CN118204065B - Preparation method of zeolite molecular sieve for VOCs treatment - Google Patents
Preparation method of zeolite molecular sieve for VOCs treatment Download PDFInfo
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- CN118204065B CN118204065B CN202410628227.4A CN202410628227A CN118204065B CN 118204065 B CN118204065 B CN 118204065B CN 202410628227 A CN202410628227 A CN 202410628227A CN 118204065 B CN118204065 B CN 118204065B
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 64
- 239000010457 zeolite Substances 0.000 title claims abstract description 64
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 43
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000001913 cellulose Substances 0.000 claims abstract description 16
- 229920002678 cellulose Polymers 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 239000010902 straw Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 claims abstract description 6
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 238000007146 photocatalysis Methods 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000004408 titanium dioxide Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000010382 chemical cross-linking Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- 239000010419 fine particle Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 3
- 201000010099 disease Diseases 0.000 claims description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 230000008092 positive effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000011069 regeneration method Methods 0.000 description 17
- 230000008929 regeneration Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 238000001994 activation Methods 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
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- 230000018109 developmental process Effects 0.000 description 4
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- 230000036541 health Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
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- 239000002154 agricultural waste Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
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- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- 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
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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- 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
- B01J20/28054—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 surface properties or porosity
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
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- B01J20/34—Regenerating or reactivating
- B01J20/3441—Regeneration or reactivation by electric current, ultrasound or irradiation, e.g. electromagnetic radiation such as X-rays, UV, light, microwaves
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- General Health & Medical Sciences (AREA)
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Abstract
The invention provides a preparation method of a zeolite molecular sieve for treating VOCs, which relates to the technical field of environmental engineering waste gas treatment and comprises the following steps: A. pretreating rape straw, grinding, cleaning and drying to obtain modified bio-based cellulose; B. preparing nano-scale zeolite with an optimized pore structure by using a chemical synthesis method; C. mixing the synthesized nano zeolite with modified bio-based cellulose and activated carbon for molding; D. c, performing functionalization treatment on the composite material obtained in the step C; E. and D, carrying out photocatalysis treatment on the composite material obtained in the step D. The beneficial effects of the invention are as follows: the method is beneficial to improving the treatment efficiency and selectivity of VOCs, reduces the environmental influence and the operation cost by a sustainable method, and has positive effects on environmental protection and air quality improvement.
Description
Technical Field
The invention relates to the technical field of environmental engineering waste gas treatment, in particular to a preparation method of a zeolite molecular sieve for VOCs treatment.
Background
Volatile Organic Compounds (VOCs) are one of the important sources of air pollution, mainly from industrial emissions, transportation, solvent and fuel combustion for home use, and the like. The emission of VOCs has a serious impact on human health and the environment, including carcinogenic risk, ozone layer destruction and deterioration of air quality. Therefore, developing efficient VOCs treatment technology has important environmental and social significance.
The existing VOCs treatment technology mainly comprises an adsorption method, a catalytic combustion method, a biological treatment method and the like. Among them, the adsorption method is widely used because of its simple operation and low cost. Among the numerous adsorbents, activated carbon is commonly used because of its high specific surface area and strong adsorption capacity. However, activated carbon has some disadvantages, such as difficulty in regeneration after saturation of adsorption, high long-term use cost, and low adsorption efficiency for certain specific VOCs.
Zeolite molecular sieves as a novel adsorbent material have shown great potential in the remediation of VOCs. The zeolite molecular sieve has good pore structure and higher specific surface area, and can effectively adsorb VOCs. However, conventional zeolite molecular sieves also have limitations such as a pore structure and surface characteristics that do not fully meet the adsorption requirements of specific VOCs, and a balance between adsorption performance and cost.
How to solve the technical problems is the subject of the present invention.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of the zeolite molecular sieve for treating VOCs, which is beneficial to improving the treatment efficiency and selectivity of the VOCs, reduces the environmental influence and the operation cost by a sustainable method and has positive influence on environmental protection and air quality improvement.
The technical scheme adopted for solving the technical problems is as follows: the invention provides a preparation method of a zeolite molecular sieve for VOCs treatment, which comprises the following steps:
A. pretreating rape straw, grinding, cleaning and drying to obtain modified bio-based cellulose;
a. selecting dried and disease-free rape stalks;
b. Thoroughly cleaning with distilled water;
c. Grinding into fine particles with the particle size of 0.5-1mm;
d. 2% sodium hydroxide solution is used for chemical treatment, for every 100g of dried rape straw, 2g of sodium hydroxide is used for dissolving in enough water, the ground rape straw particles are soaked in the sodium hydroxide solution, complete immersion is ensured, the soaking time is 1-2h, and stirring is carried out to ensure uniform reaction;
e. And cleaning again, drying again by using distilled water, wherein the drying temperature is 60-70 ℃, and the drying time is 2-4h.
