgelegtem Salz der polymeren bzw. copolymeren Carbonsäuren Granulierflüssigkeit in der Menge zugemischt, daß vorzugsweise 15 bis 45 Gew.-Teile, insbesondere 18 bis 40 Gew.-Teile, bezogen auf das feuchte Granulat, an flüssigen Bestandteilen vorhanden sind. Dabei kann der Anteil an zugesetztem freiem, nicht als Kristallwasser, oder in vergleichbarer Form gebundenem Wasser in der Granulierflüssigkeit sehr gering und allein abhängig sein von der Menge und der Konzentration der eingesetzten polymeren bzw. copolymeren Carboxylat-Lösung. Vorzugsweise enthält die Granulierflüssigkeit jedoch mindestens 2 Gew.-Teile, beispielsweise 5 bis 35 Gew.-Teile und insbesondere 5 bis 25 Gew.-Teile, bezogen auf das feuchte Granulat, an freiem Wasser.To produce the moist, non-dried granules, 100 parts by weight of zeolite are calculated as an anhydrous substance, or to a homogeneous mixture of zeolite and optionally in powder form submitted salt of the polymeric or copolymeric carboxylic acid granulating liquid in the amount admixed that preferably 15 to 45 parts by weight, in particular 18 to 40 parts by weight, based on the moist granules, are present in liquid components. The proportion of free, not in the form of water of crystallization or water bound in a similar way in the granulating liquid be small and solely dependent on the amount and concentration of the polymer or copolymeric carboxylate solution. However, 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 in free water.
Die Granulierung kann in üblichen Misch- und Granuliervorrichtungen diskontinuierlich oder kontinuierlich durchgeführt werden. Geeignet sind z. B. Granuliervorrichtungen, die aus einem horizontal angeordneten oder gegen die Horizontale geneigten, zylindrischen Behälter bestehen, in deren Längsachse eine mit Mischwerkzeugen und Förderschaufeln ausgerüstete Welle rotiert. Die Zuführung der Granulierflüssigkeit kann durch die in der Wandung oder an der hohen Welle angebrachte Sprühdüse erfolgen. Sofern kontinuierlich gearbeitet wird, können zwei hintereinander geschaltete Mischer verwendet werden, wobei im ersten Mischer die Herstellung des trockenen oder, falls eine wäßrige Zeolith-Suspension eingesetzt wird, feuchten Vorgemisches und im zweiten Mischer die Granulierung unter Zusatz der Tensid- und Polycarboxylat-haltigen Granulierflüssigkeit erfolgt. Ein kontinuierliches Arbeiten ist auch in einem Mischer möglich, wobei in einer ersten Mischstrecke entweder die Pulverströme und/oder die Pulverströme und die Zeolith-Suspension vereinigt und homogenisiert werden und das Gemisch nach dem Weitertransport in einer nachfolgenden Mischstrecke mit der Tensid- und Polycarboxylat-haltigen Granulierflüssigkeit behandelt und granuliert wird. Vorzugsweise wird die Granulierflüssigkeit mittels Düsen auf das in Bewegung gehaltene Gemisch aufgesprüht. Die Granulierung wird im allgemeinen bei normalen bis mäßig erhöhten Temperaturen, vorzugsweise bei Temperaturen zwischen 20 und 40°C durchgeführt und erfordert im allgemeinen eine Zeit von 5 bis 15 Minuten.The granulation can be carried out batchwise or continuously in conventional mixing and granulating devices be performed. Are suitable for. B. pelletizers, which are arranged horizontally or consist of cylindrical containers inclined to the horizontal, one in the longitudinal axis with Mixing tools and conveyor blades equipped shaft rotates. The feeding of the granulating liquid can be done through the spray nozzle in the wall or on the high shaft. Provided If you work continuously, two consecutive mixers can be used first mixer the production of the dry or, if an aqueous zeolite suspension is used, wet premix and in the second mixer the granulation with the addition of surfactant and polycarboxylate Granulating liquid takes place. Continuous work is also possible in a mixer, wherein in a first mixing section either the powder streams and / or the powder streams and the zeolite suspension be combined and homogenized and the mixture after further transport in one subsequent mixing section treated with the surfactant and polycarboxylate-containing granulating liquid and is granulated. The granulating liquid is preferably sprayed onto the fluid in motion Sprayed mixture. The granulation is generally normal to moderately elevated temperatures, preferably at temperatures between 20 and 40 ° C and generally requires 5 to 15 minutes.
