CA1057272A - Process for producing grit-free zeolitic molecular sieves - Google Patents
Process for producing grit-free zeolitic molecular sievesInfo
- Publication number
- CA1057272A CA1057272A CA236,911A CA236911A CA1057272A CA 1057272 A CA1057272 A CA 1057272A CA 236911 A CA236911 A CA 236911A CA 1057272 A CA1057272 A CA 1057272A
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- molar ratio
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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)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/33—Wastewater or sewage treatment systems using renewable energies using wind energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Detergent Compositions (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides a process for producing an A-type zeolite molecular sieve based on crystalline alumino silicates containing water of hydration and at least 99.5, by weight of particles having diameters smaller than 45 µm by hydrothermal crystallization of an aluminate sodium tetrasili-cate synthesis mixture in which the components of the synthesis mixture, which are in a molar ratio of SiO2 : Al2O3 less than 1.9 : 1 and in a molar ratio of water : alkali metal oxide of at least 30 : 1 are intimately mixed prior to the precipitation of an amorphous initial product, and after the crystallization the aluminium silicate suspension is tempered under cryatlliz-ing conditions and is sheared during at least one of the crystal-lization and the tempering. The A-type zeolitic molecular seive so obtained has 99.5% of the particles with diameters below 45 µm and a defined particle spectrum which makes is particularly use-ful as an ion exchanger, for example in the softening of water and as a phosphate substitute in detergents.
The present invention provides a process for producing an A-type zeolite molecular sieve based on crystalline alumino silicates containing water of hydration and at least 99.5, by weight of particles having diameters smaller than 45 µm by hydrothermal crystallization of an aluminate sodium tetrasili-cate synthesis mixture in which the components of the synthesis mixture, which are in a molar ratio of SiO2 : Al2O3 less than 1.9 : 1 and in a molar ratio of water : alkali metal oxide of at least 30 : 1 are intimately mixed prior to the precipitation of an amorphous initial product, and after the crystallization the aluminium silicate suspension is tempered under cryatlliz-ing conditions and is sheared during at least one of the crystal-lization and the tempering. The A-type zeolitic molecular seive so obtained has 99.5% of the particles with diameters below 45 µm and a defined particle spectrum which makes is particularly use-ful as an ion exchanger, for example in the softening of water and as a phosphate substitute in detergents.
Description
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The present invention relates to a process for produc-ing A-type zeolitic molecular sieves based on crystalline alumino silicates containing water of hydration and at least 99.5~ by weight of particles having diameters smaller than 45 ~m by .
hydrothermal crystallization o an aluminate/sodium tetrasilicate synthesis mixtuxe. The present invention also relates to the . .
molecular sieves obtainable by means of said process and to their use.
:. . .
Zeolitic molecular sieves with their specific proper-ties for ion exchange and adsorption have been known for a long time. Their synthesis com~rising heating an aaueous synthesis , ~ .
mixture with the components Na2O x b A12O3 x c SiO2 to tempera-tures between 50 and 300C. Depending on the composit~on of the . -. ~ .
.. . . . .
reactant mlxture, reactlon temperature and reactlon tlme, com-,:f pounds having the general formula NaxAlxSiyO2(x+y). n H2O of differing X-ray spectra are obtained. In these synthesis sodium can be replaced by monoval2nt or divalent ions. Thus, for ., .
example, German Patent No. 1,038,017 issued October 22, 1969 to Union Carbide Corporation describes a process ~or producing the ~J
~; 20 molecular sieve A having the summation formula 1.0 - 0.2 M2~nO o A1~03 : 1.85 - 0.5 SiO2 : Y H2O, wherein M represents a metal cation, n its valency and Y a value of up to 6. For the produc-tion of the A type a synthesis mixture in which SiO2 and A12O3 ~` (for example, in the form of sodium tetrasilicate or sodium aluminate) are pxesent in ~he molar ratio of 2:1 and water and ~ alkali metal oxide (for example, Na2O) in the molar ratio of 17.5:
- 1 is usually used.
The fact that the synthesis yields crystals whose average diameter is above approximately 2 and that a substantial portion (usually hetween 3 and 12% by weight) has a limitiny particle size above 45 ~m is common to the known processes. This proportion is referred to as grit and according to DIN 53580 it is determined by wet screeniny according to Mocker.
:. . . , , - ~ , . . , : ' . : , .. . ~ . .
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For use as adsorbents, catalyst supports or ion exch-angers the molecula~ sieves are converted in~o molded articles with a suitable hinder. The production of the molded article involves great technical expendituxe while the effect of ~he ;
sieve is reduced due to the presence of the binder. Further, because of the long diffusion paths the rate of reaction is substantially reduced, so that the drying of organic liquids is cumbersome. Further, for example, when removing me~al or radio-active metals from added water and from waste water, ion exchange and precipitation must be separated. Therefore, for the above ~-~
uses it is appropriate to use the molecular sieve in the form o~
a powder. In lacquers, too, it is used only in this form.
The present invention provides a process by means of which powdery zeolitic A-type molecular sieves, particularly for `
use as ion exchangers, e.g. for water softening, are synthesized with defined particle sizes without the formation of grit i.e.
particles of size > 45 ~m. For use of the molecular sieves of the present invention, for example, as a phosphate substitute ~ ~
in detergents, the absence of grit is imperative. Washing and ~ ~ -cleaning processes, particularl.y in machines, require that the molecular sieve remains in suspension in the wash liquor (due to a low tendency to deposit sediments) in order to assure rinsing without leaving xesidues after the completed washing process.
According to the present invention therefore there is `
provided a process for producing A-type zeolitic molecular sieves -~
based on crystalline alumino silicates containin~ water of hydra- ;~
tion and containing at least 99.5, preferably 99.9 and particul- `~
arly 99.99~ by weight of particles having diameters less than ~5 ~m by hydrothermal crystallization of an aluminate/sodium ~e~
silicate synthesis mixture, in which the components of the synth- ~ -esis mixture which are present in molar ratio between SiO2 and Al2O3 of less than l.9 : l and preferably in a molar ratio ... , ~. -. . .i , , .
between water and alkali metal oxide of at least 30 : 1, are intimately mixed prior to the precipitation of the amorphous ; initial product and that upon cr~stallization the aluminium silicate suspension is tempered under crystallizing conditions and sheared during the crystallization and/or during the tem-r~ pering.
~ ~ .
;- Thus, the process of the present invention is based .
on the following important interacting measures, which make the practically quantitative synthesis of a product having the des-ired limiting particle size and specific granular sizes possible.
