US3390093A - Detergent compositions containing hydrated alkali metal tripolyphosphates - Google Patents

Detergent compositions containing hydrated alkali metal tripolyphosphates Download PDF

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US3390093A
US3390093A US460205A US46020565A US3390093A US 3390093 A US3390093 A US 3390093A US 460205 A US460205 A US 460205A US 46020565 A US46020565 A US 46020565A US 3390093 A US3390093 A US 3390093A
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Prior art keywords
slurry
water
detergent
tripolyphosphate
alkali metal
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US460205A
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Harold E Felerstein
Shen Chung Yu
Robert R Versen
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Monsanto Co
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Monsanto Co
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Priority to GB1053384D priority Critical patent/GB1053384A/en
Priority to CA729593A priority patent/CA729593A/en
Priority to BE633146D priority patent/BE633146A/xx
Priority to NL293412D priority patent/NL293412A/xx
Priority to NO148593A priority patent/NO115087B/no
Priority to FR936183A priority patent/FR1364212A/fr
Priority to DE19631467630 priority patent/DE1467630A1/de
Priority to LU43830D priority patent/LU43830A1/xx
Priority to CH684263A priority patent/CH482829A/de
Priority to SE6043/63A priority patent/SE322307B/xx
Priority to FI1115/63A priority patent/FI41183B/fi
Priority to DK259463AA priority patent/DK114139B/da
Application filed by Monsanto Co filed Critical Monsanto Co
Priority to US460205A priority patent/US3390093A/en
Priority to GB30326/65A priority patent/GB1118795A/en
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    • 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
    • C11D3/044—Hydroxides or bases
    • 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
    • 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
    • C01B25/418—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates

Definitions

  • This invention relates to novel methods for manufacturing detergent compositions that contain hydrated alkali metal tripolyphosphates. More specifically, this invention relates to novel processes in which low bulk density detergent compositions containing at least one hydrated alkali metal tripolyphosphate can be manufactured without being spray-dried.
  • the polyphosphate that is presently preferred for use in most detergent compositions is a tripolyphosphate; particularly sodium tripolyphosphate.
  • Tripolyphosphates have a decided shortcoming which can presently be overcome (in conventional detergent manufacturing practice) as most only partially, and to that extent only by exercising very stringent precautions during the conven tional detergent processing steps. This shortcoming is the result of the tripolyphosphates susceptibility to hydrolytic degradation.
  • tripolyphosphate is generally hydrolyzed to orthophosphates and pyrophosphates which are not nearly as effective (as sequesterants) in building detergent products as is tripolyphosphate and generally, therefore, are not nearly as desirable as tripolyphosphate in the final detergent products.
  • the processes for preparing light (low bulk) density detergent compositions require that a slurry be utilized in order to achieve several specific advantages, including mainly the achievement of a better uniformity of ingredients through the final detergent products.
  • Detergent slurries are wellknown in the art, and neednt be detailed here, except to point out that those which can be used in the processes of this invention must contain at least about enough water to hydrate all of the alkali metal tripolyphosphate in the final detergent compositions that can be manufactured therefrom, and also at least enough water to initially lend fluid properties to the slurry.
  • useful slurries generally should contain at least about 10 weight percent of Water, based on the total Weight of the completely formulated slurry.
  • the slurries be fluid and initially contain at least about 20 weight percent of water (and when sodium tripolyphosphate hexahydrate is to be formed in these processes, at least about 5 Weight percent of water in excess of the amount required to pro prise said sodium tripolyphosphate hexahydrate). Because in most of the processes of this invention it will be necessary to evaporate at least part of that water which is present in the slurries (especially that amount which is in excess of the amount that can be utilized to hydrate the polyphosphate salt), some of the benefits that can accrue to those who practice the invention will be most apparent when slurries containing at most about 50 weight percent of water are utilized. Slurries differ from solutions in that the former contain more than enough materials to dissolve in the continuous aqueous phase thereof, even though the materials dispersed through the aqueous phase may have a fairly high solubility in water.
  • free water is herein intended to encompass that water which was initially in the slurry and which is present in the particular composition being referred to in an unbound (i.e., not present as the hydrate of any of the salts in the composition), unevaporated state. It should be noted that the use of the term free water with reference to a given composition at any given time does not necessarily imply that the composition referred to is in a fluid or even a semi-fluid state, since many apparently solid detergent compositions can contain as much as ten weight percent or more of free water without losing substantially all of their solid properties.
  • any water-soluble hydratable (that is, one that can be hydrated in an aqueous slurry) alkali metal tripolyphosphate salt that can be formed via the interreaction of a strong base with an alkali metal trimetaphosphate can be utilized in the manufacture of detergent compositions in accordance with the present invention.
  • the hydratable alkali metal tripolyphosphates are sodium tripolyphosphate (Na P O potassium tripolyphosphate (K P O lithium tripolyphosphate (Li P O trisodium dipotassium tripolyphosphate (N21 K P O and the like, while still further preferred is sodium tripolyphosphate.
  • sodium tripolyphosphate Na P O potassium tripolyphosphate
  • K P O lithium tripolyphosphate Li P O trisodium dipotassium tripolyphosphate (N21 K P O and the like
  • sodium tripolyphosphate Mainly because of their economic advantage over the other hydratable alkali metal polyphosphate salts described above, as well as
  • the low bulk density detergent compositions that can be made via the processes of this invention are those that contain a significant amount of the hydrated alkali metal tripolyphosphate; that is, usually at least about 10 weight percent and often as much as about 75 weight percent, based on the total weight of the final solid detergent composition. However, gene-rally, it is preferred that the final compositions contain between about and about 60 weight percent of the alkali metal tripolyphosphate salt, at least about 60 and preferably at least about 75 weight percent of which is in the hydrated state.
  • the hydrated tripolyphosphate salts need not be exposed to such high, degrading temperatures as those ordinarily utilized in detergent spray-drying operations, it will nevertheless generally be necessary to apply heat in some manner to the detergent slurries that are utilized herein in order to attain slurry temperatures of at least about 50 C. during some of the latter stages of the present processes.
