CA1083553A - Crystalline type-a zeolite powder ii - Google Patents
Crystalline type-a zeolite powder iiInfo
- Publication number
- CA1083553A CA1083553A CA288,603A CA288603A CA1083553A CA 1083553 A CA1083553 A CA 1083553A CA 288603 A CA288603 A CA 288603A CA 1083553 A CA1083553 A CA 1083553A
- Authority
- CA
- Canada
- Prior art keywords
- temperature
- tempering
- weight
- zeolite powder
- minutes
- 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
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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
- 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
-
- 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
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2815—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of type A (UNION CARBIDE trade name; corresponds to GRACE's types Z-12 or Z-12L)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides a crystalline type-A
zeolite powder having the composition 1.0 ? 0.2 M2/nO : Al2O3 :
1.85 ? 0.5 SiO2 ? y H2O, wherein M represents a metal cation, n its valency and y a value of up to 6, and containing 50% by weight of particles of a size below a maximum of 4.8 µm as well as having the following particle spectrum
The present invention provides a crystalline type-A
zeolite powder having the composition 1.0 ? 0.2 M2/nO : Al2O3 :
1.85 ? 0.5 SiO2 ? y H2O, wherein M represents a metal cation, n its valency and y a value of up to 6, and containing 50% by weight of particles of a size below a maximum of 4.8 µm as well as having the following particle spectrum
Description
~Ol33~3 The present invention re~ e-J t0 a crys-~llirle ty~ eolite powder having the composition 1.0 -~ 0.2 M2/nO : ~12O3 : 1.~5 0.5 SiO2 y ~12O, wherein M represents a metal cation, n its valency and y a value of up to 6, and containing 50~ by weight of particles of a size below a maximum of g.8llm. l~e present invention also relates to the process for produciny the crystalline zeolite powder by means of hydrothermal crystallization of an alkali-aluminate-silicate mixture and to the use of this zeolite powder in wasking, rinsing and cleaning agents.
Zeolitic molecular sieves with their specific properties for ion exchange and adsorption have been known for a long time.
Their synthesis is based on heating an aqueous synthesis mixture having the components a Na2O x b A12O3 x c SiO2 to temperatures between 50 and 300C. Depending on the composition of the starting mixture, reaction temperature and reactlon time differently structured compounds having the general formula Nax Alx Siy 2 (x+y) n H2O are obtained. These compounds can be distinguished by their X-ray spectra. Sodium can be replaced by other mono-valent or divalent metal cations.
- ~or use as adsorbents, catalyst supports or ion exchangers the molecular sieves are converted into molded articles by means of a suitable binder. The production of the molded articles means a great technical expenditure while simultaneously reducing the effect as a result of the proportion of binder. The rate of reaction also is substantially slowed down due to the long diffusion paths, whereby, for example, the drying of organic liquids is rendered cumbersome. Therefore, for many uses it makes sense to apply the molecular sieve in the ~d form of a powder. The fact that in the molecuLar-sieve synthesis crystals having an average diameter above approximately 2 ~m are obtained while a substantial proportion, usually from 3 to 12%
by weight, have a maximum particle .size above ~5 ~m is common . . -- 1 --` ~lC9~33~;~3 to the known methods ofproduction (~or example, Ger~an Patent - l 038 017). This proportion is known as grit, which, according to DIN 53580, is determined by wet screeniny accordiny to Mocker.
In a product typical of this process it is found that approximately 25% by weight of particles have diameters below lO ~m and 50%
by weight have particle diameters of 13 Ilm (D. W. sreck~ Zeolite Molecular Sieves, paye 388, John Wiley -~ Sons, New York, London, Sidney, Toronto, 1974).
