CN111068716A - VOCs separating and degrading film and preparation method thereof - Google Patents
VOCs separating and degrading film and preparation method thereof Download PDFInfo
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- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 96
- 230000000593 degrading effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 135
- 239000000919 ceramic Substances 0.000 claims abstract description 109
- 238000001471 micro-filtration Methods 0.000 claims abstract description 97
- 230000015556 catabolic process Effects 0.000 claims abstract description 51
- 238000006731 degradation reaction Methods 0.000 claims abstract description 51
- 238000000926 separation method Methods 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 claims abstract description 38
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000007598 dipping method Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 230000002195 synergetic effect Effects 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- 239000010948 rhodium Substances 0.000 claims description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 9
- 231100000719 pollutant Toxicity 0.000 description 9
- 238000001816 cooling Methods 0.000 description 6
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- 238000005303 weighing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
The invention discloses a VOCs separating and degrading film and a preparation method thereof, wherein copper nitrate, manganese nitrate and cerium nitrate are added into water and stirred to obtain a thermal catalysis system; mixing tetrabutyl titanate and isopropanol to obtain a photocatalyst system; dropwise adding the photocatalytic system into the thermal catalytic system, and stirring to obtain an active component negative carrier liquid; adding an auxiliary agent and a noble metal to obtain a load precursor; pretreating the ceramic microfiltration membrane to enable the pore size of the ceramic microfiltration membrane to be matched with the molecular size of VOCs, dipping and pulling the ceramic microfiltration membrane in a load precursor to enable a thermal-photocatalyst to be naturally loaded on the ceramic microfiltration membrane, calcining, and reducing to obtain the VOCs separation degradation membrane; according to the invention, the thermal-photocatalyst is loaded on the ceramic microfiltration membrane, so that the aperture of the membrane is reduced, and the separation and interception of VOCs gas are met; and the organic pollutants are efficiently intercepted and simultaneously decomposed in situ, so that the separation and degradation efficiency of the VOCs molecules is effectively improved, and the VOCs are thoroughly degraded.
Description
Technical Field
The invention belongs to the technical field of VOCs separation and degradation, and particularly relates to a VOCs separation and degradation film and a preparation method thereof.
Background
VOCs (volatile organic compounds) are common atmospheric pollutants in the chemical industry and are one of the main sources of atmospheric pollution. In recent years, a plurality of technologies are applied to the treatment of VOCs, wherein the thermal catalysis and photocatalytic oxidation methods can effectively degrade the VOCs due to strong oxidation capacity, and the photocatalytic technology is a low-cost green common technology and has application prospects in the directions of environmental treatment, solar energy conversion, self-cleaning and the like.
At present, the separation efficiency and the surface reaction activity of a photo-generated carrier of the existing photocatalyst method are not high, and a single technical method cannot thoroughly degrade VOCs; the thermocatalysis method has high energy consumption and is not suitable for the separation and degradation treatment of VOCs with small scale or low concentration.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a VOCs separating and degrading film and a preparation method thereof, aiming at solving the technical problems of low VOCs separating and degrading efficiency and high energy consumption in the prior art and realizing the high-efficiency separation and degradation of VOCs.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a VOCs separation degradation film, which comprises the following steps:
step 1, adding copper nitrate, manganese nitrate and cerium nitrate into water, and stirring to obtain a thermocatalysis system; mixing tetrabutyl titanate and isopropanol to obtain a photocatalyst system;
step 2, dropwise adding the photocatalytic system into the thermocatalytic system, and stirring until sol is formed to obtain an active component negative carrier liquid;
step 3, adding an auxiliary agent and a noble metal into the active component loading liquid, strongly stirring, and maintaining to obtain a loaded precursor;
step 4, pretreating the ceramic microfiltration membrane to enable the pore size of the ceramic microfiltration membrane to be matched with the molecular size of VOCs;
step 5, dipping and pulling the pretreated ceramic microfiltration membrane in a load precursor to naturally load the thermal-photocatalyst on the ceramic microfiltration membrane;
step 6, repeating the step 5 until the number of the loading layers of the thermal-photocatalyst on the ceramic microfiltration membrane meets the condition that the retention rate of different molecules in VOCs is more than 90 percent, and obtaining the thermal-photocatalytic synergetic catalytic ceramic membrane;
and 7, calcining the thermal-optical synergetic catalytic ceramic membrane, and reducing to obtain the VOCs separation and degradation film.
