CN1078179C - Preparation method for fine-crystal model A zeolite - Google Patents
Preparation method for fine-crystal model A zeolite Download PDFInfo
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- CN1078179C CN1078179C CN97116447A CN97116447A CN1078179C CN 1078179 C CN1078179 C CN 1078179C CN 97116447 A CN97116447 A CN 97116447A CN 97116447 A CN97116447 A CN 97116447A CN 1078179 C CN1078179 C CN 1078179C
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Abstract
The present invention provides a method for preparing a fine crystal grain A-type zeolite. The method comprises the following steps: firstly, a guiding agent is prepared by the method which is used for preparing a guiding agent during the synthesis of faujasites; then, silicon in the guiding agent is used as a whole silicon source of a reaction mixture, an aluminum source is added into the reaction mixture to adjust the silica alumina ratio, and acids or alkalis are added into the reaction mixture to adjust the alkalinity; the prepared reaction mixture comprises the following compositions by mole: 1.6 to 4.0 of Na2O, Al2O3, 1.8 to 3.0 of SiO2 and 95 to 220 of H2O; and finally, the mixture is crystallized by a conventional method. The crystal grain size of the NaA type zeolite prepared by the method is from 0.2 to 0.4 mum, and the calcium exchange capacity is large so that the NaA type zeolite is especially suitable to be used as an auxiliary agent for washing agents and toothpastes.
Description
The present invention relates to a kind of crystalline aluminosilicate prepare zeolite method, particularly relate to the close grain NaA type prepare zeolite method that can be used as sorbent material or water-softening chemicals use.
A type zeolite is synthetic artificial zeolite the earliest, can be used as sorbent material, siccative etc. and be widely used, be used as the additive of solid detergent again in recent years and be widely used abroad, satisfy the environmental requirement of no phosphatization to replace original tri-polyphosphate that uses, its annual production has reached more than 1,000,000 tons
Because soda soap use in hard water of solubility can generate water miscible calcium soap and thereby magnesium soap reduces its service efficiency.Generally add poly-phosphate in the prior art in the past as water-softening chemicals in synthetic detergent, but poly-phosphate can cause the serious harm to the environment and the ecosystem, therefore replacing poly-phosphate with other water-softening chemicalss is a vital task of synthetic detergent.NaA type zeolite has splendid cation exchange capacity (CEC), can be used as sorbent material or use as the ion-exchanger of Ca and Mg, thereby can be used as water-softening chemicals and become effective interpolation component of synthetic detergent, partly or entirely to substitute present employed poly-phosphate component.
Its grain size of NaA type zeolite as detergent builder should be beneficial to its dispersion in water enough for a short time, so both can overcome that the rapid subsidence that causes zeolite owing to particle is excessive causes depositing and macroparticle to the shortcomings such as wearing and tearing of washing machine, can not be attached to because particle is fine again simultaneously that to be washed on the fabric other granularity littler, distribute more evenly, then calcium ion exchange rate is faster.NaA type zeolite as detergent builder also should have sufficiently high calcium adsorptive power or calcium exchange capacity.
The method for preparing A type zeolite is a lot, generally all is that sodium aluminate solution and sodium silicate solution are mixed into glue, then 70～95 ℃ and under condition of stirring heating crystallization, perhaps be that raw material carries out crystallization with kaolin.Its grain size of A type zeolite that the method that provides in the prior art obtains is generally all greater than 1 μ m, and the calcium adsorptive power neither be very high.
USP4,150, a kind of method of the A of preparation type zeolite has been proposed in 100, be under 65 ℃, to be prepared into a kind of full-bodied gel of single-phase homogeneous that contains less water with sodium aluminate solution and sodium silicate solution, this mixture is risen to 95 ℃ from 65 ℃ as early as possible, under this temperature, only needed 5～20 minutes to get final product complete crystallization, reduce temperature then rapidly and prevent that further crystal from transforming.The condition control of this method in operating process is difficult for grasping, and the grain-size of products therefrom is 4～6 μ m, and the calcium adsorptive power is 170～200mg CaCO
3/ g anhydrous zeolite.The method that proposes among the EP392400 similarly.
USP4, the method for preparing A type zeolite that proposes in 173,622 is to add the A zeolite seed crystal of ground particle diameter less than 0.5 μ m in grain-free silica-alumina gel mixture, making grain size after crystallization is the equally distributed NaA type zeolite of 1-10 μ m.
