EP0183945B1 - Wässrige stabile Suspension wasserunlöslicher, zum Binden von Calciumionen befähigter Silikate und deren Verwendung zur Herstellung von Wasch- und Reinigungsmitteln - Google Patents

Wässrige stabile Suspension wasserunlöslicher, zum Binden von Calciumionen befähigter Silikate und deren Verwendung zur Herstellung von Wasch- und Reinigungsmitteln Download PDF

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Publication number
EP0183945B1
EP0183945B1 EP85112884A EP85112884A EP0183945B1 EP 0183945 B1 EP0183945 B1 EP 0183945B1 EP 85112884 A EP85112884 A EP 85112884A EP 85112884 A EP85112884 A EP 85112884A EP 0183945 B1 EP0183945 B1 EP 0183945B1
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EP
European Patent Office
Prior art keywords
suspension
component
water
viscosity
denotes
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP85112884A
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German (de)
English (en)
French (fr)
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EP0183945A3 (en
EP0183945A2 (de
Inventor
Manfred Dr. Diehl
Roland Bergmann
Günter Stadtmüller
Sigrid Diener
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Priority to AT85112884T priority Critical patent/ATE59673T1/de
Publication of EP0183945A2 publication Critical patent/EP0183945A2/de
Publication of EP0183945A3 publication Critical patent/EP0183945A3/de
Application granted granted Critical
Publication of EP0183945B1 publication Critical patent/EP0183945B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C11D3/1286—Stabilised aqueous aluminosilicate suspensions

