DK172765B1 - Basic aluminum chlorosulfate, process for their preparation and use as flocculant - Google Patents
Basic aluminum chlorosulfate, process for their preparation and use as flocculant Download PDFInfo
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- DK172765B1 DK172765B1 DK198900352A DK35289A DK172765B1 DK 172765 B1 DK172765 B1 DK 172765B1 DK 198900352 A DK198900352 A DK 198900352A DK 35289 A DK35289 A DK 35289A DK 172765 B1 DK172765 B1 DK 172765B1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
- C01F7/76—Double salts, i.e. compounds containing, besides aluminium and sulfate ions, only other cations, e.g. alums
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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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/786—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen containing, besides aluminium, only anions, e.g. Al[OH]xCly[SO4]z
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- Environmental & Geological Engineering (AREA)
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- Hydrology & Water Resources (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Sludge (AREA)
Abstract
Description
5 i DK 172765 B15 in DK 172765 B1
Den foreliggende opfindelse angår et basisk aluminiumchlorsulfat, fremgangsmåde til fremstilling deraf og anvendelse deraf som f 1 okkuleringsmiddel.The present invention relates to a basic aluminum chlorosulfate, process for the preparation thereof and use thereof as a fumigant.
Behandling af spildstrømme, af husspildevand, af kildevand eller af flodvand, omfatter næsten altid et trin til fjernelse af materialer i suspension. Man kender produkter, som har en koagulerende virkning på disse 10 materialer i suspension eller i opløsning i det vandige system, der skal behandles, materialer som ikke vil dekantere inden for rimelig tid ved naturlig dekantering.Treatment of waste streams, of house wastewater, of spring water or of river water, almost always includes a step for removing materials in suspension. Products known to have a coagulant effect on these 10 materials in suspension or in solution in the aqueous system to be treated are materials which will not decant within a reasonable time by natural decanting.
Disse produkter omdanner yderligere disse materialer til koagulerede fnug, som er lette at filtrere og at separere 15 fra den flydende fase.These products further convert these materials into coagulated lids which are easy to filter and to separate 15 from the liquid phase.
1 det franske patentskrift nummer 2 036 6B5, 2 226 361 og 2 534 897 omtales sådanne produkter og anvendelsen deraf.In French Patent Nos. 2 036 6B5, 2 226 361 and 2 534 897 such products and their use are mentioned.
I europæisk patentansøgningsskrift nummer 218 487 omtales 20 et produkt, som kan reducere den mængde af aluminium, som forbliver tilbage i vandet efter behandlingen.In European Patent Application Serial No. 218,487, 20 discloses a product which may reduce the amount of aluminum remaining in the water after treatment.
Man har nu fundet et meget effektivt chlorsulfat, som kan anvendes på meget enkel måde.Now a very effective chlorine sulphate has been found which can be used in a very simple way.
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Chlorsulfatet ifølge opfindelsen er et basisk aluminium chlorsulfat, der foreligger i form af en vandig opløsning, og som er ejendommelig derved, at det omfatter et produkt med formlen: 30 A1|,C1,„ (OH) 3n* ,’Ι:-ιη-Γρ ( SO.j) p X|; hvori: X betegner et jordalkalimetal, fortrinsvis calcium, 35 DK 172765 B1 2 n, m, p og k betegner molære koncentrationer (mol/1) af komponenterne i opløsning mindre end 20% af SO^'-ionerne lader 5 sig udfælde ved reaktion med bariumchlorid ved stuetemperatur, og hvis basicitet: 3n + 2k - m - 2p befinder 10 3n sig mellem 45 og 70",The chlorine sulphate according to the invention is a basic aluminum chlorine sulphate, which is in the form of an aqueous solution, which is characterized in that it comprises a product of the formula: A1, C1, "(OH) 3n *," Ι: -ιη -Γρ (SO.j) p X |; wherein: X represents an alkaline earth metal, preferably calcium, n, m, p and k represent molar concentrations (mol / l) of the components in solution less than 20% of the SO 2 ions are precipitated by reaction with barium chloride at room temperature and whose basicity: 3n + 2k - m - 2p is 10 3n between 45 and 70 ",
Man vælger med fordel sådanne produkter ifølge den oven-15 for viste bruttoformel, i hvilke forholdet mellem aluminium ækvivalent og chlor, dvs. 3 n/m er <2,8 fortrinsvis <2,75.Advantageously, such products are selected according to the gross formula shown above, in which the ratio of aluminum equivalent to chlorine, i.e. 3 n / m is <2.8 preferably <2.75.
Skønt man kunne have et stort basicitetsområde, anvender 20 man sædvanligvis produkter med basicitet på mellem 50 og 70%. Man kan foretrække afhængig af anvendelserne for produktet forskellige værdier for basiciteten. Især ved fremstillingen af drikkevand har man iagttaget restindhold af aluminium, som er desto mindre, jo højere 25 basiciteten er.Although one could have a large basicity range, 20 usually use products with a basicity of between 50 and 70%. Depending on the uses of the product, different values for the basicity may be preferred. Especially in the preparation of drinking water, residues of aluminum have been observed, which is the lower the basicity.
Den manglende udfældning med bariumsalte af størstedelen af SCV'-ionerne i produktet viser, at dette sulfat er kompleks. Bestemmelsen af det totale indhold A af sulfat 30 indeholdt i produktet gennemføres på sædvanlig måde ved udfældning af sulfatet med barium ved hjælp af en opløsning af bariumchlorid og af saltsyre, som sættes til prøven, der opvarmes til kogning. Når bariumchloridet er indført ved stuetemperatur (dvs. mellem 15 og 25 OC) i en 35 ikke-syrlig prøve i støkiometriske mængder i forhold til S042"-ionerne, som foreligger i produktet, er vægten af i i DK 172765 B1 3 ' det tørre bundfald, således som det dannes efter en times forløb, i relation med indholdet D af SOf’-ioner, der betegnes som "ikke-komplekse".The failure to precipitate with barium salts of the majority of the SCV ions in the product indicates that this sulfate is complex. The determination of the total content A of sulfate 30 contained in the product is carried out in the usual manner by precipitation of the sulfate with barium by means of a solution of barium chloride and of hydrochloric acid which is added to the sample which is heated to boiling. When the barium chloride is introduced at room temperature (i.e., between 15 and 25 ° C) in a non-acidic sample in stoichiometric amounts relative to the SO42 ions present in the product, the weight of the dry precipitate is the dry precipitate. , as formed after one hour, in relation to the content D of SOf 'ions, designated as "non-complex".
5 Difference A-B betegnes "indhold af SO^'-ioner, der er komplekse".Difference A-B is termed "content of SO ^ 'ions that are complex".
Produktet ifølge opfindelsen, der forefindes i form af en vandig opløsning indeholdende mellem 5 og 15 vægt-% af 10 aluminium udtrykt som Δ1.0., blandes med bariumchlorid i vandig opløsning (f.eks. mellem 5 og 20 g/1). Man homogeniserer, og man lader bundfaldet danne sig igennem ca. 1 time, hvorpå man frafiltrerer på en filterdigel med porøsiteLen nummer 4. Alle disse behandlinger fra 15 blandingen af chlorsulfatet med BaClj indtil filtreringen finder sted ved stuetemperatur, dvs. mellem 15 og 25 0C.The product of the invention, which is in the form of an aqueous solution containing between 5 and 15% by weight of 10 aluminum expressed as Δ1.0., Is mixed with barium chloride in aqueous solution (eg between 5 and 20 g / l). You homogenize and you let the sediment form through approx. One hour is filtered off on a filter crucible with the porous site number 4. All these treatments from the mixture of the chlorine sulfate with BaCl 2 until the filtration takes place at room temperature, ie. between 15 and 25 ° C.