USP4 has proposed in 078,042 a kind ofly to prepare the method for A type zeolite with aluminum alkoxide, and this method is the mixture that forms a kind of moisture activated silica compound and aluminum alkoxide earlier, then under preset temperature this mixture of heating until being converted into the A zeolite fully.The shortcoming of this method is that aluminum alkoxide is too expensive.USP4 proposed in 055,622 a kind ofly to produce the method for A type zeolite with aluminium making residue, but the gained zeolite properties is relatively poor.
Liu Yuming etc. have reported a kind of A type prepare zeolite method (daily chemical industry,, the 4th phase, page 1 in 1986), and its concrete steps are according to 3 Na
2O-Al
2O
3-2SiO
2-185H
2The mole proportioning of O is mixed with A, B two solution (A solution: sodium metaaluminate, sodium hydroxide, water respectively; B solution: water glass, water), A, B two solution are preheated to 40～70 ℃ respectively; Earlier A or B solution are poured in the stainless steel still, under high degree of agitation, add crystallization director and another solution rapidly, ageing certain hour under said temperature then, be warming up to 100 ℃ again and carry out crystallization, wherein the consumption of said crystallization director is 3% of a zeolite butt weight, but this directed agents is not carried out any concrete description, the i.e. composition of unexposed this directed agents and method for making in the document.The mean particle size of the A type zeolite that this method makes is about 1.5 μ m.
The purpose of this invention is to provide a kind of NaA type prepare zeolite method, make compared with prior art can prepare crystal grain thinner and have good calcium ion-exchanged capacity, be more suitable for close grain NaA type zeolite as detergent builder.
The method for preparing close grain NaA type zeolite provided by the present invention comprises
The method for preparing directed agents that is adopted during (1) according to the conventional faujusite of preparation is prepared directed agents;
(2) a kind of aluminum contained compound that will be selected from sodium metaaluminate, Tai-Ace S 150, aluminum chloride and the aluminum nitrate under agitation mixes with (1) gained directed agents and a kind of acid or alkali, the mole of gained mixture is formed met (1.6～4.0) Na
2OAl
2O
3(1.8～3.0) SiO
2(95～220) H
2The proportioning of O;
(3) with (2) gained mixture according to a conventional method in 70～110 ℃ of following crystallization 1～10 hour.
Directed agents in the step in the method provided by the present invention (1) can prepare by the whole bag of tricks of preparation faujusite directed agents in the prior art, but the method for preparing directed agents that is adopted during preferably according to the conventional NaY of the industrial preparation of generally adopting at present prepares, for example according to USP3,639,099, USP 3,671,191, USP4,166,099, the method for preparing directed agents (crystal seed) that is proposed among CN 85102733A and CN 1081425 A prepares, and the mole compositing range of the directed agents of preparing according to these ordinary methods is (11～18) NaO
2Al
2O
3(10～17) SiO
2(200～350) H
2O.
The said aluminum contained compound of step in the method provided by the present invention (2) is sodium metaaluminate or Tai-Ace S 150 preferably, and wherein most preferred is Tai-Ace S 150.
Said acid of step in the method provided by the present invention (2) or alkali are used for adjusting the basicity of reaction mixture, and it can be mineral acid such as sulfuric acid, hydrochloric acid or the nitric acid of using always, perhaps mineral alkali but the most frequently used acid is sulfuric acid, and the most frequently used alkali is sodium hydroxide.
Mole in the step in the method provided by the present invention (2) is formed the Na in the expression formula
2O represents the basicity of mixture, and it does not comprise the part that is neutralized by acid, and this method for expressing is generally to adopt in the document.
Crystallization condition in the step in the method provided by the present invention (3) is preferably 80～100 ℃ of following crystallization 2～8 hours.
Also comprise in the method provided by the present invention product after the crystallization is filtered, washs and drying.
The characteristics that prepare the method for fine-crystal model A zeolite provided by the present invention are with the whole silicon source of the silicon in the directed agents as the crystallization mixture, adjust its silica alumina ratio with adding the aluminium source again, adjust basicity with acid or alkali, that is to say and contain a large amount of crystallization directors in the crystallization mixture, so just, make the grain-size of the NaA type zeolite that crystallization synthesizes very little, the average crystal grain size has reached 0.2～0.4 μ m, and in the prior art average crystal grain size of gained NaA type zeolite generally greater than 1.0 μ m, the inventive method gained NaA type zeolite is the same with prior art in addition has a good calcium exchange capacity, therefore the NaA type zeolite that makes with the inventive method is particularly suitable for as detergent builder, also can be as the interpolation component of toothpaste.
