EP0000130A1 - Silicate-type complexing agent for alkaline-earth ions and process for its preparation - Google Patents

Silicate-type complexing agent for alkaline-earth ions and process for its preparation Download PDF

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EP0000130A1
EP0000130A1 EP78100124A EP78100124A EP0000130A1 EP 0000130 A1 EP0000130 A1 EP 0000130A1 EP 78100124 A EP78100124 A EP 78100124A EP 78100124 A EP78100124 A EP 78100124A EP 0000130 A1 EP0000130 A1 EP 0000130A1
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acid
complexing agent
alkali
activated
mineral
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EP0000130B1 (en
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Rudolf Dipl.-Chem. Dr. Fahn
Nikolaus Dipl.-Chem. Dr. Fenderl
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Sued Chemie AG
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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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth

Definitions

  • the invention relates to an adsorptive silicate complexing agent for alkaline earth ions and a method for its production.
  • ions of the octahedral layer are extracted, whereby depending on the acid concentration, temperature, time and pressure, the amount of the octahedral layer ions dissolving and also the tetrahedral layer ions soluble in acid can be varied.
  • the specific surface area and the number of micropores increase, while the ion exchange capacity decreases.
  • the invention thus relates to an adsorptive silicate complexing agent for alkaline earth ions, which is characterized in that it can be prepared by loading alkali with a material obtained by acid activation of a mineral from the montmorillonite-beidellite series.
  • montmorillonite-beidellite series The minerals from the montmorillonite-beidellite series are explained in more detail, for example, in "Ullmann's Encyclopedia of Industrial Chemistry", volume 17, pages 593 to 594.
  • This series includes montmorillonite (the main mineral of bentonite), hectorite, beidellite, saponite and nontronite.
  • an acid-activated bentonite is preferably used as the starting material, which is then loaded with alkali.
  • the production of acid-activated bentonites is known per se.
  • the starting material is preferably digested with a mineral acid, such as hydrochloric acid, sulfuric acid or nitric acid.
  • a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid.
  • organic acids such as acetic acid is also possible.
  • the acid digestion can in a ver thin suspension or by treatment of a plastic clay with concentrated acid. It is also possible to carry out the acid activation of the plastic clay in the gas phase, for example using hydrogen chloride or sulfur dioxide. After activation, the material is washed with either water or dilute acid and dried.
  • the specific surface is generally determined using the BET method.
  • an acid-activated material with a particle size of not more than about 50 / u.
  • a material can be obtained, for example, by removing the coarse fractions above 50 ⁇ , preferably above approximately 15 to 20 ⁇ , by means of a hydrocyclone treatment. You can either subject the raw material that has not yet been activated or the acid-activated material to the hydrocyclone purification. This treatment is preferably carried out with the acid-treated material, since a good separation effect is still achieved in this way even with more concentrated suspensions.
  • the coarse fractions which are separated out are usually quartz, mica, feldspar, pyrite and hematite particles, which show a minimal adsorption or ion binding capacity.
  • An alkali metal hydroxide, carbonate, phosphate or borate is preferably used to load the acid-activated material. Loading is preferably carried out by combining the acid-activated material with the alkaline substance to form a dry mixture; it can also be carried out by treatment in an aqueous suspension or paste at about 25 to 100 ° C.
  • “loading with alkali” means both the exchange of the H ions on the surface and between the layers, and also the reaction with the acidic groups of the acid-activated material. This term also includes the adsorptive bond and the intra-crystalline incorporation of the alkaline substance in the lattice of the material.
  • the complexing agent according to the invention can also be in the form of an aqueous suspension.
  • a suspension contains about 100 to 200 g of insoluble solids per liter.
  • the complexing agents according to the invention have a binding capacity for calcium ions between approximately 700 and 1000 meq / 100 g in a pH range of approximately 9 to 11, the binding capacity generally increasing at higher temperatures.
  • the binding capacity of the complexing agents according to the invention for calcium ions is thus about a power of ten greater than the ion exchange capacity of the natural bentonites, which is about 70 to 100 meq / 100 g.
  • Bentonite raw clay from the Bavarian deposits in the Moosburg-Mainburg-Landshut region is mixed with 280 to 1680, preferably 840 meq, mineral acid, preferably hydrochloric acid, based on 100 g dry clay, and heated to about 95 ° C. for 5 to 10, preferably 8 hours . The portions dissolved are separated from the solid together with the remaining acid. After washing out the acid-activated bentonite to a pH of 4-5, it is dried and ground.
  • the solid obtained in this way is subjected to an alkali treatment, alkali compounds, such as hydroxides or carbonates, preferably Na 2 CO 3 being added to the solid in amounts of about 20 to 50 parts by weight per 100 parts by weight of solid. If solid alkali compounds are used, these are ground with the solid. When using solutions of the alkali compounds, a concentrated solution is preferably kneaded into a paste of the solid. This product is then dried and ground.
  • alkali compounds such as hydroxides or carbonates, preferably Na 2 CO 3
  • the acid-activated bentonite according to Example 1 is separated after heating by hydrocyclone treatment from accompanying minerals usually contained in the bentonite, such as quartz, mica, feldspar, pyrite, etc. After removal of the coarse fractions, the finely divided solid is separated from the suspension as in Example 1, washed out, dried and ground and subjected to an alkali treatment. A product is obtained which has a higher yield in terms of Ca binding capacity, since it contains smaller amounts of inactive components than the product in Example 1.
  • the calculated amount of NaOH is presented in the form of a 20% sodium hydroxide solution.
  • the dry product is kneaded into this solution.
  • the resulting paste is dried at 80 ° C and then ground.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

