EP0993504A1 - Production of detergent granulates - Google Patents
Production of detergent granulatesInfo
- Publication number
- EP0993504A1 EP0993504A1 EP98933629A EP98933629A EP0993504A1 EP 0993504 A1 EP0993504 A1 EP 0993504A1 EP 98933629 A EP98933629 A EP 98933629A EP 98933629 A EP98933629 A EP 98933629A EP 0993504 A1 EP0993504 A1 EP 0993504A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stage
- process according
- temperature
- gas
- less
- 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 29
- 239000008187 granular material Substances 0.000 title description 18
- 238000004519 manufacturing process Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 74
- 230000008569 process Effects 0.000 claims abstract description 71
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 239000011230 binding agent Substances 0.000 claims abstract description 34
- 238000005243 fluidization Methods 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 28
- 239000011343 solid material Substances 0.000 claims abstract description 11
- 239000007921 spray Substances 0.000 claims abstract description 3
- 238000005469 granulation Methods 0.000 claims description 19
- 230000003179 granulation Effects 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 239000007858 starting material Substances 0.000 claims description 13
- 239000003945 anionic surfactant Substances 0.000 claims description 10
- 238000010923 batch production Methods 0.000 claims description 5
- 238000010924 continuous production Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 description 25
- 239000002245 particle Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- -1 alkylbenzene sulphonate Chemical class 0.000 description 10
- 239000010457 zeolite Substances 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 7
- 230000003472 neutralizing effect Effects 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 229940001593 sodium carbonate Drugs 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 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 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical class OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LVVZBNKWTVZSIU-UHFFFAOYSA-N 2-(carboxymethoxy)propanedioic acid Chemical class OC(=O)COC(C(O)=O)C(O)=O LVVZBNKWTVZSIU-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical class OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000009476 low shear granulation Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 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
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 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
- 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
- C11D11/0088—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 the liquefied ingredients being sprayed or adsorbed onto solid particles
Definitions
- the present invention relates to a process for the production of granular detergent compositions.
- a known kind of mixing process which does not involve spray drying, employs a moderate-speed granulator (a common example often colloquially being called a "ploughshare"), optionally preceded by a high-speed mixer (a common example often colloquially being called a "recycler” due to its recycling cooling system) .
- a moderate-speed granulator (a common example often colloquially being called a "ploughshare")
- a high-speed mixer a common example often colloquially being called a "recycler” due to its recycling cooling system) .
- Typical examples of such processes are described in our European patent specifications EP-A-367 339, EP-A-390 251 and EP-A-420 317.
- gas fluidisation granulators can give good control of bulk density, there is still a need for greater flexibility and in particular, for producing lower bulk density powders. Processes involving low-shear granulation are quite varied.
- WO96/04359 discloses a process whereby low bulk density powders are prepared by contacting a neutralising agent such as an alkaline detergency builder and a liquid acid precursor of an anionic surfactant in a fluidisation zone to form detergent granules.
- a neutralising agent such as an alkaline detergency builder and a liquid acid precursor of an anionic surfactant in a fluidisation zone to form detergent granules.
- the present invention now provides a process of forming a granular detergent products, the process comprising, in a gas fluidisation granulator, contacting a fluidised particulate solid material with a spray of liquid binder, whilst fluidising the solids in the granulator with at least one gas stream, wherein the gas temperature is controlled so as to be increased and/or reduced during at least one stage of the process.
- controlling the gas temperature according to the present invention leads to an increase and/or reduction in the temperature of the fluidising particulate solid material during at least one stage of the process.
- the gas temperature is controlled not so as to merely maintain a constant "bed" temperature, for example by removing heat of reaction, but so as to increase and/or decrease the actual temperature of the fluidising solids.
- the gas fluidisation granulation apparatus basically comprises a chamber in which a stream of gas, usually air, is used to cause turbulent flow of particulate solids to form a "cloud" of the solids and liquid binder is sprayed onto or into the cloud to contact the individual particles.
- a stream of gas usually air
- liquid binder is sprayed onto or into the cloud to contact the individual particles.
- the process of the present invention resolves the stickiness of the granules as they form. In many cases, it is believed that this may occur as a result of transformation of the liquid constituents into a more solid state or a state having a higher viscosity, due to the temperature variation of the process.
- the temperature increase and/or reduction must occur during at least one stage of the process, i.e. at least one stage when fluidisation and spraying are in progress.
- the process may be operated with a gas temperature below ambient during at least one stage (or all of) the process. Preferably, it is operated with a gas temperature higher during a first stage of the process than during a second stage, before or after the first stage.
