DK160416B - Process for treating raw water and sewage - Google Patents
Process for treating raw water and sewage Download PDFInfo
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- DK160416B DK160416B DK548879A DK548879A DK160416B DK 160416 B DK160416 B DK 160416B DK 548879 A DK548879 A DK 548879A DK 548879 A DK548879 A DK 548879A DK 160416 B DK160416 B DK 160416B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
iin
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Den foreliggende opfindelse angår en fremgangsmåde til behandling af råvand eller spildevand ved flokkulation.The present invention relates to a process for treating raw or wastewater by flocculation.
5 Råvand, som findes i naturen, og spildevand, som hidrører fra industrielle anlæg, indeholder sædvanligvis organiske eller mineralske stoffer i opløsning, emulsion eller suspension, og det vil i reglen være nødvendigt at fjerne sådanne stoffer med henblik på at anvende vandet eller 10 udlede det i naturen. Denne fjernelse af mineralske eller organiske stoffer gennemføres almindeligvis ved flokkulation, efterfulgt af en dekantering eller en filtrering, på en sådan måde, at man som slutprodukt opnår forholdsvis rent vand.5 Raw water found in nature and wastewater derived from industrial plants usually contain organic or mineral substances in solution, emulsion or suspension, and it will usually be necessary to remove such substances for use or to discharge the water. it in nature. This removal of mineral or organic substances is generally accomplished by flocculation, followed by decantation or filtration, in such a way as to obtain relatively pure water as the final product.
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Man kender en lang række mineralske eller organiske koaguleringsmidler, som kan anvendes til flokkulation.A wide variety of mineral or organic coagulants are known which can be used for flocculation.
Blandt de mineralske koaguleringsmidler er de mest kendte aluminiumsulfat, ferrichlorid og aluminiumpolychlorider-20 ne. Forskellige typer af organiske koaguleringsmidler, kationiske eller anioniske, har været foreslået. Således finder man en liste over sådanne koaguleringsmidler i US patentskrift nr. 3 377 274. Kationiske aminoplast-harpik-ser opnået ved kondensation af melamin og formaldehyd, 25 hvori visse -grupper, som ikke indeholder en methylol-gruppe, forefindes på saltform, er f.eks. anbefalet i FR patentskrift nr. 2 257 548.Among the mineral coagulants are the best known aluminum sulfate, ferric chloride and aluminum polychlorides. Various types of organic coagulants, cationic or anionic, have been proposed. Thus, a list of such coagulants is found in U.S. Patent No. 3,377,274. Cationic aminoplast resins obtained by condensation of melamine and formaldehyde, wherein certain groups which do not contain a methylol group, are present in salt form, are eg. recommended in FR Patent No. 2,257,548.
Ifølge dette FR patentskrift er sådanne vandopløselige 30 melamin-formaldehyd-harpikser, hvori aminogruppen, hvortil der ikke er knyttet nogen methylolgruppe, er omdannet til salt form ved hjælp af en mineralsyre eller en organisk syre, beskrevet af H.P. Wohnsiedler, Ind. and Eng.According to this FR patent, such water-soluble 30 melamine-formaldehyde resins wherein the amino group to which no methylol group is attached are converted to salt form by a mineral acid or an organic acid, described by H.P. Wohnsiedler, Ind. and Eng.
Chem. 44, 2679-2686 (1952). De har fundet udbredelse til 35 forbedring af styrken af papir i våd tilstand ifølge US patentskrift nr. 2 345 543. Den i FR patentskrift nr. 2 257 548 beskrevne proces gennemføres inden for et bestemtChem. 44, 2679-2686 (1952). They have found propagation to improve the strength of wet paper according to US Patent No. 2,345,543. The process described in FR Patent No. 2,257,548 is carried out within a particular
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2 pH-område fra pH 5 (i eksempel 3) til pH 10 (i eksempel 5), hvilket gør det nødvendigt forud for behandlingen at bestemme pH i vandet, der skal behandles, og om nødvendigt justere pH til en passende værdi (se eksempel 3).2 pH ranges from pH 5 (in Example 3) to pH 10 (in Example 5), which makes it necessary to determine, prior to treatment, the pH of the water to be treated and, if necessary, adjust the pH to an appropriate value (see Example 3).
5 Når man udøver processen, er man således undertiden nødsaget til at indføre elektrolytter (chloridioner i eksempel 3), som kan være generende med hensyn til den senere anvendelse af det behandlede vand. Inden for det samme område af den kendte teknik beskriver US patentskrift nr.Thus, when practicing the process, it is sometimes necessary to introduce electrolytes (chloride ions in Example 3) which may be bothersome to the subsequent use of the treated water. In the same field of the prior art, U.S. Pat.
10 3 484 837 udnyttelsen af kationiske vandopløselige mela- min-formaldehyd-harpikser til behandling af spildevand, nærmere bestemt til fjernelse af ikke-bionedbrydelige detergenter. Man foretrækker at gennemføre processen i nærværelse af kaliumaluminiumsulfat (alun til papirfremstil-15 ling). Som ovenfor er det i visse tilfælde nødvendigt at indstille pH i vandet, der skal behandles, på en passende værdi. Ifølge eksempel 21 indstilles pH således på 7-7,5.The utilization of cationic water-soluble melamine-formaldehyde resins for the treatment of wastewater, in particular for the removal of non-biodegradable detergents. It is preferred to carry out the process in the presence of potassium aluminum sulphate (alum for papermaking). As above, in some cases it is necessary to adjust the pH of the water to be treated to an appropriate value. According to Example 21, the pH is thus adjusted to 7-7.5.