Silikatischer Komplexbildner für Erdalkali-Ionen, erhältlich durch Beladung eines durch Säureaktivierung eines Minerals aus der Montmorillonit-Beidellit- Reihe erhaltenen Materials mit Alkali. Bevorzugtes Ausgangsmaterial ist säureaktivierter Bentonit. Die Beladung des säureaktivierten Materials kann mit einem Alkalihydroxid, -carbonat, -phosphat oder -borat durch trockenes oder nasses Vermischen erfolgen.Silicate complexing agent for alkaline earth ions, obtainable by loading alkali with a material obtained by acid activation of a mineral from the montmorillonite beidellite series. The preferred starting material is acid-activated bentonite. The acid-activated material can be loaded with an alkali metal hydroxide, carbonate, phosphate or borate by dry or wet mixing.

Description

Die Erfindung betrifft einen adsorptiv wirkenden silikatischen Komplexbildner für Erdalkali-Ionen sowie ein Verfahren zu dessen Herstellung.

Figure imgb0001
The invention relates to an adsorptive silicate complexing agent for alkaline earth ions and a method for its production.
Figure imgb0001

Ladungsdefizit der Silikatlamellen, welches durch Bindung von zum Beispiel Alkali- oder Erdalkali-Ionen ausgeglichen wird.Charge deficit of the silicate flakes, which is compensated for by binding, for example, alkali or alkaline earth ions.

Bei säureaktivierten Mineralen aus der Montmorillonit-Beidellit-Reihe werden Ionen der Oktaederschicht herausgelöst, wobei je nach Säurekonzentration, Temperatur, Zeit und Druck, die Menge der in Lösung gehenden Oktaederschicht-Ionen und auch der in Säure löslichen Tetraederschicht-Ionen variiert werden kann. Hierbei nehmen die spezifische Oberfläche und die Anzahl der Mikroporen zu, während das Ionenaustauschvermögen abnimmt.In the case of acid-activated minerals from the montmorillonite-beidellite range, ions of the octahedral layer are extracted, whereby depending on the acid concentration, temperature, time and pressure, the amount of the octahedral layer ions dissolving and also the tetrahedral layer ions soluble in acid can be varied. The specific surface area and the number of micropores increase, while the ion exchange capacity decreases.

Bei vielen Anwendungen ist es jedoch erwünscht, das durch die hohe spezifische Oberfläche bedingte gute Adsorptionsvermögen mit einem guten Ionenaustauschvermögen zu kombinieren. Dies gilt allgemein in denjenigen Fällen, in denen neben der Bindung von Kationen auch eine Bindung oder Adsorption von Molekülen, die unpolar oder mehr oder weniger stark polar sein können, angestrebt wird. Hierbei handelt es sich beispielsweise um Farbstoffmoleküle, gefärbte Polymerisationsprodukte, Eiweißsubstanzen sowie um Verunreinigungen in Fetten und Ölen.In many applications, however, it is desirable to combine the good adsorption capacity due to the high specific surface area with a good ion exchange capacity. This applies in general to those cases in which, in addition to the binding of cations, the aim is also to bind or adsorb molecules which can be nonpolar or more or less strongly polar. These are, for example, dye molecules, colored polymerization products, protein substances as well as impurities in fats and oils.

Weitere Anwendungen sind Abwässer, die neben kationischen Verunreinigungen zum Beispiel auch Öle, Fette und andere Chemikalien, wie Eiweißstoffe, Phenole, Lösungsmittelreste usw. enthalten. Ähnliche Probleme treten in der Wäscherei auf, wo einerseits die als Härtebildner im Waschwasser enthaltenen Erdalkali-Ionen und andererseits die von der Wäsche abgelösten Schmutz-, Farbstoff- und Fetteilchen entfernt werden müssen.

