CN1331659A - Process and compsn. for water recycle - Google Patents

Process and compsn. for water recycle Download PDF

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Publication number
CN1331659A
CN1331659A CN 99812909 CN99812909A CN1331659A CN 1331659 A CN1331659 A CN 1331659A CN 99812909 CN99812909 CN 99812909 CN 99812909 A CN99812909 A CN 99812909A CN 1331659 A CN1331659 A CN 1331659A
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China
Prior art keywords
flocculation agent
waste water
water
washing
agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 99812909
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Chinese (zh)
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CN1248972C (en
Inventor
J·韦弗斯
J·I·德维勒
T·J·M·范豪维尔梅伦
M·托盖
P·F·索特尔
L·G·范万特赫姆
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
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Priority claimed from GB9824398A external-priority patent/GB2343446A/en
Priority claimed from GB9915626A external-priority patent/GB2351730A/en
Application filed by Procter and Gamble Ltd filed Critical Procter and Gamble Ltd
Publication of CN1331659A publication Critical patent/CN1331659A/en
Application granted granted Critical
Publication of CN1248972C publication Critical patent/CN1248972C/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/547Tensides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/002Grey water, e.g. from clothes washers, showers or dishwashers

Abstract

A process for purification of waste water from domestic laundry washing processes and re-using the water, preferably in washing or rinsing steps. The process uses flocculents for removal of soils by floc formation and separation. The invention also relates to water purification compositions comprising primary and secondary flocculents for additions simultaneously or preferably sequentially for use in the claimed processes, the invention also relates to kits supplying unit dosages of flocculents, apparatus for separating flocs from treated water and detergent compositions comprising flocculents.

Description

The treatment process of recirculated water and the composition of use thereof
The technology of the present invention field
The present invention relates to required product and the method for washing water that the user can utilize pollution again, the washing water of pollution are such as being from washing process, especially the sewage of laundry processes.
Background technology
In many countries, the home washings custom all is labour-intensive, and needs a large amount of water in washing and wash phase.Laundry processes is especially true.Usually be that Infrastructure does not allow to use full-automatic filling/drought engine, must artificially collect water, and wastewater treatment be a problem more.These water can utilize method of wastewater treatment commonly used (Sewage treatment systems) to recycle in a usual manner, perhaps directly enter the water route.
Water purification method is well-known in the prior art, has described a kind of clarification of water method such as GB2004535A, wherein is used as flocculation agent with polyelectrolyte.These polyelectrolyte can be non-ionic types, anionic or more preferably cationic.Except adding polyelectrolyte, can also use condensing agent, such as granular mineral for helping cohesion.This treatment process allegedly is applicable to handles the water route, such as river.
GB1391578 also relates to a kind of method and composition that makes the suspended solids flocculation.Be particularly useful for removing diameter less than 10 microns particle.This patent is especially at the tap water as Urban water supply.Thereby this patent introduction is by being pre-mixed primary water well to a certain proportion of water-soluble cationic polymer and water-soluble nonionic polymkeric substance.
Not the purifying waste water of high purification muddiness treatment stage that SU891575 dividing two filtered after utilizing the Tai-Ace S 150 flocculation, utilizes polyacrylamide to handle then.SU1085942 purifies the waste water from drilling operation, wherein contains earth, petroleum products, polymkeric substance and tensio-active agent.Utilize the polyelectrolyte and the alkali-metal muriatic mixture of polyacrylamide, polyvinylamine to purify waste water.JP06071112, JP06309110, JP54073464, JP76042078 and JP51093550 also relate to the method for flocculating and purifying water.
In FR2466438, the wash clothes method of water of a kind of purification has been described, make not excess load of sewage work, and directly do not add compositions such as tensio-active agent and phosphoric acid salt to the korneforos.The flocculation agent that uses is Tai-Ace S 150 and anionic polyelectrolyte.
US5807487 handles the waste water of self-service laundry.At first water is stored in the evenly temper pond, transfers to then in second pond, make water be acidified to the pH value and be not less than 6.5.For further flocculation, add flocculation agent in second pond then, be preferably polymerize aluminum chloride, the pH value of regulating in second pond is not less than 5.0, thus the mud that obtains treated water and separate.
GB1543411 has described the method that a kind of recycle contains the waste water of synthetic detergent.At first, add water-insoluble tensio-active agent and synthetic detergent and form emulsion.Then by adding flocculation agent or destroying emulsion by electrochemical method or hyperfiltration process.
Yet what all these methods described above related to is industry law, can not solve user's set forth above specific question.
The present invention's general introduction
The invention provides a kind of treatment process of home washings process water, comprise the article of washing with from washing and/or cleaning step, contain waste water organic and/or inorganic foulants and tensio-active agent and separate, thereby being contacted with flocculant system, waste water forms floss, flocculant system comprises that (i) is selected from the main flocculation agent of polyvalent cation and polymine or its mixture and (ii) is selected from negatively charged ion and the secondary flocculation agent of nonionic polyelectrolyte or its mixture, floss is separated generation purify waste water from waste water, and it is utilized again.
According to a further aspect in the invention, a kind of treatment process of home washings process water also is provided, comprise the article of washing with from washing and/or cleaning step, contain waste water organic and/or inorganic foulants and synthetic detergent and separate, thereby being contacted with flocculant system, waste water forms floss, flocculation agent comprises that (i) is selected from the main flocculation agent of polyvalent cation and polymine or its mixture and (ii) is selected from cationic polyelectrolyte and the secondary flocculation agent of its mixture, floss is separated generation purify waste water from waste water, and it is utilized again.
Preferred described home washings process is a laundry processes.In an optimum seeking method of the present invention, purifying waste water still is used in the home washings process again, and such as dishwashing, laundry or individual clean, and in the preferred laundry processes, washs and/or cleans and all can.Preferably be used in washing step again.This washing and/or rinse water purify and can repeatedly recycle.
