CN109626393B - Preparation method of hedgehog-shaped SUZ-4 - Google Patents

Preparation method of hedgehog-shaped SUZ-4 Download PDF

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CN109626393B
CN109626393B CN201910140480.4A CN201910140480A CN109626393B CN 109626393 B CN109626393 B CN 109626393B CN 201910140480 A CN201910140480 A CN 201910140480A CN 109626393 B CN109626393 B CN 109626393B
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suz
aluminum
molecular sieve
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crystallization
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CN109626393A (en
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蒋山
高晓坤
王炳春
李进
王建青
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China Catalyst New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2002/00—Crystal-structural characteristics
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Abstract

The invention aims to provide a preparation method for synthesizing an SUZ-4 molecular sieve by using a cheap novel template agent. Firstly, preparing silicon-aluminum mixed glue solution, then adding template Ethylenediamine (EDA) and ethylamine (CHA) in any proportion and mixing. Then adding the mixture into a reaction kettle for high-temperature crystallization growth; wherein the crystallization temperature is as follows: the crystallization time is between 130 and 170 ℃, and is as follows: 2 to 5 days. Finally synthesizing the hedgehog shaped SUZ-4 molecular sieve generated by the cheap template agent. The method for synthesizing the SUZ-4 molecular sieve has simple and convenient process, not only greatly reduces the synthesis cost of the molecular sieve, but also obtains the hedgehog shaped SUZ-4 molecular sieve.

