US3772901A - Washing apparatus including means for removal of phosphates from the washing solution - Google Patents

Washing apparatus including means for removal of phosphates from the washing solution Download PDF

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US3772901A
US3772901A US00152312A US3772901DA US3772901A US 3772901 A US3772901 A US 3772901A US 00152312 A US00152312 A US 00152312A US 3772901D A US3772901D A US 3772901DA US 3772901 A US3772901 A US 3772901A
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washing
phosphate
discharge
wash water
solution
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J Ferraro
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Colgate Palmolive Co
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Colgate Palmolive Co
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00 
    • D06F39/02—Devices for adding soap or other washing agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00 
    • D06F39/10—Filtering arrangements

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  • ABSTRACT A washing machine or dishwasher includes means for admixing with waste wash water a suitable chemical compound to convert the soluble phosphate in the wash water to insoluble form before discharge of the waste solution to a sewer, drain or other means of disposal.
  • a suitable chemical compound to convert the soluble phosphate in the wash water to insoluble form before discharge of the waste solution to a sewer, drain or other means of disposal.
  • useful chemical compounds employed are calcium chloride, calcium hydroxide and aluminum sulfate, which convert soluble phosphates, including tripolyphosphate and pyrophosphate salts, to insoluble materials, which may be removed from the effluent.
  • accessories for use with conventional washing apparatuses for effecting the insolubilization reaction, and corresponding processes are also within the invention.
  • This invention relates to washing apparatuses, including automatic washing machines and dishwashers, accessories for such apparatuses and methods for washing which include means and operations for removal of phosphates from the washing solution.
  • washing apparatuses including automatic washing machines and dishwashers, accessories and processes it becomes possible for persons operating home washing machines or dishwashers to continue to employ phosphatecontaining detergents of best cleaning characteristics and to treat effluents to comply with regulations relating to phosphate discharges into sewers or ground waters.
  • the present invention provides an inexpensive treatment for phosphate-containing waste waters from washing apparatuses.
  • Embodiments of the invention are readily added to existing washing apparatuses or may be incorporated in the construction of new machines. They can be used and operated by the housewife or homeowner. They require no difficult maintenance and capital investment costs are very small. Their use decreases the load on "sewage treatment plants because the phosphates from washing operations are either removed or insolubilized. Also of great importance is the fact that the present process may be effected now, without the necessity for waiting for the construction of improved water treatment plants.
  • a Washing apparatus comprises means for holding items to be washed and a washing solution containing a soluble phosphate compound, means for moving the washing solution relative to the items to be washed, and into and out of contact with them until they are washed, means for removing the washing solution, containing soluble phosphate, from the washed items, and means for admixing a suitable chemical compound with the soluble phosphate in the removed solution before discharge thereofto a sewer, drain or other means of disposal, so as to convert the soluble phosphate to insoluble form before disposal of the used washing solution.
  • the suitable chemical compound is a compound of calcium, aluminum or iron and is added to or is otherwise contacted in stoichiometric quantity or in excess by the wash water being discharged, after which the insoluble product formed, containing the phosphate, is removed, e.g., by filtration.
  • an accessory including means for reacting or contacting the reactive chemical with the phosphate-containing wash water, is fastened onto the washing machine or a discharge line from it. Also, within the invention are processes for chemically insolubilizing the soluble phosphates and filtering off the product at a location near the washing machine or dishwasher before the waste waters are sent to a sewer, drain or other means of disposal.
  • wash water in conjunction with automatic washing machines or dishwashers have been effected in the past.
  • most of such treatments involved softening the water or adjusting its pH prior to use, so as to avoid the precipitation of lime soaps or other insoluble products in the washing solution, which products would otherwise deposit on the materials being washed, giving them objectionable films or causing a graying thereof.
  • wash waters have been treated to remove dirt and suspended materials and then have been reused.
  • the still useful phosphate and organic detergent present are maintained in a soluble condition.
  • factories wherein phosphate solutions are employed, as in metal treating operations, or in commercial installations where they are employed in cleaning compositions effluents have been collected and treated.
  • FIG. 1 is a front perspective view of a washing apparatus of the invention discharging into a standpipe;
  • FIG. 3 is a partially sectioned front elevational view of such a washing machine with means for automatically adding reactive chemical to the waste wash water before discharge to a wash tub;
  • FIG. 4 is a partially sectioned front elevational view of a similar machine equipped with a water saver and a modified means for adding reactive chemical to the waste water upon ultimate discharge;
  • FIG. 6 is an enlarged vertical sectional view of a portion of the modified chemical additive means of FIG. 4, illustrating a means of shutting off the additive feed, when desired;
  • FIG. 7 is a partially sectioned front elevational view of a washing apparatus of the invention, equipped with both chemical additive and filtering means;
  • FIG. 8 is a partially sectioned front elevational view of an apparatus of the invention comprising means for adding reactive chemical, a settling tank and a filter after the settling tank;
  • FIG. 10 is a partially sectioned front elevational view of a further embodiment of the invention in which waste wash water is passed through a treating cartridge of particulate or caked reagent;
  • FIG. 2 a similar automatic washing machine 29.
  • discharge hose 31, together with reactive chemical admixing means 33 and discharge hose portion 35 empties waste water into a laundry or wash tub 37, from which it is drained to a sewer or other disposal means.