  • trimetaphosphate ring is cleaved by the base, forming the tripolyphosphate anion, as is shown in Equation 1:
  • Equation 2 slurry as the hydrate, as shown in Equation 2:
  • M is an alkali metal cation and y is an integer which is equal to the number of water molecules that are necessary to make an identifiable hydrated salt of the particular alkali metal tripolyphosphate that results from the above-described reaction.
  • y will be a whole number Within the range of from 1 to 15.
  • M represent sodium and, therefore, that y equal 6.
  • trimetaphosphate could be either an acidic alkali metal trimetaphosphate (containing one or two acidic groups), a common alkali metal trimetaphosphate (wherein all of its alkali metal cations are the same), or a mixed cation alkali metal trimetaphosphate (in which more than one type of alkali metal cation is present therein).
  • alkali metal trimetaphosphates useful in the successful practice of the present invention are those that are watersoluble and that can be represented by the formula wherein M is an alkali metal cation, A can be either H or an alkali metal cation, and B can be either H or an alkali metal cation; and when A and/ or B are alkali metal cations, they can differ or be alike, and they do not necessarily have to be the same as M; although it is preferred that M, A and B be alkali metal cations and that they be the same (and still further preferred that all of M, A and B are sodium).
  • alkali metal trimetaphosphates encompassed by the above formula include Na P O Na HP O 2 3 9, s a e 2 a 9 a a a a s, LiH2P309, Rb3P309, CS3P309, Rb2HP309, Na2KP30g, NEIKzPaOg, Na LiP O Na2RbP30g, KzLiPgOg and tha like.
  • the amounts of strong base necessary to convert the trimetaphosphate to the desired tripolyphosphate should be adjusted to take into account the necessity first to neutralize the acidic hydrogens on the acidic trimetaphosphate molecule.
  • alkali metal trimetaphosphate and particularly sodium trimetaphosphate
  • any amount of the material up to about 60 weight percent, based on the total weight of the fully formulated slurry, or even more, can be utilized.
  • the amount of alkali metal trimetaphosphate that is actually utilized usually depends upon basically two requirements of the detergent manufacturer; the amount of tripolyphosphate which he desires in his final detergent product, and the proportion of this amount of tripolyphosphate that should be in the hydrated state.
  • the products which result from the practice of this invention should generally contain at least about weight percent of hydrated tripolyphosphate (when trimetaphosphate is used as a raw material), the slurries contemplated herein will ordinarily contain at least about 5 to 8 weight percent initially (based on the weight of the slurry solids), of one of the alkali metal trimetaphosphates.
  • the slurries contemplated herein will ordinarily contain at least about 5 to 8 weight percent initially (based on the weight of the slurry solids), of one of the alkali metal trimetaphosphates.
  • the slurries contemplated herein will ordinarily contain at least about 5 to 8 weight percent initially (based on the weight of the slurry solids), of one of the alkali metal trimetaphosphates.
  • the slurries contemplated herein will ordinarily contain at least about 5 to 8 weight percent initially (based on the weight of the slurry solids), of one of the alkal
  • the amount of alkali metal trimetaphosphate which is utilized in the aqueous slurries in the practice of this invention be from about 13 to about 60 percent by weight (based on the total weight of the fully formulated slurry just prior to the hydrating step of the processes of this invention, which step will be described in greater detail below).
  • FIGURE 1 represents a schematic diagram of one of the preferred processes of the present invention, which preferred process is illustrated in more detail in FIGURE 2.
  • the process illustrated in these drawings can be described as follows: Into a typical detergent crutcher 1, fitted with an eflicient stirrer 3 and a jacket 5 through which steam or hot or cold water can be circulated by means of lines 7 and 8, are charged (all parts being by weight) 355 parts of water, 782 parts of sodium trimetaphosphate, 14 parts of sodium carboxymethyl-cellulose, 258 parts of sodium dodecylbenzene sulfonate, and 191 parts of aqueous sodium silicate (47% solids) having an SiO /Na O ratio of 2.40, parts of lauryl monoisopropanolamide.
  • the resulting precursor slurry is stirred for about 15 minutes during which steam is passed through jacket 5 in order to increase the temperature of the precursor slurry to about 85 C.
  • the hot slurry is then pumped through lines 9 and 11 to a conven' tional vacuum type deaerator 13.
  • Deaerated slurry then passes through lines 15 and 17, through slurry pump 19, and line 21 to an eflicient blender 31 (in this instance line 21 leads to the inlet port of a conventional centrifugal pump).
  • line 21 leads to the inlet port of a conventional centrifugal pump.
  • the slurry is monitored by means of a flow meter 25 and a density meter 27.
  • a 50 weight percent aqueous solution of sodium hydroxide is pumped from the caustic storage tank 33 through line 35 and caustic metering pump 37 to heat exchanger 39 Where its temperature is increased to about 70 C. From there it is pumped through line 41 into the same entry port of blender 31 as that into which the precursor slurry is being introduced.
  • the speed of caustic metering pump 37 is adjusted (depending upon the data from flow meter 25 and density meter 27) so that for every 100 parts by weight of precursor slurry there are introduced into blender 31, 24.5 parts by weight of NaOH are introduced thereinto.
  • the granulated product 51 is gently wiped by a series of rotating stainless steel wires 55 in order to break up any soft agglomerated lumps, and then transferred via ramp 57 to transfer belt 59. From there it is dropped onto a vibrating screen 61 to break up any remaining agglomerates. At this point the detergent product contains about 12 weight percent of free water and 13 weight percent of combined (hydration) water in the form of sodium tripolyphosphate hexahydrate. This product is then passed through a conventional fluidized bed dryer 63 to remove almost all of the free water, and from there into product storage bin 65.
  • the bases that can be utilized in the practice of this invention are all of those which can cause the formation of sufficient hydroxyl ions, in the aqueous slurry, to react with the alkali metal trimetaphosphate, according to the foregoing suggested reaction. It has been found that of the group of materials known as bases, only the relatively strong ones can cause the reaction of trimetaphosphate to tripolyphosphate to occur. Thus, throughout the present specification and the appended claims, 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. For purposes of this invention, the strong bases that can be utilized are those that yield a solution pH measured at 25 C.
  • 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, etc. Economic considerations will generally dictate that strong bases which are inorganic be used.