- the gas fluidisation granulator is typically operated at a superficial air velocity of about 0.1-1.2 ms , either under positive or negative relative pressure.
- the gas temperature, and thus preferably the bed temperature may be elevated for a first period, e.g. at up to 80°C or even up to 200°C and then at one or more other stages (before or after) , it may be reduced to just above, at, or below ambient, e.g. to 30°C or less, preferably 25°C or less or even as low as 5°C or less or -10°C or less.
- the gas temperature and preferably also the bed temperature, is elevated for a first period and subsequently lowered in a second period.
- the temperature variation When the process is a batch process, the temperature variation will be effected over time. If it is a continuous process, it will be varied along the "track" of the granulator bed. In the latter case, this is conveniently effected using a granulator of the "plug flow” type, i.e. one in which the materials flow through the reactor from beginning to end.
- the gas temperature may be reduced over a relatively short period of time, for example 10 to 50% of the process time. Typically, the gas temperature may be reduced for 0.5 to 15 minutes. In a continuous process, the gas temperature may be reduced along a relatively short length of the "track" of the granulator bed, for example along 10 to 50% of the track. In both cases, the gas may be pre-cooled.
- the gas temperature is not lowered until granulation of the fluidising particulate solid material is substantially complete.
- bed temperature refers to the temperature of the fluidising solid particulate material.
- the temperature of the fluidising solid particulate material can be measured, for example, using a thermocouple probe. Whether there is a discernible powder bed or no discernible powder bed (i.e. because the mixer is being operated with a gas flow rate so high that a classical "bubbling" fluid bed is not formed) , the "bed temperature” is taken to be the temperature as measured at a point inside the fluidisation chamber about 15 cm from the gas distributor plate.
- granular detergent product encompasses granular finished products for sale, as well as granular components or adjuncts for forming finished products, e.g. by post-dosing to or with, or any other form of admixture with further components or adjuncts.
- a granular detergent product as herein defined may, or may not contain detergent material such as synthetic surfactant and/or soap.
- the minimum requirement is that it should contain at least one material of a general kind of conventional component of granular detergent products, such as a surfactant (including soap), a builder, a bleach or bleach-system component, an enzyme, an enzyme stabiliser or a component of an enzyme stabilising system, a soil anti- redeposition agent, a fluorescer or optical brightener, an anti-corrosion agent, an anti-foam material, a perfume or a colourant .
- a surfactant including soap
- the term "powder” refers to materials substantially consisting of grains of individual materials and mixtures of such grains.
- the term “granule” refers to a small particle of agglomerated powder materials.
- the final product of the process according to the present invention consists of, or comprises a high percentage of granules. However, additional granular and or powder materials may optionally be post-dosed to such a product.
- solid starting materials of the present invention are particulate and may be powdered and/or granular.
- particulate solid starting material may be introduced at any time during the time when liquid binder is being sprayed.
- solid starting material is first introduced to the gas fluidisation granulator and then sprayed with the liquid binder.
- some particulate solid starting material could be introduced at the beginning of processing in the gas fluidisation apparatus and the remainder introduced at one or more later times, either as one or more discrete batches or in continuous fashion.
- the solid starting material (s) have a particle size distribution such that not more than 5% by weight of the particles have a particle size greater than 250 ⁇ m. It is also preferred that at least 30% by weight of the particles have a particle size below 100 ⁇ m, more preferably below 75 ⁇ m.
- the present invention is also usable with larger fractions of solid starting materials (i.e. > 5% more than 250 ⁇ m, optionally also ⁇ 30% below 100 ⁇ m or 75 ⁇ m) but this increases the chance of some crystals of unagglommerated starting materials being found in the final product. This presents a cost benefit in allowing use of cheaper raw materials.
- the particulate solid starting material (s) have an average particle size below 500 ⁇ m to provide detergent powders having a particularly desired low bulk density.
- reference to an average particle size means the d 3 2 average particle diameter.
- the gas fluidisation granulator may be adapted to recycle "fines" i.e. powdered or part-granular material of very small particle size, so that they are returned to the input of the gas fluidisation apparatus and/or input of any pre-mixer.
- the fine particulates are elutriated material, i.e. they are present in the air leaving a the gas fluidisation chamber.
- the gas fluidisation granulator may optionally be of the kind provided with a vibrating bed, particularly for use in continuous mode.