Definitions

  • Sodium is preferred as the cation, but it can also be replaced by lithium, potassium, ammonium or magnesium.
  • aluminum silicates The compounds defined above which are capable of binding calcium are referred to below as "aluminum silicates" for the sake of simplicity. This applies in particular to the sodium aluminum silicates to be used with preference; all statements made for their use according to the invention and all statements regarding their production and properties apply accordingly to the entirety of all the compounds defined above.
  • the aluminum silicates which are particularly suitable for use in detergents and cleaning agents have a calcium binding capacity of preferably 50 to 200 mg CaO / g of the anhydrous aluminum silicate. If reference is made to anhydrous aluminum silicate in the following, it means the state of the aluminum silicate which is reached after drying for one hour at 800 ° C. With this drying, both the adhering and the bound water are practically completely removed.
  • the aluminum silicates are used, among other things. delivered or used in the form of an aqueous suspension. Since the transport inter alia over longer distances, the suspension properties - e.g. Suspension stability and pumpability - the aluminum silicates dispersed in the aqueous phase have certain requirements.
  • Suspensions which, in addition to the alkali aluminum silicate as stabilizer, contain ethoxylation products of 10 to 20 carbon atoms, preferably unsaturated alcohols, with 1 to 8 moles of ethylene oxide per mole of the alcohol (DE-A-25 27 388, DE-A-26 15 698) .
  • ethoxylation products 10 to 20 carbon atoms, preferably unsaturated alcohols, with 1 to 8 moles of ethylene oxide per mole of the alcohol (DE-A-25 27 388, DE-A-26 15 698) .
  • component A can be crystalline.
  • y can be a number from 1.3 to 4.
  • crystalline component A can be a type A zeolite.
  • foam-suppressing additives i.e. Compounds that improve the solubility of the added dispersants in the aqueous phase.
  • solubilizers i.e. Compounds that improve the solubility of the added dispersants in the aqueous phase.
  • foam-suppressing substances for example foam-suppressing soap, silicone defoamers, foam-suppressing triazine derivatives, all of which are known and familiar to the expert, can be used as foam suppressors.
  • foam suppressors for example foam-suppressing soap, silicone defoamers, foam-suppressing triazine derivatives, all of which are known and familiar to the expert, can be used as foam suppressors.
  • the suspension according to the invention contains a hydrophilic, but sparingly water-soluble colloid, such as polyvinyl alcohol, as a stabilizing agent.
  • a solubilizer - dimethyl sulfoxide is very suitable - if the use concentration of a stabilizer which is only slightly soluble in water is higher than about 1%.
  • the proportion of the solubilizer in the total suspension can, for example, be of the same order of magnitude as the proportion of the stabilizing agent.
  • Hydrotrophic agents such as, for example, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid or their water-soluble salts or also octyl sulfate are suitable.
  • the aluminum silicates can be naturally occurring or else synthetically produced products, the synthetically produced products being preferred. They can be prepared, for example, by reacting water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution.
  • the desired aluminum silicates are also obtained by mixing both components in the solid state in the presence of water.
  • Aluminum silicates can also be produced from Al (OH) 3 , A1 2 0 3 or Si0 2 by reaction with alkali silicate or alkali aluminate solutions. The production can also be carried out by other known processes.
  • the invention relates to aluminum silicates which have a three-dimensional space lattice structure.
  • the preferred calcium binding capacity which is approximately in the range from 100 to 200 mg CaO / g AS, usually around 100 to 180 mg CaO / g AS, is found above all in compounds of the composition:
  • This molecular formula comprises two types of different church structures (or their non-crystalline precursors), which also differ in their molecular formulas. They are: The different crystal structures are shown in the X-ray diffraction diagram.
  • the crystalline aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and dried. Depending on the drying conditions, the product contains more or less bound water.
  • the aluminum silicates do not need to be dried at all after their preparation in order to prepare a suspension according to the invention; rather - and this is particularly advantageous - an aluminum silicate that is still moist from manufacture can be used.
  • the particle size of the individual aluminum silicate particles can be different and e.g. are in the range between 0.1 ⁇ m and 0.1 mm. This refers to the primary particle size, i.e. the size of the particles obtained during the precipitation and, if appropriate, the subsequent crystallization. It is particularly advantageous to use aluminum silicates which consist of at least 80% by weight of particles with a size of 10 to 0.01 ⁇ m, in particular of 8 to 0.1 ⁇ m.
  • These aluminum silicates preferably no longer contain primary or secondary particles with diameters above 45 ⁇ m.
  • Secondary particles are particles that are formed by agglomeration of the primary particles into larger structures.
  • powdered zeolite of type A with a particularly defined particle spectrum is used as component A.
  • Such zeolite powder can according to DE-B-24 47 021, DE-B-25 17 218, DE-A-26 52 419, DE-A-26 51 420, DE-A-26 51 436, DE-A-26 51 437, DE-A-26 51 445 or DE-A-26 51 485 can be produced. They then have the particle distribution curves given there.
  • a powdery zeolite of type A can be used, which has the particle size distribution described in DE-A-26 51 485.
  • the concentration of the aluminum silicates, in particular of the powdered zeolite A can preferably be 44 to 53% by weight, in particular 46 to 52% by weight, based on the suspension, and more.
  • Component B - the dispersing component - consists of a mixture of at least: two different fatty alcohol polyglycol ethers.
  • the mixing ratio of these fatty alcohol polyglycol ethers can be any.
  • the mixing ratio - if no more than two fatty alcohol ethers are used - can be 7: 3 to 2: 8, i.e. 7 parts of ether a) to 3 parts of ether b) up to 2 parts of ether a) to 8 parts of ether b) of the formula B.
  • the mixing ratio can be 1: 1.
  • the concentration of component B in the aqueous suspension can preferably be from 1 to 2% by weight, in particular from 1.4 to 1.6% by weight. This concentration is sufficient to stabilize a suspension with a solids content of 50% by weight or more.
  • the suspension according to the invention has the advantage that it is stable to sedimentation in the temperature range from 10 to 50 ° C. and has a pumpable consistency.
  • component B is liquid at room temperature and therefore does not need to be heated.
  • the aqueous suspension according to the invention can contain, in addition to the constituents A and B mentioned and, in addition to any starting materials for the production of these constituents, substances which still remain, also further constituents in comparatively small amounts. If the suspension is to be further processed into detergents and cleaning agents, the additional substances present are expediently substances which are suitable as constituents of detergents and cleaning agents.