In contrast to the conventional processes a substant- ;~
;~ ially higher proportion of aluminium oxide is present in the sy- ~ -~ nthesis mixture. Care is taken that the precipitation is carried ~ ~
. . . .
out from an intimately mixed synthesis mixture in order to assure ~ uniform formation of nuclei. It is further essential that the -; crystallization is followed by a tempering stage, in which the conditions used for the crystallization are usually maintained.
Further, during the crystallization or during both process stages ~;, shearing forces must act on the aluminium silicate suspension.
! 20 A particularly low contant of particles having a limited size can be obtained when the measures mentioned hereinbefore are combined with the use of an alkali concentration in the synthesis mixture ~`
which is reduced as compared with that of conventional processes.
The decrease in the proportion of particles having a limited size which is brought about in like manner by the tempering and by the reduced alkali concentration is surprising insofar as is well -known, in crystallizations both the tempering and the reduction in ;
concentration result in the formation of larger crystals and the ~ ~-effects which can be obtained in the present system thus run coun-3~ ter to the prevailing teaching.
The measures according to the invention for controlling ~
the limiting particle size and the proportion of particles having ~ `
, :
, ~Si7~7'~ ~
a limited size can be chosen that a desired average particle diameter oE the crystals is obtained. The average particle diameter can have values from below 1 ~m to lS ~m and is deter- -~ mined primarily by the effect of the shearing intensity during - the crystallization. For the intended purpose according to the invention an average particle diameter of approximately 8 ~m in ` conjunction ~ith the limiting particle size below 45 ~m was found `~ to be suitable. As the values for the limiting particle size de-crease the distribution curve, which is flattened towards large ; 10 crystals, tends to an ideal Gaussian distribution. An optimum and thus practice - favourable adjustment of the proportion of the desired limiting particle size, which, according to the pre-sent invention, can be decreased to 0.01% by weight and even to ~
a lower value, can be attained only by the interaction of the ~;
important measures of the process. From studies of the sedimen s tation behaviour it can be estimated that according to the inven-tion the limiting particle size can be reduced to values of app-roximately 20 ~m. The synthesis mixture can contain SiO2 and A12O3 in molar ratios of 0.8 to 1.6 : 1, particularly about 1.3 :
1, and water and alkali metal o~ide in molar ratios of 35 to 50 -' A particularly favourable manner of carrying out the process of the present invention is that in order to precipitate the amorphous initial product, an amount of water or aluminate solution which causes at least a stirring effect is used and sod-.. . .
ium aluminate solution as well as sodium tetrasilicate solution ;
are added simultaneously while stirring thoroughly, particularly in the zone of maximum turbulence.
By "shearing", as used herein is meant any comminuting ~ ~
mechanical stress on discrete particles in suspension, i.e., a , mechanical stress due substantially to a true shearing effect.
The shearing can be carried out either discontinously or contin-uously. I~he recycling method f operation in which the material ... , . : ~ .
', , j . .' . ,' ', . ' ,' , . ,, . !. . , ;7Z7Z
to be sheared is exposecl to the action of shear forces several times in succession is preferred. A critarion thereof is the so- -called throughput fre~uenc~, which indicates the numhPr of streams passing throuyh per hour (dimension h 1) A turbine mixer, for example, the EKATO (a trademark) turbine mixer, is the preferred shear apparatus. However, a toothed-disc dissolver, dispersing pumps, rotary pumps or the like can also be used for shearing.
The shearing energy to be applied in order to obtain the limiting particle size under the operating conditions according to the invention is practically negligible as compared with the shearing energy required for drastically reducing the average particle diameter (see German Auslegeschrift 2,333,068 published September 1, 1977). Une~pectedly it was found that if the limiting particle size and the proportion of particles having a limited size are correctly adjusted, then the average particle diameter can also ~;~
be above 2 ~m without impairing an important property of the application techni~ue, namelv the capabilit~ of washing out the zeolite softening agents according to t:he present invention used in detergents. Thus, if a turbine impeller is used, then it can be operated with a rate of power input of 0.4 to 2, preferably 0.6 to 1, particularly 0.8 KW per cu m.
While the crystallization can be carried out, for example, at 94C, it was found to be advantageous to carry out the tempering at a temperature between 85 and 105C in the cxystallizing mother li~uor. Tempering times between 0.2 and 6, preferably from 0.8 to 1.8, hours, particularly one haur are favourable. The tempering time starts at the point at which the crys~allization is completed. This point i5 evident from the development of maximum X-ray line intensity and attainment of a ~
steam adsorption of approximately 22O5%. In practice an empirical ;
value determined ~y means of an optimized formula is used.
In order to optimi2e the process products for a specific , ' ' "
~7~7;~
purpose, tempering and shearing conditions in particular must be adjusted to one another, whereas with respect to the A1203/SiO2 molar ratio or also with respect to the alkali content in the synthesis mixture it is sufficient to maintain the specified limits.
Shearing which is effective towards the end of the crystallization phase can be so intensified that the average particle diameter can be decreased to very small values and the values for particles having a limited size and their percentage -in the product can thus also be reduced. However, the effect of shearing on the average particle diameter and limiting particle size or on the proportion of particles having a limited size is not parallel under all the conditions of the process. Thus, for example, with the preferred use of lower alkali concentrations in the synthesis mixture the average particle diameter increases -while the limiting particle sizes and the proportion of particles having a limited size decrease. However, when shearing was carried out during the tempering stage it affected exclusively ~ the particles having a limited size and their proportion.
; The present invention also provides an A-type zeolitic ~ -molecular sieve with at least 99.5%~ preferably 99.9% and part-icularly 99.99% of particles having diameters below 45 ~m and a - particle spectrum containing ~ ~`
fraction proportion (~m) (% by weight) : - :
<3 <15 <5 <35 -~
<10 <82 <15 <96 <2Q <100 : , ~ , . , , : . . . ..
: . , . . :
:, . .. , , . . ::
:, ,. : : , : , ~ 3572~7~
preferably Eraction proportion (~m) (~ by weight3 <3 4-15 ~5 11-35 <10 50-82 <15 79-96 <20 93-100 The A-type zeolitic molecular sieve can be obtained by means of the process measures described hereinbefore.
Finally, the invention relates to the use of the mole-cular sieve as an ion exchanger, for example, to soften water, particularly as a phosphate substitute in detergents. The products according to the invention have the advantage that they are free i from grit even during their production. Therefore, when they are used as softeners in detergents they can be readily kept in sus-pension in the wash liquors concerned and they can be rinsed out of washing machines and their loads with particular ease and with-out leaving residues.
The present invention will be further illustrated by way of the following examples.