  • alkali metal hydroxides, carbonates, and silicates having SiO /M O ratios lower than 2.0, where M is an alkali metal cation
  • sodium and potassium forms of these materials are particularly 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 sufficient to furnish enough hydroxyl ions so that at least a substantial amount or proportion (i.e., at least about one-half and preferably at least about seven-tenths) of the alkali metal trimetaphosphate in the slurry can be converted into the corresponding alkali metal tripolyphosphate.
  • the amount of the particular inorganic base that can be utilized (in the slurry) in the practice of this invention will generally be at least enough to furnish about one and preferably at least about 1.4 mole equivalents of hydroxyl ions per mole of trimetaphosphate which is present in the slurry. Because 2 moles of hydroxyl ions are necessary to convert one mole of trimetaphosphate to tripolyphosphate, it is still further preferred, when substantially complete conversion of the alkali metal trimetaphosphate is desired, that the slurry be formulated to contain at least about '2 moles of strong base per mole of trimetaphosphate therein.
  • the amount of strong base present in the detergent slurries which areutilized in the practice of the invention will generally not be more than about moles, and preferably at most about 6 moles of base per mole of trimetaphosphate in the slurries.
  • the rate of conversion of trimetaphosphate to tripolyphosphate can be increased by increasing the ionic strength (concentration) of a given detergent slurry. Therefore, those who prefer to utilize very high rates of conversion in the processes of this invention can advantageously do so by utilizing highly concentrated detergent slurries. It has also been discovered that the presence of more than about 0.5 weight percent of sodium sulfate in the slurry (while the trimetaphosphate conversion reaction is being carried out) in some way acts as a catalyst for the conversion reaction, sometimes increasing the rate of conversion as much as 50% or more.
  • the temperatures of slurries formulated with alkali metal trimetaphosphate that are utilized in accordance with this invention should generally be maintained below about C., and preferably below about l20 C. while the alkali metal trimetaphosphate is being converted to tripolyphospnate.
  • slurry temperatures above about 50 C., and preferably above about 70 C. should generally be maintained during at least the latter half of the conversion step. However, even lower temperatures than about 50 C. can be utilized if desired. (Temperatures higher than about 105 C. can be obtained in the slurries and reaction mixtures by carrying out the processes under pressures higher than atmospheric.)
  • the reaction mixture becomes a solid, seemingly, wet mass generally still containing several weight percent of free water, which can be removed if desired by subsequently drying the wet mass, or by additional absorption of the free water via hydrate formation.
  • Such delayed hydrate formation has been observed to take place even subsequent to the above-described conversion reaction. It can take place readily, for example, in compositions that contain hydratable materials such as sodium sulfate, and certain of the phosphate salts that form their hydrates at temperature below those that are generally utilized in the foaminghydration step (described above) of the processes of the present invention.
  • hydratable materials such as sodium sulfate, and certain of the phosphate salts that form their hydrates at temperature below those that are generally utilized in the foaminghydration step (described above) of the processes of the present invention.
  • foaming-hydration step When the foregoing foaming-hydration step is performed under atmospheric pressure and detergent slurries having water alone as the continuous phase, it is usually necessary to heat the slurries to a temperature between about 100 C. and about 105 C. in order to generate foam via the conversion of water to steam as described above.
  • a quantity of a relatively low boiling, completely water-miscible organic solvent such as methanol, ethanol, isopropanol, acetone, dioxane, and the like, or combinations of these, can be utilized along with the water as the fluid continuous phase in the preparation of the detergent slurries described heretofore.
  • the temperature of the reaction medium (the slurry which subsequently is converted into a solid detergent product during the foaming-hydration step) is maintained sufficiently high to generate steam-in the form of pure water vapor or as the low boiling organic solvent/water azeotrope, for example, dependin upon the composition of the slurrys fluid continuous phasewhich steam is the cause of the light density foam. It is not absolutely necessary, however, that the gas which forms the foam is steam. Actually, particularly where lower slurry temperatures and trimetaphosphate conversion rates are desired in the processes of this invention it is sometimes advantageous to create the foam, during the foaming-hydration step described heretofore, by blowing, dispersion, or injecting a gas other than steam into the slurry.
  • the gas which is injected can be 'air, oxygen, carbon dioxide, sulfur dioxide, nitrogen, nitrous oxide, hydrogen, propane, methane, ethane, argon, neon, superheated steam, hydrogen sulfide, and the like. It can also be any of a number of relatively lower boiling synthetic materials which are either gases at temperatu'es below about 100 C. and atmospheric pressure, or which can be converted readily into gases by making relatively minor adjustments in temperature and/or pressure, such as for 10 example, the fluorinated hydrocarbons including CCl F, CCl F CClF CClF and the like. Generally, it is preferred that these gaseous materials be non-reactive with the other materials in the detergent compositions at temperatures used during the practice of these processes.
  • the reaction (hydrating) mixture When conditions during the foaming-hydration step are such that the rate of hydration of the polyphosphate is relatively slow (such as when slurry temperatures below about 70 C. are utilized during the conversion of one of the alkali metal trimetaphosphates) the reaction (hydrating) mixture must generally be maintained in the foamed state for a longer period of time. than when conditions are such as to encourage a higher rate of hydration, provided most of the benefits that can be attained by practicing the present invention are desired.
  • This amount of time can be reduced (other conditions remaining the same in any given process) by using a procedure involving the injection of a gas, the gas being heated prior to its introduction into the hydrating mixture to a temperature high enough to result in the removal of some of the free water from the slurry via evaporation.
  • Heat can also be applied directly to the slurry by means of a conventional heat exchanger or through the walls of the crutcher pipe, belt, or other container in which the foaming-hydration step is being carried out.
  • the foam during the foaminghydration step can be continually generated during the entire period, or during only a portion of the latter part of the period during which the polyphosphate is hydrated.
  • suihcient foam can be generated initially, and the reaction conditions then adjusted and maintained so that at least a large proportion of the bubbles of gas are maintained (held) in the slurry until it solidifies.
  • the more (i.e., the greater the volume of) bubbles that can be generated and held in the slurry during the foaming-hydration step the lighter or lower the bulk density of the final detergent product will be.
  • the total volume of the foamed slurry should be at least about percent, and preferably at least about 200 percent (by volume) of the unaerated volume of the slurry, i.e., of the slurry volume, before it is transformed into the foamed state.
