US3303134A - Detergent processes and compositions therefor - Google Patents
Detergent processes and compositions therefor Download PDFInfo
- Publication number
- US3303134A US3303134A US135718A US13571861A US3303134A US 3303134 A US3303134 A US 3303134A US 135718 A US135718 A US 135718A US 13571861 A US13571861 A US 13571861A US 3303134 A US3303134 A US 3303134A
- Authority
- US
- United States
- Prior art keywords
- alkali metal
- slurry
- trimetaphosphate
- detergent
- tripolyphosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 111
- 238000000034 method Methods 0.000 title claims description 52
- 239000003599 detergent Substances 0.000 title description 104
- 239000002002 slurry Substances 0.000 claims description 137
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 91
- 229910052783 alkali metal Inorganic materials 0.000 claims description 76
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 43
- 239000002585 base Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 150000001340 alkali metals Chemical class 0.000 claims description 33
- AZSFNUJOCKMOGB-UHFFFAOYSA-K cyclotriphosphate(3-) Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-K 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 claims 1
- -1 alkali metal tripolyphosphate Chemical class 0.000 description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 description 35
- 239000000047 product Substances 0.000 description 29
- 229910019142 PO4 Inorganic materials 0.000 description 19
- 235000021317 phosphate Nutrition 0.000 description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 18
- 239000010452 phosphate Substances 0.000 description 18
- 238000002156 mixing Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 11
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 10
- 239000012736 aqueous medium Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 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 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 6
- 229940117927 ethylene oxide Drugs 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 5
- 150000008041 alkali metal carbonates Chemical class 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 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
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 239000000843 powder Substances 0.000 description 2
- 238000007613 slurry method Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- 241001517013 Calidris pugnax Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- 229940116985 potassium lauryl sulfate Drugs 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229940036051 sojourn Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
- C11D3/062—Special methods concerning phosphates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/40—Polyphosphates
- C01B25/41—Polyphosphates of alkali metals
-
- 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
- C11D11/02—Preparation in the form of powder by spray drying
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3958—Bleaching agents combined with phosphates
Definitions
- This invention relates to novel methods for producing detergent compositions containing alkali metal tripolyphosphates. More specifically, this invention relates to the use of alkali metal trimetaphosphates in the production of heat-dried detergent products.
- tripolyphosphates are not nearly as effective (as sequestrants) in building detergent products as is tripolyphosphate and therefore are not nearly as desirable as tripolyphosphate in the final heat-dried detergent product.
- the present invention makes it possible to either eliminate or at least alleviate all of the above-described processing difiiculties which are ordinarily associated with the use of alkali metal tripolyphosphate in the preparation of heat-dried detergent products.
- this invention makes it possible to produce heat-dried detergent compositions at a significantly lower processing cost than was heretofore practicable, and to produce detergent compositions having more desirable qualities, as compared 3,303,134 Patented Feb.
- the invention makes advantageous use of the reaction of alkali metal trimetaphosphates with a base in the presence of alkali metal ions to produce an alkali metal tripolyphosphate.
- the reaction is believed to be represented by the following series of steps:
- trimetaphosphate ring is cleaved by the base, forming the tripolyphosphate anion, as is shown in Equation 1:
- tripolyphosphate O1IO (tripoly hos hate)
- the tripolyphosphate crystallizes from the solution as the hydrate, as shown in Equation 2;
- M represent sodium and that y equal six.
- the heat-dried detergent compositions which can be made according to the practice of this invention are those that contain a significant amount of tripolyphosphate; that is, usually at least about 10 weight percent and often as much as weight percent of tripolyphosphate, based on the total weight of the heat-dried composition.
- compositions which contain the higher levels of tripolyphosphate for example, compositions containing more than about 20 weight percent of tripolyphosphate
- a substantial proportion for example, at least about 60 weight percent, and preferably at least about 75 Weight percent, of the tripolyphosphate in the heat-dried detergent compositions must be in the hydrated state.
- a slurry is ordinarily utilized in order to achieve several specific advantages, including the achievement of a better uniformity of ingredients through the final detergent product, and affording to the detergent manufacturer a greater ease of handling the formulation while it is being prepared, etc.
- the advantages of using the slurry method are so great that the socalled slurry method of preparing detergent has become the most important procedure in use today.
- Detergent slurries are well-known in the art, and neednt be detailed here, except to point out that those which relate to this invention contain more than sufficient water to hydrate all of the alkali metal tripolyphosphate in the final detergent composition.
