CN114225907A - Polycrystalline high-silicon honeycomb molecular sieve adsorbent and preparation method thereof - Google Patents

Polycrystalline high-silicon honeycomb molecular sieve adsorbent and preparation method thereof Download PDF

Info

Publication number
CN114225907A
CN114225907A CN202111582098.2A CN202111582098A CN114225907A CN 114225907 A CN114225907 A CN 114225907A CN 202111582098 A CN202111582098 A CN 202111582098A CN 114225907 A CN114225907 A CN 114225907A
Authority
CN
China
Prior art keywords
molecular sieve
adsorbent
silicon
pug
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111582098.2A
Other languages
Chinese (zh)
Inventor
黄招
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangxi Aisi New Material Technology Co ltd
Original Assignee
Jiangxi Aisi New Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangxi Aisi New Material Technology Co ltd filed Critical Jiangxi Aisi New Material Technology Co ltd
Priority to CN202111582098.2A priority Critical patent/CN114225907A/en
Publication of CN114225907A publication Critical patent/CN114225907A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s

Abstract

The invention relates to the technical field of adsorption materials, in particular to a polycrystalline high-silicon honeycomb molecular sieve adsorbent and a preparation method thereof. The preparation method comprises the following steps: s1, mixing the high-silicon composite molecular sieve raw powder and the binder to prepare pug, and then performing compression molding to obtain a blank; s2, drying the blank body by microwave, and then placing the dried blank body at 650-900 ℃ for firing for 1-3 h to obtain the adsorbent. The preparation method is simple to operate, low in cost, high in efficiency and suitable for popularization and application. The adsorbent product obtained by the invention has rich micropores, has good adsorption effect on VOC organic waste gas, can resist high temperature, and has good hydrophobic property and strength and long service life; low cost, safety, reliability, cleanness and environmental protection.