  • the wash tub may be closed off by a stopper, not shown, to provide additional flocculation or agglomeration time for the insoluble phosphate precipitate, before it is sewered.
  • the in soluble phosphate, in aqueous wash water medium may be sent directly to the sewer.
  • hot and cold water taps 39 and 41, and corresponding water inlet hoses 43 and 45 Power is obtained from receptacle through an insulated lead wire, not shown.
  • FIG. 3 there is shown an embodiment of the present washing apparatus, including a washing machine 51 having a discharge pump 53 which, at the appropriate time in the washing cycle after completion of the washing of laundry, forces the consumed wash water 55 out of the tub of the washing machine, through discharge piping 57, past one form of chemical admixing means 59, clamped or otherwise held to the piping at 61 and similarly clamped at 63, to additional discharge piping 65, through which the treated waste wash water is discharged into tub 67, from which it is sewered.
  • the admixing accessory 59 is held by an adjustable collar 66 which is fastened to a mounting means 70 held by thumbscrew 68 to tub 67.
  • Plug 64 closes a valve stem passageway, which is not in use. Such a valve will be discussed with respect to the descriptions of FIGS. 4-6. Details of structure of the illustrated automatic reagent adding mechanism 59 will be given subsequently in a description of FIG. 5.
  • valve stem 85 is depressed, preventing reactive chemical solution 87 from being fed into the discharge waste water when it is intended for that water to be subsequently fed back to washer 69 through a return line, not illustrated.
  • valve stem 85 is lifted, allowing solution or aqueous dispersion of treating chemical to feed into the waste water passing through the discharge line, because of suction generated in the Venturi, and the waste water is treated with a calcium, aluminum, iron or other suitable salt or compound or mixture thereof to produce an insoluble form of the phosphate, which is drained to a sewer or other means of disposal.
  • the stopper may be left in place until the treated waste water is all in wash tub 83, wherein it may be allowed to settle and agglomerate, after which it is dischargeable through the drain by removal of the stopper.
  • the insoluble phosphate may be removed from the material being sewered, by filtration or other separatory techniques, which will be illustrated in more detail with respect to other figures of the drawing.
  • the two-way valve in the washing machine is operated electrically and the shutoff valve for chemical reagent is operated manually.
  • both valves may be manual or both electrical or the two-way valve may be manual and the shut-off valve for additive feed may be electrically controlled.
  • Plastic or glass or other suitable container 95 has a threaded neck 97 onto which is fastened a threaded molded head portion 99, desirably made of a suitable plastic, e.g., nylon, phenol formaldehyde or polyacrylate. Molded into the head is a major passageway portion 101, having ends 103 and 105 flanged at 107 and 109 to facilitate clamping or threaded attachment to inlet and outlet hoses, through which the wash water will pass.
  • a suitable plastic e.g., nylon, phenol formaldehyde or polyacrylate.
  • a Venturi section 111 Between the passageway ends is a Venturi section 111, at the throat of which is an aspiration tip 113, through a narrow passageway of which a solution 117 of reactive chemical is drawn through dip tube 119, to be mixed into and reacted with the phosphate in the wash water at the Venturi throat 121.
  • the dip tube usually of resilient plastic, e.g., polyethylene, polypropylene, polyvinyl chloride, is usually press fitted onto the aspiration tip of the dispenser head, although in some applications it may be possible to mold it unitarily with the head.
  • the operation of the dispenser is essentially automatic, since the flowing of wash water creates a vacuum at the throat of the Venturi and draws a desired amount of reactive chemical into the throat to mix and react with the wash water.
  • the dip tube or the aspiration throat may be modified or adjusted in effective passageway size so as to adjust the proportions of reactive chemical solution to be mixed with the wash water. Otherwise, to obtain s'uchan adjustment, different heads may be employed wherein the Venturi passageway or the aspiration'passageway size is changed.
  • FIG. 6 is shown a means of effecting such modification of feed rate, although the valve portion there shown, which modifies the structure of the dispenser of FIG. 5, is primarily intended for shutting off flow entirely or for operating wide open.
  • Venturi portion 123 includes a passageway 125 in which is located a valve stem 127 having a handle portion 129 and a mushroom Shaped end 130.
  • FIGS. 7, 8 and 9 the washing machine, discharge pump and inlet line sections of the apparatuses are essentially the same as those illustrated in FIG. 3 and in FIGS. 7 and 8 the automatic dispenser for treating chemical is also like that of FIG. 3. Hence, such will not be described in detail herein.
  • a treated wash water downstream of the admixing means now containing insoluble phosphate, passes through filter 131, leaving the insoluble phosphate in the filter, from which it is dischargeable through outlet 133. Then, the filtered wash water is discharged into a tub and from there may be sent to sewer through an outlet. If desirable, the effectiveness of the filter may be tested by allowing the water to remain in tub 135 and examining it for clarity.
  • the filter illustrated is of the sharp edged Pur-o-lator type wherein the insolubles collect in the internal portion with the filtered fluid passing through filtering element 139, usually of perforated stainless steel or other suitable material, and out outlet line 141. Periodically the filter may be cleaned by rotating handle 143 which moves a scraping blade over the internal surface of the filter and cleans it of insoluble material, which is then removed through outlet 133.
  • filtering element 139 usually of perforated stainless steel or other suitable material
  • a modified design of the apparatus is illustrated in which, after adding of reagent to the waste water, the water is discharged through line 145 into settling tank 147 and after an appropriate time for agglomeration of the precipitate, the water, containing the dispersed precipitate, is allowed to pass through outlet 149, filter 151 and exit line 153, to disposal.
