CN115069220A - Metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent and preparation method and application thereof - Google Patents

Metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent and preparation method and application thereof Download PDF

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CN115069220A
CN115069220A CN202210787149.3A CN202210787149A CN115069220A CN 115069220 A CN115069220 A CN 115069220A CN 202210787149 A CN202210787149 A CN 202210787149A CN 115069220 A CN115069220 A CN 115069220A
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molecular sieve
pore molecular
nitrogen oxide
sieve crystal
metal framework
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孙敏娜
刘飞
秦雷
段晓
高慧
路宁悦
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CHANGZHI MEDICAL COLLEGE
Beijing Information Science and Technology University
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CHANGZHI MEDICAL COLLEGE
Beijing Information Science and Technology University
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Abstract

The invention discloses a metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent, which comprises the following raw materials in parts by weight: 1-5 parts of attapulgite, 1-5 parts of diatomite, 2-5 parts of activated carbon and 5-15 parts of metal framework hierarchical pore molecular sieve crystals. The production process of the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent is simple, the cost is low, the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent can be popularized in a large area, and the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent has high economic popularization value.

Description

Metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of adsorbents, and particularly relates to a metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent, and a preparation method and application thereof.
Background
Nitrogen oxides, other than nitrogen dioxide, are extremely unstable and change to nitrogen dioxide and nitric oxide when exposed to light, moisture or heat, and nitric oxide changes to nitrogen dioxide. Thus, the occupational environment is exposed to several gas mixtures, commonly known as niter fumes (gases), mainly nitrogen monoxide and nitrogen dioxide, and mainly nitrogen dioxide. Nitrogen oxides all have varying degrees of toxicity. Nitrous oxide (laughing gas) in the nitric oxide acts as an inhalation anesthetic. In addition to nitrogen dioxide, other nitrogen oxides can produce nitrogen dioxide when exposed to light, moisture or heat, and the toxic effects of nitrogen dioxide are mainly harmful to the deep respiratory tract. Nitric oxide can also bind to hemoglobin, causing methemoglobinemia. Inhaled air may have no obvious symptoms or eye and upper respiratory tract irritation symptoms, such as pharyngeal discomfort, dry cough, etc. Delayed pulmonary edema and adult respiratory distress syndrome usually appear after 6-7 hours of incubation. It can also cause pneumothorax and mediastinal emphysema. Delayed bronchiolitis with delayed onset occurs about 2 weeks after pulmonary edema has subsided, resulting in cough, progressive chest distress, respiratory distress and cyanosis. A few patients had no apparent toxic symptoms after inhalation of gas and developed the above lesions after 2 weeks. Blood gas analysis indicated a decrease in arterial blood oxygen partial pressure. Chest X-ray shows pulmonary edema or two pulmonary full-millet granular shadows.
Nitrogen oxides, mainly nitrogen monoxide and nitrogen dioxide, are an important cause of photochemical smog and acid rain, and nitrogen oxides in automobile exhaust react with hydrocarbons to form toxic smog through ultraviolet irradiation, which is called photochemical smog. Photochemical smog has a special odor, irritates the eyes, damages plants, and can reduce atmospheric visibility. Nitric acid and nitrous acid, which are generated by the reaction of nitrogen oxides with water in the air, are components of acid rain. Atmospheric nitrogen oxides are mainly derived from the combustion of fossil fuels and the incineration of plant material, as well as the conversion of nitrogen-containing compounds in farmland soils and animal waste.
Chinese patent with publication number CN201410381665.1 provides a NO x Adsorbent for controlling air pollutionThe field of adsorbents. The adsorbent is composed of lime, natural zeolite, bentonite, active carbon and metal oxide, and the components are respectively ground, mixed, added with water and aged, extruded and molded, and dried to constant mass to obtain the NO x An adsorbent. Chinese patent publication No. CN201610773445.2 provides a modified adsorbent for pod travel and a preparation method thereof. The method takes a legume travel as a raw material, and prepares a biomass adsorbent by modifying the legume travel through a treatment reaction process of isopropanol, a potassium hydroxide solution and a citric acid solution. Chinese patent with publication number CN201680043858.3 provides a passive NO x Adsorbent of the passive NO x The adsorbent is effective for adsorbing NO at or below low temperatures x And releasing adsorbed NO at a temperature above the low temperature x The passive NO of x The adsorbent comprises a noble metal and a molecular sieve having an LTL framework type. The existing adsorbent has the problems of complex preparation process and higher cost.