Description

Polycrystalline high-silicon honeycomb molecular sieve adsorbent and preparation method thereof
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a polycrystalline high-silicon honeycomb molecular sieve adsorbent and a preparation method thereof.
Background
At present, the existing VOC organic waste gas adsorption treatment in China basically adopts honeycomb activated carbon as an adsorbent, the main component of a honeycomb activated carbon product is carbon (C), the adsorption efficiency of the honeycomb activated carbon product can generally meet the requirement of working conditions, and the adsorption conversion rate can reach more than 95%. However, in the desorption process after the adsorption saturation, part of organic waste gas molecules are most active under the temperature condition of 150-170 ℃ or even higher, namely, the organic waste gas molecules can be desorbed under the condition, and when the desorption temperature of the activated carbon product exceeds 120 ℃, spontaneous combustion is easy to generate, so that the risk of fire is caused. Therefore, when honeycomb activated carbon is used as an adsorbent, most domestic equipment basically performs desorption treatment at the temperature of below 120 ℃ for safety, so that the problem of incomplete desorption is caused, and the adsorption efficiency is greatly reduced. Meanwhile, because the honeycomb activated carbon cannot be desorbed at high temperature, when the honeycomb activated carbon is discarded, the honeycomb activated carbon has to be classified as dangerous waste treatment because part of organic waste gas components still remain in the honeycomb activated carbon, and the treatment cost is quite expensive.
Aiming at the defects of the honeycomb activated carbon, a honeycomb zeolite molecular sieve is developed on the market at present as a substitute, namely, an activated carbon material is changed into a zeolite molecular sieve material, so that the defects of the activated carbon are avoided by fully utilizing the characteristics of porosity, strong adsorbability and high temperature resistance of the zeolite molecular sieve. However, a new problem occurs in the process of putting into use, namely, the general VOC organic waste gas components contain part of moisture, and the general zeolite molecular sieve material can generate an adsorption exothermic reaction after contacting water, so that the overall temperature of the adsorption box is sharply increased and generally reaches about 70 ℃, thereby causing the sharp reduction of the adsorption efficiency (under the normal temperature condition, the adsorption efficiency of the general zeolite molecular sieve material is inversely proportional to the temperature), and when the adsorption exothermic reaction is generated, the zeolite honeycomb molecular sieve product is easy to crack or even pulverize after volume expansion due to the rise of the temperature when contacting water, thereby seriously affecting the use effect and the service life.
Disclosure of Invention
The invention aims to overcome at least one of the defects of the prior art and provides a polycrystalline high-silicon honeycomb molecular sieve adsorbent, and a preparation method and application thereof. The purpose of the invention is realized based on the following technical scheme:
in a first aspect of the invention, a preparation method of a polycrystalline high-silicon honeycomb molecular sieve adsorbent is provided, which comprises the following steps:
s1, mixing the high-silicon composite molecular sieve raw powder and the binder to prepare pug, and then performing compression molding to obtain a blank; the high-silicon composite molecular sieve raw powder comprises one or more of a ZSM-5 molecular sieve, an HZSM-5 molecular sieve, a ZSM-11 molecular sieve, a 13X molecular sieve, a Y molecular sieve and a beta molecular sieve, and the silicon-aluminum ratio is more than or equal to 400: 1;
s2, drying the blank body by microwave, and then placing the dried blank body at 650-900 ℃ for firing for 1-3 h to obtain the adsorbent.
The invention adopts the polycrystalline high-silicon molecular sieve as the main raw material, and makes use of the good adsorbability and hydrophobicity of the molecular sieve to ensure that the product performance fully meets the working condition requirement of VOC organic waste gas adsorption treatment. The binder and the high-silicon composite molecular sieve raw powder are mixed to prepare the mud, so that the viscosity of the mud is increased (which is beneficial to forming) on the basis of not influencing the performance of products, the strength of a blank body is also ensured, the strength of the fired product is also greatly improved, the product is not easy to crack and pulverize in use, and the service life of the product is greatly prolonged. The product obtained by the invention has rich micropores and good adsorption effect on VOC organic waste gas, and has high temperature resistance (the temperature resistance reaches 800 ℃) and good hydrophobic property and strength because the main component adopts a polycrystalline high-silicon composite molecular sieve material. The invention not only overcomes the defects of insecurity and low adsorption efficiency of the honeycomb activated carbon; meanwhile, the defects that the common honeycomb zeolite molecular sieve is low in strength, absorbs water and releases heat to influence the adsorption effect and the service life are overcome.
