KR850000094B1 - Crystalline zeolite powder of type a(i) - Google Patents

Abstract

Crystalline zeolite powder of type A(III) is prepared in two stages from a heated sodium aluminate soln.(1) containing Al2O3 and Na2O and by the addition of a sodium silicate soln.(2) containing Na2O and SiO2. The product, having a composition of 1.0±k0.2 M2/nO: Al2O3: 1.85±0.5 SiO2yH2O (where M = Na+ ion, n = valency, and y = 0-6), is obtained by crystallization of the synthetic mixture for 15 min. at 20-175≰C. 50 wt.% of the particles have a diamter less than 4.3 microns.

Description

Method for producing crystalline zeolite powder of type A (III)

The present invention is 50% by weight particles having a particle size of less than 4. 3 microns, the particle distribution is 18 to 38% by weight less than 3 microns, 70 to 82% by weight less than 5 microns, 93 to 99 weight less than 10 microns %, Less than 15 microns of 96 to 100% by weight, 1.0 ± 0.2 M ₂ / _n O: Al ₂ O ₃ : 1.85 ± 0.5 SiO ₂ yH ₂ O (where M is sodium, potassium, lithium or cesium A cation of Group Ia metals (alkali metals) or Group IIa metals (alkaline metals) such as magnesium, calcium, strontium or barium on the same periodic table, n is the valence of these metals and y has a value up to 6 The present invention relates to a method for producing crystalline zeolite powder having A (III) type.

Still another object of the present invention is to hydrothermally crystalliz and, in some cases, produce a synthetic mixture of alkali aluminate, water and alkali silicates containing SiO ₂ , Al ₂ O ₂ , Na ₂ O and water. tempering), in which the crystalline zeolite powder of the present invention is improved by applying shearing forces instead of stirring in the crystallization or refining step.

Zeolite molecular sieves and their properties regarding ion exchange and adsorption have long been known. It is synthesized by heating a water-soluble synthetic mixture having a composition of aNa ₂ O x bAl ₂ O ₃ x cSiO ₂ to 50 to 300 ° C. Depending on the composition of the starting mixture, the reaction temperature and the reaction time, compounds of different structures with the composition of the formula Na x Al x SiyO ₂ (x + y) nH ₂ O are prepared, which are distinguished by the X-ray spectrum can do. Sodium may be replaced with cations of other monovalent or divalent metals such as potassium, lithium, cesium, magnesium, barium and strontium.

In order to use the molecular sieve as an adsorbent, catalyst carrier or ion exchanger, a suitable binder must be used to prepare the molded article. Making a molded product means that the performance of molecular sieve decreases due to the addition of the binder, and the production cost is high, and the diffusion rate is long, so that the reaction rate is considerably slowed, for example, the drying of organic liquid is hindered. Will receive. It is therefore advantageous in most cases to use the molecular sieve powder itself.

Linear formulations for the synthesis of molecular sieves (e.g., Milton's German Patent No. 1,038,017 and US Patent No. 2,882,243) typically produce crystals with an average diameter of about 2 microns or more, with large particles of 45 microns or larger. 3 to 12% by weight, which occupies a considerable proportion. Such large particles are called grit, which was confirmed by the wet sieving method of DIN 53580 (German Industrial Standard 53580) from Mocker. Typical products obtained according to this preparation were found to be about 25% by weight particles less than 10 microns in diameter and 50% by weight particles less than 13 microns (see D. W. Breck, Zeolite Molecular Sieve, p. 388 (1974)).

The present invention solves the problem by developing a method for synthesizing and preparing a grit material sieve of A (III) type having a smaller particle size than the grit material (particle size of 45 microns or more) and ions such as for water softening. The purpose is to prepare molecular sieves that are particularly useful for exchangers. In the use of molecular sieves for various purposes within the scope of the present invention, such as the use of such molecular sieves as phosphate substitutes in washing, rinsing and cleaning processes, the absence of small particle sizes and grit is essential. Particularly in the process of washing, rinsing and cleaning using a machine, the molecular sieve tends to have a little static sedimentation in order to clean the residue so that no residue remains. Therefore, the permanent suspension of the molecular sieve should be used in liquid.

