CN113145165A - Preparation method of Ni @ HS hollow-structure molecular sieve and application of molecular sieve in deamination - Google Patents
Preparation method of Ni @ HS hollow-structure molecular sieve and application of molecular sieve in deamination Download PDFInfo
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- CN113145165A CN113145165A CN202110124083.5A CN202110124083A CN113145165A CN 113145165 A CN113145165 A CN 113145165A CN 202110124083 A CN202110124083 A CN 202110124083A CN 113145165 A CN113145165 A CN 113145165A
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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
- 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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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
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Abstract
The invention relates to a preparation method of a Ni @ HS hollow structure molecular sieve and application thereof in deamination reaction, wherein a Silicalite solid structure molecular sieve is added into Ni (NO)3)2Soaking in water solution in equal volume; drying overnight, and roasting to obtain a dipped sample; TPAOH and deionized water are mixed to prepare a solution, then the solution is dripped into a dipping sample under the condition of reduced pressure suction filtration, and the dipping sample is transferred to a crystallization kettle for crystallization after suction filtration and wetting; filtering and washing the crystallized slurry, drying, and roasting to remove the template agent. The advantages are that: the supported hollow molecular sieve is synthesized by a dry glue method, so that the synthesis step is simple, the operation process is easy to control, the Ni @ HS hollow molecular sieve is synthesized more conveniently and flexibly, and meanwhile, the hollow molecular sieve shell can be ensured to keep a ZSM-5 microporous structure。
Description
Technical Field
The invention belongs to the technical field of molecular sieve preparation, and particularly relates to a preparation method of a Ni @ HS hollow-structure molecular sieve and application thereof in deamination.
Background
Due to the unique structure of a large cavity in the hollow structure molecular sieve, the hollow structure molecular sieve often shows distinctive performances in the fields of catalysis, adsorption, optics, thermal engineering and the like. The traditional method for synthesizing the hollow structure generally comprises the steps of synthesizing a precursor of the hollow structure by using a template agent, and then removing the template agent by roasting or organic solvent extraction to finally obtain a cavity. The template agent comprises inorganic template agent and organic template agent according to structure; the method comprises the following steps of classifying according to hard templates and soft templates. Later, it was found that cavity structures could also be obtained by a template-free method, and that nano-sized hollow silicon-Aluminum structures were synthesized by a template-free method, such as Venkatathri N, A novel route to synthesis of Aluminum silicon silicate hollow spheres having ZSM-5structure in presence of template, Mater.Lett. 2008.62: 462-.
Different wastes including solid, liquid and gas forms can be generated in the chemical reaction process, and the gas wastes are commonly poisonous and harmful gases such as ammonia gas and the like, so that the environment is seriously polluted. Deamination of industrial waste gas to reduce NH in atmosphere3One of the effective methods for content is that noble metals such as ruthenium (Ru) are generally carried on the industrial scale to carry out the deamination reaction of exhaust gas.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a Ni @ HS hollow structure molecular sieve and application thereof in deamination reaction, which can ensure that the shell of the hollow molecular sieve keeps a ZSM-5 microporous structure and Ni atoms can easily enter the hollow cavity of the hollow molecular sieve. When the molecular sieve is applied to deamination reaction of waste gas, Ni atoms are not easy to run off, and excellent catalytic performance can be shown under mild conditions.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a Ni @ HS hollow structure molecular sieve comprises the following steps:
1) preparing a Ni-Silicalite solid structure molecular sieve:
(a) taking Silicalite solid structure molecular sieve, adding 0.4mol/l of Ni (NO)3)2Soaking in water solution in equal volume;
(b) drying overnight, and roasting at 500-600 ℃ for 5-12 h to obtain a dipped sample Ni-Silicalite;
2) preparation of the Ni @ HS hollow structure molecular sieve:
(a) the tetrapropylammonium hydroxide TPAOH and deionized water are mixed according to the weight ratio of (0.1-0.5): (1-5) are mixed and prepared
The pH value of the solution is 8-10, then the solution is dripped into a dipped sample Ni-Silicalite under the condition of reduced pressure suction filtration, and the dipped sample Ni-Silicalite is transferred into a crystallization kettle for crystallization after suction filtration and wetting, and crystallized for 1-2 days at 160-180 ℃;
(b) and filtering and washing the crystallized slurry, drying, and roasting at 500-600 ℃ for 4-8 hours to remove the template agent to obtain the Ni @ HS hollow molecular sieve.
