EP1114138A1 - Continuous process for making a detergent composition - Google Patents
Continuous process for making a detergent compositionInfo
- Publication number
- EP1114138A1 EP1114138A1 EP99946732A EP99946732A EP1114138A1 EP 1114138 A1 EP1114138 A1 EP 1114138A1 EP 99946732 A EP99946732 A EP 99946732A EP 99946732 A EP99946732 A EP 99946732A EP 1114138 A1 EP1114138 A1 EP 1114138A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixer
- detergent
- binder
- free
- agglomeration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 126
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 238000010924 continuous production Methods 0.000 title claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 96
- 239000011230 binding agent Substances 0.000 claims abstract description 94
- 239000000843 powder Substances 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 53
- 238000005054 agglomeration Methods 0.000 claims abstract description 50
- 230000002776 aggregation Effects 0.000 claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 40
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 87
- 230000008569 process Effects 0.000 claims description 71
- 239000004094 surface-active agent Substances 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 31
- 239000004615 ingredient Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 22
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000005520 cutting process Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000000518 rheometry Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 25
- 239000010419 fine particle Substances 0.000 abstract description 8
- 230000003472 neutralizing effect Effects 0.000 abstract 2
- 239000000047 product Substances 0.000 description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 19
- 229910000323 aluminium silicate Inorganic materials 0.000 description 18
- 238000006386 neutralization reaction Methods 0.000 description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 15
- 239000008187 granular material Substances 0.000 description 15
- 238000005342 ion exchange Methods 0.000 description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 229910010272 inorganic material Inorganic materials 0.000 description 9
- 239000011147 inorganic material Substances 0.000 description 9
- 239000011236 particulate material Substances 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 235000012149 noodles Nutrition 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000000712 assembly Effects 0.000 description 6
- 238000000429 assembly Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 230000009969 flowable effect Effects 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 235000019832 sodium triphosphate Nutrition 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003093 cationic surfactant Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006677 Appel reaction Methods 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- UZABCLFSICXBCM-UHFFFAOYSA-N ethoxy hydrogen sulfate Chemical compound CCOOS(O)(=O)=O UZABCLFSICXBCM-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 244000089486 Phragmites australis subsp australis Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ZUBJEHHGZYTRPH-KTKRTIGZSA-N [(z)-octadec-9-enyl] hydrogen sulfate Chemical compound CCCCCCCC\C=C/CCCCCCCCOS(O)(=O)=O ZUBJEHHGZYTRPH-KTKRTIGZSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005563 spheronization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
Definitions
- the present invention generally relates to a continuous, non-tower process for producing a particulate detergent composition. More particularly, the invention is directed to a continuous process where a free-flowing dry neutralized detergent powder is agglomerated with a liquid or viscous paste binder to form agglomerates. The process produces detergent agglomerate having a reduced amount of fine particles and over-sized particles that require recycle.
- the first type of process involves spray- drying an aqueous detergent slurry in a spray-drying tower to produce highly porous detergent granules (e.g., tower process for low density detergent compositions).
- the various detergent components are dry mixed after which they are agglomerated with a binder such as a nonionic or anionic surfactant, to produce high density detergent compositions (e.g., agglomeration process for high density detergent compositions).
- the important factors which govern the density of the resulting detergent granules are the shape, porosity and particle size distribution of said granules, the density of the various starting materials, the shape of the various starting materials, and their respective chemical composition.
- one attempt involves a batch process in which spray- dried or granulated detergent powders containing sodium t polyphosphate and sodium sulfate are densified and spheronized in a Marumerizer®.
- This apparatus comprises a substantially horizontal, roughened, rotatable table positioned within and at the base of a substantially vertical, smooth walled cylinder.
- This process is essentially a batch process and is therefore less suitable for the large scale production of detergent powders.
- More recently, other attempts have been made to provide continuous processes for increasing the density of "post-tower" or spray dried detergent granules.
- Laid Open No.WO96/04359 (Unilever).
- Laid-open No.WO93/23,523 (Henkel) describes the process comprising pre-agglomeration by a low speed mixer and further agglomeration step by high speed mixer for obtaining high density detergent composition with less than 25 wt % of the granules having a diameter over 2 mm.
- the U.S. Patent No. 4,427,417 (Korex) describes continuous process for agglomeration which reduces caking and oversized agglomerates.
- the present invention provides a continuous process for preparing a granular detergent agglomerate having a density of at least about 500 g/l, comprising the steps of:
- the present invention produces high density detergent agglomerates for use in granular detergent compositions, having a high level of detergent surfactant and a relatively narrow particle size distribution. Furthermore, the process is inherently efficient by significantly reducing the amount of agglomerate which is outside an acceptable particle range.
- the present invention also meets the aforementioned needs in the art by providing a process which produces a granular detergent composition for flexibility in the ultimate density of the final composition from an agglomeration (e.g., non-tower) process. The process does not require the use of conventional spray drying towers which have limited capability to produce compositions having a high surfactant loading (concentration) at high bulk density (greater than 500 gm/l).
- the process described herein provides a granular detergent agglomerate having a high density of at least about 500 g/l and relatively narrow particle size distribution as measured by the geometric standard deviation of less than about 2.5, with high throughput capability and increased production efficiency, and with less recycle of material having an unacceptable particle size. While it is recognized that other processes which include classification and recycle loops are capable of producing more narrow particle size distributions measured at the final product output, the advantage of the current invention is the narrowness of the particle size distribution before any classification is done.
- agglomerates refers to particles formed by agglomerating particulate detergent materials with a binder such as surfactants and/or other solutions, whereby the agglomerate particle has a larger size than the particulate detergent materials contained therein.
- the residence time can be easily and conveniently determined by measuring the steady-state weight of agglomerate powder and ingredients in a mixer (in kg), and dividing by the mass throughout (in kg/minute) of the mixer.