  • foaming agent is intended to include synthetic organic anionic, nonionic, and even ampholytic active detergent materials that are generally compatible with the alkali metal polyphosphates in both solutions and slurries of the overall detergent compositions.
  • foaming agent includes, for example, such individual organic detergent-active ingredients as the well-known water-soluble soaps (i.e., the sodium and/or potassium salts of coconut fatty acids, oleyl fatty acids, etc); water-soluble alkylaryl sulfona-tes having from 6 to 20 carbon atoms, and preferably from 9 to 17 carbon atoms, in their alkyl chain, such as sodium dodecyloenzene sulfonate and potassium tetradecylbenzene sulfonate; water-soluble alkyl sulfates, Such as those that are manufactured by sulfating aliphatic alcohols having from 6 to 20 carbon atoms in their either branched or unbranched alkyl chains, including, typically, sodium and potassium lauryl (C sulfate, sodium and potassium hexadecyl sulfate, sodium and potassium octadecyl sulfate, etc.; as Well as alkali
  • the nonionic detergent active materials are utilized in the absence of a significant amount of one of the anionic detergent active materials in the manufacture of detergent products in accordance with this invention, an unexpectedly high slurry viscosity develops at one stage of the crutching operation. It has been found that this problem can be alleviated by adding the hydratable rripolyphosphate last or nearly last, and very slowly (i.e., over a period of 2 minutes or more) with agitation into the other detergent ingredients.
  • foaming agent also includes materials which, when added to the slurry, contribute to some extent to the tenacity or the toughness or stability of the bubbles in the foamed slurry.
  • materials include polymers that are watersoiuble to an extent sufiiciei'zt to contribute to the stability of the foam such as sodium carboxyrnethylcel-lulose; sodium hydroxyethyl cellulose, polyvinylpyrollidone; hydrolyzed and partially hydrolyzed polymers made by reacting a lower alkylene such as ethylene, propylene, and methyl vinyl ether with maleic and/or fumaric anhydride, for example, ethylenc-maieic anhydride, propylene fumaric anhydride, methyl vinyi ether-maleic anhydridc; polyvinyl alcohol; and the like.
  • the amount of foaming agent in the slurries during the foaming-hydration step of this invention can be varied considerably. Generally, more than about 0.1 weight percent, based on the wei ht of the completely formulated slurry, should be utilized when final detergent products having fairly low bulk densities are desired. However, for very low bulk densities in the final detergent products made via these processes, usually at least about 0.25 and preferably at least about 0.5 weight percent of the foaming agent should be used. Since different foaming agents perform with different degrees of efiiciency, depending upon many factors including slurry temperature, slurry solids concentration, the actual ingredients contained in the slurry, and many others, optimum concentration for each foaming agent cannot be set out herein with definity. However, it is believed Within the ability of those reasonably skilled in the art, in view of this disclosure, to ascertain the optimum concentrations for the manufacture of their oWn particular detergent product.
  • any manipulative procedure can be utilized in the practice of the present invention in order to accompiish the various steps or stages in the processes set out above.
  • the order of addition of the various ingredients in the preparation of any of the slurries, except those that contain more than a few weight percent of alkali metal trimetaphosphate is not at all critical.
  • compositions which contain tripolyphosphate should generally not be blended with the strongest bases such as sodium hydroxide unless the base is diluted to below about 50 weight percent, and preferably below about 35 weight percent, with water before the strong base is blended with the alkali metal trimetaphosphate.
  • the strong base should be effectively diluted by the Water in the slurry itself as quickly as possible after the base is added to the slurry.
  • a manufacturer is not particularly concerned about completely minimizing the degradation of the tripolyphosphate during his manufacturing operations, even this precaution need not be strictly observed.
  • one advantageous method for doing so which combines several of the unexpectedly desirable attributes from using alkali metal trimetaphosphate, and especially sodium trimetaphosphate, is to first prepare a practically completely formulated detergent slurry; which usually contains any foaming agent, antiredeposition agent, optical brighteners, bleaches, fabric softeners, alkali metal silicate or fiuosilicate corrosion inhibitors, or whatever other materials that are desired in the final detergent composition or product, but which does not contain the strong base (called herein the precursor slurry).
  • the precursor slurry then should also contain the trimetaphosphate.
  • precursor slurries having comparatively little water .(as compared to conventional detergent slurries that practically invariably contain hydrating or hydrated tripolyphosphate), but which retain their pumpability and other fluid characteristics, can be made.
  • precursor slurries containing as much as weight percent of non-volatile material can be manufactured and utilized in the processes of this invention. So long as the strong base is withheld from the precursor slurry, its low viscosity can generally be maintained almost indefinitely, with substantially no degradation of the trirnetaphosphate occurring.
  • a detergent manufacturer can prepare his precursor slurries well in advance of the time he wants to produce his final detergent product if he desires.
  • a detergent manufacturer can hold his precursor slurry for long periods of time if need be, practically with greatity, whereas, if he had prepared conventional slurry using sodium tripolyphosphate, hydrolytic degradation of the tripolyphosphate in the slurry upon prolonged storage could practically destroy the utility of the slurry for his processes.
  • the detergent manufacturer can now utilize several approaches to the final essential step in the processes of this invention. Since l 3 it is desirable that the foaming-hydration step be performed relatively quickly, and because the rate of conversion of the trimetaphosphate to tripolyphosphate is very high at elevated temperatures, the precursor slurry can be heated to a temperature above about 50 C., and preferably above about 70 C., in one of the preferred embodiments of this invention before the strong base is intermixed therewith. In that case, the conversion reaction proceeds quickly (usually within about 2 minutes when an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is utilized, for example, at the higher precursor slurry temperatures), after the strong base is blended into or with the precursor slurry.
  • an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide
  • the heat of conversion of the trimetaphosphate to tripolyphosphate, and thence to hydrated tripolyphosphate is generally sufficiently high that the conversion reaction can become essentially autocatalytic in nature if most of this heat is not deliberately removed from the slurry.
  • the conversion reaction commences immediately.
  • the heat from the conversion causes an increase in the temperature of the reaction mass, which in turn causes an increase in the rate of conversion of the trimetaphosphate to tripolyphosphate. Increases of tenfold or more in this rate of conversion can be accomplished by raising the temperature of the reaction mass about 25 C.
