CN111408344B - Nitrogen-doped petroleum coke cooked coke functional material and preparation method and application thereof - Google Patents

Nitrogen-doped petroleum coke cooked coke functional material and preparation method and application thereof Download PDF

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CN111408344B
CN111408344B CN202010243459.XA CN202010243459A CN111408344B CN 111408344 B CN111408344 B CN 111408344B CN 202010243459 A CN202010243459 A CN 202010243459A CN 111408344 B CN111408344 B CN 111408344B
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coke
petroleum coke
cooked
nitrogen
melamine
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CN111408344A (en
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李玉江
刘志鹏
王全勇
吴涛
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Shandong University
China Urban Construction Design and Research Institute Co Ltd
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China Urban Construction Design and Research Institute Co Ltd
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0259—Compounds of N, P, As, Sb, Bi
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
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Abstract

The invention belongs to the technical field of environmental pollution treatment, and particularly relates to a nitrogen-doped petroleum coke cooked coke functional material, and a preparation method and application thereof. The preparation method of the nitrogen-doped petroleum coke cooked coke functional material provided by the invention comprises the following steps: calcining the petroleum coke green coke to obtain petroleum coke cooked coke; mixing the petroleum coke cooked coke, melamine and ethanol, and drying to obtain melamine/petroleum coke cooked coke; and sintering the melamine/petroleum coke cooked coke under a protective atmosphere to obtain the nitrogen-doped petroleum coke cooked coke functional material. The nitrogen-doped petroleum coke cooked coke functional material prepared by taking petroleum coke green coke as a raw material has good adsorption performance on bisphenol A, and can be used for treating bisphenol A-containing wastewater.

Description

Nitrogen-doped petroleum coke cooked coke functional material and preparation method and application thereof
Technical Field
The invention relates to the technical field of environmental pollution treatment, in particular to a nitrogen-doped petroleum coke cooked coke functional material and a preparation method and application thereof.
Background
The petroleum coke green coke is a product formed by separating light oil from heavy oil through distillation of crude oil and then converting the heavy oil through a thermal cracking process, and the yield of the petroleum coke is continuously increased along with the continuous increase of the processing amount of petroleum and the trend of the heavy crude oil processing in China. The petroleum coke green coke has the advantages of high carbon content, low ash content and low price. However, long-term accumulation of petroleum coke green coke occupies land resources, leachate generated in the accumulation process can pollute underground water, and impurities such as sulfur, volatile matters and the like in the petroleum coke green coke can also pollute the atmospheric environment in the combustion process, so that the petroleum coke green coke is not suitable for combustion treatment.
In addition, bisphenol A is a basic chemical raw material, is mainly used for producing various high polymer materials such as polycarbonate, epoxy resin, polysulfone resin, polyphenyl ether resin and the like, can also be used for fine chemical products such as plasticizers, flame retardants, antioxidants, heat stabilizers, rubber anti-aging agents, pesticides, coatings and the like, and can easily enter a water environment along with wastewater discharged by enterprises in the using process of the bisphenol A. Since bisphenol a can cause endocrine disorders that threaten the health of fetuses and children, and can also cause cancer and metabolic disorders that are extremely harmful to humans and livestock upon entry into aqueous environments, including surface and ground waters, effective adsorbent materials must be found for their effective removal. In the prior art, carbonaceous adsorbing materials (such as graphene, graphene oxide and the like) are used for adsorbing bisphenol A, but the price is relatively high, so that the treatment cost of bisphenol A wastewater is relatively high.
Disclosure of Invention
The invention aims to provide a nitrogen-doped petroleum coke cooked coke functional material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nitrogen-doped petroleum coke cooked coke functional material, which comprises the following steps:
calcining the petroleum coke green coke to obtain petroleum coke cooked coke;
mixing the petroleum coke cooked coke, melamine and ethanol, and drying to obtain melamine/petroleum coke cooked coke;
and sintering the melamine/petroleum coke cooked coke under a protective atmosphere to obtain the nitrogen-doped petroleum coke cooked coke functional material.
Preferably, the sintering temperature is 350-750 ℃, and the time is 2-6 h; the temperature rise process of raising the temperature to the sintering temperature comprises a first-stage temperature rise and a second-stage temperature rise, wherein the temperature rise rate of the first-stage temperature rise is 8-12 ℃/min, the termination temperature of the first-stage temperature rise is 190-210 ℃, and the temperature rise rate of the second-stage temperature rise is 4-6 ℃/min.
