EP0000130B1 - 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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EP0000130B1
EP0000130B1 EP78100124A EP78100124A EP0000130B1 EP 0000130 B1 EP0000130 B1 EP 0000130B1 EP 78100124 A EP78100124 A EP 78100124A EP 78100124 A EP78100124 A EP 78100124A EP 0000130 B1 EP0000130 B1 EP 0000130B1
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acid
alkali
complexing agent
content
activated
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EP0000130A1 (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 metal ions and a method for its production.
  • clay minerals from the montmorillonite-beidellite series are natural cation exchangers and are able to bind alkaline earth and heavy metal ions in this property.
  • natural bentonite has an ion exchange capacity of about 80 to 100 meq / 100 g. The ion exchange is based on an electronegative excess charge of the layered silicate montmorillonite, the main component of the bentonites.
  • 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 is based on the object of providing a silicate composition which on the one hand has good adsorption capacity and on the other hand has good complexing capacity for alkaline earth metal ions.
  • the invention thus relates to an adsorptive-acting 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 range 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.
  • Acid digestion can be carried out in a dilute suspension or by treating 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.
  • a klarezini e rt en Material having a particle size of not more than about 50 to move out.
  • a material can be obtained, for example, by removing the coarse fractions above 50 .mu.m, preferably above about 15 to 20 .mu.m, by 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. With the coarse parts eliminated it is usually quartz, mica, feldspar, pyrite and hematite particles, which show minimal adsorption or ion binding capacity.
  • these coarse fractions would also interfere due to their greater hardness.
  • the complexing agents were used in the laundry, they would lead to increased fiber abrasion.
  • An alkali metal hydroxide, carbonate, phosphate or borate is preferably used to load the acid-activated material.
  • the 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 about 700 and 1000 meq / 100 g in a pH range from about 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 area 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 value of 4-5, it is dried and ground.
  • the solid thus obtained is subjected to alkali treatment, wherein the solid alkali metal compounds such as hydroxides or carbonates, preferably Na z C0 3 in amounts of about 20 to 50 parts by weight per 100 parts by weight of solids is added. If solid alkali compounds are used, these are mixed 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.
  • the solid alkali metal compounds such as hydroxides or carbonates, preferably Na z C0 3 in amounts of about 20 to 50 parts by weight per 100 parts by weight of solids is added. If solid alkali compounds are used, these are mixed with the solid.
  • solutions of the alkali compounds a concentrated solution is preferably kneaded into a paste of the solid. This product is then dried and ground.
  • 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)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Description

Die Erfindung betrifft einen adsorptiv wirkenden silikatischen Komplexbildner für Erdalkali-lonen sowie ein Verfahren zu dessen Herstellung.The invention relates to an adsorptive silicate complexing agent for alkaline earth metal ions and a method for its production.

Es ist bekannt, daß Tonminerale aus der Montmorillonit-Beidellit-Reihe natürliche Kationenaustauscher sind und in dieser Eigenschaft Erdalkali- und Schwermetall-lonen zu binden vermögen. Zum Beispiel hat natürlicher Bentonit ein lonenaustauschvermögen von etwa 80 bis 100 mval/100 g. Der Ionenaustausch beruht auf einer elektronegativen Überschußladung des Schichtsilikats Montmorillonit, dem Hauptbestandteil der Bentonite. Durch den natürlichen isomorphen Ersatz in der Oktaederschicht von zum Beispiel dreiwertigen Aluminium-lonen durch zweiwertige, meist Magnesiumlonen, oder auch in der Tetraederschicht von vierwertigen Silicium-lonen durch zum Beispiel dreiwertige Aluminium-lonen, ergibt sich ein elektropositives Ladungsdefizit der Silikatlamellen, welches durch Bindung von zum Beispiel Alkali- oder Erdalkali-lonen ausgeglichen wird.It is known that clay minerals from the montmorillonite-beidellite series are natural cation exchangers and are able to bind alkaline earth and heavy metal ions in this property. For example, natural bentonite has an ion exchange capacity of about 80 to 100 meq / 100 g. The ion exchange is based on an electronegative excess charge of the layered silicate montmorillonite, the main component of the bentonites. Due to the natural isomorphic replacement in the octahedron layer of, for example, trivalent aluminum ions by divalent, mostly magnesium ions, or also in the tetrahedral layer of tetravalent silicon ions by, for example, trivalent aluminum ions, there is an electropositive charge deficit of the silicate lamellae, which is due to binding is balanced by, 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 lonenaustauschvermögen 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. Here, 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 lonenaustauschvermögen 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-lonen und andererseits die von der Wäsche abgelösten Schmutz-, Farbstoff- und Fetteilchen entfernt werden müssen.Other applications are 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 in the wash water as hardening agents and on the other hand the dirt, dye and fat particles detached from the laundry have to be removed.

