DE10004054A1 - Preventing precipitation of calcium and magnesium salts in water by treatment with activated carbon which has been surface-modified with functional groups stabilizing the water hardness - Google Patents

Preventing precipitation of calcium and magnesium salts in water by treatment with activated carbon which has been surface-modified with functional groups stabilizing the water hardness

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Publication number
DE10004054A1
DE10004054A1 DE2000104054 DE10004054A DE10004054A1 DE 10004054 A1 DE10004054 A1 DE 10004054A1 DE 2000104054 DE2000104054 DE 2000104054 DE 10004054 A DE10004054 A DE 10004054A DE 10004054 A1 DE10004054 A1 DE 10004054A1
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activated carbon
water
treatment
groups
pretreated
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German (de)
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REGGI, ALESSANDRO, 61350 BAD HOMBURG, DE
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Judo Wasseraufbereitung GmbH
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Priority to DE20023050U priority Critical patent/DE20023050U1/en
Priority to DE2000104054 priority patent/DE10004054A1/en
Publication of DE10004054A1 publication Critical patent/DE10004054A1/en
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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3251—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulphur
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3255—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. heterocyclic or heteroaromatic structures
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/4602—Treatment of water, waste water, or sewage by electrochemical methods for prevention or elimination of deposits
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/56—Use in the form of a bed

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

Precipitation of poorly-soluble calcium- and/or magnesium-salts is prevented by passing water through or onto the surface of an activated carbon layer. The activated carbon having had functional groups which stabilize the water hardness formed on its surface by heat, chemical and/or electrochemical pre-treatment. An independent claim is included for apparatus comprising a water treatment space containing an activated carbon surface modified with functional groups as above.

Description

Die Erfindung betrifft ein Verfahren und eine Vorrichtung zur Verhinderung der Ausfällung von schwerlöslichen Calcium- und/oder Magnesiumverbindungen aus Wasser. The invention relates to a method and an apparatus for preventing Precipitation of poorly soluble calcium and / or magnesium compounds of water.  

Ein solches Verfahren und die entsprechende Vorrichtung sind beispielsweise bekannt durch das Lehrbuch von Alfons Gaßner "Der Installateur", Verlag Handwerk und Technik, Hamburg, 4. Auflage, 1995, Seiten 79-80.Such a method and the corresponding device are, for example known from the textbook by Alfons Gaßner "The Installer", publisher Handwerk und Technik, Hamburg, 4th edition, 1995, pages 79-80.

Zum Schutz von wasserdurchflossenen technischen Einrichtungen, beispiels­ weise Heizstäben von Waschmaschinen und Warmwasser-Boilern im Haus­ wasserbereich sowie Wasserkesseln, Leitungen und Armaturen im industriellen Umfeld, soll eine Ausfällung von schwerlöslichen Calcium- und Magnesiumver­ bindungen aus dem Wasser verhindert werden, um ein Verkalken der betrof­ fenen Einrichtungen zu vermeiden oder zumindest erheblich zu verlangsamen.To protect technical equipment through which water flows, for example wise heating elements of washing machines and hot water boilers in the house water area as well as water boilers, pipes and fittings in industrial Environment, a precipitation of poorly soluble calcium and magnesium ver Water bindings can be prevented to prevent calcification of the affected avoid open facilities or at least slow them down considerably.

Seit langem ist eine ganze Reihe von Substanzen bekannt, die zu dem oben genannten Zweck dem Wasser beigegeben werden, und deren funktionelle Gruppen die Wasserhärte stabilisieren können. Diese funktionellen Gruppen verhindern mittels des Threshold-Effektes (siehe z. B. "Römpp Chemie-Lexikon", Georg Thieme Verlag, Band T-Z, 9. Auflage, 1995, Seiten 5001-5002) das Wachstum von bereits entstandenen Kalkkristallen und bewirken somit, daß sich zur weiteren Kalkabscheidung aus dem Wasser zunächst wiederum neue Kalkkristalle bilden müssen. Der letztgenannte Vorgang läuft in der Regel jedoch nur stark gehemmt ab, wodurch die Ausfällung verhindert oder zumindest deutlich verzögert wird.A whole range of substances have been known for a long time that go to the above mentioned purpose are added to the water, and their functional Groups that can stabilize water hardness. These functional groups prevent by means of the threshold effect (see e.g. "Römpp Chemie-Lexikon", Georg Thieme Verlag, Volume T-Z, 9th edition, 1995, pages 5001-5002) das Growth of lime crystals already formed and thus cause that new ones for further lime separation from the water Lime crystals must form. The latter process usually runs however, only strongly inhibited, which prevents the precipitation or is at least significantly delayed.