Description

Preparation method of hedgehog-shaped SUZ-4
Technical Field
The invention belongs to the technical field of silicon and aluminum oxide molecular sieves, and particularly relates to a hedgehog shaped SUZ-4 prepared by mixing two cheap templates.
Technical Field
In 1992, the British BP company first discovered and prepared SUZ-4 molecular sieves. Barri et al in the presence of Si02,Al 203And adding an organic matter tetraethyl hydroxide (TEAOH) and quinuclidine into the initial gel of the mixture of KOH and NaOH as a template agent to synthesize the SUZ-4 molecular sieve. This is the first synthesis of the molecular sieve, but the synthesis method has poor repeatability, and the research development of the SUZ-4 molecular sieve is hindered to a certain extent.
In 1999, Asensi et al, which improved the reproducibility of the synthesis of SUZ-4 molecular sieves, used a new initial gel fraction of 21.2Si0 at a temperature of 150 ℃2:Al203:7.9KOH:2.6TEAOH:498.6H20 (molar ratio) in which there is no NaOH and quinuclidine, since they believe that Na ion is not an essential species for SUZ-4 synthesis, and its presence induces the generation of competitive MOR; quinuclidine is also not necessary, and the system can still generate SUZ-4 molecular sieve under the template action of TEAOH. Therefore, the route has good repeatability and reliable synthesis result, becomes a used proportion in the follow-up research, and the discovery of innovation greatly promotes the development of synthesis of the SUZ-4 molecular sieve.
In 2000, Paik Et al synthesized SUZ-4 molecular sieves with a large silica to alumina ratio (Si/A1) (8.2) using Et6-diquat-5 as a templating agent, which they thought were a result of organic macromolecules.
So far, no report on the synthesis of SUZ-4 molecular sieve by using a novel template appears again.
The present application is incorporated by reference in its entirety.
[1]Barri,S.A.I.,“Crystalline(metallo)silicates and germanates-SUZ-4”,US Pat.5118483(1992).
[2]Asensi,M.A.,Camblor,M.A.,Martinez,A.,“Zeolite SUZ-4:Re-produciblesynthesis,physicochemical characterization and catalytic evaluation for theskeletal isomerization of n-butenes”,Micropor.Mesopor.Mater.,28,427–436(1999).
[3]W.C.Paik,C.H.Shin,S.B.Hong,J.Chem.Soc.,Chem.Commun.(2000)1609.
Disclosure of Invention
The present invention provides a hedgehog shaped SUZ-4 molecular sieve, and a method for synthesizing the SUZ-4 molecular sieve using a novel template.
The method for synthesizing the SUZ-4 molecular sieve by using the novel template comprises the following steps: firstly, preparing silicon-aluminum mixed glue solution, and then adding template Ethylenediamine (EDA) and ethylamine (CHA) for mixing; then adding the mixture into a reaction kettle for high-temperature crystallization growth; wherein the crystallization temperature is as follows: the crystallization time is between 130 and 170 ℃, and is as follows: 2 to 5 days; finally obtaining the hedgehog shaped SUZ-4 molecular sieve.
Preferably, the preparation process of the silicon-aluminum sol comprises the following steps: firstly, adding water into an aluminum source and KOH to mix into a solution a, and mixing a silicon source and a double template agent into a solution b; and then fully stirring the solution a and the solution b to obtain uniform silicon-aluminum mixed sol.
Preferably, the silicon source is one of silica sol, water glass and white carbon black or is mixed in any proportion, and the aluminum source is one of aluminum powder, pseudo-boehmite, aluminum hydroxide, aluminum isopropoxide, aluminum nitrate and aluminum sulfate or is mixed in any proportion.
Preferably, the crystallization temperature is 140 ℃ to 160 ℃, and the crystallization time is as follows: 3 to 5 days.
Preferably, the molar ratio of the double-template Ethylenediamine (EDA) to the cyclic ethylamine (CHA) is (1-10): (1-10).
Preferably, the crystallized product is washed, dried and calcined. Wherein the drying temperature is 120 ℃ and the time is 4 hours, and the roasting temperature is 550 ℃ and the time is 6 hours.
Preferably, the initial molar ratio of each raw material in the preparation method is as follows: al (Al)2O3:SiO2:KOH:EDA:CHA:H2O＝1：(15～30):(5～20)：(1～10)：(1～10)：(100～2500)。
Compared with the prior art, the invention is characterized in that: the SUZ-4 molecular sieve is synthesized by using the low-cost Ethylenediamine (EDA) and the cyclic ethylamine (CHA) as double templates, so that the production cost is greatly reduced, and the method is favorable for industrial mass production. And the SUZ-4 molecular sieve synthesized by the double templates has special appearance. The following examples further illustrate the invention.
Description of the drawings:
figure 1 is an XRD spectrum of the synthesized sample of example 1.
Figure 2 is an XRD spectrum of the synthesized sample of example 2.
FIG. 3 is a scanning electron micrograph of a synthesized sample of example 2.
Figure 4 is an XRD spectrum of the synthesized sample of example 5.
Figure 5 is an XRD spectrum of the synthesized sample of example 7.
The implementation method of the invention comprises the following steps:
example 1
A solution A was prepared by adding 37.96g of deionized water to 2.48g of aluminum isopropoxide and 5.82g of KOH (85%), and stirring for 0.5h to completely dissolve the aluminum source. 30.01g of silica sol (40%), 2.55g of ethylenediamine and 6.01g of cyclohexylamine are added into 30g of deionized water, mixed and stirred uniformly to form a solution B. Then, the solution A and the solution B are mixed and stirred for 1h to form white gel. The formed gel was transferred to a 170ml Teflon reaction vessel, dynamically rotated at a rotation speed of 20r/min, and crystallized at 150 ℃ for 4 days. The obtained sample is washed, dried at 120 ℃ and roasted at 550 ℃ for 6 hours to obtain the SUZ-4 molecular sieve with the crystallinity of 85%. The XRD spectrum is shown in figure 1.
Initial gel frictionThe molar composition is as follows: 33.3SiO2:Al2O3:14.7KOH:7EDA:10CHA:798H2O
Example 2
A solution A was prepared by adding 37.96g of deionized water to 2.48g of aluminum isopropoxide and 5.82g of KOH (85%), and stirring for 0.5h to completely dissolve the aluminum source. 30.01g of silica sol (40%), 2.19g of ethylenediamine and 6.01g of cyclohexylamine are added into 30g of deionized water, mixed and stirred uniformly to form a solution B. Then, the solution A and the solution B are mixed and stirred for 1h to form white gel. The formed gel was transferred to a 170ml Teflon reaction vessel, dynamically rotated at a rotation speed of 20r/min, and crystallized at 150 ℃ for 4 days. The obtained sample is washed, dried at 120 ℃ and roasted at 550 ℃ for 6 hours to obtain the pure SUZ-4 molecular sieve with the crystallinity of 98 percent, and the Si/Al content is 15.6 measured by an X-ray fluorescence spectrum analyzer. The XRD spectrum of the sample obtained in this example is shown in FIG. 2. FIG. 3 shows an SEM image of a sample obtained in this example.