Der Erfindung liegt die Aufgabe zugrunde, eine silikatische Stoffzusammensetzung zur Verfügung zu stellen, die einerseits ein gutes Adsorptionsvermögen und andererseits ein gutes Komplexbildungsvermögen für Erdalkali-lonen besitzt.The invention is based on the object of providing a silicate composition which on the one hand has good adsorption capacity and on the other hand has good complexing capacity for alkaline earth metal ions.

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-lonen, 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-acting 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 range 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. Acid digestion can be carried out in a dilute suspension or by treating 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 SiOz-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-(Na2O+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 z 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 O + 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 ,um aus. ein derartiges Material kann beispielsweise dadurch erhalten werden, daß man die Grobanteile oberhalb 50 ,um, vorzugsweise oberhalb etwa 15 bis 20 um, 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. lonenbindungsvermögen zeigen.Particularly preferably, one starts from a säureaktivi e rt en Material having a particle size of not more than about 50 to move out. Such a material can be obtained, for example, by removing the coarse fractions above 50 .mu.m, preferably above about 15 to 20 .mu.m, by 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. With the coarse parts eliminated it is usually quartz, mica, feldspar, pyrite and hematite particles, which show minimal adsorption or ion binding capacity.

Bei vielen Anwendungen würden diese Grobanteile wegen ihrer größeren Härte auch stören. Beispielsweise würden sie bei einer Anwendung der Komplexbildner in der Wäscherei zu einem erhöhten Faserabrieb führen.In many applications, these coarse fractions would also interfere due to their greater hardness. For example, if the complexing agents were used in the laundry, they would lead to increased fiber abrasion.

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 trockenen 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. The 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 imgb0001
gekennzeichnet werden, worin die Symbole folgende Bedeutungen haben:

  • Me' = Natrium und Kalium (wobei das Verhältnis Na2O:K20 vorzugsweise 10 bis 100:1 beträgt)
  • Me" = Magnesium und Calcium (wobei das Verhältnis MgO:CaO vorzugsweise 0,5 bis 3:1 beträgt)
  • Me"' = Aluminium und Eisen (wobei das Verhältnis AI2O3:Fe203 vorzugsweise 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
The complexing agent according to the invention can generally by the gross formula.
Figure imgb0001
 in which the symbols have the following meanings:
  • Me '= sodium and potassium (the ratio Na 2 O: K 2 0 is preferably 10 to 100: 1)
  • Me "= magnesium and calcium (the MgO: CaO ratio preferably being 0.5 to 3: 1)
  • Me "'= aluminum and iron (the ratio Al 2 O 3 : Fe 2 0 3 preferably being 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

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-lonen zwischen etwa 700 und 1000 mval/100 g, wobei das Bindevermögen bei höheren Temperaturen im allgemeinen ansteigt. Das Bindevermögen der erfindungsgemäßen Komplexbildner für Calcium-lonen 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 about 700 and 1000 meq / 100 g in a pH range from about 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.