Filtratet indeholder yderligere SOv,!’-ionerne fra produktet ifølge opfindelsen, som ikke er udfældet i form af BaSOi, og som således er komplekse. For at finde denne 20 mængde af komplekse SO/-, nedbryder man produktet ved at tilsætte saltsyre i filtratet og påfølgende opvarmning til kogning. Man udfælder så S04’’-ionerne med Bad; i vandig opløsning mellem 5 og 15 vægt-*. Måling af massen af BaSOi i bundfaldet giver ved sammenligning med den 25 samlede mængde SOjZ- i produktet det procentvise indhold af SO^’-ioner, som er udfældelige ved Reaktionen med bariumchlorid ved stuetemperatur.The filtrate further contains the SOv, ions ions of the product of the invention, which are not precipitated in the form of BaSO1 and are thus complex. To find this 20 amount of complex SO / -, the product is decomposed by adding hydrochloric acid in the filtrate and subsequent heating to boiling. The SO 4 '' ions are then precipitated with Bad; in aqueous solution between 5 and 15% by weight *. Measurement of the mass of BaSO 1 in the precipitate, by comparison with the total amount of SO 2 Z 2 in the product, gives the percentage content of SO 2 ions which are precipitated by the reaction with barium chloride at room temperature.
Produkterne har med fordel mindre end 10?, SO^’-ioner, der 30 lader sig bundfælde, under sædvanlige betingelser, fortrinsvis <5*, dvs. at >95? af SO.^- er komplekse.Advantageously, the products have less than 10 6 SO 2 'ions which settle, under usual conditions, preferably <5 *, ie. at> 95? of SO. ^ - are complex.
Den foreliggende opfindelse angår ligeledes en fremgangsmåde til fremstilling af disse produkter.The present invention also relates to a process for the manufacture of these products.
35 Fremgangsmåden er ejendommelig ved de i krav 7 angivne træk.The method is characterized by the features of claim 7.
DK 172765 B1 4DK 172765 B1 4
Ved udtrykket aluminiumoxid forstår man ethvert produkt af typen aluminiumoxid eller aluminiumhyddroxid. Man foretrækker at anvende aluminiumoxid stammende fra den 5 såkaldte Bayerproces eller aluminiumhydroxider, der er biprodukter ved overfladebehandlinger af aluminium.The term alumina means any product of the type alumina or aluminum hydroxide. It is preferred to use alumina derived from the so-called Bayer process or aluminum hydroxides, which are by-products of aluminum surface treatments.
Man angriber med fordel aluminiumoxidet med en blanding af koncentreret saltsyre og koncentreret svovlsyre ved en 10 temperatur mellem 70 og 115 °C. Dette temperaturinterval er ikke altafgørende, det svarer blot til en reaktionstid på 1-2 timer, hvilket forligeliyt med den industrielle iværksættelse af fremgangsmåden. Man kan anbringe aluminiumoxidet i en blanding af syrerne eller lade 15 aluminiumoxidet reagerer med den ene og derpå med den anden syre, eller man kan tilsætte syrerne i flere omgange. Man foretrækker at angribe aluminiumoxidet med en blanding af saltsyre og svovlsyre, hvorpå man, i det en del af aluminiumoxidet allerede er blevet opløst, 20 tilsætter en kompletterende del af koncentreret svovlsyre.Advantageously, the alumina is attacked with a mixture of concentrated hydrochloric acid and concentrated sulfuric acid at a temperature between 70 and 115 ° C. This temperature range is not essential, it merely corresponds to a reaction time of 1-2 hours, which is in line with the industrial implementation of the process. One can place the alumina in a mixture of the acids or allow the alumina to react with one and then with the other acid, or one can add the acids several times. It is preferred to attack the alumina with a mixture of hydrochloric acid and sulfuric acid, whereupon, in part of the alumina already dissolved, a supplementary portion of concentrated sulfuric acid is added.
Man anvender med fordel saltsyre i en opløsning stærkere end 20 vægt-%, fortrinsvis en 33 vægt-% opløsning. Det er 25 ligeledes fordelagtigt at anvende svovlsyre med mindst 60 vægt-%. Mængden af saltsyre udtrykt i mol mellem 1,89 og 2,44 gange mængden af aluminiumoxid udtrykt som mol er AI^Ot, fortrinsvis mellem 1,95 og 2,40.Advantageously, hydrochloric acid is used in a solution stronger than 20% by weight, preferably a 33% by weight solution. It is also advantageous to use sulfuric acid with at least 60% by weight. The amount of hydrochloric acid expressed in moles between 1.89 and 2.44 times the amount of alumina expressed as moles is Al 2 O, preferably between 1.95 and 2.40.
30 Tilsvarende er mængden af svovlsyre udtrykt i mol (anvendt i løbet af en eller flere omgange) mellem 1,37 og 1,73 gange mængden af aluminiumoxid udtrykt som mol Al^Oi, fortrinsvis mellem 1,42 og 1,68.Similarly, the amount of sulfuric acid expressed in moles (used over one or more cycles) is between 1.37 and 1.73 times the amount of alumina expressed as moles of Al 2 O 1, preferably between 1.42 and 1.68.
35 Opløsningen af aluminiumchlorsulfatet fra trin a) bringes derpå i kontakt med jordalkalimetalforbindelsen. Denne DK 172765 B1 5 jordalkalimetalforbindelse kan f.eks. være valgt mellem calciumcarbonat, -hydroxid/ -oxid eller hydrogencarbonat.The solution of the aluminum chlorine sulphate from step a) is then contacted with the alkaline earth metal compound. This DK 172765 B1 5 alkaline earth metal compound can e.g. be selected from calcium carbonate, hydroxide / oxide or hydrogen carbonate.
Man kan anvende en blanding af disse produkter, f.eks. af calciumcarbonat og calciumhydroxid, man foretrækker 5 calciumcarbonat.A mixture of these products can be used, e.g. of calcium carbonate and calcium hydroxide, 5 calcium carbonate is preferred.
Jordalkalimetalforbindelsen foreligger med fordel i fint fordelt form, såsom i form af et pulver. Skønt man kunne arbejde ved enhver temperatur, foretrækker man at opvarme 10 aluminiumchloridsulfatopløsningen mellem 60 og 100 "C for at bringe den i kontakt med jordalkalimetalforbindelsen.The alkaline earth metal compound is advantageously present in finely divided form, such as in the form of a powder. Although capable of operating at any temperature, it is preferred to heat the aluminum chloride sulfate solution between 60 and 100 ° C to contact it with the alkaline earth metal compound.
Denne kontakt gennemføres i almindelighed i 10 eller 30 minutter, hvilket svarer til sædvanlige teknologiske 15 betingelser; men man overskrider ikke opfindelsens rammer ved at arbejde i nogle minutter eller i nogle timer.This contact is generally carried out for 10 or 30 minutes, which corresponds to the usual technological conditions; but one does not exceed the scope of the invention by working for a few minutes or for a few hours.
Mængden af jordalkalimetalforbindelse udtrykt i mol er mellem 1,63 og 1,70 gange mængden af den aluminiumoxid, 20 der indføres i trin a), udtrykt i mol Al;Ch, fortrinsvis mellem 1,65 og 1,68. Man kan, når al jordalkalimetalforbindelsen er blevet blandet med opløsningen af aluminiumchloridsulfat, lade blandingen henståunder omrøring. Temperaturen kan være vilkårlig, i 25 almindelighed etablere temperaturen sig ved mellem 30 og 60 "C.The amount of alkaline earth metal compound expressed in moles is between 1.63 and 1.70 times the amount of the alumina introduced in step a), expressed in moles Al; Ch, preferably between 1.65 and 1.68. Once all the alkaline earth metal compound has been mixed with the solution of aluminum chloride sulphate, the mixture is allowed to stir. The temperature can be arbitrary, in general, the temperature settles at between 30 and 60 ° C.