Preferably, the calcining temperature is 750-850 ℃ and the time is 5-7 h.
Preferably, the particle size of the petroleum coke green coke is less than or equal to 74 mu m.
Preferably, the mass ratio of the petroleum coke cooked coke to the melamine is 1: 0.8-1.2.
Preferably, the method for mixing the petroleum coke, the melamine and the ethanol comprises the following steps:
carrying out first mixing on melamine and ethanol at the temperature of 58-62 ℃ to obtain a melamine solution;
and secondly mixing the petroleum coke cooked coke and the melamine solution at the temperature of 58-62 ℃.
Preferably, the first mixing and the second mixing are performed in a stirring manner, and the stirring speeds of the first mixing and the second mixing are 650-750 ℃ independently, and the time is 25-35 min independently.
The invention also provides the nitrogen-doped petroleum coke cooked coke functional material obtained by the preparation method of the technical scheme.
The invention also provides the application of the nitrogen-doped petroleum coke cooked coke functional material in the technical scheme in the treatment of bisphenol A-containing wastewater.
Preferably, the pH value of the bisphenol A-containing wastewater is < 7.
The method comprises the steps of calcining petroleum coke green coke to obtain petroleum coke cooked coke, and then loading melamine on the petroleum coke cooked coke, wherein the molecular structure of the melamine contains a plurality of-NH (NH) with positive charges2The nitrogen (N) element of the six-membered ring in the melamine molecular structure is gradually doped into the six-membered ring in the petroleum coke cooked benzene ring structure to form nitrogen in the six-membered ring structure through sintering, and the doping of the nitrogen element greatly reduces the negative charge density of the petroleum coke cooked coke layer sheet, and reverses the charge of the material into positive charge, thereby greatly enhancing the electrostatic interaction between the material and negatively charged pollutants and being beneficial to the adsorption of the pollutants; meanwhile, the nitrogen is doped with hydrogen bond action between the petroleum coke cooked coke and pollutants,the method enhances the affinity and acting force between the nitrogen-doped petroleum coke cooked coke and organic pollutants, thereby greatly improving the removal efficiency of the pollutants, and the petroleum coke green coke is industrial waste. Experimental results show that the nitrogen-doped petroleum coke cooked coke functional material prepared by taking petroleum coke green coke as a raw material has good adsorption performance on bisphenol A, and can be used for treating bisphenol A-containing wastewater.
Drawings
FIG. 1 is an SEM image of petroleum coke green coke and the nitrogen-doped petroleum coke cooked coke functional material obtained in examples 1-3;
FIG. 2 is an SEM image of petroleum coke green coke and the nitrogen-doped petroleum coke cooked coke functional material obtained in examples 3-5;
FIG. 3 is an N1s XPS spectrum of the nitrogen-doped petroleum coke char functional material obtained in examples 1-3;
FIG. 4 is an N1s XPS spectrum of the nitrogen-doped petroleum coke char functional material obtained in examples 3-5;
FIG. 5 is an XRD pattern of the nitrogen-doped petroleum coke char functional material obtained in examples 1-5;
FIG. 6 is a graph showing the results of a test on the effect of bisphenol A concentration in wastewater on bisphenol A removal;
FIG. 7 is a graph showing the results of a test of the effect of pH on bisphenol A removal in bisphenol A simulated wastewater;
FIG. 8 is a Zeta potential diagram of NPC5 and bisphenol A obtained in example 5 at different pH values;
FIG. 9 is a graph showing the results of tests on the effect of wastewater treatment temperature on bisphenol A removal.
Detailed Description
The invention provides a preparation method of a nitrogen-doped petroleum coke cooked coke functional material, which comprises the following steps:
calcining the petroleum coke green coke to obtain petroleum coke cooked coke;
mixing the petroleum coke cooked coke, melamine and ethanol, and drying to obtain melamine/petroleum coke cooked coke;
and sintering the melamine/petroleum coke cooked coke under a protective atmosphere to obtain the nitrogen-doped petroleum coke cooked coke functional material.
The invention calcines the petroleum coke green coke to obtain the petroleum coke cooked coke.
In the invention, the grain diameter of the petroleum coke green coke is preferably less than or equal to 74 mu m (namely, the mesh number is more than or equal to 200 meshes); when the particle size of the petroleum coke green coke does not meet the requirement of the particle size, the petroleum coke green coke is preferably crushed and sieved to obtain the petroleum coke green coke with the particle size.