The production method of the present invention prepares an aqueous alkali aluminate solution at 30 to 100 ° C. containing 0.1 to 100 g of Al ₂ O ₃ per liter and 1 to 200 g of Na ₂ O per liter, and then adds an alkali silicate solution over 10 to 200 minutes. Supplying a clear reaction solution having a composition of SiO ₂ / Al ₂ O ₃ = 50 to 1000: 1, Na ₂ O / SiO ₂ = 0.2 to 20: 1 and H ₂ O / Na ₂ O = 4 to 300: 1 To this synthetic mixture was added an aqueous solution of sodium aluminate at 30 to 100 ° C. containing 10 to 200 g of Al ₂ O ₃ per liter and 10 to 250 g of Na ₂ O per liter, with stirring, and then the resulting synthetic mixture was Crystallization at a temperature of 20 to 175 ° C. for at least 15 minutes.

The alkali silicate solution contains 50 to 150 g of Na ₂ O per liter and 200 to 450 g of SiO ₂ per liter.

The shearing process can be carried out, for example, by introducing an energy of 0.4 to 2 Kw / m ³ .

According to one preferred method of the present invention, an aqueous sodium aluminate solution containing 10 to 200 g of Al ₂ O ₃ per liter and 10 to 250 g of Na ₂ O per liter is added stepwise to the reaction mixture, for example in two steps. At this time, the addition rate of the second step is 2 to 10 times the addition rate of the first step.

In the production method of the present invention, the shear force may be utilized by using an existing device suitable for the purpose instead of the stirrer. The use of this method improves the fineness of the particles but is not essential for carrying out the inventive process. The synthetic mixture prepared by adding a higher concentration of alkali aluminate solution may contain individual components in the same molar ratio as in the previous step. Such prior processes are described in Milton's German Patent No. 1,038,017 to Milton's US Patent No. 2,882,243 and Weber's German Patent Publication No. 1 095,795. I.e. Publication No. Weber include Na ₂ O: has been described as 1: Al ₂ O ₃ molar ratio of 2 to 4.

Shear forces can be exerted on the synthetic mixture in the crystallization step and any subsequent crude step in the inventive process. As used herein, the term "shear" refers to any mechanical stress that can break apart discrete particles present in a suspension, primarily by a true shearing action. Shearing may be performed intermittently or continuously.

Preferred as a shearing device is a turbine stirrer such as an EKATO turbine stirrer. However, crown gear melters, dispersion pumps, centrifugal pumps and other shear devices may also be used.

Although the crystallization step of the present invention can be carried out at 93 ° C., it has proven to be advantageous to carry out the crude for the crystallization mother liquor at 85 ° to 105 ° C., wherein the crude time is preferably 0.2 to 6 hours, most preferably 0.8 To 4.0 hours, in particular 3 hours. The crystallization step is preferably carried out at 93 ° C., but this temperature can be varied, for example, from 90 to 100 ° C.

The crude phase begins at the end of the crystallization. This can be detected by the maximum ion exchange capacity, the maximum X-ray line intensity, and about 22.5% water vapor absorption. In practice, however, this criterion is based on the experience determined by the optimization of the method.

The shear force can be strongly applied until the end of the crystallization step so that the average particle diameter can be reduced to very low values. This reduces the marginal particle size and its content in the product. However, shearing during the refining step affects only the limiting particles and their proportions among all particles.

die der technischen Chemie, 3rd Edition, Vol. 18, Urban ＆ Schwarzenderg, Munich, 1967).In conclusion, the present invention relates to the use of A (III) type zeolite molecular sieves which can be prepared according to the process of the present invention as phosphate substituents in ionizers such as water softening, in particular washing, rinsing and cleaning agents. . These cleaners are mixtures of cleaning agents with surfactant activity, but most of them also contain other substances, mainly inorganic additives, which are necessary for the manufacturing process or improve the cleaning results, and improve the appearance quality. Detergents vary in composition depending on the application required, which depends on the type of fiber, the dyeing and the washing temperature, as well as whether the washing is done by hand in a laundry bin, in a domestic washing machine, or in a laundry. Most cleaning agents are in the form of pourable powders, but there are also liquid or paste products (see Ullmann's Enzyklop).

die der technischen Chemie, 3rd Edition, Vol. 18, Urban & Schwarzenderg, Munich, 1967).