Denne afslutning af trinnet b) varer med fordel fra 15 minutter til 2 timer. Det er så tilstrækkeligt at 30 fraseparere jordalkalimetalsulfatet. Man kan anvende sædvanlige midler, såsom filtrering, centrifugering.This end of step b) advantageously lasts from 15 minutes to 2 hours. It is then sufficient to separate the alkaline earth metal sulfate. Conventional agents such as filtration, centrifugation can be used.
Denne separation foregår fortrinsvis over stuetemperatur, f.eks. mellem 30 og 60 nC.This separation preferably takes place above room temperature, e.g. between 30 and 60 AD.
35 Filtratet indeholder det basiske chlorsulfat ifølge opfindelsen i opløsning i vand. Man kan modificere r 6 DK 172765 B1 koncentrationen ved tilsætning af vand. Produktet ifølge opfindelsen foreligger i form af denne opløsning indeholdende efter vægt mellem 5?. og 15% aluminium udtrykt i formlen Al^Oj. Denne form udviser den fordel, 5 at den har en stabilitet {ingen tilsynekomst af fast fase) i adskillige måneder ved stuetemperatur.The filtrate contains the basic chlorine sulfate of the invention in solution in water. The concentration can be modified by the addition of water. The product of the invention is in the form of this solution containing by weight between 5. and 15% aluminum expressed in the formula Al 2 O 2. This form has the advantage of having a stable (no solid phase appearance) for several months at room temperature.
Den foreligende opfindelse angår ligeledes anvendelsen af disse produkter som koaguleringsmiddel og 10 flokkulerngsmiddel ved behandlingen af vand, især til rensning af vand til fremstilling deraf af drikkevand.The present invention also relates to the use of these products as coagulant and flocculant in the treatment of water, in particular for the purification of water for the preparation thereof of drinking water.
Blandt de basiske aluminiumchlorsulfater ifølge opfindelsen udviser sådanne, som samtidigt: 15 har en basicitet >60%, og hvis vægtforhold Cl/(total S0() er på mellem 4,5 og 8, når de anvendes inden for områdets 20 fremgangsmåder til behandling af vandige medier, en mest optimal behandlingsgrad ved flokkulering, som er mindre end tilsvarende egenskaber med hensyn til det aluminium, som forbliver i opløsning (rest Al).Among the basic aluminum chlorine sulphates according to the invention, those exhibiting at the same time: 15 have a basicity> 60% and whose weight ratio Cl / (total SO () is between 4.5 and 8 when used in the area 20 processes for aqueous media, a most optimal degree of treatment by flocculation, which is less than similar properties with respect to the aluminum remaining in solution (residue Al).
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De efterfølgende eksempler belyser opfindelsen nærmere.The following examples further illustrate the invention.
EKSEMPEL 1: 30 Præparation af et produkt ifølge opfindelsenEXAMPLE 1: 30 Preparation of a Product of the Invention
Trin a) : man indhælder i en glasreaktum indeholdende 3 mol HC1 i form af 331,9 g af en 33% opløsning og 1,45 mol 78% H.SOi, 3,09 mol af et 99" pulver af Al(OH);. Man 35 opvarmer til 70 °C, hvorpå temperaturen stabiliserer sig ved 102 "C. Man fortynder med 374 gi vand, hvorpå man DK 172765 B1 7 tilsætter 1 mol 78?, saltsyre. Temperaturen stiger til 112 °C i løbet af 20 minutter. Varigheden af dette trin er ca. 2 timer.Step a): A glass reactor containing 3 moles of HCl in the form of 331.9 g of a 33% solution and 1.45 moles of 78% H.SOi, 3.09 moles of a 99 "powder of Al (OH) is added. 35 is heated to 70 ° C, after which the temperature stabilizes at 102 ° C. It is diluted with 374 g of water, to which 1 mol of 78 µl of hydrochloric acid is added. The temperature rises to 112 ° C in 20 minutes. The duration of this step is approx. 2 hours.
5 Trin b) : man lader afkøle til 93 "C, hvorpå man i løbet af 30 minutter indfører 2,60 mol CaCO.i, dvs. 481,5 g af en 54% opslæmning af CaC03. Man lader reaktoren henståunder omrøring i 1 time og 30 minutter, og temperaturen bliver så 61 °C.Step b): Allow to cool to 93 ° C and introduce, within 30 minutes, 2.60 moles of CaCO 3, i.e. 481.5 g of a 54% slurry of CaCO 3. Allow the reactor to stir for 1 hour. hour and 30 minutes, and the temperature then becomes 61 ° C.
1010
Trin c): man lader afkøle til 40 nC, hvorpå man filtrerer i et vacuumfiltreringsapparatur. Man vasker fil Lerkagen med 100 g i vand. Den tørre kage vejer 362 g og indeholder efter vægt 7,73% aluminium udtrykt som A1.0-,, 15 53,4% SO/-, 1,35? Cl', idet resten består af calcium. Man opsamler 1100 g filtrat med densiteten 1,224, som man fortynder med 109 g i vand. Man opnår produktet, der foreligger i form af en opløsning.Step c): Allow to cool to 40 ° C, then filter in a vacuum filtration apparatus. Wash the lark cake with 100 g in water. The dry cake weighs 362 g and contains, by weight, 7.73% aluminum expressed as A1.0-, 15 53.4% SO / -, 1.35? Cl ', the remainder being calcium. 1100 g of filtrate are collected at a density of 1,224, which is diluted with 109 g in water. The product obtained in the form of a solution is obtained.
20 Opløsningen vejer 1220 g, har en densitet på 1,201 og indeholder efter vægt 10,09% Al udtrykt i form af Al. O·., 8,11% Cl", 1,8% SO/-, 1,78% kompleks SO/'- og 1,08% Ca7i, dvs. at forholdet (Al ækvivalent)/Cl er 2,6, 97,3- af SO/- er komplekse.The solution weighs 1220 g, has a density of 1,201 and contains by weight 10.09% Al expressed as Al. 0 ·, 8.11% Cl ", 1.8% SO₂ -, 1.78% complex SO / - and 1.08% Ca77, i.e. the ratio (Al equivalent) / Cl is 2.6, 97.3- of SO / - are complex.
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Basiciteten er 64,18%, og vægtforholdet Cl/(total SO,-) er 4,43.The basicity is 64.18% and the weight ratio Cl / (total SO, -) is 4.43.
EKSEMPEL 2: 30EXAMPLE 2: 30
Præparation af et andet produkt ifølge opfindelsenPreparation of another product according to the invention
Man går frem analogt med eksempel 1, men idet man anvender andre mængdeforhold af reaktionskomponenterne.One proceeds analogously to Example 1, but using other proportions of the reaction components.
35 Man går hele tiden ud fra 3,09 mol Al (OH)varigheden af DK 172765 B1 8 trin (a) er 2 timer. Trin b) varer 2 timer og begynder ved 90 °C.The starting point is always 3.09 moles Al (OH) duration of DK 172765 B1. Step (a) is 2 hours. Step b) lasts for 2 hours and begins at 90 ° C.
