WO1991017953A1 - Procede simplifie pour la production de silicates stratifies aptes au gonflement - Google Patents

Procede simplifie pour la production de silicates stratifies aptes au gonflement Download PDF

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Publication number
WO1991017953A1
WO1991017953A1 PCT/EP1991/000582 EP9100582W WO9117953A1 WO 1991017953 A1 WO1991017953 A1 WO 1991017953A1 EP 9100582 W EP9100582 W EP 9100582W WO 9117953 A1 WO9117953 A1 WO 9117953A1
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WIPO (PCT)
Prior art keywords
reaction
reaction mixture
volatile
hydrothermal
amine compounds
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Application number
PCT/EP1991/000582
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German (de)
English (en)
Inventor
Britta Liesenfeld
Hans Dolhaine
Heinz Müller
Claus-Peter Herold
Stephan Von Tapavicza
Willi WÜST
Joseph Wollmann
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to JP91506808A priority Critical patent/JPH05507054A/ja
Publication of WO1991017953A1 publication Critical patent/WO1991017953A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • C01B33/405—Clays not containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays

Definitions

  • the invention relates to a simplified synthesis process for the production of water-swellable smectite clays and, in particular, describes a possibility in a simple manner to master the difficulties which arise in the production of highly swellable hectorites, saponites and / or saponite-hectorite hybrids.
  • the last-mentioned literature reference describes in its example 1 a typical process for the production of the synthetic sheet silicates of the hectorite type to be used there.
  • An aqueous suspension is prepared from magnesium sulfate, sodium hydroxide solution, sodium silicate solution and lithium carbonate, which is then reacted for about 4 hours at 180 ° C. in a stirred autoclave.
  • the resulting product must then be filtered off from the mother liquor and the filter cake thus obtained must be washed with deionized water before the material is dried.
  • These crucial steps of filtering a primarily formed hectorite slurry with subsequent washing of the separated solid phase are also integral components of the flow diagrams 3 and 4 from the literature reference Karl-Heinz Bergk et al.
  • the invention has set itself the task of designing the known process for the production of synthetic and in particular highly swellable smectite clays in such a way that purification of the crude reaction product by filtration and subsequent washing no longer causes the previously known difficulties.
  • the invention intends to make it possible to obtain high-purity smectite clays of a given structure and swellability by simply drying up the crude reaction product obtained primarily in the hydrothermal reaction, without intensive washing of the crude reaction product being necessary.
  • the invention provides two main elements: the formation of the basic environment for the hydrothermal implementation, which acts as a reaction aid via the If smectite clay stoichiometrically required amount of alkali metal hydroxide is introduced into the reaction, certain bases will also be used if certain bases are used.
  • the reactant mixture for the hydrothermal layered silicate-forming reaction should furthermore be free or practically free of those constituents which form non-volatile reaction by-products, in particular corresponding salts, in the course of the reaction.
  • the invention accordingly relates to a process for the production of swellable sheet silicates of the smectite type by hydrothermal pressure treatment of mixtures and / or coprecipitates of the sheet silicate-forming components in the presence of an excess of water and free bases.
  • the new process is characterized in that a reaction mixture is introduced into the hydrothermal reaction stage, the base excess of which is at least partially and preferably at least predominantly formed by driftable organic amine compounds, that the mineral solid phase formed is made up of the aqueous-basic portion frees the reaction mixture and, if desired, drives off residual portions of the organic amine compounds from the solid phase.
  • the strippable bases used according to the invention are, in particular, sufficiently volatile organic amine compounds.
  • primary, secondary and / or tertiary amines and in particular corresponding unsubstituted aliphatic amines are the preferred reaction auxiliaries.
  • the last-mentioned tertiary amines can be particularly suitable auxiliaries for adjusting the basic reaction environment.
  • liquid amines in particular are used with sufficient volatility used that their separation from the crude reaction product via the gas phase together with the aqueous reaction medium and / or separated therefrom is possible without particular difficulty.
  • Corresponding amines contain, for example, up to about 20 C atoms, preferably up to about 15 C atoms in the molecule.
  • Amines with up to about 10 carbon atoms in the molecule can be of particular importance.
  • Lower aliphatic amines, each having 2 to 6 carbon atoms in the alkyl radical, are of particular importance in the course of the inventive step.
  • Lower tertiary aliphatic amines with, for example, 2 to 4 carbon atoms in each of the alkyl radicals are preferred auxiliaries for the purposes of the action according to the invention.