- useful slurries will generally contain at least about weight percent of water, based on the total weight of the slurry before it is heat-dried.
- the minimum amount of water that can be utilized in any of these slurries will be that amount below which the slurry loses some of its fluid properties and becomes too viscous to pump and handle in conventional equipment.
- conventional detergent slurries have heretofore generally contained at least about 35 weight percent of water.
- the slurries that are utilized in the practice of this invention can contain significantly less water than could comparable or equivalent conventional slurries and still be sufiiciently fluid to be utilized in conventional crutching and heat-drying facilities. Consequently, it is a preferred embodiment of the processes of the invention to heat-dry detergent compositions containing between about 70 weight percent and 80 weight percent of solids (non-volatile at 105 C.) prepared according to the procedures which will be detailed below. Since the slurries within the purview of this invention are to be ultimately heat-dried, cost considerations dictate that those detergent slurries upon which this invention will be practiced will be those containing at least about 25 weight percent of solids.
- the bases which can be utilized in the practice of this invention are all of those which can cause the formation of hydroxyl ions, in the aqueous media, for reaction with the alkali metal trimetaphosphate (in order to produce alkali metal tripolyphosphate).
- the term strong base will be intended to encompass those bases that are sufficiently strong to cause the formation of excess hydroxyl ions in aqueous media that contain dissolved alkali metal tripolyphosphate.
- the strong bases that can be utilized are those that yield a solution pH measured at 25 C. of at least about 10.2 when they are dissolved in distilled water at the 1 weight percent level.
- strong base encompasses, for example, such basic compounds as for example, alkali metal carbonates, alkali metal silicates, tri-alkali metal orthophosphates, alkali metal and alkaline earth metal oxides, and the like (which compounds do not actually contain hydroxyl anions, but which cause hydroxyl ions [high pH] to result when they are dissolved in water), as well as some of the organic quaternary ammonium hydroxides, the alkali metal hydroxides and the alkaline earth metal hydroxides such as calcium hydroxide, and magnesium hydroxide,
- alkali metal hydroxides, carbonates, and silicates having SiO /M O ratios lower than 2.0
- the sodium forms of these materials are preferred.
- the amounts of the various strong bases described above which can be utilized in this invention will vary considerably, depending upon such factors as the molecular weight of the base, its basic strength, rate of dissolution in water, etc. The amount, however, will always be sufiicient to furnish enough hydroxyl ions so that at least a substantial amount or proportion (i.e. at least about one third) of the alkali metal trimetaphosphate in the term base conversion unit will herein be intended to mean the amount of strong base that will generate two mole equivalents of hydroxyl ions per mole of trimetaphosphate in the slurry.
- the amount of strong base present in the detergent slurries which are utilized in the practice of the invention will generally not be more than about 3 base conversion units.
- any amount of alkali metal trimetaphosphate can be used in formulating detergent compositions according to the processes of this invention.
- the amount of alkali metal trimetaphosphate that is actually utilized will usually be dependent upon basically two requirements of the detergent manufacturer: the amount of tripolyphosphate which he desires in his final detergent product, and the proportion of thisv amount of tripolyphosphate that should be in the hydrated state.
- the products which result from the practice of this invention will almost invariably contain at least about 10 weight percent of hydrated tripolyphosphate, the slurries contemplated herein will ordinarily contain at least about 5 weight percent initially (based on the weight of the slurry solids) of one of the alkali met-a1 trimetaphosphates.
- the amount of alkali metal trimetaphosphate which is initially intermixed With the aqueous medium in the practice of this invention be from about to about 50 percent by Weight, based on the total weight of the slurry just before it is heat-dried (i.e., after the slurry has been completely formulated).
- trimetaphosphate to tripolyphosphate
- the actual size of the particles of trimetaphosphate that can be utilized in the practice -of this invention is not critical.
- the alkali metal trimetaphosphates can be utilized in any of the particle sizes and physical forms (i.e., flake, powder,
- the alkali metal tripolyphosphates can be employedin conventional processes for preparing heat-dried detergent products.
- the granular form is sometimes desired because of its free-flowing, ease of handling, characteristics.
- the alkali metal trimetaphosphat'es be in a finely divided state before they are mixed into the aqueous media in order to form the desired detergent slurries.