Als Substanzen kommen hierfür u. a. (niedermolekulare) Polycarbonsäuren und ihre Derivate wie z. B. Polyacrylate, Polymethacrylate, Polymaleinsäure, Polymalein-Anhydrid oder Lactone in Frage, ebenso Polymere mit Sulfonsäure- und/oder Sulfonatgruppen, aber auch Polyalkohole, Phenole und ihre Deri­ vate, Polycarbonyle und ihre Derivate, Aldehyde, Ketone oder Chinone sowie auch Polyphosphate. As substances come u. a. (low molecular weight) polycarboxylic acids and their derivatives such as B. polyacrylates, polymethacrylates, polymaleic acid, Polymaleic anhydride or lactones in question, as well as polymers with sulfonic acid and / or sulfonate groups, but also polyalcohols, phenols and their deri vate, polycarbonyls and their derivatives, aldehydes, ketones or quinones as well also polyphosphates.  

Nachteilig bei den bekannten Verfahren zur Härtestabilisierung des Wassers mit diesen Substanzen ist, daß die Substanzen dem Wasser in gelöster Form zudosiert werden müssen. Dies macht einerseits den Einsatz von relativ auf­ wendigen Dosiereinrichtungen erforderlich, andererseits wird fachkundiges Personal benötigt, das im Umgang mit den entsprechenden Chemikalien geschult ist. Zumindest im Hauswasserbereich ist zudem die Bevorratung und Handhabung von Chemikalien hochgradig unerwünscht, weil es hier leicht zu einer Über- oder Unterdosierung kommen kann, die regelmäßige Nachführung der Chemikalien oft vergessen wird und während der Lagerung derselben eine nicht geringe Unfallgefahr beispielsweise durch spielende Kinder besteht.A disadvantage of the known methods for stabilizing the hardness of the water with these substances is that the substances are the water in dissolved form must be added. On the one hand, this makes the use of relative manoeuvrable dosing devices required, on the other hand becomes specialized Personnel needed to handle the appropriate chemicals is trained. At least in the domestic water area, there is also a supply and Handling chemicals is highly undesirable because it is easy to do here an overdosing or underdosing, regular follow-up chemicals are often forgotten and one during storage there is no small risk of accidents, for example, from children playing.

Aufgabe der vorliegenden Erfindung ist es demgegenüber, ein Verfahren und eine Vorrichtung der eingangs beschriebenen Art vorzustellen, mit denen die Ausfällung von schwerlöslichen Calcium- bzw. Magnesiumverbindungen aus dem Wasser automatisch und ohne die Notwendigkeit zur dauernden und fort­ gesetzten Handhabung von Chemikalien möglichst weitgehend verhindert wird.In contrast, the object of the present invention is a method and to introduce a device of the type described above, with which the Precipitation of poorly soluble calcium or magnesium compounds the water automatically and without the need to go on and on handling of chemicals is prevented as far as possible.

Erfindungsgemäß wird diese Aufgabe hinsichtlich des Verfahrens ebenso über­ raschend einfach wie wirkungsvoll dadurch gelöst, daß das zu behandelnde Wasser durch eine Aktivkohleschicht hindurch oder an der Oberfläche von Aktivkohlematerial vorbei geleitet wird, und daß auf der Oberfläche der Aktiv­ kohle durch eine thermische und/oder chemische und/oder elektrochemische Vorbehandlung funktionelle Gruppen zur Härtestabilisierung gebildet wurden.According to the invention, this object is also achieved with regard to the method solved surprisingly simply and effectively in that the to be treated Water through an activated carbon layer or on the surface of Activated carbon material is passed and that on the surface of the active coal by a thermal and / or chemical and / or electrochemical Pretreatment functional groups for hardness stabilization were formed.