The present invention provides a p~ocess by means of whlch powdered, zeolitic type-A molecular sieves intended for use as lon exchanyers, for example, as water softeners, can be synthesized without a proportion of yrit (particles~ 45 ~m) and with smaller particle sizes. The absence of yrit as well as a smaller particle size is indispensable for the use of these molecular sieves within the scope of the invention, for example, as a phosphate substitute in washing, rinsing and cleansing agents. Washing and cleansing procedures, particularly in . machines, require that the molecu].ar sieve remains in suspension in the wash liqucr (due to low tendency for sedimenta-tion) in order to attain rinsing without residues on completion of the procedure.
Accordiny to the present invention there is provided a ; crystalline type-A zeolite powder having, the composition 1.0 +
` 0.2 M2/n-: ~12O3 : 1.85 + 0.5 SiO2 y H2O, wherein M represents ~-a metal cation, n its valency and y a value of up to 6, and containing 50~ by weight of particles below a maximum of 4.8 ~m as well as having-the following particle spectrum fraction proportion (~m) (~ by weiyht) ~ :
< 3 lO to 18 < 5 55 to 70 ~lO 93 to 99 <15 96 to lO0
Zeolitic molecular sieves with their specific properties for ion exchange and adsorption have been known for a long time.
Their synthesis is based on heating an aqueous synthesis mixture having the components a Na2O x b A12O3 x c SiO2 to temperatures between 50 and 300C. Depending on the composition of the starting mixture, reaction temperature and reactlon time differently structured compounds having the general formula Nax Alx Siy 2 (x+y) n H2O are obtained. These compounds can be distinguished by their X-ray spectra. Sodium can be replaced by other mono-valent or divalent metal cations.
- ~or use as adsorbents, catalyst supports or ion exchangers the molecular sieves are converted into molded articles by means of a suitable binder. The production of the molded articles means a great technical expenditure while simultaneously reducing the effect as a result of the proportion of binder. The rate of reaction also is substantially slowed down due to the long diffusion paths, whereby, for example, the drying of organic liquids is rendered cumbersome. Therefore, for many uses it makes sense to apply the molecular sieve in the ~d form of a powder. The fact that in the molecuLar-sieve synthesis crystals having an average diameter above approximately 2 ~m are obtained while a substantial proportion, usually from 3 to 12%
by weight, have a maximum particle .size above ~5 ~m is common . . -- 1 --` ~lC9~33~;~3 to the known methods ofproduction (~or example, Ger~an Patent - l 038 017). This proportion is known as grit, which, according to DIN 53580, is determined by wet screeniny accordiny to Mocker.
In a product typical of this process it is found that approximately 25% by weight of particles have diameters below lO ~m and 50%
by weight have particle diameters of 13 Ilm (D. W. sreck~ Zeolite Molecular Sieves, paye 388, John Wiley -~ Sons, New York, London, Sidney, Toronto, 1974).
The present invention provides a p~ocess by means of whlch powdered, zeolitic type-A molecular sieves intended for use as lon exchanyers, for example, as water softeners, can be synthesized without a proportion of yrit (particles~ 45 ~m) and with smaller particle sizes. The absence of yrit as well as a smaller particle size is indispensable for the use of these molecular sieves within the scope of the invention, for example, as a phosphate substitute in washing, rinsing and cleansing agents. Washing and cleansing procedures, particularly in . machines, require that the molecu].ar sieve remains in suspension in the wash liqucr (due to low tendency for sedimenta-tion) in order to attain rinsing without residues on completion of the procedure.
Accordiny to the present invention there is provided a ; crystalline type-A zeolite powder having, the composition 1.0 +
` 0.2 M2/n-: ~12O3 : 1.85 + 0.5 SiO2 y H2O, wherein M represents ~-a metal cation, n its valency and y a value of up to 6, and containing 50~ by weight of particles below a maximum of 4.8 ~m as well as having-the following particle spectrum fraction proportion (~m) (~ by weiyht) ~ :
< 3 lO to 18 < 5 55 to 70 ~lO 93 to 99 <15 96 to lO0
- 2 -.. . ~ . . .. . . . .