B. Preparing nano-scale zeolite with an optimized pore structure by using a chemical synthesis method;
a. Using tetraethoxysilane as a silicon source, aluminum hydroxide as an aluminum source, cetyltrimethylammonium bromide as a template agent, and according to 1:0.1: mixing at a ratio of 0.2 using distilled water as solvent, and a small amount of ethanol may be added to improve mixing;
b. adding a proper amount of sodium hydroxide or hydrochloric acid into the mixture obtained in the step B-a, and adjusting the pH value to 10-11;
c. heating the mixed solution obtained in the step B-B at 80-100 ℃ for 4-6 hours to promote the formation of zeolite;
d. standing the reaction mixture obtained in the step B-c, and aging for 24-48 hours to form a uniform gel structure;
e. baking the gel obtained in the step B-d to remove the template agent and form a pore structure, wherein the baking temperature is 540-560 ℃ and the duration is 5-6h;
f. Steam activation treatment is used to increase the porosity and surface active sites, the activation temperature is 180-200deg.C, and the duration is 1.5-2.5h.
C. Mixing the synthesized nano zeolite with modified bio-based cellulose and activated carbon for molding;
a. Mixing nano zeolite, modified bio-based cellulose and active carbon according to the ratio of 1:1:1, and pretreating the active carbon: firstly, distilled water is used for cleaning, surface impurities are removed, active carbon is dried at 60-80 ℃ until the active carbon is completely dried, and screening is carried out through a proper screen;
b. Adding polyvinyl alcohol as a binder, wherein the addition amount of the polyvinyl alcohol is 5-10% of the total weight of the mixture obtained in the step C-a, and in the addition process, the polyvinyl alcohol is firstly dissolved in water to form a dilute solution and then uniformly added into the mixture of zeolite, modified bio-based cellulose and activated carbon;
c. Extruding the mixture obtained in the step C-b into a required shape such as strips, granules and the like under proper pressure by an extruding machine;
d. And (3) curing, namely placing the extruded material into an oven, and curing at the temperature of 150-160 ℃ for 2-2.5 hours to enhance the structural stability and mechanical strength of the material, and naturally cooling the material to room temperature after curing.
D. C, performing functionalization treatment on the composite material obtained in the step C;
a. Soaking the material obtained in the step C in an ethanol solution containing 1-5% of 3-aminopropyl triethoxysilane;
b. Chemical crosslinking is carried out at 60-80 ℃ for 2-4h, wherein zeolite molecular sieve material soaked with APTES ethanol solution is put into a constant-temperature water bath or oven, and the temperature of 60-80 ℃ is maintained for 2-4h so as to allow APTES molecules to react with hydroxyl groups on the surface of the material to form chemical bonds;
c. And (3) performing heat treatment at 100-120 ℃ for 1-3h, namely transferring the material into an oven after chemical crosslinking is completed, and performing heat treatment at a set temperature to further stabilize the chemical crosslinking structure.
E. and D, carrying out photocatalysis treatment on the composite material obtained in the step D.
A. coating titanium dioxide suspension on the surface of the composite material:
The preparation of the titanium dioxide suspension comprises the following steps:
Dispersing titanium dioxide powder in a proper amount of ethanol or deionized water solvent to prepare a suspension, wherein the concentration of the suspension can be adjusted as required, the concentration is generally kept at a lower concentration and is 1-5%, and an ultrasonic processor is used for carrying out ultrasonic dispersion on the suspension to ensure that titanium dioxide particles are uniformly dispersed;
The coating process comprises the following steps: soaking zeolite molecular sieve material in titanium dioxide suspension for at least 30min, adjusting specific time according to porosity of the material and adsorption efficiency of TiO2, taking out the material after soaking, and air drying at room temperature or using slight hot air to accelerate drying;
And then putting the zeolite molecular sieve material coated with titanium dioxide into an oven, and performing heat treatment at 100-150 ℃ for 1-2 hours to solidify the titanium dioxide coating, wherein uniform coating of the titanium dioxide is crucial to ensure photocatalytic efficiency, and ultrasonic dispersion is a key step for realizing the point, so that the titanium dioxide is ensured not to excessively accumulate or aggregate in the coating process, and the blocking of the porosity and adsorption performance of the zeolite molecular sieve is avoided.