Example 1 7 kg of commercial moist hydrate, i.e. an aluminium oxide hydrate having a water content of 42.5%, which can be det-ermined by means of the loss on ignition, is dissolved in 50 litres of a 12% by weight solution of caustic soda at 100C. The clear solution thus obtained is cooled to 80C. The further ; -treatment is carried out in a 60-litre glass vessel, which is fitted with a mixer. The power consumption can be measured wikh a superposed ammeter. The velocity of stirring is infiniteIy variable. The mixer is an Eka~o ( a trademark) turbine mixer according to DIN 28131 and has a diameter of 15 cm. The agitating tank has a diameter of 40 cm and 4 baffles, each baffle being : .. . . . .....
7~
,,, arranged at an angle of 90.
The precipitation is initiated by dosing in 8.8 litres of sodium tetrasilicate, which contains 26.5% by weight of SiO2 and 8% by weight of Na2O, with a tube ending approximately 0.5 cm above -the disc of the turbine mixer.
Prior to the start of the precipitation, 15 litres of aluminate solution are put into the agitating tank. The remainder is added to the reaction mixture simultaneously with the sodium tetrasilicate. The precipitation is completed after 30 minutes.
The precipitated product i5 amorphous to X-rays. In the reaction mixture the components are in the molar ratio of H2O : Na2O = 33 and Si2 A123 = 1-3 At the end of the precipitation the mixer has an energy :~
consumption of 0.8 XW per cu m. The temperature of the reaction mixture is increased to 90C with the aid of steam. The course of the starting crystallization is ohserved by means of the Ca-bonding power.
By Ca-bonding power is meant the ion exchangeability of -~
1 g of the product dried for 2 hours at 200C. For its determin~
ation this amount is added to 1 litre of water, which contains ;~
CaC12 corresponding to 300 mg of CaO. This is followed by filter-ing and the amount of CaO remaining in the water is titrated com~
plexometrically. The difference with respect to the initial 300 mg constitutes the bonding power of the zeolite. The crystalliz-ation is completed when the Ca-bonding power ceases to change. ;~
After a reaction time of 80 minutes the Ca-bonding power reaches `
the value of 16.4 and then remains constant.
Upon completed crystalli2ation the temperature is raised 30 to 95C, followed by tempering for 30 minutes while shearing. The ,~ -crystalline product thus obtained is then washed to pH 10.0, -~whereupon it is dried in a drying cabinet at 200C. It has the ; ;
~ 8 -i7~
.
;~ X-ray diffraction pattern of the zeolite A, as indicated in the German Patent No. 1 038 017.
In order to determine the limiting particle size, wet - screening is carried out in accordance with DIN 53580. For this purpose, the sample, suspended in water, is put into a Mocker tester and is kept in a turbulent motion by water sprayed from rotating nozzles. The fine particles are flushed through the fabric of the test sieve while the coarse particles remain on the test sieve. The residue is tested on the sieve and weighed. A ~
sieve according to DIN 4188, i.e., a sieve having a width of mesh ~ ~-of 45 ~m is used as the test sieve fabric.
The product thus obtained has a proportion of 0.010~ of particles having a limited size > 45 ~m and this proportion was determined in the manner described above.
An analysis of granular sizes on a sedimentation balance is used for the further characterization of the product.
The sample to be measured is dispersed in water with the `
aid of an Ultra-Turrax and the sedim~ntation is then observed. ~
The particle distribution is as follows: `
fraction ~ proportion (~m~ (% by weight) ` <3 7 9 `~
; <5 14.9 <10 60.4 <15 85.9 <20 95 :
;~ <25 99 3 ` <30 100.0 -~ Example 2 5.5 kg of moist hydrate having a water content of 42.5 are dissolved in 50 litres of a 10~ by weight solution of caustic soda. The reactor described in Example 1 is fitted with a ~5~ 2r~
propeller mixer having a diameter of 15 cm according to DIN 28131.
During the precipitation and crystallization the energy consump-tion of the mixer is 0.3 KW per cu m. As in example 1, 15 litres of the aluminate solution were put into the reactor first, in order to assure sufficient efficiency of the mixer at the begin-ning of the addition of sodium tetrasilicate. The rest of the aluminate liquor is added within 30 minutes. At the same time 6.8 litres of sodium tetrasilicate containing 26.5% of SiO2 and 8~ of Na2O are added directly on the propellerO The synthesis mixture thus obtained which has a molar ratio of S 2 2 3 ~ ?
and H2O : Na2O = 39 : 1 is then crystallized at 93C. After 90 minutes a Ca-bonding power of 168 mg of CaO per gram is obtained and the reaction is completed.
The propeller is then replaced by a turbine mixer as described in Example 1, whereupon tempering is carried out at the same temper- ~ `
ature (i.e., 93~C) under the action of shearing energy, the energy ;~
consumption being 0.8 KW per cu m. After 1 hour the reaction is terminated, the product is washed to pH 10.0 and then spraydried. ; ' The A-type zeolite obtained is~radiographically pure and, in the grit determination according to Mocker (DIN 53580), it no longer ~;
has any measurable proportion of particles > 45 ~m. The accuracy of measurement of this method is 0.001%. An analysis of granular sizes on the sedimentation balance shows the following particle ~
distribution: f ; `-fraction proportion (~m) (% by weight) <3 15-3 <5 35.2 <10 82.6 ;
<15 96.3 <20 100.0 ~ ~
~ , . - ,.:
`:
., - 10 ;
,, , : . .: : . . ~ .. : . .
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Example 3 A synthesis mixture is produced analogously to that of example 2. It contains the components SiO2 and A12O3 in the ratio of 1.3 : 1 as well as water and sodium oxide in the ratio of 39 : 1. After the preclpitation stage a turbine mixer having a diameter of 10 cm is used for shearing during the crystalliza-tion. The energy consumption is 0.6 KW per cu m and the crystall-ization temperature 90C. After 110 minutes the Ca-bonding power of the crystallized zeolite reaches a Einal value of 161 mg of CaO per gram. The turbine mixer is then replaced by a 3-stage MIG ( a trademark) mixer of the firm of Ekato, whereupon the syn-thesis mixture is tempered at an energy-consumption of 0.1 KW per cu m for 4 hours at 92C while stirring (no shearing). The pro-duct obtained :is a radiographically pure zeolite and has a pro-portion of 0.13~ of particles having a limited size (which can be determined with the Mocker tester) and the following particle spectrum (as determined on a sedimentation balance):
fraction proportion m) (% by weight) -~
<3 4 2 <5 10.8 ;
<10 50.3 <15 78.6 <25 98.1 ` <30 99.5 ; Example 4 5.5 kg of commercial moist hydrate are dissolved in 53 litres of an 11% by weight solution of caustic soda. The aluminate solution ohtained is pumped into a 60-litre reactor by means of a Static ( a trademark) Mixer. Ahead of the mixing unit 8.2 litres -' of sodium tetrasilicate are added. After the mixing process a '~
`:
' ''' ~
~5~'~'7~
mixture clear as water flows into the reactor. At the bottom of the reactor the solution is drawn off by suction and, while re-cycling at 40 h 1, it is pumped by a rotary pump in a shearing manner. The pump has an energy consumption of 1.8 KW per cu m.