Ved behandling af spildevand og råvand optræder et sær-20 ligt vanskeligt problem, nemlig flokkulation af suspensioner eller emulsioner med lave koncentrationer, dvs. mindre end 1 gram per liter. Det kræves faktisk, at de anvendte koaguleringsmidler ikke kun bevirker flokdannelse, men også, at de dannede flokke er tilstrækkeligt 25 store til at kunne dekanteres. Til dato har man stort set kun kunnet opnå tilfredsstillende resultater ved anvendelse af mineralske koaguleringsmidler. De kendte organiske koaguleringsmidler fører i almindelighed til mindre tilfredsstillende resultater. De mineralske koagulerings-30 midler, som udmærker sig ved ikke at være så dyre, udviser imidlertid en række ulemper: især er de meget følsomme med hensyn til pH-værdien i vandet, som skal behandles, og ved anvendelsen frigør de elektrolytter, som kan være meget generende af hensyn til den senere an-35 vendelse af det behandlede vand.In the treatment of wastewater and raw water, a particularly difficult problem arises, namely the flocculation of suspensions or emulsions with low concentrations, ie. less than 1 gram per liter. In fact, it is required that the coagulants used not only cause flocculation but also that the flocs formed are sufficiently large to decant. To date, only satisfactory results have been obtained using mineral coagulants. The known organic coagulants generally lead to less satisfactory results. However, the mineral coagulants, which are distinguished by not being so expensive, exhibit a number of drawbacks: in particular, they are very sensitive to the pH of the water to be treated and in use release the electrolytes which can be very troublesome in view of the later use of the treated water.
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Det har nu vist sig, at kvaterniserede aminoplast-harpik-ser (produkter opnået ved kondensation af et aldehyd med en amin eller et amid), hvori aldehydet er glyoxal eller en blanding af glyoxal og formaldehyd, og hvori nitro-5 genforbindelsen er melamin, eventuelt indeholdende en smule urinstof, besidder flokkulerende egenskaber, som kan sammenlignes med de mineralske koaguleringsmidler til anvendelse ved rensning af vand, som kun indeholder små mængder suspenderet eller emulgeret stof, ligesom disse 10 harpikser har afblegende egenskaber.It has now been found that quaternized aminoplast resins (products obtained by condensing an aldehyde with an amine or amide) wherein the aldehyde is glyoxal or a mixture of glyoxal and formaldehyde and wherein the nitrogen compound is melamine, optionally containing a bit of urea, has flocculating properties comparable to the mineral coagulants for use in purifying water containing only small amounts of suspended or emulsified substance, and these resins have bleaching properties.
Opfindelsen angår derfor en fremgangsmåde til behandling af råvand eller spildevand med et ringe indhold af suspenderede eller emulgerede stoffer, nærmere bestemt med 15 en koncentration af sådanne stoffer på under 1 g/1, ved hjælp af en kationisk aminoplast-harpiks i form af et til salt omdannet eller kvaterniseret kondensationsprodukt af en amin eller et amid og et aldehyd, og fremgangsmåden ifølge opfindelsen er ejendommelig ved, at man uden brug 20 af andre elektrolytiske additiver og uden forudgående indstilling af pH i mediet, der skal behandles, anvender en kvaterniseret aminoplast-harpiks som eneste behandlingsmiddel, i hvilken harpiks aldehydet er glyoxal eller en blanding af glyoxal og formaldehyd, og den nitro-25 genholdige forbindelse er melamin eller melamin med et maksimalt indhold af urinstof på 0,2 mol pr. mol melamin.The invention therefore relates to a process for treating raw water or wastewater with a low content of suspended or emulsified substances, more particularly with a concentration of such substances below 1 g / l, by means of a cationic aminoplast resin in the form of a salt converted or quaternized condensation product of an amine or amide and aldehyde, and the process of the invention is characterized in that without the use of other electrolytic additives and without prior adjustment of the pH of the medium to be treated, a quaternized aminoplast is used. resin as the only treating agent in which the resin aldehyde is glyoxal or a mixture of glyoxal and formaldehyde and the nitrogen-containing compound is melamine or melamine with a maximum urea content of 0.2 moles per ml. mol of melamine.