  • pump 155 is employed to assist in pulling the fluid through filter 151.
  • chemical reagent addition means 157 is of a different design but still operates on the aspiration or Venturi principle. It is clamped to the outlet piping or is threaded onto it at 159 and 161.
  • the solution or suspension of precipitant chemical is above the outlet to the piping but the opening or orifice of the aspiration tube is small enough so that there is no flow unless the decrease in pressure due to discharge of waste wash water through the Venturi is also obtained.
  • the wash water now containing suspended insoluble phosphate, enters piping coil 163, which functions as a holding area for the wash water, permitting completion of any precipitate-producing reaction and enabling the precipitate to be agglomerated so as to facilitate filtering or other separation from the water.
  • the precipitate is filtered off at filter 165, which may be self-cleaning and which is held to the piping by clamps 167 and 169. Then it passes through pump 171 and is sent to sewer through final discharge line 173.
  • FIG. 10 is illustrated a treating apparatus like that of FIG. 8, with the difference that, instead of a Venturi means for admixing treating chemical with the waste wash water, a cartridge of such chemical in solid form or packed in with a passageway forming matrix, such as glass wool, polyurethane foam or a packed bed, is used.
  • a cartridge of such chemical in solid form or packed in with a passageway forming matrix, such as glass wool, polyurethane foam or a packed bed, is used.
  • a chemical may be calcium hydroxide, calcium oxide, sometimes calcium carbonate, and corresponding aluminum, zinc, magnesium, iron and other such compounds, if the solubility thereof is greater than that of the corresponding phosphate or polyphosphate.
  • cartridge 175, containing finely divided (through 100 mesh, on 325 mesh) calcium hydroxide 177 distributed through a lesser weight 10 to 50 percent of glass W001 178 is reacted with phosphate-containing waste water 179, removes the phosphate from it and acts to filter out or otherwise hold most of the phosphate in the cartridge, which may be constructed so as to be disposable.
  • Any Ca(OH) forced through the reaction accessory may react with the phosphate in the water in tank 147 and be filtered out by filter 165.
  • the invention may be applied to other home appliances which would normally discharge water containing soluble phosphate, usually accompanied by water soluble synthetic organic anionic detergent salt, too.
  • water containing soluble phosphate usually accompanied by water soluble synthetic organic anionic detergent salt
  • the phosphates discharged by a dishwashing machines may be removed, as may be those used in floor and wall scrubbing machines.
  • the accessories of the invention may be adapted for utilization with wash tubs or other containers or passages into which phosphatecontaining cleaning waters may be discharged.
  • the accessories and the invention are applicable to removing soluble phosphates from washing solutions used to mop floors, clean walls, shampoo carpeting or hand wash clothing, as well as those for automatically washing dishes or laundry.
  • the present invention may remove other chemical constituents of washing solutions which are insolubilized, occluded or otherwise entrapped, adsorbed or absorbed by the inorganic compound or component employed.
  • silicates and carbonates are removable, as are soaps, organic fluorescent brighteners, dyes and synthetic organic detergents.
  • bactericidal or fungicidal compounds are insolubilized or otherwise carried down with the insoluble phosphates being precipitated.
  • the means for addition of treating chemical solution needs not be operated on the aspiration or Venturi principle. More complex systems can be employed, including a pump for the additive driven by the flow of waste water so as to proportion the addition of reactive chemical correctly, or electrically operated pumping'or valve means may be utilized, timed with the washing machine cycle. Such structures are more complex and more expensive than the simple means illustrated but under some circumstances may be preferred.
  • the treatment chemical may often be added as a liquid, in aqueous solution, but sometimes suspensions, powders, or even solid blocks, past which the waste water flows, are usefully operative.
  • a preferred treatment is with a comparatively insoluble hydroxide (or an oxide which is convertible to the hydroxide) such as calcium hydroxide. This is used as a fine suspension in water, usually of 10 to percent concentration. Means may be provided for maintaining the suspension uniform (a stirrer may be used) and particle sizes can be small enough to feed through the aspirator opening.
  • the chemical addition means may be held in place on the washing machine, standpipe, washtub or other suitable structure and can even be located in a fixed sewer line carrying the machine discharge.
  • the discharge line may be flexible or rigid and the installation of the chemical addition means may be permanent or temporary. Similar considerations apply to the installation of the means for removing the insoluble products resulting from chemical treatment.
  • various other types of filters may be used, including centrifugal, cartridge, plate and frame, and diatomaceous earth bed filters. Centrifugal separators, where applicable, may be employed and in some instances, it may be desirable only to rely on sedimentation or settling out of the insoluble materials, after which they may be removed by hand, vacuum or in other suitable manner.
  • the filtration means is equipped with an automatic or semiautomatic self-cleaning device, such as are found on various filters of this type, e.g., Pur-o-lator filters, manufactured by the Pur-o-lator Company. Even if the filters have to be cleaned periodically, this may be done only about once a week for the average household and the filter size will normally be chosen accordingly. Thus, the only appreciable effort required by the user of a washing apparatus is to clean the filter, make sure that the reactive chemical is periodically replaced and to make tests, if considered desirable, on the effluent to ascertain whether the treatment of the phosphate and/or its removal as insoluble phosphate has been completed.