Preferably, the binder in step S1 includes silica sol, aluminum sol, SiO2-Al2O3One or more of composite sol, water glass, phosphoric acid, sodium tripolyphosphate solution, sodium hexametaphosphate solution, aluminum dihydrogen phosphate solution and vegetable gum.
Preferably, the silica sol, alumina sol, SiO2-Al2O3The composite sol has an average particle diameter of 100 to 600 nm.
Preferably, the concentration of the binder in the step S1 is 10-30 wt%, and the addition amount of the binder is 15-40 wt% of the raw powder of the high-silicon composite molecular sieve.
The invention adopts the low-concentration binder, has lower binder content, does not influence the performance of the adsorbent product, can ensure the strength of the green body, and greatly improves the strength of the fired product.
Preferably, step S1 specifically includes: mixing the high-silicon composite molecular sieve raw powder and a binder, kneading in a kneading machine for 10-25 min to prepare pug, pouring the kneaded pug into a vacuum pug mill to prepare a pug segment, and then putting the pug segment into an extruding machine for extrusion molding.
Preferably, the microwave drying in the step S2 is specifically to control the surface temperature of the blank body to be 90-130 ℃ and perform microwave irradiation for 15-60 min.
Preferably, the firing temperature in the step S2 is 700-800 ℃, and the strength of the fired product is also greatly improved.
Preferably, the step S1 further includes adding one or more of sepiolite powder, calcium chloride, magnesium oxide, barium sulfate whisker and carbon nanotube, and mixing to obtain a pug. In this case, the amount of the binder added is 15 to 40 wt% of the total mass of all the raw materials.
Sepiolite powder has strong adsorption capacity. The special structure of sepiolite determines that it possesses zeolite, water channels and pores throughout the structure and large surface area, it has tubular through channels with cross-sectional area of 0.36nm x 1.06nm and up to 900m2·g-1The theoretical surface area of (a); a large amount of water or polar substances, including low polar substances, may be adsorbed in the channels and pores. The calcium chloride has good specific adsorption performance on heavy metals. The magnesia can improve the compactness and rheological property of the pug, has high fireproof and insulating properties, and can also be used as an adsorbent to improve the adsorption effect of the honeycomb molecular sieve. The barium sulfate whisker not only has excellent weather resistance and ageing resistance, but also can increase the wear resistance and the impact strength of the molecular sieve adsorbent, and obviously improve the toughness of the honeycomb molecular sieve adsorbent. The carbon nano tube has the characteristics of nano structure, stable performance and large specific surface area, and has excellent adsorption effect on volatile organic compounds. Calcium chloride is compounded with high-silicon composite molecular sieve raw powder, sepiolite powder or carbon nano tubes, so that the system adsorption effect on heavy metals is formed, and the adsorption removal rate of the heavy metals in the waste gas reaches 99.5%. The magnesium oxide and barium sulfate crystal whiskers improve the mechanical property of the honeycomb molecular sieve adsorbent and prolong the service life.
Preferably, the mass ratio of the raw materials is as follows: 100 parts of high-silicon composite molecular sieve raw powder and one or more of the following substances: 3-8 parts of sepiolite powder, 3-8 parts of calcium chloride, 3-8 parts of magnesium oxide, 3-8 parts of barium sulfate whisker and 3-10 parts of carbon nano tube.
Preferably, step S2 is followed by step S3: placing the adsorbent in a reactor, introducing pyridine steam under the protection of inert gas to perform hydrophobic treatment on the adsorbent, wherein the reaction temperature is 115-170 ℃, and the reaction time is 1-4 hours; and then cooling to 50 ℃ or below, and continuously introducing inert gas for desorption for 1-2 h.