- finely divided is meant that the trimetaphosphate granules, flakes or power etc. should be small enough so that at least about 80 (weight) percent of them will pass through a US. Standard 100 mesh screen. In some applications of the invention it will be advantageous if the particles of the phosphate are small enough so that at least about 80 (weight) percent of them could pass through a US. Standard 200 mesh' screen.
- ingredients such as water, surface active agents, bases, and builders such as alkali metal trimetaphosphate, etc.
- the ingredients can be blended together in any manner which is conventient to the slurry formulator without detracting appreciably from the benefits that can result from practicing the invention.
- conventional detergent heat-drying plant facilities including crutchers, pumps, spraying facilities, etc., although no particular types of equipment are critical.
- a vessel fitted with a means for blending the various materials which will be formulated into the detergent slurry, and a conventional heat-drying facility such as, for example, a steam or'hot flue-gas heated drum-drier, or a conventional spray-drying facility. It is also generally most convenient to prepare the slurry first by charging into the mixing vessel the Water, followed by the remainder of the materials from which the slurry is made. For optimum results in the practice of certain embodiments of the invention, either the alkali metal trimetaphosphate or the strong inorganic bases (described above) should be added to the slurry during the latter stages of its preparation.
- One of the more important elements involved in the processes of this invention relates to the temperature of the detergent slurry containing the alkali metal trimetaphosphates and strong bases described herein. It has been found, for example, that when the temperatures of concentrated detergent slurries containing the proper ingredients are raised significantly above about 50 C., and particularly, when their temperatures are raised to above about 75 C., the rate of conversion of the alkali metal trimetaphosphates is extremely high. In one instance, for example, more than 85% of the sodium trimetaphosphate in a slurry containing 60% of the solids at about 75 C. is converted to sodium tripolyphosphate in less than 7 minutes.
- this invention as herein described) be heat-dried within about 2 hours, and preferably within about 30 minutes, of the time the alkali metal trimetaphosphate is intermixed with the inorganic base in the aqueous medium, or within about 1 hour, and preferably within about 20 minutes of the time at which the aqueous slurry (containing the trimetaphosphate plus base) is heated to a temperature above about C.
- Example I In a conventional detergent crutcher are charged 4,000 parts of water, 1,340 parts of sodium dodecylbenzene sulfonate, 1,040 parts of sodium sulfate, 540 parts of sodium silicate (dry' basis) having an SiO /Na O ratio of 2.40, and 40 parts of detergent grade sodium carboxymethylcellulose. The resulting mixture is stirred for about 5 minutes, during which time 1,600 parts of a 50% aqueous solution of NaOH are also blended into the mixture, after which the temperature of the blend is about 40 C. Then 3,070 parts of sodium trimetaphosphate is added to the blend. Stirring is continued for about 20 minutes, during which time the viscosity of the slurry is continuously monitored.
- the apparent viscosity of the slurry after 20 minutes is only about 460 units, which viscosity can be described as very fluid. About 60 percent of the trimetaphosphate is converted into tripolyphosphate during this time. 7
- the slurry is pumped (continuously) into heat-exchange relationship with a heater, so that the temperature of the slurry is quickly raised to about 85 C. From the heater, the slurry is quickly transferred to a conventional pressure pump, and from the-re to a conventional spray-drying tower where it is heat-dried.
- the amount of time (prior to the drying step) during which the temperature of the slurry is about 80 C. is only about 3 minutes. Yet more than 95 weight percent of the sodium trimetaphosphate initially added to the slurry is converted into tripolyphosphate by the time the slurry is sprayed. No difi'iculty is encountered with theviscosity of the slurry, dur-' ing either the crutching or the spray-drying operations.
- Example ll Into a conventional detergent crutcher are charged 7,400 parts of a condensation product of tridecyl alcohol with ethylene oxide (containing an average of 30 moles of ethylene oxide per mole of alcohol), 3,800 parts (dry basis) of sodium silicate (having an SiO /Na O ratio of 4.0), 50 parts of sodium carboxymethylcellulose, 22,280 parts of water (including that from the silicate), 25,300 parts of sodium sulfate, and 29,500 parts of sodium trimetaphosphate. The resulting slurry is stirred for 5 minutes. Its apparent viscosity is only about 2,000 units. It contains no.lumps. This slurry is then pumped from the mixer to a high-pressure pump which is part of a conventional spray-drying facility.
- a high-pressure pump which is part of a conventional spray-drying facility.