In the invention, the calcining temperature is preferably 750-850 ℃, more preferably 800 ℃, and the time is preferably 5-7 h, more preferably 6 h. In addition, the calcining condition can enable the generation of petroleum coke green coke to have a graphene-like layered structure, which is beneficial to further increasing the specific surface area, providing a proper nitrogen doping site for the subsequent nitrogen doping reaction, and simultaneously forming a six-membered ring structure by carbon atoms, so that pi-pi interaction can be generated between the carbon atoms and bisphenol A, and the adsorption effect is enhanced.
After the petroleum coke is obtained, the invention mixes the petroleum coke cooked coke, melamine and ethanol, and then dries the mixture to obtain the melamine/petroleum coke cooked coke (namely the petroleum coke cooked coke loaded with melamine). In the invention, the ethanol can dissolve the melamine, is beneficial to fully contacting the melamine and the petroleum coke cooked coke powder and uniformly adsorbing the melamine and the petroleum coke cooked coke powder, and the ethanol is easy to volatilize, has low toxicity and high safety.
In the invention, the mass ratio of the petroleum coke cooked coke to the melamine is preferably 1: 0.8-1.2, and more preferably 1: 1. In the invention, the melamine is used in a proper amount in the proportion, and the nitrogen content in the obtained product can be increased on the premise of ensuring the experimental safety, so that the adsorption performance of the nitrogen-doped petroleum coke cooked coke functional material on bisphenol A can be further improved.
In the present invention, the ethanol is preferably anhydrous ethanol. The invention has no special limitation on the dosage of the ethanol, and can uniformly disperse the petroleum coke cooked coke and the melamine. In the embodiment of the invention, the dosage ratio of the petroleum coke cooked coke to the ethanol is preferably 1g: 18-22 mL, and more preferably 1g:20 mL.
The method for mixing the petroleum coke cooked coke, the melamine and the ethanol is not particularly limited, and the melamine/petroleum coke cooked coke which is uniformly mixed can be obtained. In the embodiment of the present invention, the method for mixing petroleum coke, melamine and ethanol preferably comprises the following steps:
carrying out first mixing on melamine and ethanol at the temperature of 58-62 ℃ to obtain a melamine solution;
and secondly mixing the petroleum coke cooked coke and the melamine solution at the temperature of 58-62 ℃.
In the present invention, the temperature of the first mixing is more preferably 60 ℃, the temperature of the second mixing is more preferably 60 ℃, the first mixing and the second mixing are preferably performed by stirring, the stirring speeds of the first mixing and the second mixing are preferably 650 to 750rpm, more preferably 700rpm, independently, and the time is preferably 25 to 35min, more preferably 30min, independently. In the invention, the melamine and the ethanol are firstly mixed at a high temperature, and the melamine can be dissolved in the ethanol, so that the melamine and the petroleum coke are uniformly mixed in the second mixing process.
And secondly, obtaining a mixed solution of the petroleum coke cooked coke, the melamine and the ethanol, and drying the mixed solution of the petroleum coke cooked coke, the melamine and the ethanol to obtain the melamine/petroleum coke cooked coke. The drying mode and parameters are not particularly limited, and the dried melamine/petroleum coke cooked coke can be obtained, in the embodiment of the invention, the drying is preferably carried out in a dryer, the drying temperature is preferably 75-85 ℃, more preferably 80 ℃, and the drying time is preferably 25-35 min, more preferably 30 min.
After the melamine/petroleum coke cooked coke is obtained, the melamine/petroleum coke cooked coke is sintered under the protective atmosphere to obtain the nitrogen-doped petroleum coke cooked coke functional material.
The protective atmosphere in the present invention is not particularly limited, and any conventional protective atmosphere may be used, such as a nitrogen atmosphere and an inert gas atmosphere, and a nitrogen atmosphere is more preferable.