Harpikserne bestående af melamin/glyoxal/formaldehyd eller melamin/urinstof/glyoxal/formaldehyd er særligt virk-30 somme til denne anvendelse. Harpikser af denne type er i sig selv kendte, og visse er f.eks. beskrevet i FR patentskrift nr. 1 602 233, hvor det anføres, at de bevirker en temporær forøgelse af styrken af papir i våd tilstand. Disse kvaterniserede harpikser udviser, i sam-35 menligning med mineralske koaguleringsmidler, den fordel, at de er mindre følsomme over for pH-betingelserne i vandet, og de frigiver ikke elektrolytter til vandet. Endvi-The resins consisting of melamine / glyoxal / formaldehyde or melamine / urea / glyoxal / formaldehyde are particularly effective for this application. Resins of this type are known per se, and some are e.g. disclosed in FR Patent Specification No. 1,602,233, which states that they cause a temporary increase in the strength of wet paper. These quaternized resins, in comparison with mineral coagulants, have the advantage of being less sensitive to the pH conditions of the water and do not release electrolytes to the water. Endvi-
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4 dere ændrer de ikke på vandets pH, de kan anvendes alene uden at det er nødvendigt at tilsætte additiver (aktiveret siliciumdioxid eller et andet organisk flokkula-tionsmiddel), og endelig giver de mindre mængder slam end 5 de kendte mineralske produkter, i særdeleshed fordi de anvendes i mindre doseringer, hvilket også reducerer det nødvendige apparatvolumen. Desuden kan de forureninger, som hidrører fra kondensationsharpikserne anvendt ifølge opfindelsen, lettere dehydratiseres, end tilfældet er med 10 de mineralske produkter, og på grund af, at flokkule-ringsmidlet i sig selv er organisk, kan det lettere forbrændes. De kvaterniserede kondensationsharpikser, som anvendes ved fremgangsmåden ifølge opfindelsen, er desuden mere lagerstabile end kationiske melamin-formal-15 dehyd-harpikser i form af salte. Naturligvis er de tillige mindre følsomme over for pH-betingelserne, og det er derfor i reglen ikke nødvendigt at foretage en forudgående justering af pH i vandet, der skal behandles.4 they do not change the pH of the water, they can be used alone without the need to add additives (activated silica or other organic flocculant), and finally they give less amounts of sludge than 5 the known mineral products, especially because they are used in smaller doses, which also reduces the required device volume. In addition, the contaminants resulting from the condensation resins used according to the invention can be more easily dehydrated than is the case with the mineral products, and because the flocculant itself is organic, it can be more easily combusted. Furthermore, the quaternized condensation resins used in the process of the invention are more stable in stock than cationic melamine formaldehyde resins in the form of salts. Of course, they are also less sensitive to the pH conditions and therefore it is usually not necessary to make a prior adjustment of the pH of the water to be treated.
20 Herudover gælder der, at de kvaterniserede kondensationsharpikser som anvendes ved fremgangsmåden ifølge opfindelsen, i lighed med andre kationiske aminoplast-har-pikser udviser flokkulerende og afblegende egenskaber over for vand, som indeholder større mængder suspenderet, 25 emulgeret eller opløst stof.In addition, the quaternized condensation resins used in the process of the invention, like other cationic aminoplast resins, exhibit flocculating and bleaching properties against water containing greater amounts of suspended, emulsified or dissolved substance.
De kvaterniserede kondensationsharpikser som kan anvendes ved fremgangsmåden ifølge opfindelsen, fremstilles ved i vandigt medium ved en pH-værdi på mellem 5 og 8 og en 30 temperatur på under 100 °C at kondensere melaminen, eller melaminen og urinstoffet, med glyoxal eller fortrinsvis en blanding af glyoxal og formaldehyd. Herefter kvater-niseres produktet ved samme temperatur, fortrinsvis ved hjælp af dimethylsulfat ifølge den i FR patentskrift nr.The quaternized condensation resins which can be used in the process of the invention are prepared by condensing the melamine, or melamine and urea, with glyoxal or preferably a mixture in aqueous medium at a pH of between 5 and 8 to a temperature below 100 ° C. of glyoxal and formaldehyde. Thereafter, the product is quaternized at the same temperature, preferably with the aid of dimethyl sulphate according to the one described in FR patent no.
35 1 602 233 beskrevne procedure. De mest fordelagtige mol- forhold er 2-4 mol glyoxal og 0,5 til 3 mol formaldehyd for hvert mol melamin, fortrinsvis 3 mol glyoxal og 1 til35 1 602 233 described. The most advantageous mole ratios are 2-4 moles of glyoxal and 0.5 to 3 moles of formaldehyde for each mole of melamine, preferably 3 moles of glyoxal and 1 to
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5 3 mol formaldehyd per mol melamin. Kvaternlserlngen gennemføres med 0,2 til 0,5 mol dimethyl sul fat per mol melamin. Man kan uden vanskelighed tilsætte op til 0,2 mol urinstof per mol melamin. Herved nedsætter man harpik-5 sernes viskositet og forbedrer deres lagerstabilitet. Harpikserne opnås i vandig opløsning i koncentrationer på op til 20% aktiv bestanddel, og de er særdeles stabile i denne form.5 3 moles of formaldehyde per mole of melamine. The quaternization is carried out with 0.2 to 0.5 moles of dimethyl sulphate per mole of melamine. Up to 0.2 moles of urea per mole of melamine can be added without difficulty. This reduces the viscosity of the resins and improves their storage stability. The resins are obtained in aqueous solution at concentrations of up to 20% active ingredient and they are extremely stable in this form.