B. the desorption efficiency is tested under UV illumination, the illumination intensity is 1.5 mW/cm, and the time is 30-60min.
The beneficial effects of the invention are as follows:
1. Environmental protection and resource recycling
In the preparation process, rape straw is used as a source of bio-based cellulose, so that the recycling of agricultural wastes is promoted, the environmental pollution is reduced, and the biomass material is used as a raw material to accord with the principles of sustainable development and green chemistry. The use of the rape straw of the invention is helpful for reducing the waste generated by agricultural activities, and converting the waste into valuable products, thereby reducing the environmental cost of waste treatment.
2. Improving VOCs treatment efficiency
According to the invention, by precisely controlling the synthesis conditions of the nano zeolite, the obtained zeolite molecular sieve has an optimized pore structure, so that the efficiency of adsorbing VOCs is greatly improved, and more VOCs molecules can be effectively captured due to the larger specific surface area and proper pore size. The composite of the zeolite and the activated carbon ensures that the material has stronger adsorption capacity, and the combination of the high specific surface area of the activated carbon and the selective adsorption of the zeolite provides a double adsorption mechanism.
3. Reducing operating costs and improving reproducibility
The titanium dioxide coated by the invention provides an effective photocatalytic regeneration path, and the zeolite molecular sieve can be regenerated by illumination, so that the energy consumption of the traditional regeneration method (such as high-temperature treatment) is reduced. Because zeolite molecular sieves are easily regenerated and have a longer service life, the material replacement frequency can be reduced in long-term operation, and the overall cost is reduced.
4. Enhancing adsorption selectivity of specific VOCs
The functional community introduced by APTES treatment of the present invention enables zeolite molecular sieves to more effectively adsorb specific types of VOCs, with such selective adsorption being particularly effective for treating specific industrial emissions or specific pollutants in the environment.
5. Environmental protection and human health dual benefits
The invention effectively controls and reduces the emission of VOCs, is beneficial to improving the air quality and reduces the harm to the environment and the human health. The invention indirectly reduces the generation of surface ozone by reducing the emission of VOCs, thereby resisting urban heat island effect and climate change.
6. Improving the strength and stability of the material
The combination of the zeolite, the activated carbon and the bio-based cellulose improves the overall mechanical strength of the material, so that the material is more suitable for industrial application. Meanwhile, the zeolite molecular sieve subjected to special treatment has good thermal stability, can stably operate in a wider temperature range, and is suitable for different industrial environments.
7. Strong adaptability and wide application potential
Because of the adsorption performance and selectivity of the zeolite molecular sieve, the zeolite molecular sieve can be adjusted according to different VOCs, and is suitable for various industrial emission and environmental pollution occasions. The invention can be used for treating VOCs in industrial emission, and can also be applied to the fields of indoor air purification, automobile exhaust treatment and the like.
8. Contribution to sustainable development
The application of this technology helps achieve a sustainable development goal by utilizing biomass waste and reducing environmental pollution. The development and application of the invention are an important progress in the fields of green chemistry and environmental engineering, and provide a new direction for future environmental protection materials and technologies.
Detailed Description
Technical characteristics of the present solution can be clearly illustrated, and the present solution is illustrated below by means of specific embodiments.
Example 1
The embodiment is a preparation method of a zeolite molecular sieve for VOCs treatment, which comprises the following steps:
A. pretreating rape straw, grinding, cleaning and drying to obtain modified bio-based cellulose;
a. selecting dried and disease-free rape stalks;
b. Thoroughly cleaning with distilled water;
c. Grinding into fine particles with the particle size of 0.8mm;
d. Carrying out chemical treatment by using 2% sodium hydroxide solution, soaking the ground rape straw particles in the sodium hydroxide solution for 2 hours, and stirring to ensure uniform reaction;
e. And cleaning again and drying again by using distilled water, wherein the drying temperature is 60 ℃ and the drying time is 3 hours.