- particle size distribution refers to the mass- basis distribution of agglomerate particle sizes, where the distribution is described by the geometric mean and geometric standard deviation.
- the mass- basis geometric mean and standard deviation are most commonly measured using standard sieve analysis methods.
- the present invention is directed to a continuous process which produces free-flowing, granular detergent agglomerates.
- the process can produce a product having a density of at least about 500 g/l, a narrow product size distribution at the output of the agglomeration step, and improved process efficiency by virtue of its low recycle rate.
- the first step of the process prepares a dry neutralized material in the form of a free-flowing powder.
- the dry neutralized material is obtained by the dry neutralization of an acid precursor of an anionic detergent surfactant with a water-soluble alkaline inorganic particulate material in a high speed mixer, whereby the acid precursor is partially or completely neutralized to the anionic surfactant.
- an excess of the alkaline inorganic particulate material is used to ensure that the acid precursor is sufficiently neutralized under the high speed mixing conditions.
- a particulate water-soluble alkaline inorganic material is continuously introduced into the high speed mixer in the form of fine particles.
- a liquid acid precursor of the anionic surfactant is introduced into the mixer and is well dispersed and adsorbed onto the surface of the fine particles of the alkaline inorganic material. Neutralization of the acid precursor to the corresponding salt occurs quickly. The rate and capacity for neutralization of the acid precursor to the salt increases as the alkaline inorganic material is reduced to a finer particle size with a higher reactive surface area. Because of the inherent binding capacity of the liquid, there is typically some intermediate agglomeration associated with the first step to form the dry neutralized material.
- the extent of this intermediate agglomeration is controlled primarily by the amount of liquid addition and the shear rate of the mixer.
- the mean particle size of the dry neutralized material is generally within the range of about 50 to 500 microns, preferably about 100 to 250 microns.
- the bulk density of the dry neutralized material of the first mixer is at least 500 g/l, more typically at least 600 g/l, and preferably from about 650 to 800 g/l.
- the mixer consists of a device with mixing tools operating at a tip speed of at least 10 m/s, and a narrow gap between the tool tip(s) and the mixer wall or other fixed element of less than 2 cm.
- the mean residence time of the first mixer is in range from about 0.2 to about 50 seconds, more preferably from about 1 to about 30 seconds.
- Examples of the high speed mixer for the first step are a Lodige CB Mixer manufactured by the Lodige company (Germany), a Turbilizer manufactured by Bepex Company (USA), and a Schugi Flexomatic (e.g., Model FX-160) manufactured by the Schugi company (Netherlands).
- a Lodige CB Mixer manufactured by the Lodige company (Germany)
- a Turbilizer manufactured by Bepex Company (USA)
- a Schugi Flexomatic e.g., Model FX-160 manufactured by the Schugi company (Netherlands).
- the particulate water-soluble alkaline material is preferably sodium carbonate, alone or in combination with other materials such as sodium bicarbonate or silicate. Alkaline materials having other salts, such as lithium and potassium, can also be used. While aqueous alkaline materials such as sodium hydroxide can also be used in combination with the particulate alkaline material, their use should minimized to prevent the resulting intermediate agglomerate from being sticky or poor flowability.
- the carbonate is preferably of a finely divided powder having an mean diameter of from 0.1 to 100 microns, preferably from 2 to 25 microns, and more preferably from 5 to 15 microns. Typically the moisture content of the carbonate will be less than about 2%, more preferably less than 1 %.
- the carbonate can comprise from about 25% to about 80% by weight of the resulting agglomerate, preferably about 30% to about 60%.
- a preferred method of reducing the carbonate to the finely divided size is by the use of a suitable grinder capable of producing such finely ground carbonate from commercially available carbonate stock, such as the process described in WO 98/20104, published May 14, 1998, and incorporated herein by reference.
- Commercially available carbonate typically has a median particle size of about 50-150 microns, and contains less than 2%, preferably less than 1 % moisture.
- a preferred grinder used for this purpose is an air-classifier mill, such as the Mikro-ACM CX Model 300 available from Hosokawa Micron Powder Systems, Summit, New Jersey.
- the particle size distribution of the ground carbonate is determined by any instrument which approximates such particle size as the diameter of a spherical particle occupying the same volume as the particle being measured.
- the median particle size is that size which has 50% by volume of the particles being smaller and 50% by volume being larger.
- a suitable instrument for measuring the particle size of the ground carbonate is the Malvern Series 2600 Optical Laser, available from Malvern Instrument Company, Malvern, Pennsylvania.
- the amount of alkaline inorganic material is preferably in an amount to neutralize at least 80% of the acid precursor by the time the material leaves the first mixer. Typically, the stoicheometric amount of alkaline inorganic material will be at least twice that needed to fully neutralize the acid precursor.
- the neutralization of the acid precursor with alkaline powder by dispersion/adsorption is well known in the art. See “Synthetic Detergents", A.S. Davidsohn & B. Midlewsky, 7th ed., pp. 202-209.
- the amount of liquid acid precursor that can be added in this step is up to about 30 weight %.
- acid precursors of detergent surfactants that are more crystalline than alkylbenzene sulfonate, such as alkyl sulfuric acid generally more of acid precursor can be loaded into the mixer.
- the liquid acid precursor preferably selected from a conventional C ⁇
- HLAS C ⁇
- HAS a primary, branched-chain and random C10-
- the acid precursor comprises at least 50% of HLAS.
- at least 50% by weight of the detergent surfactant in the final detergent product is derived from the neutralization of the acid precursor in the first step.
- particulate inorganic and organic detergent ingredients can be added into the first step mixer.
- Such other particulate detergent ingredients are described herein after.
- the addition of the other particulate detergent ingredients into the process can improve the physical properties of the dry neutralized material.
- the dry neutralized material will contain less than about 5% by weight of such particulate builder material.
- the alkaline inorganic material carbonate
- the moisture content of the reaction mixture defined as water not firmly bound as water of hydration or crystallization to inorganic salts at a temperature of 135°C, should not be so high that it can lead to substantial agglomeration of the powders.
