CN113149025B - Spherical LTJ zeolite, and preparation method and application thereof - Google Patents
Spherical LTJ zeolite, and preparation method and application thereof Download PDFInfo
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- 239000010457 zeolite Substances 0.000 title claims abstract description 72
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 32
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 25
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 24
- 239000012065 filter cake Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000011541 reaction mixture Substances 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 238000006482 condensation reaction Methods 0.000 abstract description 11
- KCDAMWRCUXGACP-UHFFFAOYSA-N ethyl 2-cyano-3-phenylprop-2-enoate Chemical compound CCOC(=O)C(C#N)=CC1=CC=CC=C1 KCDAMWRCUXGACP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KCDAMWRCUXGACP-DHZHZOJOSA-N ethyl (e)-2-cyano-3-phenylprop-2-enoate Chemical compound CCOC(=O)C(\C#N)=C\C1=CC=CC=C1 KCDAMWRCUXGACP-DHZHZOJOSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a spherical LTJ zeolite, a preparation method and application thereof, belonging to the technical field of zeolite materials and comprising the following steps: preparing a silicon-aluminum gel mixture by taking an aluminum source, alkali and a silicon source as raw materials; crystallizing the silicon-aluminum gel mixture at 40-60 ℃ in a sealed environment through hydrothermal reaction to prepare spherical LTJ zeolite; the preparation method has the advantages of low crystallization temperature, short time and simple operation steps, and the synthesized LTJ zeolite particles have the particle size of 0.2-0.4 mu m and spherical appearance; the application of the spherical LTJ zeolite in catalyzing condensation reaction of benzaldehyde and ethyl cyanoacetate, wherein the benzaldehyde conversion rate is 91.8%, and the selectivity of alpha-ethyl cyanocinnamate is 100%, so that the spherical LTJ zeolite has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of zeolite materials, and particularly relates to spherical LTJ zeolite as well as a preparation method and application thereof.
Background
Zeolite is a kind of inorganic crystal with regular and uniform pore channel structure, and its basic structural unit of skeleton is TO 4 Tetrahedra (T = Si, al, etc.), T atoms are interconnected by oxygen bridges to form a structure having specific micropores or cages. Due to their unique pore size and shape, large specific surface area, high hydrothermal stability, and tunable acidity, zeolites are widely used as catalysts, ion exchangers, adsorbents, and novel functional materials. In recent years, with the development of science and technology, the application of zeolite in some emerging industries, such as biomedicine, electronics and sensor technology, is gradually developed. Therefore, the preparation and application of zeolite materials have become one of the current research hotspots.
An increasing number of zeolites have been synthesized and used in various areas of life, however, there are few reports on the preparation and use of LTJ zeolites, a member of the zeolite family. Therefore, in order to further expand the application range of zeolite, it is necessary to find a low-cost, fast and convenient preparation method of LTJ zeolite, which lays a foundation for the application of LTJ zeolite.
Disclosure of Invention
In order to solve the problems, the invention provides spherical LTJ zeolite and a preparation method and application thereof.
The invention is realized by the following technical scheme:
the first object of the present invention is to provide a method for preparing spherical LTJ zeolite, comprising the steps of:
(1) Preparing a silicon-aluminum gel mixture by taking an aluminum source, alkali and a silicon source as raw materials;
(2) And crystallizing the silicon-aluminum gel mixture in a sealed environment at 40-60 ℃ through hydrothermal reaction to obtain the spherical LTJ zeolite.
Preferably, in the step (1), the specific preparation process of the silicon-aluminum gel mixture comprises the following steps:
dissolving alkali and an aluminum source in water to prepare a solution A; slowly adding a silicon source into the solution A under stirring to form a silica-alumina gel mixture.
Preferably, in step (1), the base is potassium hydroxide.
Preferably, in step (1), the aluminum source is sodium aluminate, aluminum hydroxide or aluminum sulfate.
Preferably, in step (1), the silicon source is silica sol, siO thereof 2 The mass fraction is 30%.
Preferably, in the step (1), the silicon source amount of the chemical component of the silicon-aluminum gel mixture is SiO 2 Calculated by Al, the aluminum source is calculated as 2 O 3 Calculated by K, the amount of alkali used 2 O is SiO in the silicon-aluminum gel mixture 2 :Al 2 O 3 :K 2 O:H 2 The molar ratio of O is 4.8-12.4.