Initial gel molar composition: 33.3SiO2:Al2O3:14.7KOH:6EDA:10CHA:798H2O
Example 3
A solution A was prepared by adding 37.96g of deionized water to 2.48g of aluminum isopropoxide and 5.82g of KOH (85%), and stirring for 0.5h to completely dissolve the aluminum source. 30.01g of silica sol (40%), 1.82g of ethylenediamine and 6.01g of cyclohexylamine are added into 30g of deionized water, mixed and stirred uniformly to form a solution B. Then, the solution A and the solution B are mixed and stirred for 1h to form white gel. The formed gel was transferred to a 170ml Teflon reaction vessel, dynamically rotated at a rotation speed of 20r/min, and crystallized at 150 ℃ for 4 days. The sample was washed, dried at 120 ℃ and calcined at 550 ℃ for 6 hours, and the spectrum of the sample for this experiment was identical to that of example 2 except that the degree of crystallinity was 80%.
Initial gel molar composition: 33.3SiO2:Al2O3:14.7KOH:5EDA:10CHA:798H2O
Example 4
A solution A was prepared by adding 37.96g of deionized water to 2.48g of aluminum isopropoxide and 5.82g of KOH (85%), and stirring for 0.5h to completely dissolve the aluminum source. 30.01g of silica sol (40%), 1.09g of ethylenediamine and 6.01g of cyclohexylamine were added to 30g of deionized water, and mixed and stirred uniformly to form a solution B. Then, the solution A and the solution B are mixed and stirred for 1h to form white gel. The formed gel was transferred to a 170ml Teflon reaction vessel, dynamically rotated at a rotation speed of 20r/min, and crystallized at 150 ℃ for 4 days. The sample was washed, dried at 120 ℃ and calcined at 550 ℃ for 6 hours, and the spectrum of the sample for this experiment was the same as that of example 2 except that the crystallinity was 74%.
Initial gel molar composition: 33.3SiO2:Al2O3:14.7KOH:3EDA:10CHA:798H2O
Example 5
A solution A was prepared by adding 37.96g of deionized water to 2.48g of aluminum isopropoxide and 5.82g of KOH (85%), and stirring for 0.5h to completely dissolve the aluminum source. 30.01g of silica sol (40%), 3.28g of ethylenediamine and 6.01g of cyclohexylamine are added into 30g of deionized water, mixed and stirred uniformly to form a solution B. Then, the solution A and the solution B are mixed and stirred for 1h to form white gel. The formed gel was transferred to a 170ml Teflon reaction vessel, dynamically rotated at a rotation speed of 20r/min, and crystallized at 150 ℃ for 4 days. The obtained sample is washed, dried at 120 ℃ and roasted at 550 ℃ for 6 hours, and the characteristic peak of the sample begins to transform MOR. The XRD spectrum of the sample obtained in this example is shown in FIG. 4. Initial gel molar composition: 33.3SiO2:Al2O3:14.7KOH:9EDA:10CHA:798H2O
Example 6
A solution A was prepared by adding 37.96g of deionized water to 2.48g of aluminum isopropoxide and 5.82g of KOH (85%), and stirring for 0.5h to completely dissolve the aluminum source. 30.01g of silica sol (40%), 3.64g of ethylenediamine and 6.01g of cyclohexylamine are added into 30g of deionized water, mixed and stirred uniformly to form a solution B. Then, the solution A and the solution B are mixed and stirred for 1h to form white gel. The formed gel was transferred to a 170ml Teflon reaction vessel, dynamically rotated at a rotation speed of 20r/min, and crystallized at 150 ℃ for 4 days. The sample was washed, dried at 120 ℃ and calcined at 550 ℃ for 6h, and the spectrum of the sample for this experiment was identical to that of example 5.
Initial gel molar composition: 33.3SiO2:Al2O3:14.7KOH:10EDA:10CHA:798H2O
Example 7
A solution A was prepared by adding 37.96g of deionized water to 2.48g of aluminum isopropoxide and 5.82g of KOH (85%), and stirring for 0.5h to completely dissolve the aluminum source. 30.01g of silica sol (40%) and 3.64g of ethylenediamine were added to 30g of deionized water, and the mixture was stirred to form a solution B. Then, the solution A and the solution B are mixed and stirred for 1h to form white gel. The formed gel was transferred to a 170ml Teflon reaction vessel, dynamically rotated at a rotation speed of 20r/min, and crystallized at 150 ℃ for 4 days. And washing the obtained sample, drying at 120 ℃, and roasting at 550 ℃ for 6h to obtain the pure SUZ-4 molecular sieve. The characteristic peaks of the samples are in the MFI series. Figure 5 shows the XRD spectrum of the sample obtained in this example.
Initial gel molar composition: 33.3SiO2:Al2O3:14.7KOH:10EDA:0CHA:798H2O
Example 8
A solution A was prepared by adding 37.96g of deionized water to 2.48g of aluminum isopropoxide and 5.82g of KOH (85%), and stirring for 0.5h to completely dissolve the aluminum source. 30.01g of silica sol (40%) and 6.01g of cyclohexylamine were added to 30g of deionized water, mixed and stirred uniformly to form a solution B. Then, the solution A and the solution B are mixed and stirred for 1h to form white gel. The formed gel was transferred to a 170ml Teflon reaction vessel, dynamically rotated at a rotation speed of 20r/min, and crystallized at 150 ℃ for 4 days. The resulting sample was washed, dried at 120 ℃ and calcined at 550 ℃ for 6h to give the pure MFI spectrum as in example 7.
Initial gel molar composition: 33.3SiO2:Al2O3:14.7KOH:0EDA:10CHA:798H2O
Example 9
The procedure of example 2 was repeated except that the crystallization time was 3 days and the crystallinity of the synthesized SUZ-4 molecular sieve was 85%.
Example 10
The procedure of example 2 was repeated except that the crystallization time was 5 days and the crystallinity of the synthesized SUZ-4 molecular sieve was 100%.
Example 11
The procedure of example 2 was repeated except that the crystallization temperature was 130 deg.c and the crystallinity of the synthesized SUZ-4 molecular sieve was 79%.
Example 12
The procedure of example 2 was repeated except that the crystallization temperature was 140 deg.c and the crystallinity of the synthesized SUZ-4 molecular sieve was 86%.
Example 13
The procedure of example 2 was repeated except that the crystallization temperature was 160 deg.c and the result of synthesizing the sample was close to that of example 2 and the crystallinity was 100%.
Example 14
The procedure of example 2 was repeated except that the crystallization temperature was 170 deg.c and the crystallinity of the synthesized SUZ-4 molecular sieve was 88%.