Trin a): 5Step a): 5
Sluttemperatur : 113,4 "CFinal temperature: 113.4 "C
HC1 : 3,0 mol 10 H.;SOj : 2,6 molHCl: 3.0 mol 10 H; SO 2: 2.6 mol
Trin b):Step b):
15 Sluttemperatur : 63 "CEnd temperature: 63 "C
CaCOj : 2,6 mol i form af en 5 4 % væs ke 20CaCO 2: 2.6 moles in the form of a 4 4% liquid 20
Efter fraseparering af calciumsulfatet (trin c) og fortynding med vand opnår man følgende produkt, idet de anførte procentandele er vægt-% i opløsningen.After separation of the calcium sulfate (step c) and dilution with water, the following product is obtained, the percentages given being by weight in the solution.
25 Procentandele i opløsningen25 Percentages in solution
AljOj : 10,59¾AljOj: 10.59¾
Cl : 8,35¾ 30Cl: 8.35¾30
Total S042- : 2, 13%Total SO42-: 2, 13%
Komplekst S042- : 2,13% 35 Rest Ca : 0,77% DK 172765 B1 9 (Al ækvivalent)/Cl : 2,65Complex S042-: 2.13% Residue Ca: 0.77% DK 172765 B1 9 (Al equivalent) / Cl: 2.65
Basicitet : 61,29 5 Komplekse SO^'-ioner : 100, 00?.Basicity: 61.29 5 Complex SO 2 ions: 100, 00 ?.
Cl/(total SCV’-) : 3,92 EKSEMPEL 3: 10Cl / (total SCV'-): 3.92 Example 3: 10
Præparation af et andet produkt ifølge opfindelsenPreparation of another product according to the invention
Man går frem analogt med eksempel 1, men idet man anvender andre mængdeforhold af reaktionskomponenterne.One proceeds analogously to Example 1, but using other proportions of the reaction components.
15 Man går ud fra 3,09 mol Al (OH).., varigheden af trin a) cr 2 timer. Trin b) varer 2 timer og begynder ved 90 ‘C.The starting point is 3.09 mol Al (OH) .., the duration of step a) cr 2 hours. Step b) lasts 2 hours and begins at 90 ° C.
Trin a) :Step a):
20 Sluttemperatur : 112 "CFinal temperature: 112 "C
HC1 : 2,81 mol H;S04 : 2 , 25 mol 25HCl: 2.81 mol H; SO 4: 2, 25 mol 25
Trin b):Step b):
Sluttemperatur : 62 nCFinal temperature: 62 AD
30 CaCOj : 2,38 mol i form af en 54% væske.CaCO 2: 2.38 moles in the form of a 54% liquid.
Efter fraseparering af calciumsulfatet (trin c)) og fortynding med vand opnår man følgende produkt, idet 35 producentandelene er anført som vægi-% af opløsningen.After separation of the calcium sulfate (step c) and dilution with water, the following product is obtained, with the 35 percent of the manufacturer being listed as the weight percent of the solution.
DK 172765 B1 10DK 172765 B1 10
Procentandele i opløsningPercentages in solution
Al.Oj : 9,96¾ 5 Cl : 7,72?·Al.Oj: 9.96¾ 5 Cl: 7.72? ·
Total S04.,2- : 1,50 oTotal SO4, 2-: 1.50 o
Kompleks 50./- : 1,50?.Complex 50./-: 1.50 ?.
1010
Rest Ca : 0,66? (Al ækvivalent)/Cl : 2,69 15 Basicitet : 63,2%Rest Ca: 0.66? (Al equivalent) / Cl: 2.69 Basicity: 63.2%
Komplekse SO^'-ioner : 100%Complex SO 2 ions: 100%
Cl/(totalSO/') : 5,15 20 EKSEMPEL 4:Cl / (total SO 2): 5.15 Example 4:
Produkter, som ikke er i overensstemmelse med opfindelsen 25Products not in accordance with the invention 25
Deres bruttoformel udtrykkes på samme form soro formlerne for produkterne ifølge opfindelsen.Their gross formula is expressed in the same form as the soro formulas for the products of the invention.
4a) man fremstiller et basisk alurainiumchlorsulfal ifølyc 30 den kendte teknik, som foreligger i form af en opløsning indeholdende udtrykt i vægt-%:4a) preparing a basic aluminum chlorosulfal according to the prior art, which is in the form of a solution containing by weight:
Al ; 10,3 (udtrykt som A1:0.<) 35 Cl : 9,09 m DK 172765 B1 11Eel ; 10.3 (expressed as A1: 0. <) 35 Cl: 9.09 m DK 172765 B1 11
Total SO.f" : 2,49Total SO.f ”: 2.49
Basicitet : 51,32*, 5 idet basiciteten er defineret som for produktet ifølge opfindelsen.Basicity: 51.32 *, 5 where the basicity is defined as for the product according to the invention.
Koncentrationen af komplekse SO/'"-ioner er 1,64, dvs. at 1,64 dvs. 65,9% af sulfatet er komplekst.The concentration of complex SO 2 ions is 1.64, ie 1.64 ie 65.9% of the sulfate is complex.
10 2,492.49
Forholdet (Al ækvivalent)/Cl er 2,37, og forholdet Cl/(Total SO/) er 3,65. Produktet er fremstillet ved reaktion mellem alumin.iumoxid og HC1 og II.:S04, således 15 som det er omtalt i fransk patentskrift nr. 2 036 685.The ratio (Al equivalent) / Cl is 2.37 and the ratio Cl / (Total SO /) is 3.65. The product is prepared by reaction between alumina and HCl and II.:SO4, as disclosed in French Patent Specification No. 2,036,685.
4b) man fremstiller et andet basisk aluminiumchlorsulfat, der foreligger i form af en opløsning indeholdende udtrykt i vægt-%: 204b) another basic aluminum chlorosulfate is prepared which is in the form of a solution containing in% by weight: 20
Al : 8,3 (udtrykt som Al ..O·.)Al: 8.3 (expressed as Al .. O ·.)
Cl : 5,21 25 Total SO,7- : 5,02Cl: 5.21 Total SO, 7-: 5.02
Basiciteten er : 49,8%Basicity is: 49.8%
Koncentrationen af komplekse SO/7'-ioner er 1,5, dvs. at 30 1,5 dvs. 29,9% af sulfatet er komplekst.The concentration of complex SO / 7 'ions is 1.5, ie. that 1.5 29.9% of the sulfate is complex.
5, 025, 02
Forholdet (Al ækvivalent)/Cl er 3,32, og forholdetThe ratio (Al equivalent) / Cl is 3.32 and the ratio
Cl/(total SO/7”) er 1,04.Cl / (total SO / 7 ”) is 1.04.
35 DK 172765 B1 1235 DK 172765 B1 12
Dette produkt er fremstillet ved en fremgangsmåde, som omfatter et trin til præparation af en væske af calciumchlorid og af calciumcarbonat en chlorcarbonat-holdig væske), et trin til kontaktskabelse mellem 5 clilorcarbonatvæsken og aluminiumsulfatet, derpå et trin til separation af den således opnåede reaktionsblanding, hvorved man fraseparerer en kage af calciumsulfat fra et filtrat indeholdende det basiske aluminiumchlorsulfat.This product is prepared by a process comprising a step of preparing a liquid of calcium chloride and of calcium carbonate a chlorocarbonate-containing liquid), a step of contacting between the chlorocarbonate liquid and the aluminum sulfate, then a step of separating the reaction mixture thus obtained. separating a cake of calcium sulfate from a filtrate containing the basic aluminum chlorosulfate.
