CN112517053A - Preparation method of high-performance supported catalytic filler - Google Patents
Preparation method of high-performance supported catalytic filler Download PDFInfo
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- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
The invention provides a method for preparing a high-performance catalytic filler by coating Polydopamine (PDA) auxiliary seed crystals, belonging to the technical field of catalytic rectification. The invention prepares the catalytic filler taking the molecular sieve as the active component by a secondary growth method, obtains a polydopamine transition layer on the surface of the filler by utilizing the property that PDA can be adhered to the surface of an organic or inorganic material, further prepares a seed crystal layer which is completely covered and firmly loaded on the surface of the filler, and finally prepares the high-performance load type catalytic filler by a hydrothermal method. The method is suitable for preparing the molecular sieve active film layer on the surfaces of various fillers, can overcome the problem of uneven distribution of the seed crystals by the dipping-coating method, obtains the high-performance load type catalytic filler, is simple to operate, and is suitable for industrial application.
Description
The technical field is as follows:
the invention belongs to the technical field of catalytic rectification, and particularly relates to a preparation method of a high-performance supported catalytic filler.
Background art:
the catalytic rectification technology is taken as a model for successful application of a process strengthening concept in chemical industry, can well meet the requirements of process strengthening and green chemical industry, has lower energy consumption and volume occupation compared with conventional operation, and draws wide attention of people. The realization of the technology mainly depends on the catalytic packing which couples the chemical reaction and the rectification separation in the same equipment, and the type and the structure of the catalytic packing influence the mixed contact mode of vapor, liquid and solid phases at the reaction section of the catalytic rectification tower so as to influence the reaction and the separation process and finally influence the reaction conversion rate and the process energy consumption.
At present, the most industrially applied is the filled catalytic filler, which means that solid catalyst particles are filled into small bags of a wire mesh or a glass wire mesh and then compounded with a stainless steel wire mesh to prepare the catalytic filler. The filling type catalytic filler is a liquid-solid and vapor-liquid contact type structure, a liquid phase contacts with a solid catalyst and a gas phase respectively to generate catalytic reaction and mass transfer separation, and the reaction and the separation are alternately carried out in a tower. Although the filled catalytic filler has the advantages of simple manufacture, large amount of catalyst in unit volume and the like, the filled catalytic filler is essentially in a catalytic filler form which realizes high catalytic activity at the cost of sacrificing a mass transfer wall surface, and in the catalytic rectification process, the catalytic reaction process generated in the filled catalytic filler is greatly influenced by mass transfer, so that a catalyst layer cannot be fully utilized. Therefore, how to improve the vapor-liquid mass transfer of the reaction section in the catalytic distillation tower and reduce the pressure drop in the tower becomes a research hotspot in the technical field of catalytic distillation.
Supported catalytic fillers are an effective solution to the above problems. The surface-loaded molecular sieve catalytic filler has the characteristics of pressure reduction, high mass transfer efficiency and the like, can realize the high-efficiency integrated coupling of catalysis and rectification, improves the vapor-liquid mass transfer in the catalytic rectification tower, and effectively reduces the pressure drop in the tower. Chinese patent CN01110335.3 discloses a preparation method of a regular corrugated packing supported beta molecular sieve membrane catalyst for etherification, which comprises the following steps: the beta molecular sieve membrane catalytic filler is prepared on the surface of the filler by a hydrothermal synthesis method by taking a ceramic regular filler as the filler. Chinese patent CN 101003001A discloses a preparation method of an aluminum filler loaded molecular sieve membrane layer: and treating the filler as an aluminum source in the synthesis process of the molecular sieve membrane by using the aluminum or aluminum alloy filler as a carrier. However, the conventional supported catalytic packing has a common problem that the supported catalytic packing has a small catalyst supporting amount and is easy to fall off, and thus the supported catalytic packing is difficult to apply to an industrial catalytic rectifying tower.
The invention content is as follows:
the invention provides a method for preparing high-performance catalytic filler by coating PDA auxiliary crystal seeds, which can uniformly and fully load the crystal seeds with different particle sizes on the surfaces of various fillers, further obtain a high-performance molecular sieve membrane layer by a secondary growth method, and has strong universality and practicability.