The A (III) type crystalline zeolite powder produced by the present invention has the advantage of being manufactured in a grit-free form and composed of small particles. Therefore, when it is used as a phosphate counterpart in cleaning agents and cleaning agents, not only can it be easily suspended in the use liquid but also can be easily rinsed out from washing and cleaning machines, in particular.

The use of the alkali aluminum silicate of the present invention has the advantage that it does not cause any environmental pollution by phosphate anymore, and when the molecular sieve of the present invention is used as a cleaning agent to the extent that eutrophication in lakes, seas and rivers is known to date Will not cause. Besides the substitution of phosphate as molecular sieve, the cleaning agents of the present invention are the same as those used in the prior art. Thus, conventional surfactants or detergents such as anionic, cationic and nonionic detergents can be used. Such detergents include alkyl residues such as higher alkyl sulfate detergents, in particular sodium lauryl sulfate, potassium lauryl sulfate, sodium octadecyl sulfate, sodium coconut fatty alcohol sulfate, sodium octanyl sulfate and sodium alkyl (C ₁₄ -C ₁₈ ) sulfate. Alkali metal salts, such as alkali metal sulfates having 8 to 22 carbon atoms, and sodium octanyl sulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfonate, sodium octadecyl sulfonate, potassium dodecyl sulfonide, ammonium dodecyl Corresponding long chain aliphatic sulfonates such as sulfonates, sodium sulfone, higher alkyl ether sulfates, higher alkyl glyceryl ether sulfonates, higher alkyl phenol polyethylene oxide sulfates, polyoxyethyl ethers of fatty alcohols, 3 to 20 moles of ethylene oxide; Such as condensed isooctyl and nonylphenol Polyethylene oxide condensates with higher alkyl phenols, sodium O-xylene sulfonate, potassium xylene sulfonate, potassium tertiary octylbenzene sulfonate, potassium dodecyl toluene sulfonate, sodium P-xylene sulfonate, sodium propyl naphthalene sulfonate, Sodium butylnaphthalene sulfonate, lauramido dipropyldimethylbenzylammonium chloride and N-diethylamino oleylamide hydrochloride can be used.

It can also be added to bleaches such as sodium fiborate, water repellents such as borax, as well as other additives including sodium carbonate, sodium sulfate and potassium carbonate and polyvinyl alcohol, carboxymethyl cellulose and the like. Deviant materials may not be added if necessary. Detergent compositions may contain essentially the aforementioned materials. POC is a poly (hydroxycarboxylate) prepared by the Cannizzaro reaction of poly (aldehyde carboxylate) (see US Pat. No. 3,923,742 to Haschke). Unless stated otherwise, all parts and percentages are by weight.

The process of the present invention is illustrated in more detail by the following examples.

Example 1

550 L of an aqueous sodium aluminate solution containing 78 g of Na ₂ O per 1 L and 5 g of Al ₂ O ₃ per 1 L are placed in a 2m ₃ tank at 70 ° C. 300 L of water glass liquid (d = 1.35 kg / L) containing 7.4% of Na ₂ O and 25.7% of SiO ₂ was supplied over 40 minutes while stirring with a 3-sig Mig stirrer. The solution is clear. To this solution is first added 100 liters of an aqueous sodium aluminate solution at 70 ° C. over 15 minutes, followed by an additional 900 liters of the same aqueous sodium aluminate solution at 70 ° C. over 60 minutes. The sodium aluminate solution contains 160 g Na ₂ O per liter and 106 g Al ₂ O ₃ per liter. The reaction mixture is warmed to 85 ° C. and crystallized for 3 hours. The crystalline product thus prepared is a pure A (III) type zeolite (in X-ray photographs) having a 50 wt% portion of 3.8 μ or less and having the following particle distribution:

Particle size was measured by the Coulter Counter measurement method.