Denne fremgangsmåde er beskrevet i europæisk 10 patentansøgningsskrift nummer 218 487.This process is described in European Patent Application Serial No. 218,487.
Man har på dette produkt ved kvasielastisk diffusion af lys målt en tilsyneladende hydrodynamisk diameter φζ på70 nm (700A).An apparent hydrodynamic diameter ζζ of 70 nm (700A) has been measured for this product by quasi-elastic diffusion of light.
15 4c) Man fremstilcr et produkt af samme art som i 4b) . Koncentrationerne er: 20 Al : 8,55 (som Al.004c) A product of the same kind as in 4b) is produced. The concentrations are: 20 Al: 8.55 (as Al.00
Cl : 6,82Cl: 6.82
Total SO,’" : 2,74 25Total SO, δ: 2.74
Kompleks SO/' : 1,93Complex SO / ': 1.93
Basiciteten er : 57‘i 30 Procentandelen er kompleks SO/- er således 1,93 = 70,4*, og 2,74 forholdet (Al ækvivalent)/Cl er 2,64, og forholdet Cl/(Total S0/‘) er 2,49.The basicity is: 57'i The percentage is complex SO / - is thus 1.93 = 70.4 *, and the 2.74 ratio (Al equivalent) / Cl is 2.64, and the ratio Cl / (Total S0 / ') is 2.49.
35 5 DK 172765 B1 13 EKSEMPEL 5:EXAMPLE 5:
Dette eksempel belyser anvendelsen af produktet ifølge opfindelsen.This example illustrates the use of the product of the invention.
Man sammenligner produktet ifølge opfindelsen med produkterne fra ovenstående sammenligningseksempel 4.The product according to the invention is compared with the products of the above Comparative Example 4.
Man gennemfører forsøg ved den såkaldte jartest, idet man 10 anvender følgende fremgangsmåde: - bæreglas på 1 liter, - temperatur 15 "C, 15 - flodvand, - jar-test "hydrokure" type SLH6, 20 - hurtig omrøring i 1 minut og 30 sekunder efter tilsætning af flokkuleringsmiddel og derpå langsom omrøring, dvs. tilstrækkelig til, at der sker cn sammenflydning, men under undgåelse af dekantering af flokkene.Experiments are carried out in the so-called soil test, using the following procedure: - 1 liter carrier glass, - temperature 15 "C, 15 - river water, - jar test" hydrocure "type SLH6, 20 - rapid stirring for 1 minute and 30 seconds after the addition of flocculant and then slow stirring, ie sufficient for confluence, but avoiding decanting the flocks.
2525
Man lader derpå dekantere i 3, 10 eller 20 minutter, således som det er vist i tabellerne 1-7.It is then allowed to decant for 3, 10 or 20 minutes, as shown in Tables 1-7.
- måling af restindholdet af aluminium i vandet ved cn 30 polyometisk metode under anvendelse af chromazurol efter filtrering af det i 20 minutter dekanterede vand over et filter med porestørrelse 0,45 ym.- measuring the residual aluminum content in the water by a 30 polyometric method using chromazurol after filtering the decanted water for 20 minutes over a 0.45 µm pore filter.
DK 172765 B1 14 I de efterfølgende tabeller er angivet den type vand, der skal behandles, pH værdien, uklarheden udtrykt som NTU og de organiske indholdsstoffer udtrykt i mg oxygen pr. liter vand.DK 172765 B1 14 The following tables indicate the type of water to be treated, the pH value, the cloudiness expressed as NTU and the organic constituents expressed in mg of oxygen per day. liters of water.
55
De i tabellen angivne produkter er kendetegnet ved nummeret på det tilsvarende eksempel. Man anfører uklarheden af vand ved overfladen efter x minutter dekantering, slut-pH samt de organiske materialer og 10 aluminium som restindhold i vandet (rest-Al) udtrykt i ppb (pg/liter).The products listed in the table are characterized by the number of the corresponding example. The turbidity of water at the surface is indicated after x minutes of decantation, final pH and the organic materials and aluminum as residue in the water (residual Al) expressed in ppb (pg / liter).
Tabellerne 1-7 viser de opnåede resultater.Tables 1-7 show the results obtained.
15 TABEL 1TABLE 1
Vandtype ; vand fra floden Seine 20 pH : 7,97Water type; water from the river Seine 20 pH: 7.97
Uklarhed ; 42 NTUObscurity; 42 NTU
Organiske materialer (MO) : 6,96 mg 0_/l 25 I I 1-—-1-Γ--1-1Organic materials (MO): 6.96 mg 0 / l 25 I I 1 -—- 1-Γ - 1-1
I 1 Mængde | Uklarhed i superna- | | | IIn 1 Quantity | Blur in superna- | | | IN
I Produkt I i g/m3 1 natant | IIII Product I in g / m3 1 natant | III
I (nr. af| (som |-,-1-|slut | |Rest | 30 Ieks) IΛ1 _.(),) I 3» I 10' | 20' | pil |M.O. | Λ1 | I-1--—I--1-l·---1-1—I---1 I ^3 I 4 I 2,1 I 1,45 I 1,3 I 7,7 (2,76| 148 [ I 1 I 4 I 1,8, I 1,35 I 1,2 I 7,8412,72 i 97 |I (No. of | (as | -, - 1- | end | | Remainder | 30 Ieks) IΛ1 _. (),) I 3 »I 10 '| 20 '| arrow | M.O. | Λ1 | I-1 - I-1-l · --- 1-1-I --- 1 I 3 I 4 I 2.1 I 1.45 I 1.3 I 7.7 (2.76 | 148 [I 1 I 4 I 1.8, I 1.35 I 1.2 I 7.8412.72 i 97 |
1-->—____I_I_I_1__1______I_I1 -> -____ I_I_I_1__1______I_I