In order to realize the scheme, the invention adopts the following technical scheme:
a method for preparing a high-performance supported catalytic filler is characterized by comprising the following specific steps:
(1) pretreatment of the filler: ultrasonically removing oil stains on the surface of the filler by using alkali liquor and ethanol, placing the filler into a conical flask filled with prepared buffer solution, simultaneously adding a certain mass of dopamine hydrochloride, placing the conical flask into a constant-temperature shaking bed, and shaking for a certain time to polymerize dopamine on the surface of the filler to form a polydopamine coating, thereby obtaining a pretreated filler;
(2) seed crystal coating: adding a molecular sieve serving as a seed crystal into a conical flask filled with a prepared buffer solution, obtaining a uniformly dispersed molecular sieve seed crystal suspension under an ultrasonic condition, placing the filler pretreated in the step (1) into the seed crystal suspension, vibrating at a constant temperature for a certain time to uniformly and fully adhere the seed crystal to the surface of the filler, taking out the filler coated with the seed crystal, soaking the filler in ultrapure water, drying in a blast drying oven, and roasting in a muffle furnace at 250-400 ℃ for 2-6 h to solidify the seed crystal layer;
(3) preparing a catalytic filler: and (3) putting the filler precoated with the seed crystal in the step (2) into a crystallization kettle with a polytetrafluoroethylene lining, adding a prepared secondary growth liquid, sealing the crystallization kettle, moving the crystallization kettle into a drying box for high-temperature crystallization for a certain time, taking out the crystallization kettle, ultrasonically cleaning the crystallized filler with ultrapure water, drying the filler, and then putting the filler into a muffle furnace for high-temperature roasting to obtain the catalytic filler.
Preferably, the packing used in step (1) includes, but is not limited to, stainless steel, ceramic structured packing and random packing.
Preferably, the buffer solution is tris-hcl buffer solution, and the pH of the buffer solution is 8.5 at 25 ℃.
Preferably, the concentration of the dopamine solution in the step (1) is 0.1-5 mg/mL, the shaking temperature is 25 ℃, and the shaking time is 6-24 h.
Preferably, the grain size of the seed crystal in the step (2) is 80-1000 nm, and the concentration of the seed crystal suspension is 0.5-5 wt%.
Preferably, in the step (2), the shaking temperature of the filler in the seed crystal suspension is 25 ℃, and the shaking time is 5-360 min.
Preferably, the secondary growth liquid comprises a composition of 4TPAOH:25SiO2:xAl2O3:1750H2The value of x of the ZSM-5 synthetic liquid of O with different silicon-aluminum ratios is determined according to the silicon-aluminum ratio of the molecular sieve, the crystallization temperature is 120-180 ℃, the crystallization time is 24-72 hours, the roasting temperature is 550 ℃, and the roasting time is 4-10 hours.
The invention has the beneficial effects that: according to the invention, by utilizing the characteristic that PDA can be adhered to the surfaces of various organic or inorganic materials under a weakly alkaline condition, a polydopamine transition layer is obtained on the surface of the filler, a seed crystal layer which is completely covered and firmly loaded is further prepared on the surface of the filler, and finally, the high-performance loaded catalytic filler is prepared by a hydrothermal method. The invention effectively solves the problems that the molecular sieve membrane layer is easy to fall off and the catalytic activity is low because the crystal seeds are influenced by gravity and are unevenly distributed on the surface of the filler in the preparation process of the catalytic filler taking the molecular sieve as the active component. In addition, the prepared high-performance catalytic filler can realize the high-efficiency coupling of reaction and separation in the catalytic distillation process, and has strong competitiveness. The catalytic filler prepared by the invention obtains better effect in the reaction of preparing cyclohexyl acetate by adding acetic acid and cyclohexene.
Drawings
FIG. 1 is a schematic flow chart of PDA-assisted seed coating for preparing catalytic packing;
FIG. 2 is a scanning electron micrograph of catalytic filler obtained by PDA assisted seed coating;
fig. 3 is a scanning electron micrograph of the catalytic filler obtained by dip-coating.
Detailed Description
In order to facilitate understanding of the method proposed by the present invention, the method for preparing the catalytic filler proposed by the present invention is further illustrated by the following examples in conjunction with the accompanying drawings. It is clear that the examples are only intended to illustrate the process proposed by the invention, not all examples, and that the present protection is not restricted to the following examples.