- the liquid binder comprises an acid precursor of an anionic surfactant and the particulate solid starting material comprises an inorganic alkaline material.
- the process of the present invention is especially suited to this kind of granulation, especially when the temperature is elevated in the first part of the process. In that way, the neutralisation reaction can proceed much nearer to completion, before the end of the granulation operation, than would otherwise be the case.
- bed temperature is increased by increasing the gas temperature during any neutralisation reaction, preferably for a substantial part of the neutralisation reaction.
- the acid precursor may for example be the acid precursor of a linear alkylbenzene sulphonate (LAS) or primary alkyl sulphate (PAS) anionic surfactant or of any other kind of anionic surfactant.
- LAS linear alkylbenzene sulphonate
- PAS primary alkyl sulphate
- Suitable materials for use as the inorganic alkaline material include alkali metal carbonates and bicarbonates, for example sodium salts thereof.
- the neutralising agent is very preferably present at a level sufficient to neutralise fully the acidic component. If desired, a stoichiometric excess of neutralising agent may be employed to ensure complete neutralisation or to provide an alternative function, for example as a detergency builder, e.g. if the neutralising agent comprises sodium carbonate.
- the liquid binder may alternatively or additionally contain one or more other liquid materials such as liquid nonionic surfactants and/or organic solvents.
- the total amount of acid precursor will normally be as high as possible, subject to the presence of any other components in the liquid and subject to other considerations referred to below.
- the acid precursor may constitute at least 98% (e.g. at least 95%) by weight of the liquid binder, but could be at least 75%, at least 50% or at least 25% by weight of the binder.
- the binder can even, for example, constitute 5% or less by weight of the binder.
- the acid precursor can be omitted altogether if required.
- the weight ratio of all acid precursor (s) to nonionic surfactants will normally be from 20:1 to 1:20. However, this ratio may be, for example, 15:1 or less (of the anionic), 10:1 or less, or 5:1 or less.
- the nonionic may be the major component so that the ratio is 1:5 or more (of the nonionic), 1:10 or more, or 1:15 or more. Ratios in the range from 5:1 to 1:5 are also possible.
- the maximum amount of anionic incorporated in the salt form is preferably no more than 70%, more preferably no more than 50% and most preferably no more than 40%.
- a soap in the granules, this can be achieved by incorporating a fatty acid, either in solution in the liquid binder or as part of the solids.
- the solids in any event must then also comprise an inorganic alkaline neutralising agent to react with the fatty acid to produce the soap.
- the liquid binder will often be totally or substantially non- aqueous, that is to say, any water present does not exceed 25% by weight of the liquid binder, but preferably no more than 10% by weight. However, if desired, a controlled amount of water may be added to facilitate neutralisation. Typically, the water may be added in amounts of 0.5 to 2% by weight of the final detergent product. Any such water is suitably added prior to or together or alternating with the addition of the acid precursor.
- an aqueous liquid binder may be employed.
- adjuncts for subsequent admixture with other components to form a fully formulated detergent product.
- Such adjuncts will usually, apart from components resulting from the liquid binder, mainly consist of one, or a small number of components normally found in detergent compositions, e.g. a surfactant or a builder such as zeolite or sodium tripolyphosphate.
- aqueous liquid binders for granulation if substantially fully formulated products.
- typical aqueous liquid binders include aqueous solutions of alkali metal silicates, water soluble acrylic/maleic polymers (e.g. Sokalan CP5) and the like.
- the particulate solid starting material may be contacted and mixed with a first portion of the liquid binder, e.g. in a low-, moderate- or high-shear mixer (i.e. a pre-mixer) to form a partially granulated material.
- a low-, moderate- or high-shear mixer i.e. a pre-mixer
- the latter can then be sprayed with a second portion of the liquid binder in the gas fluidisation granulator, to form the granulated detergent product .
- liquid binder In such a two-stage granulation process, it is preferred, but not absolutely necessary, for the total of liquid binder to be dosed only in the partial granulation pre-mixer and fluidisation steps. Conceivably, some could be dosed during or before partial granulation premixing and/or fluidisation. Also, the content of the liquid binder could be varied between these first and second stages.
- the extent of granulation in the pre-mixer (i.e. partial granulation) and the amount of granulation in the gas fluidisation granulator is preferably determined in accordance with the final product density desired.
- Preferred amounts of liquid binder to dosed at each of the two stages may be varied thus : -
- R appropriate mixer for this step is a high-shear Lodige CB
- a low- or high-shear mixer granulator has a stirring action and/or a cutting action which are operated independently of one another. Preferred types of low- or high-shear mixer/
- R R granulators are mixers of the Fukae FS-G series; Diosna V series ex Dierks & Sohne, Germany; Pharma Matrix ex T.K.