Example 2

Fiborate-containing cleaner

Sodium aluminum silicate according to Example 1 (drying at 90 ° C. for 6 hours, water content of 16.8 wt%): 45.0 wt%

Sodium Fiborate: 20.0 wt% Detergent Powder: 35.0 wt%

Detergent powders are prepared, for example, by heating and drying the following composition:

ABS (Sodium Dodecylbenzene Sulfonate) 21.0%

Ethoxylated Uji Alcohol (1 mol Uji Alcohol + 14 mol ethylene oxide) 7.5%

Soap (sodium salt of saturated C ₁₈ -C ₂₂ essential fatty acids) 7.2%

Water glass (Na ₂ O 3.3 SiO ₂ ) 9.0%

Magnesium sulfate 4.5%

Carboxymethylcellulose 2.0%

Opt ical brigtener 0.6%

Soluble complexes such as sodium citrate, or nitrile

Triacetic acid (NTA), or ethylenediamine tetraacetic acid

(EDTA), or sodium triphosphate, or POC, etc.] 9.0%

Sodium sulfate 35.0%

Water residue

The cleaning agent is prepared by mixing three components in powder form.

Example 3

Cleaners that do not contain fiborate

Ethoxylated C ₁₁ -C ₁₅ oxoalcohol (1 mol oxoalcohol + 3 mol ethylene oxide): 2.0 wt% ^* , Ethoxylated C ₁₁ -C ₁₅ oxoalcohol (1 mol oxoalcohol + 13 mol ethylene oxide): 5.0 wt% ^** , sodium aluminum silicate prepared according to Example 1 (drying at 90 ° C. for 6 hours, water content of 16.8 wt%): 40.0 wt%, soda (sodium carbonate): 15.0 wt%, sodium citrate: 5.0 wt%, water glass (Na ₂ O · 3.3 SiO ₂ ): 4.0 wt%, carboxymethyl cellulose: 1.5 wt%, optical brightener: 0.2 wt%, sodium sulfate: 23.0 wt%, water: residue.

The cleaning agent is prepared by spraying a powder particle consisting of the remaining components with an ethoxylated product, which is a nonionic surfactant.

^* This component can be replaced with an equivalent amount of Uji alcohol + 5 moles of ethylene oxide.

^** This component can be replaced with an equivalent amount of Uji alcohol + 14 moles of ethylene oxide.

Claims (1)

1ℓ Al ₂ O ₃ 0.1 to 100g and 1ℓ Na ₂ O 1 to 200g containing 30 to prepare a sodium aluminate aqueous solution of 100 ℃ and here in 1ℓ Na ₂ O 50 to 150g and 1ℓ SiO ₂ 200 to each party to the party per A sodium silicate solution containing 450 g was fed over 10 to 200 minutes to give SiO ₂ / Al ₂ O ₃ = 50 to 1000: 1, Na ₂ O / SiO ₂ = 0.2 to 20: 1 and H ₂ O / Na ₂ O = 4 to 300: A clear reaction solution having a composition of 1 was prepared, and then a solution of sodium aluminate at 30 to 100 ° C. containing 10 to 200 g of Al ₂ O ₃ per liter and 10 to 250 g of Na ₂ O per liter in the synthetic mixture. Is added in two stages, that is, the addition rate of the second stage is 2 to 10 times faster than the first stage, and the mixture is stirred, and the resulting synthetic mixture is crystallized at 20 to 175 ° C. for at least 15 minutes. 1.0 ± 0.2M ₂ / _n O: Al ₂ O ₃ : 1.85 ± 0.5 SiO ₂ · y · H ₂ O (wherein M is a sodium cation , n is its valence, y is a value up to 6), 50% by weight of the particles do not exceed 4.3μ and the particle distribution is 18 to 38% by weight less than 3 microns, 70 to less than 5 microns A process for producing crystalline zeolite powder of type A (III), wherein 82% by weight, less than 10 microns, 93 to 99% by weight, and less than 15 microns, 96 to 100% by weight.