  • reaction mixtures containing at least predominantly oxidic and / or hydroxide reactants are used as the starting material for the hydrothermal reaction. These mixtures are essentially free of non-volatile foreign components, i. H. the amount of the non-volatile foreign matter is not more than 5% by weight, preferably not more than 1% by weight.
  • the feed mixtures contain, as volatile mixture components, the water required for hydrothermal synthesis and the volatile bases for setting the basic reaction environment.
  • Highly swellable smectite clays of the type concerned according to the invention contain sodium in their layer lattice as alkali metal components and optionally at most approximately equal proportions of lithium, which are incorporated in oxidic form.
  • the sodium hydroxide is used in excess. This is necessary for two reasons: If salts are used in the layered silicate synthesis - For example, of the type of magnesium chloride and / or lithium carbonate - introduced, the acid components of these salts equivalent amounts of sodium hydroxide are required to form the appropriate neutral salts to be water-soluble and finally separated from the layered silicate.
  • the excess sodium hydroxide during the synthesis stage, the basic environment of the reaction mixture and thus the formation of a highly swellable layered silicate clay with a pronounced crystal structure should be guaranteed.
  • the process according to the invention proposes a novel way: the base excess of the reaction mixture required in the stated sense should not be formed by sodium hydroxide as before, but by the use of selected organic amine compounds, as previously defined. This makes an independent and previously unknown process of the synthesis accessible:
  • the primary reaction product in the process of the invention are suspensions of a non-or only slightly swollen, finely divided sheet silicate of the desired formula, which is separated from the accompanying liquid phase by simple separation operations, in particular by filtration, and, if desired, also further cleaning operations. in particular can be subjected to a water wash.
  • the sheet silicate isolated and purified in this way shows the presence of Nitrogen, although the bound base amounts in the
  • these small bound proportions of the basic amine compounds used in the synthesis can be driven off.
  • the extent to which the amine compounds are stripped off converts the swelling capacity of the layered silicate formed, and ultimately the desired highly swellable mineral material is formed.
  • the use of very limited amounts of free alkali metal hydroxide and in particular sodium hydroxide can be advantageous.
  • the process according to the invention provides that a primarily formed mineral solid phase of limited swellability is separated from the aqueous-basic portion of the reaction mixture by phase separation, in particular by filtration, if desired the washed mineral material is washed and the amine residue 1 by means of a stronger base, in particular by means of aqueous alkali hydroxide.
  • the treatment of the primary mineral material with limited swellability and its residual proportion of bound organic amine bases is preferably carried out at elevated temperatures, for example in the temperature range around 100 ° C., in particular in the temperature range from about 60 to 150 ° C.
  • the process is carried out at normal pressure or even at slightly reduced pressures in order to promote the stripping of the organic amine compounds. They can be separated off by distillation, in a particular embodiment of the process according to the invention the removal of these residual amine portions is combined with the drying of the swellable layered silicate now formed. But steaming out with superheated steam can also be an effective measure in In terms of the final cleaning and formation of the desired swelling assets.
  • alkali hydroxide in particular aqueous NaOH, is preferably introduced beforehand and / or simultaneously into the layered silicate product.
  • alkali hydroxide amounts are generally required which correspond at least approximately to the ion exchange capacity of the respective layered silicate. In terms of quantity, these are very small amounts. For example, about 1 to 1.3 mmol of NaOH per g of layered silicate correspond to the stoichiometric amount required for amine exchange on hectorites. Accordingly, it is preferred according to the invention to use the alkali metal hydroxide to drive off the amine in this amount range, it being preferred to work with 2-3 times the amount of the stoichiometrically required amount.
  • the reactants containing magnesium, aluminum and silicon are introduced as oxidic and / or hydroxide reaction components.
  • Mixed compounds, such as sodium silicate and / or sodium aluminate, can be added to the reaction mixture in a manner known per se. It is essential for the invention in this preferred embodiment that the use of disruptive amounts of foreign constituents, such as are introduced into the reaction mixture, for example when magnesium salts are used, for example of the type of magnesium sulfate or magnesium chloride, and thus is dispensed with the subsequent separation and purification of the crude reaction product.
  • the swellable layered silicates formed can be freed of residual water by simple drying. This drying can be carried out at normal pressure and / or at reduced pressure and can be accelerated by using elevated temperatures.
  • the portions of the reaction mixture which are driven off via the vapor phase can, if desired, be condensed and used in whole or in part in circulation for further reaction mixtures.