A pyridine film is attached to the inner surface of the adsorbent in a mode of steaming pure pyridine on the adsorbent. The hydrophobicity of the molecular grade pure pyridine is utilized to change the chemical property, the specific surface area, the pore volume and the pore size distribution of the inner surface of the adsorbent material; the pyridine film on the surface of the organic ligand is peeled off in an inert gas high-pressure desorption mode by utilizing the difference of the bonding strength of the exposed metal ions on the inner surface of the adsorbent and the organic ligand to the pyridine, and the strong adsorption capacity of the adsorbent to gas molecules is recovered. The pyridine film on the surface of the metal ions is stable in the desorption process by adopting proper pressure and inert gas, and the finally modified honeycomb molecular sieve adsorbing material can effectively solve the problems of reduced adsorption performance and internal structure damage of target gaseous molecules caused by the hydrophilicity of the metal ions, so that the adsorption performance of the honeycomb molecular sieve adsorbing material on nonpolar organic molecules in the presence of water molecules is improved, and the structural stability of the honeycomb molecular sieve adsorbing material is maintained.
Preferably, the mass ratio of the introduced pyridine to the inert gas in the hydrophobic treatment process is 0.1-1: 100, the mass ratio of the pyridine to the adsorbent is 0.5-1.5: 100.
preferably, the inert gas comprises one or more of nitrogen, helium, argon.
In a second aspect of the invention, there is provided a polycrystalline high-silicon honeycomb molecular sieve adsorbent prepared according to any one of the above preparation methods.
In a third aspect of the invention, the application of the polycrystalline high-silicon honeycomb molecular sieve adsorbent in VOC organic waste gas treatment is provided.
The invention can obtain at least one of the following beneficial effects:
the invention adopts the polycrystalline high-silicon molecular sieve as the main raw material, and makes use of the good adsorbability and hydrophobicity of the molecular sieve to ensure that the product performance fully meets the working condition requirement of VOC organic waste gas adsorption treatment. The binder and the high-silicon composite molecular sieve raw powder are mixed to prepare the mud, so that the viscosity of the mud is increased (which is beneficial to forming) on the basis of not influencing the performance of products, the strength of a blank body is also ensured, the strength of the fired product is also greatly improved, the product is not easy to crack and pulverize in use, and the service life of the product is greatly prolonged. The preparation method disclosed by the invention is simple to operate, low in cost, high in efficiency and suitable for popularization and application.
The adsorbent product obtained by the invention has rich micropores and good adsorption effect on VOC organic waste gas, and has high temperature resistance (the temperature resistance reaches 800 ℃) as the main component adopts a polycrystalline high-silicon composite molecular sieve material, good hydrophobic property and strength and long service life. The invention not only overcomes the defects of insecurity and low adsorption efficiency of the honeycomb activated carbon; meanwhile, the defects that the common honeycomb zeolite molecular sieve is low in strength, absorbs water and releases heat to influence the adsorption effect and the service life are overcome.
In the prior VOC organic waste gas treatment process in China, about 80 percent of the processes are adsorption-desorption-incineration-discharge, the annual demand of the adsorbent is about 150 thousands of cubes, and 90 percent of the processes are honeycomb activated carbon. The market price of the honeycomb activated carbon is about 4000 yuan/cubic, the service life is about 1 year, the treatment cost of hazardous waste is about 5000-. The market price of the product adopting the invention is about 30000 yuan/cube, the service life is about 5 years, the treatment cost of hazardous waste is zero, and the comprehensive cost is about 6000 yuan/year/cube; and is safe, reliable, clean and environment-friendly.
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.
In the preferred embodiment of the present invention, the Si/Al ratio refers to SiO2/Al2O3The molar ratio of (A) to (B); silicon to aluminum ratio of ZSM-5 molecular sieve>400. Silicon-aluminum ratio of HZSM-5 molecular sieve>150. Silica to alumina ratio of ZSM-11 molecular sieve>200. Silicon to aluminum ratio of 13X molecular sieve>2.8 Si/Al ratio of Y molecular sieve>100. Silicon-aluminum ratio of beta molecular sieve>100。
Example 1
A preparation method of a polycrystalline high-silicon honeycomb molecular sieve adsorbent comprises the following steps:
s1, taking high-silicon composite molecular sieve raw powder, adding an aluminum dihydrogen phosphate solution (with the concentration of 20 wt%) with the mass of 25 wt% of the raw powder, mixing, kneading in a kneading machine for 15min to prepare pug, pouring the pug into a vacuum pug mill to prepare a pug segment, and then putting the pug segment into an extruding machine to extrude and form a blank; the raw powder of the high-silicon composite molecular sieve is a ZSM-5 molecular sieve with the silicon-aluminum ratio of more than or equal to 400: 1.
And S2, placing the green body into an industrial microwave oven, controlling the surface temperature of the green body to be 120 ℃, irradiating for 30min, taking out, placing into a kiln, and firing for 2h at 750 ℃ to obtain the molecular sieve adsorbent.
Example 2
A preparation method of a polycrystalline high-silicon honeycomb molecular sieve adsorbent comprises the following steps:
s1, taking 100 parts of high-silicon composite molecular sieve raw powder, 4 parts of calcium chloride and 6 parts of carbon nano tubes, adding a binder (the concentration is 15 wt%) accounting for 15 wt% of the total mass of the raw materials, mixing, kneading in a kneading machine for 10min to prepare pug, then pouring the pug into a vacuum pug mill to prepare a pug segment, and then putting the pug segment into an extruding machine to extrude and form to obtain a blank; wherein the binder is 12 wt% of sodium hexametaphosphate solution, the high-silicon composite molecular sieve raw powder comprises a ZSM-5 molecular sieve and an HZSM-5 molecular sieve (the mass ratio is 8: 1), and the silica-alumina ratio is more than or equal to 400: 1;
and S2, placing the green body into an industrial microwave oven, controlling the surface temperature of the green body to be 90 ℃, irradiating for 60min, taking out, placing into a kiln, and firing for 3h at 650 ℃ to obtain the molecular sieve adsorbent.
Example 3
A preparation method of a polycrystalline high-silicon honeycomb molecular sieve adsorbent comprises the following steps:
s1, taking the high-silicon composite molecular sieve raw powder, adding 40 wt% of binder, mixing, kneading in a kneading machine for 25min to obtain pug, pouring the pug into a vacuum pug mill to obtain a pug segment, and extruding and molding the pug segment in an extruding machine to obtain a blank; the silicon-aluminum ratio of the high-silicon composite molecular sieve raw powder is more than or equal to 400:1, and the composite crystalline phase is; the binder comprises silica sol and alumina sol with the average particle size of 100-600 nm and the concentration of 30 wt%, the high-silicon composite molecular sieve raw powder comprises a ZSM-5 molecular sieve and a Y molecular sieve (the mass ratio is 10: 1), and the silica-alumina ratio is more than or equal to 400: 1;
s2, placing the green body into an industrial microwave oven, controlling the surface temperature of the green body to be 130 ℃, irradiating for 15min, taking out, placing into a kiln, and firing for 1h at 900 ℃ to obtain a molecular sieve adsorbent;
s3: placing the obtained adsorbent in a tubular reactor, introducing nitrogen to remove air in the reactor, and introducing pyridine steam along with the nitrogen to perform hydrophobic treatment on the adsorbent, wherein the mass ratio of the pyridine to the nitrogen is 0.2: 100, the mass ratio of pyridine to adsorbent is 1.5: 100, the reaction temperature is 120 ℃, and the reaction time is 4 hours; then the temperature is reduced to 50 ℃ or below, and nitrogen is continuously introduced for desorption for 2 h.
Example 4
A preparation method of a polycrystalline high-silicon honeycomb molecular sieve adsorbent comprises the following steps:
s1, taking 100 parts of high-silicon composite molecular sieve raw powder, 5 parts of sepiolite powder and 6 parts of calcium chloride, adding a binder accounting for 35 wt% of the total mass of the raw materials, mixing, kneading in a kneading machine for 20min to prepare pug, and pouring the pug into a vacuum pug mill to prepare mudPutting the mud section into an extruder to be extruded and molded to obtain a blank; the binder comprises 10 wt% of SiO2-Al2O3Composite sol (Si: Al ═ 1: 1), 15 wt% sodium tripolyphosphate solution, and SiO2-Al2O3The average particle size of the composite sol is 100-600 nm, the high-silicon composite molecular sieve raw powder comprises a ZSM-5 molecular sieve, a 13X molecular sieve and a beta molecular sieve (the mass ratio is 10: 1: 1), and the silicon-aluminum ratio is more than or equal to 400: 1;
s2, placing the green body into an industrial microwave oven, controlling the surface temperature of the green body to be 100 ℃, irradiating for 45min, taking out, placing into a kiln, and firing for 2h at 850 ℃ to obtain a molecular sieve adsorbent;