In the invention, the sintering temperature is preferably 350-750 ℃, and the time is preferably 2-6 h; the heating process of heating to the sintering temperature preferably comprises a first-stage heating and a second-stage heating, wherein the heating rate of the first-stage heating is preferably 8-12 ℃/min, more preferably 10 ℃/min, the termination temperature of the first-stage heating is preferably 190-210 ℃, more preferably 200 ℃, and the heating rate of the second-stage heating is preferably 4-6 ℃/min, more preferably 5 ℃/min; after the temperature is raised to the end temperature of the first-stage temperature raising, the second-stage temperature raising is preferably carried out by directly changing the temperature raising rate. In the invention, in the preferable sintering process, the melamine and the petroleum coke are formed into carbon nitride in the first-stage heating process, the carbon nitride is decomposed and doped into the petroleum coke cooked graphene-like layer in the second-stage heating process and the subsequent sintering process, so as to obtain the nitrogen-doped petroleum coke cooked coke functional material, and the preferable sintering process is favorable for fully converting the melamine into the carbon nitride and fully doping the carbon nitride into the petroleum coke cooked graphene-like layer.
The equipment used for sintering is not particularly limited, and the sintering conditions can be realized.
The invention also provides the nitrogen-doped petroleum coke cooked coke functional material obtained by the preparation method in the technical scheme; the mass percentage of carbon element in the nitrogen-doped petroleum coke-fired functional material is preferably 83-93%, more preferably 91.87-92.97%, the mass percentage of nitrogen element is preferably 3-7%, more preferably 3.22-6.11%, the mass percentage of oxygen element is preferably 2-4%, more preferably 2.02-3.97%, and the specific surface area is preferably 35.927-96.375 m2/g。
The invention also provides the application of the nitrogen-doped petroleum coke cooked coke functional material in the technical scheme in the treatment of bisphenol A-containing wastewater; the nitrogen-doped petroleum coke cooked coke functional material is preferably used as a bisphenol A adsorption material.
In the invention, the pH value of the bisphenol A-containing wastewater is preferably less than 7, and more preferably 4-6. In the invention, when the pH value of the wastewater containing bisphenol A is less than 7, the nitrogen-doped petroleum coke cooked coke functional material is provided with positive charges, and particularly when the pH value is 4-6, the material has stronger positive electricity, can generate stronger electrostatic attraction with the bisphenol A with negative charges, enhances the adsorption capacity of the material, and improves the removal capacity of the bisphenol A; on the contrary, when the pH value of the wastewater containing bisphenol a is greater than 7, the nitrogen-doped petroleum coke cooked coke functional material has negative charges, and electrostatic repulsion exists between the nitrogen-doped petroleum coke cooked coke functional material and bisphenol a, so that the adsorption effect on bisphenol a is reduced, and the adsorption effect is influenced.
In the invention, the temperature for treating the wastewater containing the bisphenol A is preferably 10-60 ℃, more preferably 30-40 ℃, the time is preferably 40-48 h, the wastewater is preferably maintained in an oscillation state in the treatment process of the wastewater containing the bisphenol A, and the rotation speed of the oscillation is preferably 150-200 rpm.
The dosage of the nitrogen-doped petroleum coke cooking functional material is not particularly limited, and a person skilled in the art can select a proper dosage according to the concentration of bisphenol A contained in the wastewater, and in the embodiment of the invention, when the concentration of bisphenol A in the wastewater containing bisphenol A is 10-200 mg/L, the dosage of the nitrogen-doped petroleum coke cooking functional material is preferably 7.0-8.0 g/L.
The nitrogen-doped petroleum coke soft coke functional material provided by the invention, the preparation method and the application thereof are described in detail below with reference to the examples, but the nitrogen-doped petroleum coke functional material and the preparation method and the application thereof are not to be construed as limiting the scope of the invention.
Example 1
Crushing petroleum coke green coke, sieving with a 200-mesh sieve, and calcining the undersize product at 800 ℃ for 6h to obtain petroleum coke cooked coke;
respectively weighing petroleum coke cooked coke, melamine and absolute ethyl alcohol according to the proportion of 1g:1g:20 mL; then adding the weighed melamine into absolute ethyl alcohol, and stirring at the rotating speed of 700rpm for 30min at the temperature of 60 ℃ to obtain melamine dispersion liquid; adding petroleum coke cooked coke into the melamine dispersion liquid, and stirring at the rotating speed of 700rpm for 30min at the temperature of 60 ℃ to obtain a uniform mixed solution; placing the mixed solution in a dryer at 80 ℃ and drying for 30min to obtain melamine/petroleum coke cooked coke;
and (2) placing the melamine/Petroleum Coke cooked Coke in a tube furnace, heating to 200 ℃ at a heating rate of 10 ℃/min in the nitrogen atmosphere, then heating to 350 ℃ at a heating rate of 5 ℃/min, and sintering at a constant temperature for 2h to obtain a nitrogen-Doped Petroleum Coke cooked Coke functional material, namely N-processed Petroleum Coke, which is recorded as NPC 1.