- a 50% solution of sodium hydroxide is metered into the slurry at the rate of 22 parts per parts of the slurry (approximately 2.5 moles of NaOH per mole of sodium trimetaphosphate present therein).
- the slurry is then pumped directly to a conventional spray tower, where it is heatdried.
- the amount of time that a given portion of the slurry remains in the conduit between the high-pressure pump and the spray nozzles is only about 2 minutes.
- the resulting detergent product contains 38.2 weight percent of sodium tripolyphosphate hexahydrate (about 9 2% of that theoretically possible from the trimetaphosphate) and only about 3 weight percent of unconverted sodium trimetaphosphate. Note that in this example, only about 22,200 parts of water have to be evaporated in the heat-drying step. This amounts to only about 20 weight percent of the total weight of the detergent slurry, just before it is heat-dried.
- the remainder of the inorganic phosphate can be composed of any or several of a number of water-soluble phosphate salts, especially those which have been found to be useful in detergents, such as, for example, alkali metal pyrophosphate, alkali metal tripolyphosphate, alkali metal tetrapolyphosphtae, alkali metal hexametaphosphate, alkali metal orthophosphates, and the like, particularly when the alkali metal is either sodium or potassium, or a mixture of them.
- the phosphate salts that are present in these blends with the trimetaphosphate are there because of economic and other considerations during the manufacture of the trimetaphosphate.
- the inorganic phosphate salt blends described above be substantially (i.e., at least about 97, and preferablymore than 99 weight percent) soluble in water.
- phosphate salt blends as those described aboveare utilized in the practice of this invention they will preferably be in a finely divided state (i.e., at least about 80 percent by weight of the particles thereof will ordinarily be small enough to pass through a U8. Standard 80-mesh screen).
- the trimetaphosphate comprises at least about weight percent of the phosphate salt blend, and preferably, will represent more than about 25 weight percent of the phosphate salt blend.
- the blend of phosphate salts can be prepared (before they are added to the aqueous medium) either as simple physical blends of the individual crystalline (or amorphous) powders, granules, or flakes, etc., if desired, or as part of a mixture with other of the ingredients that will be utilized in the detergent slurries.
- the phosphate blend can be an intimate blend of phosphates that is prepared from a common melt, for example, which, after being cooled has been ground to produce the phosphate blend.
- a particularly preferred phosphate blend which can be utilized in another of the specific embodiments of this invention is one which contains both sodium trimetaphosphate and sodium tripolyphosphate.
- the tripolyphosphate part of this preferred blend usually consists almost entirely of the Form II crystalline modification.
- the sodium trimetaphosphate can represent any proportion of the blend which is more than about 10 weight percent.
- Example III Into a conventional detergent crutcher are charged 4,000 parts of water, 2,168 parts of sodium sulfate, 330 parts (dry basis) of sodium silicate having a SiO /Na O ratio of 210, 1,135 parts of Na CO 42 parts of sodium carboxymethylcellulose, and 635 parts of an alkyl phenol-ethyleneoxide condensation product (containing an average of moles of ethylene oxide per mole of dodecylphenol). The temperature of the resulting mixture is then raised to 85 C.
- the resulting slurry is metered continuously into a separate mixing vessel into which is also continuously metered a finely divided phosphate blend which contains about 45.5 weight percent of sodium trimetaphosphate and about 54.0 weight percent of Form II sodium tripolyphosphate.
- the rates of adding slurry and phosphate blend into the mixing vessel are adjusted so that the phosphate blend is intermixed with'the slurry at a rate which is proportionate to thedesired total tripolyphosphate content of the final detergent product; i.e. at. a ratio of slurry to phosphate blend of 8,310/1,808 in this'case, to yield a product containing 30.0 weight percent (dry basis) of sodium tripolyphosphate. Sojourn time in the mixing vessel is about 1 minute.
- the resulting mixture is continuously withdrawn from the mixing vesselthrough a conventional high-pressure pump and then spray-dried conventionally within 3 minutes of the time that the phosphate blend is added to the slurry, yielding a detergent product having excellent physical and functional properties, and containing 27.0 weight percent (dry basis) of sodium tripolyphosphate, about weight percent of which is hydrated.
- the proportion of sodium tripolyphosphate in the final product which is hydrated is substantially the same as the proportion of tripolyphosphate which would theoretically result from the trimetaphosphate in the phosphate blend.