  • an indication of the stability of the suspension according to the invention is provided by a simple test in which the aluminum silicate suspension is produced in the desired concentration and which contains a dispersant according to the invention and optionally other substances, for example detergent components such as pentasodium triphosphate, in different amounts.
  • a dispersant according to the invention for example detergent components such as pentasodium triphosphate
  • the suspension should generally be at most so far removed that the protruding clear or silicate-free solution does not make up more than 20%, preferably not more than 10%, in particular not more than 6% of the total height.
  • the amount of additives should be kept so that the suspension can be pumped back into the storage container and pipe or hose lines again after 12 hours, preferably after 24 hours and in particular also after 48 hours.
  • the settling behavior of the suspension which may also contain other constituents, is checked at room temperature - with a total height of the suspension of 10 cm. They are perfectly pumpable even after 4 or 8 days. This information on the stability of the suspension also only gives indications; It depends on the individual case which suspension stability is to be set.
  • the suspension can be prepared by simply mixing its constituents, the aluminum silicates e.g. can be used as such or - if necessary from the production stage - already moist or in an aqueous suspension. It is particularly advantageous to add aluminum silicates that are still moist from their manufacture, e.g. may be present as a filter cake to stir in component B.
  • the suspension according to the invention is characterized by high stability. It has a low viscosity, which is well below the viscosity of known suspensions, especially in the low temperature range.
  • the rheopexic flow behavior is eliminated in the suspension according to the invention.
  • Their stabilizing effect is particularly valuable in the case of aluminum silicates with particle sizes of 5 to 30 ⁇ m. It is pumpable so that it is easy to handle when wet Aluminum silicates enables.
  • the suspension can be pumped around perfectly even after long interruptions in the pumping process. Due to its high stability, the suspension can also be transported in conventional tank and tank wagons without fear of the formation of unusable or disruptive residues. This makes the suspension ideal as a form of delivery of aluminum silicates for delivery to, for example, detergent manufacturers.
  • the suspension can be stored at room temperature or at higher temperatures, transported by piping, pumps or in some other way.
  • the suspension is usually handled at temperatures between room temperature - usually preferred - and around 50 ° C.
  • the suspension according to the invention is particularly suitable for further processing to appear dry, pourable or free-flowing products, for example for the production of powdered water softeners, e.g. on the way of spray drying.
  • the suspension is therefore of considerable importance in the production of powder detergents. There are no annoying residues when the aqueous suspension is fed to the drying apparatus. Furthermore, it has been shown that the suspension of the invention enables processing into extremely dust-free products.
  • the suspension according to the invention is already as such, i.e. usable without further processing with or without further additives which have a growing, bleaching and / or cleaning effect, for example as water softeners, washing or cleaning agents and in particular as liquid abrasives with increased suspension stability.
  • a particularly important use of the suspension is the further processing into dry-appearing, free-flowing or free-flowing detergents and cleaning agents which contain further compounds in addition to the suspension components.
  • the suspension according to the invention is particularly suitable for the production of powder detergents.
  • an aqueous, flowable premix of the individual constituents of the agents is used and these are converted into a pourable product in the usual way.
  • the aluminum silicates defined above are used in the form of the suspension according to the invention.
  • the suspension according to the invention can be processed by any known method in the production of solid, pourable detergents and cleaning agents.
  • a suspension according to the invention for example from a storage container - is mixed with at least one washing, bleaching or cleaning component of the agent to be produced, and the mixture is then mixed by any method converted into the powdered product.
  • a complexing agent is advantageously added, i.e. a compound that is able to complexly bind the alkaline earth metal ions responsible for water hardness, especially magnesium and calcium ions.
  • the suspension according to the invention can be combined with substances capable of binding water of crystallization. This is expediently carried out by spraying the suspension onto the compounds which are capable of binding water of crystallization and which are present in a mixer, so that a solid, dry-appearing product is finally obtained with constant mixing.
  • the suspension according to the invention is preferably mixed with at least one further compound having a washing, bleaching or cleaning action in the form of a "slurry" and subjected to spray drying. This shows further surprising advantages of the claimed aluminum silicate suspension. It has been shown that very low-dust products can be obtained when the suspension according to the invention is used in the spray drying. The products obtained by spray drying have a high calcium binding capacity and are easily wettable.
  • Detergents which have been produced using the suspension described above can be composed in various ways. In general, they contain at least one water-soluble surfactant which does not belong to the dispersants used according to the invention and which are present in the claimed aluminum silicate suspensions. In addition to at least one further compound which has a washing, bleaching or cleaning action and is inorganic or organic, they contain an aluminum silicate as defined above as a calcium-binding compound. In addition, other customary auxiliaries and additives, which are usually present in smaller amounts, can be present in such agents.
  • a zeolite A filter cake according to DE-A-26 51 485 is produced.
  • the powdery zeolite of type A obtained in this way has the particle spectrum given there.
  • the zeolite A filter cake (component A) is stirred with a dissolver and then tempered to 45 ° C. in a 50 liter vessel. There the stabilizer (component B) is stirred in at 75-76 rpm with a MIG stirrer 15 ', the temperature of the slurry rising to 50 ° C.
  • stabilizers component B.
  • the cloud points These stabilizers are determined according to DIN 53 917, page 3, point 8.2 10% in 25% butyl diglycol solution (BDG solution).
  • Examples 1 to 10 are examples according to the invention:
  • Examples 11 to 22 are comparative examples:
  • the suspension according to the invention advantageously has a viscosity which is significantly lower than in the prior art.