  • an automatic or semiautomatic self-cleaning device such as are found on various filters of this type, e.g., Pur-o-lator filters, manufactured by the Pur-o-lator Company.
  • the housewife or other user of the home washing apparatus may conveniently re-fill the dispenser with reactive chemical and clean out the filter or separating means, if necessary, it is of importance that the addition and filtration means be located near the washing apparatus.
  • the addition and filtration means be located near the washing apparatus.
  • such equipment is not attached to the washing apparatus or included in its structure and accessible to the housewife, it will be located within no more than 20 feet, preferably within or 10 feet.
  • door or other access means will be provided to facilitate replacement of reactive chemical and cleaning of the filter or settling tank.
  • the invented methods may be applied to waste waters from the use of washing compositions containing widely varying proportions of phosphates and the phosphates may be in any of various forms.
  • the invention is intended for the treatment of sodium tripolyphosphate and to a lesser extent tetrasodium pyrophosphate, monobasic, dibasic and tribasic sodium phosphates.
  • other phosphates which may be effective additives to detergents may be employed and the various phosphates may be present as other alkali metal and soluble metal salts.
  • home laundry apparatus waste waters When home laundry apparatus waste waters are being treated they will usually contain from one-third to two cupsful of detergent per 8 to 30 gallons of wash water.
  • Such detergent for good cleaning power, will normally comprise from about 2 to percent of phosphorus and its density will be from about 0.2 to v1.2 grams per cubic centimeter.
  • the phosphorus concentration in the wash water will be from about 2 to 40 grams of phosphorus per 30 to 115 liters or from about 0.003 to 0.13 percent.
  • the concentration will be from 0.01 to 0.1 percent of phosphorus, which corresponds to about 0.02 to 0.2 percent P 0 or 0.03 to 0.3 percent of POI.
  • phosphates utilized in washing clothing in addition to the phosphates utilized in washing clothing, other phosphates, principally including chlorinated phosphate dishwashing agents of known types, are often employed in dishwashing compositions, with or without the conventional polyphosphates or orthophosphates, previously mentioned.
  • concentrations of such materials approximate those given for the laundering detergent phosphates because, although lesser amounts of dishwashing composition are utilized, the water employed is also much less than is used for laundering.
  • the organic detergents generally employed in clothes washing include higher alkyl aryl sulfonates, principally higher linear alkyl benzene sulfonate, sodium salt; higher alkyl sulfates, principally sodium lauryl-, myristyl-, palmityl-, and stearyl sulfates; sodium higher fatty acid monoand diglyceride sulfates; sodium higher fatty acid soaps; sodium poly-lower alkoxy ether sulfates; sodium alkyl phenoxy poly-lower alkoxy sulfates; sodium higher olefin sulfates and sulfonates; sodium N-lauroyl sarcoside; sodium higher fatty acid amides of N-methyl taurine (lgepon T type); and sodium higher fatty acid isethionates (lgepal A type).
  • sodium salts instead of the sodium salts, other water soluble salts may be employed, including the potassium, ammonium, mono-, diand tri-lower alkyland alkanolamine and magnesium salts, in suitable circumstances.
  • nonionic cleaning materials such as the block copolymers of ethylene oxide, propylene oxide and propylene glycol (Pluronics); mixed polymers of lower alkylene oxides, e.g., ethylene oxide and propylene oxide; the alkyl phenoxy polyoxyethylene ethers; higher fatty alcohol poly-lower alkylene oxides; higher fatty acid esters of poly-lower alkylene glycols; sugar or sugar derivative alcohol esters and ethers of higher fatty acids and higher fatty alcohols, and poly-lower alkylene glycols.
  • Pluronics block copolymers of ethylene oxide, propylene oxide and propylene glycol
  • mixed polymers of lower alkylene oxides e.g., ethylene oxide and propylene oxide
  • the alkyl phenoxy polyoxyethylene ethers e.g., higher fatty alcohol poly-lower alkylene oxides
  • higher fatty acid esters of poly-lower alkylene glycols e.g.,
  • the polymeric materials will usually have molecular weights of from 500 to 50,000, preferably from 1,000 N plications their presence may be tolerated and even de- M sirable.
  • higher refers to aliphatic, preferably alkyl radicals of 10 to 18 carbon atoms, and lower refers to those of one to four carbon atoms, preferably 2 to 3.
  • the inorganic phosphate content of laundry deteru gents will usually be in the range of from 10 to 45 percent thereof, the greater quantities effecting better cleaning.
  • dishwashing formulations which are essentially inorganic, the phosphate content will normally be from 40 to 95 percent.
  • the organic detergent constituent of home laundry detergents will generally constitute from 5 to 35 percent thereof, preferably from 10 to 25 percent.
  • the balance of the composition may in clude water, sometimes as water of hydration, e.g., from 1 to 15 percent; and various adjuvants, including foaming agents, e.g., lauric myristic diethanolamide; bactericides, e.g., trichlorocarbanilide; soil antiredeposition agents, e.g., polyvinyl alcohol, sodium carboxymethylcellulose; fillers, e.g., sodium sulfate; coloring agents; hydrotropes; anti-foaming ingredients; lanolin derivatives, as emollients; and perfumes. Percentages of each of these materials will usually be small and the total thereof, excluding water and solvent, will generally not exceed about 10 to 20 percent of the composition.