10 Ifølge opfindelsen anvendes de kvaterniserede harpikser i doseringer (udtrykt som 100% ren harpiks) på mellem 2 og 500 ppm, fortrinsvis mellem 4 og 20 ppm til rensning af råvand og mellem 30 og 300 ppm til rensning af spildevand. Det er desuden muligt at anvende de omhandlede har-15 pikser i kombination med andre koaguleringsmidler, såsom mineralske eller organiske koaguleringsmidler, anioniske såvel som kationiske, f.eks. vandopløselige acrylcopoly-mere på basis af acrylamid.According to the invention, the quaternized resins are used in dosages (expressed as 100% pure resin) of between 2 and 500 ppm, preferably between 4 and 20 ppm for purification of raw water and between 30 and 300 ppm for purification of wastewater. In addition, it is possible to use the present resins in combination with other coagulants such as mineral or organic coagulants, anionic as well as cationic, e.g. water-soluble acrylic copolymers based on acrylamide.
20 Som allerede nævnt kan de kondenserede melamin/glyoxal/ formaldehyd- eller melamin/urinstof/glyoxal/formaldehyd-harpikser anvendes inden for et stort pH-område, i praksis ved pH-værdier på mellem 4,5 og 8, og det er således ikke nødvendigt at foretage en forudgående justering af 25 pH i det vand, der skal behandles.As already mentioned, the condensed melamine / glyoxal / formaldehyde or melamine / urea / glyoxal / formaldehyde resins can be used within a large pH range, in practice at pH values of between 4.5 and 8, and thus no prior adjustment of 25 pH is needed in the water to be treated.
I lighed med alle andre koaguleringsmidler er det af betydning at foretage blandingen af koaguleringsmidlet og vandet, som skal bringes til at flokkulere, så hurtigt 30 som muligt. Til dette formål er det tilrådeligt at anvende eksempelvis en vandstrålepumpe. De dannede flokke opnår almindeligvis optimal størrelse efter en halv times forløb. 1As with all other coagulants, it is important to make the mixture of the coagulant and water to be flocculated as quickly as possible. For this purpose, it is advisable to use, for example, a water jet pump. The flocks formed generally achieve optimum size after half an hour. 1
Som nævnt i det foregående er de kvaterniserede melamin/ glyoxal/formaldehyd- eller melamin/urinstof/glyoxal/for-maldehyd-harpikser i særlig grad anvendelige til behand- 6As mentioned above, the quaternized melamine / glyoxal / formaldehyde or melamine / urea / glyoxal / formaldehyde resins are particularly useful for treatment.
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ling af råvand (overfladevand eller grundvand) og spildevand (industrielle udledninger, skærevæsker indeholdende metalpartikler og lignende), hvori de faste, mineralske eller organiske stoffer befinder sig i suspension eller 5 på mere eller mindre kolloid form (lerarter, bentonitter, tangarter, støvpartikler, jernoxider og lignende) eller i emulsion (olier, carbonhydrider eller lignende), eller hvori partiklerne er farvede (tekstilfarver og lignende).raw water (surface or groundwater) and wastewater (industrial discharges, cutting fluids containing metal particles and the like) in which the solid, mineral or organic substances are in suspension or in more or less colloidal form (clays, bentonites, seaweeds, dust particles, iron oxides and the like) or in emulsion (oils, hydrocarbons or the like) or in which the particles are colored (textile colors and the like).
De omhandlede harpikser kan ligeledes med held anvendes 10 til suspensioner og emulsioner i relativt høje koncentrationer.The resins in question can also be used successfully for suspensions and emulsions at relatively high concentrations.
Behandlingen ifølge opfindelsen muliggør en genanvendelse af det behandlede vand, idet virkningen af behandlingen 15 består i at befri vandet for urenheder, uden at der samtidigt sker noget totalt tab af de øvrige egenskaber, som vandet eventuelt kan besidde som følge af tilstedeværelsen af vigtige opløste forbindelser. Dette er f.eks. tilfældet ved visse skærevæsker, som indeholder antikor-20 rosive additiver, dvs. væsker, som efter at være blevet befriet for indholdet af metalpartikler stadig besidder deres antikorrosive egenskaber, således at de påny kan anvendes efter deres formål. Dette er også tilfældet for emulsioner af typen olie-i-vand eller vand-i-olie. Be-25 handlingen ifølge opfindelsen muliggør en adskillelse af de flydende faser og genanvendelse af den vandige fase.The treatment according to the invention enables the reuse of the treated water, the effect of the treatment 15 being to liberate the water from impurities without at the same time any total loss of the other properties which the water may possibly possess due to the presence of important dissolved compounds. . This is e.g. in the case of certain cutting fluids containing anticorrosive additives, ie. liquids which, after being liberated from the contents of metal particles, still possess their anti-corrosive properties so that they can be reused according to their purpose. This is also the case for oil-in-water or water-in-oil emulsions. The treatment according to the invention allows separation of the liquid phases and reuse of the aqueous phase.
Man kan også nævne vand indeholdende farvestof, som efter behandling kan genanvendes. 1 35You can also mention water containing dye which can be recycled after treatment. 1 35
De følgende eksempler illustrerer nærmere den foreliggende opfindelse.The following examples further illustrate the present invention.