Das Nachtrocknen kann durch Einleiten heißer Gase in einer dritten Mischstrecke, z. B. einer Wirbelschicht, oder auch nach dem Austragen der Granulate aus dem Mischer beispielsweise in einer Rüttelstrekke, einem Freifalltrockner oder auch in dünner Schicht auf einem Transportband erfolgen. Bevorzugt ist die Trocknung in einer Wirbelschicht, wobei die Temperatur des Granulats vorzugsweise zwischen 60 und 85°C und insbesondere zwischen 65 bis 80°C liegt. Dabei wird die Trocknung so weit durchgeführt, bis das in der Granulationsstufe zugesetzte Wasser bis auf einen Anteil von weniger als 5 Gew.-%, vorzugsweise weniger als 3 Gew.-%, jeweils bezogen auf das getrocknete Granulat, entfernt ist. Zusätzlich können bei der Trocknung noch weitere Wasseranteile, die ursprünglich mit dem Zeolith bzw. einem nicht wasserfrei eingesetzten (co-)polymeren Salz eingebracht wurden, entfernt werden. Derartige "übertrocknete" Granulate können anwendungstechnische Vorteile aufweisen, beispielsweise beim Zusatz zu Waschmitteln, die feuchtigkeitsempfindliche Wirkstoffe enthalten. Vorzugsweise sollte jedoch die Entwässerung des Zeoliths nicht unter einen Wassergehalt von 18 Gew.-%, bezogen auf Zeolith, getrieben werden, um eine Aktivitätsverminderung zu vermeiden. Zweckmäßigerweise liegt der Wassergehalt der Granulate in einem Bereich, bei dem das Wasserbindungsvermögen des Zeoliths weitgehend abgesättigt ist, d. h. bei dem der Zeolith einen Wassergehalt von insgesamt 19 bis 22 Gew.-% besitzt.The drying can be carried out by introducing hot gases in a third mixing section, e.g. B. a fluidized bed, or also after the granules have been discharged from the mixer, for example in a vibratory conveyor, a free fall dryer or in a thin layer on a conveyor belt. The is preferred Drying in a fluidized bed, the temperature of the granules preferably 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 step to a level of less than 5% by weight, preferably less than 3% by weight, based in each case on the dried granules, is removed. In addition, at the drying process still contains more water, originally with the zeolite or a non-anhydrous one inserted (co) polymeric salt were removed. Such "over-dried" granules can have application technology advantages, for example when added to detergents contain moisture-sensitive active ingredients. However, drainage of the zeolite should preferably be used not to be driven below a water content of 18% by weight, based on zeolite, in order to reduce the activity to avoid. The water content of the granules is expediently in a range in which the water binding capacity of the zeolite is largely saturated, d. H. where the zeolite has a total water content of 19 to 22% by weight.
Die Granulate besitzen vorzugsweise ein Schüttgewicht von 780 bis 980 g/l, insbesondere von 800 bis 950 g/l. Aufgrund ihrer dichten Packung und ihres geringen Porenvolumens ist ihr Aufnahmevermögen für flüssige bzw. pastenförmige Waschmittelbestandteile, insbesondere nichtionische Tenside und Schauminhibitoren, beispielsweise Paraffinöl oder Silikonöl, gegenüber spezifisch leichteren Trägerkörnern etwas vermindert, beträgt jedoch immer noch 15 bis maximal 20 Gew.-% ohne nennenswerte Beeinträchtigung der Rieselfähigkeit der Granulate. Dieses angesichts der hohen Packungsdichte und des gegebenenfalls bereits enthaltenen Gehalts der Granulate an nichtionischen Tensiden immer noch überraschend hohe Adsorptionsvermögen reicht für die üblichen Anwendungsgebiete, insbesondere für einen Einsatz als Mischungskomponente in Wasch- und Reinigungsmitteln, vollkommen aus.The granules preferably have a bulk density of 780 to 980 g / l, in particular from 800 to 950 g / l. Due to their tight packing and their small pore volume, their absorption capacity is for liquid or pasty detergent ingredients, especially nonionic surfactants and foam inhibitors, for example paraffin oil or silicone oil, something compared to specifically lighter carrier grains reduced, but is still 15 to a maximum of 20 wt .-% without significant impairment the flowability of the granules. This in view of the high packing density and if necessary already contained in the granules of nonionic surfactants still surprisingly high Adsorption capacity is sufficient for the usual areas of application, in particular for use as Compound component in detergents and cleaning agents, completely from.
Die durch das erfindungsgemäße Verfahren erhaltenen Granulate zeichnen sich durch ein Kornspektrum aus, in dem der Feinanteil (Teilchendurchmesser kleiner 0,1 mm) im allgemeinen unter 10 % und der Grobanteil (Teilchendurchmesser größer 2 mm) im allgemeinen bis 40 % beträgt. Vorzugsweise ist der Gehalt an Feinanteilen kleiner als 7 % und beträgt insbesondere 0 bis 5 %, während der Gehalt an Grobanteilen vorzugsweise 2 bis 32 % beträgt. Die Grob- und Feinanteile werden abgesiebt. Die Grobanteile werden gemahlen und dem Produkt zugemischt, während die Feinanteile bzw. der Staub in die Granulation zurückgeführt werden.The granules obtained by the process according to the invention are distinguished by a grain spectrum in which the fine fraction (particle diameter less than 0.1 mm) generally less than 10% and the Coarse fraction (particle diameter greater than 2 mm) is generally up to 40%. Preferably, the Fines content less than 7% and is in particular 0 to 5%, while the content of Coarse fractions are preferably 2 to 32%. The coarse and fine particles are sieved. The rough shares are ground and mixed into the product, while the fines or dust in the Granulation can be attributed.