The synthesis mixture, which has a ratio of SiO2 : A12O3 = 1.6 : 1 and H2O : Na2O = 37 : 1, is heated to 95C. The crystallization is completed after 50 minutes. The temperature is then increased to 105C and tempering is carried out for 30 minutes while shear-ing continuously. The product obtained has a grit proportion of 0.03~ above 45 ~m as determined according to Mocker and the foll-owing particle spectrum (as determined on a sedimentation balance):
fraction proportion (~m)(% by weight) <3 8-5 <5 16.2 <1063.5 `~ ~-<1586.4 ~;
<2097.8 ;
<25 99.6 ~30 100.0 ` ~-Example 5 `~-4.5 kg of commercial moist hydrate are dissolved in 50 litres of an 8% by weight solution of caustic soda. The solution obtained is then thoroughly mixed with 4.3 litres of sadium tetra~
silicate according to the method described in Example 1. The ~-crystallization is then carried out at 92C under the action of shear forces in the manner described in example 1, the energy consumption being 1 KW per cu m. ;
Upon completed crystallization, tempering is carried out with the same shearing energy and at a temperature of 94 C . The ; zeolite A obtained, which is radiographically pure, contains no limiting particle size of 45 ~m and has the following particle spectrum: -,:: ., . ,; , . ,, , , , . ; , . :
~ , . . - ~ . . ~ .
r - ~
~57;~7,~
fract.ion proportion ~.
(~Im) (% by weight) ~3 5.3 <5 13.1 <10 50 3 <20 96.8 <25 100.0 All the zeolite .ion exchangers produced according to the examples 1 to 5 can at least partially replace the phosphates used heretofore in the conventional detergents. The detergents produced with said ion exchangers leave no deposits which can be ~ ;
seen with the na:ked eye on the la~ndry.
,,,, ~, , 's' ~
',' ,':
', ...
' ' ~ : , ' . :
.
. ~ .
' ~' ; ;' .
,, ~ :' - 13 - .
, 3, '';'~ ' . , ' ' . ' ' , ' ' ', ' '
The present invention relates to a process for produc-ing A-type zeolitic molecular sieves based on crystalline alumino silicates containing water of hydration and at least 99.5~ by weight of particles having diameters smaller than 45 ~m by .
hydrothermal crystallization o an aluminate/sodium tetrasilicate synthesis mixtuxe. The present invention also relates to the . .
molecular sieves obtainable by means of said process and to their use.
:. . .
Zeolitic molecular sieves with their specific proper-ties for ion exchange and adsorption have been known for a long time. Their synthesis com~rising heating an aaueous synthesis , ~ .
mixture with the components Na2O x b A12O3 x c SiO2 to tempera-tures between 50 and 300C. Depending on the composit~on of the . -. ~ .
.. . . . .
reactant mlxture, reactlon temperature and reactlon tlme, com-,:f pounds having the general formula NaxAlxSiyO2(x+y). n H2O of differing X-ray spectra are obtained. In these synthesis sodium can be replaced by monoval2nt or divalent ions. Thus, for ., .
example, German Patent No. 1,038,017 issued October 22, 1969 to Union Carbide Corporation describes a process ~or producing the ~J
~; 20 molecular sieve A having the summation formula 1.0 - 0.2 M2~nO o A1~03 : 1.85 - 0.5 SiO2 : Y H2O, wherein M represents a metal cation, n its valency and Y a value of up to 6. For the produc-tion of the A type a synthesis mixture in which SiO2 and A12O3 ~` (for example, in the form of sodium tetrasilicate or sodium aluminate) are pxesent in ~he molar ratio of 2:1 and water and ~ alkali metal oxide (for example, Na2O) in the molar ratio of 17.5:
- 1 is usually used.
The fact that the synthesis yields crystals whose average diameter is above approximately 2 and that a substantial portion (usually hetween 3 and 12% by weight) has a limitiny particle size above 45 ~m is common to the known processes. This proportion is referred to as grit and according to DIN 53580 it is determined by wet screeniny according to Mocker.
:. . . , , - ~ , . . , : ' . : , .. . ~ . .
~7Z I~Z
For use as adsorbents, catalyst supports or ion exch-angers the molecula~ sieves are converted in~o molded articles with a suitable hinder. The production of the molded article involves great technical expendituxe while the effect of ~he ;
sieve is reduced due to the presence of the binder. Further, because of the long diffusion paths the rate of reaction is substantially reduced, so that the drying of organic liquids is cumbersome. Further, for example, when removing me~al or radio-active metals from added water and from waste water, ion exchange and precipitation must be separated. Therefore, for the above ~-~
uses it is appropriate to use the molecular sieve in the form o~
a powder. In lacquers, too, it is used only in this form.
The present invention provides a process by means of which powdery zeolitic A-type molecular sieves, particularly for `
use as ion exchangers, e.g. for water softening, are synthesized with defined particle sizes without the formation of grit i.e.
particles of size > 45 ~m. For use of the molecular sieves of the present invention, for example, as a phosphate substitute ~ ~
in detergents, the absence of grit is imperative. Washing and ~ ~ -cleaning processes, particularl.y in machines, require that the molecular sieve remains in suspension in the wash liquor (due to a low tendency to deposit sediments) in order to assure rinsing without leaving xesidues after the completed washing process.
According to the present invention therefore there is `
provided a process for producing A-type zeolitic molecular sieves -~
based on crystalline alumino silicates containin~ water of hydra- ;~
tion and containing at least 99.5, preferably 99.9 and particul- `~
arly 99.99~ by weight of particles having diameters less than ~5 ~m by hydrothermal crystallization of an aluminate/sodium ~e~
silicate synthesis mixture, in which the components of the synth- ~ -esis mixture which are present in molar ratio between SiO2 and Al2O3 of less than l.9 : l and preferably in a molar ratio ... , ~. -. . .i , , .
between water and alkali metal oxide of at least 30 : 1, are intimately mixed prior to the precipitation of the amorphous ; initial product and that upon cr~stallization the aluminium silicate suspension is tempered under crystallizing conditions and sheared during the crystallization and/or during the tem-r~ pering.
~ ~ .