- sodium trimetaphosphate is almost completely converted to tripolyphosphate
- Form II sodium tripolyphosphate does not hydrate significantly, and, because of the extremely short period of time between the mixing of the phosphate blend into the aqueous medium and its actually being heat-dried, the tripolyphosphate has had little opportunity to degrade (hydrolyze).
- the slurries should be heat-dried within about 5 minutes of the time thephosphate blend is intermixed therewith. However, beneficial results can still be noted it the slurry is sprayed within about 20 minutes of this time. It is also not necessary, in the plactice of this aspect of the invention for the trimetaphosphate. and tripolyphosphate to be added to the aqueous medium simultaneously.
- slurry can be prepared by first heating the mixtures of materials in the absence of the base or the phosphate blend, for example, then mixing the phosphate blend into the hotaqueous medium in the crutcher, and sub.. sequently transferring the resulting mixture to the pump (from which the slurry is transported to the spray nozzles) and intermixing the Na CO at a point just before the pump.
- the CO gas which is produced by the reaction of sodium'trimetaphosphate' with Na cO can aid indeveloping pressure for use in the spraying operation, as well as to make possible the production of a lighter density heat-dried detergent product.
- the processes of this invention can also be advantageously applied as continuous processes for the preparation of heat-dried detergents containing hydrated alkali metal tripolyphosphates.
- Such continuous processes were generally not practicable heretofore, because of the relatively long periods of aging which conventional de-. tergent slurries had to undergo in order for most of,
- the tripolyphosphates contained therein to hydrate prior to the heat-drying step.
- su'fiicient blending of trimetaphosphate and strong base can be accomplished within a transporting vessel suchas'a pipe or a conduit by properly placed bafiles, screen's, etc. (the placement and specific design of which are well within the ability of anyone skilled in the art), or even by the turbulence. which normally occurs in'such vessels.
- Example IV exemplifies the substantial benefits that can result from utilizing the inven-' weight per minute) at which the respective ingredients are utilized.
- Example IV The following dry ingredients are continuously metered onto a belt conveyor; detergent grade sodium carboxymethylcellulose (20), a commercial blend of weight In this example the" figures' in parenthesis percent sodium sulfate plus 40 weight percent of sodium dodecylbenzene sulfonate (1,625), and sodium trimetaphosphate (1,550). The mixture is then dropped into a mixing tank (fitted with a fairly eificient anchor-type stirrer), and continuously intermixed at this point with water (825) at a temperature of about 80 0, sodium silicate solution (625) containing 40 weight percent of solids, and having an SiO /Na O ratio of 3.0, and a 35 weight percent solution of sodium hydroxide (200).
- the mixing tank is designed so that the amount of time the materials are blended therein is about two minutes, after which the resulting slurry is withdrawn, transported immediately into the high-pressure pump of a conventional spray-drying facility, and spray-dried, utilizing conventional spraying techniques (i.e. dried countercurrently at a rate of 20,000 pounds of slurry per hour with an initial air temperature of about 270 C).
- the resulting detergent contains only about 4 weight percent of unconverted trimetaphosphate.
- Example IV It will be noted from Example IV that by utilizing the invention under optimum processing conditions it is no longer necessary for a detergent manufacturer to build and maintain large expensive crutching tanks and storage (hold) tanks in his detergent plant. Detergent manufacturers can readily appreciate this particular advantage of the invention.
- Typical examples of other materials that can be included in the slurries contemplated herein include those organic (detergent) surface active agents which are conventionally present in detergent compositions (and which are compatible with tripolyphosphate), such as the anionic, nonionic, as well as some of the ampholytic surfactants, including for example, such individual detergent active ingredients as the well-known water-soluble soap (i.e. the sodium and/or potassium salts of coconut fatty acids, oleyl fatty acids, etc.), water-soluble alkylaryl sulfonates (i.e. sodium dodecylbenzene sulfonate, etc.), water soluble alkyl sulfates (i.e.
- sodium and potassium lauryl sulfate sodium and potassium alkyl glyceryl ethers such as those derived from tallow and coconut oil, sodium coconut oil fatty acid monoglyceride sulfate, etc.
- fatty alkylamides i.e. N- dodecyl monoethanolamide, N-octadecyl diethanolamide, etc.
- alcohol-alkylene oxide condensates i.e. alcohols having from 8-20 carbon atoms, in either straight chain or branched chain configuration having from about 6-30 moles of ethylene oxide and/or propylene oxide per mole of alcohol, etc.
- alkylphenol-alkylene oxide condensates i.e.