B. Preparing nano-scale zeolite with an optimized pore structure by using a chemical synthesis method;
a. Using tetraethoxysilane as a silicon source, aluminum hydroxide as an aluminum source, cetyltrimethylammonium bromide as a template agent, and according to 1:0.1: mixing at a ratio of 0.2, using distilled water as solvent, and adding a small amount of ethanol;
b. adding a proper amount of sodium hydroxide or hydrochloric acid into the mixture obtained in the step B-a, and adjusting the pH value to 11;
c. Heating the mixed solution obtained in the step B-B for 5 hours at 80 ℃;
d. standing the reaction mixture obtained in the step B-c, and aging for 48 hours;
e. baking the gel obtained in the step B-d at 550 ℃ for 6 hours;
f. the activation treatment was carried out using steam at an activation temperature of 200℃for a duration of 2h.
C. Mixing the synthesized nano zeolite with modified bio-based cellulose and activated carbon for molding;
a. Mixing nano zeolite, modified bio-based cellulose and active carbon according to the ratio of 1:1:1, and pretreating the active carbon: firstly, distilled water is used for cleaning, surface impurities are removed, active carbon is dried at 70 ℃ until the active carbon is completely dried, and screening is carried out through a screen;
b. Adding polyvinyl alcohol as a binder, wherein the addition amount of the polyvinyl alcohol is 8% of the total weight of the mixture obtained in the step C-a, and in the addition process, the polyvinyl alcohol is firstly dissolved in water to form a dilute solution and then uniformly added into the mixture of zeolite, modified bio-based cellulose and activated carbon;
c. Extrusion molding;
d. And (3) solidifying, namely putting the extruded material into an oven, solidifying at the temperature of 155 ℃ for 2 hours, and naturally cooling the material to room temperature after solidification.
D. C, performing functionalization treatment on the composite material obtained in the step C;
a. soaking the material obtained in the step C in an ethanol solution containing 3% of 3-aminopropyl triethoxysilane;
b. Chemical crosslinking is carried out at 70 ℃ for 3 hours, namely the zeolite molecular sieve material soaked with APTES ethanol solution is put into a constant-temperature water bath or an oven, and the temperature of 70 ℃ is maintained for 3 hours;
c. heat treatment at 120 deg.c for 2 hr, after chemical crosslinking, transferring the material into oven and heat treatment at set temperature;
E. and D, carrying out photocatalysis treatment on the composite material obtained in the step D.
A. coating titanium dioxide suspension on the surface of the composite material:
The preparation of the titanium dioxide suspension comprises the following steps:
dispersing titanium dioxide powder into a proper amount of ethanol solvent to prepare a suspension with the concentration of 3%, and performing ultrasonic dispersion on the suspension by using an ultrasonic processor to ensure that titanium dioxide particles are uniformly dispersed;
The coating process comprises the following steps: soaking zeolite molecular sieve material in titanium dioxide suspension for 1h, wherein the soaking time is regulated according to the porosity of the material and the adsorption efficiency of TiO2, taking out the material after soaking, airing at room temperature, and accelerating drying by using slight hot air;
Then putting the zeolite molecular sieve material coated with titanium dioxide into an oven, and performing heat treatment at 120 ℃ for 1.5 hours to solidify the titanium dioxide coating;
b. The desorption efficiency was tested under UV light with an illumination intensity of 1.5 mW/cm for 50min.
Example two
Similar to the preparation method of the first embodiment, the difference is that in the step A, the cleaned rape stalks are ground into fine particles, and the particle size is 1mm.
Example III
Similar to the preparation method of example one, except that in step B-C, the mixed solution obtained in step B-B was heated at 80℃for 4 hours to promote the formation of zeolite; the reaction mixture obtained in steps B-c was then allowed to stand and aged for 36 hours.
Example IV
Similar to the preparation of example one, the difference is that in steps B-f, a steam activation treatment is used to increase the porosity and surface active sites, the activation temperature being 180 ℃ for a duration of 2h.
Example five
Similar to the preparation of example one, except that in step C-b, 5% polyvinyl alcohol was added as binder.
Example six
The preparation was similar to that of example one, except that in step D-a, the material was immersed in an ethanol solution containing 1% APTES and chemically crosslinked at 70℃for 3 hours.
Control experiment
1. VOCs adsorption efficiency test
Experimental materials and apparatus:
VOCs (toluene used).
Gas chromatography-mass spectrometry (GC-MS).
A closed vessel (volume 5 liters).
Microinjectors (for accurate injection of VOCs).
Scale (precision 0.01 g).
Zeolite molecular sieve samples (5 grams per sample from six examples plus commercially available zeolite molecular sieve product as a comparative example).