  • foaming agents e.g., lauric myristic diethanolamide
  • bactericides e.g., trichlorocarbanilide
  • soil antiredeposition agents e.g., polyvinyl alcohol, sodium carb
  • liquid heavy duty detergents contain substantial proportions of water, generally major proportions' thereof, e.g., 60 to percent.
  • various compositions are herein described to illustrate the detergents which may be employed, it is clearly within the inventive concept that other phosphate-containing detergent materials may have the soluble phosphates thereof removed by this method.
  • the wash waters treated contain the dirt, grease,
  • the treating chemical may be any material capable of reacting with the soluble phosphate to produce an insoluble compound.
  • suitable inorganic and organic compounds although the least expensive and most readily available useful materials are water soluble inorganic salts and other compounds such as oxides and hydroxides which, although not very soluble, (not soluble to the extent of over 100 g./l. at to C.), form less soluble phosphates.
  • the salts are preferably those of inexpensive strong acids, such as sulfuric acid and hydrochloric acid but other soluble salts, including bromides, nitrates, sultites, acetates, propionates, and similar materials may be used
  • the cations of the treating compounds are usually calcium, aluminum or iron but other cations which form insoluble phosphates, including barium, magnesium and copper are also useful, as are those of other metals and radicals which perform a similar function but are usually more expensive or less readily available.
  • the treating chemical should not react preferentially with a detergent ingredient other than the phosphates.
  • the treating chemical will be calcium hydroxide, calcium oxide, calcium chloride, calcium carbonate, aluminum chloride, aluminum sulfate, alum, ferric chloride, ferrous chloride or any suitable mixture thereof.
  • Calcium sulfate will rarely be employed, because of its relatively poor solubility.
  • the concentration of treating chemical in I aqueous solution or dispersion will normally be as high as feasible, generally from 2 to 80 percent and preferably from 30 to 70 percent, so that the volume of liquid to be added will not be overly great, requiring a larger container and more installation space. It is preferrred that the quantity of such liquid employed should be relatively small, compared to the waste wash water being treated.
  • ion exchange agent e.g., anion exchange agent, calcium hydroxide or iron oxide
  • anion exchange agent calcium hydroxide or iron oxide
  • phosphate it is only important that phosphate be taken up by the chemical and thereby be insolubilized.
  • ion exchange agents there are certain disadvantages. The ion exchange agents release other ions to the waste water, which may be less acceptable than the chlorides, sulfates and water of the present processes, and often require rejuvenation, which releases the phosphate in soluble form again, creating a disposal problem.
  • disposal may be effected by drying a filter cake or other means for collecting insoluble phosphate material and collecting such cakes for burial or burning off of organic material, followed by industrial use of the insoluble phosphate material.
  • ion exchange agents one is left with a dilute aqueous solution of the phosphate, which would require evaporation off of the moisture before the unwanted phosphate could be disposed of.
  • Such a treatment is usually much less efficient for removing phosphate from waste wash waters than those previously described. Evaporation of the waste waters and disposal of the phosphate, although possible, would be economically disadvantageous, compared to the preferred methods of the invention described above.
  • the chemical reactions to produce the insoluble phosphates may be effected almost instantaneously. Yet, under some circumstances, it may be desired to hold the reactive chemical with the soluble phosphate material for a comparatively long period of time to make sure that the reaction has gone to completion or e that the insoluble product is in desired form to be separated from the accompanying liquid.
  • the reaction may take place in as little as l/lO of a second or less or as long as 5 hours but generally will be complete within from 1 second to 1 hour. Under such conditions, the flow rate of the wash water may be comparatively great, e.g., from 1 to 100 gallons per minute, usually from 10 to 40 p.p.m.
  • Such a flow rate may create a vaccum in the aspiration tube of about three inches to 2 feet of water and cause a flow through such tube, which y may be restricted to adjust the flow rate, such that the contents of the container of treating chemical will be admixed with the waste water during all of the time of passing of the waste water through the Venturi.
  • Such period will usually be from about 20 seconds to 3 minutes and will generally be about a minute or two.
  • the phosphate produced including polyphosphate or similar compound, will be of a solubility such that most of it will be undissolved in the quantity of wash water employed. Under usual operations at least percent of the soluble phosphate present in the waste water will be removable as insoluble phosphate and under ideal conditions this may be percent or more, up to almost l00 percent.
  • the solubility of the phosphate will preferably be such that less than 10, preferably less than 5 parts per million of phosphorus will be present as soluble phosphate or similar compound in the wash water being discharged.
  • pH adjustment of the wash water may be effected, if necessary or desirable, usually by addition of a non-phosphate buffering agent or an acid or base to the treating chemical solution, so that the pH is in the range of 5 to 12.
  • a non-phosphate buffering agent or an acid or base to the treating chemical solution, so that the pH is in the range of 5 to 12.
  • the pH should be in the range of 5 to 8 and for the precipitation of calcium phosphates this may be from 8 to 12.
  • pl-ls of about 8 to 10.7 at washing concentrations and the treating chemicals may help to adjust pl-ls, little additional pl-l control is necessary, but with other preparations, such as dishwashing compounds, acid or acid side buffers, e.g., citric acid, sodium acetate, may be employed to lower the very high pHs of such solutions.
  • the temperature at which treatment is effected may be automatically controlled by heat exchanger means but will usually be that at which the wash water is discharged or to which it is cooled during holding in a tank or tub.
  • useful phosphate removal is obtained at 10 to 90C., preferably 15' to 80C. and most usually at 20 to 65C.
