US3620979A - Process of forming free-flowing, particulate mixtures of phosphates and silicates - Google Patents
Process of forming free-flowing, particulate mixtures of phosphates and silicates Download PDFInfo
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- US3620979A US3620979A US723907A US3620979DA US3620979A US 3620979 A US3620979 A US 3620979A US 723907 A US723907 A US 723907A US 3620979D A US3620979D A US 3620979DA US 3620979 A US3620979 A US 3620979A
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- alkali metal
- phosphate
- silicate
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- solution
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- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 22
- 235000021317 phosphate Nutrition 0.000 title description 28
- 150000004760 silicates Chemical class 0.000 title description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 title 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 34
- 239000010452 phosphate Substances 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 30
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 229910052681 coesite Inorganic materials 0.000 claims abstract 3
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract 3
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 3
- 229910052682 stishovite Inorganic materials 0.000 claims abstract 3
- 229910052905 tridymite Inorganic materials 0.000 claims abstract 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 18
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 8
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical group [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 6
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 34
- 229910000318 alkali metal phosphate Inorganic materials 0.000 abstract description 16
- 238000001704 evaporation Methods 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 239000004115 Sodium Silicate Substances 0.000 description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 14
- 229910052911 sodium silicate Inorganic materials 0.000 description 14
- 239000003599 detergent Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 5
- 235000011008 sodium phosphates Nutrition 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 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 4
- 239000011734 sodium Substances 0.000 description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- -1 (KPO L Chemical compound 0.000 description 1
- GIXFALHDORQSOQ-UHFFFAOYSA-J 2,4,6,8-tetraoxido-1,3,5,7,2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraoxatetraphosphocane 2,4,6,8-tetraoxide Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)O1 GIXFALHDORQSOQ-UHFFFAOYSA-J 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 241001460678 Napo <wasp> Species 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000007973 cyanuric acids Chemical class 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
- 238000004090 dissolution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- NUHSROFQTUXZQQ-UHFFFAOYSA-N isopentenyl diphosphate Chemical compound CC(=C)CCO[P@](O)(=O)OP(O)(O)=O NUHSROFQTUXZQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 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 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 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
-
- 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
-
- 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
- B01J2/30—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using agents to prevent the granules sticking together; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
-
- 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
-
- 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
- C11D3/08—Silicates
Definitions
- the invention relates to producing free-flowing, strong, discrete, granular particles that contain a mixture of a hydratable phosphate and a silicate, and which dissolve rapidly and completely in water.
- a sodium phosphate e.g., sodium tripolyphosphate
- these may include anionic or nonionic synthetic surfactants, antiredeposition agents, such as sodium carboxymethylcellulose, extenders, perfumes, bleaching agents, e.g., chlorinated cyanurates, alkaline cleansers, e.g., soda ash, caustic soda, and the like.
- anionic or nonionic synthetic surfactants such as sodium carboxymethylcellulose
- extenders perfumes
- bleaching agents e.g., chlorinated cyanurates
- alkaline cleansers e.g., soda ash, caustic soda, and the like.
- the above phosphate built detergent when used in conventional dishwashers or cleansing equipment, is known to be corrosive to both the metal and enamelware it contacts.
- an alkali metal silicate normally sodium silicate
- the added alkali metal silicate also increases the alkali content of the detergent formulation, thereby improving detergency and buffering it against acid soils removed during cleansing.
- This patented duplex mixture has certain drawbacks. Initially, it can only be formed with the less alkaline silicates, i.e., SiO /Na O weight ratios of 3.22:] to 2.40:1. Further, when high silica to phosphate mole ratios, e.g., at least 1:1, are desired in the mixture for optimum corrosion inhibition, only the less alkaline (SiO /Na O of 3.22:1) silicates can be employed to obtain the patentees duplex product.
- an alkali metal silicate preferably a sodium silicate having an SiO,/Na O weight ratio of below 2411
- an alkali metal silicate preferably a sodium silicate having an SiO,/Na O weight ratio of below 2411
- a hydratable alkali metal phosphate either in a granular form (-10 to +200 mesh) or powdered form (-100 mesh) is used as one of the feed reactants.