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  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
EP85112884A 1984-12-05 1985-10-11 Wässrige stabile Suspension wasserunlöslicher, zum Binden von Calciumionen befähigter Silikate und deren Verwendung zur Herstellung von Wasch- und Reinigungsmitteln Expired - Lifetime EP0183945B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85112884T ATE59673T1 (de) 1984-12-05 1985-10-11 Waessrige stabile suspension wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von waschund reinigungsmitteln.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3444311 1984-12-05
DE19843444311 DE3444311A1 (de) 1984-12-05 1984-12-05 Waessrige stabile suspension wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln

Publications (3)

Publication Number Publication Date
EP0183945A2 EP0183945A2 (de) 1986-06-11
EP0183945A3 EP0183945A3 (en) 1988-03-30
EP0183945B1 true EP0183945B1 (de) 1991-01-02

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EP85112884A Expired - Lifetime EP0183945B1 (de) 1984-12-05 1985-10-11 Wässrige stabile Suspension wasserunlöslicher, zum Binden von Calciumionen befähigter Silikate und deren Verwendung zur Herstellung von Wasch- und Reinigungsmitteln

Country Status (14)

Country Link
US (1) US4671887A (ko)
EP (1) EP0183945B1 (ko)
JP (1) JPS61138698A (ko)
KR (1) KR900000881B1 (ko)
CN (1) CN1004358B (ko)
AT (1) ATE59673T1 (ko)
BR (1) BR8506078A (ko)
DE (2) DE3444311A1 (ko)
ES (1) ES8701685A1 (ko)
FI (1) FI77890C (ko)
NO (1) NO163865C (ko)
SU (1) SU1454256A3 (ko)
YU (1) YU44272B (ko)
ZA (1) ZA858544B (ko)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0287514A1 (de) * 1987-04-15 1988-10-19 Ciba-Geigy Ag Waschmittel für die Nachwäsche von faserreaktiven Färbungen, Verfahren zu dessen Herstellung und dessen Verwendung
DE3818657A1 (de) * 1987-06-06 1988-12-15 Degussa Waessrige stabile suspension wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
EP0294574A3 (de) * 1987-06-06 1989-04-26 Degussa Aktiengesellschaft Wässrige stabile Suspension wasserunlöslicher zum Binden von Calciumionen befähigter Silikate und deren Verwendung zur Herstellung von Wasch- und Reinigungsmitteln
ES2045012T3 (es) * 1987-06-06 1994-01-16 Degussa Suspension acuosa estable de silicatos insolubles en agua, capacitados para la fijacion de iones de calcio y su utilizacion para la preparacion de agentes de lavado y limpieza.
DE3835918A1 (de) * 1988-10-21 1990-04-26 Henkel Kgaa Verfahren zur herstellung von tensidhaltigen granulaten
DE4109501A1 (de) * 1991-03-22 1992-09-24 Degussa Waessrige stabile suspension wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
IT1250437B (it) * 1991-07-01 1995-04-07 Paolo Colombo Sospensioni acquose stabili e facilmente pompabili di zeolite
US5476610A (en) * 1991-07-22 1995-12-19 Henkel Kommanditgesellschaft Auf Aktien Process for stabilizing aqueous zeolite suspensions
DE4203789A1 (de) * 1992-02-10 1993-08-12 Henkel Kgaa Verfahren zur stabilisierung von waessrigen zeolith-suspensionen
CN101554163B (zh) * 2008-04-08 2012-12-12 中国农业科学院农业环境与可持续发展研究所 农药助剂及其制备方法