Figure imgb0002
Other applications include wastewater which, in addition to cationic impurities, also contains oils, fats and other chemicals such as proteins, phenols, solvent residues, etc. Similar problems occur in the laundry, where on the one hand the alkaline earth ions contained as hardening agents in the washing water and on the other hand the dirt, dye and fat particles detached from the laundry have to be removed.
Figure imgb0002

Es wurde nun überraschenderweise gefunden, daß man eine derartige Stoffzusammensetzung erhält, wenn ein durch Säureaktivierung eines Minerals aus der Montmorillonit-Beidellit-Reihe erhaltenes Material mit Alkali beladen wird.It has now surprisingly been found that such a composition of matter is obtained when a material obtained by acid activation of a mineral from the montmorillonite-beidellite series is loaded with alkali.

Gegenstand der Erfindung ist somit ein adsorptiv wirkender silikatischer Komplexbildner für Erdalkali-Ionen, der dadurch gekennzeichnet ist, daß er durch Beladung eines durch Säureaktivierung eines Minerals aus der Montmorillonit-Beidellit-Reihe erhaltenen Materials mit Alkali herstellbar ist.The invention thus relates to an adsorptive silicate complexing agent for alkaline earth ions, which is characterized in that it can be prepared by loading alkali with a material obtained by acid activation of a mineral from the montmorillonite-beidellite series.

Die Minerale aus der Montmorillonit-Beidellit-Reihe sind beispielsweise in "Ullmanns Enzyklopädie der technischen Chemie", Band 17, Seiten 593 bis 594 näher erläutert. In diese Reihe fallen der Montmorillonit (das Hauptmineral der Bentonite), der Hectorit, der Beidellit, der Saponit und der Nontronit.The minerals from the montmorillonite-beidellite series are explained in more detail, for example, in "Ullmann's Encyclopedia of Industrial Chemistry", volume 17, pages 593 to 594. This series includes montmorillonite (the main mineral of bentonite), hectorite, beidellite, saponite and nontronite.

Erfindungsgemäß wird bevorzugt ein säureaktivierter Bentonit als Ausgangsmaterial verwendet, der dann mit Alkali beladen wird. Die Herstellung von säureaktivierten Bentoniten ist an sich bekannt. Zur Aktivierung wird das Ausgangsmaterial vorzugsweise mit einer Mineralsäure, wie Salzsäure, Schwefelsäure oder Salpetersäure, aufgeschlossen. Auch die Verwendung von organischen Säuren, wie Essigsäure, ist möglich. Der Säureaufschluß kann in einer verdünnten Suspension oder durch Behandlung einer plastischen Tonmasse mit konzentrierter Säure erfolgen. Ferner ist es möglich, die Säureaktivierung des plastischen Tons in der Gasphase, zum Beispiel mit Chlorwasserstoff oder Schwefeldioxid, durchzuführen. Nach der Aktivierung wird das Material entweder mit 'Wasser oder verdünnter Säure gewaschen und getrocknet.According to the invention, an acid-activated bentonite is preferably used as the starting material, which is then loaded with alkali. The production of acid-activated bentonites is known per se. For activation, the starting material is preferably digested with a mineral acid, such as hydrochloric acid, sulfuric acid or nitric acid. The use of organic acids such as acetic acid is also possible. The acid digestion can in a ver thin suspension or by treatment of a plastic clay with concentrated acid. It is also possible to carry out the acid activation of the plastic clay in the gas phase, for example using hydrogen chloride or sulfur dioxide. After activation, the material is washed with either water or dilute acid and dried.

Erfindungsgemäß hat sich ein säureaktiviertes Material mit einem Si02-Gehalt von etwa 68 bis 74 Gew.-%, einem Al2O3(+Fe2O3)-Gehalt von etwa 15 bis 20 Gew.-%, einem Erdalkali-(CaO+MgO)- Gehalt von etwa 1 bis 4 Gew.-% und einem Alkali-(Na20+K20)-Gehalt von etwa 1 bis 2 Gew.-%, Rest gebundenes Wasser, das eine spezifische Oberfläche von etwa 200 bis 350 m2/g hat, als besonders geeignet erwiesen. Die spezifische Oberfläche wird im allgemeinen nach der BET-Methode bestimmt.According to the invention, an acid-activated material with an SiO 2 content of approximately 68 to 74% by weight, an Al 2 O 3 (+ Fe 2 O 3 ) content of approximately 15 to 20% by weight, an alkaline earth metal ( CaO + MgO) content of about 1 to 4% by weight and an alkali (Na 2 0 + K 2 0) content of about 1 to 2% by weight, remainder bound water, which has a specific surface area of about 200 to 350 m 2 / g has proven to be particularly suitable. The specific surface is generally determined using the BET method.