Further, in step 1, the mass ratio of Cu2+: Mn2+: Ce2+: H2O in the thermal catalysis system is as follows: (3-4): (3-4): 1-2): 6-9); in the photocatalysis system, tetrabutyl titanate and isopropanol are mixed according to the volume ratio of (1-1.5): (2-3) mixing.
Further, in the step 3, the auxiliary agent is one or more of silica sol, phosphoric acid, urea, pseudo-boehmite, citric acid and a silane coupling agent; the mass ratio of the auxiliary agent to the active component loading liquid is (1-3): 5, mixing.
Further, in the step 3, the molar concentration of the noble metal is 0.5-5%; the noble metal is one or more of platinum, palladium and rhodium; the curing process is carried out at room temperature for 5-6 h.
Further, in the step 3, in the process of intensive stirring, the stirring speed is 400-600r/min, and the stirring time is 5-10 h.
Further, in step 4, when the ceramic microfiltration membrane is pretreated, the following steps are specifically performed:
step 41, carrying out ultrasonic cleaning on the ceramic microfiltration membrane;
step 42, baking the cleaned ceramic microfiltration membrane;
43, putting the ceramic microfiltration membrane in the step 42 into dilute nitric acid; wherein the mass fraction of the dilute nitric acid is 5-7%; heating in water bath, taking out, cleaning, and baking.
Further, in step 6, the number of the thermal-photocatalyst supporting layers on the ceramic microfiltration membrane is 1-3.
Further, in step 6, each time of dipping is 30-40min, the pulling speed is 1-3cm/min, and drying treatment is carried out at 50-80 ℃ until no sol drops on the ceramic microfiltration membrane.
Further, in step 7, the calcination process is carried out in an air atmosphere at the temperature of 300-; the reduction process adopts hydrogen to reduce for 6-9 h.
The invention also provides a VOCs separating and degrading film which is prepared by the preparation method of the VOCs separating and degrading film.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a VOCs separation degradation film, which adopts a ceramic microfiltration membrane as a base membrane, and loads a thermal catalyst and a photocatalyst on the ceramic microfiltration membrane, so that the aperture of the film is reduced, and the separation and interception of VOCs gas are met; meanwhile, the VOCs molecules on the membrane surface and inside the membrane are catalyzed and degraded under the heating and ultraviolet irradiation; the ceramic microfiltration membrane realizes the matching of the pore size and the molecular size of VOCs through the load of a thermal-photocatalyst, can efficiently intercept organic pollutants and decompose the organic pollutants in situ, effectively improves the separation and degradation efficiency of the VOCs molecules, and realizes the thorough degradation of the VOCs.
The VOCs separation and degradation film is used as a novel pollutant interception and degradation integrated technology, can efficiently intercept organic pollutants and decompose the organic pollutants in situ, and the molecular radius of gaseous pollutants is relatively small; after the ceramic microfiltration membrane is pretreated, the problem of matching of the membrane aperture and VOCs molecules is solved, the ceramic microfiltration membrane is used for the primary gas interception process, and in addition, a photo-thermal catalyst needs to be loaded on the surface of the base membrane of the ceramic microfiltration membrane, the photo-thermal catalyst can play a role in reducing the membrane aperture, and the functions of thermal-photo catalysis and membrane aperture adjustment are realized at the same time. The VOCs separating and degrading film has excellent performance under the photo-thermal condition, the matching of pore size and VOCs molecular size is realized through the load of a load photo-thermal catalyst, the VOCs are subjected to in-situ degradation while the VOCs are subjected to primary interception and concentration, macromolecules in the VOCs are passively migrated into the film material after the initial degradation of the film surface, and the macromolecules are continuously contacted with internal catalytic active sites in the migration process until mineralization due to the pore size matching.