- a "layering agent” or “flow aid” may be introduced at any appropriate stage. This is to improve the granularity of the product, e.g. by preventing aggregation and/or caking of the granules.
- Any layering agent flow aid is suitably present in an amount of 0.1 to 15% by weight of the granular product and more preferably in an amount of 0.5 to 5%.
- Suitable layering agents/flow aids include crystalline or amorphous alkali metal silicates, aluminosilicates including zeolites, Dicamol, calcite, diatomaceous earths, silica, for example precipitated silica, chlorides such as sodium chloride, sulphates such as magnesium sulphate, carbonates such as calcium carbonate and phosphates such as sodium tripolyphospate. Mixtures of these materials may be employed as desired.
- additional components may be included in the liquid binder or admixed with the solid neutralising agent at an appropriate stage of the process.
- solid components can be post-dosed to the granular detergent product .
- anionic surfactant which optionally may be produced by a neutralisation step
- further anionic surfactants, or nonionic surfactant as mentioned above also, cationic, zwitterionic, amphoteric or semipolar surfactants and mixtures thereof may be added at a suitable time.
- suitable surfactants include those generally described in "Surface active agents and detergents" Vol I by Schwartz and Perry.
- soap derived from saturated or unsaturated fatty acids having, for example having an average of C 10 to C 18 carbon atoms may also be present.
- the detergent active is suitably incorporated at a level of 5 to 40%, preferably 10 to 30% by weight of the final granular detergent product.
- a complete detergent composition often contains a detergency builder.
- a detergency builder may be introduced with the solid material and/or added subsequently as desired.
- the builder may also constitute a neutralising agent, for example sodium carbonate, in which case sufficient material will be employed for both functions.
- the total amount of detergency builder in the granular product is suitably from 5 to 95%, for example from 10 to 80%, preferably from 15 to 65%, more preferably from 15 to 50% by weight.
- Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate as disclosed in GB-A-1 437 950. Any sodium carbonate will need to be in excess of any used to neutralise the anionic acid precursor if the latter is added during the process.
- Suitable builders include crystalline and amorphous aluminosilicates, for example zeolites as disclosed in GB-A-1 473 201; amorphous aluminosilicates as disclosed in GB-A-1 473 202; and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250; and layered silicates as disclosed in EP-B-164 514.
- Inorganic phosphate builders for example, sodium, orthophosphate, pyrophosphate and tripolyphosphate, may also be present, but on environmental grounds those are no longer preferred.
- Aluminosilicates whether used as layering agents and/or incorporated in the bulk of the particles may suitably be present in a total amount of from 10 to 60% and preferably an amount of from 15 to 50% by weight.
- the zeolite used in most commercial particulate detergent compositions is zeolite A.
- maximum aluminium zeolite P zeolite MAP described and claimed in EP-A-384 070 may be used.
- Zeolite MAP is an alkali metal aluminosilicated of the P type having a silicon to aluminium ratio not exceeding 1.33, preferably not exceeding 1.15, and more preferably not exceeding 1.07.
- Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates ; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates , dipicolinates , hydroxyethyliminodiacetates , alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts.
- a copolymer of maleic acid, acrylic acid and vinyl acetate is especially preferred as it is biodegradable and thus environmentally desirable. This list is not intended to be exhaustive.
- Especially preferred organic builders are citrates, suitably used in amounts of from 5 to 30%, preferably from 10 to 25% by weight; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15%, preferably from 1 to 10% by weight. Citrates can also be used at lower levels (eg 0.1 to 5%) by weight for other purposes.
- the builder is preferably present in alkali metal salt, especially sodium salt, form.
- the builder system may also comprise a crystalline layered silicate, for example, SKS-6 ex Hoechst, a zeolite, for example, zeolite A and optionally an alkali metal citrate.
- the granular composition resulting from the process of the present invention may also comprise a particulate filler (or any other component which does not contribute to the wash process) which suitably comprises an inorganic salt, for example sodium sulphate and sodium chloride.
- a particulate filler or any other component which does not contribute to the wash process
- the filler may be present at a level of 5 to 70% by weight of the granular product .
- the present invention also encompasses a granular detergent product resulting from the process of the invention (before any post-dosing or the like) .