Preferably, in the step (2), the crystallization time is 8 to 14 hours.
Preferably, in the step (2), the crystallized reaction mixture is filtered, and the filter cake is washed by deionized water until the pH value of the washing solution is 8-9; the filter cake was dried at 100 ℃ for 24h.
It is a second object of the present invention to provide spherical LTJ zeolite prepared by the above preparation method.
The third purpose of the invention is to provide the application of the spherical LTJ zeolite in catalyzing the Knoevenagel condensation reaction of benzaldehyde and ethyl cyanoacetate.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a preparation method of spherical LTJ zeolite, which comprises the steps of preparing a silicon-aluminum gel mixture by taking an aluminum source, a silicon source and alkali as raw materials, and preparing the LTJ zeolite successfully by carrying out hydrothermal reaction on the silicon-aluminum gel mixture at the low temperature of 40-60 ℃, wherein the preparation method has the advantages of short time and simple operation steps, and the particle size of the synthesized LTJ zeolite is 0.2-0.4 mu m and has a spherical shape;
(2) The spherical LTJ zeolite prepared by the method can be applied to catalyzing condensation reaction of benzaldehyde and ethyl cyanoacetate, the conversion rate of the benzaldehyde is 91.8%, the selectivity of the product alpha-ethyl cyanocinnamate is 100%, and the spherical LTJ zeolite has a good application prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern of LTJ zeolite powder obtained in example 1;
fig. 2 is a scanning electron micrograph of LTJ zeolite powder obtained in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.
The following experimental methods and detection methods, unless otherwise specified, are all conventional methods; the following reagents and starting materials were all commercially available unless otherwise specified.
Example 1
A preparation method of spherical LTJ zeolite comprises the following steps:
(1) Weighing 22.68g of potassium hydroxide and 1.64g of sodium aluminate, adding the potassium hydroxide and the sodium aluminate into a beaker, adding 68.82g of deionized water, heating and stirring to completely dissolve the raw materials to prepare a solution A;
(2) Weighing 15.02g of silica sol, slowly adding the silica sol into the solution A under stirring, and continuously stirring for 20min after the addition is finished to form a silicon-aluminum gel mixture;
(3) Transferring the silicon-aluminum gel mixture to a stainless steel synthesis kettle with a polytetrafluoroethylene lining, sealing, placing in an oven, setting the temperature of the oven to be 40 ℃, and crystallizing for 8 hours;
(4) After the reaction is finished, taking out the synthesis kettle, carrying out suction filtration on the reaction mixture, and washing the filter cake with deionized water until the pH value of the washing solution is 8; and drying the filter cake at 100 ℃ for 24h to obtain the spherical LTJ zeolite.
The spherical LTJ zeolite prepared by the embodiment is used for catalyzing the condensation reaction of benzaldehyde and ethyl cyanoacetate, and has high activity. 0.22g of spherical LTJ zeolite prepared in the example, 11mmol of benzaldehyde and 11mmol of ethyl cyanoacetate are added into a high-pressure reaction kettle, and then the mixture is stirred and heated to 80 ℃ to react for 2 hours. Stopping heating and stirring, cooling the reaction kettle to room temperature, centrifugally separating the catalyst, and measuring the composition of the filtrate by using a gas chromatograph. The conversion rate of benzaldehyde was 91.8%, and the selectivity of ethyl alpha-cyanocinnamate was 100%.
Example 2
A preparation method of spherical LTJ zeolite comprises the following steps:
(1) Weighing 20.98g of potassium hydroxide and 1.64g of sodium aluminate, adding the potassium hydroxide and the sodium aluminate into a beaker, adding 62.88g of deionized water, heating and stirring to completely dissolve the raw materials to prepare a solution A;
(2) Weighing 13.82g of silica sol, slowly adding the silica sol into the solution A under stirring, and continuously stirring for 20min after the addition is finished to form a silicon-aluminum gel mixture;
(3) Transferring the silicon-aluminum gel mixture to a stainless steel synthesis kettle with a polytetrafluoroethylene lining, sealing, placing in an oven, setting the temperature of the oven to be 40 ℃, and crystallizing for 14 hours;
(4) After the reaction is finished, taking out the synthesis kettle, carrying out suction filtration on the reaction mixture, and washing the filter cake with deionized water until the pH value of the washing solution is 9; and drying the filter cake at 100 ℃ for 24h to obtain the spherical LTJ zeolite.