Example 1
The method provided by the invention is adopted to prepare the catalytic filler through the following steps:
(1) pretreatment of the filler: ultrasonically removing surface oil stains from a stainless steel theta ring filler with the specification of 3 multiplied by 3 by using alkali liquor and ethanol, placing the stainless steel theta ring filler into a conical flask containing a Tris (hydroxymethyl) aminomethane-hydrochloric acid (Tris-HCl) buffer solution with the pH value of 8.5 at 25 ℃, simultaneously adding dopamine hydrochloride to ensure that the concentration of the dopamine solution is 2 mg/mL, and oscillating the dopamine solution for 24 hours at 25 ℃ to ensure that dopamine is polymerized on the surface of the theta ring to form a polydopamine coating, thus obtaining the pretreated filler;
(2) seed crystal coating: adding 3 g of all-silicon Silicalite-1 molecular sieve with the diameter of 100 nm serving as seed crystal into a conical flask containing 100 mL of Tris-HCl buffer solution, obtaining uniformly dispersed 3 wt% seed crystal suspension under the ultrasonic condition, placing the pretreated filler into the seed crystal suspension, oscillating for 60 min at 25 ℃, uniformly and fully adhering the seed crystal to the surface of the filler, taking out the filler coated with the seed crystal, soaking and washing the filler with ultrapure water, drying, and then placing in a muffle furnace, roasting for 6 h at 250 ℃ to solidify the seed crystal layer;
(3) preparing a catalytic filler: 10 g of the above-mentioned pre-seeded filler was placed in a 100 mL crystallization vessel and added with a pre-prepared composition of 4TPAOH:25SiO2:0.3125Al2O3:1750H2And (3) sealing the crystallization kettle, then transferring the sealed crystallization kettle into a blast drying oven, crystallizing at 175 ℃ for 72 hours, taking out, ultrasonically cleaning the crystallized filler with ultrapure water, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the catalytic filler. The scanning electron microscope image obtained is shown in FIG. 2, and it can be seen from the image that HZSM-5 molecular sieve is successfully loaded on the surface of the filler. In addition, it can be seen that the molecular sieve completely covered the filler surface and had a rough surface with intergranular voids.
The activity of the prepared catalytic filler was tested in an autoclave by addition reaction of cyclohexene and acetic acid as probes. 20 g of different types of catalytic fillers, 3.84 g of cyclohexene and 14.12 g of acetic acid are added into a 50 ml high-pressure reaction kettle, the mixture is sealed and then reacts for 4 hours at 120 ℃, and after the test is finished, the high-pressure reaction kettle is quenched by an ice-water mixture, so that the reaction is stopped in time and the cyclohexene is prevented from volatilizing due to high temperature. The reaction product is separated from the catalytic filler and then analyzed by gas chromatography, and the yield of the cyclohexyl acetate product is about 9 percent.
Comparative example 1
The catalytic filler is prepared by adopting a traditional etching method through the following steps:
(1) pretreatment of the filler: ultrasonically removing surface oil stains from a stainless steel theta ring filler with the specification of 3 multiplied by 3 by using alkali liquor and ethanol, placing the stainless steel theta ring filler into a conical flask containing concentrated hydrochloric acid, oscillating the stainless steel theta ring filler for 30 min at the temperature of 25 ℃ for etching, cleaning the etched filler with ultrapure water, and then placing the cleaned filler into a blast drying oven for drying;
(2) seed crystal coating: adding 3 g of all-silicon Silicalite-1 molecular sieve with the diameter of 100 nm serving as a seed crystal into a conical flask filled with 100 mL of Tris-HCl buffer solution, obtaining a uniformly dispersed 3 wt% molecular sieve seed crystal suspension under an ultrasonic condition, immersing a theta ring filler subjected to etching treatment into the seed crystal suspension, taking out the filler after 5s, drying the filler, washing the filler with ultrapure water after repeating three times, drying, and roasting the washed filler in a muffle furnace at 250 ℃ for 6 h to solidify the seed crystal layer;
(3) preparing a catalytic filler: the same as in example 1. The scanning electron microscope image obtained is shown in FIG. 3, from which it can be seen that HZSM-5 molecular sieve is successfully loaded on the surface of the filler. But the prepared catalytic filler has the defects of smooth and compact surface, pinholes and the like.