:
: . . . . . .
- - . . ~
~IL()~335~i3 The present invent:ion ~lso provides a pr~cess ~or producing the crystalline zeolite powder ~ccor~ing to the invention by hydrothen~al crystallization of an alkali alurninate/
water/silicate synthesis mixkure containing SiO2, Al2O3 and Na2O
and water, if required with a subsequent tempering stage. ~D~ring the crystallization or in the tempering stage stirring may be replaced by the action of shearing forces. This process is characterized in that an aqueous caustic soda solution is heated to a temperature between 30 and 80C, that, while stirring, a sodium-aluminate liquor which contains 0.1 to 500 g of NaOH per litre is heated to a temperature from 30 to 100C and is mixed with an alkali metal silicate solution having a temperature of 30 to 80C within a period of 10 to 200 minutes while stirring, where-upon a sodium-aluminate liquor containing 10 to 200 g of A12O3 per litre and 10 to 250 g of Na2O per litre and having a tempera-ture between 30 and 100C is added within 10 to 200 minutes while - stirring and that the synthesis mixture thus obtained is allowed-to crystallize at a temperature between 20 and 175C within at :~:
least 15 minutes.
In a-preferred manner of carrying out the process sodium tetrasilicate can be used as alkali metal silicate solution.
In the process according to the invention stirring may be replaced by the action of shearing forces. Conventional devices -~
`` can be used for this purpose. This conventional measure increases the particle fineness but is not required for carrying out the process according to the invention.
In the process according to the invention shearing forces may be allowed to act on the synthesis mixture, which can contain the individual components in molar ratios a.s they are used in known processes (Eor example, German Patent 1 038 017 and laid-open German Specification 1 095 795), during the crystallixa-tion and possibly during the subsequent tempering stage.
~y "shearing" is meant any comminut:ing mechanical stress
:
: . . . . . .
- - . . ~
~IL()~335~i3 The present invent:ion ~lso provides a pr~cess ~or producing the crystalline zeolite powder ~ccor~ing to the invention by hydrothen~al crystallization of an alkali alurninate/
water/silicate synthesis mixkure containing SiO2, Al2O3 and Na2O
and water, if required with a subsequent tempering stage. ~D~ring the crystallization or in the tempering stage stirring may be replaced by the action of shearing forces. This process is characterized in that an aqueous caustic soda solution is heated to a temperature between 30 and 80C, that, while stirring, a sodium-aluminate liquor which contains 0.1 to 500 g of NaOH per litre is heated to a temperature from 30 to 100C and is mixed with an alkali metal silicate solution having a temperature of 30 to 80C within a period of 10 to 200 minutes while stirring, where-upon a sodium-aluminate liquor containing 10 to 200 g of A12O3 per litre and 10 to 250 g of Na2O per litre and having a tempera-ture between 30 and 100C is added within 10 to 200 minutes while - stirring and that the synthesis mixture thus obtained is allowed-to crystallize at a temperature between 20 and 175C within at :~:
least 15 minutes.
In a-preferred manner of carrying out the process sodium tetrasilicate can be used as alkali metal silicate solution.
In the process according to the invention stirring may be replaced by the action of shearing forces. Conventional devices -~
`` can be used for this purpose. This conventional measure increases the particle fineness but is not required for carrying out the process according to the invention.
In the process according to the invention shearing forces may be allowed to act on the synthesis mixture, which can contain the individual components in molar ratios a.s they are used in known processes (Eor example, German Patent 1 038 017 and laid-open German Specification 1 095 795), during the crystallixa-tion and possibly during the subsequent tempering stage.
~y "shearing" is meant any comminut:ing mechanical stress
- 3 -"
1~3ss3 oE discrete particles in suspensioll, l.e., a stress which is due primarily to real shearing action. The shearing can be carrie(l out continuously or discon-tinuousl~. A turbine irnpeller, for example, the EKAI'O (a trade mark) turbine impeller, is preferred as the shear device. Ilowever, shearing can also be performed with a toothed-disc dissolver, dispensing pump, rotary pump, etc.
