CN112678844A - Method for regulating morphology of molecular sieve - Google Patents
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Abstract
The invention discloses a method for regulating and controlling the appearance of a molecular sieve. The method comprises the following steps: respectively preparing a material A and a material B, wherein the material A contains water, a silicon source and an organic template agent R; the material B contains an aluminum source and water; respectively adding the material A and the material B as two material flows into a supergravity reactor for reaction and aging, controlling the pH value of a system to be more than 9 through an acid-base regulator, and then discharging the supergravity reactor to obtain aged slurry; crystallizing the aged slurry to obtain a molecular sieve; wherein the morphology of the molecular sieve is regulated and controlled by adjusting the supergravity rotating speed and the volume flow ratio of the material A and the material B. The molecular sieve with different crystal grain sizes in the shapes of fusiform, cuboid and the like can be obtained by the method.
Description
Technical Field
The invention relates to a method for regulating and controlling the appearance of a molecular sieve, belonging to the technical field of zeolite molecular sieve synthesis.
Background
Zeolite is a microporous crystalline aluminosilicate having a framework generally of the general chemical formula [ M2(I),M(II)]O·Al2O3·nSiO2·mH2O, (wherein, M (I) and M (II) are monovalence and divalent metals (usually Na, Ca, Ka, etc., n is zeolite Si/Al ratio) and silicon-oxygen tetrahedron and aluminum-oxygen tetrahedron are connected with each other through covalent bond.
CN200910148591.6 discloses a ZSM-5 zeolite and a synthetic method thereof. The synthesis method of the zeolite comprises the steps of mixing and crystallizing a silicon dioxide solid silicon source, an aluminum source, alkali, water and treated seed crystals. The zeolite has a mesopore area of not less than 10m2And/g, the mesopore volume is not less than 0.03mL/g, and the ratio of the intensity of a diffraction peak with the 2 theta of 7.8 +/-0.2 degrees to the intensity of a diffraction peak with the 2 theta of 23.0 +/-0.2 degrees in an XRD diffraction pattern is more than 1. CN200910169617.5 discloses a method for synthesizing ZSM-5 zeolite. The method comprises the steps of mixing amorphous silicon dioxide solid silicon source, aluminum source, water and ZSM-5 synthesis mother liquor, then crystallizing at the temperature of 110-200 ℃ for 8-24 hours, and filtering, washing and drying the crystallized mixture to obtain the ZSM-5 zeolite. CN201010546164.6 discloses a method for synthesizing ZSM-5 zeolite with a hierarchical pore structure under the action of a silane coupling agent. CN201210073742.8 discloses a method for preparing ZSM-5 zeolite molecular sieve microspheres, which utilizes methyl-containing organic siloxane and tetraethoxysilane as silicon sources to prepare the ZSM-5 zeolite molecular sieve microspheres by a one-step method, the microspheres are composed of fine ZSM-5 zeolite crystal grains, the addition amount of the methyl-containing siloxane is changed, and the size of the microspheres can be changedThe particle size is adjusted to 3-8 mu m, and the ZSM-5 zeolite molecular sieve microspheres have uniform size, good dispersibility, simple preparation process and easy mass preparation, and can be applied to the aspects of catalysis, adsorption, separation and the like.
The process described in the above patent does not involve the control of the zeolite morphology. In addition, although the amount of the template agent is reduced in some methods, the required aging time and crystallization time are still longer, the crystallization temperature is higher, and the synthesis process for preparing the molecular sieve is more complicated.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for regulating the appearance of a molecular sieve. The method can realize the regulation and control of the morphology of the molecular sieve. And further when the method is adopted for synthesizing the molecular sieve, the dosage of the template agent can be reduced, the environmental pollution is reduced, the synthesis steps are simple and convenient, the industrialization is easy, the aging time and the crystallization time are greatly shortened, the crystallization temperature is greatly reduced, the crystallization efficiency is high, and the obtained molecular sieve has the characteristic of uniform granularity.
In order to solve the technical problem, the invention provides a method for regulating and controlling the appearance of a molecular sieve, which comprises the following steps:
(1) respectively preparing a material A and a material B, wherein the material A contains water, a silicon source and an organic template agent R, and optionally contains a mineralizer F; material B contains an aluminum source and water, and optionally a phosphorus source;
(2) respectively adding the material A and the material B as two material flows into a supergravity reactor for reaction and aging, controlling the pH value of a system to be more than 9 through an acid-base regulator, and then discharging the supergravity reactor to obtain aged slurry;
(3) crystallizing the aged slurry obtained in the step (2) to obtain a molecular sieve;
wherein the morphology of the molecular sieve is regulated and controlled by adjusting the supergravity rotating speed and the volume flow ratio of the material A and the material B.