The present invention comprises that also the water that family uses purifies pack, and it comprises the flocculation agent of at least one unitary dose, and a unitary dose comprises the 0.5-250g flocculation agent, and optionally comprises the instrument that is used for removing from treating water floss.
The present invention comprises that also the water of the moisture cleansing composition that family uses purifies bag, and it comprises flocculation agent, and the instrument of unitary dose flocculation agent is provided, and optionally comprises the instrument of removing floss from waste water.
In another embodiment of the invention, a kind of washing container that carries out the home washings method also is provided, wherein by removing granular solids, make from the washing of washing process and the purification of waste water of cleaning step, described washing container comprises internal layer and skin, described the first layer forms the surface that links up, thereby washing water are contained in the washing container, and the described second layer is provided with and can makes that water flows through, trapped particles solid filter screen simultaneously.
According to a further aspect in the invention, also provide a kind of detergent composition that contains secondary flocculation agent.
Preferred described secondary flocculation agent is present in the detergent composition with doses, after described amount will make washing articles washing and removes, is adding when becoming owner of flocculation agent, and this remaining pair flocculation dosage is enough to promote throwing out.
Detailed description of the present invention
Add flocculation agent: water treatment steps
After the aqueous wash medium that contains washing composition is washed clothes and/or other article, perhaps to add after rinse water cleans, need to give up washing lotion or rinse water are separated with institute washing product.Washing process can be any home washings process, has a bath dishwashing, hard surface cleaning or wash clothes such as the individual.In general, washing process is a laundry processes, and waste water needs to separate with wet clothes.Except containing detergent ingredients, also contain granulous and/or gelationus dirt in the waste water, dirt is organism and/or inorganics.In the methods of the invention,, just can isolate waste water, thereby in washing container, carry out the water treatment of postorder, perhaps extract liquid collecting and in processing vessel, handle by from water, taking washing articles away such as wet clothes.
Then flocculant system with solid form, be added in the waste water such as powder or tablet, perhaps be added in the water such as the aqueous solution with liquid form, perhaps be added in the water with the solidliquid mixture form.The secondary flocculation agent of advocating peace can simultaneously or add in the waste water successively.
Flocculation agent
Flocculation agent comprises the flocculant system of being made up of main flocculation agent and secondary flocculation agent.Main flocculation agent is selected from polyvalent cation and polymine.For example polyvalent cation is a salt, comprises polymer salt such as aluminium, divalence magnesium or ferric iron.Preferred example is an aluminium salt.Aluminum ions preferred source is an aluminum chloride.Aluminum ions another preferably originated and is Tai-Ace S 150.Aluminum ions another preferably originated and is polymerize aluminum chloride.Aluminum ions another preferably originated and is the sulfuric acid pure aluminium silicate.The mixture of being made up of more than one aluminium sources also is suitable for.Also preferred sexavalence iron ion (ferric acid radical ion) because of being dissolved in the water when it, just forms ferric ion and superoxide, thereby can increase some bleaching effects in the water utilizing again, when being utilized as the laundry step again, and the advantage highly significant of this effect.Yet owing to the existence of ferric ion causes the water variable color, so iron cpd is not preferably adopted.
The preferred polyvalent metal aluminum ion that adopts.Anhydrous salt or salt hydrate both can use, but the preferred salt hydrate that adopts.Find that particularly Tai-Ace S 150 and aluminum chloride are especially useful, they can form floss rapidly, thereby and float on the waste water surface and be removed easily.The special improvement of the present invention is to use hydrated aluminum salt as flocculation agent.Owing to find AlCl 3.6H 2O and Al 2(SO 4) 3.16H 2O is handling domestic washing waste water, especially can promote well that floss floats on the water surface, the therefore preferred AlCl that uses during washing liquid 3.6H 2O and Al 2(SO 4) 3.16H 2O.In one embodiment of the invention, main flocculation agent preferably adopts the mixture of Tai-Ace S 150 and aluminum chloride.Salt hydrate is especially first-selected.The mixture of Tai-Ace S 150 and aluminum chloride salt comprises weight percent 5-60%, is preferably 15-35%, and the Tai-Ace S 150 of 20-30% more preferably, and weight percent 40-95% is preferably 65-85%, more preferably the aluminum chloride of 70-80%.When containing polymine in main flocculation agent, the molecular weight height of the polyelectrolyte of mentioning below the molecular weight of suitable material is not so good as is such as being not more than 5 * 10 6, preferably be not more than 1.5 * 10 6, more preferably be not more than 1 * 10 6
The secondary flocculation agent that is suitable for is organic polyelectrolyte, and an aspect of of the present present invention preferably adopts the high-molecular weight cationic polymers.Yet according to another preferred embodiment of the present invention, secondary flocculation agent preferably adopts negatively charged ion and/or nonionic polyelectrolyte.
A lot of synthetic cationic polymers materials that are suitable for can use, and these all are high-molecular weight polymeric amide or polyamine usually.Especially first-selected is polyacrylamide derivative.According to the viscosity of measuring, molecular weight (Mw) scope is preferably 10 4To 10 7Molecular weight is preferably 4 * 10 6More than, more preferably 5 * 10 6More than.Molecular weight is preferably 6 * 10 6About or be higher than 6 * 10 6
Cationic polyelectrolyte preferably cationoid activity (participating in the amount of side groups per-cent that reaction provides cation radical) greater than 20%, more preferably greater than 30%, most preferably greater than 40 or 60% polymkeric substance.Particularly preferred this material molecule amount is 4 * 10 6More than, and cationoid activity is greater than 40%.The material that is suitable for can make by the copolyreaction of acrylamide and quaternary ammonium polyacrylamide.The example of the polymkeric substance that is suitable for comprises Zetag89, Praestol611BC, Calfloc 1552,1506 and 1508, and Polymin KP97 (trade(brand)name).