35 DK 172765 B1 TABEL 2 15DK 172765 B1 TABLE 2 15
Vandtype : vand fra floden Marne 5 pH : 8,02Water type: water from river Marne 5 pH: 8.02
Uklarhed : 60 NTUObscurity: 60 NTU
Organiske matr. (M.O.) : 6,68 mg 0.;/l 10Organic matr. (M.O.): 6.68 mg 0.; / l 10
I-1-1-1-1 i II-1-1-1-1 in I
I I Mængde | Uklarhed i superna- | | | |I In Quantity | Blur in superna- | | | |
I Produkt I i g/m3 | natant I I I IIn Product I in g / m3 | natant I I I I
I (nr. af| (som |-1-1-|Slut | |Rest | 15 I eks) |A],Oj) I 3' | 10' | 20' | pH |M.O.| Al | I- I--1-1-1-1---]—I-1 I 4a I 3 I 1,7 I 1,6 I 1,5 17,78 |2,94| 152 | I 4c I e I 1,7 I 1,55 | 1,45 |7,80 |2,78| 152 | I 1 I 3 I 1,8 I 1,6 I 1 , 4 17, 80 12, 661 118 |I (No. of | (as | -1-1- | End | | Remainder | 15 I ex) | A], Oj) I 3 '| 10 '| 20 '| pH | M.O. | Al | I- I - 1-1-1-1 ---] - I-1 I 4a I 3 I 1.7 I 1.6 I 1.5 17.78 | 2.94 | 152 | I 4c I e I 1.7 I 1.55 | 1.45 | 7.80 | 2.78 | 152 | I 1 I 3 I 1.8 I 1.6 I 1, 4 17, 80 12, 661 118 |
2 o I__1__'_I___I__I_i_i______I2 o I__1 __'_ I___I__I_i_i______I
TABEL 3 25TABLE 3 25
Vandtype : Vand fra floden Marne pH : 8,26 (er blevet modificeret ved tilsætning af natrium-30 hydroxid)Water type: Water from the river Marne pH: 8.26 (has been modified by the addition of sodium hydroxide)
Uklarhed : 55 NTUObscurity: 55 NTU
Organiske matr. (M.O.) : 5,94 mg O./l DK 172765 B1 16 I-1-i-1-1-1--1 I |Mængde | Uklarhed i superna- | | | | I Produkt I i g/m3 | natant 1111 I (nr. af I (som |-1-1-Islut | |Rest | 5 I eks) [ Al.Oj) | 3' | 10’ | 20' | pH |M.O.| Al [ I-1-,---1---1---[-1--1---1 I 4a 1 3 I 1,55 | 1,55 | 1,35 17,90 } 2,12[ 216 | I 4c 1 3 I 1,6 I 1,55 I 1,3 |7,92 |2,14j 212 | I 1 1 3 I 1,7 I 1,55 I 1,45 |7,97 |2,08| 165 ( I o I_1_I_I_I_1__I_1-1 TABEL 4Organic matr. (M.O.): 5.94 mg O./l DK 172765 B1 16 I-1-i-1-1-1--1 I | Quantity | Blur in superna- | | | | In Product I in g / m3 | natant 1111 I (No. of I (as | -1-1-Islut | | Rest | 5 I ex) [Al.Oj) | 3 '| 10 '| 20 '| pH | M.O. | Al [I-1 -, --- 1 --- 1 --- [- 1--1 --- 1 I 4a 1 3 I 1.55 | 1.55 | 1.35 17.90} 2.12 [216 | I 4c 1 3 I 1.6 I 1.55 I 1.3 | 7.92 | 2.14j 212 | I 1 1 3 I 1.7 I 1.55 I 1.45 | 7.97 | 2.08 | 165 (I o I_1_I_I_I_1__I_1-1 TABLE 4
Vandtype : Vand fra floden Oise 15 pH : 7,99Water Type: Water from River Oise 15 pH: 7.99
Uklarhed : 9,9 NTUObscurity: 9.9 NTU
20 Organiske matr. (M.O.) : 5,64 mg O^/l20 Organic matr. (M.O.): 5.64 mg O ^ / l
I I I I I I II I I I I I I I
I (Mængde | Uklarhed i superna- | | | |I (Quantity | Blur in superna- ||||
I Produkt I i g/m3 | natant I I I IIn Product I in g / m3 | natant I I I I
I (nr. af I (som |-1-1-|Slut | (Rest | 25 I eks) 1 Al^O.i) | 3' | 10' | 20' | pH |M.O.| Al | I-i------1-1--1----,-1-1---| I 1 I 3 I 1,0 I 0,88 1 0,80 |7,88 |2,94| 89 | I 4a I 3 I 0,98 I 0,93 | 0,91 |7,84 | 3,101 123 | I 4b I 3 I 1,2 I 1,02 I 0,91 |7,82 |3,08| 120 | 30 I_L____L__I___L__I___1-L-1 TABEL 5 DK 172765 B1 17I (No. of I (as | -1-1- | End | (Remaining | 25 Ex) 1 Al ^ Oi) | 3 '| 10' | 20 '| pH | MO | Al | Ii ---- --1-1--1 ----, - 1-1 --- | I 1 I 3 I 1.0 I 0.88 1 0.80 | 7.88 | 2.94 | 89 | I 4a I 3 I 0.98 I 0.93 | 0.91 | 7.84 | 3.101 123 | I 4b I 3 I 1.2 I 1.02 I 0.91 | 7.82 | 3.08 | 120 | 30 I_L ____ L__I ___ L__I ___ 1-L-1 TABLE 5 DK 172765 B1 17
Vandtype : Vand fra floden Oise 5 pH : 8,24 (efter tilsætning af natriumhydroxid)Water Type: Water from River Oise 5 pH: 8.24 (after addition of sodium hydroxide)
Uklarhed : 21 NTUObscurity: 21 NTU
10 Organiske matr. (M.O.) : 6,92 mg O./l i i-1-i i i i 15 I I Mængde | Uklarhed i superna- | | | |10 Organic matr. (M.O.): 6.92 mg O./l i i-1-i i i i 15 I I Quantity | Blur in superna- | | | |
I Produkt I i g/m3 j natant I I I II Product I in g / m3 j natant I I I I
I (nr. af I (som |-1-1-|Slut | |Rest | (eks) |Al,Oj) I 3' I 10' | 20' | pH |M.O.| Al | ,-1-1-1-1---1—i—I--1 20 I 1 I 3 I 0,94 I 0,83 | 0, 72 18, 08 12, 861 163 | I 4a I 3 I 1,05 I 1 | 0,99 |8,03 12,8 61 242 | I 4b I 3 I 1,25 I 0,99 | 0, 93 18, 02 12, 88 ( 238 |I (No. of I (as | -1-1- | End | | Rest | (ex) | Al, Oj) I 3 'I 10' | 20 '| pH | MO | Al |, -1-1- 1-1 --- 1 — i — I - 1 20 I 1 I 3 I 0.94 I 0.83 | 0, 72 18, 08 12, 861 163 | I 4a I 3 I 1.05 I 1 | 0.99 | 8.03 12.8 61 242 | I 4b I 3 I 1.25 I 0.99 | 0, 93 18, 02 12, 88 (238 |
I--I_I___I____1_____I____I_I_____II - I_I ___ I____1_____I____I_I_____I
25 Man ser, at selv med et meget basisk vandmateriale gør produktet ifølge opfindelsen det muligt at befinde sig under den maksimale koncentration på 2 yg/1, som er tilladt som tilladelig i Europarådets direktiv af 15. juli 1980.25 It is seen that even with a very basic water material, the product according to the invention makes it possible to be below the maximum concentration of 2 µg / l allowed as permitted by the Council of Europe Directive of 15 July 1980.