Auf diese Weise kann automatisch und ohne den Einsatz von Chemikalien allein durch den Kontakt des zu behandelnden Wassers mit Oberflächen des entsprechend vorbehandelten Aktivkohlematerials die erwünschte Wirkung einer weitgehenden Verhinderung von Kalkausfällungen erreicht werden. Der Benutzer muß dazu nicht wie bisher in regelmäßigen Abständen Chemikalien dem zu behandelnden Wasser zudosieren, sondern es reicht aus, wenn eine gewisse Menge von entsprechend vorbehandeltem Aktivkohlematerial mit dem Wasser in Kontakt gebracht wird.This way it can be done automatically and without the use of chemicals solely through the contact of the water to be treated with surfaces of the the desired effect in accordance with pretreated activated carbon material extensive prevention of lime deposits can be achieved. The Users do not have to use chemicals at regular intervals as before the water to be treated, but it is sufficient if one certain amount of appropriately pretreated activated carbon material with the  Water is brought into contact.

Aus der Literatur sind verschiedene Verfahren an sich bekannt, mit denen auf Aktivkohleoberflächen "saure Oberflächenoxide", die den oben genannten funk­ tionellen Gruppen entsprechen, gebildet werden können. Der erfindungs­ gemäße Vorschlag, derartig behandelte Aktivkohle zur Verhinderung von Kalk­ ausfällungen in der Wasserbehandlung einzusetzen, ist der Literatur nicht einmal andeutungsweise zu entnehmen.Various methods are known per se from the literature, with which on Activated carbon surfaces "acidic surface oxides", the funk tional groups correspond, can be formed. The invention according proposal, activated carbon treated in this way to prevent limescale The literature does not use precipitates in water treatment can be inferred once.

Andererseits ist es schon lange an sich bekannt, Aktivkohle zur Reinigung von Wasser einzusetzen (siehe z. B. "Römpp Chemie-Lexikon", Georg Thieme Verlag, Band A-C, 9. Auflage, 1995, Seite 83). Eine Eignung zur Härtestabilisierung wird derartigen Aktivkohlefiltern jedoch in der Literatur ausdrücklich abgesprochen (siehe z. B. den Firmenprospekt "NORIT LIQUID­ PURE" der Firma Norit Adsorptions GmbH, Düsseldorf, 1982). Auch gibt es keine Hinweise auf die erfindungsgemäß vorgeschlagene Vorbehandlung der Aktivkohle in diesem Zusammenhang.On the other hand, it has long been known per se to use activated carbon for cleaning Use water (see eg "Römpp Chemie-Lexikon", Georg Thieme Verlag, volume A-C, 9th edition, 1995, page 83). Aptitude for Such activated carbon filters are however hardness stabilized in the literature expressly agreed (see e.g. the company brochure "NORIT LIQUID PURE "from Norit Adsorptions GmbH, Düsseldorf, 1982). There are also no evidence of the pretreatment of the proposed according to the invention Activated carbon in this context.

Bei einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden bei der Vorbehandlung der Aktivkohle als funktionelle Gruppen Carboxyl-Gruppen, Carboxylate, Lactone, Sulfonsäure-Gruppen, Sulfonate, Hydroxyl-Gruppen, Carbonyl-Gruppen, Chinone oder Mischungen aus diesen gebildet. Diese Gruppen finden sich als für den oben beschriebenen Threshold- Effekt verantwortliche funktionelle Gruppen bei den erwähnten Substanzen Polycarbonsäuren und ihre Derivate wie z. B. Polyacrylate, Polymethacrylate, Polymaleinsäure, Polymalein-Anhydrid, Lactone, Polymere mit Sulfonsäure- und/oder Sulfonatgruppen, Polyalkohole, Phenole und ihre Derivate, Polycarbonyle und ihre Derivate, Aldehyde, Ketone oder Chinone wieder.In a preferred embodiment of the method according to the invention are used in the pretreatment of activated carbon as functional groups Carboxyl groups, carboxylates, lactones, sulfonic acid groups, sulfonates, Hydroxyl groups, carbonyl groups, quinones or mixtures of these educated. These groups are found as for the threshold- Effect responsible functional groups for the substances mentioned Polycarboxylic acids and their derivatives such. B. polyacrylates, polymethacrylates, Polymaleic acid, polymaleic anhydride, lactones, polymers with sulfonic acid and / or sulfonate groups, polyalcohols, phenols and their derivatives, Polycarbonyls and their derivatives, aldehydes, ketones or quinones again.

