CN111908450A - Preparation method of red fluorescent carbon dots and application of red fluorescent carbon dots in shale gas desulfurization - Google Patents
Preparation method of red fluorescent carbon dots and application of red fluorescent carbon dots in shale gas desulfurization Download PDFInfo
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Abstract
The invention discloses a preparation method of red fluorescent carbon dots and application of the red fluorescent carbon dots in shale gas desulfurization. According to the method, hydrogen sulfide gas in the shale gas is treated by using a carbon dot aqueous solution containing ferric ions to be oxidized into elemental sulfur, the aqueous solution is irradiated by visible light, so that a large amount of singlet oxygen is generated by the carbon dots, the reduced ferrous ions are oxidized into ferric ions, and the high-efficiency circulation of the ferric ions in the application of shale gas desulfurization is finally realized. The carbon dots serving as a novel nano photocatalytic material have the advantages of cheap and easily-obtained raw materials, simple and various synthetic methods, green and environment-friendly preparation process and capability of preparing products in large scale. The mixed aqueous solution composed of the carbon dots and the ferric ions prepared by the invention realizes the effective removal of the hydrogen sulfide gas in the shale gas, has higher desulfurization efficiency and continuous operability, and shows great practical application value.
Description
Technical Field
The invention relates to the technical field of preparation and desulfurization of fluorescent carbon dots, in particular to a preparation method of red fluorescent carbon dots and application of the red fluorescent carbon dots in shale gas desulfurization.
Background
The energy structure of China mainly comprises coal for a long time, and the exploitation and combustion of a large amount of coal not only destroys the ecological balance, but also discharges a large amount of toxic and harmful gas, so that the environmental problem of China is increasingly prominent, and the survival and social and economic development of human beings are seriously influenced. The development and utilization of new energy sources are of great significance in alleviating this environmental problem. The shale gas is a clean and efficient novel energy resource, is unconventional natural gas which exists in rich organic matter shale and an interlayer thereof and mainly exists in adsorption and free states, mainly contains methane, and can be used in multiple fields of resident gas, urban heat supply, power generation, automobile dye, chemical production and the like. According to prediction, the shale gas resource in China has a wide prospect, can be collected and stored up to 36 billions of cubic meters, and has great economic value. However, the produced shale gas usually contains a certain concentration of hydrogen sulfide gas, and the toxic acidic substance not only can be corrosive to shale gas well strings and equipment, which leads to increase of production cost, but also can cause catalyst poisoning when being used as a chemical raw material, thereby affecting product yield and quality. More seriously, the shale gas after combustion can produce acid rain effect, bringing serious health hazard and environmental pollution. At present, shale gas desulfurization methods are numerous, and can be divided into dry desulfurization, wet desulfurization and membrane separation desulfurization according to the action mechanism. The dry desulfurization comprises an iron oxide method, a zinc oxide method, an active carbon method, a molecular sieve method and the like, and has the advantages of simple process, convenient operation and low energy consumption, but the solid desulfurizing agent needs to be replaced regularly, and the large-scale application is difficult to realize. Wet desulfurization can be classified into chemical absorption, physical absorption and physical-chemical absorption, and the desulfurization process is characterized by being recyclable and continuous due to the adoption of a renewable solvent such as Methyldiethanolamine (MDEA), but amine liquid is frequently polluted by foaming, degradation, heat-stable salt and the like in the use process, so that the normal operation of a desulfurization system is seriously influenced, and the desulfurization cost is high. The membrane separation method utilizes different permeation rates of gas when the gas penetrates through a polymeric membrane for separation, has simple flow, does not need power equipment, and has low energy consumption, but has the defects of difficult achievement of high purification degree, hydrocarbon loss and influence on the yield of natural gas. Therefore, the development of a novel desulfurizer which is low in price and can be used in a large scale and in a recycling manner has high practical application value for quickly and efficiently removing the hydrogen sulfide gas.