Beispiel 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 area 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 value 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 NazC03 in Mengen von etwa 20 bis 50 Gewichtsteilen je 100 Gewichtsteile Feststoff zugesetzt werden. Bei Verwendung von festen Alkaliverbindungen werden diese mit dem Feststoff vermahfen. 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 thus obtained is subjected to alkali treatment, wherein the solid alkali metal compounds such as hydroxides or carbonates, preferably Na z C0 3 in amounts of about 20 to 50 parts by weight per 100 parts by weight of solids is added. If solid alkali compounds are used, these are mixed 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 2.Example 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 3.Example 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 ,um sind, wird abgetrennt, und der Feststoff wird wie in Beispiel 1 getrocknet, gemahlen und beispielsweise wie folgt alkalibehandelt:

  • 3a : Einmahlen von 25 Gew.-% gemahlener wasserfreier Soda
  • 3b : Einmahlen von 50 Gew.-% gemahlener wasserfreier Soda
  • 3c : Einkneten von 20 Gew.-% NaOH in wäßriger Suspension
  • 3d : Einkneten von 40 Gew.-% NaOH in wäßriger Suspension zu 3c und 3d:
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, about 98% of the particles of which are smaller than 20 μm are separated off and the solid is dried, ground and, as in example 1, alkali treated as in Example 1:
  • 3a: Grinding of 25% by weight of ground anhydrous soda
  • 3b: Grinding in 50% by weight of ground anhydrous soda
  • 3c: Kneading of 20% by weight NaOH in aqueous suspension
  • 3d: Kneading 40% by weight NaOH in aqueous suspension to 3c and 3d:

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.

Anwendungsbeispiel.Application 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 Zugabe 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 imgb0002

  • K = Ca-Bindevermögen (mg CaO/g Aktivsubstanz)
  • A = Ausgangs-Konzentration des eingesetzten Hartwassers (300 mg CaO/1)
  • R = Restgehalt der zentrifugierten Lösung (mg CaO/1)
  • S = Konzentration des silikatischen Komplexbildners = 1 g/I
  • T = Trockensubstanzgehalt des silikatischen Komplexbildners (nach Trocknung bei 105°bis zur Gewichtskonstanz).
Figure imgb0003
 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 by adding dist. 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 imgb0002
  • K = Ca binding capacity (mg CaO / g active substance)
  • A = initial concentration of the hard water used (300 mg CaO / 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 imgb0003

Claims (10)

1. Siliceous complexing agent for alkaline earth ions, with the empirical formula
(Me1 2 0) (Me" 0) MeIII 2 O3 (Si02)Z in which the symbols have the following meaning:
MeI = sodium and potassium (in which case the ratio Na20:K2O is preferably 10 to 100:1)
Me" = magnesium and calcium (in which case the ratio MgO:Ca is preferably 0.5 to 3:1)
MeIII = aluminium and iron (in which case the ratio Al2O3:Fe2O3 is preferably 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

produced by charging with alkali a material obtained by acid activation of a mineral from the montmorillonite/beidellite series.
2. Complexing agent according to Claim 1, characterised by the use of acid-activated bentonite as starting material.
3. Complexing agent according to Claims 1 and 2 in the form of an aqueous suspension with a content of insoluble solids of about 100 to 200 g/litre.
4. Method for the production of the complexing agent according to Claim 1, characterized in that a material obtained by acid activation of a mineral from the montmorillonite/beidellite series is charged with alkali.
5. Method according to Claim 4, characterised in that acid-activated bentonite is used as starting material.
6. Method according to Claim 4 or Claim 5, characterised in that one starts from an acid-activated material with an Si02 content of about 68 to 74% by weight, with an Al2O3(+Fe2O3) content of about 15 to 20% by weight, with an alkaline earth (CaO+MgO) content of about 1 to 4% by weight and with an alkali (Na20+K2O) content of about 1 to 2% by weight, the remainder being bound water which has a specific surface of about 200 to 350 m2/g.
7. Method according to one of Claims 4 to 6, characterised in that one starts from an acid-activated material with a particle size of not more than about 50 ,um.
8. Method according to one of Claims 4 to 7, characterised in that one starts from an acid-treated mineral, in which the coarse fractions above about 15 to 20 ,um have been removed by a hydrocyclone treatment.
9. Method according to one of Claims 4 to 8 characterised in that the charging of the acid-activated material with an alkali hydroxide, alkali carbonate, alkali phosphate or alkali borate is effected by dry or wet mixing.
10. Method according to one of Claims 4 to 9, characterised in that the charging of the acid-activated material is effected 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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EP0000130B1 true EP0000130B1 (en) 1981-08-26