Drawings
FIG. 1 is a flow chart of the preparation and action principle of a VOCs separating and degrading film according to the present invention;
FIG. 2 is a temperature rise curve of the VOCs separating and degrading membrane in example 1 under the condition of microwave power of 400W;
FIG. 3 is a graph showing the toluene removal efficiency of the VOCs separating and degrading membrane of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
As shown in the attached figure 1, the invention provides a preparation method of a film for separating and degrading VOCs, which comprises the following steps:
step 1, adding copper nitrate, manganese nitrate and cerium nitrate into water, and stirring to obtain a thermal catalysis system, wherein in the thermal catalysis system, Cu is contained2+:Mn2+:Ce2+:H2The mass ratio of O is as follows: (3-4): (3-4): 1-2): 6-9);
tetrabutyl titanate and isopropanol are mixed according to the volume ratio of (1-1.5): (2-3) to obtain a photocatalyst system;
step 2, dropwise adding the photocatalytic system into the thermocatalytic system, and stirring until sol is formed to obtain an active component negative carrier liquid;
step 3, adding an auxiliary agent and noble metal into the active component loading liquid, and intensively stirring for 5-10h at the stirring speed of 400-; curing for 5-6h at room temperature to obtain a load precursor; the auxiliary agent is one or more of silica sol, phosphoric acid, urea, pseudo-boehmite, citric acid and a silane coupling agent; the mass ratio of the auxiliary agent to the active component loading liquid is (1-3): 5, mixing in proportion; the molar concentration of the noble metal is 0.5 to 5 percent; the noble metal is one or more of platinum, palladium and rhodium;
step 4, pretreating the ceramic microfiltration membrane to enable the pore size of the ceramic microfiltration membrane to be matched with the molecular size of VOCs; specifically, the method comprises the following steps:
step 41, carrying out ultrasonic cleaning on the ceramic microfiltration membrane for 10-15 min;
42, putting the cleaned ceramic microfiltration membrane into a baking oven at the temperature of 110-;
and 43, putting the baked ceramic microfiltration membrane in the step 42 into dilute nitric acid, heating in a water bath for 2-3h, taking out, cleaning and baking for later use.
Step 5, dipping and pulling the pretreated ceramic microfiltration membrane in a load precursor, wherein the dipping time is 30-40min each time, and the pulling speed is 1-3cm/min, so that the thermal-photocatalyst is naturally loaded on the ceramic microfiltration membrane; drying the ceramic microfiltration membrane at 50-80 ℃ until no sol drops on the ceramic microfiltration membrane;
step 6, repeating the step 5 until the number of the thermal-photocatalyst loading layers on the ceramic microfiltration membrane meets the condition that the retention rate of different molecules in VOCs is more than 90 percent, and the number of the thermal-photocatalyst loading layers on the ceramic microfiltration membrane is 1-3; obtaining a thermal-optical synergetic catalytic ceramic membrane;
step 7, placing the thermal-optical synergetic catalytic ceramic membrane into a muffle furnace, and calcining for 5-6 hours in an air atmosphere at the temperature of 300-; and then, reducing by using hydrogen for 6-9h to obtain the VOCs separation and degradation film.
According to the preparation method of the VOCs separation and degradation film, the ceramic microfiltration membrane is used as a base membrane, the ceramic microfiltration membrane is subjected to thermal-optical catalyst natural impregnation loading for a plurality of times in a thermal-optical catalytic system, and the VOCs separation and degradation film is obtained after calcination and reduction. According to the VOCs separation and degradation film, the optimal number of loading layers is limited and obtained by taking the retention rate of different molecules in VOCs as 90%, the loading layers are finely regulated and controlled by combining the catalytic degradation efficiency of different VOCs molecules, the universal membrane pore size is obtained, and the matching of the membrane pore size and the VOCs molecular size is realized; by adopting the ceramic microfiltration membrane as a base membrane and loading the thermal catalyst and the photocatalyst on the ceramic microfiltration membrane, the aperture of the membrane is reduced, and the separation and interception of VOCs gas are met; meanwhile, the VOCs molecules on the membrane surface and inside the membrane are catalyzed and degraded under the heating and ultraviolet irradiation; the ceramic microfiltration membrane realizes the matching of the pore size and the molecular size of VOCs through the load of a thermal-photocatalyst, can efficiently intercept organic pollutants and decompose the organic pollutants in situ, effectively improves the separation and degradation efficiency of the VOCs molecules, and realizes the thorough degradation of the VOCs.