s3: placing the obtained adsorbent in a tubular reactor, introducing nitrogen to remove air in the reactor, and introducing pyridine steam along with the nitrogen to perform hydrophobic treatment on the adsorbent, wherein the mass ratio of the pyridine to the nitrogen is 1: 100, the mass ratio of the pyridine to the adsorbent is 1: 100, the reaction temperature is 165 ℃, and the reaction time is 1 h; then the temperature is reduced to 50 ℃ or below, and nitrogen is continuously introduced for desorption, wherein the desorption time is 1 h.
Example 5
A preparation method of a polycrystalline high-silicon honeycomb molecular sieve adsorbent comprises the following steps:
s1, taking 100 parts of high-silicon composite molecular sieve raw powder, 4 parts of magnesium oxide, 5 parts of barium sulfate whisker and 6 parts of carbon nano tube, adding a binder accounting for 20 wt% of the total mass of the raw materials, mixing, kneading in a kneading machine for 20min to prepare pug, then pouring the pug into a vacuum pug mill to prepare a pug segment, and then putting the pug segment into an extruding machine to extrude and form to obtain a blank; the binder is water glass and vegetable gum (mass ratio is 2: 1), the total concentration of the binder is 25 wt%, the high-silicon composite molecular sieve raw powder comprises a ZSM-5 molecular sieve and a ZSM-11 molecular sieve (mass ratio is 5: 1), and the silica-alumina ratio is more than or equal to 400: 1;
s2, placing the green body into an industrial microwave oven, controlling the surface temperature of the green body to be 110 ℃, irradiating for 30min, taking out, placing into a kiln, and firing for 2h at 700 ℃ to obtain a molecular sieve adsorbent;
s3: placing the obtained adsorbent in a tubular reactor, introducing nitrogen to remove air in the reactor, and introducing pyridine steam along with the nitrogen to perform hydrophobic treatment on the adsorbent, wherein the mass ratio of the pyridine to the nitrogen is 0.5: 100, the mass ratio of pyridine to adsorbent is 1.2: 100, the reaction temperature is 130 ℃, and the reaction time is 3 hours; then the temperature is reduced to 50 ℃ or below, and nitrogen is continuously introduced for desorption, wherein the desorption time is 1.5 h.
Example 6
A preparation method of a polycrystalline high-silicon honeycomb molecular sieve adsorbent comprises the following steps:
s1, 100 parts of ZSM-5 molecular sieve raw powder (the silica-alumina ratio is more than 400:1), 6 parts of sepiolite powder, 5 parts of calcium chloride, 6 parts of magnesium oxide, 5 parts of barium sulfate whisker and 8 parts of carbon nano tube, adding aluminum dihydrogen phosphate solution (the concentration is 20 wt%) accounting for 30 wt% of the total mass of the raw materials, mixing, kneading in a kneader for 15min to prepare pug, then pouring the pug into a vacuum pug mill to prepare a pug segment, and then putting the pug segment into an extruder to extrude and form a blank;
s2, placing the green body into an industrial microwave oven, controlling the surface temperature of the green body to be 120 ℃, irradiating for 30min, taking out, placing into a kiln, and firing for 2h at 800 ℃ to obtain a molecular sieve adsorbent;
s3: placing the obtained adsorbent in a tubular reactor, introducing nitrogen to remove air in the reactor, and introducing pyridine steam along with the nitrogen to perform hydrophobic treatment on the adsorbent, wherein the mass ratio of the pyridine to the nitrogen is 0.75: 100, the mass ratio of the pyridine to the adsorbent is 1: 100, the reaction temperature is 150 ℃, and the reaction time is 2 hours; then the temperature is reduced to 50 ℃ or below, and nitrogen is continuously introduced for desorption, wherein the desorption time is 1 h.
Comparative example 1
The water-resistant honeycomb activated carbon (the main component of the activated carbon and the clay) is commercially available in a cubic shape of 100 multiplied by 100mm, the square hole size is 2.5 multiplied by 2.5mm, and the wall thickness is 1.0 mm.
The honeycomb molecular sieve adsorbent products obtained in examples 1 to 5 (same specification as the comparative example) and the honeycomb activated carbon of the comparative example 1 were used for the dynamic adsorption performance test (relative humidity 80%) of benzene and compared with the honeycomb activated carbon, and the results are shown in table 1.
TABLE 1
Dynamic adsorption Capacity/%) Desorption Capacity/% (200 ℃ C.)
Example 1 8.8 >99
Example 2 8.9 >99
Example 3 9.1 >99
Example 4 9.7 >99
Example 5 9.4 >99
Example 6 10.1 >99
Honeycomb active carbon 4.8 85
As can be seen from the data in Table 1, the adsorbent product of the invention has excellent adsorption performance, and compared with honeycomb activated carbon, the dynamic adsorption capacity and desorption capacity are greatly improved.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims (10)