;- Thus, the process of the present invention is based .
on the following important interacting measures, which make the practically quantitative synthesis of a product having the des-ired limiting particle size and specific granular sizes possible.
In contrast to the conventional processes a substant- ;~
;~ ially higher proportion of aluminium oxide is present in the sy- ~ -~ nthesis mixture. Care is taken that the precipitation is carried ~ ~
. . . .
out from an intimately mixed synthesis mixture in order to assure ~ uniform formation of nuclei. It is further essential that the -; crystallization is followed by a tempering stage, in which the conditions used for the crystallization are usually maintained.
Further, during the crystallization or during both process stages ~;, shearing forces must act on the aluminium silicate suspension.
! 20 A particularly low contant of particles having a limited size can be obtained when the measures mentioned hereinbefore are combined with the use of an alkali concentration in the synthesis mixture ~`
which is reduced as compared with that of conventional processes.
The decrease in the proportion of particles having a limited size which is brought about in like manner by the tempering and by the reduced alkali concentration is surprising insofar as is well -known, in crystallizations both the tempering and the reduction in ;
concentration result in the formation of larger crystals and the ~ ~-effects which can be obtained in the present system thus run coun-3~ ter to the prevailing teaching.
The measures according to the invention for controlling ~
the limiting particle size and the proportion of particles having ~ `
, :
, ~Si7~7'~ ~
a limited size can be chosen that a desired average particle diameter oE the crystals is obtained. The average particle diameter can have values from below 1 ~m to lS ~m and is deter- -~ mined primarily by the effect of the shearing intensity during - the crystallization. For the intended purpose according to the invention an average particle diameter of approximately 8 ~m in ` conjunction ~ith the limiting particle size below 45 ~m was found `~ to be suitable. As the values for the limiting particle size de-crease the distribution curve, which is flattened towards large ; 10 crystals, tends to an ideal Gaussian distribution. An optimum and thus practice - favourable adjustment of the proportion of the desired limiting particle size, which, according to the pre-sent invention, can be decreased to 0.01% by weight and even to ~
a lower value, can be attained only by the interaction of the ~;
important measures of the process. From studies of the sedimen s tation behaviour it can be estimated that according to the inven-tion the limiting particle size can be reduced to values of app-roximately 20 ~m. The synthesis mixture can contain SiO2 and A12O3 in molar ratios of 0.8 to 1.6 : 1, particularly about 1.3 :
1, and water and alkali metal o~ide in molar ratios of 35 to 50 -' A particularly favourable manner of carrying out the process of the present invention is that in order to precipitate the amorphous initial product, an amount of water or aluminate solution which causes at least a stirring effect is used and sod-.. . .
ium aluminate solution as well as sodium tetrasilicate solution ;
are added simultaneously while stirring thoroughly, particularly in the zone of maximum turbulence.
By "shearing", as used herein is meant any comminuting ~ ~
mechanical stress on discrete particles in suspension, i.e., a , mechanical stress due substantially to a true shearing effect.
The shearing can be carried out either discontinously or contin-uously. I~he recycling method f operation in which the material ... , . : ~ .
', , j . .' . ,' ', . ' ,' , . ,, . !. . , ;7Z7Z
to be sheared is exposecl to the action of shear forces several times in succession is preferred. A critarion thereof is the so- -called throughput fre~uenc~, which indicates the numhPr of streams passing throuyh per hour (dimension h 1) A turbine mixer, for example, the EKATO (a trademark) turbine mixer, is the preferred shear apparatus. However, a toothed-disc dissolver, dispersing pumps, rotary pumps or the like can also be used for shearing.
The shearing energy to be applied in order to obtain the limiting particle size under the operating conditions according to the invention is practically negligible as compared with the shearing energy required for drastically reducing the average particle diameter (see German Auslegeschrift 2,333,068 published September 1, 1977). Une~pectedly it was found that if the limiting particle size and the proportion of particles having a limited size are correctly adjusted, then the average particle diameter can also ~;~
be above 2 ~m without impairing an important property of the application techni~ue, namelv the capabilit~ of washing out the zeolite softening agents according to t:he present invention used in detergents. Thus, if a turbine impeller is used, then it can be operated with a rate of power input of 0.4 to 2, preferably 0.6 to 1, particularly 0.8 KW per cu m.
While the crystallization can be carried out, for example, at 94C, it was found to be advantageous to carry out the tempering at a temperature between 85 and 105C in the cxystallizing mother li~uor. Tempering times between 0.2 and 6, preferably from 0.8 to 1.8, hours, particularly one haur are favourable. The tempering time starts at the point at which the crys~allization is completed. This point i5 evident from the development of maximum X-ray line intensity and attainment of a ~
steam adsorption of approximately 22O5%. In practice an empirical ;
value determined ~y means of an optimized formula is used.
In order to optimi2e the process products for a specific , ' ' "
~7~7;~
purpose, tempering and shearing conditions in particular must be adjusted to one another, whereas with respect to the A1203/SiO2 molar ratio or also with respect to the alkali content in the synthesis mixture it is sufficient to maintain the specified limits.
Shearing which is effective towards the end of the crystallization phase can be so intensified that the average particle diameter can be decreased to very small values and the values for particles having a limited size and their percentage -in the product can thus also be reduced. However, the effect of shearing on the average particle diameter and limiting particle size or on the proportion of particles having a limited size is not parallel under all the conditions of the process. Thus, for example, with the preferred use of lower alkali concentrations in the synthesis mixture the average particle diameter increases -while the limiting particle sizes and the proportion of particles having a limited size decrease. However, when shearing was carried out during the tempering stage it affected exclusively ~ the particles having a limited size and their proportion.
; The present invention also provides an A-type zeolitic ~ -molecular sieve with at least 99.5%~ preferably 99.9% and part-icularly 99.99% of particles having diameters below 45 ~m and a - particle spectrum containing ~ ~`
fraction proportion (~m) (% by weight) : - :
<3 <15 <5 <35 -~
<10 <82 <15 <96 <2Q <100 : , ~ , . , , : . . . ..
: . , . . :
:, . .. , , . . ::
:, ,. : : , : , ~ 3572~7~
preferably Eraction proportion (~m) (~ by weight3 <3 4-15 ~5 11-35 <10 50-82 <15 79-96 <20 93-100 The A-type zeolitic molecular sieve can be obtained by means of the process measures described hereinbefore.
Finally, the invention relates to the use of the mole-cular sieve as an ion exchanger, for example, to soften water, particularly as a phosphate substitute in detergents. The products according to the invention have the advantage that they are free i from grit even during their production. Therefore, when they are used as softeners in detergents they can be readily kept in sus-pension in the wash liquors concerned and they can be rinsed out of washing machines and their loads with particular ease and with-out leaving residues.