Besonders bevorzugt ist eine Variante des erfindungsgemäßen Verfahrens, bei der durch die Vorbehandlung der Aktivkohle eine partielle Oxidation der Aktivkohleoberfläche bewirkt wird.A variant of the method according to the invention is particularly preferred for partial oxidation of the activated carbon surface due to the pretreatment of the activated carbon  is effected.

Dies kann beispielsweise durch Behandlung der Aktivkohle mit oxidierenden Säuren, insbesondere mit Salpetersäure und/oder Schwefelsäure und/oder Phosphorsäure erreicht werden.This can be done, for example, by treating the activated carbon with oxidizing agents Acids, especially with nitric acid and / or sulfuric acid and / or Phosphoric acid can be achieved.

Alternativ oder zusätzlich kann bei weiteren Varianten der Erfindung die Aktiv­ kohle mit Oxidationsmitteln, insbesondere mit Peroxodisulfaten und/oder Wasserstoffperoxid und/oder Kaliumpermanganat und/oder Chlor und/oder Chlordioxid und/oder Ozon, vorbehandelt werden.Alternatively or additionally, the active can be used in further variants of the invention coal with oxidizing agents, in particular with peroxodisulfates and / or Hydrogen peroxide and / or potassium permanganate and / or chlorine and / or Chlorine dioxide and / or ozone, are pretreated.

Eine weitere Möglichkeit der Vorbehandlung der erfindungsgemäß eingesetzten Aktivkohle kann in einer elektrochemischen, insbesondere anodischen Behand­ lung der Aktivkohle bestehen. Dabei wird die Aktivkohle vorzugsweise als Anode geschaltet.Another possibility for the pretreatment of those used according to the invention Activated carbon can be treated in an electrochemical, in particular anodic, treatment activated carbon. The activated carbon is preferably used as Anode switched.

Zur Erzielung des erfindungsgemäßen Ergebnisses kann die Aktivkohle auch thermisch bei Temperaturen < 200°C, vorzugsweise bei ca. 400°C vorbehandelt werden.The activated carbon can also be used to achieve the result according to the invention thermally pretreated at temperatures <200 ° C, preferably at approx. 400 ° C become.

Bei einer besonders bevorzugten Weiterbildung wird die Aktivkohle unter Ein­ wirkung von Luft oder noch besser unter Zufuhr von reinem Sauerstoff vorbe­ handelt. Dadurch werden die gewünschten Oxydationsprozesse an der Aktiv­ kohleoberfläche beschleunigt.In a particularly preferred development, the activated carbon is under one effect of air or even better with the addition of pure oxygen acts. This will activate the desired oxidation processes accelerated coal surface.

Bevorzugt wird die Aktivkohle in Form einer Schüttung bzw. eines Festbettes zumindest partiell vom zu behandelnden Wasser durchströmt.The activated carbon is preferably in the form of a bed or a fixed bed at least partially flows through the water to be treated.

Eine besonders gute Härtestabilisierung wird erreicht, wenn die Aktivkohle bei der Wasserbehandlung gleichzeitig einem Elektrolyseprozess unterworfen wird, bei dem die Aktivkohleschüttung vorzugsweise als Anode geschaltet ist. A particularly good hardness stabilization is achieved if the activated carbon the water treatment is simultaneously subjected to an electrolysis process, in which the activated carbon bed is preferably connected as an anode.  

Das Ergebnis kann noch verbessert werden, wenn die Strömungsverhältnisse des zu behandelnden Wassers so eingerichtet und/oder der Elektrolysestrom so modifiziert werden, daß an der Kathode Kalkpartikel gebildet, anschließend vom durchströmenden Wasser zu der als Anode geschalteten Aktivkohle transportiert und dort mittels der funktionellen Gruppen stabilisiert und am weiteren Wachstum gehindert werden.The result can still be improved if the flow conditions of the water to be treated and / or the electrolysis current be modified so that lime particles are formed on the cathode, then from the water flowing through to the activated carbon connected as an anode transported and stabilized there by means of the functional groups and on further growth can be hindered.

Eine ebenfalls besonders bevorzugte Ausführungsform stellt die Ausbildung eines Aktivkohlewirbelbettes dar. Die Korngröße der Aktivkohlepartikel liegt bevorzugt im Bereich zwischen etwa 0,1 mm und ca. 10 mm.Training is another particularly preferred embodiment an activated carbon fluidized bed. The grain size of the activated carbon particles is preferably in the range between approximately 0.1 mm and approximately 10 mm.

In den Rahmen der vorliegenden Erfindung fällt auch eine Vorrichtung zur Ver­ hinderung der Ausfällung von schwerlöslichen Calcium- und/oder Magnesium­ verbindungen aus Wasser gemäß dem oben beschriebenen Verfahren. Die Vorrichtung weist einen Zulauf für zu behandelndes Wasser und einen Ablauf für behandeltes Wasser auf und unterscheidet sich von bekannten Vorrichtun­ gen der gattungsbildenden Art dadurch, daß in einem Behandlungsraum zwi­ schen dem Zulauf und dem Ablauf Aktivkohle vorgesehen ist, auf deren Ober­ fläche durch eine thermische und/oder chemische und/oder elektrochemische Vorbehandlung funktionelle Gruppen zur Härtestabilisierung gebildet wurden.An apparatus for ver also falls within the scope of the present invention prevention of the precipitation of poorly soluble calcium and / or magnesium connections from water according to the procedure described above. The Device has an inlet for water to be treated and an outlet for treated water and differs from known devices gen of the generic type in that in a treatment room between between the inlet and the outlet activated carbon is provided on the upper area by a thermal and / or chemical and / or electrochemical Pretreatment functional groups for hardness stabilization were formed.

Bei einer bevorzugten Ausbildungsform der erfindungsgemäßen Vorrichtung liegt Aktivkohle in Form einer Schüttung mit mittlerer Partikelgröße zwischen 0,1 mm und 10 mm vor.In a preferred embodiment of the device according to the invention there is activated carbon in the form of a bed with a medium particle size 0.1 mm and 10 mm.

Bei einer weiteren, besonders bevorzugten Ausführungsform umfaßt die Vor­ richtung eine Einrichtung zur elektrolytischen Behandlung der Aktivkohle im Behandlungsraum. In a further, particularly preferred embodiment, the front comprises direction a device for the electrolytic treatment of activated carbon in the Treatment room.  

Alternativ oder zusätzlich kann bei weiteren Ausführungsformen die erfindungs­ gemäße Vorrichtung auch eine Einrichtung zur thermischen Behandlung der Aktivkohle im Behandlungsraum, insbesondere eine elektrische Heizeinrichtung umfassen.Alternatively or additionally, the fiction, in other embodiments according device also a device for thermal treatment of the Activated carbon in the treatment room, especially an electric heating device include.

Prinzipiell können die vorstehend genannten Merkmale erfindungsgemäß je­ weils einzeln für sich oder zu mehreren in beliebigen Kombinationen Verwen­ dung finden. Die gezeigten und beschriebenen Ausführungsformen sind nicht als abschließende Aufzählung zu verstehen, sondern haben vielmehr beispiel­ haften Charakter für die Schilderung der Erfindung.In principle, the features mentioned above can be used according to the invention use it individually or in groups of any combination find. The embodiments shown and described are not to be understood as a final list, but rather have an example liable character for the description of the invention.

Claims (16)