While in the present case, the crystallization can be carried out, for example, at 93C, it has been found to be advantageous to carry out the tempering at a temperature between 85and 105C in the crystallization mother liquor. Tempering times between 0.2 and 6, preferably between 0.8 and 4.0, particu-larly 3 hours are favourable. The tempering time commences at the point at which t-he crystallizationis completed. This point is evident from the development of maximum ion exchange capacity, on attaining maximum X-ray line intensity and an adsorption of water vapour of approximately 22.5%. In practice the tempering time is based on an empirical value determined by means of optimum formulation.
- Shearing forces acting to the end of the crystallization phase can be so intensified that the average particle diameter can be reduced to very small values. The values for the maximum particle size and its percentage in the product can also be reduced. However, shearing carried out during the tempering phase exclusively influences the maximum particle size and its proportion in the.product.
The invention also provides for the use of the ~ crystalline type-A zeolite powder according to the invention - - as an ion exchanger, for example, for the softening of water, . particularly as a phospha-te substitute in washing, rinsing and cleansing agents.~
.
. ' ~
j:
- ~L0~35S3 These deteryents are combina-tions of surfac~ active crude washing substances. However, in most cases they also contain other substan-tially inorganic additives, which con~ribute -to a successful washing procedure and are necessary for the production process and for the external quality of the production.
Depending on the use concerned the cornposition of the detergents varies and depends particularly on the fiber type, coloration and washing temperature. It also depends on whether -the washing operation is carried out by hand, for example, in a tub, in a household washing machine or in a laundry. Most detergents are pourable powders. However, liquid and pasty products are also avallable (see Ullmann's Enzyklopadie der technischen Chemie, Third Edition, Vol. 18 Urban ~ Schwarzenberg, Munich 1967).
The crystalline type-A zeolite powder according to the invention has the advantage that it is free from grit and contains smaller particles even during its production. Therefore, when using it as a phosphate substitute in washing and cleansing agents it can be easily kept in suspension in the liquors concerned and can be rinsed out with particular ease from washing and cleaning machines and their charge without leavinq residues.
The present invention will be further described by way of the following Examples.
Example 1 560 litres of a solution of caustic soda (Na2O = 63 g per litre) having a temperature of 70C are put into a tub of 2-cu m capacity.
While stirring with a three-stage Mig impeller 300 litres of sodium tetrasilicate (~ = 1.35 kg per l;tre) containing 8.0%
of NaO per litre and 26.7% of A12O3 per litre are added within 40 minutes to the solution of caustic soda. The solution remains clear.
100 litres of an aqueous sodium-aluminate liquor :
- 5 _ , ,. ,:- . :, .
- ~ .
~33S~i3 having a temperature of 70C and containing 147 g o~ Na2O per litre and 103 g of A12O3 per lltre are added first to the solution in 15 minutes, whereupon 900 litres of the same liquor are added in 98 minutes. The reaction mixture is heated to 85C
andis crystallized for 3 hours. An X-ray-photographically pure type-A zeolite having the following particle spectrum is obtained:
fraction proportion (~m) (~ by weight) lO < 3 ~m 15 < 5 um 62 <lO ~m 98 <15 ~m 99 The proportion of 50% by weight is below 4.3 ~m. The particle size is de-termined by measuring with the Coulter coun-ter.