- This product will have a bulk density determined by the exact nature of the process. If the process does not involve a pre-mixer to effect partial granulation, a final bulk density of 350-750 g/1 can normally be expected. As mentioned above, use of a pre-mixer enables the final bulk density to be 350-650 g/1 or 550-1300 g/1, respectively, according to whether option (i) or (ii) is utilised.
- granular detergent products resulting from the present invention are also characterised by their particle size ranges.
- not more than 10% by weight has a diameter > 1.4 mm and more preferably, not more than 5% by weight of the granules are above this limit. It is also preferred that not more than 20% by weight of the granules have a diameter > 1 mm.
- the granules can be distinguished from granules produced by other methods by mercury porosimetry. The latter technique cannot reliably determine the porosity of individual unagglomerated particles but is ideal for characterising the granules.
- a fully formulated detergent composition produced according to the invention might for example comprise the detergent active and builder and optionally one or more of a flow aid, a filler and other minor ingredients such as colour, perfume, fluorescer, bleaches, enzymes.
- the fluidising air temperature was varied from 20°C to 80°C in the first stage followed by a second stage at 20°C.
- a Spraying System nozzle SUE25 was used operating with an atomising air pressure of 5 bar.
- Example I and II are control examples where there was no temperature variation.
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- 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)
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9712587.6A GB9712587D0 (en) | 1997-06-16 | 1997-06-16 | Production of detergent granulates |
GB9712587 | 1997-06-16 | ||
PCT/EP1998/003669 WO1998058048A1 (en) | 1997-06-16 | 1998-06-12 | Production of detergent granulates |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0993504A1 true EP0993504A1 (en) | 2000-04-19 |
EP0993504B1 EP0993504B1 (en) | 2002-03-27 |
Family
ID=10814308
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98933629A Revoked EP0993504B1 (en) | 1997-06-16 | 1998-06-12 | Production of detergent granulates |
Country Status (18)
Country | Link |
---|---|
EP (1) | EP0993504B1 (en) |
CN (1) | CN1170917C (en) |
AR (1) | AR013093A1 (en) |
AU (1) | AU725182B2 (en) |
BR (1) | BR9810165A (en) |
CA (1) | CA2294287A1 (en) |
DE (1) | DE69804457T2 (en) |
EA (1) | EA002160B1 (en) |
ES (1) | ES2174457T3 (en) |
GB (1) | GB9712587D0 (en) |
HU (1) | HUP0003031A3 (en) |
ID (1) | ID24618A (en) |
IN (1) | IN189876B (en) |
PL (1) | PL186896B1 (en) |
TR (1) | TR199903104T2 (en) |
TW (1) | TW432108B (en) |
WO (1) | WO1998058048A1 (en) |
ZA (1) | ZA985194B (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9526097D0 (en) * | 1995-12-20 | 1996-02-21 | Unilever Plc | Process |
GB9712580D0 (en) * | 1997-06-16 | 1997-08-20 | Unilever Plc | Production of detergent granulates |
GB9712583D0 (en) | 1997-06-16 | 1997-08-20 | Unilever Plc | Production of detergent granulates |
GB9713748D0 (en) * | 1997-06-27 | 1997-09-03 | Unilever Plc | Production of detergent granulates |
ES2226153T3 (en) | 1997-07-14 | 2005-03-16 | THE PROCTER & GAMBLE COMPANY | PROCEDURE FOR MANUFACTURING A DETERGENT COMPOSITION OF LOW DENSITY CONTROLLING THE AGLOMERATION THROUGH THE SIZE OF PARTICLES. |
EP1002043B1 (en) | 1997-07-14 | 2007-08-22 | The Procter & Gamble Company | Process for making a low density detergent composition by controlled agglomeration in a fluid bed dryer |
WO1999003965A1 (en) | 1997-07-15 | 1999-01-28 | The Procter & Gamble Company | Process for making high-active detergent agglomerates by multi-stage surfactant paste injection |
US6440342B1 (en) | 1998-07-08 | 2002-08-27 | The Procter & Gamble Company | Process for making a low density detergent composition by controlling nozzle height in a fluid bed dryer |