Fig. 1 is X-ray diffraction (XRD) the crystalline phase figure of embodiment 1 gained sample, and used instrument is a Japanese D/MAX-IIIA type of science (CuK α).
Fig. 2 is scanning electron microscope (SEM) photo (3500 times) of embodiment 1 gained sample, and used instrument is ISI-60A.
Fig. 3 is the SEM photo (3500 times) of embodiment 2 gained samples.
Fig. 4 is the XRD crystalline phase figure of Comparative Examples 1 gained sample.
Fig. 5 is the SEM photo (4300 times) of Comparative Examples 1 gained sample.
The following examples will the present invention is described further.The measuring method of calcium exchange capacity is with after a certain amount of sample and the exchange of excessive ionic calcium soln in following Comparative Examples and embodiment, isolate solid and measure to inhale that remaining calcium ion amount draws in the surplus liquid, the condition of exchange is: zeolite: calcium chloride: water=0.8: 1: 20, the exchange temperature is 30 ℃, and be 20 minutes swap time.
Under agitation (Chang Ling oil-refining chemical factory catalyst plant is produced, wherein SiO with 100ml water glass
2Content is 250.0 grams per liters, basicity Na
2O is 80.0 grams per liters, proportion d
4 20=1.25) and the 70.8ml sodium aluminate solution (producer is the same, wherein Al
2O
3Content is 40.0 grams per liters, Na
2O is 276.2 grams per liters, proportion d
4 20=1.30) mix, and ageing at room temperature 24 hours, crystallization director obtained.
(Beijing Chemical Plant produces with 36.5 gram sodium hydroxide, chemical pure purity 95 heavy %, join after being dissolved in 16 ml deionized water down together) and mix in the top described crystallization director, (Chang Ling oil-refining chemical factory catalyst plant is produced, wherein Al under agitation to add 205.2 milliliters of alum liquors then again
2O
3Content is 90.0 grams per liters, d=1.27, down with) and thorough mixing even, this reaction mixture was descended static crystallization 6 hours at 90 ℃, filter then, wash and drying, its X-ray diffraction of gained sample (XRD) crystalline phase figure sees Fig. 1, and scanning electron microscope (SEM) photo is seen Fig. 2, and its calcium exchange capacity of analysis revealed is 320mgCaCO
3/ g anhydrous zeolite, Fig. 2 show that its average crystal grain size is about 0.3 μ m.
Embodiment 2
According to CN85102733A in embodiment 1 identical method to prepare mole proportioning be 17.6Na
2OAl
2O
319SiO
2369H
2Join in this crystallization director after crystallization director 945 gram of O is dissolved in 322 gram NaOH in 1697 ml waters then and mix, it is even to add 1010 milliliters of alum liquors and thorough mixing again, then with this reaction mixture 95 ℃ of following crystallization 2 hours, filter, wash drying then, figure is identical with Fig. 1 for its XRD crystalline phase of gained sample, the SEM photo is seen Fig. 3, and its calcium exchange capacity of analysis revealed is 295mgCaCO
3/ g anhydrous zeolite.
Embodiment 3
With preparing the crystallization director of same amount with the described identical method of embodiment 1, and it is even under agitation 123.4 milliliters of alum liquors to be joined in this crystallization director thorough mixing, join in this mixture after being dissolved in 30.8 gram sodium hydroxide in 163 ml deionized water again and mix, then with the gained reaction mixture in 90 ℃ of following crystallization 5 hours, filtration washing drying then, figure is identical with Fig. 1 for its XRD crystalline phase of gained sample, the SEM photo is similar to Fig. 2, the average crystal grain size is about 0.3 μ m, and calcium exchange capacity is 290mgCaCO
3/ g anhydrous zeolite.
Embodiment 4
With preparing the crystallization director of same amount with the described identical method of embodiment 1, and under agitation (Chang Ling oil-refining chemical factory catalyst plant is produced, wherein Al with 142 milliliters of sodium aluminate solutions
2O
3Content is 100.0 grams per liters, Na
2O is 155.0 grams per liters, d=1.25) it is even to join in this crystallization director thorough mixing, again under agitation to wherein adding 150 gram dilute sulphuric acids (concentration is 26 heavy %), then with the gained reaction mixture 90 ℃ of following crystallization 6 hours, filter then, wash and drying, figure is identical with Fig. 1 for its XRD crystalline phase of gained sample, and the SEM photo is similar to Fig. 2, grain size is 0.2～0.4 μ m, and calcium exchange capacity is 318mgCaCO
3/ g anhydrous zeolite.