  • lf calcium hydroxide is used much of the excess may be filtered out with the phosphate, resulting in little material added to the waste water discharged. However, even if soluble salts are used and the excess is not removed the treating chemical discharged to the sewer may be useful because it can help to decrease the amount of additives needed at a sewage treatment plant.
  • EXAMPLE 1 One and cups ('10 ounces) of a heavy duty spray dried commercial detergent powder, containing approximately 35 percent sodium tripolyphosphate, 8 percent sodium silicate of a Na O:SiO ratio of about 1:2, 25 percent of sodium higher linear alkyl (12 to 15 carbon atoms) benzene sulfonate, 15 percent of sodium sulfate, percent of water and about percent of adjuvants and other minor constituents, including optical brightener and soil dispersant, are added to the tub of a top loading automatic washing machine containing about nine pounds of a mixed batch of soiled clothing and about 17 gallons of water, at 70C. The detergent concentration in the washing machine at such a charge is about 0.15 percent.
  • the pH is about 9.5 and decreases to about 8.5 as the clothing is washed and the soil on it is removed. Agitation is effected automatically, using a vertical agitator of conventional design for moving the wash water into and out of contact with the laundry. Instead of such an agitator, a corresponding spray-, spinning surface impact-, vibrator-,
  • tumbleror pumpmeans may be employed to create the desired wash water circulation.
  • waste wash water is discharged from the washing machine by the opening of a valve and the acutation of a discharge pump in the machine.
  • the wash water is pumped into tub 83, into which has been previously placed about 2 ounces of finely divided (through 100, on 325 mesh sieve) calcium hydroxide powder.
  • the turbulence created by the water entering the tub is sufficient to mix the calcium hydroxide adequately with the waste wash water and produces a copious precipitate of calcium phosphate and other insoluble calcium salts.
  • the production of the precipitate is immediate but the material is allowed to remain in the tub for an additional 10 minutes, to agglomerate the precipitate and help to sorb or trap other constituents of the waste wash water.
  • the wash water is filtered through a Pur-O-Lator filter of the type illustrated in FIG. 8 and the filtrate is pumped to a sewer, drain or other means of disposal.
  • a filter with openings of correct sizes to trap the calcium phosphate and other insoluble particles of the waste wash water, is subsequently used with additional treatment of other wash waters and upon being loaded with the phosphate, is cleaned'by turning of the scraping blade handle and removal of the bottom plug. The product resulting is burned to remove organic material and the calcium phosphate and other inorganic insolubles are recovered for subsequent use or are discarded. Samples taken of the effluent liquid from the filter show that it contains less than 5 parts per million of phosphates, expressed as elemental phosphorus.
  • some of the treated phosphate-containing waste wash water is left in the tub, such as about 3 gallons, and the first rinse water is pumped into this.
  • the rinse water contains some phosphate to be treated and the excess calcium hydroxide in the treated waste water in the tub insolubizes the phosphate in the first rinse. This too, is allowed to stand for a period of time, from l0 minutes to an hour. Then it is filtered and the filtrate is found to contain as little as four or five p.p.m. of phosphorus.
  • EXAMPLE 2 In a series of experiments like that of Example 1, the same weights of calcium oxide, calcium chloride, alum, aluminum sulfate, aluminum chloride, ferrous chloride and ferric sulfate are used, the detergent employed is a heavy duty laundry detergent of the type described, a low foaming laundry detergent or a cold water laundry detergent, operating temperatures range from 20C. to C andpl-ls are from 7 to 10. Charges of detergent are varied from one-half to 2 cups. Yet, under these varied conditions, the copious precipitate of calcium phosphate is still formed and is either discharged directly to the sewer or is filtered, by a plate and frame filter, filter paper, automobile oil filter,” packed glass wool or diatomaceous earth.
  • the pH, with the calcium compounds, is preferably kept at about 9 and with the aluminum compounds is maintained about 7.5 by the addition of citric acid.
  • Example 3 The experiment of Example 1 is repeated, except for the fact that the apparatus of F IG. 1 is employed.
  • the chemical additive is either calcium chloride or aluminum sulfate and the heavy duty laundry detergent concentration is 1.8 g./l.
  • the weight of calcium chloride employed is 60 g. and the aluminum sulfate is used to the extent of g. in the discharged wash water, in both cases at concentrations in the reagent solution of about 40 percent.
  • the vacuum in the Venturi is about a foot of water and is sufficient to draw the solution out of the bottle into the flowing waste wash water substantially regularly over the period of about two minutes in which the wash water is being pumped from the washing machine.
  • the effluent is pumped directly to the standpipe, without filtration, but when it is filtered, using apparatus like that shown in FIG. 7, the wash water being sewered is found to be very low in phosphate content, containing 0.001 percent, as p in the case of the calcium chloride treatment and 0.025 percent, when treated with aluminum sulfate. This compares with 0.053 percent, when untreated. Analyses of the linear tridecyl benzene sulfonate detergent present indicate that this too was diminished to 0.0015 percent and 0.00062 percent, respectively, from 0.024 percent.
  • Another desirable result of following the procedure of this example is that the content of optical brighteners or fluorescent dyes in the detergent products also is appreciably diminished. It is considered important by some authorities that such materials should not be discharged in large quantities into lakes and rivers and the present method provides a simple means for eliminating them, together with other undesirable chemicals. Enzymes and bleaches in the detergents are also either eliminated or reduced manifold by the present procedures.