- the granular form is preferred, particularly in a predominantly -20 +100 mesh size range.
- the hydratable phosphate may be either sodium tripolyphosphate, u r o tetrasodium pyrophosphate, Nla P O trisodium orthophosphate, Na PO sodium trimetaphosphate, (NaPO or the corresponding potassium salts, namely, potassium tetrametaphosphate, (KPO L, or potassium pyrophosphate, K P O
- the preferred embodiment is sodium tripolyphosphate which is most popularly used in detergent mixes.
- a hydratable phosphate e.g., sodium tripolyphosphate
- a agitated reaction chamber such as a Hobart mixer, rotary drum or other agitated vessel, heated to a temperature of 60 to 100 C. (preferably 60to 75 C.), and maintained in a state of constant agitation.
- an alkali metal silicate preferably a potassium or sodium silicate solution having an SiO /M O weight ratio of below 2.40:1, wherein M is either sodium or potassium.
- An especially useful sodium silicate solution is the Philadelphia Quartz Company product D-brand silicate which contains 14.7 percent Na O; 29.4 percent SiO and 55.9 percent H O.
- the silicate solution is dispersed onto the heated bed of hydratable phosphate, preferably through spray nozzles or other line distributing means at a rate that does not cause the resulting mixture to become excessively sticky.
- Water is constantly evaporated from the resulting mixture to prevent the incoming alkali metal silicate solution from causing the discrete particles of the mixture to adhere into undesirably large aggregates.
- the resulting mixture remains dry-appearing without changing its granular form and without losing its discrete, particulate character.
- a major portion of the granular product that is recovered is in the desired l0 mesh range when starting with the preferred -20 mesh, granular, hydratable phosphate. If a finer hydratable phosphate feed is used, i.e., a powdered phosphate, the resulting product will contain some undersized particles, that is, smaller than 80 mesh.
- any undersized particles are recycled back to the agitated bed of hydratable phosphate to be further processed until it is of suitable product size.
- Oversize particles, if any, can be crushed so that the desired product size, l +80 mesh, is separated, and any undersized fraction is recycled to the agitated, hydratable phosphate bed for further processing.
- a sodium silicate solution such as the D-brand silicate which contains about 55 percent water can be used as received from the manufacturer and added directly to the sodium tripolyphosphate.
- sufficient water may be added to the silicate solution to reduce the viscosity of the solution to a suitable, workable level.
- the added water permits the silicate solution to be more readily dispersed throughout the bed of hydratable phosphate.
- the addition of excessive amounts of water is undesirable because this water must be evaporated from the mixture and increases the reaction time and heat input required to prepare the final product.
- Si0 to sodium tripolyphosphate mole ratio at a level of at least 1:1 in order to provide good corrosion inhibition.
- This and higher mole ratios of silicate to sodium tripolyphosphate are sufficient to materially reduce or eliminate undue corrosion of metal equipment that contacts the present silicate-phosphate product when it is incorporated in a final detergent formulation. Examples of some sodium silicate solutions which have been found effective in the present invention are listed below:
- EXAMPLE 1 dropwise at a rate of about 0.2 gram/minute. Water was continuously evaporated from the mixture during the run. The rate of addition of the silicate solution was controlled by observing the mixture; if the discrete particles of the mixture commenced to adhere into undesirably large aggregates, the
- EXAMPLE 2 The procedure of example 1, run 1, was repeated, except that Kasil 88," a proprietary product containing 9.1 weight percent K 0, 19.9 weight percent SiO and 71 weight percent H O was used in place of the sodium silicate solution.