  • the manufacturer can be reasonably assured that his foaming-hydration step will not require an excessively long time.
  • steam and foam can usually be generated in detergent slurries which are treated like that described immediately above (precursor slurry strong base) within a few minutes of the time the strong base is intermixed with the hot precursor slurry.
  • Another method by which a manufacturer can accomplish this same result is by passing the fairly cool, completely formulated slurry (containing both trimetaphosphate and strong base) through a steam-traced pipe, using higher than atmospheric pressures and temperatures above about 105 C. if desired to obtain still higher conversion rates. Before the conversion has been completed it is generally preferred that the slurry be deposited into or onto some container in order for the above-described foaming-hydration step to be completed in the absence of an excessive amount of agitation.
  • the slurry can be dumped into a pan or other container, or onto a movable belt from the internally agitated vessel shortly before the foamed slurry solidifies in order to minimize the agitation during this setting up period.
  • the strong base should be'thoroughly and evenly distributed through the slurry before the solidification stage is reached, however.
  • the hot precursor slurry can be metered into a conventional mixing device in which the precursor slurry can be thoroughly and quickly intermixed with the strong base, which is also metered into the device at a rate calculated to yield the desired final product. Then the completely formulated slurry can be poured or dropped or pumped from the mixing device onto or into a container and there permitted to either begin or continue to foam and subsequently solidify into the final detergent product.
  • This method is described hereinbefore and is illustrated in FIGURES l and 2.
  • Cold precursor slurry can be metered through an electric or steam-traced pipe or series of pipes prior to its being inserted into the mixing device.
  • the completely formulated slurry When such a procedure is utilized continuously, it is convenient and advantageous to pour the completely formulated slurry onto a movable belt that is designed to hold fluid substances.
  • the slurry can then foam and steam on the belt, and subsequently solidify thereon.
  • the lighter density product can be passed through a drying oven usually operated at a temperature which. does not excessively degrade the hydrated tripolyphosphate) when it is desired to remove some of the excess free water that may be present.
  • This drying oven step is not essential for the successful practice of the invention, however.
  • the hot, completely formulated slurry can be held in a pipe or conduit or other container under higher than atmospheric pressure, if desired, until the temperature of the slurry reaches the boiling point of the water therein.
  • the tower can contain warm, dry air to aid in the removal of some of the free water, but the temperature in the tower should generally be held considerably lower than those that are utilized in conventional spray-drying operations.
  • foaming, hydration and solidification during the drop through the Warm tower can result in the formation of a low bulk density detergent product via a completely different .mechanism then is conventionally employed in similar equipment (i.e., a spray-drying tower).
  • one of the particularly prefer-red embodiments of the present invention involves the efiicient utilization of heat resulting from (a) the reaction of the trimetaphosphate with the strong base, and (b) the hydration of the resulting tripolyphosphate.
  • the heat evolved during these chemical processes is utilized to both (a) raise the temperature of the slurry to that at which the steam is formed and (b) to cause the evaporation of some of the free water from the resulting particulated, light density product.
  • the interreaction of the trimetaphosphate and the strong base be carried out in such a way that the reaction is essentially adiabatic, in which practically none of the heat resulting from the exothermic reaction is allowed to escape from the slurry, so that the tempera ture of the slurry is increased by the internal addition of such heat of reaction into it.
  • the initial temperature of the final slurry (containing both trimetaphosphate and strong base, as Well as any other desired detergent ingredients) be at least a certain minimum level, the actual value of which certain minimum temperature being determined by several factors including, for example (a) the total amount of trimetaphosphate that is to be reacted with the strong base (generally the larger this amount the lower the initial temperature needs to be), (b) the type of tripolyphosphate hydrate to be made (the heats of hydration differ), (c) the proportions and kinds of other ingredients in the slurries (this effect is relatively minor, however) and (d) the final reaction temperature expected (i.e., the temperature of the slurry during the foaminghydration step).
  • the initial temperature of the slurry (immediately after the trimetaphosphate and the sodium hydroxide are intermixed) must be at least about 80 C. (in order for the heats of reaction described above to carry the temperature of the slurry to about 105 C., which is about its boiling point under 1 atmosphere of pressure).
  • Element Range Percent water in slurry 20-50 Percent sodium trimetaphosphate 1560 Percent NaOH 4-16 Temperature 2 45-90 In terms of percent by Weight of the slurry immediately prior to the beginning of the reaction of NaOH with trimetaphosphate.
  • Example I Just after the sodium trimetaphosphate and the NaOH have been intermixed (immediately prior to the beginning of their interreaction) This particularly preferred embodiment of the present invention is illustrated in Example I, below. It should be understood that when relatively lower amounts (within the above range) of sodium trimetaphosphate are to be converted in these processes, relatively higher initial slurry temperatures must be used, and when relatively larger amounts of trimetaphosphates are to be converted, relatively lower temperatures can be used.
  • EXAMPLE I Into a conventional stainless steel mixing vessel which is fitted with a conventional paddle-type stirrer and jacketed so that either hot or cold water or steam can be used in the jacket, are charged 2,000 parts of water, 900 parts of sodium dodecylbenzene sulfonate, 600 parts of sodium lauryl sulfate, 1,000 parts of sodium sulfate, 2,840 parts of sodium trimetaphosphate, 1,140 parts of sodium silicate (47% solids) having an SiO /Na O ratio of 2.40 and 55 parts of detergent grade sodium carboxymethylcellulose. The resulting precursor slurry is stirred for about minutes, during which time the temperature of the slurry is raised to 80 C. by circulating steam through the mixer jacket.
  • Example I no dilficulty whatever is experienced with respect to lumps in either the precursor or the completely formulated slurries.
  • anhydrous sodium tripolyphosphate instead of sodium trimetaphosphate, many troublesome lumps of undissolved, partially hydrated tripolyphosphate would probably have formed, especially if the high temperature modification had been utilized, which lumps are generally not desired by detergent manufacturers in either their slurries or in their final detergent products.
  • Conventional-detergent B and the Invention Product used as a basis for the data in Table 2 contained about 20 weight percent of a mixture of sodium dodecylbenzene sulfonate and lauryl isopropanolamide, plus about 50 weight percent of sodium tripolyphosphate, about 5 Weight percent of sodium silicate solids, about 23 weight percent of sodium sulfate, and a total of about 2.5 weight percent of minor adjuvants.