The spherical LTJ zeolite prepared by the embodiment is used for catalyzing the condensation reaction of benzaldehyde and ethyl cyanoacetate, and has high activity. The reaction conditions and steps are the same as those in example 1, the conversion rate of the corresponding benzaldehyde is 91.4%, and the selectivity of the alpha-ethyl cyanocinnamate is 100%.
Example 3
A preparation method of spherical LTJ zeolite comprises the following steps:
(1) Weighing 20.68g of potassium hydroxide and 1.20g of aluminum hydroxide, adding the potassium hydroxide and the aluminum hydroxide into a beaker, adding 65.83g of deionized water, heating and stirring to completely dissolve the raw materials to prepare a solution A;
(2) Weighing 15.62g of silica sol, slowly adding the silica sol into the solution A under stirring, and continuously stirring for 20min after the addition is finished to form a silicon-aluminum gel mixture;
(3) Transferring the silicon-aluminum gel mixture to a stainless steel synthesis kettle with a polytetrafluoroethylene lining, sealing, placing in an oven, setting the temperature of the oven to be 40 ℃, and crystallizing for 8 hours;
(4) After the reaction is finished, taking out the synthesis kettle, carrying out suction filtration on the reaction mixture, and washing the filter cake with deionized water until the pH value of the washing solution is 9; and drying the filter cake at 100 ℃ for 24 hours to obtain the spherical LTJ zeolite.
The spherical LTJ zeolite prepared by the embodiment is used for catalyzing the condensation reaction of benzaldehyde and ethyl cyanoacetate, and has high activity. The reaction conditions and steps are the same as those in example 1, the conversion rate of the corresponding benzaldehyde is 91.5%, and the selectivity of the alpha-ethyl cyanocinnamate is 100%.
Example 4
A preparation method of spherical LTJ zeolite comprises the following steps:
(1) Weighing 22.62g of potassium hydroxide and 1.52g of aluminum hydroxide, adding the potassium hydroxide and the aluminum hydroxide into a beaker, adding 75.83g of deionized water, heating and stirring to completely dissolve the raw materials to prepare a solution A;
(2) Weighing 13.60g of silica sol, slowly adding the silica sol into the solution A under stirring, and continuously stirring for 20min after the addition is finished to form a silicon-aluminum gel mixture;
(3) Transferring the silicon-aluminum gel mixture to a stainless steel synthesis kettle with a polytetrafluoroethylene lining, sealing, placing in a drying oven, setting the temperature of the drying oven to be 40 ℃, and crystallizing for 14 hours;
(4) After the reaction is finished, taking out the synthesis kettle, carrying out suction filtration on the reaction mixture, and washing the filter cake with deionized water until the pH value of the washing solution is 8; and drying the filter cake at 100 ℃ for 24 hours to obtain the spherical LTJ zeolite.
The spherical LTJ zeolite prepared by the embodiment is used for catalyzing the condensation reaction of benzaldehyde and ethyl cyanoacetate, and has high activity. The reaction conditions and steps are the same as those in example 1, the conversion rate of the corresponding benzaldehyde is 91.6%, and the selectivity of the alpha-ethyl cyanocinnamate is 100%.
Example 5
A preparation method of spherical LTJ zeolite comprises the following steps:
(1) Weighing 23.78g of potassium hydroxide and 1.48g of aluminum hydroxide, adding the potassium hydroxide and the aluminum hydroxide into a beaker, adding 68.83g of deionized water, heating and stirring to completely dissolve the raw materials to prepare a solution A;
(2) Weighing 14.68g of silica sol, slowly adding the silica sol into the solution A under stirring, and continuously stirring for 20min after the addition is finished to form a silicon-aluminum gel mixture;
(3) Transferring the silicon-aluminum gel mixture to a stainless steel synthesis kettle with a polytetrafluoroethylene lining, sealing, placing in a drying oven, setting the temperature of the drying oven to be 60 ℃, and crystallizing for 8 hours;
(4) After the reaction is finished, taking out the synthesis kettle, carrying out suction filtration on the reaction mixture, and washing the filter cake with deionized water until the pH value of the washing solution is 9; and drying the filter cake at 100 ℃ for 24h to obtain the spherical LTJ zeolite.