The present invention will be further illustrated by way of the following examples.
Example 1 7 kg of commercial moist hydrate, i.e. an aluminium oxide hydrate having a water content of 42.5%, which can be det-ermined by means of the loss on ignition, is dissolved in 50 litres of a 12% by weight solution of caustic soda at 100C. The clear solution thus obtained is cooled to 80C. The further ; -treatment is carried out in a 60-litre glass vessel, which is fitted with a mixer. The power consumption can be measured wikh a superposed ammeter. The velocity of stirring is infiniteIy variable. The mixer is an Eka~o ( a trademark) turbine mixer according to DIN 28131 and has a diameter of 15 cm. The agitating tank has a diameter of 40 cm and 4 baffles, each baffle being : .. . . . .....
7~
,,, arranged at an angle of 90.
The precipitation is initiated by dosing in 8.8 litres of sodium tetrasilicate, which contains 26.5% by weight of SiO2 and 8% by weight of Na2O, with a tube ending approximately 0.5 cm above -the disc of the turbine mixer.
Prior to the start of the precipitation, 15 litres of aluminate solution are put into the agitating tank. The remainder is added to the reaction mixture simultaneously with the sodium tetrasilicate. The precipitation is completed after 30 minutes.
The precipitated product i5 amorphous to X-rays. In the reaction mixture the components are in the molar ratio of H2O : Na2O = 33 and Si2 A123 = 1-3 At the end of the precipitation the mixer has an energy :~
consumption of 0.8 XW per cu m. The temperature of the reaction mixture is increased to 90C with the aid of steam. The course of the starting crystallization is ohserved by means of the Ca-bonding power.
By Ca-bonding power is meant the ion exchangeability of -~
1 g of the product dried for 2 hours at 200C. For its determin~
ation this amount is added to 1 litre of water, which contains ;~
CaC12 corresponding to 300 mg of CaO. This is followed by filter-ing and the amount of CaO remaining in the water is titrated com~
plexometrically. The difference with respect to the initial 300 mg constitutes the bonding power of the zeolite. The crystalliz-ation is completed when the Ca-bonding power ceases to change. ;~
After a reaction time of 80 minutes the Ca-bonding power reaches `
the value of 16.4 and then remains constant.
Upon completed crystalli2ation the temperature is raised 30 to 95C, followed by tempering for 30 minutes while shearing. The ,~ -crystalline product thus obtained is then washed to pH 10.0, -~whereupon it is dried in a drying cabinet at 200C. It has the ; ;
~ 8 -i7~
.
;~ X-ray diffraction pattern of the zeolite A, as indicated in the German Patent No. 1 038 017.
In order to determine the limiting particle size, wet - screening is carried out in accordance with DIN 53580. For this purpose, the sample, suspended in water, is put into a Mocker tester and is kept in a turbulent motion by water sprayed from rotating nozzles. The fine particles are flushed through the fabric of the test sieve while the coarse particles remain on the test sieve. The residue is tested on the sieve and weighed. A ~
sieve according to DIN 4188, i.e., a sieve having a width of mesh ~ ~-of 45 ~m is used as the test sieve fabric.
The product thus obtained has a proportion of 0.010~ of particles having a limited size > 45 ~m and this proportion was determined in the manner described above.
An analysis of granular sizes on a sedimentation balance is used for the further characterization of the product.
The sample to be measured is dispersed in water with the `
aid of an Ultra-Turrax and the sedim~ntation is then observed. ~
The particle distribution is as follows: `
fraction ~ proportion (~m~ (% by weight) ` <3 7 9 `~
; <5 14.9 <10 60.4 <15 85.9 <20 95 :
;~ <25 99 3 ` <30 100.0 -~ Example 2 5.5 kg of moist hydrate having a water content of 42.5 are dissolved in 50 litres of a 10~ by weight solution of caustic soda. The reactor described in Example 1 is fitted with a ~5~ 2r~
propeller mixer having a diameter of 15 cm according to DIN 28131.
During the precipitation and crystallization the energy consump-tion of the mixer is 0.3 KW per cu m. As in example 1, 15 litres of the aluminate solution were put into the reactor first, in order to assure sufficient efficiency of the mixer at the begin-ning of the addition of sodium tetrasilicate. The rest of the aluminate liquor is added within 30 minutes. At the same time 6.8 litres of sodium tetrasilicate containing 26.5% of SiO2 and 8~ of Na2O are added directly on the propellerO The synthesis mixture thus obtained which has a molar ratio of S 2 2 3 ~ ?
and H2O : Na2O = 39 : 1 is then crystallized at 93C. After 90 minutes a Ca-bonding power of 168 mg of CaO per gram is obtained and the reaction is completed.
The propeller is then replaced by a turbine mixer as described in Example 1, whereupon tempering is carried out at the same temper- ~ `
ature (i.e., 93~C) under the action of shearing energy, the energy ;~
consumption being 0.8 KW per cu m. After 1 hour the reaction is terminated, the product is washed to pH 10.0 and then spraydried. ; ' The A-type zeolite obtained is~radiographically pure and, in the grit determination according to Mocker (DIN 53580), it no longer ~;
has any measurable proportion of particles > 45 ~m. The accuracy of measurement of this method is 0.001%. An analysis of granular sizes on the sedimentation balance shows the following particle ~
distribution: f ; `-fraction proportion (~m) (% by weight) <3 15-3 <5 35.2 <10 82.6 ;
<15 96.3 <20 100.0 ~ ~
~ , . - ,.:
`:
., - 10 ;
,, , : . .: : . . ~ .. : . .
i7~7~
Example 3 A synthesis mixture is produced analogously to that of example 2. It contains the components SiO2 and A12O3 in the ratio of 1.3 : 1 as well as water and sodium oxide in the ratio of 39 : 1. After the preclpitation stage a turbine mixer having a diameter of 10 cm is used for shearing during the crystalliza-tion. The energy consumption is 0.6 KW per cu m and the crystall-ization temperature 90C. After 110 minutes the Ca-bonding power of the crystallized zeolite reaches a Einal value of 161 mg of CaO per gram. The turbine mixer is then replaced by a 3-stage MIG ( a trademark) mixer of the firm of Ekato, whereupon the syn-thesis mixture is tempered at an energy-consumption of 0.1 KW per cu m for 4 hours at 92C while stirring (no shearing). The pro-duct obtained :is a radiographically pure zeolite and has a pro-portion of 0.13~ of particles having a limited size (which can be determined with the Mocker tester) and the following particle spectrum (as determined on a sedimentation balance):
fraction proportion m) (% by weight) -~
<3 4 2 <5 10.8 ;
<10 50.3 <15 78.6 <25 98.1 ` <30 99.5 ; Example 4 5.5 kg of commercial moist hydrate are dissolved in 53 litres of an 11% by weight solution of caustic soda. The aluminate solution ohtained is pumped into a 60-litre reactor by means of a Static ( a trademark) Mixer. Ahead of the mixing unit 8.2 litres -' of sodium tetrasilicate are added. After the mixing process a '~
`:
' ''' ~
~5~'~'7~
mixture clear as water flows into the reactor. At the bottom of the reactor the solution is drawn off by suction and, while re-cycling at 40 h 1, it is pumped by a rotary pump in a shearing manner. The pump has an energy consumption of 1.8 KW per cu m.