  • Conventional-detergent A is a well-known nonionic detergent.
  • EXAMPLE II A precursor slurry similar to that prepared in Example I is formulated, except that 3,100 parts of a physical blend containing about 50 Weight percent of sodium trimetaphosphate and 50 weight percent of anhydrous 1 7 high temperature crystalline modification sodium tripolyphosphate are utilized in place of the sodium trimetaphosphate.
  • a precursor slurry is prepared which is similar to that made according to Example I, above. Its temperature is about 45 C. It is then continuously metered into a stain-' less steel conduit having an inside diameter of about 1 inch. The conduit is traced for a distance of about 30 feet with a pressurized steam jacket to heat the precursor slurry to a temperature near boiling. The heated precursor slurry is joined by a 50 weight percent aqueous solution of sodium hydroxide metered into a mixing nozzle at a rate proportional to 2.01 moles of NaOH per mole of sodium trimetaphosphate in the precursor slurry.
  • the mixing nozzle is equipped with an agitator and several baffles spaced and designed to achieve quick and intimate mixing of the precursor slurry with the strong base.
  • the temperature of the resulting completely formulated slurry is raised to about 115 C. by the heat of reaction and the pressure is increased to above about p.s.i.g. From the open end of the mixing nozzle the slurry is discharged onto a moving belt, where steam is quickly generated and the product foams, and solidified into a soft, spongy material. After being air cooled the final detergent product has a bulk density of about 0.65.
  • the cooled spongy material can be easily disintegrated into a free flowing granular product or properly sized for laundry detergents.
  • the processes of the present invention can be advantageous in detergent manufacture in many ways, some of which have been mentioned heretofore. Additionally, however, it is a very valuable advantage that manufacturers can now utilize a hydratable polyphosphate (the trimetaphosphate) in only one physical form for the manufacture of a variety of forms and types of products.
  • the final relatively low bulk density detergent products can be passed through a compressing machine and then ground to produce a product having a higher bulk density if desired. Control of the density of the final detergent products can also be obtained by utilizing a small amount of a conventional anti-foam agent in the slurry during the foaming-hydration step.
  • the more antifoam agent such as the well-known silicones, for example
  • a detergent product having practically any desired final formula (provided it also contains a substantial amount of one of the desired hydrated tripolyphosphates) can be manufactured via the processes of this invention.
  • Manufacturers of tableted or formed detergents can also utilize this invention to advantage.
  • EXAMPLE IV A part of the soft, spongy, particulated product of Example III is taken from the moving belt (before it is cooled and air dried) and in addition introduced into a conventional soap milling machine (often called a plodder).
  • a conventional soap milling machine often called a plodder.
  • the temperature of the detergent is maintained at about 100 C.
  • the detergent is milled very briefly (because it is already homogeneous) and then extruded on conventional equipment into bar form at a temperature of from about 50 C. to about 100 C. preferably from about 50 C. to about C. After they are cooled to about 25 C., the resulting detergent bars are uniform, homogeneous and excellent detergent laundry bars.
  • Detergent bars and tablets can also be produced by simply compressing in suitable conventional molding equipment any of the porous, particulated products resulting from processes such as are illustrated in FIGURE 2 and Example 1, above, under pressures of from about 200 to about 4000 pounds per square inch.
  • This cellular structure combined with the overall formed shape (such as in the form of a bar of soap or practically any other desired shape) can result from a closely controlled release of steam during the foaming-hydration step of the processes of this invention.
  • the total amount of steam that is formed should be controlled so that very little, if any of the steam bubbles out of the foamed slurry.
  • the reaction rate, and/ or concentration of the alkali metal trimetaphosphate and other hydratable poly-phosphate materials in the slurry should be controlled or regulated so that the total amount of steam and/or other gas that is generated in the slurry is not more than about four times the total unaerated volume of the completely formulated slurry (i.e., the foamed slurry volume is preferably less than about 5 times its unaerated volume).
  • the volume of the foamed slurry can be increased to about 8 or even 10 times the unaerated volume of the slurry without an excessive breaking of the steam or gas bubbles within the foam before it solidifies (which breaking and excessive evolution of steam or gas from the slurry at or near the time the slurry solidified can result in the particulation of the final detergent product, which is generally not desired in the manufacture of formed solid products having cellular internal structures).
  • the greater proportion of the free water initially in the slurries should be removed or tied up via hydration of the tripolyphosphate, and other hydratable materials in the composition such as sodium sulfate, sodium silicate and the like. Generally, it is preferred that at least about 50 weight percent of the free water be bound as the hydrate of the tripolyphosphate.
  • This limitation on the amount of gas generated in the slurry can be accomplished, for example, by intermixing the strong base and trimetaphosphate at a fairly low temperature, so that a large part of the heat from the conversion of trimetaphosphate to tripolyphosphate can be consumed in raising the temperature of the slurry to the boiling point of the water contained therein, or to that point at which some other gas is generated therein. Some of the heat can also be removed from the slurry by means of appropriately placed heat exchangers.
  • Another procedure that can be efiectively utilized for the manufacture of formed low bulk density solid detergent products is one that involves the passage of a completely formulated slurry through a hot conduit, under pressure if necessary in order to prevent the evolution of steam through most of the tripolyphosphate hydration period. Then, when there remains only a fraction of the hydration to be completed, which fraction is sufiicient to cause the formation of about the desired amount of foam in the slurry, the slurry is poured into a mold or container. At this point, the temperature is generally at or above the temperature above which gas is formed in the slurry.
  • the continued hydration causes the generation of gas in the slurry, and also the final solidification of the slurry into the desired cellular product.
  • the correct proportion of gas can be injected into the slurry shortly prior to the time it solidifies in any particular desired manner, as outlined above.
  • Detergent products that are manufactured via the preferred processes of the present invention i.e., via reaction of a sodium trimetaphosphate with a strong base containing sodium cations, such as sodium hydroxide
  • a sodium trimetaphosphate with a strong base containing sodium cations, such as sodium hydroxide can be specifically identified as such due to the surprising fact that the crystalline sodium tripolyphosphate hexahydrate contained therein yields peculiar (but specific and reproducible) results when tested via conventional difierential thermal analysis (D.T.A.) techniques.