- the moisture content of the powder material in the first mixer will be less than about 5%, more preferably less than about 2%.
- a detergent material is obtained containing the salt of the anionic surfactant, wherein preferably at least 80%, more preferably at least 90%, and most preferably all, of the acid precursor of the anionic surfactant has been neutralized.
- the detergent material exiting the first mixer can optionally be processed in an optional intermediate step, before passing as the free-flowing powder into the agglomeration mixer of the second step.
- Such intermediate step can be a mixing step where optional liquid or particulate materials can be added.
- Such optional liquid material is generally added at a level of less than 10% by weight of the free-flowing powder, and can include nonionic surfactants or other binder liquids herein described.
- Such optional particulate material can be a free-flow aid, such as zeolite or a carbonate.
- the mixer can be a static mixing device such as a baffled box mixer, or a mechanical mixer such as a Schugi, drum or cage mixer.
- Such optional step can be advantageously used to add a liquid material (as in the case of a nonionic surfactant) that may interfere with effective dry neutralization of the acid precursor in the first step, or with effective agglomeration in the second step.
- Second Step Agglomeration
- the second step prepares a granular detergent agglomerate from the free-flowing powder and an agglomerating binder.
- the resultant free-flowing powder from the first step is fed into a second mixer.
- the second mixer is preferably a completely separate mixer, though it can be a subsequent downstream zone of the first mixer, so long as it satisfies the mixing conditions.
- the second step comprises dispersing an agglomeration binder onto the free-flowing powder of the first step to form the detergent agglomerate.
- the amount of the agglomeration binder used can be from about 1 % to about 50% (active basis), preferably from 5% to about 35% (active basis) by weight of the detergent agglomerates.
- the invention can accommodate a broad range of surfactant paste levels based on rheological properties and modifications thereof in the process.
- the resulting detergent agglomerates have a mean particle size of about 250 microns to about 1200 microns, more preferably about 400 microns to about 1000 microns, and a relatively narrow particle size distribution at the output of the second agglomeration step having a geometric standard deviation of less than about 2.5, preferably less than about 2.0.
- the second step of the process It is preferred to operate the second step of the process at an operating temperature sufficiently high to promote effective agglomeration of the free- flowing powder with the agglomeration binder, though not so high in temperature such that there is excessive agglomeration or "balling" of the powder into large clumps.
- the operating temperature of combined material of the second step, within the second mixer is from about 30 to 70°C.
- the temperature of the agglomeration binder can be controlled independently such that the agglomeration binder can be in the form of either a flowable liquid, which can be sprayed or dripped into the mixing zone of the second mixer, or a thick viscous paste which needs to be mechanically dispersed into particles within the mixing zone.
- the flowable liquid agglomeration binder can be sprayed on the agglomerates in the second mixer using single fluid or air-atomizing spray nozzles, which can be easily selected for the service required.
- the flowable liquid can also be dripped or introduced into the mixer as a stream of liquid from a pipe. It is important that the flowable liquid, though, be well dispersed and distributed within the powder in order for the powder particles to efficiently and effectively adhere to and coat the outer surface of the agglomeration binder.
- Typical tip speed of the chopper blades is at least about 3 m/sec, preferably greater than about 15 m/sec, and more preferably greater than about 20 m/sec.
- Typical chopper designs include at least four radial blade positions. This is well suited to the ploughshare design of mixers with internal choppers, for example a Lodige KM mixer manufactured by the Lodige company (Germany). Mixers can be equipped with lance tubes through which a binding fluid can be injected onto the chopper locations.
- the lance tubes can be subdivided into smaller diameter tube streams, where the cross sectional area of the openings of each (sub-divided) stream is less than about 80 mm 2 , most preferably less than about 1 mm 2 .
- the combination of paste injection rate divided across the number of streams and the chopper cutting speed results in cutting of the individual streams into fine units of binder, where the calculated volume of paste in each stream per cut is less than about 1 ml, most preferably less than about 0.01 ml, and most preferably from about 0.00005 ml to about 0.01 ml, or an average equivalent diameter of less than about 13 mm, and more preferably less than about 4 mm.
- Binder particles of this size are torn apart into smaller sizes within the second mixer as a result of the coating and embedding of the finely-divided powder onto the binder particle, until the agglomerate achieves a size within a range where the strength of the agglomerate particle will resist further reduction.
- This agglomerate size range is generally from about 50 microns to about 2000 microns, and spans beyond the range of acceptable average detergent particle size (about 250 to 1200 microns) to include both fines (agglomerates and particles less than 250 microns) and overs (agglomerates greater than 1400 microns).
- agglomeration binder it is most preferable to form and disperse the agglomeration binder into droplets or particles having an equivalent diameter of from about 0.5 mm to about 1 mm. This particle size is comparable to the size of the desired detergent agglomerate. Binder particles within this size range will tend not to be torn into smaller sizes. The result of dispersing the agglomerate binder within this size range will be a resulting detergent agglomerate having a significantly narrower particle size range, with minimal amounts of overs and fines.
- the binder volume per cut can be calculated from the cutting rate, and the binder volume rate.
- the cutting rate, in cuts/sec is "chopper revolutions/sec x chopper blades/revolution", where each chopper blade makes a cut.
- the binder volume rate, in ml/sec is "binder mass / binder density”, where the binder mass is in kg/sec, and the binder density is in kg/ml.
- the binder volume per cut is then "binder volume rate / cutting rate”.
- the tubes that are used to inject the (sub-divided) binder streams are located such that their discharge openings are slightly upstream of the choppers; in this way, the ploughshare tools in the mixer sweep the binder streams and intermediate particles into the choppers, where the binder is finely divided and coated with powder.
- Another embodiment is to supplement the above sub-divided binder injectors with additional mechanisms to disperse the binder, such as by the addition of compressed air in the binder line at or before the opening of the binder tube into the mixer.
