DE2951192A1 - METHOD FOR THE PRODUCTION OF SODIUM ALUMINOSILICATE ZEOLITES OF SMALL AND UNIFORM PARTICLE SIZE, THE ZEOLITES OBTAINED THEREOF AND THEIR USE - Google Patents

Description

-AI-

TER MEER - MÜLLER - STEINMEISTER

ι Patent Office Authorized Representative

Prof. Representative · before the European Patwrt Office - Mandatalrw «greet pres ! 'Office european des brevet *

Dipl.-Chem. Dr. N. ter Meer Dipl.-Ing. H. Steinmeister Dipl.-Ing. F. E Müller Siekerwall 7 Triflstrasse 4. SleRerwall 7, O-8000 MÖNCHEN 22 D-4800 BIELEFELD

f Dec. 9, 1979

Case: O38-O64
tM / th

J.M.HUBER CORPORATION,

Navesink & River Road, City of Locust, State of New Jersey, United States of America

Process for the production of sodium aluminosilicate zeolites of smaller and more uniform Particle size, the zeolites obtained and their use.

Priorities: December 20, 1978, USA, No. 971,584 November 21, 1979, USA, No. 093,345

030028/0721

SYNTHESIS OF ZEOLITES SMALLER AND UNIFORM SIZE

The invention relates to the preparation of zeolites and more particularly Process for the preparation of Zeolite-A and -X and mixtures of -Λ and -X, which are zeolites smaller and more uniform Big ones, which have a high magnesium exchange capacity, and a method for producing zeolite-Y.

Naturally occurring, hydrated metal aluminum silicates are used referred to as zeolites and are well known as synthetic absorbers. The most common of these zeolites are sodium aluminozeolites. Zeolites basically consist of a three-dimensional network from SiO, - and AlO.-tetrahedra. The tetrahedra are linked by sharing oxygen atoms, so that the ratio the oxygen atoms to the totality of the aluminum and silicon atoms equals two or O / (A1 + Si) = 2. The electrovalence of each aluminum-containing tetrahedron is balanced by the inclusion a cation, for example a sodium ion, into the crystal. This balance can be expressed by the formula Al "/ Na" = 1 will. The spaces between the tetrahedra are created by water molecules that are in the process of being dehydrated taken. The main products of these forms are known in the art as Zeolite-A, Zeolite-X, and Zeolite-Y.

The zeolites-Α, -X and -Y differ from other zeolites and silicates due to their X-ray powder diffraction patterns and certain physical characteristics. The composition and the density are among the features that are used for identification

030028/0721

these zeolites are important.

The basic formula for all crystalline sodium zeolites can be represented as follows :

Na ₂ O: Al ₂ O ₃ : xS i0 ₂ : yl ^ O,

where the values for χ and y fall within a certain range. The x value for a given zeolite varies somewhat, since the aluminum atoms and the silicon atoms occupy essentially equivalent positions in the network. Minor differences in the relative amounts of these atoms do not significantly change the crystal structure or physical properties of these zeolites. For zeolite-A, the average value for χ is approximately 1.85, so the x value falls in the range of 1.85 + 0.5. For zeolite-X, the x value falls in the 2.5 + 0.5 range.

The formula for Zeolite-A can be expressed as follows: 1.0 + 0.2 Na ₂ OiAl ₂ O ₃ : 1.85 + 0.5 SiO ^ yH ₂ O.

The formula for zeolite X may be expressed as follows: 0.9 + 0.2 Na ₂ 0: Al ₂ 0: SiO ^ 2.5 + yH ₂ O.

The formula for zeolite-Y can be expressed as follows: 0.9 + O, 2 Na ₂ O: Al ₂ O ₃ : 4.5 + 1.5 SiO ₂ : yH ₂ O,

where y can be any value up to 6 for zeolite-A, any value up to

to B for zeolite-X and any value up to 9 for zeolite-Y.

Zeolite-A is fully described in U.S. Patent No. 2,882,243.

030028/0721

Zeolite-X is detailed in U.S. Patent No. 2,882,244 described. Zeolite-Y is described in U.S. Patent No. 3,130,007 described in detail. The manufacturing processes are in these Patents also described. Other prior patents relating to Zeolite A include U.S. Patents 2,982,619, 3,058,805, 3,110,251, 3,119,659 and 4,041,135, which describe various processes for the preparation of zeolite-A. Other previous patents dealing with Zeolite-X are U.S. patents 2 979 381, 3 341 284, 3 692 475, 3 594 121, 3 690 823 and 4 016 246.

This invention is concerned with making zeolite-A, zeolite-X, and mixtures of -A and -X of smaller and more uniform size Big thanks to a unique process in which the molar ratios of the reaction substances are used differ from those of previous inventions.

The aim of this invention is to produce zeolites with a very high exchange capacity for calcium and magnesium ions and very high rate of calcium depletion superior to similar zeolites already present.

Another object of this invention is the manufacture of Controlled particle size zeolites used as ion exchange material useful in water loosening and cleaning products as well as filler in paper, rubber and plastics and as non-settling matting substances.

030028/0721

- ir -

In one aspect, the invention is concerned with manufacturing methods for zeolites of small and uniform size with high magnesium exchange capacities caused by the the following steps:

a) The formation of an aqueous sodium aluminate solution;

b) The formation of an aqueous sodium silicate solution;

c) The mixture of the sodium aluminate solution and the sodium silicate solution at a temperature of 40 to 120 ° C;

d) The reaction of the mixed sodium silicate and sodium aluminate at a temperature slightly higher than the mixing temperature, the reaction mixture having the following molar ratios of the components having:

(1) Water to Sodium Oxide 10: 1 to 35: 1

(2) Sodium oxide to silica 1: 1 to 4: 1

(3) silica to alumina 1: 1 to 10: 1

e) Continuing the reaction with these molar ratios to form the zeolite, the molar ratios and the Reaction time can be regulated so that small-form zeolite is obtained, the average particle size of which is less than 2 microns in diameter; and

f) the recovery of the zeolite.

In one embodiment of the invention, the becomes small and uniform Zeolite-A with high magnesium exchange capacity is formed when

03.00 28707 21

the reaction mixture has a water / sodium oxide molar ratio of between 10: 1 and 35: 1, preferably between 15: 1 and 20: 1, most preferably about 20: 1; the molar ratio in relation to sodium oxide / silicic acid should in this case be between 1: 1 and 4: 1, preferably between 1: 1 and 2.5: 1, better between 1.5: 1 and 2: 1 and best around 2: 1; and the molar ratio in relation to silica / alumina had to be between 1: 1 and 10: 1, preferably between 1.4: 1 and 10: 1, better between .above 2.0: 1 and 4.5: 1, better between 3: 1 and 8: 1 and preferably 3: 1. In a separate embodiment where the sodium oxide / silica molar ratio is less than 4: 3, the silica / alumina molar ratio is at least 3: 1. When the sodium oxide / silica molar ratio is at least 4: 3, the sodium oxide / alumina molar ratio is at least 4: 1. In addition, when the SiO: Al-O ₃ molar ratio is 2.0: 1 or less, the maximum reaction temperature is about 80 C. Outer earth. it follows that as this ratio decreases, the number of compositions of the variables decreases.

The particle size of Zeolite-A can be regulated by adjusting the molar ratio in relation to silica / alumina, with the particle size decreasing when the molar ratio in relation to silica / alumina increases, and the particle size ztmiamt when the molar ratio in relation to silica / alumina increases. Clay decreases.

030028/0721

Al

The particle size can also be regulated by either regulates the molar ratio in terms of sodium oxide / alumina or the alumina concentration, the particle size decreasing when the molar ratio in relation to sodium oxide / alumina is reduced or the alumina concentration decreases and the particle size increases, as the sodium oxide / alumina molar ratio decreases or the alumina concentration increases.

This zeolite-A has a calcium carbonate exchange capacity that is higher than 230 mg calcium carbonate per gram of zeolite, and a magnesium carbonate exchange capacity higher than 90, and preferably higher than 120 mg magnesium carbonate per gram zeolite. The particles obtained have a narrow differential Gaussian frequency distribution in terms of percentages by weight, having an average particle size no greater than 2.1 microns with at least 90% by weight between 0.1 and 4.0 microns, wherein the cumulative percentage population is at least 35% less than one micron and not over 5% more than 5 microns.

This zeolite-A preferably has a calcium carbonate exchange capacity which is higher than 250 mg calcium carbonate per g zeolite, and a magnesium exchange capacity higher than 140 mg Carbonate per gram of zeolite. 90% of its particles are smaller than 2 microns. The zeolite particles obtained preferably have

0 300 28/07 21

a tight differential Gaussian see frequency distribution in In terms of weight percentages with an average particle size of not more than 1.6 microns with at least 9OZ des Weight between 0.1 and 4.0 microns, where the cumulative percentage Population is at least 64% less than one micron, and not more than 1% more than 2.0 microns. It is usable as ion exchange material in water softeners and cleaning agents; as a filler in paper, rubber and plastics and as a non-settling matting agent.

In a further embodiment, zeolite-X becomes smaller and of uniform size with a high magnesium exchange capacity when the reaction mixture is related to a molar ratio on water / sodium oxide of between 25: 1 and 90: 1, preferably between 30: 1 and 60: 1, most preferably about 30: 1; the In this case, the molar ratio in relation to sodium oxide / silica should be between 1: 1 and 3: 1, preferably between 1.2: 1 and 1.7: 1, most preferably about 1.6: 1; and the molar ratio With regard to silica / alumina, it should be between 5: 1 and 10: 1, preferably between 6: 1 and 8: 1, ideally at about 7.3: 1.

This zeolite-X has a calcium carbonate exchange capacity higher than 205 mg of potassium carbonate per gram of zeolite, and a Magnesium exchange capacity greater than 130 mg magnesium carbonate per gram of zeolite, the zeolite particles obtained

030028/0721

a tight differential Gaussian see frequency distribution in In terms of weight percentages, with an average Particle size no greater than 2.2 microns, with at least 90% by weight is between 0.1 and 5.0 microns, wherein the cumulative percentage population is at least Al% less than one micron, and not more than 5% more than 3.2 microns.

For this zeolite-X, preferably 90% of the particles are less than 2 microns. It preferably has a calcium carbonate exchange capacity, that is greater than 230 mg calcium carbonate per g of Zcolit and a Magncsiun carbonate exchange capacity that is greater is as 135 mg magnesium carbonate per g zeolite. It can be used as an ion exchange material in water softeners and detergents; as a filler in paper, rubber and plastics; and as a non-settling matting agent.

In another embodiment, a composition is made from 20 to 80% zeolite-X and from 20 to 80% zeolite-A formed if the reaction mixture has a water / sodium oxide molar ratio of between 10: 1 and 60: 1, preferably between 20: 1 and 50: 1, better between 25: 1 and 35: 1, and best around 30: 1; the molar ratio in terms of sodium oxide / silica In this case, it should be between 0.5: 1 and 3: 1, preferably between 1.4: 1 and 3: 1, better between 1.6: 1 and 2: 1, and best at about 1.7: 1; and the molar ratio in terms of silica / clay should be between 2: 1 and 15: 1,

030028/0721

preferably between 2: 1 and 10: 1, more preferably between 2; 1 and 8: 1, at best around 5.3: 1.

This composition of Zeolite-A and Zeolite-X has a calcium carbonate exchange capacity, which is greater than 220 mg calcium carbonate per gram zeolite and a magnesium exchange capacity, which is greater than 115 mg magnesium carbonate per gram zeolite, the zeolite particles obtained having a narrow differential Gaussian frequency distribution in terms of percent by weight have, with an average particle size of not greater than 5.4 microns with at least 90% by weight between 0.1 and 10.0 microns, wherein the cumulative percentage population is at least 37% less than one micron, and not more than 5% more than 5 microns.

With this composition of Zeolite-A and Zeolite-X, preferably 90% of the parts are less than 2 microns. It preferably has a calcium carbonate exchange capacity which is higher than 230 mg calcium carbonate per g zeolite and a magnesium exchange capacity which is higher than 135 mg magnesium carbonate per g zeolite. It can be used as an ion exchange material in water softeners and cleaning agents; as a filler in paper, cast iron and plastics and as a non-settling matting agent.

In another embodiment of this invention, Zcolit-Y is made by adding sand in a sodium hydroxide solution to a

035028/0721

-M-

Pressure of at least 100 psig, preferably 140 psig, is released and heated to at least 130 ° C, the sodium silicate so formed is activated with clay, whereby a sodium aluminate solution is formed and the sodium aluminate solution to the sodium silicate solution is given so that all of the sodium alurainate solution is added within 30 seconds to avoid a reaction to form that consists of a mother liquor of sodium silicate and an amorphous sodium aluminosilicate dye that in its entirety has a certain composition, the mixture being heated to a temperature of 80 to 120 C, then the Geraisch implemented at a temperature of 80 to 120 C. and the zeolite produced is recovered. The sodium silicate solution has a silica / sodium oxide molar ratio of between 2.4: 1 and 2.8: 1, preferably about 2.4: 1. That Sodium silicate is activated with from 50 to 2,000 ppm of clay at a temperature of 15 to 100 C for a period of at least 10 minutes, preferably with from 400 to 600 ppm alumina at room temperature, more preferably with about 500 ppm alumina. The sodium silicate solution is heated to a temperature of between 80 and 120.degree. C., preferably 90.degree. The sodium aluminate solution is also heated to a temperature of between 80 and 120 ° C, preferably to 90 ° C. The composition of the reaction mixture has a sodium oxide / silica molar ratio of between 0.5 and 1.0: 1, preferably about 0.56: 1. It has a molar ratio in terms of silica

03002870721

-H-

acid / alumina of between 7: 1 and 30: 1, preferably between 7: 1 and 10: 1 and more preferably about 7.8; 1, In addition, the reaction mixture has a molar ratio with respect to water / sodium oxide of between 10: 1 and 90: 1, preferably between 20: 1 and 40: 1, and most preferably about 20: 1. The reaction mixture is reacted at a temperature of 80 to 120 C until crystalline zeolite Y forms, preferably at a temperature of 80 to 100 C, better at a temperature of about 100 C. The sodium silicate mother liquor can be recycled as a source of the sodium silicate solution will.