  • D.T.A. conventional difierential thermal analysis
  • a process which comprises forming an aqueous slurry containing (a) at least about 8% by weight of a water-soluble alkali metal trimetaphosphate salt, (b) an amount, sufiicient to convert a major proportion of said trimetaphosphate salt to a tripolyphosphate, of a base of a strength such that a 1% by weight solution of the base in distilled water provides a pH of at least about 10.2 at C., (c) an amount of water at least 5% in excess of that required to hydrate said tripolyphosphate and equal to at least about 10% by weight but not more than by weight of said slurry; interspersing a gas in said slurry to form a foam; said gas being selected from the group consisting of water vapor and gases which are non-reactive with the other materials in said slurry at temperatures of from about 50 C. to 135 C.; and maintaining the temperature of said foam within the range of from about 50 C. to about 135 C. while removing sufficient free water from
  • alkali metal trimetaphosphate is sodium trimetaphosphate and said alkali metal tripolyphosphate is sodium tripolyphosphate hexahydrate.
  • said slurry also contains at least about 0.1 weight percent of a foaming agent selected from the group consisting of water soluble organic detergent active materials and water-soluble organic polymer materials.
  • foaming agent is a water soluble organic anionic surface active agent which is compatible with said alkali metal tripolyphosphate.
  • said surface active agent is a fatty alcohol sulfate containing from about 6 to about 22 carbon atoms.
  • said strong base is selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal silicates having Si /M O ratios, wherein M is an alkali metal cation, below about 2.
  • a process which comprises forming an aqueous slurry by intermixing with water at least about 10 weight percent, based on the weight of the total solids of said slurry, of trisodium trimetaphosphate; interspersing a gas into at least a portion of said slurry to thereby form a light density foam, said gas being selected from the group consisting of water vapor and gases which are non-reactive with the other materials in said slurry at temperatures of from about 50 C.
  • a process which comprises the steps of (a) rapidly mixing into a stream of a precursor slurry a metered quantity of an aqueous basic solution said precursor slurry being at a temperature of from 50 C. to 135 C. and containing at least about 8% by weight of a Watersoluble alkali metal trimetaphosphate salt, an amount of water such that subsequent to the addition of said basic solution the slurry contains from about 10% by weight to about 50% by weight of water, and at least about 0.1% by weight of a foaming agent selected from the group consisting of water-soluble organic detergent active materials and water-soluble organic polymer materials, and said basic solution being of a concentration such that said metered quantity thereof contains an amount of base sufficient to convert a major portion of said trimetaphosphate salt to a tripolyphosphate and such that said slurry subsequent to the addition of said basic solution contains an amount of water at least in excess of that required to hydrate said tripolyphosphate, said base being of such strength that a 1% by weight solution thereof in distilled water provides
  • said base is selected from the group consisting of alkali metal hydroxides, alkali metal carbonates and alkali metal silicates having SiO /M O ratios (where M is an alkali metal cation) below about 2.
  • alkali metal trimetaphosphate is sodium trimetaphosphate
  • said slurry initially contains from about 13% by weight to about 60% by weight of said sodium trimetaphosphate
  • said foaming agent is selected from the group consisting of anionic and nonionic detergent active materials and is present in said slurry in an amount equal to at least about 0.5% by weight of said slurry
  • the stream of said slurry to which said basic solution is added is at a temperature of from about 50 C.
  • said slurry subsequent to the addition of said basic solution, contains at least 20% by Weight of water, and said metered quantity of said basic solution contains a quantity of base at least stoichiometrically equivalent to the sodium trimetaphosphate present in said slurry but not more than six times that required to react with said sodium trimetaphosphate.
  • a process as in claim 14, wherein said strong base is sodium hydroxide.
  • a process which comprises intermixing water and sodium trimetaphosphate to thereby form a fluid dispersion having a continuous aqueous phase and a dispersed phase containing sodium trimetaphosphate, the total amount of said sodium trimetaphosphate in said dispersion being between about 8 and about weight percent; adjusting the temperature of at least a portion of said dispersion to between about 60 C.
  • said blend additionally contains an effective amount of a water-soluble foaming agent selected from the group consisting of water-soluble organic detergent active materials and water-soluble organic polymer materials.
  • foaming agent is a water-soluble organic detergent which is compati'ble with sodium tripolyphosphate.
  • anionic organic detergent is an alkylol sulfate containing from 8 to 20 carbon atoms in its alkyl chain.
  • a foaming agent to thereby form an aqueous slurry containing between about 10 and about 60 weight percent of said sodium trimetaphosphate and at least about 0.5 weight percent of said foaming agent, said foaming agent being selected from the group consisting of water-soluble organic detergent active materials and Water-soluble organic polymer materials; adjusting the temperature of at least a portion of said slurry to between about 70 C.
  • aqueous solution containing at most about 50 weight percent, based on the weight of said solution, of sodium hydroxide, and containing therein from about 2 to about moles of said sodium hydroxide per mole of said trimetaphosphate in said portion to thereby form a blend; and thereafter maintaining the temperature of said blend below about 120 C. and at the boiling point of the water in said blend until a substantial proportion of said water is converted into steam, whereby a light density foam is formed in said portion and sufficient water is removed from said foam to result in the formation of a solid, porous composition containing sodium tripoly-phosphate hexahydrate.
  • a process which comprises forming a slurry initially containing from about 20 to about 50 weight percent of water, from about to about 60 weight percent of trisodium trirnetaphosphate, from about 4 to about 16 weight percent of sodium hydroxide, and at least about 0.5 weight percent of a water-soluble anionic organic detergent; adjusting the temperature of at least a portion of said slurry to from about 45 to about 90 C.; permitting the temperature of said portion to increase to the boiling point of the water in said portion as a result of the exothermic reaction of said sodium hydroxide with said sodium trimetaphosphate; maintaining the temperature of said portion at about said boiling point until a substantial proportion of the Water in said portion is converted into steam, whereby said portion is initially converted into a light density foamed slurry and sulficient water is removed from said foamed slurry to thereby convert said foamed slurry into a solid, porous composi- 1 tion containing from about 20 to about 93 weight percent of sodium tripolyphosphate hex
  • a process for manufacturing a formed solid com position containing hydrated alkali metal tri-polyphosph-ate and a multitude of gas-filled cells comprises the steps of (a) intermixing sodium trimetaphosphate, water, and a strong base selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal silicates having SiO /M O ratios (where M is an alkali metal cation) below about 2, to thereby form a fluid slurry containing from about 10 to about 60 weight percent of said sodium trimetaphosphate, at least about 10 weight percent of water and an amount of said strong base, equal to at least about the stoichiometric amount required to convert said trimetaphosphate to tripolyphosphate;
  • step (c) is performed at a temperature below about 120 C.