Nonionic and anionic polymer are well-known as flocculation agent in the prior art, and a selection process of the present invention is that secondary flocculation agent comprises nonionic and/or anionic flocculant.The negatively charged ion or the nonionic polyelectrolyte that are suitable for are generally water-soluble polymer amount acrylamide polymer.These can be methacrylamide polymers, but preferred acrylamide polymer.Also can be other monomer and the copolymerization of (methyl) acrylamide, thus make it possess anion characteristic.Preferred polymkeric substance is such as the high-molecular weight polyacrylamide, and molecular weight is more than 100 ten thousand, and usually between 200 ten thousand to 3,000 ten thousand, common limiting viscosity (dl/g) is more than 5, and is common more than 8.For the very high high molecular weight polymers that also can be suitable for, limiting viscosity even can be greater than 10 is usually between 12 to 16 or higher.(with 1% solution in the deionized water is benchmark to the soltion viscosity of preferred polymkeric substance, and 25 ℃ with 5.11sec -1Shearing rate in the Fann viscometer, measure) be at least 350cps, be preferably at least 500, perhaps even at least 1000cps.Molecular weight is preferably more than 2 * 10 6, but be not more than 20 * 10 6
The negatively charged ion activity of the anionic polyelectrolyte that is suitable for (participating in the amount of side groups per-cent that reaction provides anion-radicals) is greater than 5%, perhaps greater than 10%, even greater than 20%.More preferred example comprises negatively charged ion and non-ionic polyacrylamide, such as the Magnafloc from AlliedColloids TMSeries..This flocculation agent is preferably high molecular, such as Magnafloc155 and/or Magnafloc351, is ultra-high molecular weight perhaps, such as Magnafloc919.
Preferred aspect of the present invention can be before main flocculation agent adds or add the pH regulator agent simultaneously in waste water, and the pH regulator agent is an acid source.Because polyvalent cation is initial and negatively charged ion, such as the phosphoric acid salt that exists in the waste water, silicate and carbonate react, and add acid source used main flocculation dosage is reduced, and therefore add acid source for preferred.The acid amount of adding in the waste water preferably makes the pH value of waste water be about 2.5 to 7.The acid source that is suitable for can be any acid, but special optimization acid, such as dicarboxylic acid or poly carboxylic acid.The example that is suitable for comprises oxysuccinic acid, citric acid, tartrate, toxilic acid, pentanedioic acid, hexanodioic acid, succsinic acid and composition thereof.Polymerization of carboxylic acid comprises polyacrylic acid and their multipolymer.
According to a particularly preferred embodiment of the present invention, when especially secondary flocculation agent comprises negatively charged ion and nonionic polyelectrolyte, also in waste water, add the agent of alkali source pH regulator.The alkali source pH regulator agent that is suitable for will be discussed in more detail below.Yet particularly preferred alkali source should be a carbonate buffer agent, such as yellow soda ash or salt of wormwood.Be preferably in to add in waste water, to add at least before the alkali source and become owner of flocculation agent.This can be by according to dosage adding after the flocculant system or according to dosage adding alkali source after becoming owner of flocculation agent and realize according to dosage adding separately.Yet, preferably add simultaneously with main flocculation agent, preferably also add simultaneously with secondary flocculation agent, the form of main flocculation agent and alkali source is selected, thereby main flocculation agent is released in the waste water quickly than alkali source.For example, main flocculation agent adds with the solution form that can be released into fast in the waste water.Yet more preferably flocculation agent according to dosage adds with the powder/granule form.The main flocculation agent granularity that makes adding just can realize above-mentioned discharging earlier less than the granularity of alkali source, for example, alkali source particulate geometric mean size is at least greater than 25 microns of main flocculation agent particle geometric mean sizess, perhaps even big at least 50 microns, or big at least 75 microns.In addition, can provide a kind of alkali source that discharges at a slow speed, outside surface scribbles or is enclosed with water-soluble or easily cracked coating, and this coating can be released alkali source after the sentence expires.
Term used herein " geometric mean particle diameter " refers to and utilizes knownly with the granulometry technology of quality when the basis, preferably adopts dry sieve method to measure how much mass median diameters of one group of discrete particle.The method for sieving that is suitable for is according to IS03118 (1976) method.The device that is suitable for is that to utilize step sizing be the Ro-Tap test screen vibrator type B of 8 inches sieves." geometric standard deviation " of term particle size distribution used herein or " spacing " refer to the geometric widths to the best-fit logarithm nominal function of particle size data above-mentioned, can be by the 50th of cumulative distribution ThPercentage point place diameter removes the ratio of the 84.13rd percentage point place diameter and represents (D 84.13/ D 50); Referring to people such as Gotoh, Power TechnologyHandbook, pp.6-11, Marcel Dekker 1997.
After finishing the dissolving of flocculation reaction and alkali source, the pH value that contains the waste water of floss is preferably 4.0-7.0, is preferably 4.5-6.5.
The generation bubble because polyvalent metal ion that exists in alkali source and the waste water or other acid source react, therefore adding alkali source can have other benefit.This helps floating of floss.
When using cationic polyelectrolyte, also contain the polyvalent metal ion of higher concentration in the water behind the removal floss.Thereby can help to precipitate the polyvalent metal ion of removing high density owing to add alkali source, put from this, it also is useful adding alkali source.In some cases, by treated water being flow through contain the bed of solid packing and alkali source, such as the husky bed that contains carbonate, perhaps make treated water flow through positively charged ion or mixed-bed ion exchange resin bed, thereby can remove unwanted high concentration ion, thereby can replace directly adding alkali source.
A preferred aspect of the present invention is added main flocculation agent and secondary flocculation agent simultaneously in waste water.In addition, main flocculation agent added before secondary flocculation agent.Two kinds of compositions can be metered into simultaneously, but main flocculation agent and secondary flocculation agent are selected form separately respectively, thereby main flocculation agent preferentially is distributed in the waste water than secondary flocculation agent.