At its broadest level, this invention is based on four distinct discoveries: (1) the discovery that the type of zeolite formed is determined by how long it takes for the zeolite to form at a given reaction temperature; (2) on the discovery that the reaction time required to crystallize a zeolite at a given temperature is mainly a function of the molar ratio in terms of water / sodium oxide, while the molar ratios in terms of sodium oxide / silica and silica / alumina have a weaker effect on implementation time; (3) on the discovery that the magnesium exchange capacity of zeolite-A is a function of the particle size of the zeolite ; and (4) on the discovery that the particle size of a zeolite is a function of the molar ratio in relation to

030028/0721

Silica / alumina, sodium oxide / alumina and the alumina concentration is.

The zeolites of small and uniform particle size of these Invention are made using these four discoveries in a reaction mixture that has a high molar ratio in relation to silica / alumina, while the other oxide mole ratios are regulated to be the desired Produce zeolite. In the known process for the production of zeolites, a reaction mixture of sodium-aluminum-silicate-water prepared, which has a certain composition. This mixture is kept at a certain temperature, until crystals form. Then the crystals are separated from the reaction mixture. For crude ratios in relation on silica / alumina higher than two, the urea sedimentation mixture consists of sodium silicate mother liquor and an amorphous one Sodium aluminosilicate dye. When this two-phase reaction mixture is reacted at elevated temperatures, nothing visually perceptible occurs for a certain period of time, but afterwards During this period, rapid crystallization of the zeolite occurs and the zeolite can be separated from the reaction mixture will.

This invention is based in part on the discovery that for any single source of silica, the type of zeolite formed

030028/0721

is determined by the implementation time, which at a given Implementation temperature is necessary so that the crystallization process begins. If the reaction time is short, hydroxysodalite forms, but if the reaction time is longer, it forms Zeolite-A. With an even longer reaction time, zeolite-X is formed. If the implementation time is between the period which is necessary for the formation of Zeolite-A and that which is necessary for the formation of Zeolite-X, one forms Composition of Zeolite-A and Zeolite-X. The reaction time depends on the source of the silica or whether the Silica has been activated or not. The preferred reaction time for each individual source of silica can be can easily be determined by experiment.

The reaction time necessary for crystallization at a certain temperature can be regulated in various ways, but the main measure to regulate the conversion time is to regulate the molar ratio in relation to water sodium oxide of the conversion mixture. The reaction time required to form a zeolite is directly proportional to the molar ratio used in relation to water / sodium oxide. If for example, If the source of the silica is not activated with alumina, the preferred water / sodium oxide molar ratio is Formation of Zeolite A between 15: 1 and 20: 1; for the production of Zeolit-X it is between 30: 1 and 60: 1 and for the production of a

030028/0721

- IA -

The composition of Zeolite-X and Zeolite-A is between 25: 1 and 35: 1. A possible explanation for this is that a higher ratio in terms of water / sodium oxide means that the solution is more dilute, meaning it takes longer before the conversion sites come together, resulting in a longer conversion time. Hence, one would get a zeolite-A in a reaction mixture with a molar ratio of sodium oxide / silica and silica / alumina at which zeolite-X would normally be formed reduce the water / sodium oxide ratio. The regulation of the molar ratio in relation to water / sodium oxide is the main measure for determining which type of zeolite is formed and is analogous to the regulation process for a proportional automatic cone device.

This relationship between the water / sodium oxide molar ratio and the kind of zeolite formed is not up to now been known. Prior U.S. Patents 2,882,243 and 2,882,244, for example, give a water / sodium oxide molar ratio of 35 to 200 for the manufacture of Zeolite-A an and a water / sodium oxide molar ratio of 35 to 60 for the production of zeolite-X. This would mean, that the reaction mixture for producing zeolite-A would have to have a higher molar ratio in terms of water / sodium oxide than the reaction mixture to produce zeolite-A, which is not the case. In U.S. Patent 3,119,659 the molar ratio is

030028/0721

nis in relation to water / sodium oxide for the production of zeolite ^ A from 20 to 100 while the water / sodium oxide molar ratio to produce Zeolite-X is from 30 to 60. None of the above patents state that the water / sodium oxide molar ratio for the production of Zeolite-X must be higher than for the production of zeolite-A.

Another method of regulating the conversion time necessary for crystallization at a certain temperature is the regulation of the molar ratio in terms of sodium oxide / silica of the conversion mixture. The conversion time required to form a zeolite is inversely proportional to the molar ratio used in relation to sodium oxide / silica. The effect of the molar ratio on sodium oxide / silica is not as pronounced as the water / sodium oxide molar ratio.

One possible theory related to why an increasing The molar ratio of sodium oxide / silica reduces the reaction time, What is necessary to form a zeolite is that the increase in the sodium oxide / silica molar ratio for a given molar ratio Water / sodium oxide reduces the viscosity of the reaction mixture.

The regulation of the molar ratio in relation to silica / alumina of the conversion mix also affects the conversion time,

030028/0721

295.1J92

those at a given reaction temperature for crystallization is necessary, but the effect is much less than the effect of the sodium oxide / Silica, which in turn is far less than the effect of the water / sodium oxide molar ratio. For a given Molar ratio of water / sodium oxide and for a given molar ratio of sodium oxide / silica the reaction time necessary to form a zeolite is straightforward proportional to the silica / alumina molar ratio.

At a given temperature, the reaction time can be be reduced by quickly adding the sodium aluminate solution to the sodium silicate solution, preferably up a way that all of the sodium aluminate solution is within of 30 seconds is added, and even better when added at the same time. In this way, the Conversion time, which is necessary for crystallization at a given conversion temperature, can be increased, by increasing the water / sodium oxide ratio, decreasing the sodium oxide / silica molar ratio, the silica / alumina molar ratio is increased and the two substances are slowly added.

Using these criteria, it has been determined that the preferred reaction time for the formation of Zeolite-A is about 1/2 to 8 hours; for zeolite-X it is about 1/2 to 8 hours and for mixtures of zeolite-A and -X about 4 to 8 hours.

030028/0721

This invention is also based on the discovery that the magnesium exchange capacity of zeolite-A is a function of the zeolite particle size is. As the particle size decreases, the magnesium exchange capacity increases. If in the case of zeolite A the average diameter is 2.4 microns, is the Hagnesiua capacity only 62 mg / g, when the average diameter is 1.1 microns, the magnesium capacity is about 124 mg / g, and when the average diameter is 0.8 microns, the magnesium capacity is 159 mg / g.

Much more important than the effect of the silica / alumina molar ratio on the reaction time is the effect of the silica / alumina molar ratio on the particle size. The reason this
The effect is unknown, but the particle size of the zeolite increases with the decrease in the silica / alumina molar ratio
Conversion mixture. The particle size decreases as the silica / alumina molar ratio in the reaction mixture increases. For example, the silica / alumina molar ratio of zeolite-A is 1.85 + 0.5. Therefore, a zeolite-A formed in a reaction mixture with a silica / alumina molar ratio of 10.1 would have a smaller particle size than
a zeolite-A, which was formed into a "reaction mixture ait a" molar ratio in relation to silica / alumina of 2: 1. This means that the particle size of a zeolite can be regulated according to the molar ratio of silica / alumina of the reaction agent

030028/0721

regulated. If the particle size was to be increased, the silica / alumina molar ratio of the reaction mixture would be regulated so that it approximates the silica / alumina molar ratio of the desired product. For zeolite A this ratio is 1.85 + 0.5. For Zeolite-X it is 2.5 + 0.5. In order to reduce the particle size, the molar ratio of silica / alumina of the reaction mixture would be regulated in such a way that it differs from the molar ratio of silica / alumina of the desired product.

In the case of zeolite A down to the _{SiO 2} : Al 2 O ratio of 2 or above and in the case of zeolite X , the silica / alumina molar ratios of the reaction mixtures used in this invention are higher than the silica / alumina molar ratios of the desired product . Therefore, to increase the particle size of either Zeolite-X or Zeolite-A or a composition of both, one would decrease the silica / alumina molar ratio of the reaction mixture. To reduce the particle size, one would increase the silica / alumina molar ratio of the reaction mixture.

Other measures to regulate the particle size of the end product include regulating either the sodium oxide / Alumina or the alumina concentration of the reaction mixture. The particle size is inversely proportional to the molar ratio in terms of sodium oxide / alumina and directly proportional to the alumina concentration. The effects of the sodium oxide / alumina pickling ratio and the effects of the alumina concentration on

30G2 & / G721

on the particle size are of a similar extent as the effect of the silica / alumina ratio.

Since the molar ratio of silica / alumina, sodium oxide / alumina and the alumina concentration are all related, it is currently unclear which factor is predominant here, but any variable or a combination of these variables can be used to regulate the particle size.

The molar ratio of sodium oxide / silica in the reaction mixture also influences the particle size of the end product, but the extent of this effect is much smaller than the effect of the silica / alumina molar ratio. In the case of a constant In the molar ratio of silica / alumina, the particle size is inversely proportional to the molar ratio of sodium oxide / silica. As the sodium oxide / silica molar ratio increases, the particle size decreases. With the decrease in the molar ratio Sodium oxide / silica, the particle size increases. Hence the effect of the sodium oxide / silica molar ratio of the reaction mixture on the particle size in connection with the effect of the molar ratio silica / alumina of the reaction mixture on the particle size to regulate the particle size to be used.

The water / sodium oxide molar ratio of the reaction mixture affects

030028/0721

the particle size of the end product also flows, but this does The effect is smaller than the effect of the molar ratio Sodium Oxide / Silica. The reaction temperature influences the particle size as well.

Although the batch composition and the reaction temperature are used Particle size regulation are used, there are conditions under which accumulation can take place. Accumulation leads to a product that does not have the expected particle size or properties. Those described in the patent examples Procedures aim “at optimal conditions under which accumulation does not take place. When the temperature of the raw materials at the time of mixing is too low or the sodium oxide or Water concentrations in the solutions used are significantly changed, an accumulation can be expected. In the extreme case, a bimodal distribution occur. These effects can be overcome by methods such as longer addition times, reverse addition sequence, higher movement speeds, etc. The essential point is that these processes do not really regulate the immediate particle size, but only change the degree of accumulation. Just that Batch composition and the reaction temperature regulate the immediate particle size and the type of product formed.

According to this invention, zeolites become smaller and more uniform Big ones with high magnesium exchange capacities produced by

030028/0721

ORIGINAL INSPECTED

- 24 -

a sodium aluminate solution and a NatriumsilikatlBsung is formed, and mixing the sodium aluminate solution and the NatriumsilikatlBsung for producing a reaction mixture for SiO ": A1 ₂ 0_-molar ratios greater than 2 are, this mixture comprises a Natriumsilikatrautterlauge aluminosilikatfarbstoff and an amorphous sodium. For ratios of 2 or less, the mixture contains a sodium aluminate mother liquor. The reaction mixture is heated and reacted at a temperature of 40 to 120 ° C., preferably 60 to 100 ° C., until the desired zeolite is formed and the desired zeolite is obtained from the mother liquor. In a preferred method, the sodium silicate and the sodium silicate solution are preheated to a temperature of 50 to 120 ° C., preferably to 60 to 100 ° C., before mixing takes place. After mixing, an exothermic reaction takes place which increases the temperature by approximately 10 ^° C. The reaction then takes place at this temperature. The zeolite is then recovered from the reaction mixture using conventional solids separation techniques such as filtration. The mother liquor or the filtrate can be recycled to provide dissolved sodium and silicic acid or sodium and alumina values.

In one aspect, the sodium silicate solution used in this process can be formed by dissolving sand in a sodium hydroxide solution at a pressure of at least 100 psig and a temperature of at least 130 ° C to produce a sodium silicate solution having a silica / sodium oxide molar ratio of between 2.4: 1 and 2.8: 1.

030028/072

The word "sand" wixd vXß follows defined in the usual way; "A loose substance, which consists of. Small, but easily indivisible granules, which are mostly less than two millimeters in diameter, consist in most cases of quartz and are formed from rock weathering. Sand is mainly used in the manufacture of mortar and glass, as Abrasives or used for foundry molds. " To dissolve the sand, a temperature of at least 130 C is used because it is more difficult to dissolve sand at lower temperatures.

The sodium silicate solution is activated with preferably 50 to 2,000 ppm alumina and is heated to a temperature of between 40 to 120 C for at least 10 minutes, preferably with 400 to 600 ppm alumina at room temperature. Alumina concentrations Less than 50 ppm clay will not activate the silica. Cause alumina concentrations of over 2,000 ppm the precipitation of the clay from solution as an amorphous sodium aluminosilicate. Preferably the molar ratio silica / sodium oxide is 2.4: 1 to 2.8: 1, since this sodium silicate solution is normally cheaper to make than solutions with higher silica / sodium oxide ratios such as Water glass. The activation of the sodium silicate solution is necessary in the manufacture of zeolite-Y, but optional in the manufacture of zeolite-A and -X and mixtures of -A and -X.

After a sodium silicate solution is formed and either activated or not activated, it becomes a sodium aluminate solution mixed with the sodium silicate solution, as if by addition

03-00.Z8V07 21

- 23 for the formation of a conversion device.

When the sodium silicate source has been activated with clay, it has the preferred urea composition for the formation of zeolite-A The water / sodium oxide molar ratio is between 25: 1 and 35: 1 Molar ratio of sodium oxide / silica of between 1.4: 1 and 2: 1 and a molar ratio of silica / alumina of between 3: 1 and 7: 1. If the sodium silicate source has not been activated with clay, the preferred reaction mixture has a molar ratio in relation to each other on water / sodium oxide of between 15: 1 and 20: 1, a molar ratio in relation to sodium oxide / silica of between 1.5: 1 and 2: 1 and a silica / alumina molar ratio of between 2: 1 and 4: 1.