Example 1
Embodiment 1 provides a method for preparing a membrane for separating and degrading VOCs, comprising the following steps:
step 1, weighing quantitative copper nitrate, manganese nitrate and cerium nitrate reagents according to requirements, adding the copper nitrate, manganese nitrate and cerium nitrate reagents into water, and stirring to obtain a thermal catalysis system; wherein Cu in the thermocatalytic system2+:Mn2+:Ce2+:H2The mass ratio of O is as follows: 3:3:1: 6; mixing tetrabutyl titanate and isopropanol according to a volume ratio of 1:2 to obtain a photocatalyst system;
step 2, dropwise adding the photocatalytic system into the thermocatalytic system, and stirring until sol is formed to obtain an active component negative carrier liquid;
step 3, adding silica sol and platinum into the active component loading liquid, and stirring strongly for 5 hours at the stirring speed of 600 r/min; curing for 5-6h at room temperature to obtain a load precursor; the mass ratio of the silica sol to the active component loading liquid is 3:5, mixing in proportion; the molar concentration of platinum is 0.5%;
step 4, pretreating the ceramic microfiltration membrane to enable the pore size of the ceramic microfiltration membrane to be matched with the molecular size of VOCs; specifically, the method comprises the following steps:
step 41, carrying out ultrasonic cleaning on the ceramic microfiltration membrane for 10 min;
42, putting the cleaned ceramic microfiltration membrane into a 120 ℃ oven, and baking for 1 h;
and 43, putting the baked ceramic microfiltration membrane in the step 42 into dilute nitric acid with the mass fraction of 5%, heating in a water bath for 2 hours, taking out, and cleaning and baking for later use.
Step 5, dipping and pulling the pretreated ceramic microfiltration membrane in a load precursor, wherein the dipping time is 30min each time, and the pulling speed is 1cm/min, so that the thermal-photocatalyst is naturally loaded on the ceramic microfiltration membrane; the number of the thermal-photocatalyst loading layers on the ceramic microfiltration membrane is 1; baking in an oven at 80 deg.C for 1 hr, and naturally cooling;
step 6, putting the thermal-optical synergetic catalytic ceramic membrane into a muffle furnace, and calcining for 5 hours in an air atmosphere at 500 ℃; and then, reducing by using hydrogen for 6 hours to obtain the VOCs separation and degradation film.
The microwave temperature rise experiment is carried out on the VOCs separation and degradation film prepared in the embodiment 1 once, and the temperature rise curve of the VOCs separation and degradation film when the microwave power is 400W is obtained, as shown in FIG. 2, it can be seen from FIG. 2 that the VOCs separation and degradation film prepared according to the above conditions has good temperature rise effect, can rise to more than 300 ℃ in a short time, and the temperature reaches the degradation temperature of a plurality of gases, so that various types of atmospheric pollutants can be degraded and removed.
As shown in fig. 3, fig. 3 shows a graph of the removal efficiency when the VOCs separation and degradation film is used to remove toluene, and it can be seen from fig. 3 that when the VOCs separation and degradation film is used to remove toluene, the removal efficiency is high, and as time goes on, the removal efficiency can reach more than 80%.
Example 2
Embodiment 2 provides a method for preparing a VOCs separation degradation membrane, which includes the following steps:
step 1, weighing quantitative copper nitrate, manganese nitrate and cerium nitrate reagents according to requirements, adding the copper nitrate, manganese nitrate and cerium nitrate reagents into water, and stirring to obtain a thermal catalysis system; wherein, in the thermocatalytic system, Cu2+:Mn2+:Ce2+:H2The mass ratio of O is as follows: 4:4:1: 8;
mixing tetrabutyl titanate and isopropanol according to a volume ratio of 1.2:2.5 to obtain a photocatalyst system;
step 2, dropwise adding the photocatalytic system into the thermocatalytic system, and stirring until sol is formed to obtain an active component negative carrier liquid;
step 3, adding phosphoric acid and palladium into the active component loading liquid, and stirring strongly for 8 hours at the stirring speed of 500 r/min; curing for 5-6h at room temperature to obtain a load precursor; mixing phosphoric acid and active component loading liquid according to the mass ratio of 2: 5; the molar concentration of palladium is 2%;
step 4, pretreating the ceramic microfiltration membrane to enable the pore size of the ceramic microfiltration membrane to be matched with the molecular size of VOCs; specifically, the method comprises the following steps:
step 41, carrying out ultrasonic cleaning on the ceramic microfiltration membrane for 12 min;
42, putting the cleaned ceramic microfiltration membrane into a drying oven at 110 ℃ for drying for 1.5 h;
and 43, putting the baked ceramic microfiltration membrane in the step 42 into dilute nitric acid with the mass fraction of 6%, heating in a water bath for 2.5 hours, taking out, cleaning and baking for later use.