1. Verfahren zur Verhinderung der Ausfällung von schwerlöslichen Calcium- und/oder Magnesiumverbindungen aus Wasser, dadurch gekennzeichnet, daß das zu behandelnde Wasser durch eine Aktivkohleschicht hin­ durch oder an der Oberfläche von Aktivkohlematerial vorbei geleitet wird, und daß auf der Oberfläche der Aktivkohle durch eine thermi­ sche und/oder chemische und/oder elektrochemische Vorbehand­ lung funktionelle Gruppen zur Härtestabilisierung gebildet wurden.1. A method for preventing the precipitation of sparingly soluble calcium and / or magnesium compounds from water, characterized in that the water to be treated is passed through an activated carbon layer through or past the surface of activated carbon material, and that on the surface of the activated carbon through a thermal and / or chemical and / or electrochemical pretreatment functional groups for hardness stabilization were formed. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß bei der Vorbehandlung der Aktivkohle als funktionelle Gruppen Carboxyl- Gruppen, Carboxylate, Lactone, Sulfonsäure-Gruppen, Sulfonate, Hydroxyl-Gruppen, Carbonyl-Gruppen, Chinone oder Mischungen aus diesen gebildet werden.2. The method according to claim 1, characterized in that in the Pretreatment of activated carbon as functional groups carboxyl Groups, carboxylates, lactones, sulfonic acid groups, sulfonates, Hydroxyl groups, carbonyl groups, quinones or mixtures are formed from these. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß durch die Vorbehandlung der Aktivkohle eine partielle Oxidation der Aktivkohleoberfläche bewirkt wird.3. The method according to claim 1 or 2, characterized in that by the pretreatment of the activated carbon a partial oxidation of the Activated carbon surface is effected. 4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die Ak­ tivkohle mit oxidierenden Säuren, insbesondere mit Salpetersäure und/oder Schwefelsäure und/oder Phosphorsäure, vorbehandelt wird. 4. The method according to claim 3, characterized in that the Ak Carbon with oxidizing acids, especially with nitric acid and / or sulfuric acid and / or phosphoric acid, pretreated becomes.   5. Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß die Aktivkohle mit Oxidationsmitteln, insbesondere mit Peroxodisul­ faten und/oder Wasserstoffperoxid und/oder Kaliumpermanganat und/oder Chlor und/oder Chlordioxid und/oder Ozon, vorbehandelt wird.5. The method according to claim 3 or 4, characterized in that the activated carbon with oxidizing agents, in particular with peroxodisul faten and / or hydrogen peroxide and / or potassium permanganate and / or chlorine and / or chlorine dioxide and / or ozone, pretreated becomes. 6. Verfahren nach einem der Ansprüche 3 bis 5, dadurch gekenn­ zeichnet, daß die Aktivkohle elektrochemisch, insbesondere an­ odisch vorbehandelt wird.6. The method according to any one of claims 3 to 5, characterized records that the activated carbon electrochemically, in particular is pretreated. 7. Verfahren nach einem der Ansprüche 3 bis 6, dadurch gekenn­ zeichnet, daß die Aktivkohle thermisch bei Temperaturen < 200°C, vorzugsweise bei ca. 400°C vorbehandelt wird.7. The method according to any one of claims 3 to 6, characterized records that the activated carbon is thermally at temperatures <200 ° C, is preferably pretreated at about 400 ° C. 8. Verfahren nach einem der Ansprüche 6 oder 7, dadurch gekenn­ zeichnet, daß die Aktivkohle unter Sauerstoffzufuhr vorbehandelt wird.8. The method according to any one of claims 6 or 7, characterized records that the activated carbon pretreated with oxygen becomes. 9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Aktivkohle als Schüttung vorliegt, an der das zu behandelnde Wasser vorbeiströmt oder diese zumindest teilweise durchströmt.9. The method according to any one of the preceding claims, characterized characterized in that the activated carbon is in the form of a bed at which the water to be treated flows past or at least this partially flowed through. 10. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Aktivkohle als Wirbelbett vorliegt und vom zu behandelnden Wasser durchströmt wird.10. The method according to any one of the preceding claims, characterized characterized in that the activated carbon is present as a fluidized bed and from water to be treated is flowed through. 11. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekenn­ zeichnet, daß die Aktivkohle während der Wasserbehandlung einer Elektrolyse unterworfen wird. 11. The method according to any one of claims 1 to 9, characterized records that the activated carbon during the water treatment of a Is subjected to electrolysis.   12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß die Ak­ tivkohle als Anode geschaltet wird, und daß an der Kathode Kalkpartikel gebildet, anschließend vom durchströmenden Wasser zur Aktivkohle transportiert und dort mittels der funktionellen Grup­ pen stabilisiert und am weiteren Wachstum gehindert werden.12. The method according to claim 11, characterized in that the Ak tivkohle is switched as an anode, and that on the cathode Lime particles formed, then the water flowing through them transported to the activated carbon and there by means of the functional group stabilized and prevented from further growth. 13. Vorrichtung zur Verhinderung der Ausfällung von schwerlöslichen Calcium- und/oder Magnesiumverbindungen aus Wasser gemäß dem Verfahren nach einem der vorhergehenden Ansprüche mit ei­ nem Zulauf für zu behandelndes Wasser und einem Ablauf für be­ handeltes Wasser, dadurch gekennzeichnet, daß in einem Behand­ lungsraum zwischen dem Zulauf und dem Ablauf Aktivkohle vorge­ sehen ist, auf deren Oberfläche durch eine thermische und/oder chemische und/oder elektrochemische Vorbehandlung funktionelle Gruppen zur Härtestabilisierung gebildet wurden.13. Device for preventing the precipitation of poorly soluble Calcium and / or magnesium compounds from water according to the method according to one of the preceding claims with egg nem inlet for water to be treated and an outlet for be acted water, characterized in that in one treatment space between the inlet and the outlet activated carbon can be seen on their surface by a thermal and / or chemical and / or electrochemical pretreatment functional Hardness stabilization groups were formed. 14. Vorrichtung nach Anspruch 13, dadurch gekennzeichnet, daß die Aktivkohle in Form einer Schüttung mit mittlerer Partikelgröße zwi­ schen 0,1 mm und 10 mm vorliegt.14. The apparatus according to claim 13, characterized in that the Activated carbon in the form of a bed with medium particle size between 0.1 mm and 10 mm. 15. Vorrichtung nach Anspruch 13 oder 14, dadurch gekennzeichnet, daß die Vorrichtung eine Einrichtung zur elektrolytischen Behand­ lung der Aktivkohle im Behandlungsraum umfaßt, wobei die Aktiv­ kohle vorzugsweise als Anode geschaltet ist.15. The apparatus according to claim 13 or 14, characterized in that the device is a device for electrolytic treatment tion of the activated carbon in the treatment room, the active coal is preferably connected as an anode. 16. Vorrichtung nach einem der Ansprüche 13 bis 15, dadurch gekenn­ zeichnet, daß die Vorrichtung eine Einrichtung zur thermischen Be­ handlung der Aktivkohle im Behandlungsraum, insbesondere eine elektrische Heizeinrichtung umfaßt.16. The device according to one of claims 13 to 15, characterized records that the device is a device for thermal loading act of activated carbon in the treatment room, especially a electric heater includes.
DE2000104054 2000-02-01 2000-02-01 Preventing precipitation of calcium and magnesium salts in water by treatment with activated carbon which has been surface-modified with functional groups stabilizing the water hardness Ceased DE10004054A1 (en)