The carbon dots are a novel carbon-based nano luminescent material, the particle size is usually below 10 nanometers, and the carbon dots have the advantages of cheap and easily-obtained raw materials, simple and various preparation methods, stable and adjustable optical properties, easily-modified surface functional groups, strong electron transfer or transport capacity and the like, and show great application prospects in the field of energy. Particularly, under the excitation of visible light, the carbon dots can be used as a photosensitizer to effectively generate singlet oxygen, thereby realizing the specific application of organic molecules or metal ions for oxidation. For example, a blue light carbon dot prepared from citric acid and ethylenediamine as raw materials generates singlet oxygen by irradiation of ultraviolet light, and a divalent manganese ion is oxidized into a trivalent manganese ion, and then rapid oxidation of 3,3 ', 5, 5' -tetramethylbenzidine is realized within 10 seconds at a neutral pH. For another example, the magnesium and nitrogen co-doped carbon dots are synthesized by taking the bougainvillea spectabilis leaf extract as a carbon source, and can generate a large amount of hydroxyl radicals under the irradiation of sunlight, so that the degradation effect of methyl blue of nearly 99.1% under the irradiation of 120 minutes is realized. These examples have successfully demonstrated that carbon dots are an excellent photocatalyst for the oxidation of metal ions or organic substances. However, no relevant report is available to realize the application research of sustainable hydrogen sulfide removal in shale gas by using the redox capability of carbon dots.
Disclosure of Invention
The invention aims to provide a preparation method of a red fluorescent carbon dot, and the prepared carbon dot has redox capacity.
The invention also aims to provide the application of the carbon dots prepared by the preparation method in the aspect of shale gas desulfurization.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a red fluorescent carbon dot comprises the following steps:
(1) adding sulfanilic acid into aqueous hydrogen halide solution, performing ultrasonic treatment to form transparent solution, adding o-phenylenediamine, and performing further ultrasonic oscillation to obtain transparent mixed solution; wherein the molar ratio of the sulfanilic acid to the o-phenylenediamine is 1.2: 1;
(2) transferring the transparent mixed solution into a stainless steel reaction kettle, carrying out hydrothermal reaction for 4-24h at the temperature of 140-;
(3) filtering the reaction solution with a filter membrane, and adjusting the pH value of the filtrate to 7-7.5; adding methanol or ethanol to make the solution turbid, centrifuging, and vacuum drying to obtain green carbon dot powder.
Preferably, the hydrogen halide in the step (1) is hydrogen chloride or hydrogen bromide, and the concentration of the aqueous hydrogen halide solution is 0.1 mol/L.
Preferably, the pore size of the filter membrane in step (3) is 0.2 μm.
Preferably, the centrifugation rotating speed in the step (3) is 8000-10000rpm, and the centrifugation time is 10-20 min.
Preferably, the temperature of the vacuum drying in the step (3) is 40-50 ℃ and the time is 10-12 h.
The invention also provides application of the carbon dots prepared by the preparation method in shale gas desulfurization, which comprises the following specific steps: firstly, shale gas and oxygen are mixed according to the volume ratio of 85-95%: 5-15% of the raw materials are uniformly mixed, then the mixture is introduced into an acidic aqueous solution containing ferric ions and carbon dots, and the mixture is placed under an incandescent lamp for irradiating for at least 15min, wherein the power of the incandescent lamp is not less than 200W.
Preferably, the ferric ion is one or more of ferric trichloride, ferric sulfate and ferric nitrate.
As shown in fig. 4, firstly, the hydrogen sulfide gas in the shale gas is absorbed by the ferric iron ion-containing aqueous solution under the acidic condition, and is oxidized into elemental sulfur, then the singlet oxygen generated by the carbon dots under the visible light is reacted with the obtained ferrous iron ions to obtain ferric iron ions again, and the newly generated ferric iron ions are reacted with the hydrogen sulfide gas again, so that the high-efficiency circulation of the ferric iron ions to the hydrogen sulfide removal is realized.
Compared with the prior art, the invention has the following beneficial effects:
1. the carbon dots are simple in preparation process, cheap and easily available in raw materials, and can be prepared in batches.
2. The carbon dots prepared by the method are rich in halogen elements, and show strong absorption in the range of 300-750 nm in the visible light region; under the excitation of visible light, a remarkable red fluorescence is emitted, and the wavelength is 715 nanometers.
3. The mixed aqueous solution of the invention has good stability, can remove over 90 percent of hydrogen sulfide gas, and realizes 24 hours of continuous working time.