Überraschenderweise zerfallen die Granulate ungeachtet ihrer hohen Packungsdichte und ihres hohen Gehaltes an wasserunlöslichen Bestandteilen in kaltem Wasser schnell und vollständig und hinterlassen in den Einspülvorrichtungen von Waschautomaten keine Rückstände, d. h. sie besitzen ein sehr gutes Einspülvermögen. Diese vorteilhafte Eigenschaft macht sich auch nach dem Imprägnieren mit nichtionischen Tensiden sowie im Gemisch mit anderen pulverförmigen Waschmittelkomponenten bemerkbar.Surprisingly, the granules disintegrate regardless of their high packing density and their high Content of water-insoluble components in cold water quickly and completely and leave in no residue is left in the washing-up devices of washing machines, d. H. they have a very good one Einspülvermögen. This advantageous property is also evident after impregnation with nonionic Surfactants and in a mixture with other powder detergent components are noticeable.
In einer bevorzugten Ausführungsform enthalten die Granulate 2 bis 25 Gew.-% an Tensiden und insbesondere 4 bis 20 Gew.-% an anionischen und/oder nichtionischen Tensiden. Besonders vorteilhafte Granulate enthalten 75 bis 90 Gew.-% Zeolith, der in Pulverform oder als eine Mischung aus 94 bis 73 Gew.-% Pulver und 6 bis 27 Gew.-%, jeweils bezogen auf Zeolith, einer wäßrigen Suspension vorgelegt wurde, 2 bis 10 Gew.-% Natriumsalz eines Copolymeren aus Acrylsäure und Maleinsäure und 4 bis 20 Gew.-% flüssige Niotenside. In einer weiteren bevorzugten Ausführungsform enthalten die Granulate Zeolith wie oben, 3 bis 8 Gew.-% Natriumsalz eines Copolymeren aus Acrylsäure und Maleinsäure und 6 bis 11 Gew.-% Aniontenside, insbesondere Alkylbenzolsulfonat und Fettalkoholsulfat.In a preferred embodiment, 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, in powder form or as a mixture of 94 to 73 % By weight of powder and 6 to 27% by weight, based in each case on zeolite, of an aqueous suspension 2 to 10% by weight sodium salt of a copolymer of acrylic acid and maleic acid and 4 to 20 % By weight liquid nonionic surfactants. In a further preferred embodiment, 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 of anionic surfactants, in particular alkylbenzenesulfonate and fatty alcohol sulfate.
Die Granulate können mit flüssigen Waschmittelbestandteilen imprägniert werden, die auf anderen Wegen nicht oder nur unter Wirkungsverlust in übliche pulverförmige bzw. granulare Wasch- und Reinigungsmittel eingearbeitet werden können. Hierzu zählen Schauminhibitoren, insbesondere Paraffinkohlenwasserstoffe, Silikone, Silikonharze und von langkettigen Fettsäuren abgeleitete Bis-Acyl-Alkylendiamine sowie deren Gemische. Weitere adsorbierbare Wirkstoffe sind Fettsäurealkylolamide und kationische Weichmacher, wie langkettige Fettreste aufweisende quartäre Ammoniumsalze, ferner fettlösende Lösungsmittel wie Terpene. Bevorzugt werden die Granulate jedoch als Trägerkörner für flüssige nichtionische Tenside und Schauminhibitoren eingesetzt. Als "flüssig" werden diejenigen Bestandteile angesehen, die bei Raumtemperatur oder bei der Bearbeitungstemperatur zwischen 25 ° C und etwa 80 ° C, vorzugsweise bis 75 ° C, in flüssiger Form vorliegen. Dabei kann es von Vorteil sein, Bestandteile, die beispielsweise bereits bei Raumtemperatur flüssig sind, aber eine unerwünscht hohe Viskosität aufweisen, vor der Imprägnierung der Trägerkörner zu erwärmen.The granules can be impregnated with liquid detergent ingredients that are on others Because of no or only loss of effectiveness in conventional powder or granular detergents and cleaning agents can be incorporated. These include foam inhibitors, especially paraffin hydrocarbons, Silicones, silicone resins and bis-acyl-alkylenediamines derived from long-chain fatty acids as well as their mixtures. Other adsorbable active ingredients are fatty acid alkylolamides and cationic Plasticizers, such as long-chain fatty quaternary ammonium salts, and also fat-dissolving solvents like terpenes. However, the granules are preferred as carrier grains for liquid nonionic Surfactants and foam inhibitors used. Those components that are considered "liquid" are those Room temperature or at the processing temperature between 25 ° C and about 80 ° C, preferably up to 75 ° C, in liquid form. It can be advantageous to use components that already exist, for example are liquid at room temperature but have an undesirably high viscosity before impregnation to heat the carrier grains.