Family Cites Families (21)

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DE144492C (ko) *
AT330930B (de) * 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
AT335590B (de) * 1974-08-29 1977-03-25 Henkel & Cie Gmbh Flussiges bis pastenformiges wasch- und reinigungsmittelkonzentrat und verfahren zur herstellung
DE2447021C3 (de) * 1974-10-02 1984-03-22 Degussa Ag, 6000 Frankfurt Kristallines Zeolithpulver des Typs A und das Verfahren zu seiner Herstellung
AT335035B (de) * 1974-10-10 1977-02-25 Henkel & Cie Gmbh Stabile suspensionen wasserunloslicher, zum binden von calciumionen befahigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
DE2517218B2 (de) * 1975-04-18 1977-05-05 Henkel & Cie GmbH, 4000 Düsseldorf; Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, 6000 Frankfurt Kristallines zeolithpulver des typs a
DE2615698A1 (de) * 1976-04-09 1977-10-20 Henkel & Cie Gmbh Stabile suspensionen wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
DE2633463A1 (de) * 1976-07-26 1978-02-02 Henkel Kgaa Verfahren zur reinigung von fahrzeugen
DE2651445A1 (de) * 1976-11-11 1978-05-18 Degussa Kristallines zeolithpulver des typs a ii
DE2651436A1 (de) * 1976-11-11 1978-05-18 Degussa Kristallines zeolithpulver des typs a iii
DE2651420A1 (de) * 1976-11-11 1978-05-18 Degussa Kristallines zeolithpulver des typs a v
DE2651419A1 (de) * 1976-11-11 1978-05-18 Degussa Kristallines zeolithpulver des typs a iv
DE2651485A1 (de) * 1976-11-11 1978-05-24 Degussa Kristallines zeolithpulver des typs a i
DE2651437A1 (de) * 1976-11-11 1978-05-18 Degussa Kristallines zeolithpulver des typs a vi
DE2652419A1 (de) * 1976-11-17 1978-05-18 Bosch Siemens Hausgeraete Elektrische kaffeemaschine mit einer anzeigevorrichtung
DE2734296A1 (de) * 1977-07-29 1979-02-08 Degussa Verfahren zur herstellung von feinteiligen, zum kationenaustausch befaehigten wasserunloeslichen silikaten
NZ188469A (en) * 1977-10-06 1980-12-19 Colgate Palmolive Co Detergent composition comprising a univalent cation-exchanging zeolite a nonionic detergent and builder salts
BE874420A (fr) * 1978-03-02 1979-08-23 Unilever Nv Procede de production de compositions detergentes
DE3209631A1 (de) * 1982-03-17 1983-09-29 Degussa Ag, 6000 Frankfurt Waessrige stabile suspension wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
US4405483A (en) * 1982-04-27 1983-09-20 The Procter & Gamble Company Stable liquid detergents containing aluminosilicate ion exchange material
ATE32328T1 (de) * 1983-08-22 1988-02-15 Henkel Kgaa Stabilisierte, waessrige zeolith-suspension.

Also Published As

Publication number Publication date
CN1004358B (zh) 1989-05-31
KR900000881B1 (ko) 1990-02-17
DE3444311A1 (de) 1986-06-05
JPH0349320B2 (ko) 1991-07-29
YU44272B (en) 1990-04-30
NO163865C (no) 1990-08-01
YU178885A (en) 1988-02-29
JPS61138698A (ja) 1986-06-26
BR8506078A (pt) 1986-08-19
EP0183945A3 (en) 1988-03-30
NO854521L (no) 1986-06-06
DE3581066D1 (de) 1991-02-07
ES549563A0 (es) 1986-12-01
FI77890B (fi) 1989-01-31
US4671887A (en) 1987-06-09
FI854767A (fi) 1986-06-06
CN85108614A (zh) 1987-02-18
EP0183945A2 (de) 1986-06-11
FI854767A0 (fi) 1985-12-02
ES8701685A1 (es) 1986-12-01
KR860005006A (ko) 1986-07-16
NO163865B (no) 1990-04-23
FI77890C (fi) 1989-05-10
SU1454256A3 (ru) 1989-01-23
ATE59673T1 (de) 1991-01-15
ZA858544B (en) 1986-06-25

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