Further, the super-gravity rotating speed is 10-4000 rpm, preferably 1000-3000 rpm; the volume flow ratio of the material A to the material B is 0.1-10, preferably 0.5-5.
Further, the molecular sieve is one or more of ZSM-5, ZSM-11, X-type molecular sieve, Y-type molecular sieve, Beta, mordenite and SAPO-34, and preferably, the molecular sieve is ZSM-5 molecular sieve.
Further, the molar ratio of each raw material in the material A is as follows: h2O/SiO2＝5-1000，R/SiO2＝0.1-200，F/SiO20-100; using SiO as silicon source in material A2The calculated addition is taken as a reference, and the molar ratio of the raw materials in the material B is as follows: Si/Al 20- ∞, P/SiO2＝0-50，H2O/SiO2＝1-1000。
Further, in the material A, the dosage of the organic template agent R and a silicon source (SiO is used as the SiO)2Calculated) is R/SiO20.1-200, preferably R/SiO2The molar ratio of (b) is 10 or less, and may be 0.6 or less, or may be 0.5 or less.
Further, in the material A, the amount of the mineralizer F and a silicon Source (SiO)2Calculated) molar ratio of F/SiO2＝0.1-100。
Further, in the material B, P/SiO2The molar ratio of (A) to (B) is from 0 to 50, and may be from 0.1 to 50.
Further, the aged slurry obtained in the step (2) can be aged for 0 to 100 hours at room temperature.
Further, in the step (2), the reaction conditions of the hypergravity reactor are as follows: the residence time is less than 120min, preferably less than 30min, more preferably 3min to 8 min.
Further, the crystallization conditions in step (3) are as follows: the crystallization time is 10min-15 days, preferably 10min-2 days, and further 10min-120 min; the crystallization temperature is 60 to 300 ℃, preferably not more than 160 ℃, and further not more than 130 ℃.
Further, after the crystallization in the step (3), conventional post-treatment steps, namely cooling, washing and separating, drying, roasting and the like, can be further included to prepare the molecular sieve.
Further, the template agent R is at least one of tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, n-propylamine, n-butylamine, n-hexylamine, methylamine, ethylamine, ethylenediamine, diethanolamine, hexamethylene diisocyanate, hexamethylenediamine, hexamethylenetetramine and derivatives thereof (urotropin and derivatives thereof). The silicon source is at least one of silica sol, ethyl orthosilicate and silicate, and the aluminum source is at least one of aluminum sulfate, aluminum isopropoxide and aluminate. The water may be deionized water. The phosphorus source is at least one of phosphate. The mineralizer is fluoride, such as at least one of potassium fluoride and sodium fluoride.
Further, the pH regulator is an alkali metal hydroxide, such as at least one of sodium hydroxide and potassium hydroxide. The pH value of the system is controlled to be above 9 by adopting an acid-base regulator. The acid-base regulator can be added along with the material A or the material B according to actual conditions, and can also be independently added into a system.
The method for regulating the morphology of the molecular sieve is realized by adopting a supergravity reactor and regulating the supergravity rotating speed and the feeding volume flow ratio of the material A and the material B, and can obtain the morphologies such as fusiform, cuboid and the like with different grain sizes.
The method can also reduce the crystallization temperature, shorten the aging and crystallization time, effectively improve the synthesis efficiency and reduce the cost under the condition of reducing the dosage of the template agent, and has the characteristics of good parallelism, repeatability, operability and the like, thereby having better practicability and effectiveness.
The method can also reduce the dosage of the organic template agent and reduce the cost.
The ZSM-5 molecular sieve prepared by the method for synthesizing the molecular sieve is applied to the cracking reaction of a butene solid bed, the reaction temperature is 550 ℃, and the volume space velocity is 10h-1In the process, after the reaction time is 6 hours, the catalyst has a good catalytic effect, the conversion rate of the butylene reaches over 70 percent, the selectivity of the propylene reaches over 40 percent, and an unexpected technical effect is achieved.
Drawings
FIG. 1 is an SEM photograph of the molecular sieve obtained in example 1;
FIG. 2 is an XRD spectrum of the molecular sieve obtained in example 1;
FIG. 3 is an SEM photograph of the molecular sieve obtained in example 2;
FIG. 4 is an XRD spectrum of the molecular sieve obtained in comparative example 1.
Detailed Description
The following examples further illustrate the synthesis of the molecular sieve provided by the present invention, but the scope of the present invention is not limited by these examples.
The analysis (XRD) of the crystal phases of the starting materials and the products was carried out on an X' pert PRO X-ray powder diffractometer from Pasacaceae, using Cu Ka rays as the X-ray source, at a tube pressure of 40kV and a tube flow of 40 mA. Scanning Electron Microscope (SEM) photographs of the samples were taken on a scanning electron microscope, type S-4800II, Hitachi.