Geeignete nichtionische Tenside sind Alkoxylierungsprodukte mit 10 bis 20 Kohlenstoffatomen im hydrophoben Rest und 3 bis 20 Glykolethergruppen. Hierzu zählen Ethoxylierungsprodukte von Alkoholen, vicinalen Diolen, Aminen, Thioalkoholen, Fettsäureamiden und Fettsäuren. Ebenso kommen auch Blockpolymere aus Ethylenoxid und Propylenoxid, die unter der Bezeichnung Pluronic (Firma BASF/Wyandotte) handelsüblich sind, in Betracht. Weiterhin können Alkylglykoside bzw. Alkylpolyglykoside sowie deren Gemische mit den genannten Ethoxylierungsprodukten verwendet werden.Suitable nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic residue and 3 to 20 glycol ether groups. These include ethoxylation products of alcohols, vicinal diols, amines, thio alcohols, fatty acid amides and fatty acids. Block polymers also come from ethylene oxide and propylene oxide, which are sold under the name Pluronic (BASF / Wyandotte) are customary in the trade. Furthermore, alkyl glycosides or alkyl polyglycosides and their Mixtures with the ethoxylation products mentioned can be used.
Bevorzugte nichtionische Tenside, die an dem Granulat adsorbiert sein können und mit diesen zusammen als rieselfähiges Gemisch vorliegen, leiten sich von Alkoholen mit 12 bis 18 C-Atomen ab, die gesättigt oder olefinisch ungesättigt, linear oder in 2-Stellung methylverzweigt (Oxo-Rest) sein können. Ihre Umsetzungsprodukte mit Ethylenoxid (EO) bzw. Propylenoxid (PO) sind wasserlösliche bzw. in Wasser dispergierbare Gemische von Verbindungen mit unterschiedlichem Alkoxylierungsgrad, wobei die im folgenden angegebene Anzahl der EO- bzw. PO-Gruppen einem statistischem Mittelwert entspricht.Preferred nonionic surfactants, which can be adsorbed on the granules and with them together as a free-flowing mixture are derived from alcohols with 12 to 18 carbon atoms, which saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical). Your Reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or in water dispersible mixtures of compounds with different degrees of alkoxylation, the following specified number of EO or PO groups corresponds to a statistical mean.
Beispiele für bevorzugte ethoxylierte Fettalkohole sind C12-C18-Kokosalkohole mit 3 bis 12 EO, C16-C18-Talgalkohol mit 4 bis 16 EO, Oleylalkohol mit 4 bis 12 EO sowie aus anderen nativen Fettalkoholgemischen erhältliche Ethoxylierungsprodukte entsprechender Ketten- und EO-Verteilung. Aus der Reihe der ethoxylierten Oxoalkohole sind beispielsweise solche der Zusammensetzung C12-C15 mit 5 bis 10 EO und C14-C15 mit 6 bis 12 EO geeignet. Weiterhin sind Alkoxylate geeignet, die EO-Gruppen und PO-Gruppen enthalten, beispielsweise C12-C18-Alkohole der Formel R-(PO)a-(EO)b bzw. R-(EO)b-(PO)c, worin a Zahlen von 1 bis 3, b Zahlen von 5 bis 20 und c Zahlen von 1 bis 10 bedeuten, wobei b größer als c sein soll.Examples of preferred ethoxylated fatty alcohols are C 12 -C 18 coco alcohols with 3 to 12 EO, C 16 -C 18 tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO available from other native fatty alcohol mixtures -Distribution. From the series of ethoxylated oxo alcohols, for example those of the composition C 12 -C 15 with 5 to 10 EO and C 14 -C 15 with 6 to 12 EO are suitable. Also suitable are 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.
Das Aufbringen der flüssigen, gegebenenfalls erwärmten Zusatzstoffe, insbesondere das Aufbringen der nichtionischen Tenside und der Schauminhibitoren auf das Granulat kann durch Zumischen, vorzugsweise Aufsprühen erfolgen, wobei das Trägermaterial zweckmäßigerweise durch geeignete Mischvorrichtungen in Bewegung gehalten wird. Eine weitere Nachbehandlung des körnigen Adsorbates ist nicht erforderlich. Allerdings kann ein mehrstündiges Ruhenlassen des Produktes bei hohen Gehalten an aufgebrachtem flüssigen Material zweckmäßig sein, da dessen Diffusion in das Korninnere einige Zeit in Anspruch nimmt. Die Behandlung der Granulate mit den flüssigen Zusatzstoffen führt zu einem weiteren Anstieg des Schüttgewichtes, das bis auf Werte von über 1 000 g/l ansteigen kann.The application of the liquid, optionally heated additives, in particular the application of the nonionic surfactants and the foam inhibitors on the granules can be added by mixing, preferably Spraying take place, the carrier material expediently by suitable mixing devices in Movement is kept. Further treatment of the granular adsorbate is not necessary. However, leaving the product to rest for several hours at high levels of applied liquid material may be useful, 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 Bulk density, which can rise to values of over 1 000 g / l.