Drawings
FIG. 1 is a transmission electron micrograph of a carbon dot prepared according to example 1 of the present invention;
FIG. 2 is a UV-VIS absorption spectrum of a carbon dot prepared according to example 1 of the present invention;
FIG. 3 is a photoluminescence curve of a carbon dot prepared in example 1 of the present invention under 500 nm illumination;
FIG. 4 is a reaction schematic diagram of the present invention for removing hydrogen sulfide from shale gas.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
Firstly, putting 2.0g of sulfanilic acid into a 100mL conical flask, then adding 35mL of 0.1mol/L hydrogen chloride aqueous solution, and forming transparent solution through ultrasound; subsequently, 1.0g of o-phenylenediamine was added and further subjected to ultrasonic vibration to disperse the sample uniformly. Then, the transparent mixture was transferred to a stainless steel reaction vessel (150 ml) and stored in a sealed state. Preheating a high-temperature oven to 200 ℃ (the heating rate is 5 ℃/min), putting the stainless steel reaction kettle into the oven for reaction for 6 hours, closing the oven after the reaction is finished, opening the oven door, and naturally cooling to room temperature. Then filtering out large particle impurities by using a 0.2 mu m filter membrane, and adding a certain amount of alkaline solution into the filtrate to neutralize the pH value to be about 7. And finally, adding methanol to enable the solution to be turbid, centrifuging for 10min at the rotating speed of 10000rpm/min, and placing the obtained carbon dot powder in a vacuum oven at 40 ℃ to heat for 12 hours to obtain green carbon dot powder.
FIG. 1 is a transmission electron micrograph of a carbon dot prepared according to the present example; it can be seen that the synthesized carbon dots are uniformly dispersed, have an average size of 4.2 nm, and have highly graphitized carbon cores and amorphous shells with a crystal nucleus spacing of 0.21 nm.
FIG. 2 is a graph showing the UV-VIS absorption spectrum of the carbon dots prepared in the present example; it can be seen that strong absorption is exhibited in the visible region 300-.
FIG. 3 is a photoluminescence curve of the prepared carbon dots under 500 nm illumination in the example; it can be seen that under the excitation of visible light, a distinct red fluorescence is emitted, with a wavelength of 715 nm.
Example 2
Firstly, putting 2.0g of sulfanilic acid into a 100mL conical flask, then adding 35mL of 0.1mol/L hydrogen bromide water solution, and forming transparent solution through ultrasound; 1.0g of o-phenylenediamine was then added and further shaking was carried out to disperse the sample uniformly. Then, the transparent mixture was transferred to a stainless steel reaction vessel (150 ml) and stored in a sealed state. Preheating a high-temperature oven to 200 ℃ (the heating rate is 5 ℃/min), putting the stainless steel reaction kettle into the oven for reaction for 6 hours, closing the oven after the reaction is finished, opening the oven door, and naturally cooling to room temperature. Then filtering out large particle impurities by using a 0.2 mu m filter membrane, and adding a certain amount of alkaline solution into the filtrate to neutralize the pH value to be about 7. And finally, adding a methanol solution to enable the solution to be turbid, centrifuging for 20min at the rotating speed of 8000rpm/min, and heating the obtained carbon dot powder in a vacuum oven at the temperature of 50 ℃ for 10 hours to obtain green carbon dot powder.
The uv-vis absorption spectrum and photoluminescence curve of the carbon dots prepared in this example are similar to those of the carbon dots prepared in example 1.
Example 3
0.1g of carbon dot powder and 0.60g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 90%: 10% of mixed gas. The mixed gas was introduced into a reaction vessel and reacted for 15 minutes under irradiation of a 200W incandescent lamp, and then the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.1%.
Example 4
0.15g of carbon dot powder and 0.60g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 90%: 10% of mixed gas. After a reaction for 15 minutes under the irradiation of a 200W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.09%.
Example 5
0.20g of carbon dot powder and 0.60g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 90%: 10% of mixed gas. After a reaction for 15 minutes under the irradiation of a 200W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.09%.
Example 6
0.05g of carbon dot powder and 0.60g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 90%: 10% of mixed gas. After a reaction for 15 minutes under the irradiation of a 200W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.36%.
Example 7
0.1g of carbon dot powder and 0.50g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 90%: 10% of mixed gas. After a reaction for 15 minutes under the irradiation of a 200W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.17%.
Example 8
0.1g of carbon dot powder and 0.40g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 90%: 10% of mixed gas. After reacting for 15 minutes under the irradiation of a 200W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.20%.
Example 9
0.1g of carbon dot powder and 0.70g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 90%: 10% of mixed gas. After a reaction for 15 minutes under the irradiation of a 200W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.09%.
Example 10
0.1g of carbon dot powder and 0.60g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 85%: 15% of mixed gas. After a reaction for 15 minutes under the irradiation of a 200W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.09%.
Example 11
0.1g of carbon dot powder and 0.60g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 95%: 5% of mixed gas. After reacting for 15 minutes under the irradiation of a 200W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.13%.