[ example 1 ]
Preparing a material A: 2.3g of hexamethylenediamine, 1g of sodium fluoride and 6.7g of silica sol were added to 7.5g of water and stirred uniformly. Preparing a material B: 0.09g of aluminum sulfate octadecahydrate is added into 7.5g of water and stirred evenly. The solution is introduced into a supergravity reactor in two paths, the supergravity rotating speed is adjusted to be 1500rpm, and the volume flow of the solution A and the volume flow of the solution B are controlled to be N (A): and N (B) is 1, the pH value of the system is controlled to be about 9.5 by a sodium hydroxide solution, and the retention time is 5min, so that the liquid to be crystallized is obtained. Then placing the mixture into a crystallization kettle, heating to 120 ℃, stirring at 150rpm for crystallization for 2 hours, cooling to room temperature after the reaction is finished, washing and centrifuging for 3 times by deionized water, drying for 12 hours at 80 ℃, and roasting to obtain the final product. The XRD pattern of the sample is shown in FIG. 2, and the product can be seen to have a characteristic ZSM-5 diffraction peak. The SEM photograph of the product is shown in FIG. 1, and it can be seen that the sample exhibits a uniform fusiform morphology.
[ example 2 ]
The same conditions as in example 1 were used, with the volumetric flow ratio being varied to n (a): and (B) 0.5, and adjusting the rotating speed of the hypergravity reactor to 3000rpm to obtain a final product. The sample XRD pattern is similar to that of fig. 2, with characteristic ZSM-5 diffraction peaks. The SEM photograph of the product is shown in FIG. 3, and the sample can be seen to be in a cuboid shape.
[ example 3 ]
Preparing a material A: 2g of hexamethylenetetramine, 1g of sodium fluoride and 6.7g of silica sol are added to 7.5g of water and stirred uniformly. Preparing a material B: 0.09g of aluminum sulfate octadecahydrate is added into 7.5g of water and stirred evenly. The solution is introduced into a supergravity reactor in two paths, the supergravity rotating speed is adjusted to be 1500rpm, and the volume flow of the solution A and the volume flow of the solution B are controlled to be N (A): and N (B) is 1, the pH value of the system is controlled to be about 9.5 by a sodium hydroxide solution, and the retention time is 5min, so that the liquid to be crystallized is obtained. Then placing the mixture into a crystallization kettle, heating to 150 ℃, stirring at 150rpm for crystallization for 24 hours, cooling to room temperature after the reaction is finished, washing and centrifuging for 3 times by deionized water, drying for 12 hours at 80 ℃, and roasting to obtain the final product. The sample XRD pattern is similar to that of fig. 2, with characteristic ZSM-5 diffraction peaks. SEM pictures of the products can see that the samples present uniform fusiform shapes.
[ example 4 ]
The same conditions as in example 3 were used, with the volumetric flow ratio being varied to n (a): and (B) 2, and adjusting the rotating speed of the hypergravity reactor to 1000rpm to obtain a final product. The sample XRD pattern is similar to that of fig. 2, with characteristic ZSM-5 diffraction peaks. The SEM pictures can show that the sample presents a uniform fusiform appearance.
[ example 5 ]
The same conditions as in example 3 were used, with the volumetric flow ratio being varied to n (a): and (B) 0.5, and adjusting the rotating speed of the hypergravity reactor to 3000rpm to obtain a final product. The sample XRD pattern is similar to that of fig. 2, with characteristic ZSM-5 diffraction peaks. The SEM picture of the obtained product shows that the sample is in a cuboid shape.
[ COMPARATIVE EXAMPLE 1 ]
For comparison, no hypergravity reactor was introduced. The synthesis method comprises the following steps: preparing a material A: 2.3g of hexamethylenediamine, 1g of sodium fluoride and 6.7g of silica sol were added to 7.5g of water and stirred uniformly. Preparing a material B: 0.09g of aluminum sulfate octadecahydrate is added into 7.5g of water and stirred evenly. And (3) uniformly mixing the material A and the material B, aging for 30min, then placing the mixture into a crystallization kettle, heating to 120 ℃, crystallizing for 2h under stirring of 150rpm, cooling to room temperature after the reaction is finished, washing and centrifuging for 3 times by using deionized water, drying for 12h at 80 ℃, and roasting to obtain a final product. The XRD pattern of the resulting product is shown in FIG. 4, and the product is seen to be amorphous.