Nach dem Aufbringen des flüssigen Zusatzstoffes können die Körner gegebenenfalls noch mit einem feinteiligen Pulver als Puderungsmittel bestäubt bzw. oberflächlich beschichtet werden. Hierdurch kann die bei hohen, 15 % übersteigenden Gehalten an nichtionischen Tensiden die Rieselfähigkeit der Granulate verbessert und das Schüttgewicht geringfügig erhöht werden. Geeignete Puderungsmittel weisen eine Korngröße von 0,001 bis höchstens 0,1 mm, vorzugsweise von weniger als 0,05 mm auf und können in Anteilen von 0,03 bis 3, vorzugsweise 0,05 bis 2 Gew.-%, bezogen auf das mit Zusatzstoff beladene Adsorptionsmittel, angewendet werden. In Frage kommen beispielsweise feinpulvrige Zeolithe, Kieselsäureaerogel (Aerosil(R)), farblose oder farbige Pigmente, wie Titandioxid. Im allgemeinen ist eine solche Nachbehandlung jedoch überflüssig, zumal durch sie die Lösungseigenschaften nicht verbessert werden.After the application of the liquid additive, the grains can optionally be dusted with a finely divided powder as powdering agent or coated on the surface. As a result, the free-flowing properties of the granules can be improved and the bulk density can be increased slightly if the content of nonionic surfactants exceeds 15%. 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. For example, 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.
Die Waschmitteladditive können mit dem körnigen bzw. pulverförmigen Waschmittel, beispielsweise einem Turmsprühpulver sowie dessen Gemischen mit weiteren Pulverkomponenten, wie Persalze, Enzymgranulate, Bleichaktivatoren bzw. Entschäumer enthaltenden Granulaten, in bekannter Weise vereinigt und vermischt werden. Das hohe Schüttgewicht und das günstige Einspülverhalten der erfindungsgemäßen Additive überträgt sich auf diese komplexen Gemische. In der Praxis enthalten die Waschmittel im allgemeinen 10 bis 40 Gew.-% des erfindungsgemäßen Additivs.The detergent additives can be mixed with the granular or powder detergent, for example a tower spray powder and its mixtures with other powder components, such as persalt, enzyme granules, Bleach activators or defoamers containing granules, combined in a known manner and be mixed. The high bulk density and the favorable flushing behavior of the inventive Additives are transferred to these complex mixtures. In practice, the detergents contain general 10 to 40 wt .-% of the additive according to the invention.
Die Granulierung erfolgte in einem Mischgranulator, bestehend aus einem horizontal angeordneten zylindrischen Mischer mit einer in der Mittelachse rotierenden, mit Mischorganen bestückten Drehwelle (Pflugscharmischer, Bauart Lödige) mit einem Fassungsvermögen von 130 l und einer daran angeschlossenen, mit einer Drehzahl von 1 200 bis 1 500 Umdrehungen/Minute betriebenen Messermühle. In dem Mischgranulator wurden die pulverförmigen Bestandteile sowie gegebenenfalls die wäßrige Zeolith-Suspension vorgelegt und zu einem homogenen Gemisch verarbeitet. Nach dem Mischen, das ca. 10 Sekunden bis 1 Minute in Anspruch nahm, wurde mittels Düsen die Granulierflüssigkeit im Verlauf von 1 bis 5 Minuten eingesprüht und das Gemisch unter ständigem Mischen noch weitere 1 bis 3 Minuten granuliert. Das den Mischer verlassende Granulat wurde in einer Wirbelschicht mit heißen, strömenden Trockengasen (70°C) getrocknet. In allen Beispielen betrug der Feinanteil (Teilchendurchmesser kleiner 0,1 mm) weniger als 7 % und der Grobanteil (Teilchendurchmesser größer 2 mm) weniger als 32 %.The granulation was carried out in a mixing granulator consisting of a horizontally arranged one cylindrical mixer with a rotating shaft rotating in the central axis and equipped with mixing elements (Ploughshare mixer, type Lödige) with a capacity of 130 l and a connected Knife mill operated at a speed of 1,200 to 1,500 revolutions / minute. By doing The pulverulent constituents and optionally the aqueous zeolite suspension were mixed granulators submitted and processed into a homogeneous mixture. After mixing, this is about 10 seconds took 1 minute, the granulating liquid was sprayed in the course of 1 to 5 minutes by means of nozzles sprayed in and the mixture was granulated for a further 1 to 3 minutes with constant mixing. That the Granules leaving the mixer were placed in a fluidized bed with hot, flowing dry gases (70 ° C.) dried. In all examples, the fine fraction (particle diameter less than 0.1 mm) was less than 7% and the coarse fraction (particle diameter larger than 2 mm) less than 32%.
Das eingesetzte Zeolith-Pulver war feinkristalliner, sprühgetrockneter Zeolith vom Typ NaA, der 20 Gew.-% gebundenes Wasser enthielt. Die wäßrige Zeolith-Suspension war 48 Gew.-%ig. Das Natriumsalz des verwendeten Acrylsäure-Maleinsäure-Copolymers (Sokalan(R)CP5 der Firma BASF/Deutschland) wies eine relative Molekülmasse von ca. 70 000 auf und wurde als 40 Gew.-%ige Lösung eingesetzt; die Mengenangaben beziehen sich auf wasserfreie Substanz.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.