Example 2 Perborate-Containing Detergent , 45.0~ by weight of sodium aluminium silicate obtained according to example l (dried for 6 hours at 90C, water content 16.8% by weight), 20.0~ by weight of sodium perborate, 35.0% by a detergent powder, produced, for example, by hot-air drying and having the following composition:
21.0~ by weight of ABS (dodecyl benzene sulphonate), 7.5% by weight of ethoxylated tallow alcohol (l mole of tallow alcohol + 14 moles of ethylene oxide), 7.2~ by weight of SO.lp (sodium salt of saturated substantiallY C18 ~ C22 fatty acids)~
-- 9% by weight of sodiurn tetrasilicate (Na2O 3.3 sio2?,
1~3ss3 oE discrete particles in suspensioll, l.e., a stress which is due primarily to real shearing action. The shearing can be carrie(l out continuously or discon-tinuousl~. A turbine irnpeller, for example, the EKAI'O (a trade mark) turbine impeller, is preferred as the shear device. Ilowever, shearing can also be performed with a toothed-disc dissolver, dispensing pump, rotary pump, etc.
While in the present case, the crystallization can be carried out, for example, at 93C, it has been found to be advantageous to carry out the tempering at a temperature between 85and 105C in the crystallization mother liquor. Tempering times between 0.2 and 6, preferably between 0.8 and 4.0, particu-larly 3 hours are favourable. The tempering time commences at the point at which t-he crystallizationis completed. This point is evident from the development of maximum ion exchange capacity, on attaining maximum X-ray line intensity and an adsorption of water vapour of approximately 22.5%. In practice the tempering time is based on an empirical value determined by means of optimum formulation.
- Shearing forces acting to the end of the crystallization phase can be so intensified that the average particle diameter can be reduced to very small values. The values for the maximum particle size and its percentage in the product can also be reduced. However, shearing carried out during the tempering phase exclusively influences the maximum particle size and its proportion in the.product.
The invention also provides for the use of the ~ crystalline type-A zeolite powder according to the invention - - as an ion exchanger, for example, for the softening of water, . particularly as a phospha-te substitute in washing, rinsing and cleansing agents.~
.
. ' ~
j:
- ~L0~35S3 These deteryents are combina-tions of surfac~ active crude washing substances. However, in most cases they also contain other substan-tially inorganic additives, which con~ribute -to a successful washing procedure and are necessary for the production process and for the external quality of the production.
Depending on the use concerned the cornposition of the detergents varies and depends particularly on the fiber type, coloration and washing temperature. It also depends on whether -the washing operation is carried out by hand, for example, in a tub, in a household washing machine or in a laundry. Most detergents are pourable powders. However, liquid and pasty products are also avallable (see Ullmann's Enzyklopadie der technischen Chemie, Third Edition, Vol. 18 Urban ~ Schwarzenberg, Munich 1967).
The crystalline type-A zeolite powder according to the invention has the advantage that it is free from grit and contains smaller particles even during its production. Therefore, when using it as a phosphate substitute in washing and cleansing agents it can be easily kept in suspension in the liquors concerned and can be rinsed out with particular ease from washing and cleaning machines and their charge without leavinq residues.
The present invention will be further described by way of the following Examples.
Example 1 560 litres of a solution of caustic soda (Na2O = 63 g per litre) having a temperature of 70C are put into a tub of 2-cu m capacity.
While stirring with a three-stage Mig impeller 300 litres of sodium tetrasilicate (~ = 1.35 kg per l;tre) containing 8.0%
of NaO per litre and 26.7% of A12O3 per litre are added within 40 minutes to the solution of caustic soda. The solution remains clear.
100 litres of an aqueous sodium-aluminate liquor :
- 5 _ , ,. ,:- . :, .
- ~ .
~33S~i3 having a temperature of 70C and containing 147 g o~ Na2O per litre and 103 g of A12O3 per lltre are added first to the solution in 15 minutes, whereupon 900 litres of the same liquor are added in 98 minutes. The reaction mixture is heated to 85C
andis crystallized for 3 hours. An X-ray-photographically pure type-A zeolite having the following particle spectrum is obtained:
fraction proportion (~m) (~ by weight) lO < 3 ~m 15 < 5 um 62 <lO ~m 98 <15 ~m 99 The proportion of 50% by weight is below 4.3 ~m. The particle size is de-termined by measuring with the Coulter coun-ter.