  • Example 4 The procedure of Example 1 is repeated with a wide variety of commercial heavy duty laundry detergent compositions based upon linear higher alkyl benzene sulfonate, olefin sulfonate and lauryl polyethoxy sulfate detergents and sodium tripolyphosphate builder salt, but with a cartridge of calcium hydroxide distributed in glass wool being used, as per FIG. 10. In other cases, instead of the calcium hydroxide, of which about onehalf pound is present in the cartridge, together with one-half pound or somewhat less of glass wool, there may be employed calcium carbonate, quicklime or mixtures thereof.
  • the wash water When the wash water is passed through the cartridge, it reacts with the calcium hydroxide to produce calcium phosphates or polyphosphates and these, although insoluble, being of small enough particle size to flow through the cartridge, are discharged into the tank (147) and are filtered off by the filter (151).
  • Several tubs of waste wash water are passed through the cartridge and still the content of phosphate, expressed as phosphorus, is below p.p.m. in the effluent.
  • a pump is sometimes used or is shown after the filter. In some cases, it will be desirable to place this pump upstream of the filter to provide more pressure to force the liquid through the filter, especially when the filter has become nearly full of insoluble material.
  • EXAMPLE 5 A series of in vitro experiments is run with nine of the best selling commercial heavy duty laundry detergents on the market to determine whether and to what extent phosphates may be removed from them by present treatments. In each case, 1.8 liters of detergent solution in which the detergent is present at a concentration of 0.18 percent are employed and such solutions are treated with solutions or dispersions of aluminum sulfate, calcium hydroxide, calcium chloride, aluminum chloride, calcium oxide, ferric or ferrous chloride, or mixtures thereof. The amount of treating chemicals employed varies from 1 to 3 g./l. In some cases aluminum sulfate is used, followed by calcium hydroxide. In other cases, calcium chloride is mixed with aluminum sulfate and is employed. In still other experiments aluminum sulfate is mixed with calcium carbonate. In most of the experiments, the individual treating chemicals are employed alone.
  • a washing apparatus comprising means for holding items to be washed and a washing liquid containing a soluble phosphate compound, means for moving the washing liquid relative to the items to be washed and into and out of contact with them until they are washed, means for removing the washing liquid, containing soluble phosphate, from the washed items, and means for contacting the soluble phosphate in the removed liquid with a suitable chemical compound before discharge of the washing liquid to a sewer or drain or other disposal thereof, so as to convert the soluble phosphate to insoluble form.
  • a washing apparatus which includes a home washing machine, wherein the washing liquid is an aqueous solution comprising a phosphate salt and the chemical compound that reacts with the soluble phosphate is one which produces an insoluble phosphate-containing compound before discharge of the removed solution to the sewer, drain or other means of disposal.
  • a washing apparatus which comprises a discharge pump, a discharge line and means to contact waste wash water with reactive chemical compound to convert the soluble phosphate therein to insoluble form.
  • a washing apparatus wherein the means for adding reactive chemical adds it to the discharge line, is adjacent to the other components of the apparatus and is such that the reactive chemical compound contacts the discharged washing solution in the discharge line during the discharge thereof in stoichiometric proportion or excess during substantially all of the time period in which the discharge of the washing solution is effected after washing.
  • a washing apparatus wherein the reactive chemical compound is calcium hydroxide which is added to the discharged washing solution in the discharge line as a liquid
  • the means for contacting the wash water with the reactive chemical compound include a container for the liquid, a Venturi restriction, having a throat section, in the discharge passage and means communicating the liquid in the container with the throat of the Venturi so as to feed the reactive chemical liquid to the Venturi when wash water is flowing through it.
  • a washing apparatus wherein downstream of the point of contact or addition of the reactive chemical compound there is present a holding means to retain the washing solution and reactive chemical compound for a period of time long enough to produce a precipitate of insoluble phosphatecontaining compound in cake, coating or layer form or of particle size large enough to be filterable.
  • a washing apparatus wherein the holding means is a tank built into the structure of a home washing apparatus, which tank is large enough to hold all the washing solution and from which said solution is discharged, after chemical reaction, by displacement with rinse water.