- alkylphenol having an alkyl group with from about 6 to about 20 carbon atoms in the chain, with from about 6 to about 30 moles of ethylene oxide and/or propylene oxide per mole of alkylphenol), and the like.
- other conventional detergent builders can be present in these compositions.
- such materials as the alkali metal phosphates such as the soluble hexametaphosphates, etc. can be utilized.
- alkali metal sulfates, alkali metal silicates, as well as anti-redeposition agents such as the carboxymethylcelluloses and the polyvinylalcohols and small amounts of organic optical bleaches.
- chemical bleaches such as the alkali metal perborates and chlorinated organic bleaches can be used in the slurries and heat-dried detergent compositions with which this invention is concerned.
- the invention need not be limited to being practiced with slurries that contain all of the ingredients usually found in conventional heatdried detergent compositions.
- the invention is of great value, because of the extremely low levels of tripolyphosphate degradation products that can be present in heat-dried products made according to this invention, as compared to the large amount of tripolyphosphate degradation that normally occurs when conventional processes are utilized for their preparation.
- a process for manufacturing a heat-dried composition containing hydrated penta alkali metal tripolyphosphate comprises the steps of preparing an aqueous slurry containing at least about 10 weight percent, based on the total weight of said slurry, of water, at least about 5 weight percent based on the total weight of said slurry of an alkali metal trimetaphosphate, and an alkali metal base, said alkali metal base being one which provides at 1 weight percent concentration in distilled water a solution pH measured at 25 C.
- said alkali metal base being present in said aqueous slurry in an amount at least sufficient to convert at least about one third of said alkali metal trimetaphosphate to said hydrated penta alkali metal tripolyphosphate, and thereafter heat-drying said aqueous slurry.
- a process for manufacturing a heat-dried detergent composition containing hydrated penta alkali metal tripolyphosphate comprises the steps of preparing an aqueous slurry containing at least about 10 weight percent of water from about 8 to about 64 weight percent, based on the weight of said detergent composition, of an alkali metal trimetaphosphate; and a base selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, alkali metal silicates having an SiO /M O ratio, where M is an alkali metal cation, lower than 2, and mixtures thereof in an amount sufficient to convert at least about one third of said alkali metal trimetaphosphate to said hydrated penta alkali metal tripolyphosphate, and thereafter heat-drying the resulting mixture.
- a process for manufacturing a heat-dried composition which process comprises the steps of preparing an aqueous slurry containing at least about 20 weight percent, based on the total weight of said slurry, of water,
- a process for manufacturing a heat-dried detergent composition containing hydrated sodium tripolyphosphate comprises the steps of preparing an aqueous slurry containing a mixture of at least two substantially Water soluble sodium polyphosphate salts and sodium hydroxide, said sodium polyphosphate salts containing from about 10 to about 95 weight percent of sodium trimetaphosphate and being present in said slurry in a substantially water soluble amount such that at least about weight percent of said sodium trimetaphosphate, based on the weight of said slurry, is present in said slurry, and the weight ratio of said sodium hydroxide to said sodium trimetaphosphate in said slurry being between about 1:4 and about 2:1; and thereafter heat-drying said slurry, whereby at least about one third of said sodium trimetaphosphate is converted to said sodium tripolyphosphate.
- a process for the manufacture of a heat-dried detergent composition containing hydrated penta alkali metal tripolyphosphate which process comprises the steps of mixing together in at least about percent based on the weight of the resulting mixture, of water, at least about 10 weight percent, based on the weight of said resulting mixture, of alkali metal trimetaphosphate; and a base; said base being selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, alkali metal silicates having an SiO /M O ratio lower than 2, wherein M is an alkali metal cation, and mixtures thereof, and being present in the resulting mixture in an amount suflicient to furnish at least about 2 mol equivalents of hydroxyl ions per mol of said alkali metal trimetaphosphate, holding the resulting mixture at a temperature above about 50 C. until at least about 30 weight percent of said alkali metal trimetaphosphate has been converted to tripolyphosphate, and thereafter heat-drying the resulting base
- a process for manufacturing a heat-dried detergent composition containing hydrated sodium tripolyphosphate comprises the steps of mixing together in at least about 10 percent, based on the weight of the resulting mixture, of water, at least about 10 weight percent, based on the weight of said heat-dried detergent composition, of sodium trimetaphosphate and an amount of sodium hydroxide suflicient to furnish between about 1.5 and about 8 mole equivalents of hydroxyl ions per mole of said sodium trimetaphosphate, subjecting the resulting mixture to a temperature above about 50 C. while at least about 30 weight percent of said sodium trimetaphosphate is converted to tripolyphosphate, and heat-drying the resulting reaction product within about 2 hours of the time said resulting mixture is prepared.
