CN115845805A - Preparation method of nitrogen-doped Fe-BTC derived carbon-based material for activating peroxymonosulfate - Google Patents
Preparation method of nitrogen-doped Fe-BTC derived carbon-based material for activating peroxymonosulfate Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 24
- 230000003213 activating effect Effects 0.000 title claims abstract description 6
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- 238000003756 stirring Methods 0.000 claims abstract description 177
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 57
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 23
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- 238000004043 dyeing Methods 0.000 claims abstract description 18
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 12
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- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 26
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- 239000000843 powder Substances 0.000 claims description 20
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- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 10
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 9
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
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- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical group [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
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Abstract
The invention discloses a preparation method of a nitrogen-doped Fe-BTC derived carbon-based material for activating peroxymonosulfate, which relates to the technical field of organic metal framework materials and comprises the following steps: s1, preparing a metal organic framework material Fe-BTC; s2, preparing a carbon oxide-based material; s3, preparing a Fe-BTC derived carbon-based material; and S4, post-processing. The mixing device used in the step S3 comprises an upper stirring barrel, a lower stirring barrel and a main stirring rod penetrating through the upper stirring barrel and the lower stirring barrel. According to the invention, the Fe-BTC colloid is mixed with the carbon oxide based material, and the nitrogen-doped Fe-BTC derived carbon-based particles are obtained by anhydrous toluene treatment and the surface of the material is loaded with diethylenetriamine under the nitrogen protection atmosphere, so that the adsorbing material with strong catalytic activity and high stability can be obtained, the treating effect on pollutants in printing and dyeing wastewater is particularly good, the proportion of the nitrogen-doped Fe-BTC derived carbon-based particles to peroxymonosulfate is further optimized, and the practicability is strong.
Description
Technical Field
The invention relates to the technical field of organic metal framework materials, in particular to a preparation method of a nitrogen-doped Fe-BTC derived carbon-based material for activating peroxymonosulfate.
Background
With the rapid development of economy, the environmental pollution problem becomes more serious day by day, and the discharge of industrial, agricultural and domestic sewage has a great influence on the ecological environment. The methods commonly used for wastewater treatment include microbiological methods, physical adsorption methods, and chemical methods, among which the solid phase adsorption method is considered to be one of the simplest and effective water pollution control methods because of its easy operation.
In recent years, the research of metal-organic framework materials is more and more paid attention to, and the metal-organic framework materials have multiple properties such as porosity, large specific surface area, multiple metal sites and the like, so that the metal-organic framework materials are applied to the field of chemical engineering.
Nitrogen doping is to dope nitrogen atoms into a carbon-based material to destroy a pi conjugated structure in the original carbon-based material, so that local electron rearrangement is caused. The conventional nitrogen doping method is divided into an in-situ synthesis method and a post-treatment method. The in-situ synthesis method can be classified into an activation method, a hydrothermal method, a chemical vapor deposition method, a template method, a sol-gel method, and the like; the aftertreatment process refers to the introduction of a nitrogen source into an existing carbon material under certain conditions. Generally, nitrogen sources such as ammonia, ammonia water and urea are mixed with carbon sources, and nitrogen doping of the carbon materials can be effectively realized through high-temperature heat treatment, so that the catalytic activity of the catalyst is improved. Meanwhile, the existence of nitrogen defects is beneficial to the adsorption of the peroxymonosulfate and improves the adsorption efficiency, but the nitrogen doping process method for activating the peroxymonosulfate in the Fe-BTC derived carbon-based material still needs to be improved.
Disclosure of Invention
In view of the above-mentioned problems, the present invention provides a method for preparing a nitrogen-doped Fe-BTC-derived carbon-based material that activates peroxymonosulfate.
The technical scheme of the invention is as follows:
a method for preparing nitrogen-doped Fe-BTC derived carbon-based material activated with peroxymonosulfate, comprising the steps of:
s1, preparing a metal organic framework material Fe-BTC: weighing 3-5 parts by weight of ferric chloride hexahydrate and 2.5-4.5 parts by weight of trimesic acid, adding the ferric chloride hexahydrate and the trimesic acid into 22-28 parts by weight of a dimethylformamide solution together, stirring and mixing for 10-15 min to obtain a mixed solution, heating the mixed solution to 160-165 ℃ under a vacuum condition for 20-24 h to obtain Fe-BTC colloid, and cleaning the Fe-BTC colloid for 3 times by using a dimethylformamide solution with the mass concentration of 40% to obtain the cleaned Fe-BTC colloid;
s2, preparing a carbon oxide based material: placing 6-7 parts by weight of carbon black in a tubular furnace for heating, heating to 800-900 ℃ at a heating rate of 15-20 ℃/min under the protection of nitrogen atmosphere, preserving heat for 1-2 h, cooling to room temperature to obtain carbon black powder, mixing the carbon black powder with 3-4 parts by weight of potassium persulfate powder and 2-3 parts by weight of phosphorus pentoxide powder, adding the mixture into 18-25 parts by weight of concentrated sulfuric acid solution, stirring and mixing at 75-80 ℃ for 4-5 h, taking out, and performing suction filtration to neutrality by using deionized water to obtain a carbon oxide-based material;
s3, preparing the Fe-BTC derived carbon-based material: mixing the cleaned Fe-BTC colloid obtained in the step S1 with the carbon oxide-based material obtained in the step S2, then dropwise adding 32-40 parts by weight of anhydrous toluene and stirring, heating to 100-105 ℃ while dropwise adding and stirring, introducing nitrogen gas, dropwise adding 0.5-0.8 part by weight of diethylenetriamine solution under the nitrogen protection atmosphere, and refluxing for 12 hours to obtain Fe-BTC derived carbon-based particles;
s4, post-processing: and (4) centrifugally separating the Fe-BTC derived carbon-based particles obtained in the step (S3), washing and filtering for 3 times by using an ethanol solution, cleaning for 2-3 times by using ultrapure water, drying for 2h at the temperature of 120-150 ℃, and grinding to obtain the nitrogen-doped Fe-BTC derived carbon-based particles.
Further, the stirring speed in the step S1 is 100 to 120rpm. The stirring speed is adjusted to ensure that ferric chloride hexahydrate and trimesic acid are fully dissolved into the dimethylformamide solution.
Further, in the step S1, the mass concentration of the trimesic acid is more than or equal to 98%, and the dimethylformamide solution is analytically pure.
Further, the stirring method in the step S2 is magnetic stirring, the stirring speed is 300-400 rpm, and the mass concentration of concentrated sulfuric acid is 80%. The uniform components of the prepared carbon oxide-based material are ensured by selecting a proper stirring mode and a proper stirring speed.
Further, in the step S3, the dropping speed of the anhydrous toluene is 0.4-0.6 mL/S, the stirring speed is 50-100 rpm, the anhydrous toluene is dispersed by using ultrasound while dropping and stirring, the ultrasound power is 3-3.5 KW, the ultrasound dispersion is continued for 5-8 min after the dropping and stirring are finished, the anhydrous toluene is analytically pure, and the diethylenetriamine solution is analytically pure. The mixing of the Fe-BTC colloid with the carbon oxide-based material can be further promoted by the ultrasonic dispersion.
Further, the volume fraction of the nitrogen introduced in the steps S2 and S3 is more than or equal to 99%.
Further, the centrifugal separation factor of the centrifugal separation in the step S4 is 3000g, and the mass concentration of the ethanol solution is 40%. Separation of impurities can be facilitated by centrifugal separation.
Further, the nitrogen-doped Fe-BTC derived carbon-based particles are applied to treatment of printing and dyeing wastewater, and the nitrogen-doped Fe-BTC derived carbon-based particles are mixed with peroxymonosulfate in a ratio of 5:1 part by weight of the sodium persulfate solution is added into the printing and dyeing wastewater for treatment, the treatment temperature is 25-28 ℃, and the peroxymonosulfate is potassium peroxymonosulfate. The nitrogen-doped Fe-BTC derived carbon-based particles are applied to treatment of printing and dyeing wastewater, so that pollutants in the printing and dyeing wastewater can be effectively removed, and the catalyst has good catalytic activity and stability.
Further, the mixing device used in the step S3 comprises an upper mixing tank, a lower mixing tank and a main mixing rod penetrating through the upper mixing tank and the lower mixing tank, wherein the main mixing rod is provided with a plurality of mixing blades from top to bottom inside the upper mixing tank, the main mixing rod is provided with mixing blades at the bottom inside the lower mixing tank, the upper mixing tank and the lower mixing tank are communicated through a flow guide pipe, and the top parts of the upper mixing tank and the lower mixing tank are both provided with liquid inlet pipes;
the main stirring rod is provided with a main gear at the middle position of the upper stirring barrel and the lower stirring barrel, the main gear is externally meshed with a plurality of driven gears with the radiuses increasing from small to large in a rotating mode, the center of the top of each driven gear is rotatably connected with the bottom of the upper stirring barrel through a rotating shaft, a thread bulge is arranged at the bottom of each driven gear, an auxiliary stirring rod is arranged below the thread bulge and is rotatably connected with the top wall of the lower stirring barrel, auxiliary stirring blades are arranged at the bottom of each auxiliary stirring rod, the auxiliary stirring blades are arranged at equal intervals in height, the smaller the radiuses of the auxiliary stirring blades are, the heights of the auxiliary stirring blades corresponding to the driven gears are lower, a rotating ring is sleeved on the upper portion of each auxiliary stirring rod, the auxiliary stirring rods are connected with the rotating ring in a sliding and synchronous rotating mode through limiting strips arranged on two sides of the outer wall of the top of the auxiliary stirring rods, threaded grooves used for being in butt joint with the thread bulges are arranged at the center of the upper surface of the rotating ring, an electric push rod is arranged on the top surface of the lower stirring barrel on one side of each rotating ring, and an electric push rod output end of the electric push rod used for pushing the rotating ring to rise;
be located the inside every that corresponds of agitator down the liquid level height department at supplementary stirring leaf place all is equipped with a level sensor, level sensor and the controller electric connection that is located agitator top down for the electric putter of the driven gear one side that the control corresponds opens and stops, go up and be equipped with a plurality of dead lever around the agitator.
The beneficial effects of the invention are:
(1) According to the preparation method of the nitrogen-doped Fe-BTC derived carbon-based material for activating peroxymonosulfate, disclosed by the invention, fe-BTC colloid is mixed with a carbon oxide-based material, and diethylenetriamine is loaded on the surface of the material under the nitrogen protection atmosphere through anhydrous toluene treatment to obtain nitrogen-doped Fe-BTC derived carbon-based particles, so that an adsorbing material with strong catalytic activity and high stability can be obtained, the treatment effect on pollutants in printing and dyeing wastewater is particularly good, the proportion of the nitrogen-doped Fe-BTC derived carbon-based particles to the peroxymonosulfate is further optimized, and the practicability is high.
(2) The mixing device used in the step S3 of the invention is provided with two mixing tanks, and is specially used for mixing the Fe-BTC colloid and the carbon oxide-based material in the step S3, so that the mixture in the two mixing tanks can be stirred in real time, the Fe-BTC colloid which is not added can be ensured not to be solidified, the stirring efficiency under different liquid level heights can be improved through the main gear and the driven gear which are arranged on the main stirring rod, the auxiliary stirring blades with different liquid level heights are sequentially started along with the rising of the liquid level height, and the driven gears corresponding to the auxiliary stirring blades with different liquid level heights have different radiuses, so that the rotating speeds are different, the rotating speed is lower when the liquid level is higher, the stirring efficiency is greatly improved, the continuity is strong, and the Fe-BTC colloid to be used can not be solidified.
Drawings
FIG. 1 is a schematic view of the overall structure of a mixing apparatus used in step S3 of the present invention;
FIG. 2 is a schematic diagram showing the structure of the middle part of the main stirring rod of the mixing device used in step S3 of the present invention;
FIG. 3 is a schematic view of the internal structure of the mixing tank of the mixing apparatus used in step S3 of the present invention;
FIG. 4 is a schematic view of the internal structure of the lower stirring barrel of the mixing device used in step S3 of the present invention;
FIG. 5 is a front view of the middle portion of the main stirring rod of the mixing device used in step S3 of the present invention;
FIG. 6 is a schematic view of the butt joint of the screw thread groove and the screw thread protrusion of the mixing device used in step S3 of the present invention;
FIG. 7 is a process flow diagram of a method of making the present invention.
The device comprises an upper stirring barrel, a lower stirring barrel, a main stirring rod, a stirring blade, a main gear, a driven gear, a rotating shaft, a thread protrusion, a 4-flow guide pipe, a liquid inlet pipe, an auxiliary stirring rod, an auxiliary stirring blade, a rotating ring, a 63-limiting strip, a 64-thread groove, an electric push rod, a 71-push plate, a 8-liquid level sensor, a 81-controller and a 9-fixing rod, wherein 1-the upper stirring barrel, 2-the lower stirring barrel, 3-the main stirring rod, 31-the driven gear, 34-the rotating shaft, 35-the thread protrusion, 4-the flow guide pipe, 5-the liquid inlet pipe, 6-the auxiliary stirring rod, 61-the auxiliary stirring blade, 62-the rotating ring, 63-the limiting strip, 64-the thread groove, 7-the electric push rod, 71-the push plate, 8-the liquid level sensor, the 81-controller and the 9-fixing rod.
Detailed Description
Example 1
A method for preparing a nitrogen-doped Fe-BTC-derived carbon-based material activated with peroxymonosulfate, as shown in fig. 7, comprising the steps of:
s1, preparing a metal organic framework material Fe-BTC: weighing 4 parts by weight of ferric chloride hexahydrate and 3.5 parts by weight of trimesic acid, adding the ferric chloride hexahydrate and the trimesic acid into 25 parts by weight of a dimethylformamide solution together, wherein the mass concentration of the trimesic acid is 99%, the dimethylformamide solution is analytically pure, stirring and mixing the mixture for 12min at a stirring speed of 110rpm to obtain a mixed solution, heating the mixed solution to 163 ℃ under a vacuum condition for 22h to obtain Fe-BTC colloid, and cleaning the Fe-BTC colloid for 3 times by using the dimethylformamide solution with the mass concentration of 40% to obtain the cleaned Fe-BTC colloid;
s2, preparing a carbon oxide based material: putting 6.5 parts by weight of carbon black into a tubular furnace for heating, heating to 850 ℃ at a heating rate of 18 ℃/min under the protection of nitrogen atmosphere, keeping the volume fraction of nitrogen at 99%, keeping the temperature for 1.5h, cooling to room temperature to obtain carbon black powder, mixing the carbon black powder with 3.5 parts by weight of potassium persulfate powder and 2.5 parts by weight of phosphorus pentoxide powder, adding the mixture into 23 parts by weight of concentrated sulfuric acid solution, stirring and mixing for 4.5h at 78 ℃, wherein the stirring method is magnetic stirring, the stirring speed is 350rpm, the mass concentration of concentrated sulfuric acid is 80%, taking out, and performing suction filtration to neutrality by using deionized water to obtain the carbon oxide-based material;
s3, preparing the Fe-BTC derived carbon-based material: mixing the cleaned Fe-BTC colloid obtained in the step S1 and the carbon oxide-based material obtained in the step S2, then dropwise adding 36 parts by weight of anhydrous toluene and stirring, heating to 103 ℃ while dropwise stirring, introducing nitrogen into the nitrogen under the nitrogen protection atmosphere, wherein the volume fraction of the nitrogen is 99%, dropwise adding 0.6 part by weight of diethylenetriamine solution, refluxing for 12 hours, the dropwise adding speed of the anhydrous toluene is 0.5mL/S, the stirring speed is 70rpm, dispersing by using ultrasound while dropwise adding and stirring, the ultrasonic power is 3.2KW, continuing to perform ultrasonic dispersion for 6 minutes after the dropwise adding and stirring are finished, the anhydrous toluene is analytically pure, and the diethylenetriamine solution is analytically pure, so as to obtain Fe-BTC derived carbon-based particles;
s4, post-processing: and (4) centrifugally separating the Fe-BTC derived carbon-based particles obtained in the step (S3), washing and filtering for 3 times by using an ethanol solution, wherein the centrifugal separation factor of the centrifugal separation is 3000g, the mass concentration of the ethanol solution is 40%, washing for 2 times by using ultrapure water, drying for 2 hours at the temperature of 130 ℃, and grinding to obtain the nitrogen-doped Fe-BTC derived carbon-based particles.
Example 2
The present embodiment is different from embodiment 1 in that: the method parameters of step S1 are different.
S1, preparing a metal organic framework material Fe-BTC: weighing 3 parts by weight of ferric chloride hexahydrate and 2.5 parts by weight of trimesic acid, adding the 3 parts by weight of ferric chloride hexahydrate and 2.5 parts by weight of trimesic acid into 22 parts by weight of dimethylformamide solution, wherein the mass concentration of the trimesic acid is 98%, the mass concentration of the dimethylformamide solution is analytically pure, stirring and mixing the mixture for 10min at the stirring speed of 100rpm to obtain mixed solution, heating the mixed solution to 160 ℃ under a vacuum condition for 20h to obtain Fe-BTC colloid, and cleaning the Fe-BTC colloid for 3 times by using the dimethylformamide solution with the mass concentration of 40% to obtain the cleaned Fe-BTC colloid.
Example 3
The present embodiment is different from embodiment 1 in that: the method parameters of step S1 are different.
S1, preparing a metal organic framework material Fe-BTC: weighing 5 parts by weight of ferric chloride hexahydrate and 4.5 parts by weight of trimesic acid, adding the weighed materials into 28 parts by weight of a dimethylformamide solution, wherein the mass concentration of the trimesic acid is 98%, the mass concentration of the dimethylformamide solution is analytically pure, stirring and mixing the materials for 15min at a stirring speed of 120rpm to obtain a mixed solution, heating the mixed solution to 165 ℃ under a vacuum condition for 24h to obtain Fe-BTC colloid, and cleaning the Fe-BTC colloid for 3 times by using the dimethylformamide solution with the mass concentration of 40% to obtain the cleaned Fe-BTC colloid.
Example 4
The present embodiment is different from embodiment 1 in that: the method parameters of step S2 are different.
S2, preparing a carbon oxide based material: putting 6 parts by weight of carbon black into a tubular furnace for heating, heating to 800 ℃ at a heating rate of 15 ℃/min under the protection of nitrogen atmosphere, keeping the volume fraction of nitrogen at 99%, keeping the temperature for 1h, cooling to room temperature to obtain carbon black powder, mixing the carbon black powder with 3-4 parts by weight of potassium persulfate powder and 2 parts by weight of phosphorus pentoxide powder, adding the mixture into 18-25 parts by weight of concentrated sulfuric acid solution, stirring and mixing for 4h at the temperature of 75 ℃, wherein the stirring method is magnetic stirring, the stirring speed is 300rpm, the mass concentration of concentrated sulfuric acid is 80%, taking out, and performing suction filtration to neutrality by using deionized water to obtain the carbon oxide-based material.
Example 5
The present embodiment is different from embodiment 1 in that: the method parameters of step S2 are different.
S2, preparing a carbon oxide based material: heating 7 parts by weight of carbon black in a tubular furnace, heating to 900 ℃ at a heating rate of 20 ℃/min under the protection of nitrogen atmosphere, keeping the volume fraction of nitrogen at 99%, keeping the temperature for 2h, cooling to room temperature to obtain carbon black powder, mixing the carbon black powder with 4 parts by weight of potassium persulfate powder and 3 parts by weight of phosphorus pentoxide powder, adding the mixture into 25 parts by weight of concentrated sulfuric acid solution, stirring and mixing for 5h at the temperature of 80 ℃, stirring by magnetic stirring at a stirring speed of 400rpm and a mass concentration of concentrated sulfuric acid at 80%, taking out, and performing suction filtration to neutrality by using deionized water to obtain the carbon oxide-based material.
Example 6
The present embodiment is different from embodiment 1 in that: the method parameters of step S3 are different.
S3, preparing the Fe-BTC derived carbon-based material: mixing the cleaned Fe-BTC colloid obtained in the step S1 and the carbon oxide-based material obtained in the step S2, then, dropwise adding 32 parts by weight of anhydrous toluene and stirring, heating to 100 ℃ while dropwise stirring, introducing nitrogen into the nitrogen under the nitrogen protection atmosphere, wherein the volume fraction of the nitrogen is 99%, dropwise adding 0.5 part by weight of diethylenetriamine solution, refluxing for 12 hours, the dropwise adding speed of the anhydrous toluene is 0.4mL/S, the stirring speed is 50rpm, dispersing by using ultrasound while dropwise adding and stirring, the ultrasonic power is 3KW, continuing to perform ultrasonic dispersion for 5 minutes after the dropwise adding and stirring are finished, the anhydrous toluene is analytically pure, and the diethylenetriamine solution is analytically pure, so that the Fe-BTC derivative particles are obtained.
Example 7
The present embodiment is different from embodiment 1 in that: the method parameters of step S3 are different.
S3, preparing the Fe-BTC derived carbon-based material: and (2) mixing the cleaned Fe-BTC colloid obtained in the step (S1) with the carbon oxide-based material obtained in the step (S2), dropwise adding 40 parts by weight of anhydrous toluene and stirring, heating to 105 ℃, introducing nitrogen into the nitrogen under the nitrogen protection atmosphere, wherein the volume fraction of the nitrogen is 99%, dropwise adding 0.8 part by weight of diethylenetriamine solution, refluxing for 12 hours, the dropwise adding speed of the anhydrous toluene is 0.6mL/S, the stirring speed is 100rpm, dispersing by using ultrasound while dropwise adding and stirring, the ultrasonic power is 3.5KW, continuing to perform ultrasonic dispersion for 8 minutes after the dropwise adding and stirring are finished, the anhydrous toluene is analytically pure, and the diethylenetriamine solution is analytically pure, so as to obtain the Fe-BTC derivative carbon-based particles.
Example 8
The present embodiment is different from embodiment 1 in that: the method parameters of step S4 are different.
S4, post-processing: and (4) centrifugally separating the Fe-BTC derived carbon-based particles obtained in the step (S3), washing and filtering for 3 times by using an ethanol solution, wherein the centrifugal separation factor of the centrifugal separation is 3000g, the mass concentration of the ethanol solution is 40%, washing for 2 times by using ultrapure water, drying for 2 hours at the temperature of 120 ℃, and grinding to obtain the nitrogen-doped Fe-BTC derived carbon-based particles.
Example 9
The present embodiment is different from embodiment 1 in that: the method parameters of step S4 are different.
S4, post-processing: and (4) centrifugally separating the Fe-BTC derived carbon-based particles obtained in the step (S3), washing and filtering for 3 times by using an ethanol solution, wherein the centrifugal separation factor of the centrifugal separation is 3000g, the mass concentration of the ethanol solution is 40%, washing for 3 times by using ultrapure water, drying for 2h at the temperature of 150 ℃, and grinding to obtain the nitrogen-doped Fe-BTC derived carbon-based particles.
Example 10
In this example, the nitrogen-doped Fe-BTC derived carbon-based particles prepared by the method of example 1 were applied to the treatment of printing and dyeing wastewater, and the nitrogen-doped Fe-BTC derived carbon-based particles were mixed with peroxymonosulfate in a ratio of 5:1 part by weight of the sodium persulfate salt is added into the printing and dyeing wastewater for treatment, the treatment temperature is 26 ℃, and the peroxymonosulfate is potassium peroxymonosulfate.
Example 11
The present embodiment is different from embodiment 10 in that:
in this example, the nitrogen-doped Fe-BTC derived carbon-based particles prepared by the method in example 1 were applied to the treatment of printing and dyeing wastewater, and the nitrogen-doped Fe-BTC derived carbon-based particles were mixed with peroxymonosulfate in a ratio of 5:1 part by weight of the sodium persulfate salt is added into the printing and dyeing wastewater for treatment, the treatment temperature is 25 ℃, and the peroxymonosulfate is potassium peroxymonosulfate.
Example 12
In this example, the nitrogen-doped Fe-BTC derived carbon-based particles prepared by the method of example 1 were applied to the treatment of printing and dyeing wastewater, and the nitrogen-doped Fe-BTC derived carbon-based particles were mixed with peroxymonosulfate in a ratio of 5:1 part by weight of the sodium persulfate salt is added into the printing and dyeing wastewater for treatment, the treatment temperature is 28 ℃, and the peroxymonosulfate is potassium peroxymonosulfate.
Example 13
In this embodiment, the embodiment 1 is further optimized, as shown in fig. 1, 3, and 4, the mixing device used in step S3 in embodiment 1 includes an upper stirring barrel 1, a lower stirring barrel 2, and a main stirring rod 3 penetrating through the upper stirring barrel 1 and the lower stirring barrel 2, the main stirring rod 3 is provided with a plurality of stirring blades 31 from top to bottom inside the upper stirring barrel 1, the main stirring rod 3 is provided with the stirring blades 31 at the bottom inside the lower stirring barrel 2, the upper stirring barrel 1 and the lower stirring barrel 2 are communicated with each other through a flow guide pipe 4, and the top of each of the upper stirring barrel 1 and the lower stirring barrel 2 is provided with a liquid inlet pipe 5;
as shown in fig. 1, 2, 5 and 6, the main stirring rod 3 is provided with a main gear 32 at the middle position of the upper stirring barrel 1 and the lower stirring barrel 2, the main gear 32 is externally engaged with and rotatably connected with a plurality of driven gears 33 with the radius from small to large, the top center of the driven gear 33 is rotatably connected with the bottom of the upper stirring barrel 1 through a rotating shaft 34, the bottom of each driven gear 33 is provided with a thread protrusion 35, an auxiliary stirring rod 6 is arranged below the thread protrusion 35, the auxiliary stirring rod 6 is rotatably connected with the top wall of the lower stirring barrel 2, the bottom of the auxiliary stirring rod 6 is provided with auxiliary stirring vanes 61, the auxiliary stirring vanes 61 corresponding to the driven gears 33 with the smaller radius are arranged at equal intervals in height, the lower part of the auxiliary stirring vanes 61 is lower, the upper part of the auxiliary stirring rod 6 is sleeved with a rotating ring 62, the auxiliary stirring rod 6 is slidably and synchronously rotatably connected with the rotating ring 62 through a limit strip 63 arranged at both sides of the top outer wall thereof, the center of the upper surface of the rotating ring 62 is provided with a thread groove 64 for abutting against the thread protrusion 35, the top surface of the lower stirring barrel 2 at one side of each rotating ring 62 is provided with an electric push rod 7, the top of the lower stirring barrel 2 is provided with an electric push rod 7 for pushing the electric push rod 7, the electric push rod 3, the electric push rod 7 for pushing the electric push rod 3, and the electric push rod 7 for pushing the electric push rod 3 for pushing the commercial use;
as shown in fig. 4, be located 2 inside liquid level height departments that correspond every auxiliary mixing leaf 61 place of agitator down and all be equipped with a level sensor 8, level sensor 8 with be located 2 top of agitator controller 81 electric connection down for the electric putter 7 of the driven gear 33 one side that the control corresponds opens and stops, goes up and is equipped with a plurality of dead lever 9 around the agitator 1, and level sensor 8 and controller 81 are the commercial product.
The working principle is as follows: when step S3 is performed and the mixing apparatus of the present invention is used, the cleaned Fe-BTC colloid obtained in step S1 needs to be mixed with the carbon oxide-based material obtained in step S2, two substances are injected through the liquid inlet pipe 5 of the upper stirring barrel 1, the main stirring rod 3 is turned on to stir the mixture inside the upper stirring barrel 1 through the stirring blade 31, after stirring for 15min, the draft tube 4 is opened to introduce the mixture into the lower stirring barrel 2, stirring is continued through the stirring blade 31 of the main stirring rod 3 in the lower stirring barrel 2, and simultaneously anhydrous toluene is dropped through the liquid inlet pipe 5 of the lower stirring barrel 2, and simultaneously the mixture of the Fe-BTC colloid and the carbon oxide-based material is continuously introduced;
when the liquid level in the lower stirring barrel 2 reaches the liquid level sensor 8 corresponding to the lowest auxiliary stirring blade 61, a signal is transmitted to the controller 81, the corresponding electric push rod 7 is opened to push the push plate 71 to move upwards, so that the rotating ring 62 moves upwards along the limiting strip 63 of the auxiliary stirring rod 6, the threaded groove 64 is in butt joint with the threaded protrusion 35 of the corresponding driven gear 33 in rotation, the rotation direction of the auxiliary stirring rod 6 is clockwise, the threaded groove 64 and the threaded protrusion 35 are buckled automatically in the rotation process, the threaded groove and the threaded protrusion 35 cannot fall off in the stirring process, the driven gear 33 and the corresponding auxiliary stirring rod 6 can be driven to rotate by the main gear 32 after the butt joint is completed, the corresponding auxiliary stirring blade 61 is driven to rotate, the auxiliary stirring is carried out, and meanwhile, the stirring is also continuously carried out in the upper stirring barrel 1 to avoid the solidification of the Fe-BTC colloid;
when the liquid level in the lower stirring barrel 2 reaches the liquid level sensor 8 corresponding to the next auxiliary stirring blade 61, the corresponding push rod motor 7 is started in the same way to rotate the auxiliary stirring blade 61, and the radiuses of the driven gears 33 corresponding to the auxiliary stirring blades 61 with different liquid level heights are different, so that the rotating speeds are different, and the higher the liquid level is, the lower the rotating speed is.
Examples of the experiments
A simulation experiment was conducted on the use of nitrogen-doped Fe-BTC-derived carbon-based particles in example 10 in the treatment of printing and dyeing wastewater to study the adsorption efficiency of the nitrogen-doped Fe-BTC-derived carbon-based particles prepared by the method of the present invention to congo red in printing and dyeing wastewater, and a comparison was made between example 1 (i.e., example 10), examples 6 and 7, and examples 11 and 12, and a comparison was made with conventional Fe-BTC materials, and the results are shown in the following table.
TABLE 1 adsorption amount of Congo Red in various examples and comparative examples
As can be seen from the data in table 1, compared with the comparative example, the adsorption efficiency of the nitrogen-doped Fe-BTC derived carbon-based particles of the present invention to congo red in printing and dyeing wastewater is significantly better, while the adsorption efficiency of the nitrogen-doped Fe-BTC derived carbon-based particles obtained by further optimizing the preparation parameters in example 1 to congo red in printing and dyeing wastewater is the best, the difference between example 11 and example 12 is not large, and the higher the temperature is, the smaller the promotion effect is on the adsorption efficiency.
Claims (9)
1. A method for preparing nitrogen-doped Fe-BTC derived carbon-based material activated with peroxymonosulfate, comprising the steps of:
s1, preparing a metal organic framework material Fe-BTC: weighing 3-5 parts by weight of ferric chloride hexahydrate and 2.5-4.5 parts by weight of trimesic acid, adding the ferric chloride hexahydrate and the trimesic acid into 22-28 parts by weight of a dimethylformamide solution together, stirring and mixing for 10-15 min to obtain a mixed solution, heating the mixed solution to 160-165 ℃ under a vacuum condition for 20-24 h to obtain Fe-BTC colloid, and cleaning the Fe-BTC colloid for 3 times by using a dimethylformamide solution with the mass concentration of 40% to obtain the cleaned Fe-BTC colloid;
s2, preparing a carbon oxide-based material: putting 6-7 parts by weight of carbon black into a tubular furnace for heating, heating to 800-900 ℃ at a heating rate of 15-20 ℃/min under the protection of nitrogen atmosphere, preserving heat for 1-2 h, cooling to room temperature to obtain carbon black powder, mixing the carbon black powder with 3-4 parts by weight of potassium persulfate powder and 2-3 parts by weight of phosphorus pentoxide powder, adding into 18-25 parts by weight of concentrated sulfuric acid solution, stirring and mixing at the temperature of 75-80 ℃ for 4-5 h, taking out, and performing suction filtration to neutrality by using deionized water to obtain the carbon oxide-based material;
s3, preparing the Fe-BTC derived carbon-based material: mixing the cleaned Fe-BTC colloid obtained in the step S1 with the carbon oxide-based material obtained in the step S2, then dropwise adding 32-40 parts by weight of anhydrous toluene and stirring, heating to 100-105 ℃ while dropwise adding and stirring, introducing nitrogen gas, dropwise adding 0.5-0.8 part by weight of diethylenetriamine solution under the nitrogen protection atmosphere, and refluxing for 12 hours to obtain Fe-BTC derived carbon-based particles;
s4, post-processing: and (4) centrifugally separating the Fe-BTC derived carbon-based particles obtained in the step (S3), washing and filtering for 3 times by using an ethanol solution, cleaning for 2-3 times by using ultrapure water, drying for 2h at the temperature of 120-150 ℃, and grinding to obtain the nitrogen-doped Fe-BTC derived carbon-based particles.
2. The method of claim 1, wherein the stirring speed in step S1 is 100 to 120rpm.
3. The method for preparing nitrogen-doped Fe-BTC derived carbon-based material activated by peroxymonosulfate according to claim 1, wherein the mass concentration of the trimesic acid in the step S1 is not less than 98%, and the dimethylformamide solution is analytically pure.
4. The method for preparing nitrogen-doped Fe-BTC derived carbon-based material activated with peroxymonosulfate as claimed in claim 1, wherein the stirring method in step S2 is magnetic stirring, the stirring speed is 300-400 rpm, and the mass concentration of concentrated sulfuric acid is 80%.
5. The method according to claim 1, wherein in step S3, the dropping speed of the anhydrous toluene is 0.4-0.6 mL/S, the stirring speed is 50-100 rpm, the anhydrous toluene is dispersed by using ultrasound while being dropped and stirred, the ultrasound power is 3-3.5 KW, the ultrasound dispersion is continued for 5-8 min after the dropping and stirring is finished, the anhydrous toluene is analytically pure, and the diethylenetriamine solution is analytically pure.
6. The method of claim 1, wherein the nitrogen-doped Fe-BTC derived carbon-based material activated with peroxymonosulfate is introduced into steps S2 and S3 in a volume fraction of nitrogen gas greater than or equal to 99%.
7. The method of claim 1, wherein the centrifugation factor of the centrifugation in the step S4 is 3000g, and the ethanol solution has a concentration of 40% by mass.
8. The method of claim 1, wherein the nitrogen-doped Fe-BTC-derived carbon-based particle is applied to the treatment of printing and dyeing wastewater, and the nitrogen-doped Fe-BTC-derived carbon-based particle is mixed with the peroxymonosulfate in a ratio of 5:1 part by weight of the sodium persulfate solution is added into the printing and dyeing wastewater for treatment, the treatment temperature is 25-28 ℃, and the peroxymonosulfate is potassium peroxymonosulfate.
9. The method for preparing nitrogen-doped Fe-BTC derived carbon-based material for activating peroxymonosulfate according to claim 1, wherein the mixing device used in the step S3 comprises an upper stirring barrel (1), a lower stirring barrel (2) and a main stirring rod (3) penetrating through the upper stirring barrel (1) and the lower stirring barrel (2), the main stirring rod (3) is provided with a plurality of stirring blades (31) inside the upper stirring barrel (1) from top to bottom, the main stirring rod (3) is provided with stirring blades (31) at the bottom inside the lower stirring barrel (2), the upper stirring barrel (1) and the lower stirring barrel (2) are communicated through a flow guide pipe (4), and the top of the upper stirring barrel (1) and the top of the lower stirring barrel (2) are both provided with a liquid inlet pipe (5);
the main stirring rod (3) is arranged at the middle position of the upper stirring barrel (1) and the lower stirring barrel (2) and is provided with a main gear (32), the main gear (32) is externally meshed and rotatably connected with a driven gear (33) with a plurality of radii from small to large, the top center of the driven gear (33) is rotatably connected with the bottom of the upper stirring barrel (1) through a rotating shaft (34), each driven gear (33) is provided with a thread bulge (35) at the bottom, an auxiliary stirring rod (6) is arranged below the thread bulge (35), the auxiliary stirring rod (6) is rotatably connected with the top wall of the lower stirring barrel (2), the bottom of the auxiliary stirring rod (6) is provided with an auxiliary stirring blade (61), the height of the auxiliary stirring blade (61) corresponding to the driven gear (33) with smaller radius is set at equal intervals, the upper part of the auxiliary stirring rod (6) is sleeved with a rotating ring (62), the auxiliary stirring rod (6) is provided with a limit strip (63) arranged on two sides of the top outer wall of the auxiliary stirring blade (61) and is provided with the rotating ring (62), the sliding surface of the rotating ring (62) is provided with a sliding connection groove (64), and the upper surface of the rotating ring (35) is provided with an electric stirring ring (7), the output end of the top of the electric push rod (7) is provided with a push plate (71) for pushing the rotating ring (62) to rise;
be located agitator (2) inside corresponds every down liquid level height department at auxiliary stirring leaf (61) place all is equipped with a level sensor (8), level sensor (8) and controller (81) electric connection that is located agitator (2) top down for electric putter (7) of driven gear (33) one side that the control corresponds open and stop, it is equipped with a plurality of dead lever (9) around agitator (1) to go up.
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