Therefore, how to develop a metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent with simple production process, low cost, large-area popularization and high economic popularization value, and a preparation method and application thereof are technical problems to be solved by technical personnel in the field.
Disclosure of Invention
In view of the above, the invention provides a metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent, and a preparation method and an application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent comprises the following raw materials in parts by weight: 1-5 parts of attapulgite, 1-5 parts of diatomite, 2-5 parts of activated carbon and 5-15 parts of metal framework hierarchical pore molecular sieve crystals.
The technical effects of the invention are as follows: the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent has the advantages of large specific surface area, moderate pore diameter, uniform distribution, high adsorption speed, less impurities and the like, has strong adsorption effect on harmful gases such as nitrogen oxide and the like, and can better ensure the absorption effect on nitrogen oxide by the interaction of various materials when being matched with attapulgite, diatomite and active carbon.
Further, the metal framework hierarchical pore molecular sieve crystal comprises the following raw materials in parts by weight:
500 parts of any one of saturated zinc chloride aqueous solution, saturated zinc chloride aqueous solution or saturated zinc chloride aqueous solution;
1-50 parts of any one of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide and N, N-dimethylacrylamide;
20-100 parts, preferably 20-50 parts, of any one of 2-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2, 5-diaminobenzenesulfonic acid or o-aminobenzenesulfonic acid.
The invention also provides a preparation method of the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent, which comprises the following steps:
(1) weighing the raw materials according to the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent;
(2) respectively grinding the raw materials, and then mixing and ultrasonically stirring to obtain a raw material mixture;
(3) drying and aging the raw material mixture, carrying out extrusion molding on the aged raw material to obtain thin strips, crushing the thin strips into small segments, carrying out extrusion again, repeatedly extruding and crushing for more than 3 times, and finally forming to obtain the thin strips, namely the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent.
The technical effects of the invention are as follows: the invention has simple production process, lower cost, large-area popularization and higher economic popularization value. The metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent prepared by the preparation method has the advantages of large specific surface area, moderate pore diameter, uniform distribution, high adsorption speed, less impurities and the like, has strong adsorption effect on harmful gases such as nitrogen oxide and the like, and can better ensure the absorption effect on nitrogen oxide by the interaction of various materials when being matched with attapulgite, diatomite and active carbon.
Further, the raw materials are respectively ground to the granularity of 200-600 meshes in the step (2).
Further, the ultrasonic frequency of the step (2) is 40-60kHz, and the ultrasonic time is 0.5-2 hours.
Further, the drying temperature in the step (3) is 80-100 ℃, and the drying time is 4-6 hours.
Further, the aging time in the step (3) is 1-3 hours, the extrusion molding adopts 10-20 tons of pressure, the diameter of the thin strip is 2-2.5 millimeters, and the length of the small segment is 3-4 millimeters.
The technical effect of adopting the further technical scheme is as follows: crushing and polishing, and increasing the contact area and being convenient to carry after the particles become small.
Further, the preparation method of the metal framework hierarchical pore molecular sieve crystal comprises the following steps:
weighing the raw materials according to the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent; pouring any one of saturated zinc chloride aqueous solution, saturated zinc chloride aqueous solution or saturated zinc chloride aqueous solution into any one of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide and N, N-dimethylacrylamide, and mixing and stirring to obtain mixed solution;
adding any one of 2-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2, 5-diaminobenzenesulfonic acid or o-aminobenzenesulfonic acid into the mixed solution, mixing and stirring, sealing, pressurizing at constant temperature, heating in a water bath, and cooling to room temperature to obtain the metal framework hierarchical pore molecular sieve crystal.