The experimental steps are as follows:
(1) Weighing zeolite molecular sieve samples of each example by using a precision scale to ensure that the weight of each sample is consistent and is 5g;
(2) Toluene of known concentration was injected into the closed vessel, and the toluene was precisely injected to a desired initial concentration of 100 mg/L using a microinjector.
(3) The weighed zeolite molecular sieve sample was placed in a vessel containing toluene.
(4) The sample was exposed to toluene vapor for 2 hours to ensure that the adsorption reached equilibrium.
(5) The toluene concentration before and after exposure was determined using GC-MS.
(6) Toluene concentration data before and after adsorption were recorded.
The adsorption efficiency is calculated as follows:
Adsorption efficiency (%) = (initial concentration (mg/L) -final concentration (mg/L))/initial concentration (mg/L) ×100%
The following are specific results of the adsorption efficiencies of VOCs of six examples, one comparative example:
From the above data, it can be seen that example one shows the relatively highest adsorption efficiency (54.26%), which in the preparation stage of nano zeolite, the optimized temperature, time and pH value help to form more effective pore structure, thus increasing the adsorption capacity to VOCs, and in addition, pretreatment of rape straw and use of polyvinyl alcohol help to increase the adsorption efficiency of the final product.
The adsorption efficiency of the second example is slightly lower than that of the first example (53.91%), and the increase of the particle size may lead to the reduction of the surface area due to the slightly larger grinding particle size of the rape straw, thus slightly affecting the adsorption performance.
The adsorption efficiency of example three was significantly reduced (36.50%) due to the reduction in heating time and aging time during the preparation of the nano zeolite, which affected the formation of pore structure, thereby reducing the number of adsorption sites.
The adsorption efficiency of example four (48.75%) is higher than example three because a lower activation temperature is used in the steam activation process, which helps to maintain the integrity of the pore structure, thereby increasing the adsorption efficiency.
The adsorption efficiency (40.87%) of example five was somewhat reduced compared to example four, since the reduction in the amount of polyvinyl alcohol added affected the overall stability and pore distribution of the final material, and thus the adsorption efficiency.
The adsorption efficiency (42.04%) of example six was similar to that of example five, although example six used a lower concentration of APTES in the functionalization process, indicating that the reduction in APTES concentration had some effect on adsorption efficiency, but to a limited extent.
In contrast, the adsorption efficiency of commercial zeolite molecular sieves is the lowest (15.71%), which affects its ability to adsorb VOCs due to its pore structure, surface characteristics, and lower purity and optimization.
2. Regeneration effect test
Experimental materials and apparatus
The same experiment was carried out.
Experimental procedure
(1) Each sample was saturated for adsorption according to one step of the experiment.
(2) According to the regeneration method of each example, the saturated zeolite molecular sieve is subjected to a regeneration treatment, i.e., irradiated with a UV lamp for, e.g., 1 hour.
(3) The regenerated sample was subjected to repeated adsorption experiments of experiment one.
(4) The concentration of toluene was again determined using GC-MS.
(5) Toluene concentration data before and after re-adsorption were recorded.
The calculation formula of the regeneration effect is as follows:
regeneration effect (%) =adsorption efficiency after re-adsorption (%)/primary adsorption efficiency (%) ×100%
The following are specific results of the regeneration effect test for six examples, one comparative example:
From the above data, it is shown that example one shows the best regeneration effect (91.12%), and that the optimization of the materials and preparation method ensures that the higher adsorption performance is maintained even during regeneration. The regeneration effect of the other examples (two to six) was slightly lower than that of example one, but still exhibited better regeneration capability. Although the regeneration effect of these examples is slightly lower than that of example one, they still retain the ability to maintain higher adsorption efficiency after regeneration.
The regeneration effect of the commercial zeolite molecular sieve is the lowest (60.46%), and the material quality and the pore structure of the commercial zeolite molecular sieve are poorer than those of the zeolite molecular sieve prepared by the scheme. During adsorption and regeneration, its performance is significantly reduced and commercially available materials are limited in this regard.
The technical features of the present invention that are not described in the present invention may be implemented by or using the prior art, and are not described in detail herein, but the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, but is also intended to be within the scope of the present invention by those skilled in the art.