In the step 1) (b), the drying overnight is carried out for 6-12 h at the temperature of 60-80 ℃.
The Ni @ HS hollow molecular sieve obtained in the step 2) (b) has the following properties: the particle diameter is 500-800 nm, and the specific surface area is 150m2/g～450m2The total pore volume is 0.1mL/g to 0.3mL/g, the average pore diameter is 0.42 nm to 0.62nm, and the relative crystallinity is 90 percent to 100 percent.
The application of the Ni @ HS hollow-structure molecular sieve in the deamination reaction is characterized in that the deamination rate of the Ni @ HS hollow-structure molecular sieve in the deamination reaction of refinery catalytic cracking flue gas is more than 99% at 400-550 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1) the supported hollow molecular sieve is synthesized by a dry glue method, so that the synthesis step is simple, the operation process is easy to control, the Ni @ HS hollow molecular sieve is synthesized more conveniently and flexibly, and the shell of the hollow molecular sieve can be ensured to keep a ZSM-5 microporous structure;
2) compared with the traditional supported copper catalyst, the Ni @ HS synthesized by the method has the advantages that the supported nickel atoms are wrapped in the cavity and are not easy to lose in the chemical reaction process.
3) The Ni @ HS hollow molecular sieve is applied to the deamination reaction of waste gas, shows excellent deamination rate under mild conditions, and replaces the existing supported noble metals such as: desirable products of ruthenium (Ru) catalysts.
Drawings
FIG. 1 is a TEM image of a sample of the molecular sieve synthesized in example 1.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example 1
The preparation method of the Ni @ HS hollow molecular sieve comprises the following steps:
taking 2g of Silicalite solid structure molecular sieve, adding 0.4mol/l Ni (NO)3)2In aqueous solution, equal volume of impregnation. Drying at 80 ℃ overnight, and roasting at 550 ℃ for 4h to obtain the Ni-Silicalite impregnated sample.
5mL of TPAOH is dissolved in 10mL of deionized water to obtain a solution, the pH value of the solution is about 9, 2g of spherical Ni-Silicalite molecular sieve is weighed and transferred to a Buchner funnel with filter paper, and the prepared solution is dropwise added into the raw material on the filter paper in a reduced pressure suction filtration state. After being filtered and moistened, the mixture is transferred to a crystallization kettle and crystallized for 48 hours at the temperature of 170 ℃. Cooling the crystallized slurry to room temperature, and performing vacuum filtration on the obtained powder until the pH value of the washing liquid is close to neutral; the drying is carried out for 10 hours at the temperature of 70 ℃; then roasting for 6 hours at 550 ℃, wherein the obtained molecular sieve is Ni @ HS-1 in the label, the Ni @ HS-1 hollow structure molecular sieve is used as a cocatalyst, and the refinery catalytic cracking flue gas is NH at 500-600 ℃ in the presence of ammonia3The conversion rate is very high, the removal rate is more than 99 percent, and the properties are shown in table 1. In this example, the molecular sieve was designated as Ni @ HS-1, and a transmission electron micrograph (TEM image) is shown in FIG. 1.
Example 2
The preparation method of the Ni @ HS hollow molecular sieve comprises the following steps:
5g of Silicalite solid molecular sieve is taken and 0.4ml of Ni (NO) is added3)2In aqueous solution, equal volume of impregnation. Drying at 60 ℃ overnight, and roasting at 550 ℃ for 6h to obtain the Ni-Silicalite impregnated sample.
Dissolving 30mL of TPAOH in deionized water to obtain a solution with the pH value of about 9, weighing 5g of spherical Ni-Silicalite molecular sieve, transferring the spherical Ni-Silicalite molecular sieve to a Buchner funnel with filter paper, and performing suction filtration under reduced pressureThe previously prepared solution was then added dropwise to the stock on the filter paper. After being filtered and moistened, the mixture is transferred to a crystallization kettle and crystallized for 48 hours at the temperature of 170 ℃. Cooling the crystallized slurry to room temperature, and performing vacuum filtration on the obtained powder until the pH value of the washing liquid is close to neutral; the drying is carried out for 10 hours at the temperature of 70 ℃; then roasting for 6 hours at 550 ℃, wherein the obtained molecular sieve is Ni @ HS-2 in the label, the Ni @ HS-2 hollow structure molecular sieve is used as a cocatalyst, and the refinery catalytic cracking flue gas is NH at 500-600 ℃ in the presence of ammonia3The conversion rate is very high, the removal rate is more than 99 percent, and the properties are shown in table 1.