Step 5, dipping and pulling the pretreated ceramic microfiltration membrane in a load precursor, wherein the dipping time is 35min each time, and the pulling speed is 2cm/min, so that the thermal-photocatalyst is naturally loaded on the ceramic microfiltration membrane; the number of the thermal-photocatalyst loading layers on the ceramic microfiltration membrane is 2; baking in an oven at 70 deg.C for 1 hr, and naturally cooling;
step 6, putting the thermal-optical synergetic catalytic ceramic membrane into a muffle furnace, and calcining for 9 hours at 400 ℃ in an air atmosphere; and then, reducing by using hydrogen for 7h to obtain the VOCs separation and degradation film.
The VOCs separation and degradation film prepared in example 2 was loaded twice and subjected to a microwave heating experiment. Experiments show that the temperature rising effect of the VOCs separating and degrading film is good, the temperature can rise to more than 300 ℃ in a short time, the temperature reaches the degradation temperature of a plurality of gases, and the film can degrade and remove various types of atmospheric pollutants and achieve higher removal rate.
Example 3
Embodiment 3 provides a method for preparing a VOCs separation degradation membrane, comprising the following steps:
step 1, weighing quantitative copper nitrate, manganese nitrate and cerium nitrate reagents according to requirements, and adding the copper nitrate, manganese nitrate and cerium nitrate reagents into the mixtureStirring in water to obtain a thermal catalytic system; wherein, in the thermocatalytic system, Cu2+:Mn2+:Ce2+:H2The mass ratio of O is as follows: 4:4:2: 9;
mixing tetrabutyl titanate and isopropanol according to a volume ratio of 1.5:3 to obtain a photocatalyst system;
step 2, dropwise adding the photocatalytic system into the thermocatalytic system, and stirring until sol is formed to obtain an active component negative carrier liquid;
step 3, adding urea and rhodium into the active component loading liquid, and stirring strongly for 10 hours at the stirring speed of 400 r/min; curing for 5-6h at room temperature to obtain a load precursor; mixing urea and active component loading liquid according to the mass ratio of 2.5: 5; the molar concentration of rhodium is 4%;
step 4, pretreating the ceramic microfiltration membrane to enable the pore size of the ceramic microfiltration membrane to be matched with the molecular size of VOCs; specifically, the method comprises the following steps:
step 41, carrying out ultrasonic cleaning on the ceramic microfiltration membrane for 15 min;
42, putting the cleaned ceramic microfiltration membrane into a 120 ℃ oven, and baking for 1 h;
and 43, putting the baked ceramic microfiltration membrane in the step 42 into dilute nitric acid with the mass fraction of 7%, heating in a water bath for 3 hours, taking out, and cleaning and baking for later use.
Step 5, dipping and pulling the pretreated ceramic microfiltration membrane in a load precursor, wherein the dipping time is 30min each time, and the pulling speed is 3cm/min, so that the thermal-photocatalyst is naturally loaded on the ceramic microfiltration membrane; the number of the thermal-photocatalyst loading layers on the ceramic microfiltration membrane is 3; baking in a baking oven at 50 ℃ for 1 hour, and naturally cooling;
step 6, putting the thermal-optical synergetic catalytic ceramic membrane into a muffle furnace, and calcining for 5 hours in an air atmosphere at 500 ℃; and then, reducing by using hydrogen for 7h to obtain the VOCs separation and degradation film.