- a process for manufacturing a heat-dried detergent composition that contains sodium tripolyphosphate, a predetermined proportion of which is hydrated which process comprises the steps of intermixing sodium trimetaphosphate, Form II sodium tripolyphosphate and from about 2 to about 8 mol equivalents, based on the amount of said sodium trimetaphosphate, of sodium hydroxide in an aqueous medium at a temperature above about 75 C., the initial weight ratio of said sodium trimetaphosphate to said sodium tripolyphosphate being about I/ 1.2 times said predetermined proportion; maintaining the temperature of the resulting mixture above about 85 C. until it is heat-dried; and heat-drying said resulting mixture within about 20 minutes after said sodium trimetaphosphate and said base are intermixed.
- a continuous process for manufacturing a spraydried composition containing hydrated sodium tripolyphosphate comprises the steps of making a fluid aqueous slurry by blending together in a flowing stream of material at least about 5 percent, based on the weight of resulting blend, of a sodium trimetaphosphate, at least about 10 percent, based on the weight of the resulting blend, of water, sodium hydroxide, the amount of said sodium hydroxide in said slurry being sufiicient to furnish between about 1.5 and about 8 mol equivalents of hydroxide ions per mol of said sodium trimetaphosphate in said slurry, and thereafter transforming said stream of material into a spray in a drying atmosphere, whereby said spray-dried composition is produced.
- a process for manufacturing a heat-dried detergent composition containing penta sodium tripolyphosphate comprises the steps of preparing an aqueous slurry containing at least about 20 weight percent of water, from about 8 to about 64 weight percent, based on the weight of said detergent composition, of sodium trimetaphosphate, and at least about 1.2. moles of sodium hydroxide per mole of said sodium trimetaphosphate, and thereafter heat-drying the resulting mixture.
- a process for manufacturing a heat-dried detergent composition containing penta sodium tripolyphosphate comprises the steps of preparing an aqueous slurry containing at least about 20 weight percent of water, from about 8 to about 64 weight percent, based on the weight of said detergent composition, of sodium trimetaphosphate, and at least about 1.2 mole equivalents of sodium carbonate per mole of said sodium trimetaphosphate, and thereafter heat-drying the resulting mixture.
- the detergent product obtained by (a) reacting together in a fluid aqueous slurry at a temperature above about 50 C. and in the presence of a surface active agent selected from the group consisting of anionic and nonanionic surface active agents, sodium trimetaphosphate and a base selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, alkali metal silicates having an SiO /M O ratio, where M is an alkali metal cation, lower than 2, and mixtures thereof; said slurry initially containing at least about 20 weight percent of water and at least about 10 weight percent of said sodium trimetaphosphate, and the amount of said base being suflicient to furnish between about 1.5 and about 8 mole equivalents of hydroxyl ions per mole of said sodium trimetaphosphate; and (b) thereafter heatdrying said fluid aqueous slurry.