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 49,5 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 20 Gew.% Sokalan CP5, 14 Gew.-% C12-C18-Fettalkohol mit 5 EO und 66 Gew.-% H2O, besprüht. Das nach der Trocknung erhaltene Granulat enthielt 88,1 Gew.-% wasserfreien Zeolith, der als Pulver vorgelegt worden war, 7 Gew.-% Sokalan CP5 und 4,9 Gew.-% C12-C18-Fettalkohol mit 5 EO. Das Schüttgewicht betrug vor dem Sieben 810 g/l; der Grobanteil betrug 17,3 %.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% by weight H 2 O, sprayed. The granules obtained after drying contained 88.1% by weight of anhydrous zeolite, which had been introduced 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%.
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 44,2 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 19,8 Gew.-% Sokalan CP5, 50,6 Gew.-% C12-C18-Fettalkohol mit 5 EO und 29,6 Gew.-% Wasser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 80,1 Gew.-% wasserhaltigen Zeolith, der als Pulver vorgelegt worden war, 5,6 Gew.-% Sokalan CP5 und 14,3 Gew.-% C12-C18-Fettalkohol mit 5 EO. Das Schüttgewicht betrug vor dem Sieben 900 g/l; der Grobanteil betrug 5 %. 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%.
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 42,5 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 13,3 Gew.-% Sokalan CP5, 62,1 Gew.-% C12-C18-Fettalkohol mit 7 EO und 24,6 Gew.-% Wasser besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 79,6 Gew.-% wasserhaltigen Zeolith, der als Pulver vorgelegt worden war, 3,6 Gew.-% Sokalan CP5 und 16,8 Gew.-% C12-C18-Fettalkohol mit 7 EO. Das Schüttgewicht betrug vor dem Sieben 850 g/l; der Grobanteil betrug 13,9 %.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%.
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 39 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 8,9 Gew.-% Sokalan CP5, 73,3 Gew.-% C12-C18-Fettalkohol mit 7 EO und 17,8 Gew.-% Wasser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 79,6 Gew.-% wasserhaltigen Zeolith, der als Pulver vorgelegt worden war, 2,2 Gew.-% Sokalan CP5 und 18,2 Gew.-% C12-C18-Fettalkohol mit 7 EO. Das Schüttgewicht betrug 870 g/l; der Grobanteil betrug 2,9 %.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 C 12 -C 18 fatty alcohol with 7 EO. The bulk density was 870 g / l; the gross share was 2.9%.
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 47,5 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 22,7 Gew.-% Sokalan CP5, 20,5 Gew.-% Natriumdodecylbenzolsulfonat und 56,8 Gew.-% Wasser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 85,9 Gew.-% wasserhaltigen Zeolith, der als Pulver vorgelegt worden war, 7,4 Gew.-% Sokalan CP5 und 6,7 Gew.-% Natriumdodecylbenzolsulfonat. Das Schüttgewicht betrug vor dem Sieben 860 g/l; der Grobanteil betrug 30,2 %.There were 100 parts by weight of zeolite, based on anhydrous substance, with 47.5 parts by weight of one Granulating liquid consisting of 22.7% by weight Sokalan CP5, 20.5% by weight sodium dodecylbenzenesulfonate and 56.8 wt% water. The granules obtained after drying contained 85.9% by weight water-containing zeolite, which had been presented as a powder, 7.4% by weight of Sokalan CP5 and 6.7% by weight Dodecylbenzenesulfonate. The bulk density before sieving was 860 g / l; the bulk was 30.2%.
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 44 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 11,25 Gew.-% Sokalan CP5, 35,75 Gew.-% Natriumdodecylbenzolsulfonat und 53 Gew.-% Wasser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 85,8 Gew.-% wasserhaltigen Zeolith, der als Pulver vorgelegt worden war, 3,4 Gew.-% Sokalan CP5 und 10,8 Gew.-% Natriumdodecylbenzolsulfonat. Das Schüttgewicht betrug 770 g/l; der Grobanteil betrug 29,8 %.100 parts by weight of zeolite, based on anhydrous substance, were mixed with 44 parts by weight of one Granulating liquid consisting of 11.25% by weight Sokalan CP5, 35.75% by weight sodium dodecylbenzenesulfonate and 53% by weight water. The granules obtained after drying contained 85.8% by weight water-containing zeolite, which was presented as a powder, 3.4 wt .-% Sokalan CP5 and 10.8 wt .-% Dodecylbenzenesulfonate. The bulk density was 770 g / l; the gross share was 29.8%.
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 46,4 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 20,25 Gew.-% Sokalan CP5, 48,7 Gew.-% C12-C18-Fettalkohol mit 7 EO und 31,05 Gew.-% Wasser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 79,6 Gew.-% wasserhaltigen Zeolith, wobei 74,4 Gew.-% als Pulver und 5,2 Gew.-% als Suspension vorgelegt worden waren, 6 Gew.-% Sokalan CP5 und 14,4 Gew.-% C12-C18-Fettalkohol mit 7 EO. Das Schüttgewicht betrug vor dem Sieben 940 g/l; der Grobanteil betrug 31,1 %.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%.