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Publication number Priority date Publication date Assignee Title
CN102951706A (en) * 2011-08-17 2013-03-06 中国石油化工股份有限公司 Processing method of wastewater containing salts and chloride ions
WO2015028836A1 (en) * 2013-08-30 2015-03-05 Sierra Plazas Julia Ines Device and method for cleaning and reusing waste water in small and medium-sized businesses

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JPH06367A (en) * 1992-06-24 1994-01-11 Takeda Chem Ind Ltd Powdery active carbon for water treatment and production thereof
JPH1110100A (en) * 1997-06-25 1999-01-19 Mitsuhashi Haguruma Seisakusho:Kk Air clean device and cleaning method using the same

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Publication number Priority date Publication date Assignee Title
US1819165A (en) * 1927-05-28 1931-08-18 Gasoline Recovery Corp Highly active carbon and its manufacture
JPS62191040A (en) * 1986-02-17 1987-08-21 Nippon Denso Co Ltd Adsorbable carbon material and its production
JPH06367A (en) * 1992-06-24 1994-01-11 Takeda Chem Ind Ltd Powdery active carbon for water treatment and production thereof
JPH1110100A (en) * 1997-06-25 1999-01-19 Mitsuhashi Haguruma Seisakusho:Kk Air clean device and cleaning method using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102951706A (en) * 2011-08-17 2013-03-06 中国石油化工股份有限公司 Processing method of wastewater containing salts and chloride ions
WO2015028836A1 (en) * 2013-08-30 2015-03-05 Sierra Plazas Julia Ines Device and method for cleaning and reusing waste water in small and medium-sized businesses

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