CN113663668B - Carbon fiber loaded room temperature catalyst for VOCs purification and preparation method thereof - Google Patents
Carbon fiber loaded room temperature catalyst for VOCs purification and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon fiber loaded room temperature catalyst for VOCs purification and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving manganese nitrate, copper nitrate, bismuth nitrate and cerium nitrate in deionized water and alcohol to form a precursor solution; heating and stirring the precursor solution to form viscous thick gel; then drying and calcining to obtain catalyst powder; step two, mixing the catalyst powder and silica sol, and then ball-milling to form mixed sol; mixing the mixed sol and the prepolymer to form catalyst curing sol; step three, electrically spraying the catalyst curing sol on the surface of the carbon fiber, and irradiating and curing the catalyst curing sol on the surface of the carbon fiber by ultraviolet light; the device for carrying out charged spraying comprises an atomizing nozzle and an electrode ring; a plurality of discharge tips are uniformly distributed in the electrode ring; the atomizing nozzle is arranged on one side of the electrode ring; the carbon fiber is positioned at the other side of the electrode ring, and an ultraviolet lamp is arranged above the carbon fiber. The invention has the advantages of uniform load, high efficiency, short curing time and the like.
Description
Technical Field
The invention belongs to the field of environmental protection, relates to a catalyst for purifying VOCs, and particularly relates to a carbon fiber loaded room temperature catalyst for purifying VOCs and a preparation method thereof.
Background
Compared with common activated carbon, the carbon fiber has larger specific surface area and more uniform void structure, can realize the rapid adsorption and desorption of VOCs, and is a good low-concentration VOCs purifying material. The manganese catalyst is a good room temperature catalyst and is widely applied to purification of organic matters such as indoor formaldehyde and the like at present.
Carbon fiber also is a good catalyst carrier simultaneously, can carry out effectual integration with absorption and catalysis, has loaded the carbon fiber material of room temperature catalyst, can effectively adsorb VOCs, and after adsorbing a certain amount of VOCs, the normal atmospheric temperature catalytic action can be reinforceed to the high concentration ozone or the high energy ion that let in the little amount of wind, realizes adsorbing the thorough decomposition of VOCs to effectively regenerate carbon fiber.
At present, room temperature catalysts are generally limited to purification of indoor formaldehyde and other small molecular weight VOCs, the problems of low purification efficiency and more intermediate products still exist in the aspect of purification of large molecular weight VOCs, the mineralization efficiency of the catalysts at room temperature needs to be improved, and the room temperature catalysts are an effective mode through adaptation of multi-component catalysts and ozone concerted catalysis, and currently, researches are rarely made. Carbon fiber is a good catalyst carrier, but in actual use, the front load needs to be sintered, and the carbon fiber cannot bear high temperature; when the catalyst dispersion is coated on the post-loaded carbon fiber, the strength of the carbon fiber is obviously reduced in a wet state, and the carbon fiber is very easy to break off during operation and difficult to produce in quantity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a carbon fiber loaded room temperature catalyst for purifying VOCs and a preparation method thereof, wherein the carbon fiber loaded room temperature catalyst comprises the following steps: after the prepared catalyst and a silica gel solution are ground, a prepolymer is added, and when the catalyst is sprayed on an activated carbon fiber carrier, a bismuth oxide photocatalyst in the catalyst can form a large number of active groups under the action of an ultraviolet lamp to act on the prepolymer, and meanwhile, quick fixation can be realized by combining with charged spraying, the binding capacity of the catalyst and the carrier carbon fiber is enhanced, and the falling off in the later use process is prevented; the carbon fiber is quickly cured after being loaded with the room-temperature catalyst, so that the damage caused by folding and drying the carbon fiber in a wet state can be avoided, the drying in a drying oven is not needed in the mode, the loaded catalyst can be repeatedly coated, and the loading efficiency is effectively improved; when the catalyst is loaded on the carbon fiber, the uniformity of the loading and the utilization efficiency of the catalyst are further improved, the size of fog drops is reduced, and the curing time is further shortened by charged spraying.
In order to achieve the above object, the present invention provides a preparation method of a carbon fiber loaded room temperature catalyst for purifying VOCs, which has the following characteristics: the method comprises the following steps:
dissolving manganese nitrate, copper nitrate, bismuth nitrate and cerium nitrate in deionized water and alcohol to form a precursor solution; heating and stirring the precursor solution to form viscous thick gel; then drying and calcining to obtain catalyst powder, wherein the main component of the catalyst is a mixture of manganese oxide, copper oxide, bismuth oxide and cerium oxide;
mixing the catalyst powder with silica sol and then ball-milling to form mixed sol; mixing the mixed sol and the prepolymer to form a catalyst curing sol;
step three, electrically spraying the catalyst curing sol on the surface of the carbon fiber, irradiating and curing the catalyst curing sol on the surface of the carbon fiber through ultraviolet light, wherein a bismuth oxide photocatalyst in the catalyst generates a large amount of high-energy active groups such as free radicals, cations and the like under the irradiation of an ultraviolet lamp, so that the crosslinking and curing of unsaturated double bonds of the prepolymer can be favorably initiated, the curing action can be completed within a few minutes, the catalyst is effectively loaded on a carbon fiber carrier, and the catalyst can be loaded for the second time without extra drying after the spraying is completed for one time, so that the working efficiency is effectively improved, and the damage of the carbon fiber caused by turnover is avoided;
the device for carrying out charged spraying comprises an atomizing nozzle and an electrode ring; a plurality of discharge tips are uniformly distributed in the electrode ring; the atomizing nozzle is arranged on one side of the electrode ring and is positioned on the central axis of the electrode ring; the carbon fiber is positioned at the other side of the electrode ring, an ultraviolet lamp is arranged above the carbon fiber, and the wavelength of a light source is 254nm;
the catalyst curing sol is sprayed out through an atomizing nozzle, passes through the electrode ring and is sprayed on the surface of the carbon fiber; when the catalyst solidified sol passes through the electrode ring, the discharge tip in the electrode ring charges the catalyst solidified sol, charged fog drops are further broken under the action of an electric field, so that the charged fog drops are more uniformly distributed on the surface of carbon fibers, the average diameter of the charged fog drops is below 50 microns, and the diameter of uncharged fog drops is generally larger than 100 microns; when the charged spraying catalyst is used for curing the sol, the sprayed liquid is ensured not to be contacted with the electrode ring and the discharge tip, and the short circuit is prevented.
Further, the invention provides a preparation method of the carbon fiber loaded room temperature catalyst for purifying VOCs, which can also have the following characteristics: the preparation method of the precursor solution in the first step comprises the following steps: dissolving manganese nitrate, copper nitrate, bismuth nitrate and cerium nitrate in deionized water to form a nitrate aqueous solution; slowly dripping glycerol with the volume equal to that of water into the aqueous solution of the nitrate to form an alcoholic solution of the nitrate; after stirring uniformly, slowly dropwise adding nitric acid to adjust the pH value to 2-5 to form a precursor solution; the molar ratio of manganese nitrate, copper nitrate, bismuth nitrate and cerium nitrate is 3.
Further, the invention provides a preparation method of the carbon fiber loaded room temperature catalyst for purifying VOCs, which can also have the following characteristics: wherein, in the step one, the precursor solution is stirred at the temperature of 40-80 ℃ until viscous thick gel is formed; drying the thick gel at 120-160 deg.c for 1-3 hr, and calcining in a muffle furnace at 400-700 deg.c for 2-4 hr to form the catalyst powder.
Further, the invention provides a preparation method of the carbon fiber loaded room temperature catalyst for purifying VOCs, which can also have the following characteristics: in the second step, the prepolymer is one or more of epoxy acrylate, bisphenol A epoxy acrylate, aliphatic polyurethane hexaacrylate and active amine.
Further, the invention provides a preparation method of the carbon fiber loaded room temperature catalyst for purifying VOCs, which can also have the following characteristics: in the second step, the catalyst powder and 10-40wt% of silica sol are mixed and then placed in a planetary ball mill for ball milling for 1-10h to form mixed sol, wherein the mass ratio of the catalyst powder to the silica sol is 1:1-1:4.
Further, the invention provides a preparation method of the carbon fiber loaded room temperature catalyst for purifying VOCs, which can also have the following characteristics: in the second step, the mixed sol and the prepolymer are mixed and stirred for 5-30min to form catalyst curing sol; wherein the mass fraction of the prepolymer in the curing sol is 1-5%.
Further, the invention provides a preparation method of the carbon fiber loaded room temperature catalyst for purifying VOCs, which can also have the following characteristics: in the device for carrying out charged spraying, the distance between the atomizing spray head and the electrode ring is 2-10cm; the width of the electrode ring is 0.5-2cm, the diameter of the electrode ring is 5-20cm, and the length of each discharge tip is 0.5-2cm.
Further, the invention provides a preparation method of the carbon fiber loaded room temperature catalyst for purifying VOCs, which can also have the following characteristics: in the device for carrying out charged spraying, the electrode ring and the discharge tip are made of aluminum alloy, steel or stainless steel, so that the device has good conductivity, and the surface of the device is subjected to insulation corrosion prevention; the electrode ring is connected with the atomizing nozzle through a plastic bracket.
Further, the invention provides a preparation method of the carbon fiber loaded room temperature catalyst for purifying VOCs, which can also have the following characteristics: the device for carrying out charged spraying further comprises a flow meter, a plunger pump and a pressure regulating valve; the flow meter, the plunger pump and the pressure regulating valve are sequentially connected with the atomizing nozzle, and the catalyst solidified sol is sprayed out of the atomizing nozzle through the flow meter, the plunger pump and the pressure regulating valve; the flow meter controls the flow of the catalyst solidified sol entering the atomizing nozzle to be 50-500ml/s, and the specific flow setting is matched with the sprinkling can; the pressure of the plunger pump and the pressure regulating valve is increased to 0.15-0.5 Mpa; the device for carrying out charged spraying also comprises a power supply, an electromagnetic valve and a high-voltage pack; the power supply, the electromagnetic valve and the high-voltage pack are sequentially connected with the electrode ring to supply power to the electrode ring; the power supply is raised to 10-30kV via the high voltage package.
The invention also discloses the carbon fiber loaded room temperature catalyst for purifying VOCs, which is prepared by the preparation method. The catalyst has good capability of catalyzing VOCs at room temperature, and can effectively mineralize undecomposed intermediate products under the synergistic effect of ozone, thereby ensuring the room-temperature catalysis performance.
The invention has the beneficial effects that:
1. at present, the manganese-based room-temperature catalyst is mainly applied to indoor formaldehyde treatment, and is difficult to be applied to the treatment of other VOCs due to the reasons of deactivation caused by intermediate products, low catalytic activity and the like. The mixed catalyst of manganese oxide, copper oxide, bismuth oxide and cerium oxide is prepared by reasonably compounding the catalyst, so that the room-temperature catalytic capability of the catalyst can be effectively improved, wherein the bismuth oxide and the cerium oxide can be used as visible-light catalysts.
2. The room temperature catalyst is loaded on the carbon fiber carrier, so that the adsorption and catalysis effects can be effectively integrated, when the VOCs are purified, the VOCs are fixed mainly by utilizing the adsorption effect of the carbon fiber in the adsorption stage, when the adsorption is saturated, ozone or high-energy ions are introduced, and under the synergistic effect of the ozone or the high-energy ions, the room temperature catalyst can thoroughly mineralize the adsorbed VOCs, so that the adsorption effect of the carbon fiber is recovered. The regeneration only needs to be carried out by introducing ozone or high-energy ions, and the vacuumizing or heating is not needed, so that the equipment investment and the operating cost are effectively saved.
3. Carbon fiber is as the carrier, and load catalyst is difficult to the volume production generally, and the main reason is that coiled carbon fiber need expand when load catalyst, need fold the upset after the solution of coating catalyst and go to dry, and wet carbon fiber structural strength is very low, and is very easy damaged, and production efficiency is extremely low. By introducing the prepolymer into the mixed sol of the catalyst, the drying can be finished by fast curing under an ultraviolet lamp, so that continuous multiple coating can be performed, and the loading capacity and the working efficiency of the catalyst are improved.
4. The catalyst is loaded again by a spray gun after being prepared into sol, generally the load is uneven, the catalyst is wasted and has low load rate, the diameter of the fog drops of the catalyst sol is obviously reduced by charged spraying, the uniformity and the utilization efficiency of the catalyst load are improved, and the curing and drying are facilitated.
Drawings
FIG. 1 is a schematic view of charged spray coating;
FIG. 2 is a flow chart of the preparation of carbon fiber supported room temperature catalyst.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The embodiment provides a room-temperature manganese oxide catalyst, and the preparation method comprises the following steps: dissolving manganese nitrate tetrahydrate in deionized water to form a manganese nitrate aqueous solution; slowly dripping glycerol with the volume equal to that of water into the aqueous solution of the manganese nitrate to form an alcoholic solution of the nitrate; after stirring evenly, slowly adding nitric acid dropwise until the pH value is 4 to form a precursor solution. The precursor solution is stirred at 60 ℃ until a viscous, thick gel is formed. And drying the thick gel at 150 ℃ for 1 hour, and calcining in a muffle furnace at 600 ℃ for 3 hours to form the room-temperature manganese oxide catalyst powder.
Example 2
The embodiment provides a room-temperature manganese oxide and copper oxide compound catalyst, and the preparation method comprises the following steps: manganese nitrate tetrahydrate and copper nitrate trihydrate are dissolved in deionized water, wherein an aqueous solution of nitrates is formed, and the molar ratio of manganese nitrate tetrahydrate to copper nitrate trihydrate is 3:1. Slowly dripping glycerol with the volume equal to that of water into the water solution of the nitrate to form an alcohol solution of the nitrate, uniformly stirring, and slowly dripping nitric acid until the pH value is 4 to form a precursor solution. The precursor solution is stirred at 60 ℃ until a viscous, thick gel is formed. Drying the thick gel for 1 hour at 150 ℃, and calcining the thick gel for 3 hours in a muffle furnace at 600 ℃ to form the room-temperature manganese oxide and copper oxide compound catalyst powder.
Example 3
The embodiment provides a room-temperature manganese oxide, copper oxide and bismuth oxide compound catalyst, and the preparation method comprises the following steps: dissolving manganese nitrate tetrahydrate, copper nitrate trihydrate and bismuth nitrate pentahydrate in deionized water, wherein an aqueous solution of nitrates is formed, the molar ratio of manganese nitrate tetrahydrate, copper nitrate trihydrate and bismuth nitrate pentahydrate being 3. Slowly dripping glycerol with the volume equal to that of water into the aqueous solution of the nitrate to form alcoholic solution of the nitrate, uniformly stirring, and slowly dripping nitric acid until the pH value is 4 to form precursor solution. The precursor solution is stirred at 60 ℃ until a viscous, thick gel is formed. Drying the thick gel for 1 hour at 150 ℃, and calcining the gel for 3 hours at 600 ℃ in a muffle furnace to form the catalyst powder compounded by the manganese oxide, the copper oxide and the bismuth oxide at room temperature.
Example 4
The embodiment provides a room-temperature manganese oxide, copper oxide, bismuth oxide and cerium oxide compound catalyst, and the preparation method comprises the following steps: dissolving manganese nitrate tetrahydrate, copper nitrate trihydrate, bismuth nitrate pentahydrate, and cerium nitrate hexahydrate in deionized water, wherein an aqueous solution of nitrates is formed, the molar ratio of manganese nitrate tetrahydrate, copper nitrate trihydrate, bismuth nitrate pentahydrate, and cerium nitrate hexahydrate being 3. Slowly dripping glycerol with the volume equal to that of water into the water solution of the nitrate to form an alcohol solution of the nitrate, uniformly stirring, and slowly dripping nitric acid until the pH value is 4 to form a precursor solution. The precursor solution is stirred at 60 ℃ until a viscous, thick gel is formed. Drying the thick gel for 1 hour at 150 ℃, and calcining the thick gel for 3 hours in a muffle furnace at 600 ℃ to form the catalyst powder compounded by manganese oxide, copper oxide, bismuth oxide and cerium oxide at room temperature.
Example 5
The embodiment provides a room-temperature manganese oxide, copper oxide, bismuth oxide and cerium oxide compound catalyst, and the preparation method comprises the following steps: dissolving manganese nitrate tetrahydrate, copper nitrate trihydrate, bismuth nitrate pentahydrate, and cerium nitrate hexahydrate in deionized water, wherein an aqueous solution of nitrates is formed, the molar ratio of manganese nitrate tetrahydrate, copper nitrate trihydrate, bismuth nitrate pentahydrate, and cerium nitrate hexahydrate being 3. Slowly dripping glycerol with the volume equal to that of water into the water solution of the nitrate to form an alcohol solution of the nitrate, uniformly stirring, and slowly dripping nitric acid until the pH value is 2 to form a precursor solution. The precursor solution is stirred at 40 ℃ until a viscous thick gel is formed. Drying the thick gel at 160 ℃ for 2 hours, and calcining the gel in a muffle furnace at 400 ℃ for 4 hours to form the catalyst powder compounded by manganese oxide, copper oxide, bismuth oxide and cerium oxide at room temperature.
Example 6
The embodiment provides a room-temperature manganese oxide, copper oxide, bismuth oxide and cerium oxide compound catalyst, and the preparation method comprises the following steps: dissolving manganese nitrate tetrahydrate, copper nitrate trihydrate, bismuth nitrate pentahydrate, and cerium nitrate hexahydrate in deionized water, wherein an aqueous solution of nitrates is formed, the molar ratio of manganese nitrate tetrahydrate, copper nitrate trihydrate, bismuth nitrate pentahydrate, and cerium nitrate hexahydrate being 3. Slowly dripping glycerol with the volume equal to that of water into the aqueous solution of the nitrate to form alcoholic solution of the nitrate, uniformly stirring, and slowly dripping nitric acid until the pH value is 5 to form precursor solution. The precursor solution is stirred at 80 ℃ until a viscous, thick gel is formed. And drying the thick gel at 120 ℃ for 3 hours, and calcining the thick gel in a muffle furnace at 700 ℃ for 2 hours to form the catalyst powder compounded by the manganese oxide, the copper oxide, the bismuth oxide and the cerium oxide at room temperature.
The room temperature catalysts obtained in examples 1 to 4 were tested for their ability to decompose ethanol under ozone synergy. The specific test conditions were as follows: test temperature 25 deg.C, relative humidity 50% RH, ethanol inlet concentration 100mg/m 3 About, the ozone concentration is about 100ppm, and the catalyst reaction space velocity is 10000h -1 . And (3) introducing the waste gas of the ethanol simulation VOCs into the catalytic bed layer, introducing ozone into the catalytic bed layer when the concentration of the inlet and the outlet is similar, and testing the concentration of the outlet ethanol. The performance test results are as follows:
| kind of room temperature catalyst | Ethanol purification efficiency (%) |
| Example 1 catalyst | 24 |
| Example 2 catalyst | 78 |
| EXAMPLE 3 catalyst | 83 |
| Example 4 catalyst | 85 |
As can be seen from the above table, the decomposition efficiency of the single manganese oxide catalyst to ethanol is lower, only 24%, under the synergistic condition of ozone, and after the copper oxide is compounded, the decomposition efficiency is rapidly increased to 78%. After the photocatalyst bismuth oxide and cerium oxide are compounded continuously, the decomposition efficiency of ethanol at room temperature is further improved and can reach more than 80%.
Example 7
The embodiment provides a carbon fiber loaded room temperature catalyst for purifying VOCs, and a preparation method of the carbon fiber loaded room temperature catalyst comprises the following steps:
step one, catalyst powder was prepared as in example 2.
And step two, mixing the catalyst powder with 20wt% of silica sol, and then placing the mixture into a planetary ball mill for ball milling for 5 hours to form mixed sol, wherein the mass ratio of the catalyst powder to the silica sol is 1:2.
And step three, electrically spraying the mixed sol on the surface of the carbon fiber, and irradiating and curing the carbon fiber surface by ultraviolet light.
The device for carrying out charged spraying is shown in figure 1 and comprises an atomizing nozzle 1 and an electrode ring 2; a plurality of discharge tips 3 are uniformly distributed in the electrode ring; the atomizing nozzle 1 is arranged on one side of the electrode ring 2 and is positioned on the central axis of the electrode ring 2; carbon fiber is arranged at the other side of the electrode ring, an ultraviolet lamp is arranged above the carbon fiber, the wavelength of the light source is 254nm, and the irradiation intensity of the ultraviolet light is 1mW/cm 2 。
The mixed sol is sprayed out through an atomizing nozzle 1, passes through an electrode ring 2 and is sprayed on the surface of the carbon fiber; when the mixed sol passes through the electrode ring 2, the discharge tips 3 in the electrode ring 2 charge the mixed sol, and charged droplets are further broken under the action of an electric field and are distributed on the surface of carbon fibers more uniformly, and the average diameter of the charged droplets is below 50 microns.
Wherein, the distance between the atomizing nozzle and the electrode ring is 5cm; the width of the electrode ring is 1cm, the diameter of the electrode ring is 10cm, and the length of each discharge tip is 1cm. The electrode ring and the discharge tip are made of stainless steel, the surface of the electrode ring is insulated and anticorrosive, and the electrode ring is connected with the atomizing nozzle through a plastic support. When the mixed sol is sprayed by charging, the sprayed liquid is ensured not to contact with the electrode ring and the discharge tip, so as to prevent short circuit.
The device also comprises a flowmeter, a plunger pump and a pressure regulating valve; the flow meter, the plunger pump and the pressure regulating valve are sequentially connected with the atomizing nozzle, and the catalyst solidified sol is sprayed out of the atomizing nozzle through the flow meter, the plunger pump and the pressure regulating valve; the flow meter controls the flow of the catalyst solidified sol entering the atomizing nozzle to be 400ml/s, and the specific flow setting is matched with the spray can; the plunger pump and pressure regulating valve raise the pressure to 0.3Mpa. The device also comprises a power supply, an electromagnetic valve and a high-voltage pack; the power supply, the electromagnetic valve and the high-voltage pack are sequentially connected with the electrode ring to supply power to the electrode ring; when the mixed sol passes through the electrode ring through the atomizing nozzle, the power supply is started, and the voltage is increased to 25kV through the high-voltage package.
Example 8
The embodiment provides a carbon fiber loaded room temperature catalyst for purifying VOCs, and a preparation method of the carbon fiber loaded room temperature catalyst is shown in fig. 2, and the preparation method specifically comprises the following steps:
step one, catalyst powder was prepared as in example 2.
And step two, mixing the catalyst powder with 20wt% of silica sol, and then placing the mixture into a planetary ball mill for ball milling for 5 hours to form mixed sol, wherein the mass ratio of the catalyst powder to the silica sol is 1:2. And mixing and stirring the mixed sol and prepolymer epoxy acrylate for 10min to form catalyst cured sol, wherein the mass fraction of the prepolymer in the cured sol is 1.5%.
And step three, electrically spraying the catalyst curing sol on the surface of the carbon fiber, and irradiating and curing the carbon fiber surface by ultraviolet light. The charged spray apparatus and process were the same as in example 7.
Example 9
This example provides a carbon fiber-supported room temperature catalyst for purifying VOCs, which is prepared substantially in the same manner as in example 6, except that: the catalyst powder in the first step is the catalyst powder prepared by the method of example 3.
Example 10
This example provides a room temperature catalyst supported by carbon fiber for purifying VOCs, which is prepared substantially in the same manner as in example 6, except that: the catalyst powder in the first step is the catalyst powder prepared as in example 4.
Example 11
The embodiment provides a carbon fiber loaded room temperature catalyst for purifying VOCs, and the preparation method comprises the following steps:
step one, catalyst powder was prepared as in example 4.
And step two, mixing the catalyst powder with 10wt% of silica sol, and then placing the mixture into a planetary ball mill for ball milling for 10 hours to form mixed sol, wherein the mass ratio of the catalyst powder to the silica sol is 1:1. And mixing and stirring the mixed sol and prepolymer epoxy acrylate for 5min to form catalyst cured sol, wherein the mass fraction of the prepolymer in the cured sol is 1%.
And step three, electrically spraying the catalyst curing sol on the surface of the carbon fiber, and irradiating and curing the carbon fiber surface by ultraviolet light. The charged spray device and process were essentially the same as in example 7, except that: in the charged spray coating device, the distance between an atomizing spray head and an electrode ring is 2cm; the width of the electrode ring is 0.5cm, the diameter of the electrode ring is 5cm, and the length of each discharge tip is 0.5cm; in the charged spraying process, the flow of the catalyst curing sol entering the atomizing nozzle is controlled by a flow meter to be 50ml/s, the pressure is increased to 0.15Mpa by a plunger pump and a pressure regulating valve, and the mixed sol passes through the atomizing nozzle and an electrode ring, a power supply is started, and the voltage is increased to 10kV through a high-voltage packet.
Example 12
The embodiment provides a carbon fiber loaded room temperature catalyst for purifying VOCs, and the preparation method comprises the following steps:
step one, catalyst powder was prepared as in example 4.
And step two, mixing the catalyst powder with 40wt% of silica sol, and then placing the mixture into a planetary ball mill for ball milling for 1h to form mixed sol, wherein the mass ratio of the catalyst powder to the silica sol is 1:4. And mixing and stirring the mixed sol and prepolymer epoxy acrylate for 30min to form catalyst cured sol, wherein the mass fraction of the prepolymer in the cured sol is 5%.
And step three, electrically spraying the catalyst curing sol on the surface of the carbon fiber, and irradiating and curing the carbon fiber surface by ultraviolet light. The charged spray device and process were essentially the same as in example 7, except that: in the charge spray coating device, the distance between an atomizing spray head and an electrode ring is 10cm; the width of the electrode ring is 2cm, the diameter of the electrode ring is 20cm, and the length of each discharge tip is 2cm; in the charged spraying process, the flow of the catalyst curing sol entering the atomizing nozzle is controlled by a flow meter to be 500ml/s, the pressure is increased to 0.5Mpa by a plunger pump and a pressure regulating valve, and the voltage is increased to 30kV through high-voltage pack when the mixed sol passes through the atomizing nozzle and passes through an electrode ring by turning on a power supply.
The drying times of the carbon fibers supported on the catalyst in examples 7 to 10 were recorded, all under appropriate ventilation conditions. The results are as follows:
| examples | Drying time |
| Example 7 | 1.5h |
| Example 8 | 47min |
| Example 9 | 7min |
| Example 10 | 4min |
As can be seen from the table above, the curing agent (silica sol) is added in the room temperature catalyst mixed sol which is not compounded with bismuth oxide and cerium oxide, and the curing time can be effectively saved by combining ultraviolet light and charged spray, but the curing time is still longer, and the requirement of continuous operation cannot be met; after the room temperature catalyst is compounded with the photocatalyst bismuth oxide and cerium oxide, the curing time is further shortened, and the requirement of continuous load operation can be basically met.
Example 13
The embodiment provides a carbon fiber loaded room temperature catalyst for purifying VOCs, and the preparation method comprises the following steps:
step one, catalyst powder was prepared as in example 4.
And step two, mixing the catalyst powder with 20wt% of silica sol, and then placing the mixture into a planetary ball mill for ball milling for 5 hours to form mixed sol, wherein the mass ratio of the catalyst powder to the silica sol is 1:2. And mixing and stirring the mixed sol and prepolymer epoxy acrylate for 10min to form catalyst curing sol.
And step three, spraying the catalyst curing sol on the surface of the carbon fiber through an atomizing spray head, and curing the catalyst curing sol on the surface of the carbon fiber through ultraviolet irradiation. Specifically, the catalyst curing sol is put through a plunger pump and a pressure regulating valve, the pressure is increased to 0.3Mpa, and the flow of the catalyst curing sol entering an atomizing nozzle is controlled by a flowmeter to be 400ml/s. An ultraviolet lamp is arranged above the carbon fiber, the wavelength of the light source is 254nm, and the irradiation intensity of the ultraviolet light is 1mW/cm 2 。
Example 13 the drying time of the catalyst-supported carbon fiber was 9min, which was higher than 4min in example 10, and it was not favorable for continuous operation, and thus it was found that the charged spray can effectively save the curing time by uniformly distributing the liquid droplets.
Claims (4)
1. A preparation method of a carbon fiber loaded room temperature catalyst for VOCs purification is characterized by comprising the following steps:
the method comprises the following steps:
step one, dissolving manganese nitrate, copper nitrate, bismuth nitrate and cerium nitrate in deionized water to form a nitrate aqueous solution; slowly dripping glycerol with the volume equal to that of water into the aqueous solution of the nitrate to form alcoholic solution of the nitrate; after stirring uniformly, adjusting the pH value to 2-5 to form a precursor solution; the molar ratio of manganese nitrate to copper nitrate to bismuth nitrate to cerium nitrate is 3; heating and stirring the precursor solution to form viscous thick gel; then drying and calcining to obtain catalyst powder;
mixing the catalyst powder with 10-40wt% of silica sol, and then ball-milling for 1-10h to form mixed sol, wherein the mass ratio of the catalyst powder to the silica sol is 1:1-1:4; mixing and stirring the mixed sol and the prepolymer for 5-30min to form catalyst curing sol, wherein the mass fraction of the prepolymer in the catalyst curing sol is 1% -5%; the prepolymer is one or two of epoxy acrylate and aliphatic polyurethane hexaacrylate;
step three, electrically spraying the catalyst curing sol on the surface of the carbon fiber, and irradiating and curing the carbon fiber surface by ultraviolet light;
the device for carrying out charged spraying comprises an atomizing nozzle and an electrode ring; a plurality of discharge tips are uniformly distributed in the electrode ring; the atomizing nozzle is arranged on one side of the electrode ring and is positioned on the central axis of the electrode ring; the carbon fiber is positioned on the other side of the electrode ring;
the catalyst curing sol is sprayed out through an atomizing nozzle, passes through the electrode ring and is sprayed on the surface of the carbon fiber; when the catalyst solidified sol passes through the electrode ring, the discharge tip in the electrode ring charges the catalyst solidified sol, and charged fog drops are further broken under the action of an electric field;
the distance between the atomizing nozzle and the electrode ring is 2-10cm; the width of the electrode ring is 0.5-2cm, the diameter of the electrode ring is 5-20cm, and the length of each discharge tip is 0.5-2cm;
the device for carrying out charged spraying also comprises a flowmeter, a plunger pump and a pressure regulating valve; the flow meter, the plunger pump and the pressure regulating valve are sequentially connected with the atomizing nozzle, and the catalyst curing sol is sprayed out of the atomizing nozzle through the flow meter, the plunger pump and the pressure regulating valve; the flow meter controls the flow of the catalyst solidified sol entering the atomizing nozzle to be 50-500ml/s; the pressure is increased to 0.15 to 0.5Mpa by a plunger pump and a pressure regulating valve;
the device for carrying out charged spraying also comprises a power supply, an electromagnetic valve and a high-voltage pack; the power supply, the electromagnetic valve and the high-voltage pack are sequentially connected with the electrode ring to supply power to the electrode ring; the power supply is raised to 10-30kV via the high voltage package.
2. The method of claim 1 for preparing a carbon fiber-supported room temperature catalyst for the purification of VOCs, wherein the method comprises the steps of:
in the first step, the precursor solution is stirred at 40-80 ℃ until viscous thick gel is formed; drying the thick gel at 120-160 ℃ for 1-3 hours, and calcining the gel in a muffle furnace at 400-700 ℃ for 2-4 hours to form catalyst powder.
3. The method of claim 1 for preparing a carbon fiber-supported room temperature catalyst for purifying VOCs, wherein the method comprises the following steps:
in the device for carrying out charged spraying, the electrode ring and the discharge tip are made of aluminum alloy, steel or stainless steel.
4. The carbon fiber-supported room temperature catalyst for VOCs purification prepared by the preparation method according to any one of claims 1 to 3.
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