  • the drying of the product and / or the removal of the free volatile base can take place, for example, at temperatures up to 300 ° C., preferably in the range between 50 and approximately 250 ° C., with particular temperatures in the range from approximately 80 to 180 ° C. Significance can come.
  • reaction product formed it has proven to be expedient to subject the reaction product formed to a time-limited thermal treatment in this final drying stage.
  • the previously specified temperature areas are measures for suitable working conditions. It may be particularly expedient to carry out such a final temperature treatment - with simultaneous expulsion of remaining portions of water and / or volatile base - in the temperature range from about 100 to 150 ° C.
  • the time period for such a final drying and / or temperature treatment results primarily from the time period required to drive off the volatile constituents. In general, this period will not exceed 1 to 2 hours.
  • the temperature treatment can be in the range of a few minutes, i.e. H. for example 5 minutes to about 45 minutes.
  • the solid reaction product obtained is expediently ground into a fine powder.
  • All suitable grinding devices for example toothed disk mills, are suitable for this.
  • magnesium hydroxide or magnesium oxide can be used as the magnesium-containing compound; in particular, amorphous silicic acid, for example precipitated silicic acid, diatomaceous earth, but also proportionally but also water glass can be used as the silicon-containing compound, with the proviso that the content registered at the same time of sodium hydroxide does not or does not significantly exceed the stoichiometrically desired proportion.
  • Aluminum hydroxide, so-called aluminum moist hydrate or aluminate lye can be used as the aluminum-containing compound, taking into account the restriction given previously for the water glass.
  • a suitable one lithium-containing compound is, for example, lithium hydroxide. If fluoride ions are to be introduced into the reaction product, appropriate proportions of sodium and / or lithium fluoride are particularly suitable.
  • the amount of the abradable amine base to be used in each case can be in a relatively wide range and - based on the magnesium oxide present in the reaction mixture - can be, for example, in the range from 0.1 to 5 mol of the base per mol of magnesium oxide. It will generally be preferred to limit the amount of this basic component as much as possible, so that preferred addition amounts of the base to the reaction mixture for the hydrothermal reaction are in the range of about 0.2 to 2 moles of the amine base per mole of magnesium oxide in the reaction mixture lie.
  • the reaction is carried out in particular under the autogenous pressure of the reaction mixture at process temperature.
  • the process temperatures in particular are the ranges from approximately 150 to 300 ° C., advantageously from approximately 200 to 270 ° C.
  • the reaction time is in the range of 1 to 100 hours, preferably between about 1 and 20 hours.
  • the reaction has usually progressed to such an extent after about 2 to 8 hours that the workup can be carried out in the sense of the drying treatment according to the invention.
  • the solids contents during the hydrothermal reaction phase are in the usual range.
  • the solids content can be increased by up to about 40% (mass fraction) in the aqueous / basic reaction mixture.
  • preference is given to worked lower solids contents which is in the range up to about 15% (mass fractions) and in particular below about 10% (mass fractions).
  • the details of the cited printed prior art for example in Karl-Heinz Bergk et al. aaO
  • corresponding mixing ratios are preferred.
  • the invention relates to the swellable smectite clays produced by the process according to the invention and to their use in particular in the context of water-based drilling fluid systems, as described in detail in EP-A 260 538.
  • Magnesium oxide was suspended in approx. 1700 g of water on the Pendraulik stirrer, lithium hydroxide was dissolved in it and the mixture of water glass, approx. 400 g of water and precipitated silica was added. After stirring for 5 minutes, the suspension is added to the autoclave, into which the amine was added after sealing.
  • Crystallization conditions 4 hours at 250 ° C.
  • the cooled suspension is divided into a plurality of partial amounts.
  • a first portion is dried in the convection oven at 120 ° C and ground without the addition of sodium hydroxide solution.
  • sodium hydroxide solution is added to the respective suspension sample in different amounts. The respective
  • the mixture is stirred vigorously for 2 minutes and then dried in a convection oven at 120 ° C and ground.
  • the X-ray diffraction analysis of the primary reaction product shows a well-defined crystalline nature. From the individual dried and ground material samples
  • the table shows that the formation of the swellability in the aftertreatment with about 1 mmol NaOH / g layered silicate sets in clearly and under the specified test conditions when using twice the amount of NaOH with 6.7 Pas a qualitatively and quantitatively high-quality result is achieved.
  • These two last defined numerical values for the additional amount of sodium hydroxide solution correspond to approximately 1-2 times the stoichiometric amount of the ion exchange capacity of the layered silicate formed.
  • Filter paper gray tape, 7.4 microns