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3935242A1 (en) * 1989-02-28 1990-09-06 Mizusawa Industrial Chem COLOR DEVELOPER AND RECORDING PAPER THEREOF

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3026403C2 (en) * 1980-07-11 1982-07-01 Süd-Chemie AG, 8000 München Means and processes for the treatment of manufacturing cycle water and waste water from the paper producing and allied industries
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
US4664820A (en) * 1985-10-28 1987-05-12 Nl Industries, Inc. Preactivated organophilic clay gellant lubricating grease thickened with preactivated organophilic clay gellant and process for preparing preactivated organophilic clay gellants
DE4327158A1 (en) * 1993-08-12 1995-02-16 Sued Chemie Ag Process for the preparation of neutral to alkaline color developer pigments
US5398385A (en) * 1994-05-02 1995-03-21 Plut; Louis Cargo transport accessory
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
US6245142B1 (en) 1999-01-12 2001-06-12 Halliburton Energy Services, Inc. Flow properties of dry cementitious materials
US6379456B1 (en) 1999-01-12 2002-04-30 Halliburton Energy Services, Inc. Flow properties of dry cementitious and non-cementitious materials
US6170575B1 (en) 1999-01-12 2001-01-09 Halliburton Energy Services, Inc. Cementing methods using dry cementitious materials having improved flow properties
US6660080B2 (en) 1999-01-12 2003-12-09 Halliburton Energy Services, Inc. Particulate flow enhancing additives

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1493455A (en) * 1923-10-04 1924-05-06 Kobelt Valerius Process of making a base-exchanging compound
GB313522A (en) * 1928-06-13 1930-09-04 Reymersholms Gamla Ind Ab Improved manufacture of artificial zeolites
FR767204A (en) * 1933-01-19 1934-07-12 Peter Spence & Sons Ltd Process for preparing base exchange products
US2076443A (en) * 1935-01-22 1937-04-06 Permutit Co Altering glauconite
FR1221950A (en) * 1958-02-17 1960-06-07 Continental Oil Co Alkalinized clays and their manufacturing process
US3326632A (en) * 1962-01-25 1967-06-20 Hojun Kogyo Kabushiki Kaisha Production of ion exchangeable substances from montmorillonite clay minerals
GB1104281A (en) * 1964-05-12 1968-02-21 Fullers Earth Union Ltd Treatment of clay minerals
US3431218A (en) * 1966-10-26 1969-03-04 Mobil Oil Corp Conversion of clays to crystalline aluminosilicates and catalysts therefrom
US3725528A (en) * 1971-02-18 1973-04-03 Yissum Res Dev Co Quantitative ion exchange process for clay
US3927171A (en) * 1974-03-29 1975-12-16 Mobil Oil Corp Zeolite production
US4102977A (en) * 1975-11-18 1978-07-25 Mizusawa Kagaku Kogyo Kabushiki Kaisha Process for the preparation of alkali aluminosilicate detergent builder
DE2635357A1 (en) * 1976-08-06 1978-02-09 Degussa PROCESS FOR PRODUCING LOW IRON ZEOLITHIC ALUMINUM SILICATES

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3935242A1 (en) * 1989-02-28 1990-09-06 Mizusawa Industrial Chem COLOR DEVELOPER AND RECORDING PAPER THEREOF
DE3935242C3 (en) * 1989-02-28 1996-08-14 Mizusawa Industrial Chem Color developer and its use

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JPS546899A (en) 1979-01-19
IT1105719B (en) 1985-11-04
EP0000130A1 (en) 1979-01-10
DE2727053C2 (en) 1982-11-25
IT7849841A0 (en) 1978-06-13
AT392958B (en) 1991-07-25
US4255276A (en) 1981-03-10
ATA434378A (en) 1980-05-15
DE2727053A1 (en) 1978-12-21
CA1110824A (en) 1981-10-20

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