The activity of the prepared catalytic filler was tested in an autoclave by addition reaction of cyclohexene and acetic acid as probes. 20 g of different types of catalytic fillers, 3.84 g of cyclohexene and 14.12 g of acetic acid are added into a 50 ml high-pressure reaction kettle, the mixture is sealed and then reacts for 4 hours at 120 ℃, and after the test is finished, the high-pressure reaction kettle is quenched by an ice-water mixture, so that the reaction is stopped in time and the cyclohexene is prevented from volatilizing due to high temperature. The reaction product is separated from the catalytic filler and then analyzed by gas chromatography, and the yield of the cyclohexyl acetate product is about 6 percent.
Example 2
The method provided by the invention is adopted to prepare the catalytic filler through the following steps:
(1) pretreatment of the filler: the difference from the embodiment 1 is that the selected filler is theta ring random packing with the specification of 2 multiplied by 3, and the rest steps are the same as the embodiment 1;
(2) seed crystal coating: the same as example 1;
(3) preparing a catalytic filler: the same as in example 1.
The activity of the prepared catalytic filler was tested in an autoclave by addition reaction of cyclohexene and acetic acid as probes. 20 g of different types of catalytic fillers, 3.84 g of cyclohexene and 14.12 g of acetic acid are added into a 50 ml high-pressure reaction kettle, the mixture is sealed and then reacts for 4 hours at 120 ℃, and after the test is finished, the high-pressure reaction kettle is quenched by an ice-water mixture, so that the reaction is stopped in time and the cyclohexene is prevented from volatilizing due to high temperature. The reaction product is separated from the catalytic filler and analyzed by gas chromatography, and the yield of the cyclohexyl acetate product is about 12 percent.
Comparative example 2
The catalytic filler is prepared by adopting a traditional etching method through the following steps:
(1) pretreatment of the filler: the difference from the comparative example 1 is that the selected filler is theta ring random packing with the specification of 2 multiplied by 3, and the rest steps are the same as the comparative example 1;
(2) seed crystal coating: the same as comparative example 1;
(3) preparing a catalytic filler: as in comparative example 1.
The activity of the prepared catalytic filler was tested in an autoclave by addition reaction of cyclohexene and acetic acid as probes. 20 g of different types of catalytic fillers, 3.84 g of cyclohexene and 14.12 g of acetic acid are added into a 50 ml high-pressure reaction kettle, the mixture is sealed and then reacts for 4 hours at 120 ℃, and after the test is finished, the high-pressure reaction kettle is quenched by an ice-water mixture, so that the reaction is stopped in time and the cyclohexene is prevented from volatilizing due to high temperature. After the reaction product is separated from the catalytic packing, the yield of the cyclohexyl acetate product is about 8 percent by gas chromatography analysis.
Example 3
The catalytic packings prepared in example 1 and comparative example 1 were packed in two tubular reactors, respectively, and subjected to stability test. The stability of the prepared catalyst was tested in a tubular reactor by a reaction in which cyclohexene and acetic acid were added as probes. The inner diameter of the tubular reactor is 8 mm, the length of the filled catalytic filler is 1 m, the mass of the filled catalytic filler is 52.14 g, the cyclohexene and the acetic acid are mixed according to the molar ratio of 1:5 and then are injected into the tubular reactor through a constant flow pump, the flow rate is 0.208 mL/min, and the reaction temperature is 120 ℃. Time-spaced samples were analyzed by gas chromatography under continuous feed conditions to obtain cyclohexyl acetate yields at different reaction times. The results show that the yield begins to drop slightly after 60 hours for the catalytic filler prepared in example 1, whereas the catalytic filler prepared in comparative example 1 begins to drop significantly after 30 hours.
The above description is only for the preferred embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and all the equivalent changes and modifications made according to the claims of the present invention should fall within the scope of the present invention.