- the air may be further pulsed to provide additional breakup of the binder stream into uniform pieces.
- vibrating elements such as reeds can be used at the injection point to further improve the uniformity of the binder dispersion.
- the most preferred embodiment uses a viscous surfactant paste binder, characterized by a shear-rate thinning viscosity that exhibits an apparent yield stress.
- the shear-rate thinning property is advantageous to transport of the paste binder, typically from a storage tank, into the mixer/agglomerator.
- the apparent yield stress property is important in mechanical cutting of the paste as well as in maintaining the structural integrity of the as-formed agglomerates, especially at high active levels of the binder.
- the shear-rate thinning and apparent yield stress properties can be measured in accordance with accepted practice in the art of rheological characterization, for example, using a parallel plate or cone and plate viscometer.
- the viscometer is typically determined using a stress ramp program, where stress ( ⁇ ) is increased from about 10 Pa to about 1000 Pa over a ramp time of about 10 minutes, and the resultant strain rate ( ⁇ ) is measured.
- the logarithm of the calculated viscosity is then plotted against the logarithm of shear rate.
- regression of log( ⁇ ) versus log( ⁇ ) typically results in a good linear fit in the strain rate range from about 0.1 to about 10 sec "1 .
- the correlation coefficient of the regression, r 2 is typically greater than 0.99.
- the downward (negative) slope of the log-log plot is indicative of shear-thinning behavior, i.e., the viscosity falls as the shear rate increases.
- the viscosity of yield-stress fluids are typically dominated by the yield-stress effects in this range of shear rates.
- the apparent yield stress ( ⁇ y ) is defined as the product of the viscosity and the shear rate at the shear rate value of 1 sec "1 .
- the value of the apparent yield stress, ⁇ y should be greater than about 20 Pa, preferably greater than about 50 Pa, and more preferably greater than about 100 Pa.
- the apparent yield stress of paste binders increases with a reduction in temperature, whereby the agglomerates can have improved physical integrity and be more resistant to smearing as the product cools.
- the preferred paste binder has a viscoelastic rheology that can be characterized by a complex shear modulus (G * ), which is the vector sum of its elastic storage (G') and viscous loss (G") parts.
- G * complex shear modulus
- the preferred embodiment employs a paste binder with a tan( ⁇ ) value that is less than 1.0, more preferably less about 0.5, over the frequency range of about 2 Hz to about 20 Hz.
- the decreasing value of tan( ⁇ ) below 1.0 means that the elastic storage modulus becomes increasingly dominant over the viscous loss modulus.
- the dominance of the elastic storage modulus aids in the mechanical cutting the paste and dispersion of the paste as discrete units of binder.
- Dispersion of highly viscoelastic binder as discrete mass units favors the formation of agglomerates by embedding powder into the discrete mass units of binder.
- the low value of tan( ⁇ ) helps to reduce the tendency for the binder to smear over the surface of the agglomerates and the internal mechanical elements of the medium-shear mixer. The reduction of smearing is advantageous in improving the operating efficiency of the process by reducing the tendency for product to make-up and adhere to the inside of the mixer.
- the above viscoelastic rheology data can be measured by one skilled in the art of rheology using oscillatory parallel plate viscometers.
- the high viscosity, apparent yield stress and viscoelastic nature of the viscous agglomeration binder is well suited to a mechanism of agglomeration wherein the solid particles coat, adhere and are embedded into the binder.
- the mixing shear of the process needs to be sufficient only to coat and embed the particles into the finely divided droplets or particles of binder; as such, the mixing shear in the second mixer is intentionally kept below a point that would extensively spread the binder over the surface of the particles.
- a viscous binder be well dispersed and distributed within the free-flowing powder in order for the powder particles to efficiently and effectively adhere to and coat the outer surface of the agglomeration binder.
- binders where the material can not feasibly be raised to a temperature that allows the material to be pumped and/or sprayed in the mixer, it will generally be required to provide a means of mechanically dispersing the binder, such as a cutting and/or shredding device.
- a means of mechanically dispersing the binder such as a cutting and/or shredding device.
- Another embodiment which is especially preferred for very stiff binders is the use of a pelletizing extruder to deliver small, uniform pellets of binder into the agglomeration mixer. This embodiment includes the use of both single and twin- screw extruders. In this case, the extruder can be used to beneficially stiffen the binder before it is injected into the mixer, as disclosed U.S. Patent 5,451 ,354, incorporated herein by reference.
- the dispersion of the binder is accomplished by extruding the binder through a die plate with many small openings, producing noodles of binder which are then fed into the agglomeration mixer.
- the noodles can be cut into pellets before being fed into the mixer, using a variety of cutter configurations that are well known in the art of extrusion/pelletization.
- a more preferred embodiment uses a fine noodle size, with a noodle cross sectional area less than about 10 mm 2 and a chopper configured to chop the noodles into short lengths of less than about 4 mm.
- a most preferred embodiment uses an even finer noodle size, with a noodle cross sectional area less than about 1 mm 2 and a chopper configured to chop the noodles into short lengths of less than about 1 mm.
- the agglomeration binder can be selected from the group consisting of anionic surfactant paste (which is most preferred), liquid silicate, cationic surfactants, aqueous or non-aqueous polymer solutions, water, and mixtures thereof.
- anionic surfactant solutions as the agglomeration binder are about 30 - 95% active NaLAS, having an alkyl chain of about 12-18 carbons; about 30 - 95% active NaAS, having an alkyl chain of about 12-18 carbons; about 30 - 95% active NaAS, having a branched alkyl chain of about 10-20 carbons; and about 20-95% active NaAExS solution, having an alkyl chain of about 10-18 carbons, and where x is from about 1-10, and a mixture of the above surfactant solutions having a net active level of 30 to 95%.
- NaAS and NaLAS surfactants having an alkyl chain from about 14- 15 carbons, and about 70-80% active
- AExS surfactants having an alkyl chain from about 12-14 carbons, an x of about 3, and about 70-80% active are particularly preferred.
- Other minor ingredients, such as polyethylene glycol, organic polymers, silicates and alkaline salts may be present in the paste compositions.
- Cationic surfactants can be quaternary ammonium surfactants are selected from mono C6-C 6, preferably C6-C10 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
- Other binders can be those disclosed in U.S. Patent 5,108,646 (Beerse et al.), and are herein incorporated by reference.
- Additional particulate detergent ingredients of the type used in the first step can optionally be added into the second step mixer, along with the free- flowing powder, and agglomerated with the binder.
- About 0-10% particulate detergent ingredients, more preferably about 2-5%, by weight of the detergent agglomerate is typically added to the second mixer.
- the second agglomeration mixer can be any types of mixer known to persons skilled in the art, as long as the mixer can maintain the above mentioned condition for the second step.
- a second mixer which conducts the second step under conditions that include (i) from about 10 seconds to about 15 minutes, more preferably from about 1 minute to about 2 minutes, of mean residence time, (ii) a tip speed of a mixing tool mounted within the mixing zone of about 0.5 to about 5 m/s; and (iii) from about 0.15 to about 7 kj/kg of specific energy condition.
- a preferred example of the second mixer is the Lodige KM Mixer manufactured by the Lodige company (Germany).
- the free-flowing powder of the first step is introduced directly into the second mixer, though optionally is can first be handled or processed thorough other mixing or transporting equipment, as herein before described.
- a resultant product is obtained having a bulk density of at least 500 g/l.
- the resultant product can be further subjected to drying, coating, fluid bed agglomeration, and/or cooling.
- the particle size distribution of the product exiting the second stage mixer is more narrow, particularly compared to the free-flowing powder.
- the narrow particle size distribution means that the product exits the second mixer with a higher weight fraction of particles in the acceptable size range; thus, the overall process can be run with a lower rate of recycle for fines (very small size particles) and overs (larger sized particles), providing higher throughput and more efficient operation.
- the resultant agglomeration product can be made with a significantly higher active level of surfactant, compared to single stage agglomeration using only one type of binder.
- the total amount of the detergent surfactants in the detergent agglomerates made by the present invention, which are included via the first step acid precursor, the second step surfactant paste agglomeration binder, and adjunct detergent ingredients, is generally from about 5% to about 80%, more preferably from about 10% to about 60%, more preferably, from about 15 to about 50%, by weight.
- the amount of the surfactant that is formed by dry neutralization of acid precursor in the present process can be from about 5% to about 40%, though is more preferably from about 10% to about 30%, and most preferably from about 15% to about 25%, by weight of the agglomerate product.
- Nonlimiting examples of the preferred anionic surfactants formed by the dry neutralization of the acid precursor in the first step of the present invention include the conventional C-
- LAS C-
- the process of the present invention is carried out using (1 ) CB and/or Schugi mixer(s) which have flexibility to inject at least one liquid ingredient per mixer, (2) KM mixer with chopper blades which has flexibility to inject at least one paste binder ingredient, (3) an optional extruder/pelletizer which has flexibility to inject at least one additional paste binder ingredient into the KM, the process can incorporate at least four different kinds of liquid ingredients over a wide range of viscosity and other rheological properties in the process. Therefore, the proposed process is beneficial for persons skilled in the art in order to incorporate into a granule making process starting detergent materials which are in liquid form and are rather expensive and sometimes more difficult in terms of handling and/or storage than solid materials.
- Optional Other Detergent Surfactants are beneficial for persons skilled in the art in order to incorporate into a granule making process starting detergent materials which are in liquid form and are rather expensive and sometimes more difficult in terms of handling and/or storage than solid materials.
- Optional other detergent surfactant can also be included in the detergent product, such as other anionic surfactants, nonionic surfactants, zwitterionic surfactants, ampholytic surfactants and cationic surfactants, and compatible mixtures thereof.
- Such other detergent surfactants can be added as liquids or powders in small amounts (generally, 10% or less) in the first or second step, or in any optional intermediate or finishing step.
- Detergent surfactants useful herein are described in U.S. Patent 3,664,961 , Norris, issued May 23, 1972, and in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, both of which are incorporated herein by reference.
- Useful cationic surfactants also include those described in U.S.
- Cationic surfactants can also be used as a detergent surfactant herein and suitable quaternary ammonium surfactants are selected from mono C6-C-
- the particulate inorganic or organic detergent ingredients that can be introduced into either one or more of the first step, the second step, or other optional step, are preferably in the form of a finely divided, free-flowing powder, and are preferably selected from the group consisting of ground soda ash or carbonates (including the excess of alkaline inorganic particulate material added in the first step), powdered sodium tripolyphosphate (STPP), hydrated tripolyphosphate, ground or powdered sodium sulphate, aluminosilicate, crystalline layered silicates, nitrilotriacetates (NTA), pyrophosphates, orthophosphates, precipitated silicates, polymers, other carbonates, citrates, the above-mentioned powdered surfactants (such as powdered alkane sulfonic acids) and internal recycle stream of powder occurring from the process of the present invention, wherein the mean diameter of the powder is from 0.1 to 500 microns, preferably from 1 to 300 microns
- the aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference.
- the particulate inorganic or organic detergent ingredients can also serve as a coating agent when added to the second mixer.
- Preferred as coating agents are phosphates, carbonates and aluminosilicates.
- the coating agent enhances the free flowability of the resulting agglomerate and can prevent or minimize over-agglomeration in the second mixer. It can be advantageous to include only carbonate or other particulate material that is not a builder material, whereby a detergent agglomerate can be made that contains little (less than 10%, preferably less than 5%, by weight) or no detergent builders. This can enable the manufacturer to process a single detergent agglomerate for use in either phosphate-built or non-phosphate built detergents.
- the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit as high of an exchange rate and capacity as provided by the sodium form.
- the aluminosilicate ion exchange material preferably can be in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
- the aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
- particle size diameter represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
- the preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
- the aluminosilicate ion exchange material has the formula
- the aluminosilicate has the formula
- aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X.
- Naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference.
- the aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCO3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCO3 hardness/gram. Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/-gram/gallon, and more preferably in a range from about 2 grains Ca ++ /gallon/minute/-gram/gallon to about 6 grains Ca ++ /gallon/minute/- gram/gallon.
- the amount of the particulate inorganic or organic detergent ingredients that can be present in the first step comprise from about 30 to 94%, preferably from 50% to 90%, by weight of the detergent agglomerate exiting the second step.
- An additional amount of the particulate inorganic or organic detergent ingredients can be added in any optional intermediate step, or in the second step, as to provide a dusting or free-flow material.
- adjunct ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference.
- the process of the present invention can be used ot make detergent agglomerates which are suitable for use as-is, after addition of any adjunct detergent ingredients, as a detergent product. However, it may be preferred to further condition or treat the detergent agglomerate via optional process steps. Such optional process steps can include screening any oversized detergent agglomerates in a screening apparatus which can take a variety of forms including but not limited to conventional screens chosen for the desired particle size of the finished detergent product.
- Another optional step, particularly when loading high levels of anionic paste in the agglomeration step includes conditioning of the detergent agglomerates by subjecting the agglomerates to additional drying, such as can be accomplished with an airlift or a fluid bed dryer.
- an internal recycle stream of fine agglomerates having a mean diameter of about 75 to 400 microns generated by elutriation from a device such as a fluidized bed dryer, fluidized bed cooler, or other classification device, can be fed into the first step mixer or second step mixer as one of the fine powders.
- the amount of such internal recycle stream can be 0 to about 60 % by weight of final product stream on an instantaneous basis, and preferably less than about 20 % by weight on an average production basis.
- the process generally entails finishing the resulting detergent agglomerates by a variety of processes including spraying and/or admixing other conventional detergent ingredients.
- the finishing step encompasses spraying perfumes, brighteners and enzymes onto the finished agglomerates to provide a more complete detergent composition.
- Such techniques and ingredients are well known in the art.
- Step 1 222 kg/hr of liquid acid precursor HLAS (97% active) is continuously dispersed and mixed by the pin tools of a Lodige CB-30 mixer along with 297 kg/hr of ground soda ash (mean particle size of 15 microns), 295 kg/hr of powdered zeolite (mean particle size of about 5 microns), 10 kg/hr of ground sodium sulfate (mean particle size of 15 microns), and less that 20% (by weight of the CB mixer throughput) an internal recycle stream of powder from step 2.
- the acid precursor is fed at about 40°C, and the powders are fed at room temperature.
- the conditions of the CB-30 mixer are as follows:
- Mean residence time about 5 seconds
- the dry neutralization of the acid precursor by the carbonate in the presence of the other particulate material results in a free-flowing powder.
- the free-flowing powder has a mean particle size of about 290 microns, a geometric standard deviation of about 2.1 , and a bulk density of about 730 g/l.
- the free-flowing powder from the CB-30 mixer is fed continuously to a Lodige KM-600 mixer having four internal chopper assemblies along its length, each chopper assembly having three levels choppers of 4 blades each (4 cuts per chopper assembly level per chopper revolution).
- a surfactant paste blend of about 48% NaAS paste (C14.5 sulfate, sodium salt; 75% active) and about 52% NaAES paste (C14.5 ethoxy-1 sulfate, sodium salt; 75% active) is prepared.
- Such a surfactant paste blend has been determined to have an apparent yield stress of 78 Pa at a shear rate of 1 sec "1 and a temperature of 60°C, as measured using a Cammed CSL-100 Controlled Stress Rheometer.
- the paste binder is continuously injected at a temperature of about 60°C across the first three choppers assemblies at a total rate of 175 kg paste/hr.
- Each paste stream to each chopper assembly is sub-divided into three smaller streams, each directed at a separate level of chopper, where each smaller stream has a discharge opening of 2 mm diameter.
- Each chopper turns at about 3500 RPM.
- the calculated mass of the discrete mass units of paste is about 0.023 grams, which is equivalent to a equivalent spherical diameter of about 3.4 mm.
- the conditions of the KM-600 mixer are as follows:
- Mean residence time about 60 seconds
- Tip speed of plowshares about 2 m/s
- the resulting granular detergent agglomerates from the step 2 has a bulk density of about 630 g/l, a mean particle size of 510 microns, a geometric standard deviation of 1.9, and an anionic surfactant level of about 37% by weight.
- the agglomerates are processed using the optional process steps of drying and cooling in a fluidized bed, and sizing using particle separation means. After sizing, the resulting acceptable agglomerate ("accept") rate is about 90% (10% by weight recycle), where the acceptable size range is a particle size between about 150 and 1180 microns.
- the resulting acceptable agglomerates have a mean particle size of about 550 microns, a geometric standard deviation of the particle size distribution of about 1.7, and a bulk density of about 680 g/l. Unacceptable large particles are ground in a mill before recycling along with unacceptable fine particles back to step 1.
- Example 2
- Step 1 231 kg/hr of liquid acid precursor HLAS (97% active) is continuously dispersed and mixed by the pin tools of a Lodige CB-30 mixer along with 586 kg/hr of ground soda ash (mean particle size of 15 microns), and less that 20% (by weight of the CB mixer throughput) an internal recycle stream of powder from step 2.
- the acid precursor is fed at about 40°C, and the powders are fed at room temperature.
- the conditions of the CB-30 mixer are as follows:
- Mean residence time about 5 seconds
- the dry neutralization of the acid precursor by the carbonate results in a free- flowing powder.
- the free-flowing powder has a mean particle size of about 290 microns, a geometric standard deviation of about 2.4, and a bulk density of about 700 g/l.