The VOCs separation and degradation film prepared in example 3 was loaded twice and subjected to a microwave heating experiment. Experiments show that the temperature rising effect of the VOCs separating and degrading film is good, the temperature can rise to more than 300 ℃ in a short time, the temperature reaches the degradation temperature of a plurality of gases, and the film can degrade and remove various types of atmospheric pollutants and achieve higher removal rate.
Example 4
Embodiment 4 provides a method for preparing a VOCs separation degradation membrane, comprising the following steps:
step 1, weighing quantitative copper nitrate, manganese nitrate and cerium nitrate reagents according to requirements, adding the copper nitrate, manganese nitrate and cerium nitrate reagents into water, and stirring to obtain a thermal catalysis system; wherein, in the thermocatalytic system, Cu2+:Mn2+:Ce2+:H2The mass ratio of O is as follows: 3.5:4:1.5: 7;
mixing tetrabutyl titanate and isopropanol according to a volume ratio of 1.5:2 to obtain a photocatalyst system;
step 2, dropwise adding the photocatalytic system into the thermocatalytic system, and stirring until sol is formed to obtain an active component negative carrier liquid;
step 3, adding pseudo-boehmite and citric acid into the active component loading liquid, adding platinum and rhodium, and stirring strongly for 8 hours at the stirring speed of 500 r/min; curing for 5-6h at room temperature to obtain a load precursor; mixing pseudo-boehmite, citric acid and active component loading liquid according to the mass ratio of 3: 5; the molar concentration of platinum and rhodium is 5 percent;
step 4, pretreating the ceramic microfiltration membrane to enable the pore size of the ceramic microfiltration membrane to be matched with the molecular size of VOCs; specifically, the method comprises the following steps:
step 41, carrying out ultrasonic cleaning on the ceramic microfiltration membrane for 13 min;
42, putting the cleaned ceramic microfiltration membrane into a drying oven at 110 ℃ for drying for 2 hours;
and 43, putting the baked ceramic microfiltration membrane in the step 42 into dilute nitric acid with the mass fraction of 6.5%, heating in a water bath for 2.5 hours, taking out, cleaning and baking for later use.
Step 5, dipping and pulling the pretreated ceramic microfiltration membrane in a load precursor, wherein the dipping time is 38min each time, and the pulling speed is 3cm/min, so that the thermal-photocatalyst is naturally loaded on the ceramic microfiltration membrane; the number of the thermal-photocatalyst loading layers on the ceramic microfiltration membrane is 2; baking in an oven at 70 deg.C for 1 hr, and naturally cooling;
step 6, putting the thermal-optical synergetic catalytic ceramic membrane into a muffle furnace, and calcining for 5.5 hours at 450 ℃ in an air atmosphere; and then, reducing by using hydrogen for 8h to obtain the VOCs separation and degradation film.
The microwave temperature rise experiment was performed on the VOCs separation degradation film prepared in example 4. Experiments show that the VOCs separation and degradation film has good heating effect, can effectively degrade and remove various atmospheric pollutants, and achieves higher removal rate.
Example 5
Embodiment 5 provides a method for preparing a VOCs separation degradation membrane, comprising the following steps:
step 1, weighing quantitative copper nitrate, manganese nitrate and cerium nitrate reagents according to requirements, adding the copper nitrate, manganese nitrate and cerium nitrate reagents into water, and stirring to obtain a thermal catalysis system; wherein, in the thermocatalytic system, Cu2+:Mn2+:Ce2+:H2The mass ratio of O is as follows: 4:3:2: 6;
mixing tetrabutyl titanate and isopropanol according to a volume ratio of 1:3 to obtain a photocatalyst system;
step 2, dropwise adding the photocatalytic system into the thermocatalytic system, and stirring until sol is formed to obtain an active component negative carrier liquid;
step 3, adding a silane coupling agent into the active component loading liquid, adding palladium and rhodium, and stirring strongly for 10 hours at the stirring speed of 400 r/min; curing for 5-6h at room temperature to obtain a load precursor; mixing a silane coupling agent and an active component loading liquid according to the mass ratio of 1: 5; the molar concentration of palladium and rhodium is 4%;
step 4, pretreating the ceramic microfiltration membrane to enable the pore size of the ceramic microfiltration membrane to be matched with the molecular size of VOCs; specifically, the method comprises the following steps:
step 41, carrying out ultrasonic cleaning on the ceramic microfiltration membrane for 14 min;
42, putting the cleaned ceramic microfiltration membrane into a drying oven at 110 ℃ for drying for 1.5 h;
and 43, putting the baked ceramic microfiltration membrane in the step 42 into dilute nitric acid with the mass fraction of 5%, heating in a water bath for 2.8 hours, taking out, cleaning and baking for later use.
Step 5, dipping and pulling the pretreated ceramic microfiltration membrane in a load precursor, wherein the dipping time is 35min each time, and the pulling speed is 2cm/min, so that the thermal-photocatalyst is naturally loaded on the ceramic microfiltration membrane; the number of the thermal-photocatalyst loading layers on the ceramic microfiltration membrane is 3; baking in an oven at 80 deg.C for 1 hr, and naturally cooling;
step 6, putting the thermal-optical synergetic catalytic ceramic membrane into a muffle furnace, and calcining for 6 hours in an air atmosphere at the temperature of 400 ℃; and then, reducing by using hydrogen for 9 hours to obtain the VOCs separation and degradation film.
Performing a microwave heating experiment on the VOCs separation degradation film prepared in the example 5; experiments show that the VOCs separation and degradation film has good heating effect, can effectively degrade and remove various atmospheric pollutants, and achieves higher removal rate.
Example 6
Embodiment 6 provides a method for preparing a VOCs separation degradation membrane, comprising the following steps:
step 1, weighing quantitative copper nitrate, manganese nitrate and cerium nitrate reagents according to requirements, adding the copper nitrate, manganese nitrate and cerium nitrate reagents into water, and stirring to obtain a thermal catalysis system; wherein, in the thermocatalytic system, Cu2+:Mn2+:Ce2+:H2The mass ratio of O is as follows: 3:3:1: 6;
mixing tetrabutyl titanate and isopropanol according to a volume ratio of 1:3 to obtain a photocatalyst system;
step 2, dropwise adding the photocatalytic system into the thermocatalytic system, and stirring until sol is formed to obtain an active component negative carrier liquid;
step 3, adding silica sol and a silane coupling agent into the active component loading solution, adding platinum and rhodium, and stirring strongly for 8 hours at the stirring speed of 450 r/min; curing for 5-6h at room temperature to obtain a load precursor; mixing silica sol, a silane coupling agent and active component loading liquid according to the mass ratio of 2: 5; the molar concentration of platinum and rhodium is 3 percent;
step 4, pretreating the ceramic microfiltration membrane to enable the pore size of the ceramic microfiltration membrane to be matched with the molecular size of VOCs; specifically, the method comprises the following steps:
step 41, carrying out ultrasonic cleaning on the ceramic microfiltration membrane for 15 min;
42, putting the cleaned ceramic microfiltration membrane into a 115 ℃ oven, and baking for 1.5 hours;
and 43, putting the baked ceramic microfiltration membrane in the step 42 into dilute nitric acid with the mass fraction of 6%, heating in a water bath for 2 hours, taking out, and cleaning and baking for later use.
Step 5, dipping and pulling the pretreated ceramic microfiltration membrane in a load precursor, wherein the dipping time is 40min each time, and the pulling speed is 1cm/min, so that the thermal-photocatalyst is naturally loaded on the ceramic microfiltration membrane; the number of the thermal-photocatalyst loading layers on the ceramic microfiltration membrane is 1; baking in an oven at 70 deg.C for 1 hr, and naturally cooling;
step 6, putting the thermal-optical synergetic catalytic ceramic membrane into a muffle furnace, and calcining for 5 hours in an air atmosphere at 500 ℃; and then, reducing by using hydrogen for 8h to obtain the VOCs separation and degradation film.
Performing a microwave heating experiment on the VOCs separation degradation film prepared in the example 6; experiments show that the VOCs separation and degradation film has good heating effect, can effectively degrade and remove various atmospheric pollutants, and achieves higher removal rate.
The above description is only illustrative of the preferred embodiments of the present invention, and any structural changes, improvements, modifications, etc. made without departing from the principle of the present invention are deemed to be within the scope of the present invention.
Claims (10)
1. A preparation method of a VOCs separation degradation film is characterized by comprising the following steps:
step 1, adding copper nitrate, manganese nitrate and cerium nitrate into water, and stirring to obtain a thermocatalysis system; mixing tetrabutyl titanate and isopropanol to obtain a photocatalyst system;
step 2, dropwise adding the photocatalytic system into the thermocatalytic system, and stirring until sol is formed to obtain an active component negative carrier liquid;
step 3, adding an auxiliary agent and a noble metal into the active component loading liquid, strongly stirring, and maintaining to obtain a loaded precursor;
step 4, pretreating the ceramic microfiltration membrane to enable the pore size of the ceramic microfiltration membrane to be matched with the molecular size of VOCs;
step 5, dipping and pulling the pretreated ceramic microfiltration membrane in a load precursor to naturally load the thermal-photocatalyst on the ceramic microfiltration membrane;
step 6, repeating the step 5 until the number of the loading layers of the thermal-photocatalyst on the ceramic microfiltration membrane meets the condition that the retention rate of different molecules in VOCs is more than 90 percent, and obtaining the thermal-photocatalytic synergetic catalytic ceramic membrane;
and 7, calcining the thermal-optical synergetic catalytic ceramic membrane, and reducing to obtain the VOCs separation and degradation film.
2. The method according to claim 1, wherein in step 1, Cu is in the thermal catalyst system2+:Mn2+:Ce2+:H2The mass ratio of O is as follows: (3-4): (3-4): 1-2): 6-9); in the photocatalysis system, tetrabutyl titanate and isopropanol are mixed according to the volume ratio of (1-1.5): (2-3) mixing.
3. The method for preparing a VOCs separating and degrading film according to claim 1, wherein in step 3, the auxiliary agent is one or more of silica sol, phosphoric acid, urea, pseudo-boehmite, citric acid and silane coupling agent; the mass ratio of the auxiliary agent to the active component loading liquid is (1-3): 5, mixing.
4. The method according to claim 1, wherein in step 3, the molar concentration of the noble metal is 0.5-5%; the noble metal is one or more of platinum, palladium and rhodium; the curing process is carried out at room temperature for 5-6 h.
5. The method as claimed in claim 1, wherein in the step 3, the stirring speed is 400-600r/min and the stirring time is 5-10 h.
6. The method according to claim 1, wherein the step 4 of pretreating the ceramic microfiltration membrane comprises the following steps:
step 41, carrying out ultrasonic cleaning on the ceramic microfiltration membrane;
step 42, baking the cleaned ceramic microfiltration membrane;
43, putting the ceramic microfiltration membrane in the step 42 into dilute nitric acid; wherein the mass fraction of the dilute nitric acid is 5-7%; heating in water bath, taking out, cleaning, and baking.
7. The method according to claim 1, wherein in step 6, the number of the thermo-photocatalyst-loaded layers on the ceramic microfiltration membrane is 1 to 3.
8. The method according to claim 1, wherein in step 6, the dipping time is 30-40min each time, the pulling speed is 1-3cm/min, and the drying treatment is performed at 50-80 ℃ until no sol drops on the ceramic microfiltration membrane.
9. The method as claimed in claim 1, wherein in step 7, the calcination is performed in an air atmosphere at 500 ℃ and 300 ℃; the reduction process adopts hydrogen to reduce for 6-9 h.
10. A membrane for separating and degrading VOCs, which is prepared by the method for preparing a membrane for separating and degrading VOCs according to any one of claims 1 to 9.
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| US20140045952A1 (en) * | 2011-04-28 | 2014-02-13 | Basf Nederland B.V. | Catalysts |
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| US20140045952A1 (en) * | 2011-04-28 | 2014-02-13 | Basf Nederland B.V. | Catalysts |
| CN103100386A (en) * | 2013-01-15 | 2013-05-15 | 汕头大学 | Preparation method of monolithic catalyst for degrading VOCS (Volatile Organic Compounds) |
| CN107096526A (en) * | 2016-02-22 | 2017-08-29 | 江苏中科睿赛污染控制工程有限公司 | A kind of catalysis oxidation VOCs composite catalyst, preparation method and purposes |
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