EP0000130B1 - Agent complexant silicaté pour ions alcalino-terreux et procédé pour sa préparation - Google Patents

Agent complexant silicaté pour ions alcalino-terreux et procédé pour sa préparation Download PDF

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Publication number
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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EP
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Prior art keywords
acid
alkali
complexing agent
content
activated
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Expired
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EP78100124A
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German (de)
English (en)
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EP0000130A1 (fr
Inventor
Rudolf Dipl.-Chem. Dr. Fahn
Nikolaus Dipl.-Chem. Dr. Fenderl
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Sued Chemie AG
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Sued Chemie AG
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Classifications

    • 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.

Landscapes

  • 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)

Claims (10)

1. Complexant silicaté pour ions alcalino-terreux dont la formule de base est la suivante:
Figure imgb0005
où les symboles ont les significations qui suivent:
Me' = Sodium et potassium (le rapport Na20:K20 étant de préférence compris entre 10:1 1 et 100:1 )
Me" = Magnésium et calcium (le rapport MgO:CaO étant de préférence compris entre 0,5:1 et 3:1)
Me"' = Aluminium et fer (le rapport Al2O3: Fe2O3 étant de préférence compris entre 3:1 et 6:1)
x = 1,5 à 6, et de préférence 3 à 6
y = 0,2 à 1 et de préférence 0,3 à 0,5
z = 6,2 à 8 et de préférence 7,5 à 8 caractérisé en ce qu'il est obtenu en fixant un matériau obtenu par activation à l'acide d'un minéral de la série montomorillonite-beidellite avec de l'alcali.
2. Complexant selon la revendication 1, caractérisé par l'utilisation de bentonite activée à l'acide pour constituer le matériau de départ.
3. Complexant selon l'une des revendications 1 ou 2, caractérisé en ce qu'il se présente sous la forme d'une suspension aqueuse contenant de 100 à 200 g/litre de produits solides insolubles.
4. Procédé de fabrication de complexant selon la revendication 1, caractérisé en ce que l'on fixe avec de l'alcali un matériau obtenu par activation à l'aide d'un minéral de la série montomorillonite-beidellite.
5. Procédé selon la revendication 4, caractérisé en ce qu'on utilise comme matériau de départ de la bentonite activée à l'acide.
6. Procédé selon la revendication 4 ou 5, caractérisé en ce que l'on part d'un matériau activé à l'acide ayant une teneur en SiO2 comprise entre environ 68 et 74% en poids, une teneur en Al2O3(+Fe2O3) comprise entre environ 15 et 20% en poids, une teneur en (CaO+MgO)-alcalino-terreux comprise entre environ 1 et 4% en poids et une teneur en (Na2O+K2O)alcalin comprise entre environ 1 et 2% en poids, le reste étant constitué par de l'eau de fixation, sa surface spécifique étant d'environ 200 à 350 m 2/g.
7. Procédé selon l'une quelconque des revendications 4 à 6, caractérisé en ce que l'on part d'un matériau activé à l'acide dont la grandeur des particules ne dépasse pas environ 50 um.
8. Procédé selon l'une quelconque des revendications 4 à 7, caractérisé en ce que l'on part d'un minéral traité à l'acide dont on a éliminé les particules grossières situées au-dessus de 15 à 20 um environ par un traitement avec un hydrocyclone.
9. Procédé selon l'une quelconque des revendications 4 à 8, caractérisé en ce que le traitement du matériau activé à l'acide est réalisé au moyen d'un hydroxyde, d'un carbonate, d'un phosphate ou d'un borate d'alcali par mélange à sec ou au mouillé.
10. Procédé selon l'une quelconque des revendications 4 à 8, caractérisé en ce que la fixation du matériau activé à l'acide est effectuée dans une suspension aqueuse ou sous forme d'une pâte à la température d'environ 25 à 100°C.
EP78100124A 1977-06-15 1978-06-09 Agent complexant silicaté pour ions alcalino-terreux et procédé pour sa préparation Expired EP0000130B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2727053A DE2727053C2 (de) 1977-06-15 1977-06-15 Adsorptiv wirkendes silikatisches Mittel zur Bindung von Erdalkali-Ionen
DE2727053 1977-06-15

Publications (2)

Publication Number Publication Date
EP0000130A1 EP0000130A1 (fr) 1979-01-10
EP0000130B1 true EP0000130B1 (fr) 1981-08-26

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ID=6011607

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EP78100124A Expired EP0000130B1 (fr) 1977-06-15 1978-06-09 Agent complexant silicaté pour ions alcalino-terreux et procédé pour sa préparation

Country Status (8)

Country Link
US (1) US4255276A (fr)
EP (1) EP0000130B1 (fr)
JP (1) JPS546899A (fr)
AT (1) AT392958B (fr)
CA (1) CA1110824A (fr)
DE (1) DE2727053C2 (fr)
ES (1) ES470773A1 (fr)
IT (1) IT1105719B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3935242A1 (de) * 1989-02-28 1990-09-06 Mizusawa Industrial Chem Farbentwickler und damit erhaltenes aufzeichnungspapier

Families Citing this family (11)

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Publication number Priority date Publication date Assignee Title
DE3026403C2 (de) * 1980-07-11 1982-07-01 Süd-Chemie AG, 8000 München Mittel und Verfahren zur Behandlung von Fabrikationskreislauf- und Abwässern der papiererzeugenden und verwandter Industrien
DE3120195C2 (de) * 1981-05-21 1986-09-04 Degussa Ag, 6000 Frankfurt Polymere Ammoniumverbindungen mit kieselsäureartigem Grundgerüst, Verfahren zu ihrer Herstellung und Verwendung
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 (de) * 1993-08-12 1995-02-16 Sued Chemie Ag Verfahren zur Herstellung von neutralen bis alkalischen Farbentwicklerpigmenten
US5398385A (en) * 1994-05-02 1995-03-21 Plut; Louis Cargo transport accessory
CN1055282C (zh) * 1995-09-21 2000-08-09 上海石油化工高等专科学校 工业碳五馏份催化加氢制造戊烷的方法
EP0885847A1 (fr) * 1997-04-25 1998-12-23 Gschwind, Mireco, Dr. Procédé pour le traitement d'eaux usées
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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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 (fr) * 1933-01-19 1934-07-12 Peter Spence & Sons Ltd Procédé de préparation de produits échangeurs de bases
US2076443A (en) * 1935-01-22 1937-04-06 Permutit Co Altering glauconite
FR1221950A (fr) * 1958-02-17 1960-06-07 Continental Oil Co Argiles alcalinisées et leur procédé de fabrication
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 (de) * 1976-08-06 1978-02-09 Degussa Verfahren zur herstellung eisenarmer zeolithischer aluminiumsilikate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3935242A1 (de) * 1989-02-28 1990-09-06 Mizusawa Industrial Chem Farbentwickler und damit erhaltenes aufzeichnungspapier
DE3935242C3 (de) * 1989-02-28 1996-08-14 Mizusawa Industrial Chem Farbentwickler sowie dessen Verwendung

Also Published As

Publication number Publication date
IT7849841A0 (it) 1978-06-13
EP0000130A1 (fr) 1979-01-10
DE2727053A1 (de) 1978-12-21
CA1110824A (fr) 1981-10-20
DE2727053C2 (de) 1982-11-25
ATA434378A (de) 1980-05-15
IT1105719B (it) 1985-11-04
US4255276A (en) 1981-03-10
ES470773A1 (es) 1979-02-01
JPS546899A (en) 1979-01-19
AT392958B (de) 1991-07-25

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