When the sodium silicate source has been activated with clay, it has the preferred urea composition for the formation of Zeolite-X Water / sodium oxide ratio of between 30: 1 and 40: 1, a molar ratio with respect to sodium oxide / silica of between 1: 1 and 1.2: 1 and a silica / alumina molar ratio of between 5: 1 and 7: 1. If the sodium silicate source does not use clay has been activated, the preferred reaction mixture has a water / sodium oxide molar ratio of between 30: 1 and 60: 1, a molar ratio Sodium oxide / silica of between 1.2: 1 and 1.7: 1 and a molar ratio of silica / alumina of between 6: 1 and 8: 1.

If the source of sodium silicate is chordes activated with clay, has

030028/0721

the preferred reaction mixture to form a mixture of zeolite-A and -X has a water / sodium oxide molar ratio of between 15: 1 and 60: 1, a molar ratio of sodium oxide / silica of between 0.7: 1 and 1.7: 1 and a molar ratio of silica / alumina between 5: 1 and 10: 1. If the sodium silicate source has not been activated with clay, the preferred one has Implementation of a molar ratio of water / sodium oxide of between 20: 1 and 50: 1, a molar ratio of sodium oxide / silica of between 1.4: 1 and 3: 1 and a silica / alumina molar ratio of between 2: 1 and 10: 1.

If the molar ratio of water / sodium oxide falls below 10: 1, there is a molar ratio of sodium oxide / silica and silica / alumina of this invention, an increased likelihood that zeolite-A instead of a composition of zeolite-A and Zeolite-X is formed. If the molar ratio of water / sodium oxide Approximately 60: 1> there is an increased molar ratios of sodium oxide / silica and silica / alumina of this invention Probability that Zeolite-X will be formed instead of an aggregation of Zeolite-A and Zeolite-X.

Zeolite-Y can be obtained from an alumina activated sodium silicate source be formed when the reaction mixture has a molar ratio of sodium oxide / silica of between 0.5: 1 and 1: 1 and a silica / alumina mol ratio of between 7: 1 and 30: 1. The preferred reaction mixture has a molar ratio of sodium oxide /

030028/0721

- , 35 -

Silicic acid γοη between 0.5: 1 and 1: 1 and a molar ratio Silica / alumina between 7: 1 and 10; 1.

The gross limits on the oxide molar ratios for making a each type of zeolite is shown in Table I.

Zeolite LIMITATIONS TABLE I. ZEOLITES COARSE A. Water/
Sodium oxide FOR PRODUCTION OF Silica /
Clay X 10 - 35 Sodium oxide /
Silica 1-10 X and A 25-90 1-4 5-10 Y 10 - 60 1-3 2-15 10 - 90 0.5 - 3 7-30 0.5 - 1

The preferred limits on oxydeol ratios for manufacture of each zeolite species using a sodium silicate source that was not activated with alumina are shown in Table II.

TABLE II

PREFERRED LIMITATIONS ON CREATING ZEOLITES (not enabled)

Zeolite Water/
Sodium Oxide Sodium oxide /
Silica Silica /
Clay A. 15-20 1.4-2 2-4 X 30-6O 1.2-1.7 6-8 X and A 2O - 50 1.6-3 2 - IO

The preferred limits on hydroxide ratios for manufacture

030028/0721

- ate -

of each zeolite species using a source of sodium silicate activated with alumina are shown in Table III.

TABLE III

PREFERRED LIMITATIONS ON CREATING ZEOLITES

(activated)

Zeolite Water/
Has rium oxide NatriuBoxyd /
Silica Silica /
Clay A. 25-35 1.4-2 3-7 X 30-40 1 -.1.2 5-7 X and A 15-60 0.7-1.7 5-10 Y 2O - 40 0.5 - 1 7-10

To ensure a high yield in relation to the desired zeolite product it is necessary that the conversion of the zeolite mixture exceeds a certain period of time. But if the implementation continued for too long the product begins to lose silica, that is, the silica / alumina molar ratio begins to decrease, and if the reaction is continued it is possible that the product will recrystallize into an undesirable zeolitic substance. There is an optimal conversion time, which is determined in part by the proportions and concentrations of the original reaction mixture, the batch size, the time required to mix the ingredients and the rate of heating. The optimal conversion time for certain molar ratios can easily be determined by testing. In general, however, the conversion times for the production are for zeolite-A from 0.5 to 8 hours and for zeolite-X 2 to 8 hours.

030028/0721

When the zeolite has been separated from the mother liquor, can the cutter liquor can be returned. The recycling of the mother liquor solves the problem of eliminating the mother liquor. Although it is possible to use the process of this invention without recycle Using the mother liquor could be an omission of the Repatriation make the procedure too expensive.

The silica / alumina pickling ratio of Zeolite X is approximate The silica / alumina molar ratio of zeolite-A is 2.5: 1.4 about 1.85: 1. As mentioned above, the particle size of the zeolite is smaller when the molar ratio of silica / alumina des Reaction mixture is higher than the molar ratio silica / alumina of the desired zeolite at molar ratios silica / Alumina higher than 2. Therefore, the zeolite-X and the zeolite-A of this invention have smaller particle sizes than that previous inventions.

Because of their small particle size, zeolite-X and zeolite-A and mixtures of this invention have a wide range of uses, such as, for example, as ion exchange material in water softening and Cleaning agents, as fillers in paper, rubber and plastics, and as a non-settling matting agent. Zeolite-Y can be used as Adsorbent can be used.

030028/0721

The zeolite-A with a smaller particle size has a larger one Magnesia exchange capacity than the zeolite-A with a larger one Particle size according to earlier inventions. This increased magnesium ion exchange capacity increases the usefulness of this Zeolite-A as an ion exchange material in water softening and Cleaning custom.

Another factor that increases the usefulness of zeolites as ion exchange material is their increased speed in relation to them on calcium carbonate depletion. These zeolites remove calcium ions faster than zeolites with larger particle sizes. The zeolite- A with the smaller particle size exchanges calcium ions faster than the Zeolite-Α with a larger particle size.

As Tables I, II and III show, the limits on the water / sodium oxide molar ratios that are used to produce Zeolite-X, Zeolite-A, a composition of Zeolite-X and Zeolite-A or zeolite-Y are required. The water / sodium oxide molar ratio is the most important factor that determines the conversion time is required to carry out the crystallization at a given conversion temperature, which in turn determines the type of zeolite formed certainly. But as stated above, there are other factors which have a smaller effect on the conversion time, such as the molar ratio sodium oxide / silica, silica / alumina, the Degree of movement and the speed at which the sodium maltninate solution is added to the sodium silicate solution. These additional factors

03002070721

- 34 -

either increase the effect of the water / sodium oxide molar ratio or decrease.

For example, either zeolite X or zeolite A may consist of a reduction mixture Vm "it to a molar ratio water / sodium oxide of 30: are formed. 1 In this case the additional factors would determine what type of zeolite is produced. When the sodium oxide / silica molar ratio is 1.2: 1 and the silica / alumina molar ratio is 8: 1, zeolite-X is formed. But when the molar ratio of sodium oxide / trickle acid is 2: 1 and the molar ratio of silica / alumina is 3: 1, zeolite-A is formed. The type of zeolite formed depends on the overall effect of the water / sodium oxide ratio and on all the additional factors mentioned above.

One result of using the principles of the invention is the ability to produce a regulated composition of Zeolite-X and Zeolite-A in the same reaction. A composition from 20 to 80% zeolite-X and 20 to 80% zeolite-A can be formed by regulating the reaction time necessary for crystallization so that it lies between the period of time is required for the production of Zeolite-X, and the period of time that is required for the production of Zeolite-A. The structure of the Composition depends on the implementation time. When the turnaround time is close to the turnaround time required to make Zeolite-X is needed, there will be significantly more Zeolite-X than Zeollt-A

030028/0721

educated. On the other hand, as the reaction time approaches that of zeolite-A, more zeolite-A than zeolite-X is formed. By regulating the reaction time, any desired composition of zeolite-X and zeolite-A can be produced.

The composition of Zeolite-X and Zeolite-A is average Particle size that is less than 2 microns in diameter. Because of its small particle size, it is useful as an ion exchange material in water softeners and detergents, as Filler in paper, rubber and plastics and as a non-settling matting substance,

Any source of sodium silicate can be used in this invention but a particularly desirable source of sodium silicate is sand dissolved in an etchant. The advantage of this source is lower Price. The sand is soaked in a sodium hydroxide solution at a pressure of at least 100 psig and a temperature of at least 130C dissolved to produce a sodium silicate solution with a silica / sodium oxide molar ratio of between 2.4: 1 and 2.8: 1. Preferably the pressure should be about 140 psig, thereby forming a sodium silicate solution having a molar ratio Silica / sodium oxide of approximately 2.4: 1. During the production of Zeolite-Y, the silica is always activated.

030 028/07 21

- at -

The time it takes to make a certain product from batches Manufacture with identical chemical composition depends on the source of the silicon dioxide. Any type of silica source has its own schedule indicating the conversion times required to form each type of zeolite. One one of the discoveries on which this invention is based is the fact that this schedule can be altered by changing the silica source, as described above, activated with clay. The alumina concentration limits are from 50 to 2000 ppm alumina critical values, since alumina concentrations below 50 ppm the sodium silicate solution not activate.

The clay used to activate the sodium silicate solution can appropriately supplied by a soluble aluminum compound such as sodium aluminate or a water soluble one Alumina salt, such as sulfuric clay. Sodium aluminate, however, is the preferred reactant because it has a tendency to introducing foreign ions into the zeolite network is limited.

There is an important difference between the effect of activation and the effect of regulating the conversion time Factors such as the water / sodium oxide molar ratio, sodium oxide / silica, silica / alumina and the rate of addition. The factors regulating the conversion time are used to regulate the conversion time necessary for the crystallization so that they position the conversion time in a schedule for manufacture a certain zeolite is adapted. Activation

030028/0721

changes the schedule, therefore the preferred oxide mole ratios change to produce a desired zeolite when a silica source is either activated or not activated (see Tables II and III above).

EXAMPLES

The invention is explained in more detail using the following examples, the particularly advantageous methods and embodiments of the compositions represent. While the examples include this invention explain, do not limit them. In the examples and throughout the description, all data relate to parts on weight, unless otherwise stated.

The following examples were carried out as described above by forming the silicate and aluminate solutions which corresponding solution was preheated to the specified temperature, and the aluminate solution in the specified time of the silicate solution was added. The resulting gel was dissolved into parts by stirring until a homogeneous slurry was obtained, and the batch was then set at the specified temperature during the reaction time. The resulting product was labeled by its calcium ion exchange capacity on a 4 mg calcium carbonate / g zeolite basis, and its magnesium ion exchange capacity based on mg magnesium carbonate / g zeolite. The resulting zeolite particles are identified by a differential Gaussian frequency distribution in terms of weight percent with an average expressed in microns

030028/0721

Particle size and a weight between 0.1 and 2.5 Microns, the cumulative percentage population is also described. These criteria are given in the tables below.

In the examples, the calcium carbonate exchange capacity was determined by placing the zeolite in an exchange solution gave, stirred for fifteen minutes, filtered out the zeolite and the filtrate with EDTA (rthylenediaminetetraacetic acid) solution titrated to see how many calcium ions were removed. The exchange solution was made up of calcium chloride to have a concentration equal to 122 g of calcium carbonate per liter was. The filtrate was buffered to pH 10, then the filtrate was given Erichrome Black T before the EDTA titration Indicator (3-hydroxy-4 - ((l-hydroxy-2-naphthyl) azo) -7-nitro-naphthalene-sulfonic acid, sodium salt) added.

The magnesium carbonate exchange capacity was determined by the zeolite was placed in an exchange solution, stirred for fifteen minutes, the zeolite was filtered out and the filtrate with EDTA solution titrated to see how many magnesium ions were removed became. The exchange solution was made from magnesium chloride, to get a concentration equal to 1000 ppm magnesium carbonate. The filtrate was buffered to pH 10, then was Erichrome Black T indicator added to the filtrate before the EDTA titration.

030028/0721

Particle size measurements were made with the Coulter counter (model TAU) carried out. The analysis of the particle size with the Coulter counter measures the sample volume and the number of particles in certain sizes. Since volume percent and weight percent are the same are if all the particles are the same? Density, weight percent is used as this is the conventional one Acts in the manner in which information about particle sizes is expressed.

The following terms were used to describe particle size of the present invention uses:

Gaussian frequency distribution: The frequency curves of the Gaussian Frequency distribution, also called symmetrical or bell-shaped Frequency curves that are known are indicated by the fact that observations that are equidistant from the central Are maximum that have the same frequency.

Average particle size: The average particle size is the size that explains 50% of the total weight. The results were confirmed by the scanning electron microscope.

Cumulative percentage population: The cumulative percentage population is the percentage of all particles counted.

The following examples deal with the preparation of Zeolite-A and the labeling of the product. In these examples the exchange numbers refer to zeolite on an anhydrous basis.

030028/0721

- 38 -

TABLE IV

COMPOSITION OF THE MIXTURE FOR THE PRODUCTION OF ZEOLITE-A

Sodium- Water/ oxide/ pebble / oWassei % Nat: rium% gravel] .- ίίίι ure Z clay sodium pebble acid/ 95.34 oxide ]. 06 0.4 2 oxide acid. Clay. 94.14 3.18 1. 57 0.52 30th 3.0 2.5 0 Ί. IΊ 3.77 J. 57 0.52 ι 25th 2.4 3.0 94.04 Λ . 7 7 1. 57 0.63 .L
2 25th 2.4 3.0 3.7 6 .1 . _r . _7th o. 7 η A.
ι 25th 2.4 2.5 yj.90 :;. 7G 1. 57 0.78 J
4th 2. ^l 2.0 ' 9 3.63 3.76 1. 87 0.75 r 25th 2.4 2.0 93.46 3. 7 5 1. 87 0.93 β 25th 2.0 2.5 93.46 3.74 1. 07 0.93 7th 25th 2.0 2.0 93.17 3.74 1. 55 0.62 /
ο 25th 2.0 2.0 93.17 4.66 1. 55 0.62 9 20th 3.0 2.5 "! 3. 1 7 4.66 1. 5 5 () .f> 2 10 20th 3.0 2.5 ■ '3.0 2 4.66 }. 66 0.66 XU
ι 1 20th 3.0 2.5 ii.02 4.65 1. 66 0.66 XX
12th 20th 2.8 2.5 93.02 4.65 1. 66 0.66 .L £ ·
ι -χ 20th 2.8 2.5 92.86 4.65 1. 79 0.71 .LJ
1 4 20th 2.8 2.5 92.86 4.64 1. 79 0.71 X τ
ι «; 20th 2.6 2.5 92.86 4.64 1. 79 0.71 X ~ J
16 20th 2.6 2.5 92.85 4.64 2. 11 0.40 XV *
1 7 20th 2.6 2.5 92.01 4.64 2. 3 2 1.16 X #
18th 20th 2.2 5.3 92.78 3.71 1. 93 0.65 X \ J
1 Q 25th 1.6 2.0 92.78 4.64 1. 93 0.65 X -7
20th 20th 2.4 3.0 92.76 4.64 2. 11 0.49 21 20th 2.4 3.0 92.73 4.64 2. 32 0.32 Z. X
OO 20th 2.2 4.3 92.73 4.64 2. 32 0.32 Z, Z.
21 20th 2.0 7.3 92.68 4.64 2. 32 0.37 Z. J
24 20th 2.0 7.3 92.66 4.63 1. 93 0.77 Z. τ
° s 20th 2.0 6.3 92.66 4.63 1. 93 0.77 Z. J
26th 20th 2.4 2.5 92.66 4.63 1. 93 0.77 Z · Ki
27 20th 2.4 2.5 92.66 4.63 1. , 93 0.77 A. /
OQ 20th 2.4 2.5 92.62 4.63 2. .32 0.44 29 20th 2.4 2.5 92.60 4.63 2. .44 0.33 Z. - /
10 20th 2.0 5.3 92.52 4.63 2. .31 0.54 O U
11 20th 1.9 7.3 92.49 4.63 1. .93 0.96 J X
OO 20th 2.0 4.3 92.49 4.62 I, .93 0.96 J Z.
11 20th 2.4 2.0 92.46 4.62 2 .57 0.35 14th 20th 2.4 2.0 92.44 4.62 2 .10 0.84 J H 20th 1.8 7.3 92.44 4.62 2 .10 0.84 J 3
16 20th 2.2 2.5 92.44 4.62 2 .10 0.84 J Ό
17th 20th 2.2 2.5 92.41 4.62 2 .57 0.41 y /
IP. 20th 2.2 2.5 92.37 4.62 2 .31 0.70 JO
T ₁ Q 20th 1.8 6.3 92.37 4.62 2 .31 0.70 df) 20th 2.0 3.3 92.30 4.62 2 .72 0.37 20th 2.0 3.3 92.23 4.62 2 .56 0.60 4? 20th 1.7 7.3 92.17 4.61 2 .30 0.92 ^ t z.
A 1 20th 1.8 4.3 92.17 4.61 2 .30 0.92 20th 2.0 2.5 4.61 Λ c: 20th 2.0 2.5 4 y
46

030028/0721

20th 2. 0 2. 5 92. 17th 4th 61 2951 192 47 20th 2. 0 2. 5 92. 17th 4th 61 2.30 0.92 48 20th 1. 6th 7th 3 92. 12th 4th 61 2.30 0.92 49 20th 1. 6th 7th 3 92. 12th 4th 61 2.88 0.39 50 20th 1. 6th 7th 3 92. 12th 4th 61 2.88 0.39 51 20th 1. 6th 7th 3 92. 12th 4th 61 2.88 0.39 52 20th 1. 6th 7th 3 92. 12th 4th 61 2.88 0.39 53 20th 1. 8th 3. 3 92. 06 4th 60 2.88 0.39 54 20th 1. 6th 5. 3 91. 98 4th 60 2.56 0.77 55 20th 2. 0 2. 0 91. 95 4th 60 2.87 0.54 56 20th 2. O 2. 0 91. 95 4th 60 2.30 1.15 57 20th 1. 5 7th 3 91. 92 4th 60 2.30 1.15 58 20th 1. 5 7th 3 91. 92 4th 60 3.06 0.42 59 20th 1. 5 6th 3 91. 86 4th 59 3.06 0.42 60 20th 1. 5 6th 3 91. 86 4th 59 3.06 0.49 61 20th 1. 8th 2. 5 91. 84 4th 59 3.06 0.49 62 20th 1. 8th Z. 5 91. 84 4th 59 2.55 1.02 63 20th 1. 8th 2. 5 91. 84 4th 59 2.55 1.02 64 20th 1. 5 5. 3 91. 77 4th 59 2.55 1.02 65 20th 1. 4th 7th 3 91. 69 4th 59 3.06 0.58 66 20th 1. 6th 3. 3 91. 68 4th 58 3.28 0.45 67 20th 1. 6th 3. 3 91. 68 4th 58 2.87 0.87 68 20th 1. 6th 3. 3 91. 68 4th 58 2.87 0.87 69 20th 1. 6th 3. 3 91. 68 4th 58 2.87 0.87 70 20th 1. 6th 3. 3 91. 68 4th 58 2.87 0.87 71 20th 1. 4th 6th 3 91. 63 4th 58 2.87 0.87 72 20th 1. 6th 3. 0 91. 60 4th 58 3.27 0.52 73 20th 1. 4th 5. 3 91. 54 4th 58 2.86 0.96 74 20th 1. 6th 2. 5 91. 43 4th 57 3.27 0.62 75 20th 1. 6th 2. 5 91. 43 4th 57 2.86 1.14 76 20th 1. 4th 3. 3 91. 20th 4th 56 2.86 1.14 77 20th 1. 6th 2. 0 91. 17th 4th 56 3.26 0.99 78 20th 1. 6th 2. 0 91. 17th 4th 56 2.85 1.42 79 20th 1. 2 7th J 91. 13th 5. 56 2.85 1.42 80 20th 1. 2 6th 3 91. 05 4th 55 3.80 0.52 81 20th 1. , 4 2. 5 90 91 4th 55 3.79 0.60 82 20th 1. .4 2. 5 90 91 4th 55 3.25 1.30 83 20th 1. .2 4th 3 90 80 4th 54 3.25 1.30 84 20th 1. .2 3. 3 90 56 4th 53 3.78 0.88 85 15th 2. .4 2. 5 90 45 6th 03 3.77 1.14 86 15th 2. .4 2. 0 90 23 6th 02 2.51 1.01 87 20th 1. .2 2. 5 90 23 4th , 51 2.51 1.25 88 15th 2. .0 2. 0 89 55 5. 97 3.76 1.50 89 15th 1. .6 2. .5 88 , 89 5. .93 2.99 1.49 90 15th 1. .6 2. 0 88 56 5. .90 3.70 1.48 91 15th 1, .6 2. 0 88 .56 5. .90 3.69 1.85 92 3.69 1.85

030028/0721

MS

pebble Umsetz-r 30th 100 ünsetz.— acid Clay addition time (sec) Temp. ^U C 30th 60 time (hours) 90 90 30th 80 4.0 TABLE V 50 50 30th 60 8.0 70 70 30th 60 2.0 50 50 30th 80 7.5 ZEOLIT-A - REQUIREMENTS 50 50 30th 60 6.0 Temperatures C 70 70 30th 60 2.5 50 50 30th 80 6.5 example 50 50 30th 60 6.5 1 70 70 30th 80 2.5 J.
2 50 50 30th 100 4.0 70 70 30th 60 1.5 4th 90 90 30th 80 0.5 t; 50 50 30th 100 4.0 «J
G 70 70 30th 60 2.0 VJ
7th 90 90 30th 80 0.5 /
η 50 50 30th 100 3.0 q 70 70 30th 100 2.0 10 90 90 30th 60 0.5 XV /
11 90 90 30th 60 0.5 X JL
12th 50 50 30th 80 8.0 13th 50 50 30th 100 3.5 14th 70 70 30th 100 2.0 15th 90 90 30th 100 1.0 16 90 90 30th 100 2.0 17th 90 90 30th 60 1.0 JL I
18th 90 90 30th 80 1.0 19th 50 50 30th 100 4.0 JL- J
20th 70 70 30th 100 1.5 21 90 90 30th 100 2.5 22nd 90 90 30th 100 0.5 91 90 90 30th 100 1.0 24 90 90 30th 60 1.0 • each 90 90 30th 80 1.0 96 50 50 30th 100 3.5 27 70 70 OJ OJ OJ
O O O 80
60
100 1.0 • Ca /
9fl 90 90 30th
30th 100
100 1.0 29 70
50
90 70
50
90 600 100 1.5
4.0
0.5 10 90
90 90
90 30th
30th
30th
30th 100
100
60
80 2.0
2.0 11 90 90 2.0 • J X.
19th 90
90
50
70 90
90
50
70 1.0
2.0
4.0
3.0 11 «JJ
14th 35 • YY
Ifi 37
38
39 40
41 49 43
44
45
46

030028/0721

- 38 -

47 50 50 30th 60 3.5 48 90 90 30th 100 0.5 49 90 90 30th 100 2.0 50 90 90 300 100 1-5 51 90 90 600 100 2-0 52 90 90 1200 100 2.0 53 90 90 30th 100 2.0 54 90 90 30th 100 1.0 55 90 90 30th 100 2.0 56 50 50 30th 60 4.5 57 70 70 30th 80 1-5 58 90 90 30th 100 2.0 59 90 90 30th 100 2-0 60 90 90 30th 100 8.0 61 90 90 30th 100 2.0 62 70 70 30th 80 1.5 63 50 50 30th 60 4.0 64 90 90 30th 100 0.5 65 90 90 30th 10 0 2.0 66 90 90 30th 100 4.0 67 90 90 30th 100 1.5 68 90 90 30th 100 1.5 69 90 90 300 100 1.5 70 90 90 600 100 1.5 71 90 90 1200 100 1.5 72 90 90 30th 100 3.0 73 70 70 30th 80 3.0 74 90 90 30th 100 3.0 75 70 70 30th 80 3.0 76 90 90 30th 100 1.0 77 90 90 30th 100 1.0 78 50 50 30th 60 4.0 79 70 70 30th 80 2.3 80 90 90 30th 100 3.0 81 90 90 30th 100 3.0 82 70 70 30th 80 3.0 83 -90 90 30th 100 2.0 84 90 90 30th 100 2.0 85 90 90 30th 10 0 2.0 86 50 50 30th 60 3.5 87 50 50 30th -60 3.5 88 70 70 30th 60 3.0 89 50 50 30th 60 2.0 90 70 70 30th 80 1.0 91 50 50 30th 60 3.5 92 70 70 30th 80 1.0

030028/0721

TABLE VI REPLACEMENT CAPACITY FOR ZEOHT-A

example
ι pebble
acid/
Clay sodium
oxide/
.Clay % Clay 42 Average
Diameter . calcium
capacity magnesium
capacity Λ.
2 2.5 7.5 0. 52 2.4 292 62 "I. 3.0 7.2 0. 52 0.9 300 134 A. 3.0 7.2 Ö. 63 1.25 274 136 H
C. 2.5 6.0 0. 78 0.86 283 145 ZJ
(L 2.0 4.8 0. 78 1.4 300 141 O
7th 2.0 4.8 0. 75 2.1 273 124 9
Q 2.5 5.0 0. 93 1.1 322 133 O
q 2.0 4.0 0. 93 1.5 304 136 10 2.0 4.0 0. 62 2.4 278 105 J. SJ
11 2.5 7.5 0. 62 0.90 295 162 J. JL
12th 2.5 7.5 0. 62 1.3 293 163 X £
τ -ι 2.5 7.5 0. 66 1.4 295 107 X J
14th 2.5 7.0 0. 66 0.93 291 158 JL "
K 2.5 7.0 0. 66 1.2 293 156 X -J ¹
1 & 2.5 7.0 0. 71 1.5 287 117 X Θ
1 7 2.5 6.5 0. 71 0.90 288 154 X I
lfl 2.5 6.5 0. 71 1.4 300 154 XU
Ί Q 2.5 6.5 0. 40 1.5 278 118 X 7
90 5.3 11.7 0. 16 0.7 270 163 XVi
91 2.0 3.2 1. 65 2.0 283 127 -X X
99 3.0 7.2 0. 65 1.1 280 137 ζ ζ
91 3.0 7.2 0. 49 0.83 335 131 ZJ
94 4.3 9.5 0. , 32 0.84 249 159 Currently
9S 7.3 14.6 0. .32 0.95 273 148 Z J
9fi 7.3 14.6 0. , 37 1.0 262 147 Z O
97 6.3 12.6 0. .77 0.7 252 147 ζ #
9R 2.5 6.0 0. .77 0.80 282 153 ZW
? Q 2.5 6.0 0. .77 1.3 295 150 ■ Jfl 2.5 6.0 0. .77 1.0 299 145 JU 2.5 6.0 0, .44 1.5 284 123 y y. 5.3 10.6 0, .33 0.75 249 145 J JL
• J-J 7.3 13.9 0 .54 Ό.86 260 149 IA 4.3 8.6 0 .96 0.93 290 142 Ji
IC 2.0 4.8 0 .96 1.1 327 155 -3 y
~ ift 2.0 4.8 0 .35 1.7 293 125 ■ J V
17th 7.3 13.1 0 .84 Ό.88 261 146 3 «
IR 2.5 5.5 0 .84 1.4 289 152 3 O
-IQ 2.5 5.5 0 .84 0.85 285 149 At 2.5 5.5 0 .41 1.7 300 109 ai 6.3 11.3 0 .70 0.95 297 123 Al 3.3 6.6 0 .70 0.94 29 ^ 2 136 H 4L
Λ "J 3.3 6.6 0 .37 1.1 251 126 ΑΆ 7.3 12.4 0 .60 O.SO 264 147 'k't 4.3 ^ 7.7 Ό .92 1.90 286 99 2.5 5.0 -0 .92 1.1 2Ö1 157 3.5 5.0 0 1.3 290 149

03002870721

47 2.5 5.0 0.92 0.87 296 134 48 2.5 - 5.0 0.92 1.7 283 124 49 7.3 11.7 0.39 1.0 255 135 50 7.3 11.7 0.39 1.0 245 144 51 7.3 11.7 0.39 0.90 259 149 52 7.3 11.7 0.39 0.84 257 151 53 7.3 11.7 0.39 1.1 272 144 54 3.3 5.9 0.77 1.1 290 103 55 5.3 8.5 0.54 0.92 255 150 56 2.0 4.0 1.15 1.3 297 140 57 2.0 4.0 1.15 2.0 293 115 58 7.3 11.0 0.42 0.9 256 145 59 7.3 11. 0 0.4-2 ■ 1.1 249 127 60 6.3 9.5 .0.49 0.95 273 127 61 6.3 9.5 0.49 1.1 234 123 62 2.5 4.5 1.02 ■ 1.2 287 157 63 2.5 4.5 1.02 1.0 281 149 64 2.5 4.5 1.02 1.7 281 113 65 5.3 8.0 0.58 1.1 250 118 66 7.3 10.2 0.45 1.5 254 143 67 3.3 5.3 0.87 1.2 265 145 68 3.3 5.3 0.87 1.5 248 136 69 3.3 5.3 0.87 1.4 264 128 70 3.3 5.3 0.87 1.4 254 127 71 3.3 5.3 0.87 1.7 239 92 72 6.3 8.8 0.52 1.6 307 145 73 3.0 4.8 0.96 1.95 292 135 74 5.3 7.4 0.62 1.4 278 148 75 2.5 4.0 1.14 1.2 288 160 76 2.5 4.0 1.14 2.0 278 86 77 3.3 4.6 0.99 1.3 272 121 78 2.0 3.2 1.42 1.2 311 118 79 2.0 3.2 1.42 2.2 300 119 80 7.3 8.8 0.52 1.6 241 144 81 6.3 7.6 0.60 1.4 300 144 82 2.5 3.5 1.30 1.3 286 145 83 2.5 3.5 1.30 1.9 288 112 84 4.3 5.2 0.88 1.2 . 290 148 85 3.3 4.0 1.14 1.6 . 274 153 86 2.5 6.0 1.01 0.92 315 157 87 2.0 4.8 1.25 1.4 289 140 88 2.5 3.0 1.50 1.6 273 134 89 2.0 4.0 1.49 0.97 275 145 90 2.5 4.0 1.48 1.2 274 129 91 1.6 3.2 1.85 1.4 312 143 92 1.6 3.2 1.85 1.8 279 155

030028/0721

Based on the above information, a linear regression analysis was carried out made, the correlation coefficient (r) for certain Variables were calculated. This analysis showed a clear correlation between the magnesium exchange capacity and the average Particle size (r = -0.581). Because of this sample, there is a Less than 1% probability that these two variables will not be correlated. There's a chance of less than 1%, that there is no correlation between the silica / alumina molar ratio and the average particle size exists (r = - 0.405) and between the molar ratio of sodium oxide / alumina and the average particle size (r = -0.469) and between the alumina concentration and the average particle size (r = +0.465). Therefore, the average particle size and the magnesium exchange capacity can be regulated by either the silica / alumina molar ratio or the molar ratio- nis sodium oxide / alumina or the alumina concentration can be regulated.

030G28A0721

TABLE VII Micron limit THE PARTICLES Max Other > 3. β it ZEOLIT-A - PROPERTIES of at least Cumulative Max 5% > 1. 2 M. Average 90% of the weight. it less than Max 5% > 2. 25 M. Particle size 1.0-4.0 a micron Max 1% > 2. OM Shark cni ί * ■ \ microns 0.1-2.0 19th Max 1% > 2. 0 M. nPf ^ P '* ^
1 2.4 0.1-2.5 96 Max 2% > 2. 5 U 2 0.9 0.1-1.6 67 Max 5% > 1. 5 M 3 1.25 0.1-2.5 92 Max 1% > 2. 6 M. 4th 0.86 0.1-4.0 58 Max 1% > 3. 5YY 5 1.4 0.1-2.5 35 Max 1% > 1. 2V 6th 2.1 0.1-2.5 86 Max 1% > 2. 6 M. 7th 1.1 0.1-5.0 58 Max 1% > 2. OM 8th 1.5 0.1-2.0 61 Max 1% > 1. 5 M 9 2.4 0.1-3.2 92 Max 1% > 2. 6M 10 0.9 0.1-2.5 68 Max 1% > 2. OM 11 1.3 0.1-2.5 56 Max 1% > 1. 5 Ji 12th 1.4 0.1-2.5 92 Max 1% > 2. 6M 13th 0.93 0.1-3.2 73 Max 1% > 2. OM 14th 1.2 0.1-2.5 55 Max 1% > 1. 5 V 15th 1.5 0.1-3.2 93 Max 1% > 3. 3M 16 0.9 0.1-3.2 64 Max 1% > 1. 2M 17th 1.4 0.1-1.6 53 Max 1% > 1. 6M 18th 1.5 0.1-4.0 98 Max 1% > 1. 6M 19th 0.7 0.1-2.5 39 Max 1% > 1. 3 M. 20th 2.0 0.1-1.6 97 Max 1% > 1. , 3M 21 1.1 0.1-2.0 95 Max 1% > 1. , 3M 22nd 0.8 0.1-2.0 94 Max 1% > 1. 3M 23 0.84 0.1-2.0 96 Max 1% > 2. .25 M 24 0.95 0.1-2.0 96 Max 1% > 2. Ό V 25th 1.0 0.1-2.0 98 Max 1% * 2. .6 Ji 26th 0.7 0.1-2.5 96 Max 1% > 1. 5 V 27 0.8 0.1-2.5 71 Max 1% > χ. 3 V 28 1.3 0.1-3.2 88 Max 1% ^> 1. .3 J ¹ 29 1.0 0.1-2.0 55 Max 1% > 2. .25 P 30th 1.5 0.1-2.0 97 Max 1% > 2. .0M 31 0.75 0.1-2.0 96 Max 1% > 1. • 5 m 32 0.86 0.1-2.0 97 Max 1% > 2 • 3m 33 0.93 0.1-4.0 83 Max 1% > 1 .0 M 34 1.1 0.1-2.0 46 Max 1% > 2 .6p 35 1.7 0.1-3.2 96 Max 1% > 1 36 0.88 0.1-2.5 73 Max 1% > 1 .3 H 37 1.4 0.1-4.0 94 Max 1% > 1 .BM 3B 0.85 0.1-2.0 50 Max 1% > 1 .6 M 39 1.7 0.1-2.0 97 Max 1% > 1 .3V 40 0.95 O ^ 1-2.0 94 Max 1% > 1 .6 » 41 0.94 0.1-2.0 82 Max 1% > 2 .6 M 42 1.1 € .1-2.0 96 Ii .0M 43 0.8 0.1-3.2 97 44 0.9 0.1-3.2 94 45 1.1 77 46 1.3

030028/0721

47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
60
81
82
83
84
85
86
87
88
89
90
91
92

0.87

1.7

1.0

1.0

0.9

0.84

1.1

1.1

0.92

1.3

2.0

0.9

1.1

0.95

1.1

1.2

1.0

1.7

1.1

0.9

1.2

1.5

1.4

1.4

1.7

1.1

0.95

1.4

1.2

2.0

1.3

1.2

2.2

1.6

1.4

1.3

1.0

1.2.

1.6

0.92

1.4

1.6

1.97

1.2

1.4

1.8

0.1-2.0 0.1-4.0 0.1-2.0 0.1-1.6 0.1-1.6 0.1-1.6 0.1-2.0 0.1-2.-5 0.1-2.0 0.1-3.2 0.1-5.0 0.1-2.0 0.1-2.0 0.1-2.5 0.1-2.0 0.1-3.2 0.1-2.5 0.1-4.0 0.1-2.0 0.1-2.0 0.1-2.0 0.1-3.2 0.1-3.2 0.1-3.2 0.1-4.0 0.1-3.2 0.1-2.0 .1-3.2 .1-3.2

0. θ,

0.1-5.0 0.1-3.2 0.1-3.2 0.1-5.0 0.1-4.0 0.1-4.0 0.1-3.2 0.1-5.0 0.1-3.2 0.1-4.0 0.1-2.0 0.1-3.2 0.1-4.0 0.1-2.5 0.1-3.2 0.1-3.2 0.1-4.0

96 54 86 80 90 95 97 86 95 71 40 96 96 95 95 80 92 56 95 97 85 53 51 54 62 91 95 95 80 48 76 76 34 80 95 79 57 86 80 98 77 71 91 95 67 53

Max 1% : > 1.3μ Max 1% : * 2.5 µ Max 1% : > 1.6μ Max 1% ; > 1.6μ Max 1% : > 1.6 μ Max 1% : > 1.6μ Max 1% : > 1.6μ Max 1% : > 2.0μ Max 1% : > 1.6 μ Max 1% : > 2.0μ Max 1% : > 3.2μ Max 1% : > 1.6μ Max 1% : > ι.6μ Max 1% : > 1.6μ Max 1% : > ι.6μ Max 1% : > 2.ομ Max 1% : > 1.6W Max 1% : ► 2.5μ Max 1% : ► 1.6Μ Max 1% : > 1.6 μ Max 1% : * ι.6μ Max 1% : > 2.5μ Max 5%: * 2.0μ Max 4%: > 2.0μ Max 2%: > 2.5μ Max 1% : * 2.0μ Max 1% ' > 1.6μ Max 1% : > 1.6μ Max 1% -: * 2.0μ Max 1% : > 3.2μ Max 1% : ·· 2.0μ Max 1% : * 3.2μ Max 1% : * 3.2μ Max 5%: ► 1.6μ Max 1% : * 2.0μ Max 1% : > 2.0μ Max 1% - > 3 .2 μ Max 1% : > 2.0 μ Max 1% · > 2.0μ Max 1% - > 1.25 μ Max 1% ^{: >} 2.0μ Max 1% · > 2.5U Max 1% ^: > 1.6μ Max 1% ^; > ι.6μ Max 1% : > 2.5μ Max 1% > 2 5μ

The following examples of the preparation of small particle size ZeoliC-A were carried out to illustrate the use of the SiO, 'Al 0 . $ 30028/0721

Table VIII

Composition of the reaction mixture for the preparation of Zeolite-A

By- haters / sodium? Silica silica solution Alumina solution play sodium oxide / acid

oxide silica alumina% Na "O% SiO" acid

Alumina% Na_O

93 15th 94 25th 95 15th 96 25th 97 20th 98 20th 99 25th 100 25th

1.6 1.5 10.6 25.8 1.6 1.5 5.5 13.4 2.4 1.5 8.3 20.2 2.4 1.5 3.3 8.2 2.4 1.0 6.2 15.3 2.0 1.0 8.5 20.8 2.4 1.0 4.0 9.8 2.0 1.0 5.2 12.8

5 Na ₂ O IAl ₂ O ₃ 17.4 15.9 14.9 13.6 19.8 10.8 19.8 10.8 15.9 13.0 13.9 14.2 15.9 13.0 13.9 14.2

Table IX Implementation Requirements -Zeolite-A

During preheating

play silica temp. ⁰ C addition conversion conversion acid. Clay time-sec. temp, ^C C time -hours

93 70 70 30th 80 1.5 94 50 50 30th 60 6.0 95 50 50 30th 60 3.5 96 50 50 30th 60 4.0 97 50 50 30th 60 5.0 98 50 50 30th 60 6.5 99 50 50 30th 60 5.0 100 50 50 30th 60 7.0

Table X Properties of the particles - Zeolite-A

At i- Avg. 1.2 Micr .Limitation Cumulative- miscellaneous 1 1 3.2 μ game particle size t, 8 from at least % less than 1 1 3.2 μ Microns 1.7. 90% of weight a micron 1 ί 2.5 μ 93 : 1.5 0.1 - 5.0 58 Max. 1 ι 2.5 μ 94 1 1.2 0.1 - 4.0 33 Max. 1 1 2.0 μ 95 1 1.3 0.1 - 4.0 44 Max. 1 1 2.0 μ 96 1 t.i 0.1 - 2.5 56 Max. 1 1 2.0 μ 97 1 1.4 0.1 - 2.5 74 Max. 1 1 2.0 μ 98 1 0.1 - 3.2 73 Max. 99 1 0.1 - 2.5 82 Max. 100 0.1 - 3.2 69 Max. k > k> k> k> t> k> k> k>

030028/0721

5t »

Table XI

Exchange capacity for zeolite-A

Example Average diameter μ Calcium capacity Magnesium capacity

298 93

296 111

294 100

311 134

291 93

270 96

289 121

270 114

93 2.2 94 1.8 95 1.7 96 1.5 97 1.2 98 1.3 99 1.1 100 1.4

030028/0721

As Examples 1 to 92 show, the following molar ratios are preferred for the preparation of zeolite A at reaction temperatures of 60 ° to 1X) ⁰ C:

Haters / Sodium Oxide 15.0 to 30.0

Sodium oxide / silica 1.2 to 3.0

Silica / alumina 2.0 to 7.3

In addition, Examples 93-100 show a further preferred combination of prerequisites for the production of zeolite-A old small particle size: The use of reaction temperatures from 60 ° to 80 ° C, conversion times from 1.5 to 7.0 hours, and the following molar ratios:

Water / sodium oxide 15.0 to 25.0

Sodium oxide / silica 1.6 to 2.4

Silica / alumina 1.0 to 1.5

Tables XII, XIII, XIV and XV show examples of the preparation of Zeolit-X and the properties of the products.

Thereafter, Tables XVI, XVII, XVIII and XIX show examples of the preparation of Geraischen of zeolite-A and zeolite-X and the

Properties of the products.

These tables also show the exchange capacities of these

Products.

030028/0721

5%

• Hater/ TABLE XII zyb ι ι COMPOSITION OF THE IMPLEMENTATION MIXTURE acid PRODUCTION OF ZEOLITE-X %Water % Sodium % Silica % Clay FOR THE 1.7 pebble 94.73 oxide 1.86 0.25 Hatriura
axyd / 1.6 acid/ 94.61 3.16 1.97 0.27 Natriue pebble 1.5 Clay 94.46 3.15 2.10 0.29 oxide 1.5 7.3 94.46 3.15 2.10 0.29 example 30th 1.5 7.3 94.36 3.15 2.10 0.40 101 30th 7.3 94.30 3.15 2.25 0.31 102 30th 7.3 TABLE XIII 3.14 103 30th 5.3 104 30th 7.3 105 30th 106

REQUIREMENTS FOR IMPLEMENTATION - ZEOLIT-X temperature C

Silica Clay Addition time (sec.) Implementation Implementation example Solution solution 30th temp. C. time (hours) 101 90 90 30th 100 8.0 102 90 90 30th 100 6.0 103 90 90 30th 100 8.0 104 90 90 30th 100 8.0 105 90 90 30th 100 8.0 106 90 90 TABLE XIV 100 8.0

PROPERTIES OF THE ZEOLITE PARTICLES

Average Particle-micron limitation of Cumulative no % Clay 5.0 Calcium- 48 example K r ole s microns at least 90% of the weight as one micr. 0.25 3.2 capacity 49 101 2.0 0.1 - 0.27 4.0 244 41 102 1.7 0.1 - 0.29 6.0 227 46 103 2.2 0.1 - 0.29 4.0 228 45 104 2.8 0.1 - 0.40 3.2 209 52 105 2.2 0.1 - 0.31 225 106 1.5 0.1 - ZEOLIT-X 235 TABLE XV EXCHANGE CAPACITY FOR Average Magnesium- pebble Sodium- diameter capacity acid/ oxide/ 2.0 135 "Example - clay Clay 1.7 140 101 7.3 12.4 2.2 139 102 7.3 11.7 2.8 136 103 7.3 11.0 2.2 140 104 7.3 11.0 1.5 155 105 5.3 8.0 106 7.3 10.2

030028/0721

TABLE XVI example

COMPOSITION OF THE REPRODUCTION MIXTURE FOR THE PRODUCTION OF ZEOLITE-A AND ZEOLITE-X

Sodium water / oxide / pebbles

Sodium silicic acid /% sodium

oxide acid clay ^ water oxide% ki es els acid e

% Clay

107 30th 2.0 7.3 95.03 XVII 3.17 1.58 0.22 108 30th 1.9 7.3 94.94 3.17 1.67 0.23 109 30th 1.8 7.3 94.84 3.16 1.76 0.24 110 30th 1.7 6.3 94.69 3.16 1.86 0.30 111 30th 1.7 5.3 94.64 3.16 1.86 0.35 112 30th 1.6 6.3 94.57 3.15 1.97 0.31 113 30th 1.7 5.3 94.51 3.15 1.97 0.37 114 30th 1.5 5.3 94.36 3.15 2.10 0.40 115 30th 1.5 3.3 94.14 3.14 2.09 0.63 116 30th 1.5 2.5 93.95 3.13 2.09 0.84 117 30th 1.5 2.5 93.95 3.13 2.09 0.84 TABEL

REQUIREMENTS FOR IMPLEMENTATION - ZEOLIT-A AND -X

Temperatures C
Example silica alumina addition time (sec. )

107 108 109 110 111 112 113 114 115 116 117

90 90 90 90 90 90 90 95 90 90 90

90 90 90 90 90 90 90 95 90 90 90

30th

30th

30th

30th

30th

30th

30 300 *

30th

30 300

Implementation Implementation temp. C. time (hours) 100 4.0 100 4.0 100 4.0 100 6.0 100 4.0 100 6.0 100 8.0 100 5.0 100 4.0 100 4.0 100 6.0

* Silicate and clay solutions added at the same time.

030028/0771

ORIGINAL INSPECTED

TABLE XVIII
ZEOLITE-Α AND -X - PROPERTIES OF PARTICLES

Average particle Micron limit - 4.0 Cumulative% less example large -micron of at least - 3.2 than a micron 9o% of the weight - 4.0 107 2.0 0.1 - 3.2 45 108 1.7 0.1 - - 4.0 48 109 1.8 0.1 ■ - 5.0 40 110 1.9 0.1 - - 4.0 38 111 1.9 0.1 - - 6.4 41 112 2.7 0.1 - - 5.0 41 113 2.7 0.1 - - 8.0 42 114 3.3 0.1 - - 10.0 42 115 2.9 0.1 - XIX A2 116 4.0 0.1 - 37 117 5.4 0.1 - 44 TABEL

EXCHANGE CAPACITY FOR A COMPOSITION OF ZEOLIT-A AND ZEOLIT-X

pebble sodium % Clay Average Calcium- magnesium acid/ oxide/ 0.22 diameter capacity capacity example Clay Clay 0.23 2.0 255 130 107 7.3 14.6 0.24 1.7 240 135 108 7.3 13.9 0.34 1.8 228 139 109 7.3 13.1 0.35 1.9 224 141 110 6.3 10.7 0.31 1.9 229 138 111 5.3 9.0 0.37 2.7 221 130 112 6.3 10.1 0.40 2.7 304 130 113 5.3 8.5 0.63 3.3 235 143 114 5.3 8.0 0.84 2.9 257 150 115 3.3 5.0 0.84 4.0 256 118 116 2.5 3.8 5.4 303 129 117 2.5 3.8

030028/0721

The following examples show the activation of the silicate solution old clay,

EXAMPLE 118

A matrix silicate solution with the composition 3.4% sodium oxide and 8.5Z silica was obtained from a sodium aluminate solution with 600 ppm alumina activated. At a temperature of 70 C, a sodium aluminate solution, also 70 C, became old of the composition of 24.21 sodium oxide and 8.32 clay, dea sodium silicate within added by thirty seconds. The resulting gel was dissolved into parts by stirring until a homogeneous slurry was obtained became. The batch was then reacted at a temperature of 80 ° C. for 2.5 hours. The entire batch composition had a water / sodium oxide molar ratio of 25: 1, a molar ratio Sodium oxide / silica of 2: 1 and a molar ratio of silica / 3: 1 clay. The resulting product was Zeolite-A, which had a calcium ion exchange capacity of 277 and a magnesium exchange capacity of 175. The resulting zeolite particles had a narrow differential Gaussian frequency distribution in terms of weight percent to having an average particle size of 1.1 microns, being at least 90% by weight was between 0.1 and 2.0 microns. The cumulative percentage population was 78% less than a micron and no more than 2% more than 1.6 microns.

EXAMPLE 119

A sodium silicate solution with the composition of 4.0% sodium oxide and 10.0% silica was made with 600 ppm alumina from a

030028/0721

became. The batch was then reacted at a temperature of 80 ° C. for six hours. The total batch composition had a water / sodium oxide molar ratio of 25: 1, sodium oxide / silica 1.7: 1 and silica / alumina 7: 1. The resulting The product was a composition of 40% Zeolite-X and 60Z zeolite-A. The product had a calcium ion exchange capacity of 284 and a magnesium exchange capacity of 139. The resulting zeolite particles showed a scarce differential Gaussian frequency distribution in terms of weight percent with an average particle size of 0.8 microns with at least 90% by weight between 0.1 and 3.2 microns lay. The cumulative percent population was 90% less than one micron and no more than 1% more than 1.3 microns.

EXAMPLE 121

A sodium silicate solution with the composition 11.2% sodium oxide and 27.15% silica was activated with 500 ppm alumina from a sodium aluminate solution. The sodium silicate was then Heated to 90 ° C for thirty minutes. At the time it was a sodium aluminate solution, also 90 C, of the composition 10.4% sodium oxide and 14.6% clay added to the sodium silicate within thirty seconds. The resulting gel was dissolved in parts by stirring until a homogeneous slurry was obtained. The batch was then reacted at a temperature of 100 ° C for 24 hours. The entire batch composition had a sodium oxide / silica molar ratio of approximately 0.56: 1, silica / alumina of approximately 7.8 and water / sodium oxide of about 20: 1. The resulting product was zeolite-Y

030028 / Q72T

Activated sodium alueinate solution. At a temperature of 70 ° C., a sodium aluminate solution, also 70 ° C., with a composition of 25.6% sodium oxide and 7.5% clay, was added to the sodium silicate within thirty seconds. The resulting gel was dissolved into parts by stirring until a homogeneous slurry was obtained . The batch was then reacted at a temperature of 80 ^° C. for 22 hours. The total batch composition had a water / sodium oxide molar ratio of 30: 1, sodium oxide / silica of 1 × 2 and silica / alumina of 7: 1. The resulting product was Zeolite-X, which had a calcium exchange capacity of 252 and a magnesium exchange capacity of 147. The resulting zeolite particles had a slightly different Gaussian frequency distribution in terms of percentages by weight on an average particle size of 2.0 microns, with at least 90% of the weight being between 0.1 and 3.2 microns. The cumulative percent population was 52% less than one micron and no more than 1% more than 4.0 microns.

EXAMPLE 120

A sodium silicate solution with the composition 3.6% sodium oxide and 9, OZ silicic acid was activated with 600 ppm clay from a sodium aluminate solution. The sodium silicate was then heated to 70 ° C for thirty minutes. At that point in time, a sodium aluminate solution, also at 70 ° C., with a composition of 29.5% sodium oxide and 5.3% alumina was added to the sodium silicate within thirty seconds. The resulting gel was dissolved into parts by stirring until a homogeneous slurry was obtained

030028/0721

ORIGINAL INSPECTED

- 5 * with a silica / alumina molar ratio of 5.2; 1,

In this way, either Zeolite-Oi, Zeolite-A A composition of -X and -A or zeolite-Y can be formed by adding sand in a sodium hydroxide solution to form a sodium silicate solution is dissolved, this is activated with clay, a sodium aluminate solution is formed and the sodium aluminate solution is quickly added to the activated sodium silicate solution.

COMPOSITIONS FOR WATER SOFTENING

As indicated above, small particle size zeolites in accordance with this invention are useful in a number of applications. For example, a water-soluble softening composition can be formed containing a binder, a solubilizing agent, water, and the zeolites of this invention. Zeolite-A, Zeolite-X or a combination of both zeolites can be used for this purpose. Sodium silicate can be used as a binder in these compositions, the silica / sodium oxide molar ratio being between 1: 1 and 3.3: 1, preferably about 2.5: 1 because this is the most common molar ratio in detergent formulas. At least 10% sodium silicate is required to bind the pearls, but above 20% sodium silicate limits the amount of sodium silicate that can be added to the system without sufficient improvement in pearl strength to warrant the low aluainosilicate levels. The most preferred binder would be a sodium polysilicate with a silica / sodium oxide ratio of 2.5: 1. In addition, IZ to 20Z of a suitable solubilizing agent, including soluble "

030028/0721

- 5β -

Sodium phosphates, carbonates, bicarbonates, tetraborates and sodium sulfates. The preferred solubilizing agent is sodium sulfate.

Some water is required in the water softening pearls. Otherwise will the ion exchange capacity of the sodium silicate is reduced. In In a preferred embodiment of the present invention, at least 66% by weight of an anhydrous base of the present invention Zeolite added 1 to 20% weight percent sodium sulfate, and the remainder is water. This suspension is then sprayed using a nozzle in a spray dryer at an inlet temperature of Dried under 540 C for the production of pearls. If the beads are dried at a temperature above 540 C, ion exchange capacity can be achieved get lost.

DETERGENT COMPOSITIONS

It can be made a detergent composition which contains a high magnesium exchange capacity. Zeolite A, zeolite X or 'a combination of these zeolites may be used according to the invention preferably by a liquid foaming agent is sprayed onto the zeolite to form a flowable powder or beads. Care must be taken that the absorptive capacity of the pigment is not exceeded. The powder or beads are then added to the detergent mixes without further drying. The powder or beads are dry blended into the dry detergent mixture.

The foam generator can be anionic, nonionic, or amphoteric, although the foam generators include the higher alkyl aryl sulfonic acids and their alkali metal and alkaline earth salts, such as the

030028/0721

Example sodium dodecylbenzenesulfonate, sodium tridecylsulfonate, Magnesiuadodecylbenzenesulfonat, Potassium tetradecylbenzenesulfonat, Aauoniuadodecy ltoluensulfonat, Lithiumpentadecylbenzenesulfonat, Sodium dioctylbenzenesulfonate, disodium dodecylbenzenesulfonate, Dinatriuadiisopropylnaphthalindisulfonat and the like, as well as the alkali metal salts of fatty alcohol esters of sulfur and sulfonic acids, the alkali metal salts of the alkylaryl (sulfothio - acid) Esters and alkylthiosulfuric acid.

Non-ionic surface-acting ingredients such as those Products made by the condensation of one or more relatively lower alkyl alcohol amines, such as methanol amines, Xthanolamine, propanolamine, with a fatty acid such as lauric acid, Cety! Acid, tall oil fatty acid, abietic acid, for the production of corresponding amides can also be used. Apart from that, you can also amphoteric compounds that act on the surface, such as -sodium-N-cocobetaaminopirbpiona'C, sodium-N-tallow-beta-aminodipropionate, sodium-N-laurylbetaiminodipropionate and others -to be used.

The use of Zeolite-A with small particle size was evaluated by including phosphate in the basic detergent mixtures replaced. Wash samples were performed on a Terg-o-tcmeter ™ machine, Model 7243. The sample washes were performed at 0.152 Detergent concentration in 120 and 240 ppm hard water (Ca: Mg »2: l) at 120 ° F ". A wash time of fifteen minutes at 125 revolutions Two rinses of five minutes per minute were used. the

03002Θ / Ό721

- 85 -

The cleaning effect was determined on contaminated test materials made of cotton, spun dakron, non-iron cotton / dakroa and Wash-and-wear cotton shirt fabrics. The cleaning value was determined using a Gardner back radiation meter model XL-IO to measure the reflection strength before and after the Measure washing. The results in Table XX show that zeolite-A with small particle sizes is the phosphate in detergent mixtures can replace and may even improve the overall cleaning effect. This is particularly possible with the 240 ppm hardness test emerged. The favorable results obtained in these samples are believed to be due to the small particle size capability of the zeolite-A can be attributed to removing calcium and magnesium ions from the solution at an extremely high rate.

030020/0721

ORIGINAL INSPECTED

- »6 - TABLE XX

MIXTURE

USE OF ZEOLIT-A WITH SMALL PARTICLE SIZE IN DETERGENTS

120 ppm hard water 240 ppn hard water

No. 1 No. 2 No. 3 No. 4

Weight% weight% Gtamm grams wt .-% grams wt. Gr -Z

Sodium tripolyphosphate 25

Zeolite-A with smaller
Particle size

, 375

25th

, 375

(Example 35) - - 25th 32.8 *, 469 —— 240 —— 25th *, 469 Richonat 45B 12th , 18 12th 3.0 , 18 12th , 18 12th , 18 Richonal A 5 , 075 5 17.8 , 075 5 , 075 5 , 075 Condensate co 3 , 045 3 22.8 , 045 3 , 045 3 , 045 Carboxymethyl
cellulose 1 , 015 1 76.4 , 015 1 , 015 1 , 015 Sodium silicate 15th , 225 15th , 225 15th , 225 15th , 225 Sodium sulfate 39 , 585 39 , 585 39 , 585 39 , 585 * (active base) 120 ppm
M- 1 Hard water
XT-O ppm hard water
O XI - /. RESULTS ν ^^^ _in
Samples χ Improvement in
% IU. J
improvement
in % Improvement ii
% cotton 39.0 34.1 Woven
Dakron 15.8 42.4 Non iron tree
wool / Dakron 17.2 20.2 Wash and wear
Cotton shirt fabric 19.9 24.8 % Total
Cleaning effect 91.9 121.5 33.4 10.7 18.8 19.7 82.6

030028/0721

COMPOSITIONS OF PAPIc H

Compositions of paper can also be made and contain zeolites of small and uniform size according to this invention, including zeolite-A, zeolite-X or a combination of both zeolites. The use of small particle size zeolite A as a filler in good paper was assessed by adding different types of entries will. These entries included bleached and unbleached ones Pulp a. Sheets of various basis weights and types of pulp were made using a Nobel and Wood paper machine. These bows were made after the following TAPPI (The American Pulp and Paper Institute) standards tested:

T - 425 m - light transmission of paper T - 452 m - lightness of paper and cardboard T - 410 tn - basic weight of paper and cardboard

Table XXI shows that the one-time run-through residue of Zeolite-A does not depend on the size, and that its residue is significantly higher than Hydrex, a registered trademark of J.M Huber Corporation for an amorphous sodium magnesium aluminosilicate. It is therefore obvious that the relationship between the retention of zeolite A is different and that it depends on the type and not on the size. It is obvious to assume that the residue behavior / on an entry effect between the crystalline substance and the pulp and not depends on mechanical effects, surprisingly See the small particle size zeolite-A according to this invention better optical effects in terms of brightness and light transmission than commercially available zeolite-A and was equivalent in comparison to the most well-known plastic for this application (Hydrex).

030028/0721

TABLE XXI

USE OF ZEOLITE-A WITH SMALL PARTICLE SIZE AS A FILLER IN FINE PAPER

DYE ZFULLER GRUNDGEW.
FABRIC 25x38x500
No./RIES g / 50.9 '75 q %
RETURNED
m HOLDERS
DYE TAPPI
BRIGHT TAPPI
LIGHT THROUGH
CASUALITY No filler 52.1 77 , 3 85.0 82.8 Small particle
size 3 50.2 74 ,1 58 86.7 86.5 Zeolite-A 6th 51.3 75 , 3 55 88.2 89.0 (Example 10) 9 50.8 75 , 9 53 89.3 90.6 Tradeable 3 52.2 77 , 2 56 85.6 84.6 Zeolite-A 6th 53.5 79 , 3 55 86.1 86.1 9 , 2 56 86.5 87.2

No filler

48.9

72.4

85.5

82.2

Small particle
size 3 51 , 5 76 , 2 41 87 , 4 86.1 Zeolite-A 6th 51 , 3 - 75 , 9 38 88 ,8th 88.5 (Example 10) 9 51 , 4 76 ,1 34 89 , 9 90.1 Hydrex * 3 50 ,1 74 ,1 28 87 , 4 86.1 6th 50 , 2 74 , 3 30th 88 , 7 88.2 9 49 ,8th 73 , 3 31 89 , 6 89.4

* Registered trademark of J.M. Huber Corporation

030028/0721

Use of the small particle size zeolite A of the present invention rated as an extender for titanium dioxide in paper, by adding it to a bleached pulp paper entry. The paper entry consisted of 50% bleached hardwood and Kraft branded 5OZ bleached softwood. Sheets were made and the properties were as described above Procedure tested. TABLE XXII shows the once through residue of zeolite-A in association with titanium dioxide These Data also suggest a different retention behavior and confirm the results obtained in a procedure with a single Filler material were obtained. The optical properties obtained with the small particle size zeolite A were significant better than in the case of substances of larger size (commercially available Zeolite-A) and were equivalent to Hydrex.

030028/0721

TABLE XXII

USE OF ZEOLIT-A WITH SMALL PARTICLE SIZE AS AN EXTENSION AGENT FOR TITANIUM DIOXYDE IN FINE PAPER

DYE

FILLER FABRIC

No filler

50% small
Particle size 3

Zeolite-A

(Example 10) 6 and 50%

Titanium dioxide 9

5OZ commercially available pr 3 Zeolite-A and 6 50% titanium dioxide 9

No filler

50% small
Particle size 3

Zeolite-A

(Example 10) 6 and 50%

Titanium dioxide 9

50% Hydrex and 50% titanium dioxide

6 9

BASIC WEIGHT 85x38x500 NO.RIES g / q m TOO ROCK-HELD

50.9 75.3

50.3 74.4

50.3

49.4 49.5

74.4

73.9 73.3 40

24

36
39

BRIGHT LIGHT TRANSMISSION

89.8
90.9

85.0 82.8

50.6 74 , 9 61 87.8 88 , 4 51.0 75 , 5 58 89.6 91 , 9 50.7 75 , 0 55 90.8 93 ,8th 50.5 74 , 7 59 87.2 87 , 7 51.3 75 .9 60 88.7 91 , 0 51.4 76 ,1 60 89.7 92 , 9 48.9 72 , 4 85.5 82 , 2 51.5 76 , 2 47 88.3 88 , 2 51.0 75 , 5 42 89.8 91 , 4

90.9 93.4

88.3 88.5

91.7 93.5

030028/0721

The use of small particle size zeolite-A as a filler in newspaper printing was evaluated using a standard Entry for newsprint was added, newsprint sheet, the 65Z made of grained wood and 35% of semi-bleached Kraft paper were made with the Noble and Wood paper machine manufactured. The sheets were printed with an application weight of 1.7 and 2.5 g printing ink / qra using a Vandercook Proofing press with a solid printing board and a counterprint of a print of 4 mils. After 24 hours the brightness was on the reverse side of the printed and unprinted sheets are checked. This information was then recorded and the results were saved as Discharge values given at 20 g / printing ink / qra (modified Version of the Larocque penetration test).

The information in Table XXIII also shows that the retention behavior of zeolite A is different than that of other special fillers, which are often used for application in newspaper printing. The results also confirm that zeolite A with a small particle size is superior to the commercially available zeolite A and shows favorable results, compared to Zeolex 22, a registered trademark of J.M. Huber Corporation for an amorphous sodium aluminosilicate.

030028/0721

Table XXIII Use of zeolite-A with small particle size in newspaper printing

Dye% residue% filler base weight Thickness measurement Tappi Tappi S / T * o> S / T

24 χ 36 χ 500 mil. mm light light transmission 2 g / 2 m dye. Deduction No./Ries g / qm nonchalance

28.8 46.9 3.0 0.76 59.3 83.7 17.1

2 30.1 49.0 3.1, 079 61.0 86.5 13.4 22

4 30.4 49.5 3.1, 079 62.3 88.0 10.4 39

2 28.8 46.9 3.0, 076 60.2 84.8 13.1 23

4 29.5 48.0 3.0, 076 61.1 85.7 9.8 43

, 084 58.6 86.4 12.3

2 30.6 49.8 3.2, 081 59.2 87.7 11.4 7

4 31.3 50.9 3.2, 081 59.6 88.8 10.6 14

No fill
substance 37 O Small
Particle
size 35 CO
O Zeolite-A 29
35 028/0 Zeolex 23 721 No
Filler material 38 Trade
more common 43 Zeolite-A

30th ,1 49.0 3 ,1 30th , 4 49.5 3 ,1 28 ,8th 46.9 3 , 0 29 , 5 48.0 3 , 0 29 , 6 48.2 3 , 3 30th , 6 49.8 3 , 2 31 , 3 50.9 3 , 2

The use of zeolite A of small particle size in the paper coating has been tested in various coating formulas. Two of these formulas were the following:

1. 87Z sprayed tone

5Z titanium dioxide 8Z dye

2. 92% sprayed clay

8% dye

These mixtures were made with 58% solids with 16 parts per hundred of the binder level (75% starch - 25% latex) and were ground using a Cowles dissolver. The paper used was Grade # 32 and was painted over 13 * / 3300 square feet using a Keegan Laboratory strings with a protruding edge. All sheets were heavily satin finished at 150 ° F and 100 psig with three kinks. the Sheets were then checked for gloss, light transmission, and lightness using the following TAPPI standards:

T-480 m paper gloss T-425 m light transmission of the paper T 452, lightness of paper and cardboard.

The results of Table XXIV show that zeolite-A with small Particle size is superior to the commercially available zeolite-A. This is particularly evident in better gloss development, but there are also significant improvements in lightness and light transmission when the product is used either as an extender for titanium or as a filler agent. Similar Effects have been observed in tests with coated cardboard.

030026/0721

TABLE XXIV

USE OF ZEOLIT-A WITH SMALL PARTICLE SIZE AS AN EXTENDOR FOR TITANOIOXYDE IN PAPER COATINGS

(87% sprayed clay - 5% TiO ₂ 8% dye)

75 degrees ΤΛΡΡΙ TAPPI

Dye gloss,% LIGHT translucent speed

Zeolite-A with

small particles _fi large

(Example 10)

More tradable

Zeolite-A 55.0 70.4 90.3

USE OF ZEOLIT-A OF SMALL PARTICLE SIZE AS A COLORANT IN PAPER COATED

(92Z sprayed clay - 8% dye)

P. _ff 75 degrees TAPPI TAPPI

^{ar Sto} gloss, % light translucent

Zeolite-A with smaller

Small plate size

(Example 10) 64.0 69.3 89.0

Commercial r

Zeolite-A 55.9 68.1 88.5

030028/0721

COMPOSITIONS FROM THE RUBBER

A compound composition can be formed which contains the zeolite A according to the invention, zeolite X or a combination of both zeolites.

The Gunai species (which are also referred to here as elastomers and whose substances are not vulcanized) used in the invention can include natural rubbers as well as artificial rubber. Examples of suitable synthetic rubbers are styrene-butadiene, butyl rubber, nitrile rubber, polybutadiene, polyisoprene, ethylene-propylene, Acrylic gurani, fluorocarbon rubbers, polysulfide rubbers, and silicone rubber. Interpolymer blends of the above artificial rubbers can be used alone or in conjunction with natural rubber. The preferred types of rubber are nitrile rubber, styrene-butadiene rubber, Natural rubber, polyisoprene and mixtures of these rubbers, because they get along better with polyester fibers, although smaller quantities other rubbers can also be used without adverse effects. The U.S. Patent 3, 036 980 is given as a reference to to demonstrate the formation of rubber compositions containing zeolites.

COMPOSITIONS OF PLASTIC

A plastic composition can be formed according to the invention Contains zeolites of small and uniform size. Either Zeolite-A, Zeolite-X, or a combination of both zeolites can be used will.

030028/0721

- 66 -

NON-SETTING MATTING COLOR

The zeolites of this invention can also be used as non-settling matte dyes. Either Zeolite-A, Zeolite- X, or a combination of both zeolites can be used.

Zeolite-A with small particle sizes was evaluated as a not absetzender Mattierungsfarbstoff in nitrocellulose lacquer and as the main extender for dyes in flat trowel latex method. Experiments with the nitrocellulose lacquer were carried out by adding the zeolite to a lacquer. The amount of zeolite corresponded to 10% by weight of the solids in the solvents. The paint and zeolite were mixed together using a Hamilton Beach Mixer Model 936 at 16,000 rpm for four minutes and the resulting mixture was then sieved through a fine mesh paint screen. The Hegman rub was determined in the usual manner and the mixture was then drawn down onto Leneta 5c paper panels using a No. 34 wire-wound coating applicator stick. The panels were dried in a vertical position at room temperature for 45 minutes under dust-free conditions. A Gardner polygon gloss meter was used to determine the gloss (60 degree increase) and reflectance (85 degree increase) of the panels. Withdrawal was rated using an accelerated test on any scale from 0 (failed) to 10 (none) after 7 days at 120 F.

The results in Table XXV show that zeolite A with a small particle size was superior to the commercially available zeolite A in all categories, and the extraordinary clarity of the zeolite A with a smaller particle size

030028/0721

Particle size-containing paint would be of significant value in particular applications.

TABLE XXV

USE OF ZEOLIT-A WITH SMALL PARTICLE SIZE THAN A NOT YOURSELF DEPOSITIVE MATTING COLOR IN NITROCELLULOSE VARNISH

Sample Hegman 60 gloss 85 reflection settling

Zeolite-A with
small particle size (example 10) 6.25 15 27 8

Commercially available

Zeolite-A 6.00 33 71 1

The use of small particle size zeolite-A as the main extender in the flat spatula latex method was rated as follows:

Part I of the ingredients were mixed. Part II of the ingredients was then added and the entire mixture blended for 10 minutes in a Cowles brand high speed mixer. At this point, _{Zeolite-A was added to} each and dispersed for 5 minutes. The relaxants (Part III) were then added to complete the mix and mixed for an additional 5 minutes. The resulting paint was drawn down onto Leneta IB paper panels using a # 34 wire-wound coating applicator stick. The panels were dried in an upright position at room temperature under dust-free conditions. A polygon glossmeter Gardner type was used to determine the shine and reflection of the panels.