- Step 2 The free-flowing powder from the CB-30 mixer is fed continuously to a Lodige KM-600 mixer having four internal chopper assemblies along its length, each chopper assembly having three levels choppers of 4 blades each (4 cuts per chopper assembly level per chopper revolution).
- a surfactant paste blend of 48% NaAS paste (C14.5 sulfate, sodium salt; 75% active) and 58% NaAES paste (C14.5 ethoxy-1 sulfate, sodium salt; 75% active) is prepared, and is determined to have an apparent yield stress of 78 Pa at a shear rate of 1 sec "1 and a temperature of 60°C, as measured using a Cammed CSL-100 Controlled Stress Rheometer.
- the paste binder is continuously injected at a temperature of about 60°C across the first three chopper assemblies at a total rate of about 182 kg paste/hr.
- Each paste stream to each chopper is sub-divided into three smaller streams, each directed at a separate level of chopper, where each smaller stream has a discharge opening of 2 mm diameter.
- Each chopper turns at about 3500 RPM.
- the calculated mass of the discrete mass units of paste is about 0.024 grams, which is equivalent to a equivalent spherical diameter of about 3.5 mm.
- the conditions of the KM-600 mixer are as follows:
- Mean residence time about 60 seconds
- Tip speed of plowshares about 2 m/s
- the resulting granular detergent agglomerates from the step 2 has a bulk density of about 550 g/l, a mean particle size of 720 microns, a geometric standard deviation of 1.9, and an anionic surfactant level of about 35% by weight.
- the agglomerates are processed using the optional process steps of drying and cooling in a fluidized bed, and sizing using particle separation means. After sizing, the resulting acceptable agglomerate ("accept") rate is about 90% (10% by weight recycle), where the acceptable size range is a particle size between about 300 and 1700 microns.
- the resulting acceptable agglomerates have a mean particle size of about 720 microns, a geometric standard deviation of the particle size distribution of about 1.7, and a bulk density of about 610 g/l. Unacceptable large particles are ground in a mill before recycling along with unacceptable fine particles back to step 1.
- Step 1 5400 kg/hr of liquid acid precursor HLAS (97% active) was continuously dispersed and mixed by the pin tools of a Littleford CB-100 mixer along with 12,040 kg/hr of finely ground soda ash (mean particle size of about 15 microns), 7200 kg/hr of powdered STPP, 3885 kg/hr of powdered sodium sulfate, and less that 20% (by weight of the CB mixer throughput) an internal recycle stream of powder from step 2.
- the acid precursor was fed at about 40° C, and the powders were fed at room temperature.
- the conditions of the CB-30 mixer were as follows:
- Mean residence time about 5 seconds
- the dry neutralization of the acid precursor by the carbonate in the presence of the other particulate material resulted in a free-flowing powder.
- the free-flowing powder had a mean particle size of about 250 microns, a geometric standard deviation of about 2.2, and a bulk density of about 680 g/l.
- Step 2 The free-flowing powder from the CB-100 mixer was fed continuously to a Lodige KM-15000 mixer with forward facing half-plows (i.e., Becker Blades), and having six internal chopper assemblies along its length, each chopper assembly having three levels of choppers, each chopper having 4 blades each (4 cuts per chopper assembly level per chopper revolution).
- a surfactant paste of NaAES paste was used as the agglomeration binder.
- the NaAES paste was the sodium salt of C14.5 ethoxy-3 sulfate (70% active) with an apparent yield stress of 135 Pa at a shear rate of 1 sec "1 and a temperature of 25°C, as measured using a Cammed CSL-100 Controlled Stress Rheometer.
- the paste binder was continuously injected at a temperature of about 30°C across the first four chopper assemblies at a total rate of 1224 kg paste/hr. Each paste stream to each chopper assembly was sub-divided into three smaller streams, each directed at a separate level of chopper, where each smaller stream had a discharge opening of 2 mm diameter. Each chopper turned at about 3500 RPM.
- the calculated average mass of the discrete mass units of paste was about 0.12 grams, which is equivalent to a equivalent spherical diameter of about 6 mm.
- the conditions of the KM-15000 mixer are as follows:
- Mean residence time about 16 seconds
- the resulting granular detergent agglomerates from the step 2 has a bulk density of about 710 g/l, a mean particle size of 310 microns, a geometric standard deviation of 2.3, and an anionic surfactant level of about 24% by weight. At this point in the process, the fraction of fine particles less than 150 microns was about 15% by weight, and the fraction of oversize particles greater than 1180 microns was about 7% by weight.
- the agglomerates were further processed using the optional process steps of cooling in a fluidized bed, and sizing using particle separation means.
- the resulting acceptable agglomerate (“accept") rate was about 85% (15% by weight recycle), where the acceptable size range was a particle size between about 150 and 1180 microns.