Claims (8)
1. A preparation method of a high-performance supported catalytic filler is characterized by comprising the following specific steps:
(1) pretreatment of the filler: ultrasonically removing oil stains on the surface of the filler by using alkali liquor and ethanol, placing the filler into a conical flask filled with prepared buffer solution, simultaneously adding dopamine hydrochloride, placing the conical flask into a constant-temperature shaking bed, and shaking to polymerize dopamine on the surface of the filler to form a polydopamine coating to obtain a pretreated filler;
(2) seed crystal coating: adding a molecular sieve serving as a seed crystal into a conical flask filled with a prepared buffer solution, obtaining a uniformly dispersed molecular sieve seed crystal suspension under an ultrasonic condition, placing the pretreated filler obtained in the step (1) into the molecular sieve seed crystal suspension, vibrating at a constant temperature to uniformly and fully adhere the seed crystal to the surface of the filler, taking out the filler coated with the seed crystal, soaking the filler in ultrapure water, drying the filler in a blast drying oven, and roasting the filler in a muffle furnace at 250-400 ℃ for 2-6 h to solidify the seed crystal layer;
(3) preparing a catalytic filler: and (3) putting the filler precoated with the seed crystal in the step (2) into a crystallization kettle with a polytetrafluoroethylene lining, adding a prepared secondary growth liquid, sealing the crystallization kettle, moving the crystallization kettle into a blast drying box, crystallizing at a high temperature, taking out the crystallized filler, cooling at room temperature, ultrasonically cleaning the crystallized filler with ultrapure water, drying, and then putting the crystallized filler into a muffle furnace for high-temperature roasting to obtain the high-performance supported catalytic filler.
2. The method of claim 1, wherein: the filler used in the step (1) comprises regular and random packing made of stainless steel and ceramic materials.
3. The method of claim 1, wherein: the buffer solution in the step (1) is a tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution, and the pH value of the buffer solution is 8.5 at 25 ℃.
4. The method of claim 1, wherein: the concentration of the dopamine solution in the step (1) is 0.1-5 mg/mL, the shaking temperature is 25 ℃, and the shaking time is 6-24 h.
5. The method of claim 1, wherein: in the step (2), the grain diameter of the seed crystal is 80-1000 nm, and the concentration of the seed crystal suspension is 0.5-5 wt%.
6. The method of claim 1, wherein: in the step (2), the oscillation temperature of the filler in the seed crystal suspension is 25 ℃, and the oscillation time is 5-360 min.
7. The method of claim 1, wherein: the secondary growth liquid in the step (3) comprises 4TPAOH (titanium dioxide: 25 SiO)2:xAl2O3:1750H2And (3) determining the x value of the ZSM-5 synthetic fluid with different silicon-aluminum ratios of O according to the silicon-aluminum ratio of the molecular sieve in the step (2).
8. The method of claim 1, wherein: the high-temperature crystallization temperature in the step (3) is 120-180 ℃, the high-temperature crystallization time is 24-72 h, the high-temperature roasting temperature is 550 ℃, and the high-temperature roasting time is 4-10 h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171294A (en) * | 1996-07-22 | 1998-01-28 | 中国石油化工总公司 | Catalytic ZSM-5/metal or ceramic compounded material and its preparation |
| CN101003001A (en) * | 2006-12-21 | 2007-07-25 | 天津大学 | Method for preparing aluminium carrier supported molecular-sieve film catalytic rectification packing |
| US20150010709A1 (en) * | 2013-07-05 | 2015-01-08 | Samuel George Beckford | Polytetrafluoroethylene thin film with polydopamine adhesive layer |
| CN105944637A (en) * | 2016-05-16 | 2016-09-21 | 四川大学 | Method for fixing metal nano-catalyst on wall surface of micro-reactor channel |
| CN107970781A (en) * | 2017-11-24 | 2018-05-01 | 上海绿强新材料有限公司 | A kind of molecular sieve ceramic membrane materials and its preparation and application for alkene purification |
-
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- 2020-12-30 CN CN202011595780.0A patent/CN112517053A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171294A (en) * | 1996-07-22 | 1998-01-28 | 中国石油化工总公司 | Catalytic ZSM-5/metal or ceramic compounded material and its preparation |
| CN101003001A (en) * | 2006-12-21 | 2007-07-25 | 天津大学 | Method for preparing aluminium carrier supported molecular-sieve film catalytic rectification packing |
| US20150010709A1 (en) * | 2013-07-05 | 2015-01-08 | Samuel George Beckford | Polytetrafluoroethylene thin film with polydopamine adhesive layer |
| CN105944637A (en) * | 2016-05-16 | 2016-09-21 | 四川大学 | Method for fixing metal nano-catalyst on wall surface of micro-reactor channel |
| CN107970781A (en) * | 2017-11-24 | 2018-05-01 | 上海绿强新材料有限公司 | A kind of molecular sieve ceramic membrane materials and its preparation and application for alkene purification |
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Application publication date: 20210319 |