DK158141B - PROCEDURE FOR MANUFACTURING AN ANION EXCHANGE AND USE THEREOF - Google Patents
PROCEDURE FOR MANUFACTURING AN ANION EXCHANGE AND USE THEREOF Download PDFInfo
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/16—Cellulose or wood; Derivatives thereof
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Abstract
Description
iin
DK 158141 BDK 158141 B
Opfindelsen angår en fremgangsmåde til fremstilling af en anion-bytter, der navnlig egner sig til rensning af spildevand, hvor et cellulosemateriale omsættes med polyethylenimin i et vandigt medium og det derved dannede produkt udvindes fra reaktionsblandingen og 5 det ejendommelige ved opfindelsen er, at der som cellulosemateriale anvendes bark, som i separate trin er forbehandlet med stærk base og stærk syre, idet omsætningen foregår ved en pH-værdi på 2 til 6.The invention relates to a process for preparing an anion exchanger which is particularly suitable for purifying wastewater, wherein a cellulose material is reacted with polyethyleneimine in an aqueous medium and the product thus obtained is recovered from the reaction mixture and the characteristic of the invention is that cellulose material is used bark which is pre-treated in separate steps with strong base and strong acid, the reaction being carried out at a pH of 2 to 6.
Rensningen af husholdnings- og industri spildevand er et stigende 10 problem, da der stilles stadig større krav til renheden af det spildevand, der udledes. Ved en spildevandsrensning har kun de metoder, der har en god effektivitet, og som kan gennemføres relativt billigt, praktisk betydning. Et middel til spildevandsrensning må derfor kunne fremstilles med så lave fabrikationsomkostninger som 15 muligt.The purification of domestic and industrial wastewater is an increasing problem, as ever-increasing demands are made on the purity of the effluent discharged. In a wastewater treatment, only those methods that have good efficiency and which can be implemented relatively cheaply have practical significance. A waste water treatment means must therefore be able to be produced with as low a manufacturing cost as possible.
Alt efter oprindelse indeholder spildevandet for det meste høj-molekylære proteiner, lavmolekylære polypeptider og aminosyrer, lipider og sukker. Til fjernelse af nitrogenholdige forbindelser fra 20 spildevand er der hidtil blevet anvendt specielle koaguleringsmetoder, ved hvilke spildevandet tilsættes stoffer, der er i stand til at danne flokkulationer med de forurenende stoffer, hvilke flokkula-tioner bundfældes under sedimentationstrinnet, hvorefter de kan udskilles fra vandet. Eksempler på sådanne flokkuleringsmidler er 25 ligninsul fonsyre og dodecylbenzensul fonsyre. Disse forbindelser er i stand til at flokkulere højmolekylære proteiner, men ikke lavmolekylære nitrogenstofholdige forbindelser, såsom polypeptider og aminosyrer. Navnlig industri spildevand, såsom fra fiskefabrikker og slagterier, lader sig derfor ikke rense med sådanne flokkulerings-30 midler i en grad, der er tilstrækkelig til at spildevandet kan udledes.Depending on the origin, the wastewater contains mostly high-molecular-weight proteins, low-molecular-weight polypeptides and amino acids, lipids and sugars. To remove nitrogenous compounds from 20 wastewater, hitherto, special coagulation methods have been used, in which the wastewater is added to substances capable of forming flocculations with the pollutants, which flocculate precipitated during the sedimentation step, after which they can be separated from the water. Examples of such flocculants are lignin sulphonic acid and dodecylbenzene sulphonic acid. These compounds are capable of flocculating high molecular weight proteins, but not low molecular weight nitrogenous compounds such as polypeptides and amino acids. In particular, industrial wastewater, such as from fish factories and slaughterhouses, cannot therefore be cleaned with such flocculants to a degree sufficient to allow the wastewater to be discharged.