The synthesis mixture, which has a ratio of SiO2 : A12O3 = 1.6 : 1 and H2O : Na2O = 37 : 1, is heated to 95C. The crystallization is completed after 50 minutes. The temperature is then increased to 105C and tempering is carried out for 30 minutes while shear-ing continuously. The product obtained has a grit proportion of 0.03~ above 45 ~m as determined according to Mocker and the foll-owing particle spectrum (as determined on a sedimentation balance):
fraction proportion (~m)(% by weight) <3 8-5 <5 16.2 <1063.5 `~ ~-<1586.4 ~;
<2097.8 ;
<25 99.6 ~30 100.0 ` ~-Example 5 `~-4.5 kg of commercial moist hydrate are dissolved in 50 litres of an 8% by weight solution of caustic soda. The solution obtained is then thoroughly mixed with 4.3 litres of sadium tetra~
silicate according to the method described in Example 1. The ~-crystallization is then carried out at 92C under the action of shear forces in the manner described in example 1, the energy consumption being 1 KW per cu m. ;
Upon completed crystallization, tempering is carried out with the same shearing energy and at a temperature of 94 C . The ; zeolite A obtained, which is radiographically pure, contains no limiting particle size of 45 ~m and has the following particle spectrum: -,:: ., . ,; , . ,, , , , . ; , . :
~ , . . - ~ . . ~ .
r - ~
~57;~7,~
fract.ion proportion ~.
(~Im) (% by weight) ~3 5.3 <5 13.1 <10 50 3 <20 96.8 <25 100.0 All the zeolite .ion exchangers produced according to the examples 1 to 5 can at least partially replace the phosphates used heretofore in the conventional detergents. The detergents produced with said ion exchangers leave no deposits which can be ~ ;
seen with the na:ked eye on the la~ndry.
,,,, ~, , 's' ~
',' ,':
', ...
' ' ~ : , ' . :
.
. ~ .
' ~' ; ;' .
,, ~ :' - 13 - .
, 3, '';'~ ' . , ' ' . ' ' , ' ' ', ' '
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing an A-type zeolite molecular sieve based on crystalline alumino silicates containing water of hydration and at least 99.5, by weight of particles having dia-meters smaller than 45 µm by hydrothermal crystallization of an aluminate sodium silicate synthesis mixture in which the components of the synthesis mixture, which are in a molar ratio of SiO2 : Al2O3 less than 1.9 : 1 and in a molar ratio of water :
alkali metal oxide of at least 30 : 1 are intimately mixed prior to the precipitation of an amorphous initial product, and after the crystallization the aluminium silicate suspension is tempered under crystallizing conditions and is sheared during at least one of the crystallization and the tempering.
alkali metal oxide of at least 30 : 1 are intimately mixed prior to the precipitation of an amorphous initial product, and after the crystallization the aluminium silicate suspension is tempered under crystallizing conditions and is sheared during at least one of the crystallization and the tempering.
2. A process according to claim 1, in which the synthe-sis mixture contains SiO2 and Al2O3 in a molar ratio between 0.8 and 1.6 : 1.
3. A process as claimed in claim 2, in which the molar ratio is about 1.3 : 1.
4. A process according to claim 1, in which the synthe-sis mixture contains water and alkali metal oxide in a molar ratio between 35 and 50 : 1.
5. A process according to claim 1, 2 or 3, in which for the precipitation of the amorphous initial product an amount of water or aluminate solution which causes at least a stirring effect and sodium aluminate solution and sodium tetrasilicate solution are added simultaneously while stirring thoroughly.
6. A process as claimed in claim 5, in which the sodium aluminate and sodium tetrasilicate solution are added in a zone of maximum turbulence.
7. A process according to the claim 1, 2 or 3, in which the shearing is carried out in a recycling manner.
8. A process according to the claim 1, in which the shearing is carried out by means of turbine mixers, toothed-disc dissolvers, dispersing pumps or rotary pumps.
9. A process according to claim 8, in which the turbine mixer is operated with a power consumption of 0.4 to 2 KW per cu m.
10. A process as claimed in claim 9, in which the power consumption is 0.6 to 1.0 KW per cu m.
11. A process as claimed in claim 9, in which the power consumption is about 0.8 KW per cu m.
12. A process according to the claim 1, in which the tempering is carried out at a temperature between 85 and 105°C
in the crystallizing mother liquor.
in the crystallizing mother liquor.
13. A process according to claim 12, in which the tem-pering is carried out for 0.2 to 6 hours.
14. A process as claimed in claim 13, in which the time is 0.8 to 1.9 hours.
15. A process as claimed in claim 13, in which the time is about l hour.
16. A zeolitic A-type molecular sieve with at least 99.5% of particles having diameters below 45 µm and a particle spectrum containing