The spherical LTJ zeolite prepared by the embodiment is used for catalyzing the condensation reaction of benzaldehyde and ethyl cyanoacetate, and has high activity. The reaction conditions and steps are the same as those in example 1, the conversion rate of the corresponding benzaldehyde is 91.2%, and the selectivity of the alpha-ethyl cyanocinnamate is 100%.
Example 6
A method for preparing spherical LTJ zeolite comprises the following steps:
(1) Weighing 23.68g of potassium hydroxide and 3.40g of aluminum sulfate, adding the potassium hydroxide and the aluminum sulfate into a beaker, adding 79.85g of deionized water, heating and stirring to completely dissolve the raw materials to prepare a solution A;
(2) Weighing 18.80g of silica sol, slowly adding the silica sol into the solution A under stirring, and continuously stirring for 20min after the addition is finished to form a silicon-aluminum gel mixture;
(3) Transferring the silicon-aluminum gel mixture to a stainless steel synthesis kettle with a polytetrafluoroethylene lining, sealing, placing in a drying oven, setting the temperature of the drying oven to be 40 ℃, and crystallizing for 8 hours;
(4) After the reaction is finished, taking out the synthesis kettle, carrying out suction filtration on the reaction mixture, and washing the filter cake with deionized water until the pH value of the washing solution is 8; and drying the filter cake at 100 ℃ for 24h to obtain the spherical LTJ zeolite.
The spherical LTJ zeolite prepared by the embodiment is used for catalyzing the condensation reaction of benzaldehyde and ethyl cyanoacetate, and has high activity. The reaction conditions and steps are the same as those in example 1, the conversion rate of the corresponding benzaldehyde is 91.2%, and the selectivity of the alpha-ethyl cyanocinnamate is 100%.
Example 7
A preparation method of spherical LTJ zeolite comprises the following steps:
(1) Weighing 28.08g of potassium hydroxide and 4.05g of aluminum sulfate, adding the potassium hydroxide and the aluminum sulfate into a beaker, adding 80.62g of deionized water, heating and stirring to completely dissolve the raw materials to prepare a solution A;
(2) Weighing 20.65g of silica sol, slowly adding the silica sol into the solution A under stirring, and continuously stirring for 20min after the addition is finished to form a silicon-aluminum gel mixture;
(3) Transferring the silicon-aluminum gel mixture to a stainless steel synthesis kettle with a polytetrafluoroethylene lining, sealing, placing in an oven, setting the temperature of the oven to be 60 ℃, and crystallizing for 8 hours;
(4) After the reaction is finished, taking out the synthesis kettle, carrying out suction filtration on the reaction mixture, and washing the filter cake with deionized water until the pH value of the washing solution is 9; and drying the filter cake at 100 ℃ for 24 hours to obtain the spherical LTJ zeolite.
The spherical LTJ zeolite prepared by the embodiment is used for catalyzing the condensation reaction of benzaldehyde and ethyl cyanoacetate, and has high activity. The reaction conditions and steps are the same as those in example 1, the conversion rate of the corresponding benzaldehyde is 90.9%, and the selectivity of the alpha-ethyl cyanocinnamate is 100%.
The LTJ zeolite prepared in examples 1 to 7 was similar to that prepared in example 1, and the structure was identified, wherein fig. 1 is an X-ray diffraction (XRD) spectrum of the LTJ zeolite powder obtained in example 1. As can be seen from figure 1, XRD characteristic peaks correspond to standard cards of LTJ zeolite one by one, and the synthesized product can be determined to be LTJ zeolite. The synthesized sample LTJ zeolite has good crystallinity, almost no impurity peak and high purity.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the LTJ zeolite powder obtained in example 1, and it can be seen from FIG. 2 that the LTJ zeolite particles have a spherical morphology and a particle size of 0.2 to 0.4. Mu.m.