[ COMPARATIVE EXAMPLE 2 ]
2.3g of hexamethylenediamine, 1g of sodium fluoride, 0.09g of aluminum sulfate octadecahydrate and 6.7g of silica sol are added into 15g of water and stirred uniformly. Directly introducing into a hypergravity reactor, adjusting the hypergravity rotation speed to 1500rpm, circularly introducing into the hypergravity reactor, controlling the pH value of the system to be about 9.5 by a sodium hydroxide solution, and recovering the solution after 5min to obtain the liquid to be crystallized. Then placing the mixture into a crystallization kettle, heating to 120 ℃, stirring at 150rpm for crystallization for 2 hours, cooling to room temperature after the reaction is finished, washing and centrifuging for 3 times by deionized water, drying for 12 hours at 80 ℃, and roasting to obtain the final product. XRD showed the sample to be amorphous.
[ COMPARATIVE EXAMPLE 3 ]
In comparative example 3, a silicon source and water were used as material B, and an aluminum source, a templating agent, an auxiliary agent and water were used as material A. Weighing 1.3g of aluminum sulfate, 90g of silica sol, 3.5g of sodium chloride, 6g of sodium hydroxide, 100g of tetrapropyl ammonium hydroxide and 200g of deionized water to respectively prepare a material A and a material B. And (3) introducing the material A and the material B into a supergravity reactor, adjusting the supergravity rotating speed to be 1500rpm, circularly entering the supergravity reactor, controlling the pH value of the system to be about 9.5 by using a sodium hydroxide solution, and recovering the solution after 5min to obtain the liquid to be crystallized. Then placing the mixture into a crystallization kettle, heating to 120 ℃, stirring at 150rpm for crystallization for 2 hours, cooling to room temperature after the reaction is finished, washing and centrifuging for 3 times by deionized water, drying for 12 hours at 80 ℃, and roasting to obtain the final product. XRD showed the sample to be amorphous.
Claims (10)
1. A method for regulating and controlling the morphology of a molecular sieve comprises the following steps:
(1) respectively preparing a material A and a material B, wherein the material A contains water, a silicon source and an organic template agent R, and optionally contains a mineralizer F; material B contains an aluminum source and water, and optionally a phosphorus source;
(2) respectively adding the material A and the material B as two material flows into a supergravity reactor for reaction and aging, controlling the pH value of a system to be more than 9 through an acid-base regulator, and then discharging the supergravity reactor to obtain aged slurry;
(3) crystallizing the aged slurry obtained in the step (2) to obtain a molecular sieve;
wherein the morphology of the molecular sieve is regulated and controlled by adjusting the supergravity rotating speed and the volume flow ratio of the material A and the material B.
2. The method of regulating as claimed in claim 1, wherein: the super-gravity rotating speed is 10-4000 rpm, preferably 1000-3000 rpm; the volume flow ratio of the material A to the material B is 0.1-10, preferably 0.5-5.
3. The method of regulating as claimed in claim 1, wherein: the molecular sieve is one or more of ZSM-5, ZSM-11, X-type molecular sieve, Y-type molecular sieve, Beta, mordenite and SAPO-34, and preferably the molecular sieve is ZSM-5.
4. The method of regulating as claimed in claim 1, wherein: the molar ratio of the raw materials in the material A is as follows: h2O/SiO2＝5-1000，R/SiO2＝0.1-200，F/SiO20-100; using SiO as silicon source in material A2The calculated addition is taken as a reference, and the molar ratio of the raw materials in the material B is as follows: Si/Al 20- ∞, P/SiO2＝0-50，H2O/SiO2＝1-1000。
5. The regulation and control method according to claim 1 or 4, wherein: in material A, R/SiO2The molar ratio of (A) is 0.6 or less, and further 0.5 or less.
6. The method of regulating as claimed in claim 1, wherein: in the step (2), the reaction conditions of the hypergravity reactor are as follows: the residence time is less than 120min, preferably less than 30 min.
7. The regulation and control method according to claim 1 or 5, wherein: in the step (2), the reaction conditions of the hypergravity reactor are as follows: the retention time is 3min-8 min.
8. The method of regulating as claimed in claim 1, wherein: the crystallization conditions in the step (3) are as follows: the crystallization time is 10min-15 days, preferably 10min-2 days; the crystallization temperature is 60-300 deg.C, preferably not more than 160 deg.C.
9. The method of regulating as claimed in claim 7, wherein: the crystallization conditions in the step (3) are as follows: the crystallization time is 10min-120min, and the crystallization temperature is not more than 130 ℃.
10. The method of regulating as claimed in claim 1, wherein: the template agent R is at least one of tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, n-propylamine, n-butylamine, n-hexylamine, methylamine, ethylamine, ethylenediamine, diethanolamine, hexamethylene diisocyanate, hexamethylene diamine, hexamethylene tetramine and derivatives thereof.
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