Det er velkendt at rense spildevand ved hjælp af ionbyttere, dog har denne metode ikke tidligere vist sig økonomisk forsvarlig. Kendte 35 ionbyttere på cellulosebasis består af cellulosephosphatestere eller cel!ulosesul fatestere, der er fremstillet ved at omsætte cellulose med SOg. Men fremstillingen af sådanne ionbyttere er for dyr til at starte en produktion heraf til spildevandsrensning.It is well known to purify wastewater using ion exchangers, however, this method has not previously proved economically sound. Known cellulose base ion exchangers consist of cellulose phosphate esters or cellulose sulphate esters prepared by reacting cellulose with SOg. But the manufacture of such ion exchangers is too expensive to start a production thereof for wastewater treatment.
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Det er fra DE AS nr. 2021629 kendt at opnå ionbyttere ved omsætning af cellulose eller cel!ulosederivater, d.v.s. vel definerede kemiske forbindelser, med polyethylenimin.It is known from DE AS No. 2021629 to obtain ion exchangers by reacting cellulose or cellulose derivatives, i.e. well-defined chemical compounds, with polyethyleneimine.
5 I US-A-3.714.010 beskrives fremstillingen af anionbyttermembraner ved imprægnering af en cellulosemembran med polyethylenimin og påfølgende krydsbinding med aldehyder eller dimethylolforbi ndel ser. Anvendelsen af rå, urensende naturprodukter som cellulosederivat er ikke beskrevet i de to patentskrifter.US-A-3,714,010 describes the preparation of anion exchange membranes by impregnating a cellulose membrane with polyethyleneimine and subsequent cross-linking with aldehydes or dimethylol compounds. The use of raw, uncleaned natural products as cellulose derivatives is not described in the two patents.
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Formålet med opfindelsen er at fremstille en ionbytter, som er effektiv til spildevandsrensning, og som kan fremstilles billigt.The object of the invention is to prepare an ion exchanger which is effective for wastewater treatment and which can be manufactured inexpensively.
Denne ionbytter skal fjerne anioniske organiske forbindelser, såsom proteiner og andre nitrogenforbindelser, fra spildevandet. Ion-15 bytteren skal også kunne regenereres for at gøre fjernelsesproblemet hvad angår den brugte ionbytter mindst mulig. Dette formål opnås med fremgangsmåden ifølge opfindelsen.This ion exchanger must remove anionic organic compounds, such as proteins and other nitrogen compounds, from the wastewater. The ion-15 exchanger must also be regenerated to minimize the removal problem of the used ion exchanger. This object is achieved with the method according to the invention.
Det er overraskende, at det ved fremgangsmåden ifølge opfindelsen 20 anvendte udgangsmateriale har et betydeligt større antal reaktive grupper, der er i stand til at reagere med polyethylenimin, således at en derved frembragt anionbytter besidder en væsentligt højere ionbytterkapacitet end en ionbytter fremstillet af ren cellulose eller et defineret cellulosederivat.Surprisingly, the starting material used in the process of the invention 20 has a significantly greater number of reactive groups capable of reacting with polyethyleneimine, so that an anion exchanger thus produced has a significantly higher ion exchange capacity than an ion exchanger made from pure cellulose or a defined cellulose derivative.
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Udvindingen af ionbytteren fra reaktionsblandingen kan ske ved dekantering, filtrering eller en anden adskil!el sesmetode, og ionbytteren kan efter udskillelsen fra reaktionsblandingen vaskes og/eller tørres. Men det er hensigtsmæssigt at forhandle ionbytteren 30 uden forudgående vask og tørring, og først vaske den med vand umiddelbart før anvendelse.The ion exchanger is recovered from the reaction mixture by decantation, filtration or another separation method, and the ion exchanger can be washed and / or dried after separation from the reaction mixture. However, it is convenient to negotiate the ion exchanger 30 without prior washing and drying, and first washing it with water immediately before use.
Reaktionen mellem barken og polyethyleniminen kan ske ved omgivelsestemperatur, dog er det for at afkorte reaktionstiden og forøge 35 omsætningsgraden hensigtsmæssigt at arbejde ved forhøjede temperaturer, fordelagtigt i området fra 40 til 90°C, fortrinsvis i området fra 60 til 70°C.The reaction between the bark and the polyethylene imine can take place at ambient temperature, however, in order to shorten the reaction time and increase the conversion rate, it is convenient to operate at elevated temperatures, advantageously in the range of 40 to 90 ° C, preferably in the range of 60 to 70 ° C.
Reaktionsblandingens pH-værdi indstilles hensigtsmæssigt til en 3The pH of the reaction mixture is suitably adjusted to a 3
- DK 158141B- DK 158141B
pH-værdi i området fra 4 til 5, hvilket kan ske ved hjælp af en syre, fortrinsvis saltsyre. Reaktionstiden afhænger af de øvrige reaktionsbetingelser, navnlig også af, om omsætningen sker under henstand eller under omrøring. Reaktionstiden er forholdsvis lang og 5 ligger almindeligvis mellem 2 timer og 4 dage.pH value in the range of 4 to 5, which can be accomplished by an acid, preferably hydrochloric acid. The reaction time depends on the other reaction conditions, in particular also on whether the reaction takes place during standstill or with stirring. The reaction time is relatively long and generally lies between 2 hours and 4 days.
Reaktionshastigheden afhænger af koncentrationen af polyethylen-iminopløsningen. Denne koncentration skal derfor være mindst 1 vægt%, dog helst mindst 2 vægt%, hvilket kan opnås ved at anvende en 10 opløsning indeholdende 5 til 40 vægt%.The rate of reaction depends on the concentration of the polyethylene imine solution. Therefore, this concentration should be at least 1% by weight, but preferably at least 2% by weight, which can be achieved by using a solution containing 5 to 40% by weight.
Polyethyleniminopløsningen kan anvendes flere gange, da den efter den første anvendelse og også efter flere ganges anvendelse endnu indeholder tilstrækkelig polyethylenimin til at kunne anvendes til 15 yderligere reaktion. Almindeligvis forbruges 5 til 10% af polyethylenimi nen ved fremstillingen af ionbytteren.The polyethyleneimine solution can be used several times since after the first use and also after several times it still contains enough polyethyleneimine to be used for further reaction. Generally, 5 to 10% of the polyethylene imine is consumed in the preparation of the ion exchanger.
For at opnå en god aktivering af materialet og binde tilstrækkelig polyethylen til cellulosen eller cellulosederivatet ligger reak-20 tionstiden hensigtsmæssigt mellem 1 og 4 dage.In order to obtain a good activation of the material and to bind sufficient polyethylene to the cellulose or cellulose derivative, the reaction time is conveniently between 1 and 4 days.
Som udgangsmateriale anvendes hensigtsmæssigt bark, som giver en overraskende høj ionbytterkapacitet.As a starting material, bark is suitably used which provides a surprisingly high ion exchange capacity.
25 Et andet foretrukket udgangsmateriale, er en blanding, der kan opnås fra bark, når denne behandles i separate trin med al kali lud og med svovlsyre, således som beskrevet i en sideløbende ansøgning indleveret samme dag. De forbindelser, der findes i et sådant udgangsprodukt, er ikke defineret, men det er dog klart, at de indeholder 30 svovlholdige, stærkt sure grupper, såsom sure sulfatestergrupper eller sulfonsyregrupper, såvel som carboxyl syregrupper og hydroxyl-grupper.Another preferred starting material is a mixture obtainable from bark when treated in separate steps with all potassium lye and with sulfuric acid, as described in a parallel application filed the same day. The compounds found in such a starting product are not defined, but it is clear that they contain 30 sulfur-containing, highly acidic groups, such as acid sulfate ester groups or sulfonic acid groups, as well as carboxylic acid groups and hydroxyl groups.
Dette udgangsmateriale fremstilles hensigtsmæssigt ved, at findelt 35 bark, der har en middel parti kel større! se på fra 0,5 til 5 mm, fortrinsvis fra 1 til 3 mm, først behandles med en alkalilud, navnlig natronlud, på mindst 5 vægt%, fortrinsvis på fra 20 til 40 vægt%, at materialet derefter vaskes med vand, hensigtsmæssigt til en pH-værdi under 9, hvorefter det behandles med en 50 til 65 vægt% svovlsyre ogThis starting material is conveniently prepared by having finely divided bark having a mean particle size greater! consider from 0.5 to 5 mm, preferably from 1 to 3 mm, first treated with an alkali liquor, in particular baking soda, of at least 5% by weight, preferably of from 20 to 40% by weight, then the material is washed with water, conveniently for a pH below 9, after which it is treated with a 50 to 65% by weight sulfuric acid and
DK 158141 BDK 158141 B
4 til slut påny vaskes med vand, fortrinsvis til en pH-værdi på over 4. Behandlingstiden med al kali lud ligger mellem 0,5 og 20 timer, fortrinsvis mellem 3 og 10 timer, og behandlingen med svovlsyre ligger mellem 0,5 og 8 timer, og fortrinsvis mellem 1 og 6 timer.Finally, 4 is again washed with water, preferably to a pH greater than 4. The treatment time with all potassium liquor is between 0.5 and 20 hours, preferably between 3 and 10 hours, and the treatment with sulfuric acid is between 0.5 and 8 hours. and preferably between 1 and 6 hours.
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Navnlig når den ionbytter, der er fremstillet ved reaktionen med polyethylenimin, anvendes til spildevandsrensning, er det hensigtsmæssigt at blande anionbytteren med aktiveret lerjord, fortrinsvis Al2°3, hvorh°s blandingsforholdet mellem ionbytteren og aktiveret 10 lerjord hensigtsmæssigt ligger mellem 2:1 og 1:4, f.eks. 1:2. Denne sidste værdi gælder navnlig når blandingen anvendes til rensning af kommunalt spildevand.In particular, when the ion exchanger produced by the reaction with polyethyleneimine is used for wastewater purification, it is convenient to mix the anion exchanger with activated clay soil, preferably Al : 4, e.g. 1: 2. This latter value is especially true when the mixture is used for municipal wastewater treatment.
Lerjorden kan hensigtsmæssigt aktiveres ved behandling med salpe-15 tersyre, skønt andet aktiveret lerjord også kommer i betragtning.The clay soil can conveniently be activated by treatment with nitric acid, although other activated clay soil is also considered.
Ionbytteren fremstillet ved fremgangsmåden ifølge opfindelsen har en overraskende stor effektivitet ved spildevandsrensning, navnlig høj selektivitet overfor proteiner, polypeptider, aminosyrer, farve-20 stoffer, huminsyrer, uorganiske anioner, såsom chromationer eller phosphationer, og andre forbindelser, der findes i husholdnings-eller erhvervs- og industrispildevand. Således kan denne ionbytter f.eks. anvendes til rensning af kommunalt spildevand, samt spildevand fra tekstilfarvevirksomheder, galvaniseringsvirksomheder, 25 slagterier og fiskefabrikker, spildevand fra koge- og vaskerier samt fra sojabønnefabrikker og lignende.The ion exchanger prepared by the process of the invention has a surprisingly high efficiency in wastewater purification, in particular high selectivity to proteins, polypeptides, amino acids, dyes, humic acids, inorganic anions such as chromium ions or phosphate ions, and other compounds found in household or commercial and industrial wastewater. Thus, this ion exchanger can e.g. used for the purification of municipal wastewater, as well as wastewater from textile dyeing companies, galvanizing companies, 25 slaughterhouses and fish factories, wastewater from boilers and laundries and from soybean factories and the like.
Når anionbytteren fremstillet ved fremgangsmåden ifølge opfindelsen blandes med cellulosekationbytter og aktiveret lerjord, såsom f.eks.When the anion exchanger prepared by the process of the invention is mixed with cellulose cation exchanger and activated clay soil such as e.g.
30 clinoptilolit, i et forhold mellem 2:2:1 og 1:1:4, kan den også anvendes til recirkulering af vand fra fiskeavl. Da clinoptilolit er i. stand til at fjerne ammonium, er det ved at anvende denne blanding muligt at opnå en fuldstændig fjernelse af nitrogenforbindelser i vand fra fiskeavl.30 clinoptilolite, in a ratio of 2: 2: 1 to 1: 1: 4, it can also be used to recycle water from fish breeding. Since clinoptilolite is capable of removing ammonium, by using this mixture it is possible to achieve complete removal of nitrogen compounds in fish breeding water.
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Anionbytteren fremstillet ved fremgangsmåden ifølge opfindelsen kan i fornøden tilfælde let regenereres ved eluering med natronlud eller en vandig opløsning, der indeholder en blanding af natronlud og kogsalt. Til regenerering anvendes hensigtsmæssigt en opløsning på 5The anion exchanger prepared by the process of the invention can, if necessary, be easily regenerated by elution with baking soda or an aqueous solution containing a mixture of baking soda and boiling salt. For regeneration, a solution of 5 is suitably used
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0,1 til 1,5 M NaOH samt 0,5 til 2 M NaCl. Efter regenerering kan der ske en reaktivering ved behandling med polyethylenimin.0.1 to 1.5 M NaOH and 0.5 to 2 M NaCl. After regeneration, reactivation may occur by treatment with polyethyleneimine.
EKSEMPELEXAMPLE
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Den cel!ulosederivatbi ånding, der anvendtes som udgangsmateriale, fremstilledes på følgende måde. Ved hjælp af en snittemaskine findeltes fyrretræsbark til en partikelstørrelse på fra 0,5 til 3 mm. Den findelte bark overhældtes i en reaktionsbeholder med 2 M 10 natronlud, indtil al barken var dækket. Reaktionsblandingen henstod i 7 timer. Derefter fjernedes natronluden og den behandlede bark vaskedes med vand indtil en pH-værdi på 9. Barken dækkedes derefter med 65% svovlsyre og blandingen henstod 4 timer. Svovlsyren fjernedes derefter, og det faste reaktionsprodukt vaskedes flere gange 15 med ledningsvand, indtil pH-værdien lå over 4.The cellulose derivatives used as starting material were prepared as follows. Using a cutting machine, pine bark is comminuted to a particle size of 0.5 to 3 mm. The finely divided bark was poured into a reaction vessel with 2 M 10 baking soda until all the bark was covered. The reaction mixture was allowed to stand for 7 hours. The baking soda was then removed and the treated bark washed with water until a pH of 9. The bark was then covered with 65% sulfuric acid and the mixture was allowed to stand for 4 hours. The sulfuric acid was then removed and the solid reaction product washed several times with tap water until the pH was above 4.
En ca. 7% polyethyleniminopløsning i vand indstilledes til pH 4,5 med saltsyre. Udgangsmaterialet, der er fremstillet som ovenfor beskrevet, dækkedes med denne opløsning, og reaktionsblandingen 20 opvarmedes 5 timer ved 70°C og henstod derefter 3 dage ved stuetemperatur. Derefter frafiltreredes det fremstillede produkt, og filtratet kunne anvendes igen.One approx. 7% polyethyleneimine solution in water was adjusted to pH 4.5 with hydrochloric acid. The starting material prepared as described above was covered with this solution and the reaction mixture was heated for 5 hours at 70 ° C and then allowed to stand for 3 days at room temperature. Then the product obtained was filtered off and the filtrate could be used again.
Umiddelbart før anvendelse vaskedes den således opnåede fugtige 25 ionbytter flere gange med vand.Immediately before use, the thus obtained moist ion exchanger was washed several times with water.
Til bestemmelse af selektivitetkoefficienter fremstilledes opløsninger af azofarvestoffer, dodecylbenzensul fonat (DBS), huminsyre og kaliumchromat, og de blev anbragt på en anionbyttersøjle. Der blev 30 anvendt en glassøjle fyldt med anionbytter og med en diameter på 2,5 cm. Lagtykkelsen var 30 cm og strømhastigheden var 15 meter pr. time. Afløbet fra søjlen analyseredes for hver 500 ml.To determine selectivity coefficients, solutions of azo dyes, dodecylbenzenesulfonate (DBS), humic acid and potassium chromate were prepared and placed on an anion exchange column. A glass column filled with anion exchanger and 2.5 cm in diameter was used. The layer thickness was 30 cm and the flow rate was 15 meters per second. hour. The drain from the column was analyzed for every 500 ml.
Den fundne selektivitetskoefficient angiver den procentuelle mængde 35 af en substans, der fortrinsvis bindes til ionbytteren i forhold til natriumchlorid, når ionbytteren behandles med en opløsning, hvori det opløste stof indeholder 50% af den pågældende substans og 50% natriumchlorid.The selectivity coefficient found indicates the percent amount of a substance which is preferably bound to the ion exchanger relative to sodium chloride when the ion exchanger is treated with a solution in which the solute contains 50% of the substance and 50% sodium chloride.
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Der opnåedes følgende selektivitetskoefficienter for de forskellige substanser:The following selectivity coefficients were obtained for the various substances:
TABEL ITABLE I
5 25 mg/liter af den pH af den opløs opløsning, der skal ning, der skal Selektivitetsbehandles_ behandles_ koefficient Rødt azofarvestof 6,8 til 7,2 675 25 mg / liter of the pH of the solution to be solved to be selectivity-treated_ treated_ coefficient Red azo dye 6.8 to 7.2 67
Gult azofarvestof 6,8 til 7,2 35 10 DBS 6,8 til 7,2 50Yellow azo dye 6.8 to 7.2 DBS 6.8 to 7.2 50
Huminsyre 6,0 til 6,5 100Humic acid 6.0 to 6.5 100
Cr04" 6,5 til 6,8 19Cr04 "6.5 to 6.8 19
En ionbytter, der fremstilles som ovenfor beskrevet, blandedes med 15 aktiveret A^O^ i et sådant mængdeforhold, at blandingen bestod af 2/3 aktiveret AlgOj og V3 ionbytter. Denne blanding blev anvendt til at prøve at fjerne phosphat fra en vandig opløsning. Blandingen anbragtes i et pilotanlæg med en diameter på 15 cm og en højde på 2 m i en lagtykkelse på 1 m. Den aktiverede lerjord er i stand til at 20 binde orthophosphat, medens ionbytteren fjerner polyphosphat og organisk phosphat. Der anvendtes en gennemløbshastighed på 10 lagvolumener pr. time svarende til ca. 175 liter spildevand pr. time. Spildevandet førtes i opadgående retning gennem søjlen.An ion exchanger prepared as described above was mixed with 15 activated A 2 O 2 in such a ratio that the mixture consisted of 2/3 activated AlgO 2 and V 3 ion exchanger. This mixture was used to try to remove phosphate from an aqueous solution. The mixture is placed in a pilot plant with a diameter of 15 cm and a height of 2 m in a layer thickness of 1 m. The activated clay soil is able to bind orthophosphate, while the ion exchanger removes polyphosphate and organic phosphate. A throughput rate of 10 layer volumes per second was used. per hour corresponding to approx. 175 liters of wastewater per hour. The wastewater was directed upwards through the column.
25 Når søjlen var mættet, blev den regenereret på følgende måde: vask med 35 liter vand, eluering med 25 liter 0,5 M NaOH, vask med 70 liter vand.When the column was saturated, it was regenerated as follows: washing with 35 liters of water, eluting with 25 liters of 0.5 M NaOH, washing with 70 liters of water.
Følgende spildevand behandledes i pilotanlægget: 30 I. Spildevand fra et biologisk filter med et totalt phosphor-indhold på 9,6 mg pr. liter.The following wastewater was treated in the pilot plant: 30 I. Wastewater from a biological filter with a total phosphorus content of 9.6 mg / ml. liter.
II. Spildevand fra et kemisk udfældningsanlæg med et totalt phos-phorindhold på 0,61 mg pr. liter.II. Sewage from a chemical precipitation plant with a total phosphorus content of 0.61 mg per liter.
35 III. Overløb fra et regnvandsbassin med et totalt phosphorindhold på 1,08 mg pr. liter.III. Overflow from a rainwater basin with a total phosphorus content of 1.08 mg per liter.
Søjlen og elueringsvæsken anvendtes 4 gange før det her beskrevne forsøg gennemførtes. Prøver af udløb fra søjlen blev taget hverandenThe column and elution liquid were used 4 times before the experiment described herein was performed. Samples of outlet from the column were taken apart
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7 time og analyseret. Resultaterne gives i de efterfølgende tabeller 2 og 3.7 hours and analyzed. The results are given in the following tables 2 and 3.
Tabel 2 5 _Kapacitet _Slam_ 3 * 3Table 2 5 _Capacity _Slam_ 3 * 3
Indløb Materialevolumen m 1 1/m spildevand.Inlet Material volume m 1 1 / m wastewater.
I ....... 320 5,5 5 0,90 II ...... 2200 38,4 5 0,13 III ..... 1800 31,6 5 0,16 10 3 3 * Der fratrækkes 0,1 m svarende til 0,1 m vaskevand.I ....... 320 5.5 5 0.90 II ...... 2200 38.4 5 0.13 III ..... 1800 31.6 5 0.16 10 3 3 * There subtract 0.1 m corresponding to 0.1 m wash water.
Tabel 3 opløse-Table 3 Solvents
Prøve opløseligt ligt poly- 15 (middelværdi) P total P opløselig ortho-P organisk P phosphatSample soluble poly (average) P total P soluble ortho-P organic P phosphate
Indløb I... 9,6 7,3 6,1 0,7 0,5Inlet I ... 9.6 7.3 6.1 0.7 0.5
Udløb I... 0,95 0,95 0,57 0,2 0,2Output I ... 0.95 0.95 0.57 0.2 0.2
Indløb II.. 0,61 0,37 0,25 0,05 0,05 20 Udløb II.. 0,06 0,06 0,01 0,03 0,02Inlet II .. 0.61 0.37 0.25 0.05 0.05 20 Outlet II .. 0.06 0.06 0.01 0.03 0.02
Indløb III. 1,08 0,51 0,38 0,11 0,04Inlet III. 1.08 0.51 0.38 0.11 0.04
Udløb III. 0,10 0,10 0,03 0,03 0,04 2^ Tabel 2 og 3 viser, at kapaciteten svarer til, at ca. 90% af phos-phatet fjernes.Expiration III. 0.10 0.10 0.03 0.03 0.04 2 ^ Tables 2 and 3 show that the capacity corresponds to approx. 90% of the phosphate is removed.
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Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803048357 DE3048357A1 (en) | 1980-12-20 | 1980-12-20 | METHOD FOR PRODUCING AN ANION EXCHANGER AND USE THEREOF |
| DE3048357 | 1980-12-20 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK561481A DK561481A (en) | 1982-06-21 |
| DK158141B true DK158141B (en) | 1990-04-02 |
| DK158141C DK158141C (en) | 1990-09-03 |
Family
ID=6119869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK561481A DK158141C (en) | 1980-12-20 | 1981-12-17 | PROCEDURE FOR MANUFACTURING AN ANION EXCHANGE AND USE THEREOF |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0054778B1 (en) |
| JP (1) | JPS57127453A (en) |
| AT (1) | ATE16897T1 (en) |
| DE (2) | DE3048357A1 (en) |
| DK (1) | DK158141C (en) |
| FI (1) | FI69572C (en) |
| NO (1) | NO153917C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2657076B1 (en) * | 1990-01-15 | 1992-09-04 | Inst Textile De France | USE OF GRAFT CELLULOSE FOR THE PURIFICATION OF WATER. |
| JPH0687974B2 (en) * | 1990-03-27 | 1994-11-09 | 忠一 平山 | Adsorption material for heat generating substances |
| DE19859746A1 (en) * | 1998-12-23 | 2000-06-29 | Georg Haertel | Materials, for removing heavy metals and organic pollutants from contaminated water, contain cellulose or starch derivative |
| DE19962197A1 (en) * | 1999-12-22 | 2001-07-05 | Innovation Pro Terra Gmbh & Co | Absorber, preferably substance for taking up and / or exchanging ions |
| DE10136527A1 (en) * | 2001-07-26 | 2003-02-13 | Fraunhofer Ges Forschung | Novel optionally crosslinked adducts for use as adsorbents or ion-exchangers are obtained by reacting functionalized renewable materials with polyalkylenepolyamines or polyalkyleneimines |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3393968A (en) * | 1964-06-08 | 1968-07-23 | Agriculture Usa | Cellulose reacted with ethyleneimine in the presence of glacial acetic acid |
| GB1351272A (en) * | 1970-05-02 | 1974-04-24 | Heraeus Gmbh W C | Methods for recovering metal ions from aqueous solutions thereof |
| US3673110A (en) * | 1970-12-28 | 1972-06-27 | Procter & Gamble | Surface-modified cellulose |
| US3714010A (en) * | 1972-01-06 | 1973-01-30 | Us Interior | Preparation of anion exchange membranes from cellulosic sheets |
| US3885069A (en) * | 1972-08-11 | 1975-05-20 | Us Agriculture | Preparation of crosslinked polyethylenimine and impregnation of cellulosic material with in situ crosslink-polymerized ethylenimine |
| JPS5810401B2 (en) * | 1974-10-01 | 1983-02-25 | サカタ コウ | Cation Cassero Sukebutsu Shitsuno Seizouhou |
-
1980
- 1980-12-20 DE DE19803048357 patent/DE3048357A1/en not_active Ceased
-
1981
- 1981-12-03 EP EP81110095A patent/EP0054778B1/en not_active Expired
- 1981-12-03 DE DE8181110095T patent/DE3173215D1/en not_active Expired
- 1981-12-03 AT AT81110095T patent/ATE16897T1/en active
- 1981-12-16 NO NO814291A patent/NO153917C/en unknown
- 1981-12-17 DK DK561481A patent/DK158141C/en not_active IP Right Cessation
- 1981-12-18 FI FI814090A patent/FI69572C/en not_active IP Right Cessation
- 1981-12-21 JP JP56205361A patent/JPS57127453A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| EP0054778A2 (en) | 1982-06-30 |
| DK561481A (en) | 1982-06-21 |
| FI814090L (en) | 1982-06-21 |
| EP0054778A3 (en) | 1982-08-25 |
| DK158141C (en) | 1990-09-03 |
| JPS57127453A (en) | 1982-08-07 |
| DE3048357A1 (en) | 1982-07-15 |
| DE3173215D1 (en) | 1986-01-23 |
| EP0054778B1 (en) | 1985-12-11 |
| NO153917C (en) | 1986-07-02 |
| FI69572B (en) | 1985-11-29 |
| NO814291L (en) | 1982-06-21 |
| JPH0351463B2 (en) | 1991-08-06 |
| NO153917B (en) | 1986-03-10 |
| FI69572C (en) | 1986-03-10 |
| ATE16897T1 (en) | 1985-12-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PBP | Patent lapsed |