Example 12
0.1g of carbon dot powder and 0.60g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 90%: 10% of mixed gas. After a reaction for 15 minutes under the irradiation of a 100W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.14%.
Example 13
0.1g of carbon dot powder and 0.60g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 90%: 10% of mixed gas. After a reaction for 15 minutes under the irradiation of a 300W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.10%.
Example 14
0.1g of carbon dot powder and 0.60g of a sample of ferric trichloride (ferric trichloride hexahydrate) were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 90%: 10% of mixed gas. After a reaction for 10 minutes under the irradiation of a 300W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.14%.
Example 15
A0.1 g sample of carbon dot powder and a 0.60g sample of ferric chloride were weighed, dissolved in a reactor containing 1000mL of deionized water, and mixed well. Firstly, measuring the content of hydrogen sulfide in the shale gas by using a high performance gas chromatography to be about 1.2%, and then uniformly mixing the shale gas with a certain amount of oxygen to prepare the shale gas with a volume ratio of 90%: 10% of mixed gas. After a reaction for 20 minutes under the irradiation of a 300W incandescent lamp, the content of each component of the gas remaining in the reaction vessel was measured, and the content of hydrogen sulfide by volume was found to be 0.09%.
In order to analyze the influence of each parameter on the hydrogen sulfide removal effect of the shale gas more intuitively, statistics are carried out on the data, and the specific conditions are shown in the following table:
from the above table, it can be found that the desulfurization effect of the shale gas is closely related to the parameters such as the carbon point dosage, the ferric trichloride dosage, the oxygen content, the incandescent lamp wattage, the reaction time and the like, and the desulfurization effect is seriously affected by higher or lower parameters. In the most ideal case of hydrogen sulfide removal, the mass ratio of carbon points to ferric ions is 1: 1.24, the oxygen proportion is 10%, the wattage of the incandescent lamp is 200W, and the irradiation time is 15 min.
Example 16
The optimal feeding amount and the optimal reaction time are selected, the same as the experimental steps of the examples 3 to 15, and after the desulfurization reaction is carried out for 1, 2, 4, 8, 12, 16, 20 and 24 hours respectively, the mixed solution containing carbon points and iron ions is observed to have good stability and no flocculent precipitate generation and color change; and after the mixed solution is continuously operated for 24 hours, more than 90% of hydrogen sulfide gas in the shale gas can be removed.
Claims (8)
1. A preparation method of a red fluorescent carbon dot is characterized by comprising the following steps:
(1) adding sulfanilic acid into aqueous hydrogen halide solution, performing ultrasonic treatment to form transparent solution, adding o-phenylenediamine, and performing further ultrasonic oscillation to obtain transparent mixed solution; wherein the molar ratio of the sulfanilic acid to the o-phenylenediamine is 1.2: 1;
(2) transferring the transparent mixed solution into a stainless steel reaction kettle, carrying out hydrothermal reaction for 4-24h at the temperature of 140-;
(3) filtering the reaction solution with a filter membrane, and adjusting the pH value of the filtrate to 7-7.5; adding methanol or ethanol to make the solution turbid, centrifuging, and vacuum drying to obtain green carbon dot powder.
2. The method of claim 1, wherein the hydrogen halide in step (1) is hydrogen chloride or hydrogen bromide, and the concentration of the aqueous hydrogen halide solution is 0.1 mol/L.
3. The method as claimed in claim 1, wherein the pore size of the filter membrane in step (3) is 0.2 μm.
4. The method as claimed in claim 1, wherein the centrifugation speed in step (3) is 8000-10000rpm, and the centrifugation time is 10-20 min.
5. The method for preparing a red fluorescent carbon dot according to claim 1, wherein the vacuum drying in step (3) is performed at a temperature of 40-50 ℃ for 10-12 hours.
6. The application of the carbon dots prepared by the preparation method according to claim 1 in shale gas desulfurization.
7. The application of claim 6, comprising the following steps: firstly, shale gas and oxygen are mixed according to the volume ratio of 85-95%: 5-15% of the raw materials are uniformly mixed, then the mixture is introduced into an acidic aqueous solution containing ferric ions and carbon dots, and the mixture is placed under an incandescent lamp for irradiating for at least 15min, wherein the power of the incandescent lamp is not less than 200W.
8. The use of claim 6, wherein the ferric ion is one or more of ferric chloride, ferric sulfate, and ferric nitrate.
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| CN114428073A (en) * | 2022-01-11 | 2022-05-03 | 江南大学 | Preparation and application of carbon dot test paper for gaseous singlet oxygen detection |
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