Another preferred mode is, secondary flocculation agent can be a detergent ingredients, be present in the whole washing process, therefore at circulation step, after washing articles separates, only add main flocculation agent and other optional composition, such as pH regulator agent and/or foamed system, perhaps add the secondary flocculation agent of these compositions and lower concentration, just flocculation reaction can take place.Therefore the present invention also comprises a kind of method, in this method, detergent ingredients includes the secondary flocculation agent that uses in the home washings process, after washing articles is separated, main flocculation agent adds in the waste water, thereby the generation floss separate floss then from waste water, thereby waste water can utilize again.
Preferred flocculant system stirs when joining in the waste water, stir after perhaps flocculation agent joins in the waste water, can adopt mechanical stirring or this mixture of hand mixing more commonly used, thereby can promote flocculation agent to be diffused into the formation that promotes floss in the waste water rapidly owing to stir, therefore stir preferred high degree of agitation.When adding flocculation agent successively, after adding each flocculation agent composition, preferably all to stir.The present invention has found a kind of mixture, with respect to the dirt amount that exists in the washings, even use small amount of flocculant, and also can be especially effectively and promptly form high-intensity floss.
To a certain extent, the amount of needed flocculation agent depends on the soil content in need purifying liquid waste.Usually, the total flocculation dosage that needs staticizes water from 0.05 with respect to waiting, or from 0.1, perhaps even from 0.5g/l to 20g/l, perhaps is lower than 10g/l, perhaps even be lower than 5g/l.
If main flocculation agent comprises polyvalent metal salt, consumption is usually with respect to water 0.005 to 10g/l to be clean, preferable amount 0.1 to 10g/l.Handling the standard volume of waste water can from 2 to 200 or from 3 to 70 or the 4-40 liter.Yet when washing in machine, the volume of pending waste water is more a little, such as the 10-100 liter, usually is about 20 to 70 liters, is more typically about 25 to 40 liters.
Therefore, when handling at this waste water, especially when using machine, the common 40-100g of preferred dosage of polyvalent cation salt, more preferably 50-120g is preferably 60-100g.
When waste water from hand washing during step, preferred flocculant dosage 0.5 is to 20g/l, usually greater than 2g/l, perhaps greater than 3g/l, perhaps even greater than 5g/l.
Can be the preferred 0.001-1g/l of the dosage of positively charged ion, negatively charged ion or non-ionic secondary flocculation agent water to be clean.Specifically, this polymer material dosage is from 0.01-2.0g/l, perhaps even be 0.1-0.8g/l.Usually, this polymer material adds in solution, and for example the concentration expressed in percentage by weight in the aqueous solution is counted 0.1-10% with aqueous solution weight, perhaps even be 1-10%.Therefore, for the pending wastewater volume of standard that is generally about 30 liters, use the solution of the 1% polymeric flocculant composition of 10-200ml or 10-100ml, be preferably 20-50ml, for highly concentrated solution, can use low relatively volume in proportion, or with the lower concentration higher volumes.
Except above-mentioned interpolation flocculation agent composition, can also in waste water, add the floss washing assistant.The floss washing assistant that is suitable for is clay and/or talcum powder for example, and/or synthetic zeolite, natural zeolite, especially long stapled Mierocrystalline cellulose and composition thereof.Other additive optionally is the fixed polymkeric substance of dyestuff in water treatment steps, thereby it can be used for collecting any residual dye removal that waste water exists.Described additive also has pH regulator agent, reodorant, spices, antiseptic-germicide, SYNTHETIC OPTICAL WHITNER, dyestuff, suds suppressor.During forming floss, the fixed polymkeric substance of dyestuff and other throw out co-precipitation perhaps become the part of floss.
The floss intensity that forms in the method for the present invention is very big, and is therefore not broken basically when isolating floss from waste water.In addition, the floss of formation preferably includes big at high proportion shape floss, such as diameter greater than 250 microns be preferably greater than 400 microns, more preferably greater than 750 microns even account at least 60% greater than 1000 microns floss, more preferably at least 80%.The floss diameter is not more than 5000 microns usually, perhaps is up to 2000 microns.The special floss weight of preferred size between 1200 to 1900 microns accounts for 70% at least.When the waste water that contains floss flows in the sieve, measure according to the ratio that flows through or be trapped in floss on the sieve that size of mesh limits.Because the large size floss can be separated rapidly, therefore be preferably large-scale floss from water purification.
The separation of floss
Utilize any common method to be described in detail below, can from waste water, isolate the floss of formation.
Make it to be easy to remove if the floss that hope forms floats,, also will be aided with the aerogenesis means except in waste water, adding the flocculation agent composition that is used to purify.Can provide a kind of when forming floss only simple in waste water the aerogenesis device of bubbling.In addition, can provide a kind of foamed system, produce the reaction of carbonic acid gas such as the bronsted lowry acids and bases bronsted lowry original position that exists in the waste water by air-generating reaction.This acid-base reaction thing also can add in the waste water, for example joins in the waste water with flocculation system, and perhaps these reactants are to exist in the waste water.Specifically, main flocculation agent is a polyvalent metal ion, and these compositions can provide acid source.In addition, can in waste water, add acid source, such as carboxylic acid, for example dicarboxylic acid or poly carboxylic acid.The example that is suitable for comprises oxysuccinic acid, and citric acid, tartrate, toxilic acid, pentanedioic acid, hexanodioic acid, or succsinic acid or its mixture, alkali source be such as carbonate, supercarbonate, sesquicarbonate or its mixture.Usually use alkaline carbonate.These compositions can join in the waste water by any relative proportion that produces gas, and they recently provide with stoichiometry usually.Also can use foamed system to guarantee that the circulation that produces is suitable with water purifying pH value.