Besonders bevorzugt geht man von einem säureaktivierten Material mit einer Teilchengröße von nicht mehr als etwa 50/u aus. Ein derartiges Material kann beispielsweise dadurch erhalten werden, daß man die Grobanteile oberhalb 50µ, vorzugsweise oberhalb etwa 15.bis 20µ, durch eine Hydrozyklonbehandlung entfernt. Man kann hierbei entweder das noch nicht aktivierte Ausgangsmaterial oder aber das säureaktivierte Material der Hydrozyklonreinigung unterziehen. Vorzugsweise führt man diese Behandlung mit dem säurebehandelten Material durch, da man auf diese Weise auch bei konzentrierteren Suspensionen noch einen guten Trenneffekt erzielt. Bei den ausgeschiedenen Grobanteilen handelt es sich üblicherweise um Quarz-, Glimmer-, Feldspat-, Pyrit- und Hämatitteilchen, die ein minimales Adsorptions- bzw. Ionenbindurgsvermögen zeigen.

Figure imgb0003
It is particularly preferred to start from an acid-activated material with a particle size of not more than about 50 / u. Such a material can be obtained, for example, by removing the coarse fractions above 50μ, preferably above approximately 15 to 20μ, by means of a hydrocyclone treatment. You can either subject the raw material that has not yet been activated or the acid-activated material to the hydrocyclone purification. This treatment is preferably carried out with the acid-treated material, since a good separation effect is still achieved in this way even with more concentrated suspensions. The coarse fractions which are separated out are usually quartz, mica, feldspar, pyrite and hematite particles, which show a minimal adsorption or ion binding capacity.
Figure imgb0003

Zur Beladung des säureaktivierten Materials wird vorzugsweise ein Alkalihydroxid, -carbonat, -phosphat oder -borat verwendet. Die Beladung erfolgt vorzugsweise dadurch, daß das säureaktivierte Material mit der alkalischen Substanz zu einem trockenem Gemisch vereinigt wird, sie kann auch durch Behandlung in einer wäßrigen Suspension oder Paste bei etwa 25 bis 100°C erfolgen.An alkali metal hydroxide, carbonate, phosphate or borate is preferably used to load the acid-activated material. Loading is preferably carried out by combining the acid-activated material with the alkaline substance to form a dry mixture; it can also be carried out by treatment in an aqueous suspension or paste at about 25 to 100 ° C.

Unter "Beladen mit Alkali" versteht man erfindungsgemäß sowohl den Austausch der H-Ionen auf der Oberfläche und zwischen den Schichten, als auch die Reaktion mit den sauren Gruppen des säureaktivierten Materials. Ferner umfaßt dieser Begriff die adsorptive Bindung sowie die innerkristalline Einlagerung der alkalischen Substanz im Gitter des Materials.According to the invention, “loading with alkali” means both the exchange of the H ions on the surface and between the layers, and also the reaction with the acidic groups of the acid-activated material. This term also includes the adsorptive bond and the intra-crystalline incorporation of the alkaline substance in the lattice of the material.

Der erfindungsgemäße Komplexbildner kann allgemein durch die Bruttoformel

Figure imgb0004
gekennzeichnet werden, worin die Symbole folgende Bedeutungen haben :

  • MeI = Natrium und Kalium (wobei das Verhältnis Na2O : K2O vorzugsweise etwa 10 bis 100 : 1 beträgt)
  • MeII = Magnesium und Calcium (wobei das Verhältnis MgO : Ca0 vorzugsweise etwa 0,5 bis 3 : 1 beträgt)
  • MeIII = Aluminium und Eisen (wobei das Verhältnis Al2O3 : Fe203 vorzugsweise etwa 3 bis 6 : 1 beträgt).
  • x = 1,5 bis 6, vorzugsweise-3 bis 5
  • y = 2 bis 1, vorzugsweise 0,3 bis 0,5
  • z = 6,2 bis 8, vorzugsweise 7,5 bis 8
The complexing agent according to the invention can generally by the gross formula
Figure imgb0004
 in which the symbols have the following meanings:
  • Me I = sodium and potassium (the ratio Na 2 O: K 2 O is preferably about 10 to 100: 1)
  • Me II = magnesium and calcium (the ratio MgO: Ca0 is preferably about 0.5 to 3: 1)
  • Me III = aluminum and iron (the ratio Al 2 O 3 : Fe 2 0 3 is preferably about 3 to 6: 1).
  • x = 1.5 to 6, preferably -3 to 5
  • y = 2 to 1, preferably 0.3 to 0.5
  • z = 6.2 to 8, preferably 7.5 to 8