Example 2 Perborate-Containing Detergent , 45.0~ by weight of sodium aluminium silicate obtained according to example l (dried for 6 hours at 90C, water content 16.8% by weight), 20.0~ by weight of sodium perborate, 35.0% by a detergent powder, produced, for example, by hot-air drying and having the following composition:
21.0~ by weight of ABS (dodecyl benzene sulphonate), 7.5% by weight of ethoxylated tallow alcohol (l mole of tallow alcohol + 14 moles of ethylene oxide), 7.2~ by weight of SO.lp (sodium salt of saturated substantiallY C18 ~ C22 fatty acids)~
-- 9% by weight of sodiurn tetrasilicate (Na2O 3.3 sio2?,
4.5~ by weight of magnesium sulphate, .
.. . . . .
33S~53 -2.0~ by wei~ht of carboxy-methyl cellulose, 0.6% by weight of optical brlc3htener, 9.0% by weight of soluble complexing-agent salt (for example, sodium citra-te, NTA, EDTA , sodium triphosphate, POC etc.), ; 35.0% by weight of sodium sulphate the rest = water.
The detergent was produced by mixing the three powdered components.
Example 3 Detergent Free from Perborate 2.0% by weight of ethoxylated Cll/C15 oxo alochol - (1 mole of oxo alcohol ~ 3 moles of ethylene oxicle), )
.. . . . .
33S~53 -2.0~ by wei~ht of carboxy-methyl cellulose, 0.6% by weight of optical brlc3htener, 9.0% by weight of soluble complexing-agent salt (for example, sodium citra-te, NTA, EDTA , sodium triphosphate, POC etc.), ; 35.0% by weight of sodium sulphate the rest = water.
The detergent was produced by mixing the three powdered components.
Example 3 Detergent Free from Perborate 2.0% by weight of ethoxylated Cll/C15 oxo alochol - (1 mole of oxo alcohol ~ 3 moles of ethylene oxicle), )
5.0% by weight of ethoxylated Cll/C15 oxo alochol (1 mole of oxo alcohol ~ 3 moles of ethylene oxide),+ ) 40.0~ by weight of sodium aluminium silicate obtained according to example 1 (dried for 6 hours at - - 90C, water content 16.8~ by weiyht), , 15.0% by weight of soda, 5.0% by weight of sodium citrate, 4.0~ by weight of sodium tetrasilicate (Na2O 3.3 SiO2), 1.5% by weight of carboxy-methyl cellulose, 0.2% by weight of optical brightener, 23.0% by weight of sodium sulphate, rest = water ) replaceable by tallow alcohol + 5 moles of ethylene oxide, ) replaceable by tallow alcohol ~ 14 moles of ethylene oxide.
The detergent is produced by spraying ethoxylation products (non-ionicsurfactants) on thepowder particles consis~lng of the other components.
.~
~: -, . ~ ,. ~
The detergent is produced by spraying ethoxylation products (non-ionicsurfactants) on thepowder particles consis~lng of the other components.
.~
~: -, . ~ ,. ~
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS;
1. A crystalline type-A zeolite powder having the composition 1.0 ? 0.2 M2/nO : Al2O3 : 1.85 ? 0.5 SiO2 ? y H2O, wherein M represents a metal cation, n its valency and y a value of up to 6, and containing 50% by weight of particles of a size below a maximum of 4.8 µm as well as having the following particle spectrum
2. A process for producing the zeolite powder of claim 1 by hydrothermal crystallization of an alkali aluminate/
water/silicate synthesis mixture containing SiO2, Al2O3, Na2O
and water in which an aqueous caustic soda solution containing from 0.1 to 500 g of NaOH per litre is heated to a temperature from 30 and 100°C, an alkali metal silicate solution having a temperature from 30 and 80°C is added while stirring or subjecting to the action of shearing forces are 10 to 200 minutes, a sodium-aluminate liquor, which contains 10 to 200 g of Al2O3 per litre and 10 to 250 g of Na2O per litre, and having a temperature between 30 and 100°C is added over 10 to 200 minutes and the synthesis mixture thus obtained is allowed to crystallize at a temperature between 20 and 175°C over at least 15 minutes.