17. A sieve as claimed in claim 16 with at least 99.9 of particles having diameters below 45 µm.
18. A sieve as claimed in claim 16 with 99.99% of particles having diameters below 45 µm.
19. A sieve as claimed in Claim 16, 17 or 18 having a particle spectrum containing
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2447021A DE2447021C3 (en) | 1974-10-02 | 1974-10-02 | Type A crystalline zeolite powder and the process for its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1057272A true CA1057272A (en) | 1979-06-26 |
Family
ID=5927336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA236,911A Expired CA1057272A (en) | 1974-10-02 | 1975-10-02 | Process for producing grit-free zeolitic molecular sieves |
Country Status (12)
| Country | Link |
|---|---|
| JP (2) | JPS5184790A (en) |
| AT (1) | AT346814B (en) |
| BE (1) | BE834110A (en) |
| CA (1) | CA1057272A (en) |
| CH (1) | CH614423A5 (en) |
| DE (1) | DE2447021C3 (en) |
| ES (1) | ES441177A1 (en) |
| FR (1) | FR2286794A1 (en) |
| GB (1) | GB1517323A (en) |
| IT (1) | IT1047260B (en) |
| NL (1) | NL180808C (en) |
| SE (1) | SE413017B (en) |
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| DE2514399A1 (en) * | 1975-04-02 | 1976-10-14 | Degussa | PROCESS FOR THE PRODUCTION OF ALUMINUM SILICATES |
| DE2651436A1 (en) | 1976-11-11 | 1978-05-18 | Degussa | TYPE A III CRYSTALLINE ZEOLITE POWDER |
| DE2660726C2 (en) * | 1976-11-11 | 1987-03-12 | Degussa Ag, 6000 Frankfurt, De | |
| DE2651419A1 (en) | 1976-11-11 | 1978-05-18 | Degussa | TYPE A IV CRYSTALLINE ZEOLITE POWDER |
| DE2651445A1 (en) | 1976-11-11 | 1978-05-18 | Degussa | TYPE A II CRYSTALLINE ZEOLITE POWDER |
| DE2651485A1 (en) | 1976-11-11 | 1978-05-24 | Degussa | TYPE A I CRYSTALLINE ZEOLITE POWDER |
| DE2660728C2 (en) * | 1976-11-11 | 1987-03-12 | Degussa Ag, 6000 Frankfurt, De | |
| DE2651437A1 (en) | 1976-11-11 | 1978-05-18 | Degussa | TYPE A VI CRYSTALLINE ZEOLITE POWDER |
| DE2651420A1 (en) | 1976-11-11 | 1978-05-18 | Degussa | TYPE A V CRYSTALLINE ZEOLITE POWDER |
| FR2392932A1 (en) * | 1977-06-03 | 1978-12-29 | Rhone Poulenc Ind | METHOD OF MANUFACTURING AN ALKALINE CRYSTALLINE SILICO-ALUMINATE, PRODUCT OBTAINED AND APPLICATION |
| DE2744784B1 (en) * | 1977-10-05 | 1978-08-17 | Basf Ag | Process for the preparation of zeolite A and its use |
| 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 |
| DE2907108A1 (en) * | 1979-02-23 | 1980-09-04 | Basf Ag | METHOD FOR PRODUCING STORAGE-STABLE, PUMPABLE AND FLOWABLE ALUMOSILICATE SUSPENSIONS BY WET MILLING |
| US4242223A (en) * | 1979-07-11 | 1980-12-30 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for receiving, storing and handling aluminum hydroxide wet hydrate |
| DE2941636A1 (en) * | 1979-10-13 | 1981-05-07 | Degussa Ag, 6000 Frankfurt | METHOD FOR CONTINUOUSLY PRODUCING FINE-PARTICULATED ZEOLITHIC SODIUM ALUMINUM SILICATES |
| JPS5663817A (en) * | 1979-10-31 | 1981-05-30 | Kojiro Takei | Manufacture of a-type zeolite of fine crystal particle |
| DE3011834A1 (en) * | 1980-03-27 | 1981-10-01 | Degussa Ag, 6000 Frankfurt | METHOD FOR PRODUCING FINE-PARTICULATE ZEOLITHIC SODIUM ALUMINUM SILICATES |
| DE3021370A1 (en) * | 1980-06-06 | 1981-12-24 | Degussa Ag, 6000 Frankfurt | METHOD FOR REDUCING THE PARTICULAR SIZE OF ZEOLITHIC 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 |
| DE3144298A1 (en) * | 1981-11-07 | 1983-05-19 | Degussa Ag, 6000 Frankfurt | SCRUBBING POWDER |
| DE3208598A1 (en) * | 1982-03-10 | 1983-09-22 | Degussa Ag, 6000 Frankfurt | METHOD FOR THE PRODUCTION OF ZEOLITES MODIFIED WITH ORGANOSILANES |
| AT380805B (en) * | 1982-03-22 | 1986-07-10 | Mizusawa Industrial Chem | METHOD FOR PRODUCING A ZEOLITE A, ZEOLITE X AND / OR Y CONTAINING ZEOLITE SLAVE FOR WASHER OR CLEANING AGENT |
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| 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 |
| DD107428B3 (en) * | 1973-11-05 | 1992-12-10 | Chemie Ag Bittrfeld Wolfen | METHOD AND DEVICE FOR PRODUCING SYNTHETIC ZEOLITE |
| AR205228A1 (en) * | 1974-11-08 | 1976-04-12 | Huber Corp J M | PROCEDURE TO PRODUCE AN AMORPHOUS ALKALINE METAL ALUMINOSILICATE PIGMENT WITH ION EXCHANGE CAPACITY |
-
1974
- 1974-10-02 DE DE2447021A patent/DE2447021C3/en not_active Expired
-
1975
- 1975-09-19 GB GB3853675A patent/GB1517323A/en not_active Expired
- 1975-09-23 ES ES441177A patent/ES441177A1/en not_active Expired
- 1975-09-26 NL NL7511360A patent/NL180808C/en not_active IP Right Cessation
- 1975-09-26 FR FR7529630A patent/FR2286794A1/en active Granted
- 1975-10-01 BE BE6045198A patent/BE834110A/en not_active IP Right Cessation
- 1975-10-01 AT AT750075A patent/AT346814B/en not_active IP Right Cessation
- 1975-10-01 IT IT6942675A patent/IT1047260B/en active
- 1975-10-01 CH CH1274275A patent/CH614423A5/en not_active IP Right Cessation
- 1975-10-02 SE SE7511094A patent/SE413017B/en not_active IP Right Cessation
- 1975-10-02 JP JP11830675A patent/JPS5184790A/en active Pending
- 1975-10-02 CA CA236,911A patent/CA1057272A/en not_active Expired
-
1981
- 1981-02-20 JP JP56023249A patent/JPS5914273B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ATA750075A (en) | 1978-04-15 |
| SE7511094L (en) | 1976-04-05 |
| IT1047260B (en) | 1980-09-10 |
| SE413017B (en) | 1980-03-31 |
| CH614423A5 (en) | 1979-11-30 |
| DE2447021C3 (en) | 1984-03-22 |
| JPS56124486A (en) | 1981-09-30 |
| DE2447021B2 (en) | 1976-10-21 |
| FR2286794A1 (en) | 1976-04-30 |
| JPS5184790A (en) | 1976-07-24 |
| JPS5914273B2 (en) | 1984-04-03 |
| GB1517323A (en) | 1978-07-12 |
| NL7511360A (en) | 1976-04-06 |
| AT346814B (en) | 1978-11-27 |
| NL180808C (en) | 1987-05-04 |
| BE834110A (en) | 1976-04-01 |
| DE2447021A1 (en) | 1976-05-13 |
| FR2286794B1 (en) | 1978-03-17 |
| ES441177A1 (en) | 1977-07-01 |
| NL180808B (en) | 1986-12-01 |
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