Example 2
The method of example 1 is used to prepare the nitrogen-doped petroleum coke soft coke functional material, except that the temperature of constant temperature sintering is 550 ℃, and the obtained nitrogen-doped petroleum coke soft coke functional material is marked as NPC 2.
Example 3
The method of example 1 is used to prepare the nitrogen-doped petroleum coke soft coke functional material, except that the temperature of constant temperature sintering is 750 ℃, and the obtained nitrogen-doped petroleum coke soft coke functional material is marked as NPC 3.
Example 4
The method of example 3 is used to prepare the nitrogen-doped petroleum coke soft coke functional material, except that the constant temperature sintering time is 4 hours, and the obtained nitrogen-doped petroleum coke soft coke functional material is marked as NPC 4.
Example 5
The method of example 3 is used to prepare the nitrogen-doped petroleum coke soft coke functional material, except that the constant temperature sintering time is 6 hours, and the obtained nitrogen-doped petroleum coke soft coke functional material is marked as NPC 5.
The morphology of the petroleum coke green coke and the nitrogen-doped petroleum coke cooked function material obtained in examples 1 to 3 is characterized, and the results are shown in fig. 1, wherein (a) is an SEM image of the petroleum coke green coke, (b) is an SEM image of the nitrogen-doped petroleum coke cooked function material obtained in example 1, (c) is an SEM image of the nitrogen-doped petroleum coke cooked function material obtained in example 2, and (d) is an SEM image of the nitrogen-doped petroleum coke cooked function material obtained in example 3. It can be seen from fig. 1 that the defect wrinkles on the NPC composite plies become more and more numerous as the sintering temperature increases.
The morphology of the nitrogen-doped petroleum coke cooked coke functional material obtained in examples 4 to 5 is characterized, and the results are shown in fig. 2, and SEM images of the petroleum coke green coke and the nitrogen-doped petroleum coke cooked coke functional material obtained in example 3 are simultaneously shown in fig. 2 for comparison, where (a) is an SEM image of the petroleum coke green coke, (b) is an SEM image of the nitrogen-doped petroleum coke cooked coke functional material obtained in example 3, (c) is an SEM image of the nitrogen-doped petroleum coke cooked coke functional material obtained in example 4, and (d) is an SEM image of the nitrogen-doped petroleum coke cooked coke functional material obtained in example 5, and as can be seen from fig. 2, as the sintering time increases, the lamellae of the nitrogen-doped petroleum coke cooked coke functional material become more ordered and regular.
The results of testing the N1s XPS spectra of the nitrogen-doped petroleum coke soft coke functional material obtained in examples 1-3 are shown in fig. 3. As can be seen from fig. 3, as the sintering temperature gradually increases, the peak shape of the spectrum changes from single peak to double peak, the peak of graphite nitrogen (graphiticN) gradually increases, which indicates that the content of graphite nitrogen increases, nitrogen in melamine is gradually converted into nitrogen of six-membered ring in benzene-like ring structure in petroleum coke green coke sheet, and the content of nitrogen forming six-membered ring also increases with the temperature.
The results of testing the N1s XPS spectra of the nitrogen-doped petroleum coke soft coke functional material obtained in examples 4-5 are shown in FIG. 4. Also for the sake of comparison, the results of example 3 are plotted in FIG. 4. As can be seen from fig. 4, when sintering is performed at 750 ℃, the peak of graphite nitrogen (graphatic N) gradually increases with the increase of sintering time, which indicates that the content of graphite nitrogen increases, and the content of nitrogen in the six-membered ring of the melamine, which is converted into the benzene ring-like structure in the petroleum coke layer sheet, also gradually increases.
The contents of the elements analyzed in FIGS. 3 to 4 are shown in Table 1. As can be seen from table 1, the method of the present invention can effectively increase the amount of nitrogen loaded.