water/silicate synthesis mixture containing SiO2, Al2O3, Na2O
and water in which an aqueous caustic soda solution containing from 0.1 to 500 g of NaOH per litre is heated to a temperature from 30 and 100°C, an alkali metal silicate solution having a temperature from 30 and 80°C is added while stirring or subjecting to the action of shearing forces are 10 to 200 minutes, a sodium-aluminate liquor, which contains 10 to 200 g of Al2O3 per litre and 10 to 250 g of Na2O per litre, and having a temperature between 30 and 100°C is added over 10 to 200 minutes and the synthesis mixture thus obtained is allowed to crystallize at a temperature between 20 and 175°C over at least 15 minutes.
3. A process as claimed in claim 2, in which subsequent tempering is effected.
4. A process as claimed in claim 3, which comprises effecting the tempering at a temperature between 85°C and 105°C
in the crystallization mother liquor.
in the crystallization mother liquor.
5. A process as claimed in claim 4, in which the tempering is effected for a time between 0.2 and 6 hours.
6. A process as claimed in claim 4, in which the tempering is effected for a time between 0.8 and 4 hours.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2651445.4-41 | 1976-11-11 | ||
| DE19762651445 DE2651445A1 (en) | 1976-11-11 | 1976-11-11 | TYPE A II CRYSTALLINE ZEOLITE POWDER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1083553A true CA1083553A (en) | 1980-08-12 |
Family
ID=5992899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA288,603A Expired CA1083553A (en) | 1976-11-11 | 1977-10-13 | Crystalline type-a zeolite powder ii |
Country Status (11)
| Country | Link |
|---|---|
| JP (3) | JPS5360898A (en) |
| BE (1) | BE860755A (en) |
| BR (1) | BR7707456A (en) |
| CA (1) | CA1083553A (en) |
| CH (1) | CH631945A5 (en) |
| DE (1) | DE2651445A1 (en) |
| ES (1) | ES463994A1 (en) |
| FR (1) | FR2370693A1 (en) |
| GB (1) | GB1571535A (en) |
| IT (1) | IT1143827B (en) |
| NL (1) | NL180738C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2734296A1 (en) * | 1977-07-29 | 1979-02-08 | Degussa | PROCESS FOR THE PRODUCTION OF FINE PARTICULAR, WATER-INSOLUBLE SILICATES ENABLED FOR CATION EXCHANGE |
| FR2444005A1 (en) * | 1978-12-15 | 1980-07-11 | Ugine Kuhlmann | INDUSTRIAL PROCESS FOR THE SEMI-CONTINUOUS MANUFACTURE OF ZEOLITE A |
| DE2856278A1 (en) * | 1978-12-27 | 1980-07-10 | Degussa | METHOD FOR PRODUCING FINE-PARTICLE SODIUM ALUMINUM SILICATES |
| DE3132379A1 (en) * | 1981-08-17 | 1983-02-24 | Degussa Ag, 6000 Frankfurt | ZEOLITE GRANULES, METHOD FOR THE PRODUCTION AND USE THEREOF |
| DE3132928C1 (en) | 1981-08-20 | 1983-01-13 | Degussa Ag, 6000 Frankfurt | Process for accelerating the setting of hydraulic cement mixtures |
| DE3444311A1 (en) * | 1984-12-05 | 1986-06-05 | Degussa Ag, 6000 Frankfurt | AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS |
| DE4309656A1 (en) * | 1993-03-25 | 1994-09-29 | Henkel Kgaa | Process for the production of very finely divided zeolitic alkali metal aluminum silicates |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1038017B (en) | 1953-12-24 | 1958-09-04 | Union Carbide Corp | Process for making crystalline zeolitic molecular sieves |
| US3310373A (en) | 1963-04-03 | 1967-03-21 | Mobil Oil Corp | Method for producing crystalline aluminosilicates |
| SE419975C (en) * | 1973-04-13 | 1986-08-18 | Henkel Kgaa | DETERGENTS AND / OR BLENDS CONTAINING A CRYSTALLINE WATER-INSULATED SILICATE PROCEDURE FOR ITS PREPARATION AND USE |
| AT330930B (en) | 1973-04-13 | 1976-07-26 | Henkel & Cie Gmbh | PROCESS FOR THE PRODUCTION OF SOLID, SPILLABLE DETERGENTS OR CLEANING AGENTS WITH A CONTENT OF CALCIUM BINDING SUBSTANCES |
| US4605509A (en) * | 1973-05-11 | 1986-08-12 | The Procter & Gamble Company | Detergent compositions containing sodium aluminosilicate builders |
| CA1037815A (en) * | 1973-06-20 | 1978-09-05 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Process for the production of solid, pourable washing or cleaning agents with a content of a calcium binding silicate |
| DE2433485A1 (en) * | 1973-07-16 | 1975-02-06 | Procter & Gamble | ALUMINOSILICATE ION EXCHANGERS SUITABLE FOR USE IN DETERGENTS |
| DE2447021C3 (en) | 1974-10-02 | 1984-03-22 | Degussa Ag, 6000 Frankfurt | Type A crystalline zeolite powder and the process for its preparation |
| DE2517218B2 (en) | 1975-04-18 | 1977-05-05 | Henkel & Cie GmbH, 4000 Düsseldorf; Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, 6000 Frankfurt | TYPE A CRYSTALLINE ZEOLITE POWDER |
-
1976
- 1976-11-11 DE DE19762651445 patent/DE2651445A1/en not_active Ceased
-
1977
- 1977-08-31 NL NL7709581A patent/NL180738C/en not_active IP Right Cessation
- 1977-09-21 FR FR7728476A patent/FR2370693A1/en active Granted
- 1977-09-29 IT IT6914777A patent/IT1143827B/en active
- 1977-10-13 CA CA288,603A patent/CA1083553A/en not_active Expired
- 1977-11-07 BR BR7707456A patent/BR7707456A/en unknown
- 1977-11-10 ES ES463994A patent/ES463994A1/en not_active Expired
- 1977-11-10 BE BE6046217A patent/BE860755A/en not_active IP Right Cessation
- 1977-11-10 CH CH1374477A patent/CH631945A5/en not_active IP Right Cessation
- 1977-11-10 JP JP13520077A patent/JPS5360898A/en active Pending
- 1977-11-11 GB GB4703277A patent/GB1571535A/en not_active Expired
-
1981
- 1981-04-08 JP JP5191781A patent/JPS5727917A/en active Granted
- 1981-04-08 JP JP5191881A patent/JPS5723696A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE2651445A1 (en) | 1978-05-18 |
| JPS6324926B2 (en) | 1988-05-23 |
| FR2370693A1 (en) | 1978-06-09 |
| ES463994A1 (en) | 1978-06-16 |
| NL180738C (en) | 1987-04-16 |
| NL180738B (en) | 1986-11-17 |
| JPS5360898A (en) | 1978-05-31 |
| BR7707456A (en) | 1978-08-01 |
| JPS5723696A (en) | 1982-02-06 |
| GB1571535A (en) | 1980-07-16 |
| BE860755A (en) | 1978-05-10 |
| FR2370693B1 (en) | 1980-08-01 |
| JPS5727917A (en) | 1982-02-15 |
| CH631945A5 (en) | 1982-09-15 |
| NL7709581A (en) | 1978-05-16 |
| IT1143827B (en) | 1986-10-22 |
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