30 TABEL 6TABLE 6
Vandtype : Vand fra floden Seine 35 pH : 7,97 DK 172765 B1 18Water type: Water from the river Seine 35 pH: 7.97 DK 172765 B1 18
Uklarhed : 42 NTUObscurity: 42 NTU
Organiske matr. (M.O.) : 6,96 mg 0../1Organic matr. (M.O.): 6.96 mg of 0 ../ 1
5 I-1 I j [ I I5 I-1 I j [I I
I IMængde | Uklarhed i superna- | | | |In Quantity | Blur in superna- | | | |
I Produkt I i g/m3 | natant I I I IIn Product I in g / m3 | natant I I I I
I (nr. af|(som |-1-1-(Slut ( (Rest | I eks) I ΑΙ.Όι) I 3' | 10’ | 20' | pli |M.O.| Al | 10 1-1-1-1-1-1-1--1--1 I 4a I 4 I 2,15 | 1,45 | 1,3 17,7 12,76 J 148 | I 2 I 3 I 2,2 I 1,2 I 1,3 |7,77 (2,72( 117 | I 1 I 4 I 3,0 I 1,40 I 1,3 17, 81 12,721 104 | I_I__I_I__1_!_I-1--1 15 TABEL 7I (No. of | (as | -1-1- (End ((Remain | Ex)) In ΑΙ.Όι) I 3 '| 10' | 20 '| pli | MO | Al | 10 1-1-1 -1-1-1-1--1--1 I 4a I 4 I 2.15 | 1.45 | 1.3 17.7 12.76 J 148 | I 2 I 3 I 2.2 I 1, 2 I 1.3 | 7.77 (2.72 (117 | I 1 I 4 I 3.0 I 1.40 I 1.3 17, 81 12.721 104 | I_I__I_I__1 _! _ I-1--1 TABLE 7
Vandtype : Vand fra floden Marne 20 pH : 8,02Water type: Water from the river Marne 20 pH: 8.02
Uklarhed : 60 NTUObscurity: 60 NTU
Organiske matr. (M.O.) : 6,68 mg 0„·/1 25 I-1-1--1-i-1-1 ( IMængde | Uklarhed i superna- | | ( |Organic matr. (M.O.): 6.68 mg 0 ° · / 1 25 I-1-1--1-i-1-1 (Quantity | Cloudiness in supernal || (|
(Produkt I i g/m3 ( natant I [ I I(Product I in g / m3 (natant I [I I
I (nr. af|(som |-1-1-|SluL | |Rest | 30 (eks) IAl_0j) | 3' | 10' | 20' | pH (M.O. | Al | 1-1--1-1-1-,-1-1-( I 4a I 3 1 1,7 I 1,6 | 1,5 (7,78 |2,94| 152 | I 4c I 3 I 1,6 ( 1,55 I 1,45 (7,80 12,781 152 | I 2 I 3 I 1,8 I 1,6 I 1, 5 17, 82 (2,72( 128 | 35 ( 1 I 3 I 1,8 I 1,6 I 1,4 |7, 80 (2, 661 118 | I______I___I_I______J_I__I I_1 EKSEMPEL 6 19 DK 172765 B1I (No. of | (as | -1-1- | SluL | | Remaining | 30 (ex) IAl_0j) | 3 '| 10' | 20 '| pH (MO | Al | 1-1--1-1 -1 -, - 1-1- (I 4a I 3 1 1.7 I 1.6 | 1.5 (7.78 | 2.94 | 152 | I 4c I 3 I 1.6 (1.55 I 1.45 (7.80 12.781 152 | I 2 I 3 I 1.8 I 1.6 I 1, 5 17, 82 (2.72 (128 | 35 (1 I 3 I 1.8 I 1.6 I 1.4 | 7, 80 (2, 661 118 | I______I___I_I______J_I__I I_1 EXAMPLE 6 19 DK 172765 B1
Dette eksempel består i en sammenligning af resultaterne med hensyn til uklarhed og restindhold af aluminium ved 5 produkterne ifølge opfindelsen fra eksemplerne 1 og 3, når man anvender dem i meget lave indholdskoncentrationer: 1, 1,5, 2 og 3 g/m* målt som Al.Oj.This example consists of a comparison of the results with respect to cloudiness and residual content of aluminum in the products of the invention of Examples 1 and 3 when used at very low content concentrations: 1, 1.5, 2 and 3 g / m * measured like Al.Oj.
Man gennemfører forsøgene ved såkaldt jar-test under brug 10 af den fremgangsmåde, der er beskrevet i eksempel 5, og under anvendelse af vand af typen vand fra floden Seine.The tests are carried out by so-called jar tests using 10 of the procedure described in Example 5 and using water of the Seine river type.
I tabel 8 er anført værdierne for pH, for uklarheden, og for mængden af organisk materiale i vandet fra floden 15 Seine, som man har målt før behandlingen ved hjælp af produkterne fra eksemplerne 1 og 3 (forsøgene Λ - P).Table 8 lists the pH values, the cloudiness, and the amount of organic matter in the 15 Seine River water measured prior to treatment using the products of Examples 1 and 3 (Experiments Λ - P).
TABEL 8 20 i-1 i-r--1 |Test nr. | pH vand | uklarhed (NTU) | M.O. (mg 0^/1)|TABLE 8 20 i-1 i-r - 1 | Test No. | pH water | obscurity (NTU) | M.O. (mg 0 ^ / 1) |
I A I I I 5,88 II A I I I 5.88 I
25 I B-C I I I 6,08 I25 I B-C I I I 6.08 I
| D-E | 8,02 | 8,2 I I| D-E | 8.02 | 8.2 I I
I F-G I 8,05 I 7,4 I II F-G I 8.05 I 7.4 I I
I H-I I I 10,0 I 5,88 II H-I I I 10.0 I 5.88 I
I J-K I I 10,0 I 5,48 II J-K I I 10.0 I 5.48 I
30 I L I 8,10 I 12,0 I 4,68 |30 I L I 8.10 I 12.0 I 4.68 |
I M-N I 8,00 I 8,3 I II M-N I 8.00 I 8.3 I I
I O-P I 7,91 I 12 I II O-P I 7.91 I 12 I I
I--1_I_1__II - 1_I_1__I
35 DK 172765 B1 20 I tabel 9 er anvendt gennemsnitsværdierne af de resultater, som er opnået ved som reference at tage produktet fra eksempel 3. De procentandele, der er vist, er opnået på følgende måde: 5 - , t ,.. værdien for x fcks. i, . , nn område for parametre x {?,) = væidien for x f eks ; 3 x 100-100 idet i = 1 eller 3, 10 N.B. De beregnede værdier er ikke påvist signifikante, med mindre deres absolutte værdi er > eller = 5¾.35 DK 172765 B1 20 Table 9 uses the average values of the results obtained by reference for the product of Example 3. The percentages shown are obtained as follows: 5 -, t, .. x fcks. i,. , nn range of parameters x {?,) = the value of x for example; 3 x 100-100 with i = 1 or 3, 10 N.B. The calculated values are not shown to be significant unless their absolute value is> or = 5¾.