  • a process for manufacturing a detergent bar composition which process comprises the steps of (a) intermixing Water, a water-soluble organic detergent active material, and a material which reacts with water at a temperature below about 135 C. to produce a water-soluble alkali metal polyphosphate hydrate to thereby form a fluid slurry;

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CA729593A CA729593A (en) 1962-06-06 Detergent process
BE633146D BE633146A (ja) 1962-06-06
NL293412D NL293412A (ja) 1962-06-06
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NO148593A NO115087B (ja) 1962-06-06 1963-05-07
DE19631467630 DE1467630A1 (de) 1962-06-06 1963-05-28 Verfahren zur Herstellung einer Reinigungsmasse
FR936183A FR1364212A (fr) 1962-06-06 1963-05-28 Compositions détergentes contenant des polyphosphates de inétaux alcalins
LU43830D LU43830A1 (ja) 1962-06-06 1963-05-29
SE6043/63A SE322307B (ja) 1962-06-06 1963-05-31
FI1115/63A FI41183B (ja) 1962-06-06 1963-05-31
CH684263A CH482829A (de) 1962-06-06 1963-05-31 Verfahren zur Herstellung einer leichten, porösen Reinigungsmasse
DK259463AA DK114139B (da) 1962-06-06 1963-05-31 Fremgangsmåde til fremstilling af et fast, porøst rensemiddel med lille rumvægt.
US460205A US3390093A (en) 1962-06-06 1965-06-01 Detergent compositions containing hydrated alkali metal tripolyphosphates
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US3620979A (en) * 1968-04-24 1971-11-16 Fmc Corp Process of forming free-flowing, particulate mixtures of phosphates and silicates
US3622516A (en) * 1967-10-06 1971-11-23 Monsanto Co Built-soap manufacturing process
US3639286A (en) * 1968-05-28 1972-02-01 Mario Ballestra Synthetic detergent in bar or cake form and the method to manufacture same
US3793212A (en) * 1971-07-23 1974-02-19 Colgate Palmolive Co Detergent composition and method of preparing same
US3887614A (en) * 1969-12-03 1975-06-03 Lion Fat Oil Co Ltd Detergent composed of hollow spherical pellets, and process for manufacturing the same
USRE32763E (en) * 1978-02-07 1988-10-11 Ecolab Inc. Cast detergent-containing article and method of making and using
USRE32818E (en) * 1978-02-07 1989-01-03 Ecolab Inc. Cast detergent-containing article and method of using
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US5674831A (en) * 1993-12-30 1997-10-07 Ecolab Inc. Method of making urea-based solid cleaning compositions
USD419262S (en) * 1999-03-12 2000-01-18 Ecolab Inc. Solid block detergent
US6060444A (en) * 1993-12-30 2000-05-09 Ecolab Inc. Method of making non-caustic solid cleaning compositions
US6124250A (en) * 1993-12-30 2000-09-26 Ecolab Inc. Method of making highly alkaline solid cleaning compositions
US6150324A (en) * 1997-01-13 2000-11-21 Ecolab, Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US6156715A (en) * 1997-01-13 2000-12-05 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6177392B1 (en) 1997-01-13 2001-01-23 Ecolab Inc. Stable solid block detergent composition
US6258765B1 (en) 1997-01-13 2001-07-10 Ecolab Inc. Binding agent for solid block functional material
US6632291B2 (en) 2001-03-23 2003-10-14 Ecolab Inc. Methods and compositions for cleaning, rinsing, and antimicrobial treatment of medical equipment
US6638902B2 (en) 2001-02-01 2003-10-28 Ecolab Inc. Stable solid enzyme compositions and methods employing them
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US20060069002A1 (en) * 2004-09-28 2006-03-30 The Procter & Gamble Company Process for preparing automatic dishwashing detergent compositions comprising potassium tripolyphosphate formed by in-situ hydrolysis
US20060069003A1 (en) * 2004-09-28 2006-03-30 The Procter & Gamble Company Automatic dishwashing detergent compositions containing potassium tripolyphosphate formed by in-situ hydrolysis

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US3506586A (en) * 1967-04-03 1970-04-14 Procter & Gamble Process for hydrating pentasodium tripolyphosphate form i
US3622516A (en) * 1967-10-06 1971-11-23 Monsanto Co Built-soap manufacturing process
US3620979A (en) * 1968-04-24 1971-11-16 Fmc Corp Process of forming free-flowing, particulate mixtures of phosphates and silicates
US3639286A (en) * 1968-05-28 1972-02-01 Mario Ballestra Synthetic detergent in bar or cake form and the method to manufacture same
US3887614A (en) * 1969-12-03 1975-06-03 Lion Fat Oil Co Ltd Detergent composed of hollow spherical pellets, and process for manufacturing the same
US3793212A (en) * 1971-07-23 1974-02-19 Colgate Palmolive Co Detergent composition and method of preparing same
USRE32763E (en) * 1978-02-07 1988-10-11 Ecolab Inc. Cast detergent-containing article and method of making and using
USRE32818E (en) * 1978-02-07 1989-01-03 Ecolab Inc. Cast detergent-containing article and method of using
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Also Published As

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FI41183B (ja) 1969-06-02
DOP1963001043A (es) 1968-05-27
ES288157A1 (es) 1963-12-01
NO115087B (ja) 1968-07-22
AT265476B (de) 1968-10-10
GB1118795A (en) 1968-07-03
SE322307B (ja) 1970-04-06
LU43830A1 (ja) 1963-11-29
BE633146A (ja)
FR1364212A (fr) 1964-06-19
CA729593A (en) 1966-03-08
CH482829A (de) 1969-12-15
NL293412A (ja)
DK114139B (da) 1969-06-02
DE1467630A1 (de) 1969-07-17
GB1053384A (ja)

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