Purify Water reuse
After isolating floss, the pure water of remaining water for utilizing again.A preferred aspect of the present invention is the washing of clothes or the water cycle use of cleaning step.According to the concrete purposes of purifying waste water and utilizing again, regulate water purifying pH value.Preferably selected to make water purification to possess and utilized desirable pH value again, but, produced desirable pH value thereby also can add the pH regulator agent for certain special utilization again to flocculation agent.For example,,, wish water purifying pH value for acid if plan to use fabric conditioner for cleaning step, less than 7, common 2-7 or 2-6.Yet, if pH is too high or too low, can before adding fabric regulator, add acid or alkali respectively, thereby produce the pH value of wishing.
If utilize is the rinse water that conduct wherein prepares to add fabric regulator again, and the concentration of the sulfate ion in the rinse water had better not be too high, thereby avoid fabric conditioner to precipitate.Use the Tai-Ace S 150 of lower concentration just can avoid this phenomenon to take place such as main flocculation agent.Therefore main flocculation agent preferably uses the not polyvalent cation of sulphate-containing ion, such as aluminum chloride or Tai-Ace S 150 and muriatic mixture, for example include weight percent 5-60%, preferred 15-35%, the more preferably Tai-Ace S 150 of 20-30%, with weight percent 40-95%, preferred 65-85%, the more preferably aluminum chloride of 70-80%.Owing to use vitriol can cause the performance of fabric softener soluble in water to reduce separately, therefore compare with independent use vitriol, find that using this mixture is preferably.In addition, also can be before adding fabric regulator, such as making spent ion exchange resin remove sulfate ion.
Other benefit of the present invention is and can takes useful composition in the purifying waste water of re-using to.For example, surfactant concentrations can reduce about 5-20 doubly, is about 10 times usually, takes the tensio-active agent that re-uses in the water to and partly helps as washing step water again.In addition, may be brought into from the spices in the washing composition and/or dyestuff and purify waste water.This water wishes to have attracting color and/or fragrance as cleaning step water again.Therefore, of the present invention another well improves and is, method for purifying water is used in combination with the washing composition that includes spices, and the fragrance of this spices is than 3,7 dimethyl-2,6, and octadiene-1-nitrile (geranyl nitrile) is stronger.This assessment realizes by five people's spices expert groups, is that the diethyl phthalate solution of 20% spices and weight percent are that the fragrance of 20% geranyl nitrile solution compares with weight percent.This comparison should be used to smell and hear bar and carry out.During the fragrance that uses a kind of like this spices to produce can be brought into and purify waste water, in steps such as clothes cleaning, utilize again.
In a further preferred embodiment, spices and/or dyestuff can add with flocculation agent, produce attracting fragrance and/or color, thereby are applicable to as rinse water.Will re-use in washing step if purify waste water, the pH value of wishing water is greater than 7.In addition, but selective flocculant makes it to produce automatically the pH value greater than 7 water, or adds the pH regulator agent before purifying waste water utilizing again.Can add any alkali, thereby obtain desirable alkaline pH value.
The special discovery, owing to adding the flocculation agent polyvalent metal salt in the water that is used in washing step again, the polyelectrolyte concentration in the water influences the effect of washings unfriendly.By using ion-exchange filter, perhaps be preferably in and add washing composition adding metal ion chelation agent in purifying waste water before, thereby overcome the above problems, thereby can optionally utilize the pH regulator agent to make the pH of water make washing composition possess top performance to alkalescence for neutrality.
The sequestrant that is suitable for comprises the water-soluble and/or insoluble washing assistant that describes below, but heavy metal ion sequestering agent preferably preferably adopts water soluble detergency promoter and heavy metal sequestering agent, the especially latter.Because the concentration of these materials even extremely low also effective, the concentration of a certain amount of these materials being added to the middle several at least ppm of generation that purify waste water is promptly available.For example, can add 0.005g/l to 10g/l.
The heavy metal ion sequestering agent
The heavy metal ion sequestering agent is the preferred sequestrant of the present invention.The heavy metal ion sequestering agent here is meant the composition with the heavy metal ion sequester.These compositions are also possessing calcium magnesium chelating ability, but preferred its has the chelating heavy metal ion, such as iron, manganese and copper, or the ability of any other metal ion that adds as flocculation agent.
Here the heavy metal ion sequestering agent of Shi Yonging includes organic phosphonates, such as amine alkylidene group poly-(alkylene phosphonic acids salt), alkali-metal ethane 1-hydroxyl diphosphonate and nitrilo trimethylene phosphonic salt.For example comprise diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxyl ethylidene 1,1 diphosphonate, 1,1 hydroxyl ethane di 2 ethylhexyl phosphonic acid and 1,1 hydroxyl ethane dimethylene phosphonic acids.
Here the preferred heavy metal ion sequestering agent that is suitable for comprises nitrilotriacetic acid(NTA) and polyaminocarboxylic acid, such as ethylenediamine tetraacetic acid (EDTA), and quadrol Succinic Acid, quadrol pentanedioic acid, 2-hydroxyl propylene diamine Succinic Acid or their salt.
Here other heavy metal ion sequestering agent of Shi Yonging comprises EP-A-317, the derivative of the iminodiethanoic acid of describing in 542 and EP-A-399,133, for example 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid.EP-A-516, iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and the aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestering agent described in 102 also are applicable to the present invention.EP-A-509, the Beta-alanine-N that describes in 382, N '-oxalic acid, aspartic acid-N, N '-oxalic acid, single acetate of aspartic acid-N-and imino-Succinic Acid sequestering agent also are applicable to the present invention.EP-A-476,257 have described the amino sequestering agent that is suitable for.EP-A-510,331 have described by collagen protein, Keratin sulfate or the casein derived sequestering agent that comes out.EP-A-528,859 have described the alkyl imino oxalic acid sequestrant that is suitable for.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2,4-tricarboxylic acid also are suitable for.Here G-NH2-the N-in addition that is suitable for, N '-Succinic Acid (GADS), quadrol-N-N '-pentanedioic acid (EDDG) and 2-hydroxyl propylene diamine-N-N '-Succinic Acid (HPDDS).
