KR850000093B1 - Crystalline zeolite powder of type a(i) - Google Patents

Abstract

Crystalline zeolite powder of type A(I) is prepared from heated sodium silicate soln. (1) by mixing it with sodium aluminate soln. (2) in two stages. The product, having a composition of 1.0±0.2 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 diameter less than 4.0 microns. (1) contains Na2O and SiO2, and (2) contains Al2O3 and SiO2.

Description

Method for preparing crystalline zeolite powder of A (I) type

The present invention is 50% by weight particles having a particle size of less than 4.0 microns, the particle distribution is 35 to 60% by weight less than 3 microns, 82 to 95% by weight less than 5 microns, 93 to 99% by weight less than 10 microns, 96 to 100% by weight, less than 15 microns, and 1. 0 ± 0.2 M ₂ / nO: Al ₂ O ₃ : 1.85 ± 0.5 SiO ₂ yH ₂ O (where M is Ia such as sodium, potassium, lithium or cesium Group A (alkali metal) or cations of group IIa metals (alkaline metals) such as magnesium, calcium, strontium or barium, where n is the valence of these metals and y has a value up to 6. A method for producing crystalline zeolite powder.

It is a further object of the present invention to hydrolyze and in some cases crudely synthesize a synthetic mixture of alkali aluminate, water and alkali silicate containing SiO ₂ , Al ₂ O ₃ , Na ₂ O and water. It is to improve the method of producing the crystalline zeolite powder of the present invention by performing shearing (shearing force) instead of performing stirring in the crystallization or control 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 general formula Na x Al x Si y O ₂ (x + y) nH ₂ O are prepared, which can be distinguished by X-ray spectra. Sodium may be substituted here with other monovalent or divalent metal cations such as potassium, lithium, cesium, magnesium, barium and strontium.

In order to use molecular sieves as adsorbents, catalyst carriers or ion exchangers, they must be converted into molded parts using suitable binders. Making a molded product implies that the performance of the molecular sieve decreases due to the participation of the binder, and at the same time, it is expensive for industrial production. Also, as the diffusion path is lengthened, the reaction rate is impaired in drying the organic liquid material. Will fall significantly. Thus, in most cases it is advantageous to use molecular sieve powder.

Prior art methods for the synthesis of molecular sieves (e.g., Milton's German Patent No. 1,038,017 and Milton's US Patent No. 2,882,243) typically produce crystals with an average diameter of about 2 microns or more, which are larger than 45 microns (limit size). Is usually 3 to 12% by weight, which accounts for a considerable proportion. This large particle is called the grit, which was confirmed by the wet seving method of DIN 53580 (German Industrial Standard 53580) of Mocker. A typical product obtained according to this preparation was 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 (I) type powdery zeolite molecular sieves having a particle size of less than 45 microns and having a particle size of less than this, and an ion exchanger such as for water softening. The purpose is to prepare molecular sieves which are particularly useful for. The use of such 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, must not only contain grit. Particularly in the washing, rinsing and cleaning process using a machine, the molecular sieve tends to have a little static sedimentation, so a permanent suspension of the molecular sieve in the liquid should be used in order to leave as little residue as possible after the end of the washing process.

The inventive process produces 0.1-100 g of Al ₂ O ₃ / l and 1-200 g of Na ₂ O / g, which is made of an aqueous alkali silicate solution and heated to 30 to 80 ° C. and preheated to 30 to 100 ° C. The aqueous sodium aluminate solution containing the solution was added by stirring for 10 to 60 minutes until the clouding point of the reaction mixture was reached, followed by SiO ₂ / Al ₂ O ₃ = 2 to 50: 1, Na ₂ O / SiO ₂ = 0.2 to 20: A turbid reaction mixture having a composition of 1 and H ₂ O / Na ₂ O = 4 to 300: 1 is obtained at 10 to 200 g of Al ₂ O ₃ / l and 10 to 250 g of Na ₂ O / l at a temperature of 10 to 100 ° C. The aqueous sodium aluminate solution was added with stirring, and the obtained synthetic mixture was crystallized at a temperature of 20 to 175 캜 for at least 15 minutes.

Shear force can be performed, for example, by introducing an energy of 0.4 to 2 kw / m ³ . The alkali silicate solution contains 50 to 150 g of Na ₂ O / l and 200 to 450 g of SiO ₂ / l.