- a surface active agent selected from the group consisting of anionic and nonanionic surface active agents, sodium trimetaphosphate and a
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE622142D BE622142A (fr) | 1961-09-05 | ||
NL137679D NL137679C (fr) | 1961-09-05 | ||
NL288064D NL288064A (fr) | 1961-09-05 | ||
US135718A US3303134A (en) | 1961-09-05 | 1961-09-05 | Detergent processes and compositions therefor |
DE1567656A DE1567656C3 (de) | 1961-09-05 | 1962-09-03 | Verfahren zur Hersteilung eines in der Wärme getrockneten Reinigungsmittels |
FR908508A FR1343578A (fr) | 1961-09-05 | 1962-09-04 | Procédé pour la fabrcation des compositions de détergents séchées thermiquementdes bouillies aqueuses et des compositions de phosphates minéraux utiles dans la préparation de ces compositions de détergents |
GB33993/62A GB1020616A (en) | 1961-09-05 | 1962-09-05 | Compositions containing tripolyphosphates |
JP37037510A JPS4842691B1 (fr) | 1961-09-05 | 1962-09-05 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US135718A US3303134A (en) | 1961-09-05 | 1961-09-05 | Detergent processes and compositions therefor |
NL288064 | 1963-01-23 |
Publications (1)
Publication Number | Publication Date |
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US3303134A true US3303134A (en) | 1967-02-07 |
Family
ID=26641877
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US135718A Expired - Lifetime US3303134A (en) | 1961-09-05 | 1961-09-05 | Detergent processes and compositions therefor |
Country Status (6)
Country | Link |
---|---|
US (1) | US3303134A (fr) |
JP (1) | JPS4842691B1 (fr) |
BE (1) | BE622142A (fr) |
DE (1) | DE1567656C3 (fr) |
GB (1) | GB1020616A (fr) |
NL (2) | NL288064A (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3345297A (en) * | 1965-12-06 | 1967-10-03 | Procter & Gamble | Process for preparing detergent granules from trimetaphosphate |
US3355390A (en) * | 1965-12-06 | 1967-11-28 | Procter & Gamble | Method for preparing homogeneous detergent slurry |
US3390093A (en) * | 1962-06-06 | 1968-06-25 | Monsanto Co | Detergent compositions containing hydrated alkali metal tripolyphosphates |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL131792C (fr) * | 1964-07-17 | |||
IS1740B (is) * | 1982-02-05 | 1999-12-31 | Albright & Wilson Uk Limited | Samsetning á hreinsivökva |
US5213706A (en) * | 1991-11-08 | 1993-05-25 | Lever Brothers Company, Division Of Conopco, Inc. | Homogeneous detergent gel compositions for use in automatic dishwashers |
LT3962B (en) | 1993-12-21 | 1996-05-27 | Albright & Wilson | Funcional fluids |
GB201020616D0 (en) | 2010-12-06 | 2011-01-19 | Univ Ariel Res & Dev Co Ltd | Device for imparting distance information |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2019665A (en) * | 1935-01-22 | 1935-11-05 | Rumford Chemical Works | Process of producing tetraphosphates |
US2244158A (en) * | 1938-11-04 | 1941-06-03 | Monsanto Chemicals | Water treating composition |
US2365190A (en) * | 1944-12-19 | Washing compositions | ||
US2622068A (en) * | 1948-06-04 | 1952-12-16 | Procter & Gamble | Process of making heat dried detergent compositions containing form ii sodium triphosphate |
US2947701A (en) * | 1955-05-09 | 1960-08-02 | Lever Brothers Ltd | Spray dried detergent composition |
-
0
- BE BE622142D patent/BE622142A/xx unknown
- NL NL137679D patent/NL137679C/xx active
- NL NL288064D patent/NL288064A/xx unknown
-
1961
- 1961-09-05 US US135718A patent/US3303134A/en not_active Expired - Lifetime
-
1962
- 1962-09-03 DE DE1567656A patent/DE1567656C3/de not_active Expired
- 1962-09-05 JP JP37037510A patent/JPS4842691B1/ja active Pending
- 1962-09-05 GB GB33993/62A patent/GB1020616A/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2365190A (en) * | 1944-12-19 | Washing compositions | ||
US2019665A (en) * | 1935-01-22 | 1935-11-05 | Rumford Chemical Works | Process of producing tetraphosphates |
US2244158A (en) * | 1938-11-04 | 1941-06-03 | Monsanto Chemicals | Water treating composition |
US2622068A (en) * | 1948-06-04 | 1952-12-16 | Procter & Gamble | Process of making heat dried detergent compositions containing form ii sodium triphosphate |
US2947701A (en) * | 1955-05-09 | 1960-08-02 | Lever Brothers Ltd | Spray dried detergent composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3390093A (en) * | 1962-06-06 | 1968-06-25 | Monsanto Co | Detergent compositions containing hydrated alkali metal tripolyphosphates |
US3345297A (en) * | 1965-12-06 | 1967-10-03 | Procter & Gamble | Process for preparing detergent granules from trimetaphosphate |
US3355390A (en) * | 1965-12-06 | 1967-11-28 | Procter & Gamble | Method for preparing homogeneous detergent slurry |
Also Published As
Publication number | Publication date |
---|---|
DE1567656A1 (de) | 1972-03-09 |
DE1567656C3 (de) | 1974-07-25 |
NL137679C (fr) | |
NL288064A (fr) | |
BE622142A (fr) | |
GB1020616A (en) | 1966-02-23 |
JPS4842691B1 (fr) | 1973-12-14 |
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