Especially preferred is diethylenetriamine pentaacetic acid, quadrol-N-N '-Succinic Acid (EDDS) and 1,1 hydroxyl ethane di 2 ethylhexyl phosphonic acid or its basic metal, alkaline-earth metal, the ammonia salt of ammonia or replacement, or its mixture.
The water cleansing composition
The present invention includes a kind of water purification pack that family uses that is suitable for that makes water purify utilization again, this pack comprises the flocculation agent of at least one unitary dose, and a unitary dose comprises the 0.03-250g flocculation agent, and preferred 0.05 to the 100g flocculation agent.As mentioned above, flocculation agent preferably includes main flocculation agent and secondary flocculation agent, and therefore preferred pack comprises main flocculation agent and the secondary flocculation agent that is used for aforesaid method, and flocculation agent preferably separates, and can throw in simultaneously or successively.The particularly preferred pack of the present invention, flocculation agent is divided into two independent unitary doses, comprise first unitary dose and second unitary dose, first unitary dose comprises 10-200g master's flocculation agent polyvalent metal ion, or 0.03-5g contains the flocculation agent of PEI, second unitary dose comprises the secondary flocculation agent of 0.01-20g, preferred 0.01 to 10g, more preferably 0.01 arrive 5g.
The material that can also comprise other in the unitary dose, such as tackiness agent, filler is handled auxiliary agent, solvent and/or disintegrating agent.Unitary dose can also comprise aforesaid bubbling system, and it can produce the floss that gas accelerates to form and float, and the disintegrating agent that can be used as unit dosage in addition guarantees that the flocculation agent snap-out release goes into dual-use function such in the waste water.Other disintegrating agent that is suitable for is the material that is usually used in pharmacy and the tablet technology, such as EP711828A, and the disintegrating agent described in EP488484A and the EP522766A.
The water scavengine agent bag can also comprise the pH regulator agent and/or the sequestrant of aforesaid unitary dose, wishes in this case to purify waste water and utilizes in the clothes washing step again.
The present invention also comprises and contains the water cleansing composition, and the water scavengine agent bag of device that is used to remove the floss of formation in addition, described device is such as one or more strainers or be used for collecting and removing from the waste water of handling the high-specific surface area utensil of floss.
Separate floss
Can from waste water, isolate the floss that forms in the method for the present invention by any method commonly used.For example, especially in the place that floss floats, use utensils such as ladle or spoon to skim or remove floss from the waste water surface, thereby removed.In addition, in floss sedimentation or showy place, above floss or below utilize siphon pipe extract out or come down in torrents/decantation goes out clear water to begin to take out of till the floss up to clear water.The waste water that contains floss can be used as offal treatment and falls.In addition, by in containing the waste water of floss, stirring, thereby remove floss, such as holding back the hairbrush that floss can be removed then with the high-specific surface area utensil.Can be designed to hairbrush electrically charged or have other surface property, such as viscosity, thus its attracted by surfaces floss.Dry then this hairbrush, dry back floss is just removed easily.In addition, remove floss by filtering, can make the water that contains floss flow through the strainer of the water side that is positioned at processing vessel, perhaps on washing container, provide one by constitute salable of strainer and movably cover or framework, thereby make water come down in torrents by strainer from washing container, perhaps strainer is one " cover ", is placed on the feed-water end of container, by this cover water purification is injected container storage or utilization more immediately.Even can spur strainer by containing the water of flocculation agent, thereby catch the floss of formation.The strainer that is suitable for comprises the strainer of being made up of any suitable sieve aperture.Sieve aperture can not be too little in order to avoid make filtration velocity too slow, makes the floss blocking filter.Similarly, the sieve aperture of strainer can not be too big, exempts to make a large amount of flosss to flow through mesh.The material that is suitable for comprises paper, fabric, and metal contains the polymeric material (polyurethane foam that has been found that the standard aperture is particularly useful) of foam materials, and perhaps mineral substance is such as the porous stone.Preferred strainer to small part is that flexible is arranged, thereby strainer can be easily mounted in washing machine or other the processing vessel.
Strainer can utilize again and intermittently clean in filtration, for example can be after drying by cleaning or strike off or other physical removal method being come relatively easily from utilizing the strainer (such as metal or plastic filter or fabric filter or hairbrush) to remove floss again.In addition, strainer can be disposable, thereby is carrying out using new strainer after one or many filters.
Another aspect of the present invention, a washing container that carries out the home washings process is provided, thereby removing granular solids from the waste water of the washing of washing process and/or cleaning step in this washing container is purified, washing container comprises internal layer and skin, the first layer forms the surface that links up, the water that is used for washing in the washing process is in this washing container, and the second layer is a filter screen, makes water flow through this layer simultaneously at the filtering particle solid.
When washing container comprises disposable filter, strainer should shift out easily and replace, for example in the bottom of washing container or in filtration vessel independently, have one and lick filtering material, when during filtering, needing to change filter material, can draw back and spill one section new filtering material.
Accompanying drawing
The preferred embodiments of the invention the figure shows the sectional view of container as shown in Figure 1.In this embodiment of the present invention, internal layer has filter screen.Internal layer 1 is adjacent to outer 2 the inside, is provided with filter screen 3 in the internal layer.
Fig. 2 is the A-A amplification sectional view of Fig. 1.As can be seen, filter screen 3 is arranged in the internal layer 1, according to preferred one side of the present invention, a movably sealing member 4 is set, and uses in washing process, makes washing or rinse water not contact filter screen 3.When finishing, washing process, removes removable sealing member 4 by drawing back loosening part 5.Removable sealing member is by yielding or flexible and can be adjacent to the resilient material that filter screen installs and make, and in the filtration step of current filtering net, thereby filter screen exposes to the open air out solid particulate is trapped on the filter screen.