In one preferred form of the invention, an aqueous sodium aluminate solution containing 10 to 200 g of Al ₂ O ₃ / l and 10 to 250 g of Na ₂ O / l is added stepwise to the reaction mixture, for example in two steps. The addition rate of the second stage is 2 to 10 times the addition rate of the first stage.

In the manufacturing method of the present invention, the shear force can be utilized by using an existing shear device suitable for the purpose instead of the stirrer. The use of this method improves the fineness of the particles but is not essential to carrying out the inventive process.

The synthetic mixture formed by adding a higher concentration of alkali aluminate solution may contain individual components in molar ratios used in the prior art methods. Such prior art is described in Milton's German Patent No. 1,038,017, Milton's US Patent No. 2,882,243 and Weber's German Patent Publication No. 1,095,795. That is, Publication No. Weber include Na ₂ O: has been described as 1: a molar ratio of Al ₂ O _{3 2} to 4.

In the inventive process, shearing forces can be applied to the synthesis mixture in the crystallization step and any subsequent crude step. As used herein, the term "shear" means all mechanical stresses that can degrade the separated particles present in the suspension, primarily based on true shearing action. Shearing may be performed intermittently or continuously.

Preferred shearing devices include turbine stirrers, such as EKATO turbine stirrers. However, crown gear melters, dispersion pumps, centrifugal pumps and other shear devices may also be used.

The crystallization step of the present invention can be carried out at 93 ℃, it was proved to be advantageous to perform the crude in the crystallization mother liquor at a temperature of 85 to 105 ℃, where the crude time is preferably 0.2 to 6 hours, 0.8 to 3.0 hours More preferably, 2 hours is most preferred.

Preferably, the crystallization step proceeds at 93 ° C., but this temperature can be changed to, for example, 90 to 100 ° C. or the like.

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

By increasing the shear force until the end of the crystallization step, the average particle size can be reduced to very low values. This reduces the marginal particle size and its content in the product. However, shearing during the refining stage affects only the marginal particle size and its particle size distribution.

Finally, the present invention is an A (I) type zeolite molecular sieve which can be prepared according to the manufacturing method of the present invention, which is used as an ion exchange resin for water softening, especially as a substitute for phosphate in washing, rinsing and cleaning agents. I am also interested in the use of.

die der technischen chemie, 3rd. edition, vol. 18, Urban & Schwarzenberg, Munich, 1967).These cleaners are a mixture of cleaning agents with surfactant activity, but most contain other additives, mainly inorganic additives, which are necessary for the manufacturing process or improve the cleaning results, and improve the appearance quality. The composition of the detergent varies depending on the application required, which depends on the type of fiber, the dye and the washing temperature, as well as whether the washing is done by hand in a washing machine, 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 & Schwarzenberg, Munich, 1967).

The A (I) type crystalline zeolite powder prepared by the present invention is advantageous in that it is manufactured in a grit-free form and composed of small particles. Therefore, when used as a phosphate substitute as a cleaning agent and a cleaning agent, not only can the suspension be easily formed in the use liquid, but also can be easily washed away from the washing machine and the purifier.

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, entrophication in lakes, seas and rivers is It does not cause as much as it is known.

-크실렌설포네이트, 칼륨 크실렌 설포네이트, 칼륨 3급 옥틸벤젠설포네이트, 칼륨 도데실톨루엔 설포네이트, 나트륨 p-크실렌 설포네이트, 나트륨 프로필 나프탈렌설포네이트, 나트륨 부틸나프탈렌 설포네이트, 라우르 아미도 디프로필디메틸벤질 암모늄클로라이드 및 N-디에틸아미노 올레일 아미드하이드로클로라이드 같은 것들이 있다.In addition to replacing the phosphate as a molecular sieve, the cleaning agents of the present invention are identical to those used in the prior art. Thus, conventional surfactants or detergents can be used, for example anionic, cationic and nonionic detergents. Such detergents include higher alkyl sulfate detergents, in particular alkali metal salts of said sulfates having 8 to 22 carbon atoms in the alkyl residues, such as lauryl sulfate, sodium octadecyl sulfate, sodium coconut fatty alcohol sulfate, sodium octaryl sulfate, sodium alkyl (C ₁₄ -C ₁₈ ) sulfate]; Also corresponding long-chain aliphatic sulfonates such as sodium octanyl sulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfonate, sodium octadecyl sulfonate, potassium dodecyl sulfonate, ammonium dodecyl sulfonate, sodium decyl sulfo Nate, higher alkyl ether sulfate, higher alkyl glyceryl ether sulfonate, higher alkyl phenol polyethylene oxide sulfate, polyoxyethyl ether of fatty alcohol, 3 to 20 moles of ethylene oxide and higher alkyl phenols (e.g. isooctyl or nonylphenol) Condensates of polyethylene oxide with sodium