DE19904657B4 (en) * | 1999-02-04 | 2012-09-20 | Glatt Ingenieurtechnik Gmbh | Process for the preparation of heavy-duty detergents and heavy-duty detergent components |
GB9913544D0 (en) * | 1999-06-10 | 1999-08-11 | Unilever Plc | Process for preparing granular detergent compositions |
GB9913542D0 (en) * | 1999-06-10 | 1999-08-11 | Unilever Plc | Process for preparing granular detergent compositions |
GB9913546D0 (en) | 1999-06-10 | 1999-08-11 | Unilever Plc | Granular detergent component containing zeolite map and laundry detergent compositions containing it |
GB9927653D0 (en) | 1999-11-22 | 2000-01-19 | Unilever Plc | Process for preparing granular detergent compositions |
DE19957036A1 (en) * | 1999-11-26 | 2001-05-31 | Henkel Kgaa | Production of particulate detergents containing components effective at different pH values involves applying a flowable acidic component onto alkali-containing particles in amount related mathematically to the particle radius |
MXPA04003892A (en) | 2001-10-25 | 2004-07-08 | Unilever Nv | Process for the production of detergent granules. |
GB0125653D0 (en) | 2001-10-25 | 2001-12-19 | Unilever Plc | Process for the production of detergent granules |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1341557A (en) * | 1970-06-02 | 1973-12-25 | ||
GB2209172A (en) * | 1987-08-28 | 1989-05-04 | Unilever Plc | Preparation of solid particulate components for detergents |
US4919847A (en) * | 1988-06-03 | 1990-04-24 | Colgate Palmolive Co. | Process for manufacturing particulate detergent composition directly from in situ produced anionic detergent salt |
GB9415904D0 (en) * | 1994-08-05 | 1994-09-28 | Unilever Plc | Process for the production of detergent composition |
-
1997
- 1997-06-16 GB GBGB9712587.6A patent/GB9712587D0/en not_active Ceased
-
1998
- 1998-06-12 ES ES98933629T patent/ES2174457T3/en not_active Expired - Lifetime
- 1998-06-12 CA CA002294287A patent/CA2294287A1/en not_active Abandoned
- 1998-06-12 EP EP98933629A patent/EP0993504B1/en not_active Revoked
- 1998-06-12 DE DE69804457T patent/DE69804457T2/en not_active Revoked
- 1998-06-12 ID IDW991607A patent/ID24618A/en unknown
- 1998-06-12 CN CNB988081911A patent/CN1170917C/en not_active Expired - Fee Related
- 1998-06-12 AU AU83382/98A patent/AU725182B2/en not_active Ceased
- 1998-06-12 BR BR9810165-0A patent/BR9810165A/en active Search and Examination
- 1998-06-12 EA EA200000024A patent/EA002160B1/en not_active IP Right Cessation
- 1998-06-12 TR TR1999/03104T patent/TR199903104T2/en unknown
- 1998-06-12 PL PL98337431A patent/PL186896B1/en not_active IP Right Cessation
- 1998-06-12 WO PCT/EP1998/003669 patent/WO1998058048A1/en not_active Application Discontinuation
- 1998-06-12 HU HU0003031A patent/HUP0003031A3/en unknown
- 1998-06-15 ZA ZA9805194A patent/ZA985194B/en unknown
- 1998-06-16 IN IN376BO1998 patent/IN189876B/en unknown
- 1998-06-16 AR ARP980102845A patent/AR013093A1/en unknown
- 1998-10-15 TW TW087117202A patent/TW432108B/en active
Non-Patent Citations (1)
Title |
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See references of WO9858048A1 * |
Also Published As
Publication number | Publication date |
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CA2294287A1 (en) | 1998-12-23 |
AU725182B2 (en) | 2000-10-05 |
PL337431A1 (en) | 2000-08-14 |
TW432108B (en) | 2001-05-01 |
AU8338298A (en) | 1999-01-04 |
EA002160B1 (en) | 2001-12-24 |
CN1267329A (en) | 2000-09-20 |
PL186896B1 (en) | 2004-03-31 |
GB9712587D0 (en) | 1997-08-20 |
DE69804457T2 (en) | 2002-10-17 |
CN1170917C (en) | 2004-10-13 |
AR013093A1 (en) | 2000-12-13 |
ID24618A (en) | 2000-07-27 |
HUP0003031A3 (en) | 2003-02-28 |
DE69804457D1 (en) | 2002-05-02 |
ES2174457T3 (en) | 2002-11-01 |
EA200000024A1 (en) | 2000-06-26 |
ZA985194B (en) | 1999-12-17 |
WO1998058048A1 (en) | 1998-12-23 |
HUP0003031A2 (en) | 2001-01-29 |
BR9810165A (en) | 2000-08-08 |
EP0993504B1 (en) | 2002-03-27 |
TR199903104T2 (en) | 2000-03-21 |
IN189876B (en) | 2003-05-03 |
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