Fig. 3 is the sectional view of another embodiment, the A-A place, and filter screen 3 is arranged in the internal layer 1, and removable sealing member 4 is arranged on the filter screen, and use loosening part 5 can hydrodynamic reciprocating sealing body 4.Preferred embodiment shown in Figure 2 because those skilled in the art are easy to find out that loosening part 5 matches with upwardly extending prominent rafter 6, can stop the filter screen of protruding prominent rafter 6 belows of water and height to contact, thereby avoid incomplete filtration.Yet remaining water can discard with granular solids, and therefore such embodiment is still very suitable.
In the embodiment shown in Fig. 1 to 3, when washing process finishes, move removable sealing member 4, exposing filter screen waste water therefrom spills, lift internal layer 1 and separate with outer 2 and maintain, thereby make current filtering net 3 and enter container 2, the while granular solids is trapped on the filter screen 3.Having removed purifying waste water of granular solids then re-uses in outer 2.
Another embodiment of the present invention as shown in Figure 5.In this embodiment, skin is provided with filter screen 3, internal layer 9 has one with cover 8 hole, lid can make internal layer form the surface that links up, thereby washing water are contained in the washing container, but remove lid when opening the hole, can flow through filter screen 3 and on filter screen 3, catch granular solids thereby purify waste water.
From top embodiment as can be seen, filter screen not necessarily expands to total inner surface or outside surface, but such embodiment also within the scope of the invention.
Can set out oral pore 8 by any movably sealing member (such as plug, or enclosing cover, the segmentation dividing plate that maybe can open and close).
Usually, filter screen only expands to the part of internal surface or outside surface.But as can be seen, filter screen itself constitutes entire exterior surface in Fig. 6.
Filter screen is made by polymeric material usually, and such as polyethylene or polypropylene, in addition, filter screen can make the suitable material that water flows through make simultaneously by any trapped particles solid.The hole of filter screen should be enough little, thereby catch solid when not hindering current, and opening of sieve also should not be too big, in order to avoid cause filtering granular solids to flow through filter screen.Usually, opening of sieve is the 10-300 micron, preferred 100-250 micron.Other material of making filter screen is metal or any other material.If filter screen itself is made by resilient material, in solid carrier, sneak into reticulated, can play strengthening effect, for example shown in Figure 4, wheel rim 11 and spoke 12 are made such as polymeric material by any sturdy material, and filter screen 13 can be made of nylon or any other elastic web materials etc.
As can be seen, the embodiment of water receptacle of the present invention is applicable to all that in all fields Clean Water Act of the present invention uses, and adds flocculant system and other optional additive thus and make solid grain thing cotton-shaped in waste water.
Embodiment example 1
Wash soiled clothes in 30 premium on currency, add the commercially available laundry detergent composition based on phosphoric acid salt of standard dose, the detergent concentration in the washing water is 2500ppm.
After finishing washing process, detergent foam disappears, and the dirt concentration in the water is 4g/l, and dirt concentration is carried out drying with sample and measured in drying oven under 120 ℃.In 30 liters of waste water, add 70g Al 2(SO 4) 3.16H 2O and AlCl 3.6H 2The mixture of O, the weight ratio of this mixture are 30: 70.After stirring 10 seconds gently, add 1wt%Polymin KP97 (trade(brand)name of BASF) solution 30ml, stirred lightly 90 seconds simultaneously.Form large-scale floss.The waste water that discharge contains floss from water receptacle is by the polyurethane foam dish then, and foam panel is caught floss and made clear water see through foam rapidly, utilizes thereby collect again.The pH value of purifying waste water that produces is about 4, and outward appearance is limpid, is suitable for utilizing as scavenging solution again.This water is used in the clothes cleaning step again,, has added the commercially available fabric softener of manufacturer recommendation dosage in this step.Example 2
The detergent composition based on phosphoric acid salt that market is bought is dissolved in 5 premium on currency, and the detergent concentration in the washing water is 5600ppm.Add the general dirt mixture that can find on soiled clothes in the water, concentration is equivalent to 2500ppm, thereby produces waste water solution.
In these 5 liters of waste water, add flocculant system, this flocculant system comprises the Aluminium chloride hexahydrate of 22.5g, 16 hydrazine aluminum sulfates of 7.5g (weight ratio of aluminum chloride and Tai-Ace S 150 is 3: 1), and the Magnafloc of 0.375g TM155.Add the yellow soda ash of 11.5g again.All these additives add simultaneously with particle form.Form floss in strong stirring back.Find the bubbling phenomenon, the floss of generation accumulates in water surface.Add flocculant system waste water before and seem muddy.Make the waste water that contains floss flow through 150 microns strainer then, strainer is caught floss and is made clear water see through strainer rapidly, collects and utilizes.The pH value of purifying waste water that produces is about 6, and outward appearance is limpid, is suitable for utilizing in the washing step of family's washing process again.Example 3
In 5 premium on currency, the detergent composition based on phosphoric acid salt of dissolving standard dose, approximately contain following composition:
Sodium alkyl benzene sulfonate 20wt%
Tripoly phosphate sodium STPP 30wt%
Yellow soda ash 15wt%
Sodium sulfate 15wt%
Water glass 10wt%
Sodium peroxoborate (water or tetrahydrate) 2.5wt%
Froth suppressor 1wt%
Magnafloc 1.6wt%
Spices, water and other are supplied 100wt%
Detergent concentration in the washing water is 2500ppm.In washing water, be dispensed into the typical dirt of 2.5g/l or 2500ppm, produce waste water.In 5 liters of waste water, add and become owner of flocculation agent, main flocculation agent comprises the Aluminium chloride hexahydrate of 11.25g and 16 hydrazine aluminum sulfates of 3.75g (weight ratio of aluminum chloride and Tai-Ace S 150 is 3: 1).Also to add the yellow soda ash of 5.5g.All these additives add simultaneously with particle form.Form floss in strong stirring back.Find the bubbling phenomenon, the floss of generation accumulates in water surface.Utilize siphon pipe below floss, to extract clear water or clear water and floss are separated, clear water is collected again utilize by strainer filtering.In addition, utilize the polyurethane foam dish to discharge solution, foam panel is caught floss and is made clear water see through foam rapidly, utilizes thereby collect clear water again.In this embodiment, utilize 150 microns strainer to filter, thereby floss and clear water are separated.The water purification outward appearance that produces is limpid, is suitable for utilizing washing step or cleaning step at family's washing process again.