Der Komplexbildner gemäß der Erfindung kann auch in Form einerwäßrigen Suspension vorliegen. Eine derartige Suspension enthält etwa 100 bis 200 g unlösliche Feststoffe je Liter.The complexing agent according to the invention can also be in the form of an aqueous suspension. Such a suspension contains about 100 to 200 g of insoluble solids per liter.

Die erfindungsgemäßen Komplexbildner haben in einem pH-Bereich von etwa 9 bis 11 ein Bindevermögen für Calcium-Ionen zwischen etwa 700 und 1000 mval/100 g, wobei das Bindevermögen bei höheren Temperaturen im allgemeinen ansteigt. Das Bindevermögen der erfindungsgemäßen Komplexbildner für Calcium-Ionen ist also um etwa eine Zehnerpotenz größer als das Ionenaustauschvermögen der natürlichen Bentonite, das bei etwa 70 bis 100 mval/100 g liegt.The complexing agents according to the invention have a binding capacity for calcium ions between approximately 700 and 1000 meq / 100 g in a pH range of approximately 9 to 11, the binding capacity generally increasing at higher temperatures. The binding capacity of the complexing agents according to the invention for calcium ions is thus about a power of ten greater than the ion exchange capacity of the natural bentonites, which is about 70 to 100 meq / 100 g.

Die Erfindung ist anhand der nachstehenden Beispiele in nicht einschränkender Weise erläutert.The invention is explained in a non-restrictive manner on the basis of the examples below.

Bei spiel 1 .Example 1 .

Bentonitischer Rohton aus den bayerischen Lagerstätten im Raum Moosburg-Mainburg-Landshut wird mit 280 bis 1680, vorzugsweise 840 mval, Mineralsäure, vorzugsweise Salzsäure,-bezogen auf 100 g Trockenton, versetzt und 5 bis 10, vorzugsweise 8 Stunden auf etwa 95°C erhitzt. Die in Lösung gegangenen Anteile werden zusammen mit der restlichen Säure vom Feststoff abgetrennt. Nach dem Auswaschen des säureaktivierten Bentonits auf einen pH-Wert von 4 - 5 wird dieser getrocknet und gemahlen.Bentonite raw clay from the Bavarian deposits in the Moosburg-Mainburg-Landshut region is mixed with 280 to 1680, preferably 840 meq, mineral acid, preferably hydrochloric acid, based on 100 g dry clay, and heated to about 95 ° C. for 5 to 10, preferably 8 hours . The portions dissolved are separated from the solid together with the remaining acid. After washing out the acid-activated bentonite to a pH of 4-5, it is dried and ground.

Der so erhaltene Feststoff wird einer Alkalibehandlung unterzogen, wobei dem Feststoff Alkaliverbindungen, wie Hydroxide oder Carbonate, vorzugsweise Na2C03 in Mengen von etwa 20 bis 50 Gewichtsteilen je 100 Gewichtsteile Feststoff zugesetzt werden. Bei Verwendung von festen Alkaliverbindungen werden diese mit dem Feststoff vermahlen. Bei Verwendung von Lösungen der Alkaliverbindungen wird vorzugsweise eine konzentrierte Lösung in eine Paste des Feststoffes eingeknetet. Dieses Produkt wird anschließend getrocknet und gemahlen.The solid obtained in this way is subjected to an alkali treatment, alkali compounds, such as hydroxides or carbonates, preferably Na 2 CO 3 being added to the solid in amounts of about 20 to 50 parts by weight per 100 parts by weight of solid. If solid alkali compounds are used, these are ground with the solid. When using solutions of the alkali compounds, a concentrated solution is preferably kneaded into a paste of the solid. This product is then dried and ground.