Embodiment 5
Repeat the operation steps of embodiment 4, different is to change crystallization temperature into 75 ℃, and crystallization time changes 8 hours into, and figure is identical with Fig. 1 for its XRD crystalline phase of gained sample, and the SEM photo is similar to Fig. 2, and grain size is 0.2～0.3 μ m, and calcium exchange capacity is 295mg CaCO
3/ g anhydrous zeolite.
Comparative Examples 1
According to " daily chemical industry " 1986 the 4th described methods of phase page 1, suppose that wherein said crystallization director is a crystallization director used when synthesizing the NaY zeolite.With 298 ml water glass (with embodiment 1) join mix and be heated in 1000 ml deionized water 50 ℃ standby, with 969 milliliters of sodium aluminate solution (Al
2O
3Content is 100 grams per liters, Na
2O/Al
2O
3Mol ratio is 2.0 grams per liters, d=1.24) join mix and be heated in 875 ml deionized water 50 ℃ standby, above the crystallization director that 392.3 grams are made by the method for embodiment 1 and the sodium aluminate solution of top described dilution join under vigorous stirring simultaneously in the water glass solution of described dilution, with the ageing of gained reaction mixture after 30 minutes, the 100 ℃ of crystallization that heat up again 1.5 hours, filtration washing is also dry then, its XRD crystalline phase of gained sample figure sees Fig. 4, the SEM photo is seen Fig. 5, its average grain size is greater than 1.0 μ m, and calcium exchange capacity is 309mgCaCO
3/ g anhydrous zeolite.
Claims (6)
1. a close grain NaA type prepare zeolite method is characterized in that this method comprises
The method for preparing directed agents that is adopted during (1) according to the conventional faujusite of preparation is prepared directed agents;
(2) a kind of aluminum contained compound that will be selected from sodium metaaluminate, Tai-Ace S 150, aluminum chloride and the aluminum nitrate under agitation mixes with (1) gained directed agents and a kind of acid or alkali, the mole of gained mixture is formed met (1.6～4.0) Na
2OAl
2O
3(1.8～3.0) SiO
2(95～220) H
2The proportioning of O;
(3) with (2) gained mixture according to a conventional method in 70～110 ℃ of following crystallization 1～10 hour.
2. according to the process of claim 1 wherein that the mole compositing range of said directed agents is (11～18) Na
2OAl
2O
3(10～17) SiO
2(200～350) H
2O.
3. according to the process of claim 1 wherein that said aluminum contained compound is sodium metaaluminate or Tai-Ace S 150.
4. according to the method for claim 3, wherein said aluminum contained compound is a Tai-Ace S 150.
5. according to the process of claim 1 wherein that said acid is sulfuric acid, hydrochloric acid or nitric acid, said alkali is sodium hydroxide.
6. according to the process of claim 1 wherein that the condition of the said crystallization of step (3) is 80～100 ℃ of following crystallization 2～8 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116447A CN1078179C (en) | 1997-09-17 | 1997-09-17 | Preparation method for fine-crystal model A zeolite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116447A CN1078179C (en) | 1997-09-17 | 1997-09-17 | Preparation method for fine-crystal model A zeolite |
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| Publication Number | Publication Date |
|---|---|
| CN1211537A CN1211537A (en) | 1999-03-24 |
| CN1078179C true CN1078179C (en) | 2002-01-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97116447A Expired - Fee Related CN1078179C (en) | 1997-09-17 | 1997-09-17 | Preparation method for fine-crystal model A zeolite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6773693B2 (en) | 2000-12-28 | 2004-08-10 | Kao Corporation | Fine zeolite particle |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US415000A (en) * | 1889-11-12 | rossiter | ||
| US4078042A (en) * | 1977-04-21 | 1978-03-07 | Continental Oil Company | Process for preparing Zeolite A |
| US4173622A (en) * | 1978-01-03 | 1979-11-06 | Fmc Corporation | Zeolite A crystals of uniformly small particle size and the manufacture thereof |
-
1997
- 1997-09-17 CN CN97116447A patent/CN1078179C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US415000A (en) * | 1889-11-12 | rossiter | ||
| US4078042A (en) * | 1977-04-21 | 1978-03-07 | Continental Oil Company | Process for preparing Zeolite A |
| US4173622A (en) * | 1978-01-03 | 1979-11-06 | Fmc Corporation | Zeolite A crystals of uniformly small particle size and the manufacture thereof |
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| Publication number | Publication date |
|---|---|
| CN1211537A (en) | 1999-03-24 |
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