The technical effect of adopting the further technical scheme is as follows: the coordination compound of the metal framework hierarchical pore class is simply and conveniently built.
Further, the pressure is increased by 3-5Bar, the water bath heating time is 3-8 days, and the water bath heating temperature is 60-93 ℃.
The technical effect of adopting the further technical scheme is as follows: and constructing a molecular sieve crystal.
The invention also provides the application of the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent or the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent prepared by the method in the environment-friendly formaldehyde removal industry.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent comprises the following steps:
(1) weighing 500 kg of saturated zinc chloride aqueous solution, 1 kg of N, N-dimethylacetamide and 20 kg of 4-aminobenzenesulfonic acid;
(2) pouring the saturated solution of zinc chloride into N, N-dimethylacetamide, mixing and stirring to obtain a mixed solution, adding 4-aminobenzenesulfonic acid into the mixed solution, mixing and stirring, sealing, heating in a constant-temperature pressurized water bath for 3 days at the temperature of 60 ℃ under the pressure of 3Bar, and cooling to room temperature to obtain the metal framework hierarchical porous molecular sieve crystal.
(3) Weighing 1 kg of attapulgite, 1 kg of diatomite, 2 kg of activated carbon and 5 kg of metal skeleton hierarchical pore molecular sieve crystals;
(4) respectively grinding the raw materials to the granularity of 200-600 meshes, and then mixing and ultrasonically stirring the raw materials, wherein the ultrasonic frequency is 40kHz, and the ultrasonic time is 0.5 hour to obtain a raw material mixture;
(5) drying the raw material mixture at the drying temperature of 80 ℃ for 4 hours, aging for 3 hours, carrying out extrusion molding on the aged raw material under the pressure of 20 tons to obtain thin strips, wherein the diameter of each thin strip is 2-2.5 millimeters, the length of each small segment is 3-4 millimeters, crushing the thin strips into small segments, carrying out extrusion again, repeatedly extruding and crushing the small segments for more than 3 times, and finally forming to obtain the thin strips, namely the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent.
Example 2
The preparation method of the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent comprises the following steps:
(1) weighing 500 kg of saturated zinc sulfate aqueous solution, 50 kg of N, N-dimethylacrylamide and 100 kg of 2-aminobenzenesulfonic acid;
(2) pouring the saturated solution of zinc sulfate into N, N-dimethylacrylamide, mixing and stirring to obtain a mixed solution, adding 2-aminobenzenesulfonic acid into the mixed solution, mixing and stirring, sealing, heating in a constant-temperature pressurized water bath at the temperature of 93 ℃ for 8 days, pressurizing by 5Bar, and cooling to room temperature to obtain the metal framework hierarchical pore molecular sieve crystal.
(3) Weighing 5 kg of attapulgite, 5 kg of diatomite, 5 kg of activated carbon and 15 kg of metal skeleton hierarchical pore molecular sieve crystals;
(4) respectively grinding the raw materials to the granularity of 200-600 meshes, and then mixing and ultrasonically stirring the raw materials, wherein the ultrasonic frequency is 60kHz, and the ultrasonic time is 2 hours to obtain a raw material mixture;
(5) drying the raw material mixture at the drying temperature of 100 ℃ for 6 hours, aging for 3 hours, carrying out extrusion molding on the aged raw material under the pressure of 15 tons to obtain thin strips, wherein the diameter of each thin strip is 2-2.5 millimeters, the length of each small segment is 3-4 millimeters, crushing the thin strips into small segments, carrying out extrusion again, repeatedly extruding and crushing the small segments for more than 3 times, and finally forming to obtain the thin strips, namely the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent.
Example 3
The preparation method of the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent comprises the following steps:
(1) weighing 500 kg of saturated zinc nitrate aqueous solution, 25 kg of N, N-dimethyl propionamide and 50 kg of 2-aminobenzenesulfonic acid;
(2) pouring the saturated zinc nitrate solution into N, N-dimethyl propionamide, mixing and stirring to obtain a mixed solution, adding 2-aminobenzenesulfonic acid into the mixed solution, mixing and stirring, sealing, heating in a constant-temperature pressurized water bath for 4Bar under pressure for 4 days at the water bath heating temperature of 70 ℃, and cooling to room temperature to obtain the metal framework hierarchical porous molecular sieve crystal.
(3) Weighing 2 kg of attapulgite, 3 kg of diatomite, 4 kg of activated carbon and 15 kg of metal skeleton hierarchical pore molecular sieve crystals;
(4) respectively grinding the raw materials to the granularity of 200-600 meshes, and then mixing and ultrasonically stirring the raw materials, wherein the ultrasonic frequency is 50kHz, and the ultrasonic time is 1 hour to obtain a raw material mixture;
(5) drying the raw material mixture, wherein the drying temperature is 80 ℃, the drying time is 4 hours, aging is carried out for 2 hours, the aged raw material is extruded and molded by adopting the pressure of 15 tons to obtain thin strips, the diameter of each thin strip is 2-2.5 millimeters, the length of each small segment is 3-4 millimeters, then the thin strips are smashed into small segments and then extruded again, and finally the thin strips are formed after repeated extrusion and smashing for more than 3 times, so that the thin strips are the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent.
Example 4
The preparation method of the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent comprises the following steps:
(1) weighing 500 kg of saturated zinc nitrate aqueous solution, 10 kg of N, N-dimethylacetamide and 45 kg of o-aminobenzenesulfonic acid;
(2) pouring the saturated solution of zinc nitrate into N, N-dimethylacetamide, mixing and stirring to obtain a mixed solution, adding o-aminobenzenesulfonic acid into the mixed solution, mixing and stirring, sealing, heating in a pressurized water bath at a constant temperature for 5 days at 70 ℃ under a pressure of 5Bar, and cooling to room temperature to obtain the metal framework hierarchical porous molecular sieve crystal.
(3) Weighing 2 kg of attapulgite, 2 kg of diatomite, 5 kg of active carbon and 15 kg of metal skeleton hierarchical pore molecular sieve crystals;
(4) respectively grinding the raw materials to the granularity of 200-600 meshes, and then mixing and ultrasonically stirring the raw materials, wherein the ultrasonic frequency is 40kHz, and the ultrasonic time is 1 hour to obtain a raw material mixture;
(5) drying the raw material mixture at 90 ℃ for 6 hours, aging for 3 hours, carrying out extrusion molding on the aged raw material under the pressure of 20 tons to obtain thin strips, wherein the diameter of each thin strip is 2-2.5 millimeters, the length of each small segment is 3-4 millimeters, crushing the thin strips into small segments, carrying out extrusion again, repeatedly extruding and crushing the small segments for more than 3 times, and finally forming to obtain the thin strips, namely the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent.
Effect test
Comparative example 1
(1) Weighing 500 kg of saturated zinc chloride aqueous solution, 100 kg of N, N-dimethylacetamide and 200 kg of 4-aminobenzenesulfonic acid;
(2) pouring the saturated solution of zinc chloride into N, N-dimethylacetamide, mixing and stirring to obtain a mixed solution, adding 4-aminobenzenesulfonic acid into the mixed solution, mixing and stirring, sealing, heating in a constant-temperature pressurized water bath for 3 days at the temperature of 60 ℃ under the pressure of 3Bar, and cooling to room temperature to obtain the metal skeleton hierarchical porous molecular sieve crystal.
(3) Weighing 10 kg of attapulgite, 10 kg of diatomite, 20 kg of activated carbon and 3 kg of metal skeleton hierarchical pore molecular sieve crystals;
(4) respectively grinding the raw materials to a particle size of 200-600 meshes, and then mixing and ultrasonically stirring the raw materials, wherein the ultrasonic frequency is 40kHz, and the ultrasonic time is 0.5 hour to obtain a raw material mixture;
(5) drying the raw material mixture at the drying temperature of 80 ℃ for 4 hours, aging for 0.5 hour, carrying out extrusion molding on the aged raw material under the pressure of 20 tons to obtain thin strips, wherein the diameter of each thin strip is 2-2.5 millimeters, the length of each small segment is 3-4 millimeters, crushing the thin strips into small segments, carrying out extrusion again, repeatedly extruding and crushing the small segments for more than 3 times, and finally forming to obtain the thin strips, namely the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent.
Comparative example 2
(1) Weighing 500 kg of saturated zinc nitrate aqueous solution, 50 kg of N, N-dimethylacetamide and 100 kg of 4-aminobenzenesulfonic acid;
(2) pouring the saturated solution of zinc nitrate into N, N-dimethylacetamide, mixing and stirring to obtain a mixed solution, adding 4-aminobenzenesulfonic acid into the mixed solution, mixing and stirring, sealing, heating in a constant-temperature pressurized water bath for 8Bar for 1 day, and cooling to room temperature to obtain the metal framework hierarchical pore molecular sieve crystal, wherein the pressure is 8 Bar.
(3) Weighing 20 kg of attapulgite, 15 kg of diatomite, 30 kg of activated carbon and 1 kg of metal skeleton hierarchical pore molecular sieve crystals;
(4) respectively grinding the raw materials to a particle size of 200-600 meshes, and then mixing and ultrasonically stirring the raw materials, wherein the ultrasonic frequency is 40kHz, and the ultrasonic time is 0.5 hour to obtain a raw material mixture;
(5) drying the raw material mixture at the drying temperature of 80 ℃ for 4 hours, aging for 5 hours, carrying out extrusion molding on the aged raw material under the pressure of 20 tons to obtain thin strips, wherein the diameter of each thin strip is 2-2.5 millimeters, the length of each small segment is 3-4 millimeters, crushing the thin strips into small segments, carrying out extrusion again, repeatedly extruding and crushing the small segments for more than 3 times, and finally forming to obtain the thin strips, namely the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent.
In comparative examples 1-2, the addition of N, N-dimethylacetamide and 4-aminobenzenesulfonic acid is out of the preferable range, and the sealing and constant-temperature pressurizing water bath heating is carried out, and the pressurizing and water bath heating time and the water bath heating temperature do not adopt the preferable technological parameters, so that the functionality of the metal skeleton hierarchical pore molecular sieve crystal material is insufficient. In addition, the proportion of the attapulgite, the diatomite, the active carbon and the metal framework hierarchical pore molecular sieve crystal is not the optimal proportion of the patent. This results in a product having poor adsorption capacity.
The method adopts GBZ/T160.29-2004 ' determination of inorganic nitrogen-containing compounds in workplace air toxic substance ' standard and time good, Xuanjuan, Zhangli, etc. ' solid molecular sieve tube sampling-ion chromatography simultaneous determination of sulfur dioxide and nitrogen oxides in workplace air [ J ]. occupational and health 2021, volume 37, period 19, pages 2619, 2621,2624, ISTIC CA,2021 ] to measure
The adsorbents obtained in examples 1 to 4 and comparative examples 1 to 2 were used to measure the formaldehyde adsorption effect, as follows:
the effect experiment is an example of treating high-concentration nitrogen oxide, and the waste gas is NO-containing gas generated by dissolving silver x The amount of waste gas is 600m 3 H, the prepared metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent is tightly filled in a device with the diameter of 20cm and the height of 50cm and with two openings capable of ventilating, and the adsorbent in the experimental example is used for testing NO with different inlet concentrations x The test indices for removal efficiency are shown in table 1:
TABLE 1
Figure BDA0003729156920000101
As can be seen from Table 1, NO according to the present invention x Adsorbent for treating NO by physical and chemical adsorption x Compared with the adsorbent, the adsorbent has the advantages of high purification speed, good treatment effect, large adsorption capacity and long replacement period, and is particularly suitable for high-concentration discharged NO x (NO、NO 2 ) The treatment characteristic can well meet the treatment requirement of high concentration for realizing large-scale industrial application.
The description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent is characterized by comprising the following raw materials in parts by weight: 1-5 parts of attapulgite, 1-5 parts of diatomite, 2-5 parts of activated carbon and 5-15 parts of metal framework hierarchical pore molecular sieve crystals.
2. The nitrogen oxide adsorbent of claim 1, wherein the metal-framework hierarchical-pore molecular sieve crystal comprises the following raw materials in parts by weight:
500 parts of any one of saturated zinc chloride aqueous solution, saturated zinc chloride aqueous solution or saturated zinc chloride aqueous solution;
1-50 parts of any one of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide and N, N-dimethylacrylamide;
20-100 parts of any one of 2-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2, 5-diaminobenzenesulfonic acid or o-aminobenzenesulfonic acid.
3. A preparation method of a metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent is characterized by comprising the following steps:
(1) weighing the raw materials according to the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent of claim 1 or 2;
(2) respectively grinding the raw materials, and then mixing and ultrasonically stirring to obtain a raw material mixture;
(3) drying and aging the raw material mixture, carrying out extrusion molding on the aged raw material to obtain thin strips, crushing the thin strips into small segments, carrying out extrusion again, repeatedly extruding and crushing for more than 3 times, and finally forming to obtain the thin strips, namely the metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent.
4. The method as claimed in claim 3, wherein in step (2), the raw materials are respectively milled to a particle size of 200-600 mesh.
5. The method for preparing the nitrogen oxide adsorbent of the metal framework hierarchical pore molecular sieve crystal according to claim 3, wherein the ultrasonic frequency in the step (2) is 40-60kHz, and the ultrasonic time is 0.5-2 hours.
6. The method for preparing the nitrogen oxide adsorbent of the metal framework hierarchical pore molecular sieve crystal series according to claim 3, wherein the drying temperature in the step (3) is 80-100 ℃, and the drying time is 4-6 hours.
7. The method for preparing the nitrogen oxide adsorbent of the metal framework hierarchical pore molecular sieve crystal according to claim 3, wherein the aging time in the step (3) is 1-3 hours, the extrusion molding adopts 10-20 tons of pressure, the diameter of the thin strip is 2-2.5 mm, and the length of the small segment is 3-4 mm.
8. The method for preparing the nitrogen oxide adsorbent of the metal-framework hierarchical-pore molecular sieve crystal according to claim 3, wherein the method for preparing the metal-framework hierarchical-pore molecular sieve crystal comprises the following steps:
weighing the raw materials according to the nitrogen oxide adsorbent with the metal framework hierarchical pore molecular sieve crystal of claim 2; pouring any one of saturated zinc chloride aqueous solution, saturated zinc chloride aqueous solution or saturated zinc chloride aqueous solution into any one of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide and N, N-dimethylacrylamide, and mixing and stirring to obtain mixed solution;
adding any one of 2-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2, 5-diaminobenzenesulfonic acid or o-aminobenzenesulfonic acid into the mixed solution, mixing and stirring, sealing, pressurizing at constant temperature, heating in a water bath, and cooling to room temperature to obtain the metal framework hierarchical pore molecular sieve crystal.
9. The method for preparing the nitrogen oxide adsorbent with the metal framework hierarchical pore molecular sieve crystal according to claim 8, wherein the pressure is 3-5Bar, the water bath heating time is 3-8 days, and the water bath heating temperature is 60-93 ℃.
10. The application of the nitrogen oxide adsorbent of metal framework hierarchical pore molecular sieve crystal type according to claim 1 or 2 or the nitrogen oxide adsorbent of metal framework hierarchical pore molecular sieve crystal type prepared by the method according to any one of claims 3 to 9 in the industry of environmental protection and formaldehyde removal.
CN202210787149.3A 2022-07-04 2022-07-04 Metal framework hierarchical pore molecular sieve crystal nitrogen oxide adsorbent and preparation method and application thereof Pending CN115069220A (en)

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