Claims (5)

1. A synthesis method of a hedgehog shaped SUZ-4 molecular sieve is characterized by comprising the following steps: firstly, adding water into an aluminum source and KOH to mix into a solution a, and mixing a silicon source and a double template agent into a solution b; fully stirring the solution a and the solution b to obtain uniform silicon-aluminum mixed sol; adding template Ethylenediamine (EDA) and cyclic ethylamine (CHA) and mixing; then adding the mixture into a reaction kettle for high-temperature crystallization growth; wherein the crystallization temperature is as follows: the crystallization time is between 130 and 170 ℃, and is as follows: 2 to 5 days; finally obtaining the hedgehog shaped SUZ-4 molecular sieve;
the silicon-aluminum mixed glue solution comprises Al2O3、SiO2And KOH, wherein the initial molar ratio of the raw materials in the preparation method is as follows: al (Al)2O3:SiO2:KOH:EDA:CHA:H2O＝1：(15～30):(5～20)：(1～10)：(1～10)：(100～2500)。
2. The method of synthesis of claim 1, wherein: the aluminum source is one of aluminum powder, pseudo-boehmite, aluminum hydroxide, aluminum isopropoxide, aluminum nitrate and aluminum sulfate; the silicon source is one of silica sol, water glass and white carbon black.
3. The method of synthesis of claim 1, wherein: the crystallization temperature is 140-160 ℃, and the crystallization time is as follows: 3 to 5 days.
4. The method of synthesis of claim 1, further comprising the steps of: washing, drying and roasting the crystallized product; wherein the drying temperature is 120 ℃ and the time is 4 hours, and the roasting temperature is 550 ℃ and the time is 6 hours.
5. A hedgehog-shaped SUZ-4 molecular sieve, characterized in that: synthesized according to the method of any one of claims 1 to 4.
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CN102241407B (en) * 2011-04-29 2013-04-17 大连理工大学 Preparation method of SUZ-4 molecular sieve
CN107285340A (en) * 2017-08-02 2017-10-24 南京大学连云港高新技术研究院 A kind of preparation method of the zeolite molecular sieves of SUZ 4
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