Beispiel 2Example 2

Für die Herstellung sehr feinteiliger silikatischer Komplexbildner wird der nach Beispiel 1 säureaktivierte Bentonit nach dem Erhitzen durch Hydrozyklonbehandlung von üblicherweise im Bentonit enthaltenen Begleitmineralien wie Quarz, Glimmer, Feldspat, Pyrit usw. abgetrennt. Nach Entfernung der Grobanteile wird der feinteilige Feststoff wie in Beispiel 1 aus der Suspension abgetrennt, ausgewaschen, getrocknet und gemahlen sowie einer Alkalibehandlung unterzogen. Man erhält hierbei ein Produkt, das hinsichtlich des Ca-Bindevermögens eine höhere Ergiebigkeit aufweist, da es gegenüber dem Produkt in Beispiel 1 geringere Mengen inaktiver Anteile enthält.For the production of very finely divided silicate complexing agents, the acid-activated bentonite according to Example 1 is separated after heating by hydrocyclone treatment from accompanying minerals usually contained in the bentonite, such as quartz, mica, feldspar, pyrite, etc. After removal of the coarse fractions, the finely divided solid is separated from the suspension as in Example 1, washed out, dried and ground and subjected to an alkali treatment. A product is obtained which has a higher yield in terms of Ca binding capacity, since it contains smaller amounts of inactive components than the product in Example 1.

Beispiel 3Example 3

Ein ähnlich feinteiliger silikatischer Komplexbildner wie in Beispiel 2 wird erhalten, wenn der nach Beispiel 1 von der restlichen Säure abgetrennte Feststoff erneut in Wasser suspendiert (ca. 200 g/l) und einer Hydrozyklonbehandlung unterzogen wird. Der Feststoffgehalt der Hydrozyklon-Feinanteilfraktion, deren Teilchen zu etwa 98 % kleiner als 20 /u sind, wird abgetrennt, und der Feststoff wird wie in Beispiel 1 getrocknet, gemahlen und beispielsweise wie folgt alkalibehandelt:

  • 3 a : Einmahlen von 25 Gew.-% gemahlener wasserfreier Soda
  • 3 b : Einmahlen von 50 Gew.-% gemahlener wasserfreier Soda
  • 3 c : Einkneten von 20 Gew.-% NaOH in wäßriger Suspension
  • 3 d : Einkneten von 40 Gew.-% NaOH in wäßriger Suspension
  • zu 3 c und 3 d :
A similarly finely divided silicate complexing agent as in Example 2 is obtained when the solid separated from the remaining acid according to Example 1 is resuspended in water (approx. 200 g / l) and subjected to a hydrocyclone treatment. The solids content of the hydrocyclone fines fraction, the particles of which are approximately 98% smaller than 20 / u, is separated off and the solid is dried, ground and, for example, alkali treated as in Example 1 as follows:
  • 3a: grinding of 25% by weight of ground anhydrous soda
  • 3 b: grinding in 50% by weight of ground anhydrous soda
  • 3 c: kneading of 20% by weight NaOH in aqueous suspension
  • 3 d: Kneading 40% by weight of NaOH in aqueous suspension
  • to 3 c and 3 d:

Die berechnete Menge NaOH wird in Form einer 20 %igen Natronlauge vorgelegt. In diese Lösung wird das trockene Produkt eingeknetet. Die entstandene Paste wird bei 80°C getrocknet und anschließend vermahlen.The calculated amount of NaOH is presented in the form of a 20% sodium hydroxide solution. The dry product is kneaded into this solution. The resulting paste is dried at 80 ° C and then ground.

AnwendungsbeispielApplication example

200 ml Wasser mit einer Ca-Härte von 30°dh (= 300 mg CaO/Liter) werden in einem 250 ml Zentrifugenglas unter Rühren auf 90°C bzw. 65 und 40°C erwärmt. Nun werden 0,2 g des erfindungsgemäßen Produktes zugesetzt und unter Rühren vollständig dispergiert. Die Suspension wird danach mit 0,5 n-NaOH auf pH 10 eingestellt und 10 min lang gerührt. Gegebenenfalls müssen Flüssigkeitsverluste infolge Verdampfung durch Zu-. gabe von dest. Wasser ausgeglichen werden. Anschließend wird die Lösung auf Raumtemperatur abgekühlt und zentrifugiert. Von der überstehenden klaren Lösung wird die Resthärte durch komplexometrische Ca-Bestimmung ermittelt. Das Ca-Bindevermögen der wasserfreien Aktivsubstanz wird wie folgt errechnet:

Figure imgb0005

  • K = Ca-Bindevermögen (mg Ca0/g Aktivsubstanz)
  • A = Ausgangs-Konzentration des eingesetzten Hartwassers (300 mg Ca0/1)
  • R = Restgehalt der zentrifugierten Lösung (mg CaO/1)
  • S = Konzentration des silikatischen Komplexbildners = 1 g/l
  • T = Trockensubstanzgehalt des silikatischen Komplexbildners (nach Trocknung bei 105°bis zur Gewichtskonstanz).
    Figure imgb0006
200 ml of water with a Ca hardness of 30 ° ie (= 300 mg CaO / liter) are heated in a 250 ml centrifuge glass with stirring to 90 ° C or 65 and 40 ° C. Now 0.2 g of the product according to the invention are added and completely dispersed with stirring. The suspension is then adjusted to pH 10 with 0.5N NaOH and stirred for 10 minutes. If necessary, loss of liquid due to evaporation through addition. administration of dest. Water to be balanced. The solution is then cooled to room temperature and centrifuged. The residual hardness of the clear solution above is determined by complexometric Ca determination. The Ca binding capacity of the anhydrous active substance is calculated as follows:
Figure imgb0005
  • K = Ca binding capacity (mg Ca0 / g active substance)
  • A = initial concentration of the hard water used (300 mg Ca0 / 1)
  • R = residual content of the centrifuged solution (mg CaO / 1)
  • S = concentration of the silicate complexing agent = 1 g / l
  • T = dry matter content of the silicate complexing agent (after drying at 105 ° to constant weight).
    Figure imgb0006

Claims (9)

1 Silikatischer Komplexbildner für Erdalkali-Ionen, dadurch gekennzeichnet, daß er durch Beladung eines durch Säureaktivierung eines Minerals aus der Montmorillonit-Beidellit-Reihe erhaltenen Materials mit Alkali hergestellt worden ist.1 silicate complexing agent for alkaline earth ions, characterized in that it has been prepared by loading an alkali with a material obtained by acid activation of a mineral from the montmorillonite-beidellite series. 2. Komplexbildner nach Anspruch 1, gekennzeichnet durch die Verwendung von säureaktiviertem Bentonit als Ausgangsmaterial.2. Complexing agent according to claim 1, characterized by the use of acid-activated bentonite as the starting material. 3. Komplexbildner nach Anspruch 1 oder 2, gekannreichnet, durch die Bruttoformel
Figure imgb0007
worin die Symbole folgende Bedeutung haben: MeI = Natrium und Kalium (wobei das Verhältnis Na2O : K2O vorzugsweise etwa 10 bis 100 : 1 beträgt) MeII = Magnesium und Calcium (wobei das Verhältnis MgO : Ca( vorzugsweise etwa 0,5 bis 3 : 1 beträgt) MeIII = Aluminium und Eisen (wobei das Verhältnis Al2O3 : Fe2O3 vorzugsweise etwa 3 bis 6 : 1 beträgt) x = 1,5 bis 6, vorzugsweise 3 bis 5 y = 0,2 bis 1, vorzugsweise 0,3 bis 0,5' z = 6,2 bis 8, vorzugsweise 7,5 bis 8 3. complexing agent according to claim 1 or 2, cannabis-enriched, by the gross formula
Figure imgb0007
 where the symbols have the following meaning: Me I = sodium and potassium (the ratio Na 2 O: K 2 O is preferably about 10 to 100: 1) Me II = magnesium and calcium (the ratio MgO: Ca (preferably about 0.5 to 3: 1) Me III = aluminum and iron (the ratio Al 2 O 3 : Fe 2 O 3 is preferably about 3 to 6: 1) x = 1.5 to 6, preferably 3 to 5 y = 0.2 to 1, preferably 0.3 to 0.5 ' z = 6.2 to 8, preferably 7.5 to 8 4. Komplexbildner nach einem der Ansprüche 1 bis 3 in Form einer wäßrigen Suspension mit einem Gehalt an unlösliche Feststoffen von etwa 100 bis 200 g/Liter.4. Complexing agent according to one of claims 1 to 3 in the form of an aqueous suspension with an insoluble solids content of about 100 to 200 g / liter. 5. Verfahren zur Herstellung der Kompbxbildner nach Anspruch 1, dadurch gekennzeichnet, daß man ein durch Säureaktivierung eines Minerals aus der Montmorillonit-Beidellit-Reihe erhaltenes Material mit Alkali belädt.5. A process for the preparation of the composite according to claim 1, characterized in that a material obtained by acid activation of a mineral from the montmorillonite-beidellite series is loaded with alkali.
Figure imgb0008
Figure imgb0008
 9. Verfahren nach einem der Ansprüche 5 bis 8, dadurch gekennzeichnet, daß man von einem säurebehandelten Mineral ausgeht, bei dem die Grobanteile oberhalb etwa 15 bis 20/u durch eine Hydrozyklonbehandlung entfernt worden sind.9. The method according to any one of claims 5 to 8, characterized in that one starts from an acid-treated mineral, in which the coarse fractions above about 15 to 20 / u have been removed by a hydrocyclone treatment. 10. Verfahren nach einem der Ansprüche 5 bis 9, dadurch gekennzeichnet, daß man die Beladung des säureaktiyierten Materials mit einem Alkalihydroxid, -carbonat, -phosphat oder -borat durch trockenes oder nasses Vermischen durchführt.10. The method according to any one of claims 5 to 9, characterized in that one carries out the loading of the acid-activated material with an alkali hydroxide, carbonate, phosphate or borate by dry or wet mixing. 11. Verfahren nach einem der Ansprüche 5 bis 10, dadurch gekennzeichnet, daß man die Beladung des säureaktivierten Materials in wäßriger Suspension oder als Paste bei etwa 25 bis 100°C durchführt.11. The method according to any one of claims 5 to 10, characterized in that one carries out the loading of the acid-activated material in aqueous suspension or as a paste at about 25 to 100 ° C.
EP78100124A 1977-06-15 1978-06-09 Silicate-type complexing agent for alkaline-earth ions and process for its preparation Expired EP0000130B1 (en)