Xylenesulfonate, potassium xylene sulfonate, potassium tertiary octylbenzenesulfonate, potassium dodecyltoluene sulfonate, sodium p-xylene sulfonate, sodium propyl naphthalenesulfonate, sodium butylnaphthalene sulfonate, lau amido dipropyl Such as dimethylbenzyl ammonium chloride and N-diethylamino oleyl amidehydrochloride.

It is also possible to add bleach such as sodium perborate, emollients such as borax as well as other additives such as sodium carbonate, sodium sulfate and potassium carbonate and PVA, CMC and the like. Other materials may not be added if necessary. The detergent composition may contain or contain essentially the substances listed above.

POC is a poly (hydroxycarboxylate) prepared by the cannizzaro reaction of poly (aldehyde carboxylate) (US Pat. No. 3,923,742 to Haschke).

Unless stated otherwise, all parts and percentages are by weight.

The method of the present invention will be further described with reference to the following examples.

Example 1

2m ³ are placed a water glass (d = 1.35kg / ℓ) 300ℓ containing 7.4% Na ₂ O and 25.6% SiO ₂ in the tank. Stirring per 1ℓ Na ₂ O 90g per 1ℓ and A ₂ lO ₃ 14g 80 ℃ sodium aluminate aqueous solution containing 500ℓ of the temperature in three steps MIG (Mig) stirrer at 50 ℃ and the water glass was added for 30 minutes. Addition was made until cloudiness formed.

To the slightly turbid solution was initially added 100 l of sodium aluminate aqueous solution having a temperature of 70 ° C. for 20 minutes and further 850 l of the same aqueous sodium aluminate solution at 70 ° C. over 60 minutes. The sodium aluminate solution contains 148 g Na ₂ O per liter and 103 g Al ₂ O ₃ per liter.

The reaction mixture was warmed to 87 ° C. and crystallized for 3 hours. The crystalline product was pure zeolite A (I) with the following particle distribution in the X-ray photograph.

50% of the total weight was less than 3.2 microns in particle size.

The particle size was measured by the Coulter Counter measurement method.

Example 2

Cleaners containing perborate

The cleaning agent is made by mixing three ingredients in powder form.

Example 3

Perborate Free Cleaner

The cleaning agent was made by spraying a nonionic surfactant ethoxylated product on the powder particles consisting of the remaining components.

* 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)

A sodium silicate aqueous solution containing 50 to 150 g of Na ₂ O per liter and 200 to 450 g of SiO ₂ per liter was prepared and heated to 30 to 80 ° C. The sodium silicate solution had a temperature of 30 to 100 ° C and Al ₂ O per liter. ₃ Aqueous solution of sodium aluminate containing 0.1 to 100 g of Na ₂ O 1 to 200 g per liter is stirred and added for 10 to 60 minutes until reaching the clouding point of the reaction mixture, and SiO ₂ / Al ₂ O ₃ = 2 to 50: 1, M ₂ O / SiO ₂ = 0.2 to 20: 1 and H ₂ O / M ₂ O = 4 to 300: 1 in a cloudy reaction mixture having a composition of 10 to 200 g of Al ₂ O ₃ per liter and Na ₂ per liter A sodium aluminate aqueous solution containing 10 to 250 g of O and having a temperature of 10 to 100 ° C. was stirred and added in two stages, in which the rate of addition of the second stage was 2 to 10 times faster than the rate of the first stage, and then obtained. The prepared synthetic mixture to crystallize at 20-175 ° C. for at least 15 minutes, 1.0 ± 0.2 M ₂ / nO: Al ₂ O ₃ 1.85 ± 0.5SiO ₂ · yH ₂ O (wherein M represents sodium anion, n represents its valency and y represents a value up to 6), and 50% by weight of particles The particle distribution is not more than 4.0μ, the particle distribution is 35 to 60% by weight less than 3 microns, 82 to 95% by weight less than 5 microns, 93 to 99% by weight less than 10 microns, 96 to 100% by weight less than 15 microns A method of producing crystalline zeolite powder of type (I).