TABLE 1 content of each element of raw petroleum coke and nitrogen-doped cooked petroleum coke functional material in examples 1-5
Figure BDA0002433318360000071
Figure BDA0002433318360000081
The specific surface areas of the petroleum coke green coke and the nitrogen-doped petroleum coke cooked coke functional material obtained in the embodiments 1 to 5 are tested, and the results are shown in table 2, it can be known from table 2 that the specific surface area of the nitrogen-doped petroleum coke cooked coke functional material is increasingly larger with the increase of the sintering temperature, and the specific surface area of the nitrogen-doped petroleum coke cooked coke functional material is increased with the extension of the sintering time when the sintering temperature is 750 ℃, which indicates that the specific surface area of the nitrogen-doped petroleum coke cooked coke functional material is increased due to the sintering time process.
Table 2 specific surface areas of petroleum coke green coke and nitrogen-doped petroleum coke cooked coke functional materials obtained in examples 1-5
Sample (I) Specific surface area (m)2/g)
Raw coke of petroleum coke 8.044
Example 1 35.927
Example 2 44.751
Example 3 65.758
Example 4 78.691
Example 5 96.375
The XRD patterns of the nitrogen-doped petroleum coke cooked functional materials obtained in examples 1 to 5 are shown in fig. 5, and as can be seen from fig. 5, each nitrogen-doped petroleum coke cooked functional material has a characteristic peak at a 2 θ of 26 °, which indicates that the nitrogen-doped petroleum coke cooked functional material has a graphene-like crystal structure, and meanwhile, as the temperature increases, the peak intensity gradually increases, which indicates that a material with a better crystal structure can be obtained at high temperature.
Test for bisphenol a removal performance:
effect of bisphenol a concentration in wastewater on bisphenol a removal:
1L of bisphenol A simulated wastewater with the concentration of 10, 20, 50, 100 and 200mg/L is prepared respectively, the bisphenol A simulated wastewater is an aqueous solution of bisphenol A, and the pH value of the simulated wastewater is adjusted to 6 by adopting 0.01mol/L hydrochloric acid aqueous solution. The initial absorbance of 5 bisphenol A simulated wastewater was measured with an ultraviolet spectrophotometer.
Adding 7g of NPC5 obtained in example 5 into the 5 parts of simulated bisphenol A wastewater respectively, then oscillating for 0.5-72 h in a constant-temperature oscillating table with the rotation speed of 150rpm to perform bisphenol A adsorption (the oscillating time is recorded as contact time), wherein the temperature of the constant-temperature oscillating table is 30 ℃, respectively taking 4mL of the 5 parts of simulated bisphenol A wastewater at regular intervals, centrifuging for 15min at the rotation speed of 9000rpm, taking supernatant, testing the absorbance of the supernatant by using an ultraviolet spectrophotometer, and calculating the adsorption quantity, wherein the result is shown in FIG. 6. As can be seen from FIG. 6, the adsorption capacity of NPC5 increases with the increase of initial concentration of pollutants, and when the oscillation time reaches 48h, the adsorption capacity reaches saturation, and the adsorption reaches equilibrium, and in the simulated wastewater with bisphenol A concentration of 200mg/L, the saturated adsorption capacity of NPC5 can reach 5.89 mg/g.
Effect of pH of bisphenol a simulated wastewater on bisphenol a removal:
preparing 10mg/L bisphenol A simulated wastewater, dividing into 8 parts, each part being 1L, respectively adjusting the pH value of 8 parts of bisphenol A simulated wastewater to 4, 5, 6, 7, 8, 9, 10 and 11 by using 0.01mol/L dilute hydrochloric acid and 0.01mol/L sodium hydroxide aqueous solution, respectively adding 7g of NPC5 obtained in example 5 into the 8 parts of simulated bisphenol A wastewater, then oscillating for 48h in a constant-temperature oscillating table at the rotation speed of 150rpm for bisphenol A adsorption, wherein the temperature of the constant-temperature oscillating table is 30 ℃, then centrifuging the 8 parts of oscillated simulated bisphenol A wastewater at the rotation speed of 9000rpm for 15min, taking supernatant, testing the absorbance of the supernatant by using an ultraviolet spectrophotometer, and calculating the removal rate of bisphenol A, and the result is shown in FIG. 7. As can be seen from fig. 7, NPC5 has a relatively good removal efficiency at pH 4 to 6, but pH 6 is considered as the optimum adsorption pH according to actual effluent pH of 5 to 9 of the enterprise, and the removal rate of bisphenol a is 81.43%.