030028/0721

Mixture Part I Water Cellosize OP-15000 AMP-95 Daxad Äthyleng IycoI Super Ad It Napco NDW Part II R-901 Huber 7OC G-Weiss

Small particle size zeolite A (Example 10)

Commercially available zeolite A part III water QP-15000 AMP-95 Texanol Napco NDW Anis co 3011

TABLE XXVI Weight, grams 150 Weight, grams No. 2 100 number 1 200 150 200 0.5 0.5 2 2 8th 8th 17th 17th 1 1 1 1 150 100 150

60

183 3 3 8 2

264

60

183 3 3 8 2 264

030028/0721

TABLE XXVII

USE OF ZEOLIT-A OF SMALL PARTICLE SIZE AS A MAIN EXTENSION IN FLAT Trowel-LATEX PROCESS

Bright, contrast 60 ° 85 ° YB relationship shine Reflection 89.6 0.968 3 7th 87.6 0.958 3 4th

Zeolite-A with small particle size (Example 10)

Commercially available zeolite-A

The results of Table XXVII show that zeolite-A with smaller Particle size better than a commercially available zeolite A as the main dye extender works in this color system. This is evidenced by the brightness and the contrast ratios which prove that Small particle size zeolite-A is significantly more effective and efficient in terms of optical properties.

It was found that zeolite-Y according to the invention is particularly has good adsorption properties, as evidenced by the typical adsorption information in Table XXVIII.

TABLE XXVIII ADSORPTION INFORMATION RELATING TO ZEOLITE-Y

pressure temperature Weight% Adsorbed substance (mm Hg) (oC) Adsorbed 25th 25th H ₂ O 700 25th 35.2 co ₂ 200 25th 26.0 n-pentane 0.07 25th 14.9 (C ₄ Fg) ₃ N 1.5 50 1.1 (C ₄ Fg) ₃ N 20th -183 21.4 krypton 700 -183 70.0 oxygen 35.7

030028/0721

The above data were obtained in the following manner: Samples of zeolite-Y obtained by dehydration at a temperature activated at about 350 C in a vacuum were examined to determine their adsorption properties. the Adsorption properties were measured on a McBain-Baker adsorption unit measured. The zeolite samples were placed in light aluminum pails housed, which were hung on quartz springs. They were activated on the spot, and so was the sample gas or steam was then let into the facility. The increase in weight of the adsorbent was measured by the spring elongations and by read a cathetometer. The pressure given in Table XXVIII for each adsorption is the pressure of the substance adsorbed. The term "wt% adsorbed" in the table refers to the percentage weight gain of the activated adsorbent.

As can be seen from the adsorption information in the table, can activated zeolite-Y can be used to create molecules that have a critical dimension that is larger than that of heptocosafluorotributylamine, separate from molecules that have smaller critical dimensions. The critical dimension of a molecule is characterized as the diameter of the smallest cylinder that can accommodate a model of the molecule being built was made using the best available van der Waals radii, Bond angles and bond lengths.

A unique property of Zeolite Y is its strong preference of polar, polarizable and saturated molecules, provided, of course, that these molecules are of a size and shape

030028/0721

»3

that allow them to enter the pore system. This is the case in contrast to charcoal and silica gel, which have a major preference based on the volatility of the substance being adsorbed.

Zeolite-Y. differs from other molecular sieve systems, such as Zeolite-X described in U.S. Patent 2 882 244, due to its special resistance to steam at elevated temperatures. This is a property which makes zeolite-Y particularly useful for processes such as gas drying .

030028/0721

Claims (1)

Claims c) mixing the sodium aluminate and sodium silicate solutions at a temperature of 40 to 120 C, d) the reaction of the mixed sodium aluminate and sodium silicate at a temperature which is slightly higher than the mixing temperature, the reaction mixture the
has the following molar ratios of the components: (1) Water / Sodium Oxide 10: 1 to 35: 1 (2) Sodium oxide / silica 1: 1 to 4: 1 (3) silica / alumina 1: 1 to 10: 1 e) the continuation of the reaction at these molar ratios to form zeolite, while the molar ratios and the urase setting time are regulated so that a zeolite with
fine particle size is obtained, the average particle size being less than 2 microns. In diameter
is, and f) recovery of the zeolite, wherein when the silica / alumina molar ratio is 2.0: 1 or less, the maximum The temperature of the reaction does not exceed 80 ° C., and in which the molar ratios selected for the reaction in the given limits behave in such a way that the particle size 030028/0721 ORIGINAL INSPECTED of the zeolite product increases when the molar ratio of silica / Alumina decreases and decreases as the silica / alumina molar ratio increases and wherein the particle size of the zeolite product is inversely proportional to the molar ratio Sodium oxide / alumina and directly proportional to the alumina concentration, and also provided that the variables of the molar ratios and the reaction temperature are within Limitations can be selected given in order to produce a fine particle size zeolite, with an average Particle size less than 2 microns. in diameter and a high magnesium exchange capacity. 2. The method according to claim 1 for the production of zeolite-A of smaller and uniform size with a high magnesium exchange capacity, characterized by the following steps a) mixing the sodium aluminate solution and the sodium silicate solution for the preparation of a reaction mixture which has a total water / sodium oxide molar ratio of between 10: 1 and 35: 1, a sodium oxide / silica molar ratio of between 1: 1 and 4: 1 and a silica / alumina molar ratio of between 1: 1 and 10: 1; wherein when the sodium oxide / silica molar ratio is less than 4: 3, the molar ratio Silica / alumina is between 3: 1 and 10: 1, and 030028/0721 ORiQlNAL INSPECTED if the molar ratio of sodium oxide / silica is more than 4; 3 is, the molar ratio of sodium oxide / alumina is higher than A; l, b) heating the mixture, c) Implementation of the mixture until the formation of zeolite A and d) Obtaining the Zeolite-A. 3. Method of making Zcolit-A of smaller and more uniform Large with a high magnesium exchange capacity according to claim 2, characterized in that the Mixture has a water / sodium oxide ratio of between 10: 1 and 35: 1, and a sodium oxide / silica ratio of between 1: 1 and 2.5: 1 and a silica / alumina ratio of between 3: 1 and 10: 1 and that the reaction mixture on a Heated temperature from 50 to 100 ° C and at this temperature is implemented. 4. Process for the production of zeolite-A of smaller and more uniform Big one with a high magnesium exchange capacity Claim 2, characterized in that the mixture has a water / sodium oxide molar ratio of 15: 1 to 30: 1, a molar ratio of sodium oxide / silica of 1.2: 1 to 3: 1, and a molar ratio of silica / alumina from 2: 1 to 7.3: 1. 5. Process for the production of zeolite-A of smaller and more uniform Large with a high magnesium exchange capacity after address 2, characterized in that the sodium silicate solution is formed by: 0300 * 8/0721 ORIGINAL INSPECTED a) dissolving sand in a sodium hydroxide solution at a pressure of at least 100 psig _; heated to a temperature of at least 130 C to form sodium silicate with a silica / sodium oxide molar ratio of between 2.4: 1 and 2.8: 1, b) activating this sodium silicate solution by treating it with from 50 to 2,000 ppm (parts per million) clay and c) heating this sodium silicate solution to between 40 ° and 120 ° C. 6. Process for the production of zeolite-A of smaller and more uniform. Large with a high magnesium exchange capacity according to claim 2, characterized in that the sodium aluminate solution and the sodium silicate solution is heated to a temperature of 50 ° to 80 ° C, that the sodium alurainate solution is added to the sodium silicate solution over a period of less than 30 seconds to form a mixture with a molar ratio of water / sodium oxide of approximately 20: 1, a molar ratio of sodium oxide / silica of approximately 1.5: 1, a molar ratio of silica / alumina of approximately 7.3: 1 that this mixture is heated to a temperature of approximately up to 90 ° C and the zeolite-A is recovered. 7. Zeolite-A, produced according to the method according to claim 2, characterized in that the resulting Zeelite particles have a narrow differential Gaussian frequency cellification in terms of percent by weight , with an average particle size of roughly over 2.1 microns. and at least 90% by weight between 0.1 and A, θ micr. that G30028 / 0721 the cumulative percentage population at least. 35% under one Micr. has and not more than 5Z more than 5 micx ,, with a Calcium carbonate exchange capacity greater than 230 mg calcium carbonate per gram of zeolite and a magnesia carbpnataus- Exchange capacity that is higher than 90 mg magnesium carbonate per gram of zeolite. 8. Process for the production of zeolite-X of smaller and more uniform Large with a high magnesium exchange capacity according to claim 1, characterized by the stages of Mixing the sodium alurainate solution and the sodium silicate solution to form a reaction mixture which is a sodium silicate herb liquor and an amorphous sodium alumina silicate which together has a water / sodium oxide molar ratio of between 25: 1 and 90: 1, a sodium oxide / silica molar ratio of between 1: 1 and 3: 1 and a silica / alumina molar ratio of between 5: 1 and 10: 1, the heating of this mixture and the reaction until the formation of zeolite-X and the recovery of the zeolite-X. 9. Process for the production of Zeolite-X of smaller and more uniform Large with a high magnesium exchange capacity according to claim 8, characterized in that the mixture a molar ratio of water / sodium oxide of between 30: 1 and 60: 1, a molar ratio of sodium oxide / silica of between 1.2: 1 and 1.7: 1 and a silica / alumina molar ratio of between 6: 1 and 8: 1. 030028/0721 10. Method of making zeolite — X of smaller and more uniform Large with a high magnesium exchange capacity according to claim 8, characterized in that that the sodium silicate solution is formed by: a) the dissolution of sand in a sodium hydroxide solution at a pressure of at least 100 psig, heated to a Temperature of at least 130 C to form a sodium silicate solution with a silica / sodium oxide molar ratio of between 2.4: 1 and 2.8: 1, b) activation of the sodium silicate solution by treatment with from 50 to 2,000 ppm (parts per million) clay and c) heating this sodium silicate solution to between AO and 120 ° C. 11. Zeolite-X, prepared by the process according to claim 8, characterized in that characterized in that the zeolite particles formed a tight differential Gaussian frequency distribution in terms of weight percent with an average particle size of η icht over 2.2 microns. and at least 90% of the weight between 0.1 and 5.0 microns. that the cumulative percentage population is at least 41% below a micr. having and not more than 5% more than 3.2 microns, the zeolite-X having a calcium carbonate exchange capacity of more than 205 mg calcium carbonate per gram of zeolite and a magnesium exchange capacity of over 130 mg of magnesium carbonate per gram of zeolite. 030028/0721 COPY 12. The method of claim 1 for preparing a composition marked by zeolite-A and zeolite-X through the steps of mixing the sodium aluminate solution and the sodium silicate solution to form a reaction mixture comprising a sodium silicate mother liquor and an amorphous sodium alumina silicate contains, which together have a water / sodium oxide ratio of between 10: 1 and 60: 1, a molar ratio Sodium oxide / silica of between 0.5: 1 and 3: 1 and a silica / alumina wood ratio of between 2: 1 and 15: 1 have the heating of this mixture and the implementation of this gene until a combination of zeolite-A and zeolite-X has been formed and obtaining the composition of zeolite-A and zeolite-X. 13. Process for the preparation of a composition of Zeolite-A and Zeolite-X according to Claim 12, characterized in that that the genic has a molar ratio of water / sodium oxide of between 20: 1 and 50: 1, a molar ratio of sodium oxide / silica of between 1.4: 1 and 3: 1 and a molar ratio silica / alumina of between 2: 1 and 10: 1. IA. Process for the preparation of a composition of Zcolit-A and Zeolite-X according to Claim 12, characterized in that that the sodium silicate solution is formed by: a) the dissolution of sand in a sodium hydroxide solution a pressure of at least 100 psig, heated to a temperature of at least 130 C to form a sodium silicate 030028/0721 COPY solution with a molar ratio of kealic acid / sodium oxide of between 2.4; 1 and 2.8; 1, b) the activation of the sodium silicate solution by treatment with from 50 to 2,000 parts per million (ppm) alumina and c) heating the sodium silicate solution to between AO and 120 ° C. 15. A water softening composition comprising a zeolite according to claim 1 contains. 16. A detergent that uses a zeolite as an ion exchange substance according to claim 1 contains. 17. Paper which, as a filler material, contains a zeolite according to claim 1 contains. 18. Rubber, which as a filler material a zeolite according to claim 1 contains. 19. Plastic, which as a filler material a zeolite according to claim contains. 20. A non-settling matting dye which has a Zeolites according to claim 1 contains. 21. A method of making a sodium silicate solution which is useful is used to form the zeolites according to the method of claim 1, characterized by the following stages: a) Dissolving sand in a sodium hydroxide solution at a pressure of at least 100 psig, heated to a temperature of 030028/0721 at least 130 C to form a sodium silicate solution with a molar ratio of silica / sodium oxide of between 2.4: 1 and 2.8: 1, b) Activation of the sodium silicate solution with from 50 to 2,000 ppm (parts / million) clay at a temperature of between 15 and 100 C for a period of at least 10 minutes and c) heating the sodium silicate solution to a temperature of between 80 ° and 120 ° C. 22. A process for the production of crystalline zeolite-Y of small particle size, wherein this process is characterized by the following steps: a) dissolving sand in a sodium hydroxide solution at a pressure of at least 100 psig and a temperature of at least 130 C to form a sodium silicate solution with a silica / sodium oxide molar ratio of between 2.4: 1 and 2.8: 1, b) the activation of the sodium silicate solution) with 50 ppm to 2000 (parts / million alumina at a temperature of 15 to 100 ° C over a period of at least 10 minutes, c) the formation of a sodium aluminate solution; d) the rapid addition of the sodium aluminate solution to the activated sodium silicate solution to form a reaction mixture which contains a sodium silicate mother liquor and an amorphous sodium aluminosilicate dye, which together have a molar ratio of sodium oxide / silica of between 0.5: 1 and 1: 1, a molar ratio of silica / alumina of between 7 : 1 and 30: 1 and a molar ratio 030028/0721 Water / sodium oxide of between 10; 1 and 90; 1 have, e) d |> e heating the mixture to a temperature of 80 to 120 ° C, f) the reaction of the mixture at a temperature of 80 to 120 C until the formation of crystalline zeolite-Y and g) the recovery of zeolite-Y. 030028/0721