EKSEMPEL 1EXAMPLE 1
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Fremstilling af harpikser, som kan anvendes ifølge opfindelsen 5Preparation of resins which can be used according to the invention 5
Harpiks AResin A
Man blander under omrøring og i nævnte rækkefølge 25,2 g (0,2 mol) melamin, 86 g (0,6 mol) vandig 40% glyoxal og 10 27,2 g (0,4 mol) formaldehyd i form af en 44% vandig op løsning. Blandingen opvarmes til 60 °C på vandbad i 2 timer, hvorefter man ved samme temperatur gradvist tilsætter 12,6 g (0,1 mol) dimethylsulfat. Efter tilsætningen opretholdes opvarmningen og omrøringen i 4 timer og 15 30 minutter. Derefter indstilles koncentrationen til 18% ved fortynding med vand. Lagerstabiliteten af den således fremstillede harpiks er mere end 6 måneder.25.2 g (0.2 mole) of melamine, 86 g (0.6 mole) of aqueous 40% glyoxal and 27.2 g (0.4 mole) of formaldehyde in the % aqueous solution. The mixture is heated to 60 ° C in a water bath for 2 hours, then 12.6 g (0.1 mole) of dimethyl sulfate is gradually added at the same temperature. After the addition, the heating and stirring are maintained for 4 hours and 30 minutes. Then the concentration is adjusted to 18% by dilution with water. The storage stability of the resin thus produced is more than 6 months.
Harpiks BResin B
2020
En blanding af 53,5 g (0,84 mol) 47% vandig formaldehyd, 180 g (1,24 mol) 40% vandig glyoxal, 5 g (0,084 mol) urinstof og 52 g (0,413 mol) melamin opvarmes til 70 °C, og blandingen holdes ved denne temperatur, indtil en ud-25 taget prøve på 1 ml af harpiksen udfælder i 100 ml destilleret vand. Derefter tilsættes gradvist 26 g (0,206 mol) dimethylsulfat, og blandingen holdes i 1 time ved omkring 75 °C. Herefter tilsættes hurtigt 685 g vand, og blandingen afkøles til 30 °C. Herved opnås en 18% har-30 piksopløsning.A mixture of 53.5 g (0.84 mole) of 47% aqueous formaldehyde, 180 g (1.24 mole) of 40% aqueous glyoxal, 5 g (0.084 mole) of urea and 52 g (0.413 mole) of melamine is heated to 70 ° C and the mixture is kept at this temperature until a sample of 1 ml of the resin precipitates in 100 ml of distilled water. Then, 26 g (0.206 mole) of dimethyl sulfate is gradually added and the mixture is maintained for about 1 hour at about 75 ° C. Then 685 g of water is quickly added and the mixture is cooled to 30 ° C. This results in an 18% resin solution.
Harpiks CResin C
Man går frem under samme betingelser som beskrevet oven-35 for under harpiks B, idet dog opvarmningen forlænges til 2 timer ved 70 °C til 75 °C efter tilsætning af dimethylsulfat. Viskositeten af den færdige 18% harpiksopløsning 8The reaction is carried out under the same conditions as described above for resin B, however the heating is extended to 2 hours at 70 ° C to 75 ° C after the addition of dimethyl sulfate. Viscosity of the finished 18% resin solution 8
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er 17 cP ved 20 °C.is 17 cP at 20 ° C.
Harpiks DResin D
5 Man går frem under samme betingelser som beskrevet for harpiks B„ idet dog opvarmningen forlænges til 5 timer ved 70 °C til 75 °C efter tilsætning af dimethylsulfat. Viskositeten af den færdige 18% harpiksopløsning er 32 cP ved 20 °C.The reaction is carried out under the same conditions as described for resin B ', but the heating is extended to 5 hours at 70 ° C to 75 ° C after the addition of dimethyl sulfate. The viscosity of the finished 18% resin solution is 32 cP at 20 ° C.
1010
Harpiks EResin E
Man går frem under samme betingelser som beskrevet for harpiks B, idet dog opvarmningen opretholdes i 5 timer 15 ved 85 °C til 90 °C efter tilsætning af dimethylsulf at. Viskositeten af den færdige 18% harpiksopløsning er 72 cP ved 20 °C.Proceed under the same conditions as described for resin B, however the heating is maintained for 5 hours at 85 ° C to 90 ° C after the addition of dimethyl sulfate. The viscosity of the finished 18% resin solution is 72 cP at 20 ° C.
Harpiks FResin F
2020
Man går frem under samme betingelser som beskrevet for harpiks C, idet man dog anvender 160,5 g (2,52 mol) vandig 47% formaldehyd.Proceed under the same conditions as described for resin C, however, using 160.5 g (2.52 moles) of aqueous 47% formaldehyde.
25 EKSEMPEL 2EXAMPLE 2
Dette eksempel beskriver flokkulation af suspensioner (40 mg/1) af fine lerpartikler i vand. For at opnå en god klaring er det nødvendigt at anvende følgende doseringer 30 af flokkulationsmiddel: 40 ppm A12(S04)g.l8H20 eller 20 ppm aluminiumpolychlorid eller 5 ppm harpiks B (på tør basis).This example describes flocculation of suspensions (40 mg / l) of fine clay particles in water. To obtain good clearance, it is necessary to use the following dosages of flocculant: 40 ppm A12 (SO4) g.18H20 or 20 ppm aluminum polychloride or 5 ppm resin B (on a dry basis).
Man konstaterer desuden, at dekanteringen varer meget længere, når man anvender mineralske produkter, end når 35Furthermore, it is found that decantation lasts much longer when using mineral products than when 35
DK 160416 BDK 160416 B
9 man anvender harpiks B.9 resin B.