NPC5 obtained in example 5 and bisphenol A were tested for Zeta potential at different pH values by the following specific test methods:
adding 0.3g of NPC5 into 15mL of deionized water, adjusting the pH to 4-11 by using 0.01mol/L dilute hydrochloric acid and 0.01mol/L sodium hydroxide, performing ultrasonic treatment on the NPC5 dispersion liquid to uniformly disperse the dispersion liquid, then filling the obtained dispersion liquid into a cuvette, and measuring the zeta potential by using a zeta potential meter; for the bisphenol A solution, 200mg/L of bisphenol A solution is taken, the pH value is adjusted to 4-11 by using 0.01mol/L dilute hydrochloric acid and 0.01mol/L sodium hydroxide, a sample is loaded into a cuvette, and a zeta potential is measured by using a zeta potential instrument.
As shown in fig. 8, it can be seen from fig. 8 that the potential difference between NPC5 and bisphenol a (bpa) is the largest, the electrostatic adsorption capacity is the strongest, and the adsorption effect of the nitrogen-doped petroleum coke char functional material on bisphenol a is the best when the pH value is 4 to 6. This conclusion is consistent with the test results described above.
Effect of wastewater treatment temperature on bisphenol a removal:
preparing 10mg/L bisphenol A simulation wastewater, dividing into 6 parts, each part being 1L, respectively adjusting the pH value of 6 parts of bisphenol A simulation wastewater to 6 by using 0.01mol/L dilute hydrochloric acid, respectively adding 7g of NPC5 obtained in example 5 into the 6 parts of simulation bisphenol A wastewater, then oscillating for 48 hours in a constant-temperature oscillating table at the rotating speed of 150rpm to adsorb bisphenol A, wherein the temperature of the constant-temperature oscillating table is respectively 10, 20, 30, 40, 50 and 60 ℃, then centrifuging the 6 parts of simulation bisphenol A wastewater after oscillation at the rotating speed of 9000rpm for 15min, taking supernatant, testing the absorbance of the supernatant by using an ultraviolet spectrophotometer, and calculating the removal rate of bisphenol A, wherein the result is shown in figure 9. As can be seen from FIG. 9, the removal rate of the bisphenol A model wastewater by NPC5 increased with the increase of the temperature, and the highest removal rate could reach 89.7%, but the rate of increase of the removal rate was small after reaching 30 ℃.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. The preparation method of the nitrogen-doped petroleum coke cooked coke functional material is characterized by comprising the following steps of:
calcining the petroleum coke green coke to obtain petroleum coke cooked coke;
mixing the petroleum coke cooked coke, melamine and ethanol, and drying to obtain melamine/petroleum coke cooked coke;
sintering the melamine/petroleum coke cooked coke under a protective atmosphere to obtain a nitrogen-doped petroleum coke cooked coke functional material;
the sintering temperature is 350-750 ℃, and the sintering time is 2-6 h; the temperature rise process of raising the temperature to the sintering temperature comprises a first-stage temperature rise and a second-stage temperature rise, wherein the temperature rise rate of the first-stage temperature rise is 8-12 ℃/min, the termination temperature of the first-stage temperature rise is 190-210 ℃, and the temperature rise rate of the second-stage temperature rise is 4-6 ℃/min;
the calcining temperature is 750-850 ℃, and the time is 5-7 h.
2. The method as claimed in claim 1, wherein the particle size of the petroleum coke green coke is less than or equal to 74 μm.
3. The preparation method according to any one of claims 1 to 2, wherein the mass ratio of the petroleum coke cooked coke to the melamine is 1: 0.8-1.2.
4. The method for preparing the petroleum coke according to the claim 1, wherein the method for mixing the petroleum coke, the melamine and the ethanol comprises the following steps:
carrying out first mixing on melamine and ethanol at the temperature of 58-62 ℃ to obtain a melamine solution;
and secondly mixing the petroleum coke cooked coke and the melamine solution at the temperature of 58-62 ℃.
5. The method according to claim 4, wherein the first and second mixing are performed by stirring, and the stirring speeds of the first and second mixing are 650 to 750rpm and 25 to 35min, respectively.
6. The nitrogen-doped petroleum coke cooked coke functional material prepared by the preparation method of any one of claims 1 to 5.
7. The use of the nitrogen-doped petroleum coke char functional material of claim 6 in the treatment of bisphenol a-containing wastewater.
8. Use according to claim 7, wherein the pH of the bisphenol A-containing waste water is < 7.
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