Abstract

On décrit un procédé simplifié pour la production de silicates stratifiés aptes au gonflement, du type smectite, par traitement sous pression hydrothermal de mélanges et/ou de co-précipités de composants formant des silicates stratifiés, en présence d'un excès d'eau et de bases libres. Le nouveau procédé est caractérisé en ce qu'on charge, dans l'étage de réaction hydrothermal, un mélange réactionnel dont l'excès en bases est formé, au moins en partie, par des composés aminés organiques entraînables, on sépare la phase de matière solide minérale formée de la fraction aqueuse basique du mélange réactionnel et on sépare, si nécessaire, de la phase de matière solide, les fractions restantes de composés aminés organiques. Les composés aminés organiques sont, de préférence, des amines primaires, secondaires et/ou notamment tertiaires, à nombre d'atomes de carbone limité. Il est en outre avantageux d'opérer au moyen de produits réactionnels, au moins en majeure partie oxydants et/ou hydroxydants, de façon que le mélange réactionnel soit essentiellement exempt de constituants étrangers non volatils.
PCT/EP1991/000582 1990-05-17 1991-03-26 Procede simplifie pour la production de silicates stratifies aptes au gonflement WO1991017953A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP91506808A JPH05507054A (ja) 1990-05-17 1991-03-26 膨潤性の層状シリケートの簡単な製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4015857.8 1990-05-17
DE19904015857 DE4015857A1 (de) 1990-05-17 1990-05-17 Vereinfachtes verfahren zur herstellung von quellfaehigen schichtsilikaten (ii)

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WO1991017953A1 true WO1991017953A1 (fr) 1991-11-28

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DE (1) DE4015857A1 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1042126C (zh) * 1991-09-03 1999-02-17 环球油品公司 合成二八面体蒙脱石粘土
CN114906857A (zh) * 2022-05-07 2022-08-16 内蒙古大学 煤矸石的处理方法及从煤矸石制得的氧化硅纳米片、多孔硅酸盐材料和铁红

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6890502B2 (en) 2001-08-24 2005-05-10 Southern Clay Products, Inc. Synthetic clay compositions and methods for making and using
US20080224087A1 (en) * 2007-03-14 2008-09-18 Ezell Ryan G Aqueous-Based Insulating Fluids and Related Methods
CN109626386B (zh) * 2018-12-24 2020-07-31 浙江工业大学之江学院 一种高纯度镁皂石的制备方法
CN115072729B (zh) * 2022-07-08 2023-05-12 西南科技大学 白云母转化为蒙脱石的方法及含蒙脱石的粉体

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2356865C2 (de) * 1972-11-14 1984-12-06 Laporte Industries Ltd., London Wasserhaltiges Magnesiumsilikat und Verfahren zu seiner Herstellung
US4623530A (en) * 1985-02-20 1986-11-18 United States Steel Corporation Crystalline magnesia-silica composites and process for producing same
DE3541666A1 (de) * 1985-11-26 1987-05-27 Hoechst Ag Verfahren zur herstellung eines kristallinen, quellfaehigen schichtsilikats vom saponit-typ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2356865C2 (de) * 1972-11-14 1984-12-06 Laporte Industries Ltd., London Wasserhaltiges Magnesiumsilikat und Verfahren zu seiner Herstellung
US4623530A (en) * 1985-02-20 1986-11-18 United States Steel Corporation Crystalline magnesia-silica composites and process for producing same
DE3541666A1 (de) * 1985-11-26 1987-05-27 Hoechst Ag Verfahren zur herstellung eines kristallinen, quellfaehigen schichtsilikats vom saponit-typ

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1042126C (zh) * 1991-09-03 1999-02-17 环球油品公司 合成二八面体蒙脱石粘土
CN114906857A (zh) * 2022-05-07 2022-08-16 内蒙古大学 煤矸石的处理方法及从煤矸石制得的氧化硅纳米片、多孔硅酸盐材料和铁红
CN114906857B (zh) * 2022-05-07 2023-11-07 内蒙古大学 煤矸石的处理方法及从煤矸石制得的氧化硅纳米片、多孔硅酸盐材料和铁红

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Publication number Publication date
DE4015857A1 (de) 1991-11-21
JPH05507054A (ja) 1993-10-14

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