Claims (8)
1. The preparation method of the zeolite molecular sieve for treating VOCs is characterized by comprising the following steps of:
A. pretreating rape straw, grinding, cleaning and drying to obtain modified bio-based cellulose;
B. preparing nano-scale zeolite with a pore structure by using a chemical synthesis method;
C. Mixing the synthesized nano zeolite with modified bio-based cellulose and activated carbon for molding;
D. and C, performing functionalization treatment on the composite material obtained in the step C, wherein the method specifically comprises the following steps:
a. Soaking the material obtained in the step C in an ethanol solution containing 1-5% of 3-aminopropyl triethoxysilane;
b. Chemical crosslinking is carried out at 60-80 ℃ for 2-4h;
c. Performing heat treatment at 100-120deg.C for 1-3h;
E. and D, carrying out photocatalysis treatment on the composite material obtained in the step D, wherein the method specifically comprises the following steps:
a. coating titanium dioxide suspension on the surface of the composite material;
b. the desorption efficiency is tested under UV illumination, the illumination intensity is 1.5 mW/cm, and the time is 30-60min.
2. The method for preparing zeolite molecular sieves for treating VOCs according to claim 1, wherein the step a specifically comprises the steps of:
a. selecting dried and disease-free rape stalks;
b. Washing with distilled water;
c. grinding into fine particles;
d. chemical treatment with 2% sodium hydroxide solution;
e. cleaning and drying again.
3. The method for preparing zeolite molecular sieves for treating VOCs according to claim 2, wherein in step A-c, the zeolite molecular sieves are ground into fine particles with the particle size of 0.5-1mm;
In the steps A-d, for every 100 g of dried rape straw, 2g of sodium hydroxide is used for dissolving in enough water, the ground rape straw particles are soaked in the sodium hydroxide solution for 1-2h, and stirring is carried out to ensure uniform reaction;
and (c) cleaning again by using distilled water in the steps A-e, wherein the drying temperature is 60-70 ℃ and the drying time is 2-4h.
4. The method for preparing zeolite molecular sieves for treating VOCs according to claim 1, wherein the step B specifically comprises the steps of:
a. Using tetraethoxysilane as a silicon source, aluminum hydroxide as an aluminum source, cetyltrimethylammonium bromide as a template agent, and according to 1:0.1: mixing at a ratio of 0.2 using distilled water as solvent;
b. adding a proper amount of sodium hydroxide or hydrochloric acid into the mixture obtained in the step B-a, and adjusting the pH value to 10-11;
c. Heating the mixed solution obtained in the step B-B for 4-6 hours at 80-100 ℃;
d. standing the reaction mixture obtained in the step B-c, and aging for 24-48 hours;
e. baking the gel obtained in the step B-d at 540-560 ℃ for 5-6 hours;
f. The water vapor is used for activating treatment, the activating temperature is 180-200 ℃ and the duration is 1.5-2.5h.
5. The method for preparing zeolite molecular sieves for treating VOCs according to claim 1, wherein the specific steps of step C are as follows:
a. Mixing nano zeolite, modified bio-based cellulose and active carbon according to the ratio of 1:1:1;
b. adding polyvinyl alcohol as a binder;
c. Extrusion molding;
d. And (5) curing.
6. The method for preparing zeolite molecular sieves for treating VOCs according to claim 5, wherein the activated carbon in step C-a is pretreated: firstly, distilled water is used for cleaning, and the activated carbon is dried at 60-80 ℃;
The addition amount of the polyvinyl alcohol in the step C-b is 5-10% of the total weight of the mixture obtained in the step C-a, and in the addition process, the polyvinyl alcohol is firstly dissolved in water to form a dilute solution and then is uniformly added into the mixture of zeolite, modified bio-based cellulose and activated carbon;
and C-d, placing the extruded material into an oven, curing at 150-160 ℃ for 2-2.5h, and naturally cooling the material to room temperature after curing.
7. The method for preparing zeolite molecular sieves for treating VOCs according to claim 1, wherein in step D-b, the zeolite molecular sieves material soaked with APTES ethanol solution is put into a constant temperature water bath or oven, and the temperature is maintained at 60-80 ℃ for 2-4 hours;
in step D-c, after chemical crosslinking is completed, the material is transferred to an oven and heat treated at a set temperature.
8. The method for preparing zeolite molecular sieves for treating VOCs according to claim 1, wherein the preparation of the titania suspension in step E-a comprises the steps of:
dispersing titanium dioxide powder into a proper amount of ethanol or deionized water solvent to prepare a suspension with the concentration of 1-5%, and carrying out ultrasonic dispersion on the suspension by using an ultrasonic processor.
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