- Kasil 88 a proprietary product containing 9.1 weight percent K 0, 19.9 weight percent SiO and 71 weight percent H O was used in place of the sodium silicate solution.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Glanulating (AREA)
Abstract
Free-flowing, fast-dissolving, completely soluble, strong, granular particles containing a mixture of a hydratable alkali metal phosphate and an alkali metal silicate wherein the SiO2 to said phosphate mole ratio is at least 1:1, were produced by maintaining the alkali metal phosphate at a temperature of 60* to 100* C., gradually adding an aqueous solution of alkali metal silicate to the alkali metal phosphate, continually evaporating water from the resulting mixture, controlling the rate of addition of the alkali metal silicate solution so that the resulting mixture is maintained in the form of discrete particles, continuing said alkali metal silicate addition until the discrete, granular particles have an SiO2 to said phosphate mole ratio of at least 1:1, and recovering dry-appearing, granular particles which yield a pH of at least 10.5 in an aqueous 1 percent solution.
Description
iiriited States Patent [72] Inventors [22] Filed Apr. 24, 11968 [45] Patented Nov. 116, 19711 [73] Assignee i MC Corporation New York, NY.
[54] PROCESS OF FORMING FREE-FLOWING,
PAlR'llllCULATE MIXTURES 01F PHOSPMATES AND SilLllCA'iiES 8 Claims, No Drawings [52] U.S. Cl 252/385, 23/106, 252/99, 252/109, 252/135, 252/387 [51] llnt.Cl ..Cl]1d17/06 C1 1d 9/14 [50] ll ieid of Search 252/385,
[ 5 6] References Cited UNITED STATES PATENTS 2,909,490 10/1959 Metziger 23/106 3,390,093 6/1968 lFeierstein etal.
Primary Examiner-Richard D. Lovering Assistant Examiner-Irwin Gluck AttorneysEugene G. Seems, Frank lanno and Milton Zucker ABSTRACT: Freeflowing, fast-dissolving, completely soluble, strong, granuiar particles containing a mixture of a hydratable alkali metal phosphate and an alkali metal silicate wherein the Si0 to said phosphate mole ratio is at least 1:1, were produced by maintaining the alkali metal phosphate at a temperature of 60 to 100 C., gradually adding an aqueous solution of alkali metal silicate to the alkali metal phosphate, continually evaporating water from the resulting mixture, controlling the rate of addition of the alkali metal silicate solution so that the resulting mixture is maintained in the form of discrete particles, continuing said alkali :metal silicate addition until the discrete, granular particles have an Si0 to said phosphate mole ratio of at least 1:1, and recovering dry-appearing, granular particles which yield a pH of at least 10.5 in an aqueous 1 percent solution.
PROCESS OF FORMING FREE-FLOWING, PARTICULA'JIIE MIXTURES OF lPllIOSlPllilATlES AND SllLllCATlES BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to producing free-flowing, strong, discrete, granular particles that contain a mixture of a hydratable phosphate and a silicate, and which dissolve rapidly and completely in water.
2. Description of the Prior Art In the process of manufacturing a dry-mixed, built, detergent formulation for use in dishwashers or cleansing, it is common to use a sodium phosphate, e.g., sodium tripolyphosphate, as the builder, along with other common ingredients; these may include anionic or nonionic synthetic surfactants, antiredeposition agents, such as sodium carboxymethylcellulose, extenders, perfumes, bleaching agents, e.g., chlorinated cyanurates, alkaline cleansers, e.g., soda ash, caustic soda, and the like. The above phosphate built detergent, when used in conventional dishwashers or cleansing equipment, is known to be corrosive to both the metal and enamelware it contacts. To inhibit such corrosion, an alkali metal silicate, normally sodium silicate, is incorporated into the detergent formulation. The added alkali metal silicate also increases the alkali content of the detergent formulation, thereby improving detergency and buffering it against acid soils removed during cleansing.
Regrettably, mixing the sodium tripolyphosphate and a silicate in a dry-mixed, detergent formulation results in serious problems. These ingredients tend to combine together into agglomerates that cake and prevent the mixture from being uniform and free flowing. Also, these agglomerates segregate in the detergent package and are not dispersed homogeneously with the remaining ingredients of the detergent formulation. Another serious difficulty is that the highly alkaline, alkali metal silicate particles irritate human skin if these particles contact the hands of the consumer during cleansing or while dispensing the detergent formulation in a dishwasher.
One solution to these problems is set forth in US. Pat. No. 2,909,490, issued to Max Metziger on Oct. 20, 1959. The patent describes the manufacture of duplex compositions of sodium tripolyphosphate and aqueous sodium silicate mixtures by contacting these ingredients at below 60 C. so that anhydrous sodium tripolyphosphate dehydrates the aqueous mixtures of sodium silicate to yield a dry-appearin g mixture.
This patented duplex mixture has certain drawbacks. Initially, it can only be formed with the less alkaline silicates, i.e., SiO /Na O weight ratios of 3.22:] to 2.40:1. Further, when high silica to phosphate mole ratios, e.g., at least 1:1, are desired in the mixture for optimum corrosion inhibition, only the less alkaline (SiO /Na O of 3.22:1) silicates can be employed to obtain the patentees duplex product. This is a disadvantage because higher alkaline ingredients, preferably those yielding products having a pH of at least 10.5 (when made up in an aqueous 1 percent solution thereof), are desired to obtain better detergency and to avoid precipitates in the dissolved detergent formulation. Also, on storage, the high free moisture content of the duplex mixture facilitates lumping and undesired absorption of atmospheric carbon dioxide which converts silicates to insoluble silica and causes clouding of the final detergent solution.
OBJECTS OF THE INVENTION It is an object of the present invention to produce free-flowing, fast-dissolving, completely soluble, strong, granular particles that contain a mixture of a silicate and a hydratable alkali metal phosphate in which the silicate to said phosphate mole ratio is at least 1:1, and the particles yield a pH of at least 10.5 in an aqueous 1 percent solution.
It is a further object of the present invention to produce free-flowing, fast-dissolving, completely soluble, strong, granular particles that contain a mixture of a sodium silicate and a hydratable sodium phosphate in which the sodium silicate has an SiO /Na O weight ratio of below about 2.40: 1.
These and other objects will be apparent from the following description of the invention.
SUMMARY OF THE INVENTION We have now found that free-flowing, strong, granular particles containing a mixture of a hydratable alkali metal phosphate and an alkali metal silicate, wherein the SiO, to said phosphate mole ratio is at least 1:1, can be produced by heating the alkali metal phosphate to a temperature of 60 to 100 C. (preferably 60-75 C.), gradually adding an aqueous solution of an alkali metal silicate (preferably a sodium silicate having an SiO,/Na O weight ratio of below 2411) to the alkali metal phosphate while said alkali metal phosphate is being agitated, maintaining the mixture of said alkali metal phosphate and the silicate at a temperature of 60 to 100 C., continually evaporating water from the resulting mixture, controlling the rate of addition of the silicate solution so that the resulting mixture is maintained in a particulate, dry-appearin g, granular form, continuing to add the silicate solution until the dry-appearing, granular particles have an SiO to said phosphate mole ratio of at least 1:1 and recovering granular particles which yield a pH of at least 10.5 in an aqueous 1 percent solution.
DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENTS In carrying out the present invention, a hydratable alkali metal phosphate, either in a granular form (-10 to +200 mesh) or powdered form (-100 mesh) is used as one of the feed reactants. The granular form is preferred, particularly in a predominantly -20 +100 mesh size range. The hydratable phosphate may be either sodium tripolyphosphate, u r o tetrasodium pyrophosphate, Nla P O trisodium orthophosphate, Na PO sodium trimetaphosphate, (NaPO or the corresponding potassium salts, namely, potassium tetrametaphosphate, (KPO L, or potassium pyrophosphate, K P O The preferred embodiment is sodium tripolyphosphate which is most popularly used in detergent mixes. When using a hydratable phosphate, e.g., sodium tripolyphosphate, as the feed reactant, it is placed in an agitated reaction chamber such as a Hobart mixer, rotary drum or other agitated vessel, heated to a temperature of 60 to 100 C. (preferably 60to 75 C.), and maintained in a state of constant agitation.
To this agitated, heated bed of hydratable phosphate is then added an alkali metal silicate, preferably a potassium or sodium silicate solution having an SiO /M O weight ratio of below 2.40:1, wherein M is either sodium or potassium. An especially useful sodium silicate solution is the Philadelphia Quartz Company product D-brand silicate which contains 14.7 percent Na O; 29.4 percent SiO and 55.9 percent H O. The silicate solution is dispersed onto the heated bed of hydratable phosphate, preferably through spray nozzles or other line distributing means at a rate that does not cause the resulting mixture to become excessively sticky. Water is constantly evaporated from the resulting mixture to prevent the incoming alkali metal silicate solution from causing the discrete particles of the mixture to adhere into undesirably large aggregates. When the alkali metal silicate solution is added in the proper manner, the resulting mixture remains dry-appearing without changing its granular form and without losing its discrete, particulate character. A major portion of the granular product that is recovered is in the desired l0 mesh range when starting with the preferred -20 mesh, granular, hydratable phosphate. If a finer hydratable phosphate feed is used, i.e., a powdered phosphate, the resulting product will contain some undersized particles, that is, smaller than 80 mesh.
The process can be carried out either in batch form or on a continuous basis. In continuous operation, any undersized particles are recycled back to the agitated bed of hydratable phosphate to be further processed until it is of suitable product size. Oversize particles, if any, can be crushed so that the desired product size, l +80 mesh, is separated, and any undersized fraction is recycled to the agitated, hydratable phosphate bed for further processing.
A sodium silicate solution such as the D-brand silicate which contains about 55 percent water can be used as received from the manufacturer and added directly to the sodium tripolyphosphate. However, in cases where the silicate solution is so viscous that pumping, spraying and/or dispersing of the solution onto the phosphate bed is impeded, sufficient water may be added to the silicate solution to reduce the viscosity of the solution to a suitable, workable level. In addition to reducing the viscosity, the added water permits the silicate solution to be more readily dispersed throughout the bed of hydratable phosphate. However, the addition of excessive amounts of water is undesirable because this water must be evaporated from the mixture and increases the reaction time and heat input required to prepare the final product.
In the manufacture of the preferred product, it is desired to maintain the Si0 to sodium tripolyphosphate mole ratio at a level of at least 1:1 in order to provide good corrosion inhibition. This and higher mole ratios of silicate to sodium tripolyphosphate are sufficient to materially reduce or eliminate undue corrosion of metal equipment that contacts the present silicate-phosphate product when it is incorporated in a final detergent formulation. Examples of some sodium silicate solutions which have been found effective in the present invention are listed below:
The above products are registered trademarks of Philadelphia Quartz Co., Philadelphia, Pa.
The following examples are given to illustrate the present invention and are not deemed to be limiting thereof.
EXAMPLE 1 dropwise at a rate of about 0.2 gram/minute. Water was continuously evaporated from the mixture during the run. The rate of addition of the silicate solution was controlled by observing the mixture; if the discrete particles of the mixture commenced to adhere into undesirably large aggregates, the
addition of the silicate solution was suspended until enough water was evaporated from the mixture to restore its dry-appearing form. The final products were dry-appearing, freeflowing, fast-dissolving, completely soluble, strong particles containing sodium silicate and sodium phosphate; the particles were analyzed, and the results are set forth in table 11. The
physical properties of the particles are also reported in table 11.
The above technique was repeated in other runs using various sodium phosphates and sodium silicate mixtures in different $10, to phosphate mole ratios. The feed materials and their properties are reported in table I, while the properties and analysis of the products are set forth in table 11.
EXAMPLE 2 The procedure of example 1, run 1, was repeated, except that Kasil 88," a proprietary product containing 9.1 weight percent K 0, 19.9 weight percent SiO and 71 weight percent H O was used in place of the sodium silicate solution. The
granular product obtained was found to have the same desirable characteristics of strength, free-flowability and rapid dissolution as the product of run 1.
TABLE I Sodium phosphate properties Sodium silicate solution Mole ratio Bulk Wt. Wt. Wt. 5101/ Run density, percent percent percent Wt. ratio phosphate N 0. Manufacturing method g./ec. Mesh size Name Na o 810; H O slog/N820 in mixture 1 Spray-dried granular SIPP 0.48 All 20 +100 D 14. 7 20. 4 55. 9 2. 00:1 2. 20:1
light-density. 2 Heavy-density rotary kiln 0.90 do D 14. 7 29.4 55.0 2. 00:1 2.20:1
granular STPP. 3 Spray-dried granular STPP 0.47 do D 14.7 29.4 55.9 2. 00:1 2. 20:1
light-density. 4 STPP powder 0. 76 Substantially all 100 D 14. 7 29. 4 55. 9 2. 00:1 2. 20:1 5 Spray-dried granular SIPP 0.48 All 20 +100 BW 19. 5 31. 2 2 49. 3 1.60:1 2. 35:1
light-density. 6 Spray-dried granular STPP 0.48 do D 14. 7 29.4 55. 0 2.00:1 3. :1
light-density. 7 .d0 14. 7 29. 4 55. 0 2. 00:1 5. 40:1 TSPP 14. 7 29. 4 55. 9 2. 00:1 1. 41:1 9 TSP d0 D 14.7 29.4 55.9 2.00:1 1.1:1
1 S'IPPsodium tripolyphos hate. 3 'ISPPtetrasodium pyrophosphate. Z Diluted with 16% addltlona water to reduce its viscosity. 1 TSP-trisodlum orthophosphate.
TABLE 11 H of Bulk Percent 01' Percent of Percent aqueous 1% Dissolving rate density, S'PPP- SIPP sodium Percent Run No Screen analysis Percent Flowability solution (0.5% 1120 S01.) g./cc. 611 0 anhy. silicate H t) 0 1 +10 mesh 10. 5 Free-flowing. 10.5 F. 50.0., 0.67 7. .2 50.0 31. S 11.0
83. 0 140 F.30 sec.
23. 0 .do 10.5 140 F.--50 Sec. 1.10 5.3 5'5. 3 29. .1 11.5 47. 9 20. 1 9. 0
31. 0 d0 10.5 70 F. see., 0. 98 8. 7 5'3 27. 8 10.5 58. F.45 sec.
Table ll -Conlinued 4 +10 mesh 38. .do 10. 70 F.180 sec., 1. 24 3. 3 54. 0 32. 4 0. 4
14. 1 140 F.45 sec. $.13 20. 0
5. 0 ..d0 11.4 70 F.100 Sec., 0. 60 2. 0 58. 3 27. 8 13. 6 39. 0 140 F.30 sec. 56. O 0
22.0 .....d() 10. 5 70 F.120 860., 0. 90 40 36. 3 68. 5 140 F.45 sec.
73. 2 .d0 10. 7 70 F.240 see, 1. 06 35 45. 6 26. 7 140 F.60 sec.
18. 2 d0 10.5 70 12-240 sec., 0.92 28. 5 72. 7 140 F.60 sec.
31. 6 .-d0 11. 3 70 F.--165 sec., 0.96 5- 66. 8 140 F.50 Sec.
STPP-GH;O-hexahydrated sodium tripolyphosphate. b S'IPP anhy.-anhydrous sodium tripolyphosphate. Free moisturenot mglegularlv hound What is claimed is: 1. Process of producing strong, free-flowing, completely soluble, dry, granular particles containing as essential ingredients a mixture of a hydratable alkali metal phosphate and an alkali metal silicate wherein the SiO to said phosphate mole ratio is at least 1:1, comprising heating said alkali metal phosphate in particulate form to a temperature of about 60 to about l00 C., gradually adding an aqueous, alkali metal silicate solution having an SiO /M O weight ratio of about 2.00:1 or below to said phosphate, wherein M is selected from the group consisting of sodium and potassium, maintaining the resulting mixture of said alkali metal phosphate and said silicate solution at a temperature of about 60 to about 100 C., continually evaporating water from said mixture, controlling the rate of addition of said aqueous, alkali metal silicate solud 69.5% TSPP (calculated as anhydrous tetrasodium pyrophosphate). 52.3% TSP (calculated as anhydrous trisodiuni orthophosphate.
tion to said mixture so that said mixture is maintained in particulate, dry, granular form, continuing to add said aqueous, alkali metal silicate solution until the dry, granular particles have an Si0 to said phosphate mole ratio of at least 121 and ;recovering dry, granular particles which yield a pH of at least 10.5 in an aqueous 1 percent solution.
2. Process of claim 1 wherein said temperature of said resulting mixture is maintained between about 60 to about 70 C.
3. Process of claim 1 wherein said phosphate is sodium tripolyphosphate.
4. Process of claim 1 wherein said phosphate is tetrasodium pyrophosphate.
5. Process of claim 1 wherein said phosphate is trisodium orthophosphate.
6. Process of claim 1 wherein said aqueous, alkali metal silicate solution has an SiO /Na- O weight ratio of about 2.00:! or below.
i 7. Process of claim 1 wherein the viscosity of said alkali metal silicate solution is reduced by adding water thereto.
8. Process of claim 1 wherein said dry-appearing, granular particles have a size of about l0 to mesh.
Claims (7)
- 2. Process of claim 1 wherein said temperature of said resulting mixture is maintained between about 60* to about 70* C.
- 3. Process of claim 1 wherein said phosphate is sodium tripolyphosphate.
- 4. Process of claim 1 wherein said phosphate is tetrasodium pyrophosphate.
- 5. Process of claim 1 wherein said phosphate is trisodium orthophosphate.
- 6. Process of claim 1 wherein said aqueous, alkali metal silicate solution has an SiO2/Na2O weight ratio of about 2.00:1 or below.
- 7. Process of claim 1 wherein the viscosity of said alkali metal silicate solution is reduced by adding water thereto.
- 8. Process of claim 1 wherein said dry-appearing, granular particles have a size of about -10 to +80 mesh.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US72390768A | 1968-04-24 | 1968-04-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3620979A true US3620979A (en) | 1971-11-16 |
Family
ID=24908197
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US723907A Expired - Lifetime US3620979A (en) | 1968-04-24 | 1968-04-24 | Process of forming free-flowing, particulate mixtures of phosphates and silicates |
Country Status (11)
Country | Link |
---|---|
US (1) | US3620979A (en) |
JP (1) | JPS4831472B1 (en) |
BE (1) | BE731431A (en) |
BR (1) | BR6908202D0 (en) |
CH (1) | CH533169A (en) |
DE (1) | DE1919093A1 (en) |
ES (1) | ES366406A1 (en) |
FR (1) | FR2006800A1 (en) |
GB (1) | GB1241393A (en) |
NL (1) | NL6906300A (en) |
SE (1) | SE345138B (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3888781A (en) * | 1972-09-05 | 1975-06-10 | Procter & Gamble | Process for preparing a granular automatic dishwashing detergent composition |
US3901831A (en) * | 1973-08-24 | 1975-08-26 | Monsanto Co | Method of making dense detergent granules |
US3950275A (en) * | 1972-08-17 | 1976-04-13 | Lion Fat & Oil Co., Ltd. | Method of manufacturing granular detergents |
US4032465A (en) * | 1975-02-03 | 1977-06-28 | Lever Brothers Company | Production of detergent compositions |
US4043789A (en) * | 1974-03-19 | 1977-08-23 | Norsk Hydro A.S | Process for manufacturing of phosphoric acid |
US4131558A (en) * | 1975-02-14 | 1978-12-26 | The Procter & Gamble Company | Process for preparing an orthophosphate-silicate detergent product |
US4169806A (en) * | 1978-08-09 | 1979-10-02 | The Procter & Gamble Company | Agglomeration process for making granular detergents |
US4228025A (en) * | 1979-06-29 | 1980-10-14 | The Procter & Gamble Company | Agglomeration process for making granular detergents |
US5180515A (en) * | 1989-07-27 | 1993-01-19 | The Procter & Gamble Company | Granular detergent compositions having low levels of potassium salt to provide improved solubility |
US5811080A (en) * | 1996-11-26 | 1998-09-22 | The Procter & Gamble Company | Process for increased flavor impact in oral care products |
EP1624049A2 (en) * | 2003-05-15 | 2006-02-08 | Kao Corporation | A sliding property improver for use in washing |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2707280A1 (en) * | 1976-02-26 | 1977-09-01 | Colgate Palmolive Co | PROCESS FOR THE PRODUCTION OF FREE-FLOWING SPRAY-DRIED PARTICLES FROM BUILDER SALT |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2909490A (en) * | 1954-07-28 | 1959-10-20 | Olin Mathieson | Manufacture of duplex composition of sodium tripolyphosphate and sodium silicate solution |
US3390093A (en) * | 1962-06-06 | 1968-06-25 | Monsanto Co | Detergent compositions containing hydrated alkali metal tripolyphosphates |
-
1968
- 1968-04-24 US US723907A patent/US3620979A/en not_active Expired - Lifetime
-
1969
- 1969-03-31 GB GB06661/69A patent/GB1241393A/en not_active Expired
- 1969-04-10 FR FR6911148A patent/FR2006800A1/fr not_active Withdrawn
- 1969-04-11 BE BE731431D patent/BE731431A/xx unknown
- 1969-04-15 DE DE19691919093 patent/DE1919093A1/en active Pending
- 1969-04-18 BR BR208202/69A patent/BR6908202D0/en unknown
- 1969-04-22 JP JP44030826A patent/JPS4831472B1/ja active Pending
- 1969-04-23 SE SE5808/69A patent/SE345138B/xx unknown
- 1969-04-23 NL NL6906300A patent/NL6906300A/xx unknown
- 1969-04-24 ES ES366406A patent/ES366406A1/en not_active Expired
- 1969-04-24 CH CH624369A patent/CH533169A/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2909490A (en) * | 1954-07-28 | 1959-10-20 | Olin Mathieson | Manufacture of duplex composition of sodium tripolyphosphate and sodium silicate solution |
US3390093A (en) * | 1962-06-06 | 1968-06-25 | Monsanto Co | Detergent compositions containing hydrated alkali metal tripolyphosphates |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3950275A (en) * | 1972-08-17 | 1976-04-13 | Lion Fat & Oil Co., Ltd. | Method of manufacturing granular detergents |
US3888781A (en) * | 1972-09-05 | 1975-06-10 | Procter & Gamble | Process for preparing a granular automatic dishwashing detergent composition |
US3901831A (en) * | 1973-08-24 | 1975-08-26 | Monsanto Co | Method of making dense detergent granules |
US4043789A (en) * | 1974-03-19 | 1977-08-23 | Norsk Hydro A.S | Process for manufacturing of phosphoric acid |
US4032465A (en) * | 1975-02-03 | 1977-06-28 | Lever Brothers Company | Production of detergent compositions |
US4131558A (en) * | 1975-02-14 | 1978-12-26 | The Procter & Gamble Company | Process for preparing an orthophosphate-silicate detergent product |
US4169806A (en) * | 1978-08-09 | 1979-10-02 | The Procter & Gamble Company | Agglomeration process for making granular detergents |
US4228025A (en) * | 1979-06-29 | 1980-10-14 | The Procter & Gamble Company | Agglomeration process for making granular detergents |
US5180515A (en) * | 1989-07-27 | 1993-01-19 | The Procter & Gamble Company | Granular detergent compositions having low levels of potassium salt to provide improved solubility |
US5811080A (en) * | 1996-11-26 | 1998-09-22 | The Procter & Gamble Company | Process for increased flavor impact in oral care products |
EP1624049A2 (en) * | 2003-05-15 | 2006-02-08 | Kao Corporation | A sliding property improver for use in washing |
EP1624049A4 (en) * | 2003-05-15 | 2006-06-14 | Kao Corp | A sliding property improver for use in washing |
Also Published As
Publication number | Publication date |
---|---|
ES366406A1 (en) | 1971-03-16 |
GB1241393A (en) | 1971-08-04 |
NL6906300A (en) | 1969-10-28 |
BE731431A (en) | 1969-09-15 |
FR2006800A1 (en) | 1970-01-02 |
CH533169A (en) | 1973-01-31 |
DE1919093A1 (en) | 1970-05-21 |
BR6908202D0 (en) | 1973-01-02 |
JPS4831472B1 (en) | 1973-09-29 |
SE345138B (en) | 1972-05-15 |
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