- the resulting acceptable agglomerates had a mean particle size of about 410 microns, a geometric standard deviation of the particle size distribution of about 2.0, and a bulk density of about 750 g/l. Unacceptable large particles are ground in a mill before recycling along with unacceptable fine particles back to step 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Glanulating (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10096098P | 1998-09-18 | 1998-09-18 | |
US100960P | 1998-09-18 | ||
PCT/US1999/020182 WO2000017304A1 (en) | 1998-09-18 | 1999-09-03 | Continuous process for making a detergent composition |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1114138A1 true EP1114138A1 (en) | 2001-07-11 |
EP1114138B1 EP1114138B1 (en) | 2005-05-11 |
Family
ID=22282421
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99946732A Expired - Lifetime EP1114138B1 (en) | 1998-09-18 | 1999-09-03 | Continuous process for making a detergent composition |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1114138B1 (en) |
JP (1) | JP2002526602A (en) |
CN (1) | CN1191348C (en) |
AT (1) | ATE295409T1 (en) |
AU (1) | AU5907499A (en) |
BR (1) | BR9913862B1 (en) |
CA (1) | CA2341405A1 (en) |
DE (1) | DE69925286T2 (en) |
WO (1) | WO2000017304A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050181969A1 (en) | 2004-02-13 | 2005-08-18 | Mort Paul R.Iii | Active containing delivery particle |
DE102005005499A1 (en) * | 2005-02-04 | 2006-08-17 | Henkel Kgaa | Process for the preparation of detergents or cleaners |
JP4785405B2 (en) * | 2005-04-14 | 2011-10-05 | 花王株式会社 | Detergent particles |
EP1918361A4 (en) * | 2005-07-12 | 2008-10-15 | Kao Corp | Detergent granule and process for production thereof |
DE602008001252D1 (en) * | 2008-05-22 | 2010-06-24 | Unilever Nv | Production of detergent granules by dry neutralization |
US8727963B2 (en) | 2008-07-31 | 2014-05-20 | Ams Research Corporation | Methods and implants for treating urinary incontinence |
WO2011005803A1 (en) * | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Continuous process for making a laundry detergent composition |
WO2011061045A1 (en) * | 2009-11-20 | 2011-05-26 | Unilever Nv | Detergent granule and its manufacture |
EP3140386B1 (en) | 2014-04-10 | 2024-02-28 | The Procter & Gamble Company | Composite detergent granules and laundry compositions comprising the same |
CN115916940A (en) * | 2020-07-03 | 2023-04-04 | 宝洁公司 | Granular laundry detergent composition |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8922018D0 (en) * | 1989-09-29 | 1989-11-15 | Unilever Plc | Detergent compositions and process for preparing them |
JPH11506162A (en) * | 1996-03-08 | 1999-06-02 | ザ、プロクター、エンド、ギャンブル、カンパニー | Aggregated high-density detergent composition containing secondary alkyl sulfate surfactant, and method for producing the same |
GB9618876D0 (en) * | 1996-09-10 | 1996-10-23 | Unilever Plc | Process for preparing high bulk density detergent compositions |
CN1242800A (en) * | 1996-11-06 | 2000-01-26 | 普罗格特-甘布尔公司 | Neutralization process for making agglomerate detergent granules |
GB9625066D0 (en) * | 1996-12-02 | 1997-01-22 | Unilever Plc | Process for the production of a detergent composition |
-
1999
- 1999-09-03 AU AU59074/99A patent/AU5907499A/en not_active Abandoned
- 1999-09-03 CA CA002341405A patent/CA2341405A1/en not_active Abandoned
- 1999-09-03 BR BRPI9913862-0A patent/BR9913862B1/en not_active IP Right Cessation
- 1999-09-03 EP EP99946732A patent/EP1114138B1/en not_active Expired - Lifetime
- 1999-09-03 WO PCT/US1999/020182 patent/WO2000017304A1/en active IP Right Grant
- 1999-09-03 CN CNB998110264A patent/CN1191348C/en not_active Expired - Fee Related
- 1999-09-03 AT AT99946732T patent/ATE295409T1/en not_active IP Right Cessation
- 1999-09-03 JP JP2000574205A patent/JP2002526602A/en not_active Withdrawn
- 1999-09-03 DE DE69925286T patent/DE69925286T2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO0017304A1 * |
Also Published As
Publication number | Publication date |
---|---|
CN1354782A (en) | 2002-06-19 |
AU5907499A (en) | 2000-04-10 |
CN1191348C (en) | 2005-03-02 |
ATE295409T1 (en) | 2005-05-15 |
WO2000017304A1 (en) | 2000-03-30 |
DE69925286D1 (en) | 2005-06-16 |
EP1114138B1 (en) | 2005-05-11 |
CA2341405A1 (en) | 2000-03-30 |
DE69925286T2 (en) | 2006-02-23 |
BR9913862A (en) | 2001-06-05 |
JP2002526602A (en) | 2002-08-20 |
BR9913862B1 (en) | 2009-05-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5489392A (en) | Process for making a high density detergent composition in a single mixer/densifier with selected recycle streams for improved agglomerate properties | |
US5516448A (en) | Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate | |
US5576285A (en) | Process for making a low density detergent composition by agglomeration with an inorganic double salt | |
JPH11508313A (en) | Method for producing low-density detergent composition | |
EP0929648B1 (en) | Process for making a detergent composition by non-tower process | |
CA2245933C (en) | Process for making a low density detergent composition by agglomeration with an inorganic double salt | |
EP1114138B1 (en) | Continuous process for making a detergent composition | |
US6794354B1 (en) | Continuous process for making detergent composition | |
JP2003521548A (en) | Method for producing low-density detergent composition by adjusting nozzle height in fluidized bed dryer | |
EP1187904B1 (en) | Process for making a granular detergent composition | |
JP5537800B2 (en) | Method for producing detergent particles | |
US6281188B1 (en) | Process for making a low density detergent composition | |
MXPA02000027A (en) | Processes for making granular detergent in a fluidized bed granulator having recycling of improperly sized particles. | |
EP1141229A1 (en) | Process for making a low bulk density detergent composition by agglomeration | |
US6951837B1 (en) | Process for making a granular detergent composition | |
US6156719A (en) | Process for making a low density detergent composition by non-tower process | |
MXPA01002871A (en) | Continuous process for making a detergent composition | |
CA2346340A1 (en) | Process for making a free flowing detergent composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20010326 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17Q | First examination report despatched |
Effective date: 20030605 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050511 Ref country code: LI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050511 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050511 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050511 Ref country code: CH Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050511 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050511 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050511 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 69925286 Country of ref document: DE Date of ref document: 20050616 Kind code of ref document: P |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20050809 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050811 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050811 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050811 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050822 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20050902 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050903 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050905 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050930 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050930 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20050930 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051019 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
ET | Fr: translation filed | ||
26N | No opposition filed |
Effective date: 20060214 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20061130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070403 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20060903 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060903 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061002 |