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 42,0 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 29,5 Gew.-% Sokalan CP5, 22,9 Gew.-% C12-C18-Fettalkohol mit 5 EO und 47,6 Gew.-% Wasser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 76,5 Gew.-% wasserhaltigen Zeolith, wobei 73,1 Gew.-% als Pulver und 13,4 Gew.-% als Suspension vorgelegt worden waren, 7,6 Gew.-% Sokalan CP5 und 5,9 Gew.-% C12-C18-Fettalkohol mit 5 EO. Das Schüttgewicht betrug vor dem Sieben 830 g/l; der Grobanteil betrug 17,5 %.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 C 12 -C 18 fatty alcohol with 5 EO. The bulk density before sieving was 830 g / l; the gross share was 17.5%.
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 41,0 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 19,5 Gew.-% Sokalan CP5, 31,3 Gew.-% C12-C18-Fettalkohol mit 7 EO und 49,2 Gew.-% Wasser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 85,5 Gew.-% wasserhaltigen Zeolith, wobei 62,5 Gew.-% als Pulver und 23 Gew.-% als Suspension vorgelegt worden waren, 5,5 Gew.-% Sokalan CP5 und 8,8 Gew.-% C12-C18-Fettalkohol mit 7 EO. Das Schüttgewicht betrug vor dem Sieben 840 g/l; der Grobanteil betrug 24,5 %.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 wt .-% C 12 -C 18 fatty alcohol with 7 EO. The bulk density before sieving was 840 g / l; the gross share was 24.5%.
Die Wiederholung der Versuche 1 bis 9, bei der 40 % der Menge des eingesetzten Polymers in fester Form zusammen mit dem Zeolith vorgelegt wurden, führte zu analogen Ergebnissen. Der Anteil des Wassers in der Granulierflüssigkeit konnte entsprechend reduziert werden.The repetition of experiments 1 to 9, in which 40% of the amount of polymer used in solid Form presented together with the zeolite led to analog results. The share of Water in the granulating liquid could be reduced accordingly.
Die Granulate aus den Versuchen 2, 8 und 9 wurden in einem Sprühmischer mit einem auf 40°C
erwärmten, flüssigen, nichtionischen Tensid besprüht, bestehend aus einem mit 5 Mol EO umgesetzten
Gemisch von Kokos- und Talgalkohol im Verhältnis 1:4. Nach einer Standzeit von einer Stunde wiesen die
Adsorbate die folgenden Schüttgewichte auf:
Die mit dem nichtionischen Tensid behandelten Granulate waren gut rieselfähig und wiesen ein einwandfreies Einspülvermögen auf, und zwar sowohl als unverschnittenes Pulver wie auch vermischt mit einem pulverförmigen Haushaltswaschmittel im Verhältnis 1:4.The granules treated with the nonionic surfactant were free-flowing and indicated perfect induction, both as unblended powder and mixed with a powdered household detergent in a ratio of 1: 4.
Claims (7)
- A process for the production of granules of zeolite and sodium or potassium salts of polymeric or copolymeric carboxylic acids, the granulation process taking place with putting in zeolite first and addition of a granulation liquid and the granules obtained being dried to form free-flowing granules having an apparent density of 750 to 1,000 g/l, characterized in that a mixture of water, surfactants and (co)polymeric carboxylates is used as the granulation liquid, the content of surfactants in the granulation liquid being at least 10% by weight.
- A process as claimed in claim 1, characterized in that the zeolite is used in the form of a powder having a water content of 17-25 by weight or in the form of a mixture of 70 to 95% by weight, based on the total quantity of zeolite, powder and 5 to 30% by weight, based on the total quantity of zeolite, of a 45 to 55% by weight agueous suspension.
- A process as claimed in claim 1 or 2, characterized in that 5 to 30% by weight of the granulation liquid consists of (co)polymeric carboxylate, 10 to 75% by weight of anionic and/or nonionic surfactants and 7 to 70% by weight of water.
- A process as claimed in any of claims 1 to 3, characterized in that granulation liquid is added to 100 parts by weight zeolite, expressed as anhydrous substance, or to a homogeneous mixture of zeolite and, optionally, salt of the polymeric or copolymeric carboxylic acid initially introduced in powder form in such a quantity that 15 to 45 parts by weight, especially 18 to 40 parts by weight, based on the moist granules, of liquid constituents are present, the granulation liquid containing at least 2 parts by weight and, more particularly, 5 to 25 parts by weight, based on the moist granules, of free water.
- A process as claimed in any of claims 1 to 4, characterized in that the granulation liquid is sprayed by means of nozzles onto the agitated mixture.
- A process as claimed in claims 1 to 5, characterized in that dried granuled which contain 70 to 92% by weight zeolite, 2 to 12% by weight of the sodium salt of polymeric or copolymeric carboxylic acids and 4 to 20% by weight liquid nonionic surfactants and which have an apparent density of 780 to 980 g/l are obtained.