Claims (28)

1, a kind of method of handling the home washings spent process water, comprise that washing articles and washing and/or cleaning step are contained waste water organic and/or inorganic foulants and synthetic detergent to be separated, waste water is contacted with flocculant system, thereby formation floss, described flocculant system comprises the main flocculation agent that is selected from polyvalent cation and polymine or its mixture and is selected from negatively charged ion and the secondary flocculation agent of nonionic polyelectrolyte and its mixture, floss is separated from waste water, generation is purified waste water, and with this utilization again of purifying waste water.
2, a kind of method of handling the home washings spent process water, comprise that washing articles and washing and/or cleaning step are contained waste water organic and/or inorganic foulants and synthetic detergent to be separated, waste water is contacted with flocculant system, described flocculant system comprises the main flocculation agent that is selected from polyvalent cation and polyvinylamine or its mixture and is selected from cationic polyelectrolyte and the secondary flocculation agent of its mixture, and with this utilization again of purifying waste water.
3, method as claimed in claim 1 or 2 is wherein also added the agent of alkali source pH regulator in the waste water.
4, method as claimed in claim 3, wherein the pH regulator agent is carbonate or any other buffering salt.
5, as claim 3 or 4 described methods, wherein main at least flocculation agent joined in the waste water before adding alkali source.
6, method as claimed in claim 5, wherein main flocculation agent and secondary flocculation agent and alkali source are metered in the waste water simultaneously, and alkali source is than the slower form of main flocculation agent dissolving.
7, each method of claim as described above, wherein in the waste water except adding flocculant system, also to add the agent of acid source pH regulator.
8, method as claimed in claim 7, wherein acid source joins in the waste water simultaneously or prior to main flocculation agent.
9, method as claimed in claim 8, wherein in first contact procedure, waste water contacts with main flocculation agent, and stirs, thus floss begins to form, and in second contact procedure, waste water contacts with secondary flocculation agent.
10, the described method of any one claim as described above, wherein the home washings process is a laundry processes.
11, the described method of any one claim as described above, wherein flocculant system is the system that can produce the floss that floats.
12, the described method of any one claim as described above is comprising the effervescent system that is provided at generation/release gas in the waste water.
13, the described method of any one claim as described above, wherein main flocculation agent contacts with waste water in order with secondary flocculation agent.
14, the described method of any one claim is as described above wherein purified waste water and is used in another laundry processes step again, and washing or clean all can.
15, the described method of any one claim as described above, wherein before utilizing, the adding sequestrant makes it the metal ion in the chelated flocculating agent in purifying waste water in again.
16,,, thereby floss is separated from waste water wherein by strainer or filter screen are mentioned from the water that contains floss as any one described method in the claim 1 to 15.
17, the composition of purifying waste water of a kind of family use comprises flocculation agent, and described flocculation agent comprises the main flocculation agent that is selected from multivalent metal cation and/or polymine and comprises negatively charged ion, the secondary flocculation agent of nonionic or cationic polyelectrolyte or its mixture.
18, the water of a kind of family use purifies pack, comprises at least one unitary dose flocculation agent, perhaps comprises the device that at least one unitary dose that contains the 0.03-250g flocculation agent is provided.
19, water as claimed in claim 18 purifies pack, comprise first unitary dose, this first unitary dose contains the main flocculation agent that is selected from multivalent metal cation or polymine or its mixture, with comprise second unitary dose, this second unitary dose contains and is selected from negatively charged ion, the secondary flocculation agent of nonionic or cationic polyelectrolyte or its mixture.
20, purify pack as claim 18 or 19 described water, comprise main flocculation agent and contain the secondary flocculation agent of negatively charged ion and/or non-ionic flocculant, and also comprise alkali source.
21, purify pack as any one described water in the claim 18 to 20, the form of used main flocculation agent and alkali source makes its dissolution rate in handling waste water slower than main flocculation agent.
22, purify pack as any one described water in the claim 18 to 21, wherein advocate peace secondary flocculation agent and alkali source all are particle forms, but alkali source provides to dissolve the slow form of total speed ratio master flocculation agent.
23, a kind of washing container that carries out the home washings process, wherein by removing granular solids, and purification is from the waste water of washing and/or cleaning step in the washing process, described washing container comprises internal layer (1) and outer (2), described the first layer forms the surface that links up, thereby washing water can be contained in this washing container in washing process, and the described second layer is provided with and can makes water flow through trapped particles solid filter screen (3) simultaneously.
24, washing container as claimed in claim 23, wherein internal layer is provided with filter screen.
25, as claim 23 or 24 described washing containers, wherein also provide movably sealing member, when it was used in washing process, this removable sealing member stoped water to contact with filter screen basically, finishes up to washing process.
26, as claim 23 or 25 described washing containers, its mesectoderm is provided with filter screen, and internal layer comprises closable taphole, and this bore closure during washing process is opened this hole and can be made water flow out skin when washing process finishes.
27, a kind of detergent composition comprises secondary flocculation agent, and this pair flocculation agent is to finish the polyelectrolyte of washing step metapedes with the amount of promotion throwing out.
28, detergent composition as claimed in claim 27, described secondary flocculation agent comprises the high-molecular weight polyacrylamide.
CN 99812909 1998-11-07 1999-11-05 Process and compsn. for water recycle Expired - Fee Related CN1248972C (en)

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