Applications Claiming Priority (2)

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DE2727053A DE2727053C2 (en) 1977-06-15 1977-06-15 Adsorptive silicate agent for binding alkaline earth ions
DE2727053 1977-06-15

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EP0000130A1 true EP0000130A1 (en) 1979-01-10
EP0000130B1 EP0000130B1 (en) 1981-08-26

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EP (1) EP0000130B1 (en)
JP (1) JPS546899A (en)
AT (1) AT392958B (en)
CA (1) CA1110824A (en)
DE (1) DE2727053C2 (en)
ES (1) ES470773A1 (en)
IT (1) IT1105719B (en)

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EP0044058B1 (en) * 1980-07-11 1984-02-29 Süd-Chemie Ag Means and method for treating process and effluent water in paper making and related industries
GB2185246A (en) * 1985-10-28 1987-07-15 Nl Chemicals Inc Preactivated organophilic clay gellant
WO1995005422A1 (en) * 1993-08-12 1995-02-23 Süd-Chemie AG Process for producing neutral to alkaline dye coupling developer pigments
US5398385A (en) * 1994-05-02 1995-03-21 Plut; Louis Cargo transport accessory

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DE3120195C2 (en) * 1981-05-21 1986-09-04 Degussa Ag, 6000 Frankfurt Polymeric ammonium compounds with a silicic acid-like backbone, process for their production and use
JP3054153B2 (en) * 1989-02-28 2000-06-19 水澤化学工業株式会社 Developer for pressure-sensitive copying paper
CN1055282C (en) * 1995-09-21 2000-08-09 上海石油化工高等专科学校 Catalytic hydrogenation process of industrial C5 fraction to produce pentane
EP0885847A1 (en) * 1997-04-25 1998-12-23 Gschwind, Mireco, Dr. Process for the treatment of waste water
US6170575B1 (en) 1999-01-12 2001-01-09 Halliburton Energy Services, Inc. Cementing methods using dry cementitious materials having improved flow properties
US6379456B1 (en) 1999-01-12 2002-04-30 Halliburton Energy Services, Inc. Flow properties of dry cementitious and non-cementitious materials
US6660080B2 (en) 1999-01-12 2003-12-09 Halliburton Energy Services, Inc. Particulate flow enhancing additives
US6245142B1 (en) 1999-01-12 2001-06-12 Halliburton Energy Services, Inc. Flow properties of dry cementitious materials

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EP0044058B1 (en) * 1980-07-11 1984-02-29 Süd-Chemie Ag Means and method for treating process and effluent water in paper making and related industries
GB2185246A (en) * 1985-10-28 1987-07-15 Nl Chemicals Inc Preactivated organophilic clay gellant
GB2185246B (en) * 1985-10-28 1989-10-18 Nl Chemicals Inc Preactivated organophilic clay gellant
WO1995005422A1 (en) * 1993-08-12 1995-02-23 Süd-Chemie AG Process for producing neutral to alkaline dye coupling developer pigments
US5398385A (en) * 1994-05-02 1995-03-21 Plut; Louis Cargo transport accessory

Also Published As

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IT7849841A0 (en) 1978-06-13
DE2727053A1 (en) 1978-12-21
CA1110824A (en) 1981-10-20
DE2727053C2 (en) 1982-11-25
ATA434378A (en) 1980-05-15
IT1105719B (en) 1985-11-04
US4255276A (en) 1981-03-10
ES470773A1 (en) 1979-02-01
JPS546899A (en) 1979-01-19
AT392958B (en) 1991-07-25
EP0000130B1 (en) 1981-08-26

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