- Granules produced by any of the claims 1 to 6, characterized in that they are preferably impregnated with up to 20% by weight, based on the adsorbate, of at least one liquid detergent constituent, preferably a liquid nonionic surfactant or a foam inhibitor.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4038609A DE4038609A1 (en) | 1990-12-04 | 1990-12-04 | METHOD FOR PRODUCING ZEOLITE GRANULES |
| DE4038609 | 1990-12-04 | ||
| PCT/EP1991/002209 WO1992010559A1 (en) | 1990-12-04 | 1991-11-25 | Process for the production of granular zeolites |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0560802A1 EP0560802A1 (en) | 1993-09-22 |
| EP0560802B1 EP0560802B1 (en) | 1995-05-10 |
| EP0560802B2 true EP0560802B2 (en) | 2002-08-28 |
Family
ID=6419545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91920221A Expired - Lifetime EP0560802B2 (en) | 1990-12-04 | 1991-11-25 | Process for the production of granular zeolites |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5399287A (en) |
| EP (1) | EP0560802B2 (en) |
| JP (1) | JP3167721B2 (en) |
| KR (1) | KR0181978B1 (en) |
| AT (1) | ATE122382T1 (en) |
| DE (2) | DE4038609A1 (en) |
| ES (1) | ES2071345T5 (en) |
| WO (1) | WO1992010559A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19549411C2 (en) * | 1994-02-11 | 1999-05-12 | Degussa | Zeolite granulates with good re:dispersibility and high bulk density |
| DE19504043C2 (en) * | 1994-02-11 | 1998-07-09 | Degussa | zeolite granules |
| DE19515256A1 (en) * | 1995-04-26 | 1996-10-31 | Degussa | Zeolite granules, process for its preparation and use |
| ES2167593T3 (en) * | 1995-09-04 | 2002-05-16 | Unilever Nv | DETERGENT COMPOSITIONS AND PROCESS TO PREPARE THEM. |
| DE19844522A1 (en) | 1998-09-29 | 2000-03-30 | Henkel Kgaa | Granulation process |
| KR100750190B1 (en) * | 2004-06-16 | 2007-08-31 | 요업기술원 | Bone Fillers Effective for Bone Repair and Methods for Making the Same |
| GB0811302D0 (en) * | 2008-06-20 | 2008-07-30 | Dow Corning | Shampoo compositions |
| JP5705525B2 (en) * | 2010-12-16 | 2015-04-22 | 花王株式会社 | Zeolite composite particles |
| RU2615506C1 (en) * | 2015-10-13 | 2017-04-05 | Александр Адольфович Ламберов | Method for granulation of zeolite as synthetic detergent component |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2652488C3 (en) * | 1976-11-18 | 1983-03-10 | Kali-Chemie Ag, 3000 Hannover | Process for the production of granules from zeolites and oxygen-releasing compounds |
| DE3316513A1 (en) * | 1983-05-06 | 1984-11-08 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | Abrasion resistant granular materials based on alkali metal aluminium silicate |
| 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 (en) * | 1984-12-10 | 1986-06-12 | Henkel KGaA, 4000 Düsseldorf | GRAINY ADSORPTION |
| GB8526999D0 (en) * | 1985-11-01 | 1985-12-04 | Unilever Plc | Detergent compositions |
| DE3545947A1 (en) * | 1985-12-23 | 1987-07-02 | Henkel Kgaa | PHOSPHATE-FREE, GRANULAR DETERGENT |
| DE3614779A1 (en) * | 1986-05-02 | 1987-11-05 | Henkel Kgaa | GRANULAR, PHOSPHATE-FREE WATER SOFTENER |
| DE3838086A1 (en) * | 1988-11-10 | 1990-05-17 | Henkel Kgaa | METHOD FOR PRODUCING HIGH DENSITY GRANULES CONTAINING ZEOLITE |
| CA2017921C (en) * | 1989-06-09 | 1995-05-16 | John Michael Jolicoeur | Formation of detergent granules by deagglomeration of detergent dough |
| 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/en not_active Withdrawn
-
1991
- 1991-11-25 ES ES91920221T patent/ES2071345T5/en not_active Expired - Lifetime
- 1991-11-25 DE DE59105474T patent/DE59105474D1/en not_active Expired - Lifetime
- 1991-11-25 EP EP91920221A patent/EP0560802B2/en not_active Expired - Lifetime
- 1991-11-25 JP JP50030992A patent/JP3167721B2/en not_active Expired - Lifetime
- 1991-11-25 KR KR1019930701683A patent/KR0181978B1/en not_active Expired - Fee Related
- 1991-11-25 AT AT91920221T patent/ATE122382T1/en not_active IP Right Cessation
- 1991-11-25 US US08/070,442 patent/US5399287A/en not_active Expired - Lifetime
- 1991-11-25 WO PCT/EP1991/002209 patent/WO1992010559A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| KR0181978B1 (en) | 1999-04-15 |
| ES2071345T3 (en) | 1995-06-16 |
| US5399287A (en) | 1995-03-21 |
| DE4038609A1 (en) | 1992-06-11 |
| EP0560802A1 (en) | 1993-09-22 |
| JPH06503109A (en) | 1994-04-07 |
| EP0560802B1 (en) | 1995-05-10 |
| DE59105474D1 (en) | 1995-06-14 |
| ATE122382T1 (en) | 1995-05-15 |
| JP3167721B2 (en) | 2001-05-21 |
| WO1992010559A1 (en) | 1992-06-25 |
| ES2071345T5 (en) | 2003-03-16 |
| KR930703424A (en) | 1993-11-30 |
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