  • a washing apparatus wherein the means for reacting a chemical compound with the soluble phosphate is an accessory which is joinable to the washing apparatus between the discharge pump and a discharge line from which used washing solution is discharged to a sewer, drain or other means of disposal.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Removal Of Specific Substances (AREA)
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US4656843A (en) * 1983-11-21 1987-04-14 Sando Iron Works Co., Ltd. Apparatus for the automatic concentration control of aqueous caustic soda solution
US5254264A (en) * 1991-12-26 1993-10-19 Duncan Armstrong Method of dispensing a substance into a flow of water
US5868937A (en) * 1996-02-13 1999-02-09 Mainstream Engineering Corporation Process and system for recycling and reusing gray water
US5876606A (en) * 1995-11-10 1999-03-02 University Of Waterloo Treatment of contaminated water
US6269667B1 (en) 1998-09-22 2001-08-07 Mainstream Engineering Corporation Clothes washer and dryer system for recycling and reusing gray water
US20060081016A1 (en) * 2004-10-18 2006-04-20 Unilever Home & Personal Care Usa, Divsion Of Conopco, Inc. Automatic dispensing device for laundry care composition
US20060107705A1 (en) * 2004-11-23 2006-05-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Automatic stand-alone dispensing device for laundry care composition
US20060272360A1 (en) * 2005-06-02 2006-12-07 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Automatic dispensing device for laundry detergent composition with intermediate chamber
US20060277953A1 (en) * 2005-06-08 2006-12-14 Conopco, Inc., D/B/A Unilever Dosing system for a concentrated laundry composition
US20080276962A1 (en) * 2007-05-07 2008-11-13 Whirlpool Corporation Recapture of ions applied in a wash process
US20150059198A1 (en) * 2013-09-02 2015-03-05 Samsung Electronics Co., Ltd. Dish washer
US20180371675A1 (en) * 2015-12-14 2018-12-27 Qingdao Haier Washing Machine Co., Ltd. Water storage tank for washing machine and washing machine

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LU78311A1 (de) * 1977-10-13 1979-06-01 Ciba Geigy Ag Neue cumarinfarbstoffe,deren herstellung und verwendung
US5320758A (en) * 1993-06-29 1994-06-14 Church & Dwight Co., Inc. Method of recycling amine saponifiers used in cleaning electronic circuit boards
DE10260156A1 (de) * 2002-12-20 2004-07-01 BSH Bosch und Siemens Hausgeräte GmbH Wäschetrockner und Verwendung eines Ultraschallzerstäubers
US20040142834A1 (en) * 2003-01-09 2004-07-22 Paul Wegner Soap and process for cleaning wash water
US20040188356A1 (en) * 2003-03-24 2004-09-30 Haydock Intellectual Properties, L.L.C. System for producing large particle precipitates
US20060011528A1 (en) * 2004-09-13 2006-01-19 Jonathan Ireland Animal water tub
US8215322B2 (en) 2008-12-22 2012-07-10 Whirlpool Corporation Dishwasher with soil removal
US20120152849A1 (en) * 2010-12-20 2012-06-21 Empire Technology Developement LLC Adsorptive flotation removal of sodium tripolyphosphate from waste liquid
US20150191375A1 (en) * 2014-01-08 2015-07-09 Thomas Adam Leahy Device For Transforming Soluble Phosphates Found In Washing Machine Wastewater Into Insoluble Form By Precipitation

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US2953159A (en) * 1955-11-23 1960-09-20 Pfenningsberg Gmbh Maschfab Washing machine
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4656843A (en) * 1983-11-21 1987-04-14 Sando Iron Works Co., Ltd. Apparatus for the automatic concentration control of aqueous caustic soda solution
US5254264A (en) * 1991-12-26 1993-10-19 Duncan Armstrong Method of dispensing a substance into a flow of water
US5876606A (en) * 1995-11-10 1999-03-02 University Of Waterloo Treatment of contaminated water
US5868937A (en) * 1996-02-13 1999-02-09 Mainstream Engineering Corporation Process and system for recycling and reusing gray water
US6269667B1 (en) 1998-09-22 2001-08-07 Mainstream Engineering Corporation Clothes washer and dryer system for recycling and reusing gray water
US6327731B2 (en) 1998-09-22 2001-12-11 Mainstream Engineering Corporation Clothes washer and dryer system for recycling and reusing graywater
US20060081016A1 (en) * 2004-10-18 2006-04-20 Unilever Home & Personal Care Usa, Divsion Of Conopco, Inc. Automatic dispensing device for laundry care composition
US7398787B2 (en) 2004-10-18 2008-07-15 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Automatic dispensing device for laundry care composition
WO2006056273A1 (en) * 2004-11-23 2006-06-01 Unilever N.V. Automatic stand-alone dispensing device for laundry care composition
US20060107705A1 (en) * 2004-11-23 2006-05-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Automatic stand-alone dispensing device for laundry care composition
US7481081B2 (en) 2004-11-23 2009-01-27 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Automatic stand-alone dispensing device for laundry care composition
US20060272360A1 (en) * 2005-06-02 2006-12-07 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Automatic dispensing device for laundry detergent composition with intermediate chamber
US20060277953A1 (en) * 2005-06-08 2006-12-14 Conopco, Inc., D/B/A Unilever Dosing system for a concentrated laundry composition
US20100139712A1 (en) * 2005-06-08 2010-06-10 The Sun Products Corporation Dosing System For A Concentrated Laundry Composition
US20080276962A1 (en) * 2007-05-07 2008-11-13 Whirlpool Corporation Recapture of ions applied in a wash process
US7851429B2 (en) 2007-05-07 2010-12-14 Whirlpool Corporation Recapture of ions applied in a wash process
US20150059198A1 (en) * 2013-09-02 2015-03-05 Samsung Electronics Co., Ltd. Dish washer
US9462929B2 (en) * 2013-09-02 2016-10-11 Samsung Electronics Co., Ltd. Dish washer
US20180371675A1 (en) * 2015-12-14 2018-12-27 Qingdao Haier Washing Machine Co., Ltd. Water storage tank for washing machine and washing machine

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CH557302A (de) 1974-12-31
FR2140608B1 (enExample) 1977-04-01
GB1348364A (en) 1974-03-13
CA993578A (en) 1976-07-20
NL7208013A (enExample) 1972-12-13
AU4307172A (en) 1973-12-13
DE2227856A1 (de) 1972-12-28
US3954403A (en) 1976-05-04
FR2140608A1 (enExample) 1973-01-19
AT317821B (de) 1974-09-10

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