1. The preparation method of the polycrystalline high-silicon honeycomb molecular sieve adsorbent is characterized by comprising the following steps of:
s1, mixing the high-silicon composite molecular sieve raw powder and the binder to prepare pug, and then performing compression molding to obtain a blank; the high-silicon composite molecular sieve raw powder comprises one or more of a ZSM-5 molecular sieve, an HZSM-5 molecular sieve, a ZSM-11 molecular sieve, a 13X molecular sieve, a Y molecular sieve and a beta molecular sieve, and the silicon-aluminum ratio is more than or equal to 400: 1;
s2, drying the blank body by microwave, and then placing the dried blank body at 650-900 ℃ for firing for 1-3 h to obtain the adsorbent.
2. The method as claimed in claim 1, wherein the binder in step S1 comprises silica sol, alumina sol, SiO2-Al2O3One or more of composite sol, water glass, phosphoric acid, sodium tripolyphosphate solution, sodium hexametaphosphate solution, aluminum dihydrogen phosphate solution and vegetable gum, wherein the silica sol, the aluminum sol and SiO2-Al2O3The composite sol has an average particle diameter of 100 to 600 nm.
3. The method for preparing the adsorbent of the polycrystalline high-silicon honeycomb molecular sieve according to claim 1, wherein the amount of the binder added in step S1 is 15-40 wt% of the raw powder of the high-silicon composite molecular sieve, and the concentration of the binder is 10-30 wt%.
4. The method for preparing the adsorbent of the polycrystalline high-silicon honeycomb molecular sieve according to claim 1, wherein the step S1 specifically comprises: mixing the high-silicon composite molecular sieve raw powder and a binder, kneading in a kneading machine for 10-25 min to prepare pug, pouring the kneaded pug into a vacuum pug mill to prepare a pug segment, and then putting the pug segment into an extruding machine for extrusion molding.
5. The method for preparing the adsorbent of the polycrystalline high-silicon honeycomb molecular sieve according to claim 1, wherein the microwave drying in step S2 is specifically to control the surface temperature of the green body to be 90-130 ℃ and the microwave irradiation time to be 15-60 min, and the firing temperature in step S2 is 700-800 ℃.
6. The method as claimed in claim 1, wherein the step S1 further comprises mixing one or more of sepiolite powder, calcium chloride, magnesium oxide, barium sulfate whisker, and carbon nanotube to form a slurry.
7. The method for preparing the adsorbent of the polycrystalline high-silicon honeycomb molecular sieve according to claim 1, wherein step S2 is followed by step S3: placing the adsorbent in a reactor, introducing pyridine steam under the protection of inert gas to perform hydrophobic treatment on the adsorbent, wherein the reaction temperature is 115-170 ℃, and the reaction time is 1-4 hours; and then cooling to 50 ℃ or below, and continuously introducing inert gas for desorption for 1-2 h.
8. The preparation method of the polycrystalline high-silicon honeycomb molecular sieve adsorbent according to claim 7, wherein the mass ratio of the introduced pyridine to the inert gas in the hydrophobic treatment process is 0.1-1: 100, the mass ratio of the pyridine to the adsorbent is 0.5-1.5: 100.
9. a polycrystalline high-silicon honeycomb molecular sieve adsorbent, which is prepared according to the preparation method of any one of claims 1 to 8.
10. The adsorbent according to claim 9, wherein the adsorbent is used in VOC organic waste gas treatment.
CN202111582098.2A 2021-12-22 2021-12-22 Polycrystalline high-silicon honeycomb molecular sieve adsorbent and preparation method thereof Pending CN114225907A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111582098.2A CN114225907A (en) 2021-12-22 2021-12-22 Polycrystalline high-silicon honeycomb molecular sieve adsorbent and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111582098.2A CN114225907A (en) 2021-12-22 2021-12-22 Polycrystalline high-silicon honeycomb molecular sieve adsorbent and preparation method thereof