Example 3
The preparation method of the Ni @ HS hollow molecular sieve comprises the following steps:
8g of Silicalite solid molecular sieve is taken and 0.4ml of Ni (NO) is added3)2In aqueous solution, equal volume of impregnation. Drying at 60 ℃ overnight, and roasting at 550 ℃ for 6h to obtain the Ni-Silicalite impregnated sample.
Dissolving 84mL of TPAOH in deionized water to obtain a solution, wherein the pH value of the solution is about 9, then weighing 8g of spherical Ni-Silicalite molecular sieve, transferring the spherical Ni-Silicalite molecular sieve into a Buchner funnel with filter paper, and dropwise adding the prepared solution into the raw material on the filter paper in a reduced pressure suction filtration state. After being filtered and moistened, the mixture is transferred to a crystallization kettle and crystallized for 48 hours at the temperature of 170 ℃. Cooling the crystallized slurry to room temperature, and performing vacuum filtration on the obtained powder until the pH value of the washing liquid is close to neutral; the drying is carried out for 10 hours at the temperature of 70 ℃; then roasting for 6 hours at 550 ℃, wherein the obtained molecular sieve is Ni @ HS-3 in the label, the Ni @ HS-3 hollow structure molecular sieve is used as a cocatalyst, and the refinery catalytic cracking flue gas is NH at 500-600 ℃ in the presence of the catalyst3The conversion rate is very high, the removal rate is more than 99 percent, and the properties are shown in table 1.
TABLE 1 comparison of physical properties and denitration rates of Ni @ HS hollow molecular sieves obtained in examples (reaction conditions: temperature 500-600 ℃ C.)
The invention adopts a dry gel conversion method (DGC) to synthesize the Ni @ HS hollow molecular sieve with a uniform and compact shell, and then the synthesized hollow molecular sieve Ni @ HS is used as a catalyst for waste gas deamination, thereby showing excellent catalytic performance under mild conditions.
Claims (4)
1. A preparation method of a Ni @ HS hollow structure molecular sieve is characterized by comprising the following steps:
1) preparing a Ni-Silicalite solid structure molecular sieve:
(a) taking Silicalite solid structure molecular sieve, adding 0.4mol/l of Ni (NO)3)2Soaking in water solution in equal volume;
(b) drying overnight, and roasting at 500-600 ℃ for 5-12 h to obtain a dipped sample Ni-Silicalite;
2) preparation of the Ni @ HS hollow structure molecular sieve:
(a) the tetrapropylammonium hydroxide TPAOH and deionized water are mixed according to the weight ratio of (0.1-0.5): (1-5) mixing the components in a molar ratio to prepare a solution, wherein the pH value of the solution is 8-10, dripping the solution into a dipped sample Ni-Silicalite under the condition of reduced pressure suction filtration, carrying out suction filtration and wetting, transferring into a crystallization kettle for crystallization, and crystallizing at 160-180 ℃ for 1-2 days;
(b) and filtering and washing the crystallized slurry, drying, and roasting at 500-600 ℃ for 4-8 hours to remove the template agent to obtain the Ni @ HS hollow molecular sieve.
2. The preparation method of the Ni @ HS hollow-structured molecular sieve of claim 1, wherein in the step (b) of step 1), the drying overnight is performed at 60-80 ℃ for 6-12 h.
3. The method for preparing the Ni @ HS hollow-structured molecular sieve according to claim 1, wherein the Ni @ HS hollow-structured molecular sieve obtained in step 2) (b) has the following properties: the particle diameter is 500-800 nm, and the specific surface area is 150m2/g～450m2Per g, total pore volume 0.1 mL/g-0.3mL/g, average pore diameter of 0.42-0.62 nm, and relative crystallinity of 90-100%.
4. The application of the Ni @ HS hollow-structure molecular sieve obtained by the preparation method according to any one of claims 1 to 3 in deamination reaction is characterized in that the deamination rate of the Ni @ HS hollow-structure molecular sieve in the deamination reaction of refinery catalytic cracking flue gas is more than 99% at 400-550 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115805097A (en) * | 2022-12-01 | 2023-03-17 | 中触媒新材料股份有限公司 | Large-grain Zn @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof |
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2021
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