EKSEMPEL 3 5 Behandling af overfladevand med henblik på at opnå vand med en uklarhed på mindre end 2 Jackson-enheder.EXAMPLE 3 5 Treatment of Surface Water to Obtain Water with a Cloud of Less Than 2 Jackson Units.
Til bestemmelse af vands uklarhed i Jackson-enheder sammenligner man vandprøvens uklarhed ved nephelometri med 10 en enhedsskala af opaliserende opløsninger, som er opnået ved at fortynde en prøvesuspension, som pr. definition har en uklarhed på 400 Jackson-enheder, med vand. Til fremstilling af denne prøvesuspension blandes 5 ml af en opløsning af 1 g hydrazinsulfat i 100 ml vand med 5 ml af 15 en opløsning af 1 g hexamethylentetramin i 100 ml vand, hvorefter denne blanding fortyndes til 100 ml med vand.To determine water cloudiness in Jackson units, the water sample cloudiness in nephelometry is compared to a unit scale of opalescent solutions obtained by diluting a sample suspension which per definition has a haze of 400 Jackson units, with water. To prepare this sample suspension, 5 ml of a solution of 1 g of hydrazine sulphate in 100 ml of water is mixed with 5 ml of a solution of 1 g of hexamethylenetetramine in 100 ml of water and then this mixture is diluted to 100 ml with water.
Overfladevandet, som skulle behandles, udviste en uklarhed på 15 Jackson-enheder. For at reducere uklarheden til 20 2 Jackson-enheder var det nødvendigt at anvende 60 ppm aluminiumsulfat eller 40 ppm aluminiumsulfat kombineret med 0,2 ppm af et anionisk flokkulationsmiddel bestående af en anionisk acrylamid-natriumacrylat-copolymer i mol-forholdet 80:20.The surface water to be treated showed a haze of 15 Jackson units. To reduce the fuzziness to 20 2 Jackson units, it was necessary to use 60 ppm aluminum sulfate or 40 ppm aluminum sulfate combined with 0.2 ppm of an anionic flocculant consisting of an 80:20 anionic acrylamide-sodium acrylate copolymer.
2525
Det samme resultat kunne opnås med 5 ppm (på tør basis) af harpiks B, og desuden er mængden af slam, som opnås med denne harpiks, fem gange mindre end den mængde, som opnås med aluminiumsulfat, hvilket er en klar gevinst med 30 hensyn til den nødvendige apparatstørrelse.The same result could be obtained with 5 ppm (on a dry basis) of resin B, and in addition, the amount of sludge obtained with this resin is five times less than the amount obtained with aluminum sulfate, which is a clear gain with respect to 30 to the required device size.
Det således behandlede vand kan enten benyttes i industrien eller omdannes til drikkevand efter påfølgende behandlinger såsom filtrering igennem aktivt kul og chlore-35 ring.The water thus treated can either be used in the industry or converted into drinking water after subsequent treatments such as filtration through activated carbon and chlorination.
DK 160416 BDK 160416 B
10 EKSEMPEL 4EXAMPLE 4
Sammenligning af harpikserne A til FComparison of the resins A to F
5 I dette eksempel undersøges klaringen af vand fra Seinen.5 In this example, the clearance of water from the Seine is examined.
Prøver af dette vand tilsættes harpikserne A til F i en dosering på 5 ppm. Der omrøres i 3 minutter med høj hastighed og i 17 minutter med lav hastighed, hvorefter man lader prøverne dekantere i 10 minutter. Derefter 10 måles uklarheden af det øverste lag.Samples of this water are added to resins A to F at a dosage of 5 ppm. Stir for 3 minutes at high speed and for 17 minutes at low speed, then allow the samples to decant for 10 minutes. Then, the cloudiness of the top layer is measured.
15 20 25 30 35 1115 20 25 30 35 11
DK 160416 BDK 160416 B
Jackson-enhederJackson devices
Prøve uden harpiks 20 harpiks A 4,5 5 " B 3,5 "C 3,6 " D 3,2 " E 5,1 " F 4,5 10Resin Sample 20 Resin A 4.5 5 "B 3.5" C 3.6 "D 3.2" E 5.1 "F 4.5 10
Det ses af disse tal, at der er relativt lille forskel på virkningen af de undersøgte harpikser.It is seen from these figures that there is relatively little difference in the effect of the resins investigated.
EKSEMPEL 5 15EXAMPLE 5 15
Sammenligning af harpikserne A til FComparison of the resins A to F
I dette eksempel undersøgtes uklarheden af vandige suspensioner indeholdende 0,5 g pr. liter bentonit efter be-20 handling med de forskellige harpikser i en mængde på 5 ppm.In this example, the turbidity of aqueous suspensions containing 0.5 g / ml was investigated. liter of bentonite after treatment with the various resins in an amount of 5 ppm.
Man fremstiller en suspension af bentonit ved at sætte bentonit til vand og lade bentonitten kvælde op i nogle 25 timer under omrøring. Man udtager derefter prøver af suspensionen, til hvilke man sætter de forskellige harpikser. Efter hurtig omrøring i 2 minutter og langsom omrøring i 15 minutter lader man prøverne dekantere i 10 minutter, udtager en del af det øverste lag og måler 30 uklarheden af dette lag.A bentonite suspension is prepared by adding bentonite to water and allowing the bentonite to swell for some 25 hours with stirring. Samples of the suspension are then taken to which the various resins are added. After rapid stirring for 2 minutes and slow stirring for 15 minutes, the samples are allowed to decant for 10 minutes, remove a portion of the upper layer and measure the cloudiness of this layer.
3535
DK 160416 BDK 160416 B
12 J ackson-enheder12 J axon units
Prøve uden harpiks 26 harpiks A 2,4 5 " B 3,4 "C 2,5 D 2,5 " E 3,5 F 2,9 10Resin Sample 26 Resin A 2.4 5 "B 3.4" C 2.5 D 2.5 "E 3.5 F 2.9 10
Som i det foregående forsøg konstaterer man, at der kun er ringe forskel på effektiviteten af de forskellige undersøgte harpikser.As in the previous experiment, it is found that there is little difference in the effectiveness of the various resins investigated.
15 EKSEMPEL 6EXAMPLE 6
Fjernelse af olie fra raffinaderi-spildevandRemoval of oil from refinery wastewater
Indholdet af olie i spildevandet fra et raffinaderi be-20 stemmes efter normen AFNOR T 90-203 fra august 1973, nærmere bestemt ved ekstraktion med carbontetrachlorid, fjernelse af carbonhydrider af andre organiske stoffer ved chromatografi på en kolonne med syntetisk silicium-dioxid modificeret med 15,5% magnesiumoxid og endelig 25 spektrofotometrisk bestemmelse i området 3420 nm.The content of oil in the wastewater from a refinery is determined according to the standard AFNOR T 90-203 of August 1973, specifically by extraction with carbon tetrachloride, removal of hydrocarbons by other organic substances by chromatography on a column of synthetic silica modified by 15 , 5% magnesium oxide and finally 25 spectrophotometric determination in the region of 3420 nm.
Spildevandet indeholdt 250 ppm olie. Det blev behandlet varmt (60-70 °C) med 5 ppm harpiks. Efter behandlingen med harpiks A indeholdt vandet 4 ppm olie. Efter behand-30 ling med harpiks B indeholdt vandet ligeledes 4 ppm olie.The wastewater contained 250 ppm of oil. It was treated hot (60-70 ° C) with 5 ppm resin. After treatment with resin A, the water contained 4 ppm of oil. After treatment with resin B, the water also contained 4 ppm of oil.
Der opnås således en fremragende fjernelse af olie med de anvendte harpikser, og rensningen kan gennemføres ved en relativt høj temperatur.Thus, excellent removal of oil is obtained with the resins used and the purification can be carried out at a relatively high temperature.
35 EKSEMPEL 7 13EXAMPLE 7 13
DK 160416 BDK 160416 B
Affarvning af spildevand fra tekstilindustrien 5 Vandprøver med pH 7, som var farvet blå af forskellige naturligt forekommende farvestoffer, blev totalt affarvet ved behandling med 200 ppm harpiks B, medens prøverne ved behandling med 400 ppm aluminiumsulfat stadig var svagt farvede.Decolourization of Wastewater from the Textile Industry 5 Water samples of pH 7, which were colored blue by various naturally occurring dyes, were totally decolorized by treatment with 200 ppm resin B, while the samples by treatment with 400 ppm aluminum sulfate were still slightly colored.
10 EKSEMPEL 8EXAMPLE 8
En spildevandsprøve indeholdende 50 ppm af et surt brunt farvestof (Brun LANAPERL) blev behandlet med 200 ppm af 15 en kvaterniseret aminoplast-harpiks (D) (på tør basis).A wastewater sample containing 50 ppm of an acidic brown dye (Brown LANAPERL) was treated with 200 ppm of a quaternized aminoplastic resin (D) (on a dry basis).
Herved blev vandprøven fuldstændigt affarvet og kunne derefter genanvendes til skylning.In this way, the water sample was completely decolorized and could then be reused for rinsing.
EKSEMPEL 9 20EXAMPLE 9 20
Behandling af en skærevæskeTreatment of a cutting fluid
En skærevæske i form af en vandig opløsning, anvendt ved forarbejdning af metaller og indeholdende overfladeaktive 25 stoffer i opløsning, korrosionsinhibitorer og bakteri-cider, er efter anvendelsen sort på grund af tilsmudsning med metalpartikler, olie og støv. Når en sådan væske behandles med 200 ppm af en kvaterniseret aminoplast-harpiks (D) (på tør basis) og derefter filtreres, bliver den 30 påny klar, samtidig med at den i det væsentlige beholder de antikorrosive egenskaber, som den oprindeligt havde.A cutting liquid in the form of an aqueous solution used in the processing of metals and containing surfactants in solution, corrosion inhibitors and bactericides is black after application due to contamination with metal particles, oil and dust. When such a liquid is treated with 200 ppm of a quaternized aminoplast resin (D) (on a dry basis) and then filtered, it becomes clear again while retaining substantially the anticorrosive properties it originally had.
Den kan derefter påny anvendes, om nødvendigt efter genjustering af indholdet af de forskellige opløste stoffer.It can then be reused if necessary after re-adjusting the contents of the various solutes.
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Claims (9)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7812092 | 1978-04-24 | ||
| FR7812092A FR2424234A1 (en) | 1978-04-24 | 1978-04-24 | RAW WATER AND WASTE WATER TREATMENT PROCESS |
| PCT/FR1979/000035 WO1979000975A1 (en) | 1978-04-24 | 1979-04-24 | Process for treating crude waters and waste waters and application thereof |
| FR7900035 | 1979-04-24 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK548879A DK548879A (en) | 1979-12-21 |
| DK160416B true DK160416B (en) | 1991-03-11 |
| DK160416C DK160416C (en) | 1991-09-16 |
Family
ID=9207520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK548879A DK160416C (en) | 1978-04-24 | 1979-12-21 | PROCEDURES FOR TREATMENT OF RAWWATER AND WASTEWATER |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0005390B1 (en) |
| JP (1) | JPS6222676B2 (en) |
| CA (1) | CA1124417A (en) |
| DE (1) | DE2961410D1 (en) |
| DK (1) | DK160416C (en) |
| ES (1) | ES479839A1 (en) |
| FR (1) | FR2424234A1 (en) |
| SU (1) | SU1003747A3 (en) |
| WO (1) | WO1979000975A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2519009A1 (en) * | 1981-12-29 | 1983-07-01 | Hoechst France | NOVEL CATIONIC AMINOPLASTIC RESIN, PROCESS FOR OBTAINING SAME AND APPLICATION THEREOF IN WATER TREATMENT |
| DE4110736A1 (en) * | 1991-04-03 | 1992-10-08 | Rotta Innovations Gmbh Dr | Heat degradable polymer particles used in water treatment - comprising amino resin matrix with immobilised functional polymer |
| US8127930B2 (en) | 2004-12-23 | 2012-03-06 | Georgia-Pacific Chemicals Llc | Amine-aldehyde resins and uses thereof in separation processes |
| US8011514B2 (en) | 2004-12-23 | 2011-09-06 | Georgia-Pacific Chemicals Llc | Modified amine-aldehyde resins and uses thereof in separation processes |
| US8702993B2 (en) | 2004-12-23 | 2014-04-22 | Georgia-Pacific Chemicals Llc | Amine-aldehyde resins and uses thereof in separation processes |
| US8757389B2 (en) | 2004-12-23 | 2014-06-24 | Georgia-Pacific Chemicals Llc | Amine-aldehyde resins and uses thereof in separation processes |
| US8092686B2 (en) | 2004-12-23 | 2012-01-10 | Georgia-Pacific Chemicals Llc | Modified amine-aldehyde resins and uses thereof in separation processes |
| US7913852B2 (en) * | 2004-12-23 | 2011-03-29 | Georgia-Pacific Chemicals Llc | Modified amine-aldehyde resins and uses thereof in separation processes |
| FR3044655B1 (en) * | 2015-12-07 | 2021-06-11 | Snf Sas | AQUEOUS EFFLUENT TREATMENT PROCESS |
| CN112062362B (en) * | 2020-09-08 | 2023-02-03 | 沙县宏盛塑料有限公司 | Treatment method of high-concentration aldehyde-containing phenolic resin wastewater |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3484837A (en) * | 1968-09-09 | 1969-12-16 | Reichhold Chemicals Inc | Process for removal of inorganic and organic matter from waste water systems |
| NL137596C (en) * | 1968-12-30 | Nobel Hoechst Chimie | ||
| US3880753A (en) * | 1971-01-18 | 1975-04-29 | American Cyanamid Co | Flocculation of suspended solids in aqueous medium by action of cyclo-1,1-diallylgrianidine polymer |
| JPS5318343B2 (en) * | 1974-01-14 | 1978-06-14 |
-
1978
- 1978-04-24 FR FR7812092A patent/FR2424234A1/en active Granted
-
1979
- 1979-04-23 ES ES479839A patent/ES479839A1/en not_active Expired
- 1979-04-23 CA CA326,159A patent/CA1124417A/en not_active Expired
- 1979-04-23 JP JP50068379A patent/JPS6222676B2/ja not_active Expired
- 1979-04-23 EP EP19790400256 patent/EP0005390B1/en not_active Expired
- 1979-04-23 DE DE7979400256T patent/DE2961410D1/en not_active Expired
- 1979-04-24 WO PCT/FR1979/000035 patent/WO1979000975A1/en unknown
- 1979-12-21 DK DK548879A patent/DK160416C/en not_active IP Right Cessation
- 1979-12-21 SU SU792854547A patent/SU1003747A3/en active
Also Published As
| Publication number | Publication date |
|---|---|
| DK548879A (en) | 1979-12-21 |
| EP0005390B1 (en) | 1981-11-25 |
| EP0005390A1 (en) | 1979-11-14 |
| DE2961410D1 (en) | 1982-01-28 |
| ES479839A1 (en) | 1979-11-16 |
| JPS6222676B2 (en) | 1987-05-19 |
| FR2424234B1 (en) | 1980-10-24 |
| FR2424234A1 (en) | 1979-11-23 |
| JPS55500260A (en) | 1980-05-01 |
| DK160416C (en) | 1991-09-16 |
| SU1003747A3 (en) | 1983-03-07 |
| WO1979000975A1 (en) | 1979-11-29 |
| CA1124417A (en) | 1982-05-25 |
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