Publications (1)

Publication Number Publication Date
CN114225907A true CN114225907A (en) 2022-03-25

Family

ID=80761459

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111582098.2A Pending CN114225907A (en) 2021-12-22 2021-12-22 Polycrystalline high-silicon honeycomb molecular sieve adsorbent and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114225907A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116328724A (en) * 2023-03-20 2023-06-27 东洋和光净化材料(江苏)有限公司 VOC adsorbent and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1034392A (en) * 1986-12-18 1989-08-02 环球油品公司 With means of nonzeolitic polymeric adsorbant separation of citric acid from fermented liquid
CN1072654A (en) * 1992-12-09 1993-06-02 复旦大学 The preparation method of hydrophobic crystalline silicon dioxide molecular sieve
WO2013093519A2 (en) * 2011-12-22 2013-06-27 Bio Nano Consulting Carbon nanotube aerogels and xerogels for co2 capture
CN104549185A (en) * 2014-12-04 2015-04-29 同济大学 Surface modification method of metal-organic framework adsorbing materials
CN109482136A (en) * 2018-12-27 2019-03-19 青岛华世洁环保科技有限公司 A kind of adsorbent and preparation method thereof
CN112246217A (en) * 2020-10-30 2021-01-22 上海绿强新材料有限公司 Integral honeycomb molecular sieve for purifying VOCs (volatile organic compounds) in zeolite adsorption rotating wheel and preparation method thereof
CN113019316A (en) * 2021-04-06 2021-06-25 山东众智发环境科技有限公司 Integral honeycomb molecular sieve adsorbent capable of being regenerated in circulating mode and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1034392A (en) * 1986-12-18 1989-08-02 环球油品公司 With means of nonzeolitic polymeric adsorbant separation of citric acid from fermented liquid
CN1072654A (en) * 1992-12-09 1993-06-02 复旦大学 The preparation method of hydrophobic crystalline silicon dioxide molecular sieve
WO2013093519A2 (en) * 2011-12-22 2013-06-27 Bio Nano Consulting Carbon nanotube aerogels and xerogels for co2 capture
CN104549185A (en) * 2014-12-04 2015-04-29 同济大学 Surface modification method of metal-organic framework adsorbing materials
CN109482136A (en) * 2018-12-27 2019-03-19 青岛华世洁环保科技有限公司 A kind of adsorbent and preparation method thereof
CN112246217A (en) * 2020-10-30 2021-01-22 上海绿强新材料有限公司 Integral honeycomb molecular sieve for purifying VOCs (volatile organic compounds) in zeolite adsorption rotating wheel and preparation method thereof
CN113019316A (en) * 2021-04-06 2021-06-25 山东众智发环境科技有限公司 Integral honeycomb molecular sieve adsorbent capable of being regenerated in circulating mode and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
徐同考: "《塑料改性实用技术》", 中国轻工业出版社, pages: 143 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116328724A (en) * 2023-03-20 2023-06-27 东洋和光净化材料(江苏)有限公司 VOC adsorbent and preparation method thereof

Similar Documents

Publication Publication Date Title
KR101916979B1 (en) Porous carbon and method for producing same
CN108409353B (en) Preparation method of SiC porous ceramic material used as smoke carrier of electronic cigarette atomizer
CN108609607B (en) Carbon aerogel with ultrahigh specific surface area and preparation method thereof
JP2002521296A (en) Method for producing mesoporous carbon using pore former
KR20130039528A (en) Method for preparing granulated carbon structure with meso-porous
CN107555430B (en) Pine needle-based activated carbon for supercapacitor and one-step carbonization preparation method thereof
US20110230331A1 (en) ADSORBING MOLDED BODY, ADSORPTION RECOVERY TREATMENT APPARATUS, AND ADSORBATE DESORBING METHOD (amended
CN114225907A (en) Polycrystalline high-silicon honeycomb molecular sieve adsorbent and preparation method thereof
CN105148843A (en) Active carbon granule, preparing method thereof and carbon tank
CN103641507B (en) Zeolite-attapulgite composite honeycomb body and preparation method thereof
CN111302342B (en) Process for manufacturing super-filtration module by using activated carbon fiber powder and carbonization and activation device
CN104607145A (en) Method for preparing bamboo charcoal with controllable aperture
CN101786815B (en) Inorganic intercalated vermiculite insulation refractory material and preparation method thereof
CN110734060A (en) Preparation method of super-capacity carbon
CN103172357A (en) Compact low expansion cordierite honeycomb ceramics heat accumulator
CN113979779B (en) Diatom active ceramic tube and preparation method and application thereof
CN106587053A (en) Preparation process of special activated carbon for desulfurization
CN102924068B (en) Wall-flow honeycomb ceramic filter for high-temperature exhaust gas purification, and preparation method thereof
CN113213963B (en) Light refractory material prepared from construction waste and preparation method thereof
Zhang et al. Synergistic effect of hierarchically porous 4A zeolite on improving the fire retardancy and reducing the fire toxicity of ammonium polyphosphate treated wood composites
CN109573980B (en) Method for preparing high-strength blocky porous carbon by pyrolysis-normal pressure carbonization
CN113117639A (en) Modified molecular sieve adsorbent and preparation method and application thereof
CN1837139A (en) Light ceramic materials and preparation process and use thereof
CN111704425A (en) Calcium silicate board containing sepiolite clay minerals and preparation method thereof
CN115925437B (en) Integral honeycomb molecular sieve for VOCs removal and preparation and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination