CN114618432B - Preparation method and application of resin-based carbon microsphere - Google Patents
Preparation method and application of resin-based carbon microsphere Download PDFInfo
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Abstract
The application discloses a preparation method and application of resin-based carbon microspheres, wherein the method comprises the following steps: (1) Oxidizing the resin white ball to obtain an intermediate product I; (2) Immersing the intermediate product I in a transition metal source solution, and loading to obtain an intermediate product II; (3) Carbonizing a mixture containing the intermediate product II and a nitrogen source in an inactive atmosphere to obtain the resin-based carbon microsphere; the resin white ball contains benzene structural units. The application designs a preparation and application method of a resin-based carbon microsphere adsorption material, and aims to provide a preparation method of a resin-based carbon microsphere adsorption material which is simple in preparation method, high in mechanical strength and high in specific surface area.
Description
Technical Field
The application relates to the technical field of adsorption materials, in particular to a preparation method and application of resin-based carbon microspheres.
Background
In recent years, research and production of activated carbon are rapidly developed, and the activated carbon has the advantages of better quality, more varieties and continuous diffusion of application range. From the original sugar, pharmaceutical and monosodium glutamate process applications to numerous fields such as solvent recovery, sewage treatment, air purification, desulfurization, gas masks, catalyst supports, blood purification, and supercapacitors. Along with the successful development of the active carbon with different types and different application characteristics, the application range of the active carbon is also widened.
The activated carbon may be classified into four kinds of powder carbon, fiber carbon, granular carbon and spherical carbon according to specific shapes. The powdered carbon has low price, but the pore structure is dispersed, and the adsorption performance is poor; the fibrous carbon has mainly micropores in pore size distribution, fast adsorption and desorption speed, high adsorption capacity and high cost. Spherical carbon has other incomparable advantages in addition to the basic properties of activated carbon. If the gas-liquid phase adsorption bed has good rolling property, the filling density is uniform when the gas-liquid phase adsorption bed is used, and the flow resistance is small in gas-liquid phase adsorption; smooth surface, regular shape, less scraps falling in the use process, high strength and low impurity content of the product. Therefore, the preparation and performance research of spherical carbon are increasingly receiving attention.
The spherical carbon can be divided into: asphalt-based spherical carbon, coal-based spherical carbon, and polymer-based spherical carbon. Although the spherical carbon prepared by asphalt has a plurality of advantages, the raw materials are wide, the price is low, the production process flow is complex, the process parameters and variables are many, and the oxidation in the preparation process does not melt the step to consume a large amount of energy, and consumes a long time, so that the production efficiency is low, the production cost is high, and the environment is not protected. Although the process of the coal-based spherical carbon is relatively simple, the defect of high ash content of the product is obvious, so that the preparation of the spherical carbon by using the polymer is paid more attention.
At present, resin is used as a precursor of carbon microspheres, but the resin is generally used for activating carbonized products. Activating carbonized product by adding chemical reagent or introducing steam and CO 2 Etc., there is disclosed a method for preparing resin-based spherical carbon by immersing carbonized spherical polymer in an alkaline alcohol solution and then subjecting the same to steam and CO 2 Activating treatment to obtain spherical active carbon with the median particle diameter of 0.02-1.0mm, and in the method, alkaline alcohol solution treatment is carried out on the carbonized primary product, so that the sphericity of the carbonized product can be kept, the pore volume and the pore diameter can be controlled, but the preparation cost of the spherical active carbon is increased, and meanwhile, unnecessary wastewater treatment expenditure is brought to the alkaline alcohol solution; the literature also discloses a spherical activated carbon prepared by taking macroporous strong acid cation exchange resin D001 as a precursor and adopting carbonization and KOH activation processes, and simultaneously, the adsorption desulfurization effect of the spherical activated carbon on dibenzothiophene is examined, and the adsorption performance is greatly improved compared with that of commercial coal-based activated carbon F400. KOH is used as an activator to a certain extentThe environmental protection cost and the operation and running costs of the process flow are increased.
Researches show that Fe, co and Ni supported catalysts, salts and oxides can interfere pyrolysis behaviors, and documents report that Fe, ni and Co can reduce tar yield in the pyrolysis process of a coal sample and have influence on coal morphology and pyrolysis products. Meanwhile, transition metals Fe, co, ni and the like can also promote the formation of graphite structures. Therefore, after the pre-oxidized product is loaded with metal, the pyrolysis process of the resin material in the carbonization process can be influenced, and the modification of the resin carbonized microspheres is realized. In the carbonization process of the resin, a nitrogen source is added, and the prepared resin-based carbon microsphere is rich in N, so that the property and the structure of the carbon microsphere are affected to a certain extent. N is located in VA group next to C atom, and one more electron than C atom, the electron density of the carbon microsphere can be increased after doping, so that the surface of the carbon microsphere presents certain alkalinity, and the carbon microsphere can be used for adsorbing acidic molecules. The literature reports the synthesis of N-doped microporous activated carbon using biomass (corncob) as a carbon source, the surface of the synthetic material being rich in nitrogen-containing functional groups (e.g., phenol-NH 2 pyridine-N) such that it is relative to CO 2 The acid gas has excellent adsorption capacity. But adopts NH in the document 3 As a nitrogen source, the nitrogen source has higher cost and higher toxicity. Organic amines and urea are used, which is less polluting than the prior art. Therefore, the invention provides the preparation method of the resin-based carbon microsphere, which has the advantages of low cost, no need of activation, simple preparation process steps and less pollution.
The small molecular organic acid wastewater has the characteristics of low pH, difficult biochemistry and the like, and meanwhile, part of small molecular organic acid is also a terminal product of the advanced oxidation reaction, and has high content, multiple types, large wastewater quantity and high treatment difficulty. The traditional activated carbon such as coconut shell carbon, wood carbon and the like is adopted to have poor adsorption effect and low TOC removal rate. Therefore, the resin-based carbon microsphere adsorbent with strong adsorption capacity and regeneration capacity on small molecular organic acid is prepared. The preparation method is simple, the operation condition is mild, the regeneration effect is good, and the prepared adsorbent has excellent adsorption performance of small molecular organic acid.
Disclosure of Invention
According to one aspect of the application, a preparation method and application of the resin-based carbon microsphere adsorption material are provided, and the application designs a preparation method and application method of the resin-based carbon microsphere adsorption material.
The method disclosed by the invention comprises the following steps: (1): preparing micron-sized resin white balls with a certain pore volume and specific surface area by adopting a suspension polymerization method, and washing and drying the micron-sized resin white balls; (2): pre-oxidizing the resin white balls obtained in the first step under an oxygen-containing atmosphere; (3): placing the pre-oxidized product into a metal salt solution, uniformly mixing and stirring, and drying to obtain pre-oxidized resin balls impregnated with metal; (4): uniformly mixing the dried product with a nitrogen source, and carbonizing in an inert atmosphere; (5): and (3) pickling the carbonized and cooled product to remove unstable metal impurities, and washing, drying and cooling to obtain the resin-based carbon microsphere. The invention has simple process and high yield, and the prepared carbon microsphere has high sphericity, uniform particle diameter, smooth surface, high mechanical strength, high specific surface area and uniform pore size distribution, and good adsorption performance, and the TOC removal efficiency of the small molecular organic acid is far better than that of commercial coconut shell carbon and wood carbon by 92% or more. Meanwhile, the adsorbent can be reused through simple regeneration treatment, and low-consumption and high-efficiency treatment of the small molecular organic acid wastewater can be effectively realized. The invention provides a simple method for preparing the resin-based carbon microsphere, provides a convenient and efficient way for removing the small molecular organic acid, has potential and value of industrial application, and has important significance for widening the engineering preparation and application of the resin-based carbon microsphere.
According to a first aspect of the present application, there is provided a method for preparing resin-based carbon microspheres, the method comprising:
(1) Oxidizing the resin white ball to obtain an intermediate product I;
(2) Immersing the intermediate product I in a transition metal source solution, and loading to obtain an intermediate product II;
(3) Mixing the intermediate product II with a nitrogen source in an inactive atmosphere, doping nitrogen and carbonizing to obtain the resin-based carbon microsphere;
the resin white ball contains benzene structural units.
Optionally, in the step (1), the pore volume of the resin white ball is 0.15-1 mL/g; specific surface area of 50-600 m 2 /g。
Optionally, in the step (1), the upper limit of pore volume of the resin white sphere is independently selected from 1mL/g, 0.8mL/g, 0.6mL/g, 0.4mL/g, 0.2mL/g, and the lower limit is independently selected from 0.15, 0.8mL/g, 0.6mL/g, 0.4mL/g, 0.2mL/g.
Alternatively, in the step (1), the upper limit of the specific surface area of the resin white sphere is independently selected from 600m 2 /g、500m 2 /g、400m 2 /g、300m 2 /g、200m 2 /g、100m 2 Per g, the lower limit is independently selected from 50m 2 /g、500m 2 /g、400m 2 /g、300m 2 /g、200m 2 /g、100m 2 /g。
Optionally, the method comprises:
1): preparing resin microspheres with a certain pore volume and specific surface area: the resin balls are synthesized by adopting a suspension polymerization process, and the resin balls are alternately washed for a plurality of times by deionized water and then are dried in a 60 ℃ oven.
2): and (3) placing the resin microspheres obtained in the first step in a muffle furnace, performing pre-oxidation treatment in an oxygen-containing atmosphere, and cooling to obtain brown resin microsphere particles.
3): immersing the pre-oxidized product in a metal salt solution with a certain concentration, uniformly stirring at a certain rotating speed, and then placing the product in an oven for drying treatment;
4): uniformly mixing the dried product with a nitrogen source, and then placing the mixture in a pyrolysis furnace, and carbonizing the mixture in an inert atmosphere;
5): and (3) placing the carbonized product into an acid solution for pickling, and drying and cooling to obtain the black resin-based carbon microsphere.
Optionally, in the step 5), the acid washing process is performed by placing the acid in 0.5M H 2 SO 4 In solution at 90 DEG CSoaking for 4 hours, washing the soaked sample for a plurality of times until the sample is neutral, and drying and cooling the sample to finally obtain the resin-based carbon microsphere.
Optionally, the step (1) includes: and (3) placing the resin white ball in an oxygen-containing atmosphere for reaction I to obtain the intermediate product I.
Optionally, the step (2) includes: placing metal salt into ethanol solution to prepare uniform solution, adding pre-oxidized sample, stirring in the metal salt solution for 4-10 h at a stirring speed of 400-600 rpm/min; and (3) placing the uniformly stirred sample in a baking oven at 60-120 ℃ for baking to obtain the immersed sample.
Optionally, the step (3) includes: and placing the nitrogen source and the pre-oxidized product into an ethanol solution, stirring and evaporating at 80 ℃, and carbonizing the solid obtained after evaporation.
Alternatively, the conditions of reaction I are: the reaction temperature is 250-300 ℃; the reaction time is 5-10 h; the temperature rising rate is 1-5 ℃/min.
Optionally, in the step (2), the transition metal source is selected from at least one of an iron source, a cobalt source, and a nickel source.
Optionally, the iron source is selected from at least one of iron salts;
the cobalt source is selected from at least one of cobalt salts;
the nickel source is selected from at least one of nickel salts.
Optionally, the iron salt is selected from at least one of nitrate of iron, hydrochloride of iron, sulfate of iron, acetate of iron;
the cobalt salt is at least one selected from the group consisting of cobalt nitrate, cobalt hydrochloride, cobalt sulfate and cobalt acetate;
the nickel salt is at least one selected from nitrate, hydrochloride, sulfate and acetate of nickel.
Optionally, in the step (3), the nitrogen source is at least one selected from melamine, dicyandiamide, urea.
Optionally, in the step (3), the conditions of doping nitrogen and carbonizing are: the temperature is 400-1200 ℃; the time is 1-18 h; the temperature rising rate is 1-10 ℃/min.
Optionally, in the step (3), the upper temperature limit of the nitrogen-doped and carbonized is independently selected from 1200 ℃, 1000 ℃, 800 ℃, 600 ℃, and the lower temperature limit is independently selected from 400 ℃, 1000 ℃, 800 ℃, 600 ℃.
Alternatively, the nitrogen-doped and carbonization may be performed sequentially in a single or multiple temperature zones, for example in 2 to 9 temperature zones; if performed in a plurality of temperature regions, the temperatures of which are different from each other, the carbonization temperature exhibits a gradient rise; the temperature gradient can be 50-200 ℃; the carbonization time in each temperature area is 0.5-10 h.
Optionally, in the step (2), the mass ratio of the intermediate product I to the transition metal source is 1: (0.001-0.1);
in the step (3), the mass ratio of the nitrogen source to the intermediate product II is (0.5-2): 1.
the mass of the transition metal source is calculated as the mass of the transition metal;
the mass of the nitrogen source is based on the mass of the nitrogen source itself.
Optionally, in the step (2), the upper mass ratio limit of the intermediate product I and the transition metal source is independently selected from 1:0.1, 1:0.05, 1:0.01, 1:0.005, the lower limit is independently selected from 1:0.001, 1:0.05, 1:0.01, 1:0.005.
in the application, the effect of metal loading on the resin white balls is to promote the carbonization process of the resin material, improve the pyrolysis rate, reduce the tar yield and realize the modification of the resin carbonized microspheres.
Optionally, the resin white ball is prepared by the following method:
reacting materials containing water, monomers, a cross-linking agent, an initiator, a pore-forming agent and a dispersing agent with II to obtain the resin white ball;
optionally, the dosages of water, dispersant, monomer, cross-linking agent, initiator and pore-forming agent in the process of preparing the resin white ball are respectively 100, 0.5-1.5, 40-60, 8-12, 0.5-1.5 and 11-16 parts by weight.
The monomer comprises an aromatic hydrocarbon;
preferably, the aromatic hydrocarbon is at least one selected from styrene and methyl styrene.
Optionally, the monomer comprises at least one of ethylene, propylene, isopropenyl, butene, isobutene, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate and aromatic hydrocarbon.
Optionally, the crosslinking agent is selected from divinylbenzene;
the initiator is at least one selected from azodiisobutyronitrile and azodiisoheptonitrile;
the pore-forming agent is at least one selected from toluene, petroleum ether, ethyl acetate and cyclohexane;
the dispersing agent is at least one selected from gelatin, polyvinyl alcohol, polyacrylate, kaolin, talcum powder and starch.
Alternatively, the resin white balls herein are prepared by suspension polymerization.
Alternatively, the conditions of reaction II are: the reaction temperature is 60-80 ℃; the reaction time is 6-10 h.
According to a second aspect of the present application, there is provided a resin-based carbon microsphere selected from any one of the resin-based carbon microspheres prepared according to the above method.
Alternatively, the specific surface area is higher than 700m calculated by DFT model 2 Per gram, average pore volume of 0.35cm 3 And the volume of micropores is mainly equal to or more than/g, and the pile ratio is 80g/100mL.
Optionally, the application takes the small molecular organic acid as model wastewater, and examines the adsorption performance of the carbon microsphere on the small molecular organic acid at room temperature under certain adsorption time, pH value and the addition ratio of the adsorbent to the model wastewater; wherein the adsorption time is 12-36h; the pH value is 1-7; the adding ratio of the adsorbent to the model wastewater is 10-100 g/L.
Alternatively, the small molecule organic acid model wastewater may be one or more organic acid mixtures.
Optionally, the resin-based carbon microsphere comprises micropores therein;
the specific surface area of the microsphere is more than 700m 2 /g; average pore volume of more than 0.35cm 3 /g。
Alternatively, the application characterizes the adsorption effect of carbon microspheres on small molecule organic acids according to an adsorption penetration curve.
Alternatively, the adsorption penetration curve of the present application is plotted as follows: accurately weighing a certain volume of carbon microspheres, loading the carbon microspheres into an adsorption column phi of 1.5cm multiplied by 18cm, allowing small molecular organic acid with a certain concentration and a certain pH value to pass through the adsorption column from bottom to top at room temperature at a certain space velocity, sampling at different times to measure TOC values, stopping running when the outlet TOC value reaches 95% or more of the TOC value of the initial solution, and calculating the adsorption capacity (recorded as TOC value) of the carbon microspheres on the small molecular organic acid. TOC with time on the abscissa t Plotting the ordinate to obtain an adsorption penetration curve; wherein the airspeed of the small molecular organic acid model wastewater is 1-10 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration is 100-2000 mg/L; the pH value is 1-7.
According to a third aspect of the present application, there is provided an adsorbent selected from at least one of the resin-based carbon microspheres prepared according to the above method, the resin-based carbon microspheres described above.
Alternatively, the adsorbent may be regenerated.
Optionally, the regeneration method is selected from any one of alkaline washing and alcohol washing.
Optionally, performing regeneration treatment on the carbon microspheres after the adsorption reaction, re-applying the carbon microspheres after the regeneration treatment to an adsorption experiment, repeating the adsorption penetration experiment, and evaluating the regeneration effect of the resin-based carbon microspheres according to the total adsorption amount of the adsorption desorption TOC for a plurality of times;
the regeneration treatment may be alkali washing or alcohol washing, wherein alkali washing is preferable;
the inorganic alkali used in the alkaline washing process is preferably NaOH, wherein the mass fraction of the NaOH is 2% -6%.
According to a fourth aspect of the present application there is provided the use of an adsorbent as described above in wastewater treatment.
Optionally, the wastewater comprises small-molecule organic acid;
preferably, the small molecule organic acid is at least one selected from acetic acid, propionic acid, n-butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, acrylic acid and salicylic acid.
Optionally, the method of treating wastewater using an adsorbent comprises:
mixing the adsorbent with the wastewater, and adsorbing to obtain the wastewater treated by the adsorbent.
Optionally, the conditions of the adsorption are: the temperature is 20-30 ℃; the time is 12-36 h.
Optionally, the mass of the adsorbent and the volume ratio of the wastewater are 10-100 g/L;
the content of the small molecular organic acid in the wastewater is 50-5000 mg/L.
Alternatively, the adsorption is performed under acidic or neutral conditions.
The preparation process of the application (1) is simple, and the application has a large-scale application prospect; (2) The pore and specific surface area of the resin-based carbon microsphere prepared finally can be adjusted by changing the conditions of the resin white sphere synthesis, pre-oxidation and carbonization processes; (3) The resin-based carbon microsphere prepared by doping treatment has excellent adsorption capacity to small molecular organic acid, which is far higher than the coconut shell carbon and wood carbon which are commercially applied at present. (4) Can provide a theoretical basis for the reuse of waste resin.
The beneficial effects that this application can produce include:
(1) The preparation of the resin-based carbon microsphere does not need activation, has less environmental pollution, and provides a theoretical basis for recycling waste resin;
(2) The resin-based carbon microsphere has high sphericity and high mechanical strength, and the structure of the carbon microsphere can be effectively regulated and controlled by changing the conditions in the synthesis, pre-oxidation and carbonization processes of the resin white sphere;
(3) The resin-based carbon microsphere has strong adsorption and removal capability on small molecular organic acid, and the adsorption performance is far better than that of commercial coconut shell carbon and wood carbon;
(4) The resin-based carbon microsphere disclosed by the invention has excellent regeneration performance, can be used for multiple times after being subjected to simple regeneration treatment, and can greatly reduce the cost.
Drawings
FIG. 1 is a diagram showing the N-type RCS-1, 6 carbon microspheres obtained in examples 1, 6 2 Adsorption-desorption isotherms;
FIG. 2 is a scanning electron microscope image of RCS-2 produced in example 2;
FIG. 3 is an optical microscope image of RCS-8 produced in example 8;
FIG. 4 is a graph showing the adsorption breakthrough of RCS-12 prepared in example 12 to acetic acid at various space velocities;
FIG. 5 shows the total TOC adsorption and desorption amount of the RCS-12 multi-regeneration cycle test prepared in example 12.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
In the examples, the characterization and analysis methods of the samples are as follows:
specific surface area of sample by N 2 Adsorption-desorption experiment test analysis, wherein the analytical instrument is Autosorb iQ Station 2 of Quanta chrome company, the test condition is that after pretreatment for 5 hours at 300 ℃, N is used for 2 The adsorbent is adsorbed at a constant temperature under the condition of 77K.
The morphological characteristics of the sample are analyzed by a Scanning Electron Microscope (SEM), the analysis instrument is a JSM6360LV scanning electron microscope, and the performance indexes are as follows: acceleration voltage is 0.5-30 kV, and amplification factor is high: 18-50000 times, resolution ratio: high vacuum 3.0nm, low vacuum 4.5nm. With an energy spectrum and EBSD analysis system.
Example 1
Into a 250mL four-necked flask equipped with a thermometer, a condenser and a stirrer, 100mL of deionized water and 0.5g of polyvinyl alcohol were added, and then, into another beaker, a mixture of 1g of azobisisobutyronitrile, 50g of methyl acrylate and 10g of styrene, 10g of divinylbenzene, 12g of petroleum ether and ethyl acetate was added to be mixed uniformly, followed by addition into the four-necked flask. Slowly riseThe reaction is carried out for 3 hours at the temperature of 70 ℃, then the temperature is increased to 75 ℃ for continuous reaction for 4 hours, and the reaction is stopped. Removing pore-forming agent by steam distillation, alternately washing with cold water and hot water until water is clear, and oven drying at 60deg.C to obtain resin white ball (pore volume of 0.357mL/g, specific surface area of 54.8 m) 2 /g). Weighing a certain mass of synthetic resin white balls, placing the white balls in a muffle furnace, pre-oxidizing the white balls in an air atmosphere, wherein the temperature is raised to 280 ℃ from room temperature at a heating rate of 5 ℃/min, and cooling the white balls after maintaining the temperature for 5 hours, and taking out the product. Weigh 3.6g Fe (NO) 3 ) 3 ·9H 2 O, after being dissolved in ethanol solution at room temperature to obtain uniform solution, 10g of pre-oxidized product is added into the uniform solution, and after stirring is carried out for 6 hours at the rotation speed of 400rpm/min, the obtained product is placed in a 100 ℃ oven for drying. And then mixing the product with melamine in a mass ratio of 1:1 in a round bottom flask, adding an excess of ethanol solution, and stirring at 80 ℃ until the solution is completely evaporated. The resulting solid mixture was placed in a muffle furnace at N 2 Carbonizing under atmosphere, wherein N 2 The flow rate is 200mL/min, the temperature is raised to 400 ℃ from room temperature in a step-type manner at a heating rate of 5 ℃/min, the temperature is raised to 500 ℃ after carbonization for 2 hours at 400 ℃, the temperature is raised to 600 ℃ after constant temperature for 2 hours, and the temperature is raised to 700 ℃ after constant temperature for 10 hours. Taking out the sample when the temperature in the furnace is lower than 50 ℃, and placing the sample in 0.5M H 2 SO 4 Soaking the carbon microsphere in the solution at 90 ℃ for 4 hours, washing the carbon microsphere with water for a plurality of times to neutrality, drying the carbon microsphere in a baking oven at 60 ℃, and cooling the carbon microsphere to obtain the resin-based carbon microsphere which is named as RCS-1.
Example 2
Into a 250mL four-necked flask equipped with a thermometer, a condenser and a stirrer, 100mL of deionized water and 1g of gelatin were added, and then a mixture of 1g of azobisisobutyronitrile, 60g of styrene, 10g of divinylbenzene, 12g of petroleum ether and ethyl acetate was added to another beaker, and after mixing uniformly, the mixture was added into the four-necked flask. Slowly heating to 70 ℃ to react for 3 hours, heating to 75 ℃ to continue the reaction for 4 hours, and stopping the reaction. Removing pore-forming agent by steam distillation, alternately washing with cold water and hot water until water is clear, and oven drying at 60deg.C to obtain resin white ball (pore volume of 0.523mL/g, specific surface area of 125.5 m) 2 /g). Weighing white synthetic resin ball, placing in muffle furnace, placing inPre-oxidizing in air atmosphere, heating to 300 ℃ from room temperature, keeping for 10h at a heating rate of 5 ℃/min, and taking out after cooling. Weigh 0.08g Ni (NO) 3 ) 2 ·6H 2 O and 2.27g Co (NO) 3 ) 2 ·6H 2 O, after being dissolved in ethanol solution at room temperature to obtain uniform solution, 10g of pre-oxidized product is added into the uniform solution, and after stirring is carried out for 6 hours at the rotation speed of 400rpm/min, the obtained product is placed in a 100 ℃ oven for drying. And then mixing the product with melamine in a mass ratio of 1:1, placing the mixture in a round bottom flask, adding excessive ethanol solution, stirring at 80deg.C until the solution is completely evaporated, placing the obtained solid mixture in an atmosphere furnace, and introducing N 2 ，N 2 The flow is 200mL/min, the temperature is raised to 400 ℃ from room temperature, then is raised to 500 ℃ after being kept constant for 2 hours, is raised to 600 ℃ after being kept constant for 2 hours, is raised to 700 ℃ after being kept constant for 2 hours, is raised to 800 ℃ after being kept constant for 10 hours, and the temperature rising rate in the whole process is kept to be 5 ℃/min. Taking out the sample when the temperature in the furnace is lower than 50 ℃, and placing the sample in 0.5M H 2 SO 4 Soaking the carbon microsphere in the solution at 90 ℃ for 4 hours, washing the carbon microsphere with water for multiple times, drying the carbon microsphere in a baking oven at 60 ℃, and cooling the carbon microsphere to obtain the resin-based carbon microsphere which is named as RCS-2.
Example 3
The same as in example 1, except that in the resin synthesis, the monomer was a mixture of 50g of acrylic acid and 10g of styrene. Other conditions are kept consistent, the pore volume of the synthetic resin white ball is 0.906mL/g, and the specific surface area is 518.6m 2 And/g. The final carbonized product was designated RCS-3.
Example 4
Example 2 was repeated except that the monomer was a mixture of 20g of methacrylic acid and 25g of styrene. Other conditions are kept consistent, the pore volume of the synthetic resin white ball is 0.171mL/g, and the specific surface area is 304.8m 2 And/g. The final carbonized product was designated RCS-4.
Example 5
The resin preparation process is the same as in example 2, a certain mass of synthetic resin white balls are weighed and placed in an atmosphere box-type muffle furnace, the temperature is raised to 280 ℃ from room temperature, the heating rate is 5 ℃/min, the resin is kept for 10 hours, and the resin white balls are taken out after being cooled. Weigh 0.08g Ni (NO) 3 ) 2 ·6H 2 O and 2.27g Co (NO) 3 ) 2 ·6H 2 O, dissolving in ethanol solution at room temperature to obtain uniform solution, adding 10g of pre-oxidized product into the uniform solution, stirring for 6 hours at the rotation speed of 400rpm/min, placing the obtained product into a 100 ℃ oven for drying, and then mixing the product with melamine according to the mass ratio of 1:1, placing the mixture in a round bottom flask, adding excessive ethanol solution, stirring at 80deg.C until the solution is completely evaporated, placing the obtained solid mixture in a muffle furnace, placing in an atmosphere furnace, and introducing N 2 ，N 2 The flow is 200mL/min, the temperature is raised to 400 ℃ from room temperature, then is raised to 500 ℃ after being kept constant for 2 hours, is raised to 600 ℃ after being kept constant for 2 hours, is raised to 700 ℃ after being kept constant for 2 hours, is raised to 800 ℃ after being kept constant for 10 hours, and the temperature rising rate in the whole process is kept to be 5 ℃/min. Taking out the sample when the temperature in the furnace is lower than 50 ℃, and placing the sample in 0.5M H 2 SO 4 Soaking in the solution at 90 ℃ for 4 hours, washing for multiple times, drying in a 60 ℃ oven, and cooling to obtain the resin-based carbon microsphere, which is named RCS-5.
Example 6
The same as in example 5, the difference from example 5 is that the pre-oxidation temperature is 300 ℃. The resin-based carbon microsphere is obtained and named RCS-6.
Example 7
The same as in example 5, except that the carbonization process was directly heated to 900℃and maintained at constant temperature for 1 hour, a resin-based carbon microsphere was obtained, which was designated as RCS-7.
Example 8
The difference from example 7 is that the carbonization process is to heat up to 900 ℃ directly and then keep the temperature for 2 hours, thus obtaining the resin-based carbon microsphere named RCS-8.
Example 9
The difference from example 8, which was similar to example 8, was that the carbonization process was directly heated to 600℃and then was maintained at constant temperature for 2 hours, to obtain resin-based carbon microspheres, which was designated as RCS-9.
Example 10
The difference from example 9 is that the carbonization process is to heat up to 700 ℃ directly and then keep the temperature for 2 hours, thus obtaining the resin-based carbon microsphere named RCS-10.
Example 11
The difference from example 10 was that the carbonization process was directly heated to 800℃and then kept at constant temperature for 2 hours, to give resin-based carbon microspheres, designated RCS-11.
Example 12
The same procedure as in example 11 was followed except that the temperature was raised from room temperature to 250℃at a heating rate of 5℃per minute for 10 hours during the pre-oxidation. The resin-based carbon microsphere is obtained and named as RCS-12.
Example 13
The difference is that the carbonization process is to heat up to 800 ℃ directly and then keep the temperature for 1h, and the resin-based carbon microsphere is obtained and named RCS-13.
Example 14
The difference is that the carbonization process is to heat up to 800 ℃ directly and then keep the temperature for 3 hours, and the resin-based carbon microsphere is obtained and named RCS-14.
Example 15
The difference is that the carbonization process is to heat up to 800 ℃ directly and then keep the temperature for 4 hours, and the resin-based carbon microsphere is obtained and named RCS-15.
Example 16
The difference is that the carbonization process is to heat up to 800 ℃ directly and then keep the temperature for 5 hours, and the resin-based carbon microsphere is obtained and named RCS-15.
Example 17
The difference with example 16 is that the carbonization process is to heat up to 800 ℃ directly and then keep the temperature for 6 hours, and the resin-based carbon microsphere is obtained and named RCS-17.
Example 18
The difference from example 17 is that the carbonization process was carried out by heating directly to 600℃and then keeping the temperature for 2 hours to obtain resin-based carbon microspheres, designated RCS-18.
Example 19
The difference is that the carbonization process is to heat up to 700 ℃ directly and then keep the temperature for 2 hours, and the resin-based carbon microsphere is obtained and named RCS-19.
Example 20
The difference is that the carbonization process is to heat up to 900 ℃ directly and then keep the temperature for 2 hours, and the resin-based carbon microsphere is obtained and named RCS-20.
Example 21
The difference from example 20 is that the mass ratio of the metal-supported product to dicyandiamide is 1:1.67, and resin-based carbon microspheres, designated RCS-21, are obtained.
Example 22
The difference from example 21 is that the mass ratio of the metal-supported product to dicyandiamide is 1:0.5, and resin-based carbon microspheres, named RCS-22, are obtained.
Example 23
The same as in example 22, except that the metal source was 0.08g Fe (NO 3 ) 3 ·9H 2 O, the resin-based carbon microsphere is obtained and named RCS-23. The specific surface area and pore volume of the resin-based carbon microspheres prepared in examples 1 to 23 are shown in Table 1.
TABLE 1 specific surface area and pore volume of resin-based carbon microspheres prepared in examples 1 to 23
As can be seen from Table 1, the specific surface area of the carbon microspheres formed by the method reaches 700m 2 And/g. Wherein, N of RCS-1, 6 2 Adsorption-desorption isotherms are shown in figure 1. The adsorption isotherm of the RCS-1 resin carbon microsphere is in a steep increasing trend in a low-pressure area, which indicates that a large number of micropores exist, the type of the adsorption isotherm is II-IV type mixed type, which indicates that mesopores exist, and the aperture of the adsorbent is larger. The adsorption isotherm of the RCS-6 resin carbon microsphere is similar to that of RCS-1, and the adsorption isotherm is similar to that of RCS-1 at a very large P/P 0 In the range, the adsorption capacity of the catalyst is less amplified, which shows that the pore size distribution of the catalyst is more uniform than that of RCS-1 type, and the adsorption capacity of a high-pressure area is increased, which shows that macropores and mesopores exist. It can be seen that the method can synthesize a high specific surface while having uniform pore diametersArea of carbon microsphere.
SEM characterization is carried out on the resin carbon microsphere RCS-2 of the example 2, and an electron microscope image is shown in FIG. 2, so that the resin-based carbon microsphere has high sphericity and the size is 400-600 mu m.
The resin-based carbon microspheres of example 8 were observed under an optical microscope, and as shown in fig. 3, the carbon microspheres were high in sphericity and uniform in size.
Example 24
5g of the resin-based carbon microspheres prepared in examples 1 to 23 and commercial coconut charcoal and wood charcoal samples were weighed and added to 50mL of 1000mg/L acetic acid solution having a pH=1.5, the TOC value of the solution before adsorption was measured to be 401.5mg/L, and after shaking at a constant temperature of 25℃for 24 hours in a closed vessel, the TOC value and TOC removal rate of the solution after adsorption were measured as shown in Table 2. It can be seen that the adsorption removal capacity of the carbon microsphere prepared by the invention to acetic acid is far higher than that of commercial coconut shell charcoal and wood charcoal.
TABLE 2 intermittent adsorption removal Capacity of different adsorbents for acetic acid
Example 25
1g of RCS-12 prepared in example 12 was weighed and added to 10mL of 1000mg/L acetic acid, propionic acid, n-butyric acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, acrylic acid, isobutyric acid, salicylic acid solution, respectively, at pH=1, and TOC values and TOC removal rates of the solutions before and after adsorption were measured as shown in Table 3. It can be seen that the prepared resin-based microsphere has excellent adsorption removal capability on various small molecular organic acids. Wherein:
TABLE 3 adsorption removal Capacity of RCS-12 different organic small molecule acids
Example 26
Accurately weighing 20mL of RCS-5 carbon microsphere, loading into adsorption column with phi of 1.5cm×18cm, and standing for 1 hr at room temperature with acetic acid solution with concentration of 1000mg/L, pH =1.5 -1 The space velocity passes through the adsorption column from bottom to top, TOC values are measured by sampling at different times, the operation is stopped when the TOC value of the outlet reaches 95% of the TOC value of the initial solution, and the adsorption penetration curve (recorded as TOC value) of the carbon microsphere to acetic acid is calculated. Plotted on the time axis and TOCt on the ordinate, as shown in FIG. 4. And regenerating the carbon microsphere after saturated adsorption by using a NaOH solution with the mass fraction of 4%, and repeating the flow of the regenerated adsorbent to obtain total TOC adsorption and desorption after repeated regeneration, as shown in figure 5 (ads represents adsorption and des represents desorption). Fig. 4 shows that increasing the space velocity within a certain range shortens the adsorption time and improves the efficiency, but has no obvious influence on the adsorption effect, and the adsorbent carbon microsphere has good adsorption removal capability on acetic acid.
Figure 5 shows that multiple adsorption and desorption have no significant effect on the total adsorption capacity of the carbon microsphere on acetic acid.
Example 27
As in example 26, the difference from example 26 is that the space velocity is 2h -1 The adsorption penetration curve is shown in fig. 4;
example 28
As in example 25, the difference from example 25 is that the space velocity is 3h -1 The adsorption penetration curve is shown in fig. 4;
it can be seen that the prepared RCS has excellent adsorption capacity to small molecules such as acetic acid, and meanwhile, repeated cyclic adsorption and desorption experiments show that the RCS has good stability.
Example 29
After the resin-based carbon microsphere prepared in the embodiment is tested by a particle intensity meter, the intensity of the single resin-based carbon microsphere exceeds the measuring range by 50N.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (23)
1. A method for preparing resin-based carbon microspheres, the method comprising:
(1) Oxidizing the resin white ball to obtain an intermediate product I;
(2) Immersing the intermediate product I in a transition metal source solution, and loading to obtain an intermediate product II;
(3) Mixing the intermediate product II with a nitrogen source in an inactive atmosphere, doping nitrogen and carbonizing to obtain the resin-based carbon microsphere;
the resin white ball contains benzene structural units;
in the step (3), the nitrogen source is at least one selected from melamine, dicyandiamide and urea;
the resin-based carbon microsphere comprises micropores;
the specific surface area of the microsphere is more than 700m 2 /g; average pore volume of more than 0.35cm 3 /g；
The transition metal source is selected from at least one of an iron source, a cobalt source and a nickel source;
the conditions for doping nitrogen and carbonizing are as follows: the temperature is 400-1200 ℃; the time is 1-18 h; the temperature rising rate is 1-10 ℃/min.
2. The method according to claim 1, wherein in the step (1), the pore volume of the resin white sphere is 0.15 to 1ml/g; specific surface area of 50-600 m 2 /g。
3. The method of claim 1, wherein step (1) comprises: and (3) placing the resin white ball in an oxygen-containing atmosphere for reaction I to obtain the intermediate product I.
4. A process according to claim 3, wherein the conditions of reaction I are: the reaction temperature is 250-300 ℃; the reaction time is 5-10 h; the temperature rising rate is 1-5 ℃/min.
5. The method according to claim 1, wherein in the step (2),
the iron source is selected from at least one of ferric salts;
the cobalt source is selected from at least one of cobalt salts;
the nickel source is selected from at least one of nickel salts.
6. The method according to claim 5, wherein the iron salt is at least one selected from the group consisting of iron nitrate, iron hydrochloride, iron sulfate, and iron acetate;
the cobalt salt is at least one selected from the group consisting of cobalt nitrate, cobalt hydrochloride, cobalt sulfate and cobalt acetate;
the nickel salt is at least one selected from nitrate, hydrochloride, sulfate and acetate of nickel.
7. The method according to claim 1, wherein in the step (2), the mass ratio of the intermediate product I to the transition metal source is 1: (0.001 to 0.1);
in the step (3), the mass ratio of the nitrogen source to the intermediate product II is (0.5-2): 1, a step of;
the mass of the transition metal source is calculated as the mass of the transition metal;
the mass of the nitrogen source is based on the mass of the nitrogen source itself.
8. The preparation method according to claim 1, wherein the resin white ball is prepared by the following method:
reacting materials containing water, monomers, a cross-linking agent, an initiator, a pore-forming agent and a dispersing agent with II to obtain the resin white ball;
the monomer comprises an aromatic hydrocarbon.
9. The method according to claim 8, wherein the aromatic hydrocarbon is at least one selected from styrene and methylstyrene.
10. The method of claim 8, wherein the cross-linking agent is selected from divinylbenzene;
the initiator is at least one selected from azodiisobutyronitrile and azodiisoheptonitrile;
the pore-forming agent is at least one selected from toluene, petroleum ether, ethyl acetate and cyclohexane;
the dispersing agent is at least one selected from gelatin, polyvinyl alcohol, polyacrylate, kaolin, talcum powder and starch.
11. The preparation method according to claim 8, wherein the mass ratio of the water, the dispersing agent, the monomer, the crosslinking agent, the initiator and the pore-forming agent is 100:0.5 to 1.5: 40-60: 8-12: 0.5 to 1.5: 11-16.
12. The process of claim 8, wherein the conditions for reaction II are: the reaction temperature is 60-80 ℃; the reaction time is 6-10 h.
13. Resin-based carbon microsphere, characterized in that the resin-based carbon microsphere is selected from any one of the resin-based carbon microspheres prepared according to the method of any one of claims 1 to 12.
14. An adsorbent, wherein the adsorbent is at least one selected from the group consisting of resin-based carbon microspheres prepared by the method according to any one of claims 1 to 12 and resin-based carbon microspheres according to claim 13.
15. The adsorbent of claim 14, wherein the adsorbent is regenerable.
16. The adsorbent of claim 15, wherein the regeneration method is selected from any one of alkaline washing and alcohol washing.
17. Use of an adsorbent according to any one of claims 14 to 16 in wastewater treatment.
18. The use according to claim 17, wherein the waste water comprises small organic acids.
19. The use according to claim 18, wherein the small molecule organic acid is selected from at least one of acetic acid, propionic acid, n-butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, acrylic acid, salicylic acid.
20. The use of claim 17, wherein the method of treating wastewater using an adsorbent comprises:
mixing the adsorbent with the wastewater, and adsorbing to obtain the wastewater treated by the adsorbent.
21. The use according to claim 20, wherein the conditions of adsorption are: the temperature is 20-30 ℃; the time is 12-36 h.
22. The use according to claim 20, wherein the adsorbent mass to waste water volume ratio is 10-100 g/L;
the content of the small-molecule organic acid in the wastewater is 50-5000 mg/L.
23. The use according to claim 20, wherein the adsorption is performed under acidic or neutral conditions.
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