TABEL 9 15 i-i-1-1 I I I Difference af | I i i------,--,-i I |Mængde |Uklarhed i supernatant | M.O | Rest | 20 I Produkt I i g/m3 | % [ | Al j I (nr. af| (som |-,-1--1 | |TABLE 9 15 i-i-1-1 I I I Difference of | I i i ------, -, - i I | Quantity | Supernatant cloudiness | M.O | Rest | 20 I Product I in g / m3 | % [| Al j I (No. of | (as | -, - 1--1 | |
Ieks) |A1.0j I 3’ I 10T | 20 | (Ί) | (?) | 1-1----------1--1-H------1——I---1 I 1 I I 14 I 9,3 I 8,9 I -0,7 I - |Ieks) | A1.0j I 3 'I 10T | 20 | (Ί) | (?) | 1-1 ---------- 1--1-H ------ 1 —— I --- 1 I 1 II 14 I 9.3 I 8.9 I -0.7 I - |
25 I 3 1 1 I 0 I 0 |0 I 0 I 0 I25 I 3 1 1 I 0 I 0 | 0 I 0 I 0 I
I I I I I I I II I I I I I I I
il I I 18 I 9,2 I 6 I 1,8 I- 10 Iil I I 18 I 9.2 I 6 I 1.8 I- 10 I
I 3 I 1,5 I 0 I 0 I 0 I 0 I o II 3 I 1.5 I 0 I 0 I 0 I 0 I o I
I I I I I I I II I I I I I I I
30 I 1 I I 20 I 9,9 I 3,3 I | | I 3 I 2 I 0 I 0 I 0 I 0 I 0 [30 I 1 I I 20 I 9.9 I 3.3 I | | I 3 I 2 I 0 I 0 I 0 I 0 I 0 [
I I 1 I I I I II I I I I I I I
I 1 I I 5,25 I 0,34 I -2,4 | - | - | I 3 I 3 I o jo |o j o 1 j 35 1-1-1-1-1-1-----1-----------1I 1 I I 5.25 I 0.34 I -2.4 | - | - | I 3 I 3 I o you | o j o 1 j 35 1-1-1-1-1-1 ----- 1 ----------- 1
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8801056A FR2626567B1 (en) | 1988-01-29 | 1988-01-29 | BASIC ALUMINUM CHLOROSULFATE, MANUFACTURING METHOD THEREOF, USE THEREOF AS FLOCCULATING AGENT |
| FR8801056 | 1988-01-29 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK35289D0 DK35289D0 (en) | 1989-01-27 |
| DK35289A DK35289A (en) | 1989-09-05 |
| DK172765B1 true DK172765B1 (en) | 1999-07-05 |
Family
ID=9362763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK198900352A DK172765B1 (en) | 1988-01-29 | 1989-01-27 | Basic aluminum chlorosulfate, process for their preparation and use as flocculant |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0327419B2 (en) |
| JP (1) | JPH0710727B2 (en) |
| KR (1) | KR910004836B1 (en) |
| CN (1) | CN1018997B (en) |
| AT (1) | ATE122324T1 (en) |
| AU (1) | AU619518B2 (en) |
| CA (1) | CA1328594C (en) |
| DE (1) | DE68922504T3 (en) |
| DK (1) | DK172765B1 (en) |
| ES (1) | ES2073449T5 (en) |
| FI (1) | FI98726C (en) |
| FR (1) | FR2626567B1 (en) |
| IE (1) | IE72505B1 (en) |
| NO (1) | NO301756B1 (en) |
| PT (1) | PT89562B (en) |
| ZA (1) | ZA89669B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2687394B1 (en) * | 1992-02-18 | 1994-03-25 | Elf Atochem Sa | NOVEL ALUMINUM POLYCHLOROSULFATES, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATIONS. |
| CN1034922C (en) * | 1994-01-12 | 1997-05-21 | 陈家盛 | Complex aluminate "PAS" and its production process |
| CA2229266C (en) * | 1995-09-18 | 2001-10-16 | Delta Chemical Corporation | Polyaluminum chlorides and polyaluminum chlorosulfates methods and compositions |
| CN101306827B (en) * | 2008-06-11 | 2010-07-28 | 中国石油天然气股份有限公司 | Method for preparing polyaluminium chloride by firing waste residues with sludge |
| JP5614644B2 (en) * | 2010-10-19 | 2014-10-29 | メタウォーター株式会社 | Membrane filtration method |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2036685A1 (en) * | 1969-01-31 | 1970-12-31 | Taki Fertilizer Manufac | Basic salts as coagulants for use in aqueous - media |
| FI53963C (en) * | 1971-02-19 | 1978-09-11 | Kali Chemie Ag | ALUMINUM CHLORIDE FRAME STATION |
| JPS5725492B2 (en) * | 1973-04-19 | 1982-05-29 | ||
| FR2317227A1 (en) * | 1975-07-10 | 1977-02-04 | Rhone Poulenc Ind | PROCESS FOR THE MANUFACTURE OF ALUMINUM HYDROXYCHLORIDES |
| JPS52113384A (en) * | 1976-02-23 | 1977-09-22 | Toyo Soda Mfg Co Ltd | Production of inorganic flocculant |
| SE425847B (en) * | 1979-11-16 | 1982-11-15 | Boliden Ab | PROCEDURE FOR PREPARING WATER-SOLUBLE BASIC ALUMINUM CHLORIDE AND / OR BASIC ALUMINUM SULPHATE CHLORIDE |
| AT364972B (en) * | 1980-06-25 | 1981-11-25 | Palkovits Johann | METHOD FOR PROTECTING METAL TUBES AGAINST CORROSION |
| JPS5760293A (en) * | 1980-09-29 | 1982-04-12 | Tokyo Shibaura Electric Co | Inspection monitoring system of nuclear reactor container inside |
| JPS5839775A (en) * | 1981-09-02 | 1983-03-08 | Mitsubishi Heavy Ind Ltd | Method and device for surface hardening of high pressure fuel injection pipe |
| FR2534897A1 (en) * | 1982-10-26 | 1984-04-27 | Ugine Kuhlmann | PROCESS FOR THE PRODUCTION OF BASIC ALUMINUM CHLOROSULFATES |
| IL79304A (en) * | 1985-07-05 | 1990-07-12 | Dow Chemical Co | Mixed metal hydroxides for thickening water or hydrophilic fluids |
-
1988
- 1988-01-29 FR FR8801056A patent/FR2626567B1/en not_active Expired - Lifetime
-
1989
- 1989-01-17 NO NO890200A patent/NO301756B1/en not_active IP Right Cessation
- 1989-01-19 DE DE68922504T patent/DE68922504T3/en not_active Expired - Fee Related
- 1989-01-19 AT AT89400156T patent/ATE122324T1/en not_active IP Right Cessation
- 1989-01-19 EP EP89400156A patent/EP0327419B2/en not_active Expired - Lifetime
- 1989-01-19 ES ES89400156T patent/ES2073449T5/en not_active Expired - Lifetime
- 1989-01-23 CA CA000588924A patent/CA1328594C/en not_active Expired - Fee Related
- 1989-01-27 FI FI890426A patent/FI98726C/en not_active IP Right Cessation
- 1989-01-27 IE IE27989A patent/IE72505B1/en not_active IP Right Cessation
- 1989-01-27 DK DK198900352A patent/DK172765B1/en not_active IP Right Cessation
- 1989-01-27 ZA ZA89669A patent/ZA89669B/en unknown
- 1989-01-27 AU AU28835/89A patent/AU619518B2/en not_active Ceased
- 1989-01-27 PT PT89562A patent/PT89562B/en not_active IP Right Cessation
- 1989-01-28 CN CN89100474A patent/CN1018997B/en not_active Expired
- 1989-01-28 KR KR1019890000946A patent/KR910004836B1/en not_active IP Right Cessation
- 1989-01-30 JP JP1020674A patent/JPH0710727B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE68922504T3 (en) | 2003-02-13 |
| DK35289A (en) | 1989-09-05 |
| ES2073449T5 (en) | 2002-12-16 |
| FR2626567B1 (en) | 1991-09-27 |
| EP0327419A1 (en) | 1989-08-09 |
| ATE122324T1 (en) | 1995-05-15 |
| FI890426A (en) | 1989-07-30 |
| KR910004836B1 (en) | 1991-07-13 |
| IE890279L (en) | 1989-07-29 |
| DE68922504T2 (en) | 1996-01-18 |
| FI98726B (en) | 1997-04-30 |
| JPH01226718A (en) | 1989-09-11 |
| CA1328594C (en) | 1994-04-19 |
| EP0327419B1 (en) | 1995-05-10 |
| JPH0710727B2 (en) | 1995-02-08 |
| PT89562A (en) | 1989-10-04 |
| DE68922504D1 (en) | 1995-06-14 |
| IE72505B1 (en) | 1997-04-23 |
| FR2626567A1 (en) | 1989-08-04 |
| AU619518B2 (en) | 1992-01-30 |
| EP0327419B2 (en) | 2002-06-12 |
| PT89562B (en) | 1994-01-31 |
| KR890011779A (en) | 1989-08-22 |
| NO890200D0 (en) | 1989-01-17 |
| DK35289D0 (en) | 1989-01-27 |
| NO890200L (en) | 1989-07-31 |
| ES2073449T3 (en) | 1995-08-16 |
| NO301756B1 (en) | 1997-12-08 |
| CN1034701A (en) | 1989-08-16 |
| FI890426A0 (en) | 1989-01-27 |
| AU2883589A (en) | 1989-08-03 |
| CN1018997B (en) | 1992-11-11 |
| ZA89669B (en) | 1989-10-25 |
| FI98726C (en) | 1997-08-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| B1 | Patent granted (law 1993) | ||
| PBP | Patent lapsed |
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