By combining the above embodiments, the prepared spherical LTJ zeolite is used for catalyzing the condensation reaction between benzaldehyde and ethyl cyanoacetate (the conversion rate of benzaldehyde can be as high as 91.8%, and the selectivity of alpha-ethyl cyanocinnamate is 100%), so that the spherical LTJ zeolite is successfully prepared, the preparation method has the advantages of low crystallization temperature (40-60 ℃), short time, simple operation steps, and spherical morphology, wherein the particle size of the synthesized LTJ zeolite particles is 0.2-0.4 μm; the prepared spherical LTJ zeolite is applied to the condensation reaction of benzaldehyde and ethyl cyanoacetate, the benzaldehyde conversion rate can reach 91.8%, the selectivity of alpha-ethyl cyanocinnamate is 100%, and the spherical LTJ zeolite has a good application prospect.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the present invention as set forth in the appended claims and their equivalents.
Claims (7)
1. A preparation method of spherical LTJ zeolite is characterized by comprising the following steps:
(1) Preparing a silicon-aluminum gel mixture by taking an aluminum source, alkali and a silicon source as raw materials;
the chemical components of the silicon-aluminum gel mixture comprise silicon source in SiO 2 Calculated by Al, the aluminum source is calculated as 2 O 3 Calculated by K, the amount of alkali used 2 O is SiO in the silicon-aluminum gel mixture 2 :Al 2 O 3 :K 2 O:H 2 The molar ratio of O is 4.8-12.4;
the silicon source is silica sol and SiO thereof 2 The mass fraction is 30%;
(2) Crystallizing the silicon-aluminum gel mixture in a sealed environment at 40-60 ℃ through hydrothermal reaction to prepare spherical LTJ zeolite;
the crystallization time is 8 to 14 hours; the LTJ zeolite has a particle size of 0.2-0.4 μm and a spherical shape.
2. The method for preparing spherical LTJ zeolite according to claim 1, wherein in the step (1), the specific preparation process of the silicon-aluminum gel mixture comprises the following steps:
dissolving alkali and an aluminum source in water to prepare a solution A; slowly adding a silicon source into the solution A under stirring to form a silica-alumina gel mixture.
3. The method for preparing spherical LTJ zeolite as claimed in claim 1 or 2, wherein in the step (1), the base is potassium hydroxide.
4. The method for preparing spherical LTJ zeolite as claimed in claim 1 or 2, wherein in the step (1), the aluminum source is sodium aluminate, aluminum hydroxide or aluminum sulfate.
5. The method for preparing spherical LTJ zeolite according to claim 1, wherein in the step (2), the crystallized reaction mixture is filtered, and the filter cake is washed with deionized water until the pH of the washing solution is 8-9; the filter cake was dried at 100 ℃ for 24h.
6. Spherical LTJ zeolite obtained by the process according to claim 1.
7. Use of the spherical LTJ zeolite according to claim 6 for catalyzing the Knoevenagel condensation reaction of benzaldehyde with ethyl cyanoacetate.
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| CN1316977A (en) * | 1998-09-10 | 2001-10-10 | B·F·谷德里奇公司 | Zeolites and method of making thereof |
| CN107601525A (en) * | 2017-10-11 | 2018-01-19 | 许昌学院 | A kind of preparation method and applications of double hemispherical W zeolites |
| CN107922206A (en) * | 2015-09-01 | 2018-04-17 | 东曹株式会社 | The manufacture method of AEI type zeolites |
| EP3449999A1 (en) * | 2017-08-31 | 2019-03-06 | Umicore Ag & Co. Kg | Passive nitric oxide adsorber |
| CN111943221A (en) * | 2020-08-27 | 2020-11-17 | 许昌学院 | K-F type zeolite, preparation method thereof and application thereof in aldol condensation reaction |
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| CN1316977A (en) * | 1998-09-10 | 2001-10-10 | B·F·谷德里奇公司 | Zeolites and method of making thereof |
| CN107922206A (en) * | 2015-09-01 | 2018-04-17 | 东曹株式会社 | The manufacture method of AEI type zeolites |
| EP3449999A1 (en) * | 2017-08-31 | 2019-03-06 | Umicore Ag & Co. Kg | Passive nitric oxide adsorber |
| CN107601525A (en) * | 2017-10-11 | 2018-01-19 | 许昌学院 | A kind of preparation method and applications of double hemispherical W zeolites |
| CN111943221A (en) * | 2020-08-27 | 2020-11-17 | 许昌学院 | K-F type zeolite, preparation method thereof and application thereof in aldol condensation reaction |
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