CN115445574B - Preparation method of N, S co-doped hydrothermal carbon and application thereof in removing Cr (VI) in water - Google Patents
Preparation method of N, S co-doped hydrothermal carbon and application thereof in removing Cr (VI) in water Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a preparation method of N, S co-doped hydrothermal carbon and application thereof in removing Cr (VI) in water, and relates to a preparation method of hydrothermal carbon and application thereof. The method aims to solve the technical problem that the existing carbon-containing adsorbent has poor Cr (VI) removal effect. The method comprises the following steps: adding corn stalk powder and thiourea into water, and preparing the N, S co-doped hydrothermal carbon by a one-step low-temperature hydrothermal method, wherein the N, S co-doped hydrothermal carbon is used as an adsorbent for removing Cr (VI) in the water. The adsorption quantity of Cr (VI) in water is 98.84mg/g, and the adsorption equilibrium time is 36h. Can be used in the field of Cr (VI) containing wastewater treatment.
Description
Technical Field
The invention relates to a preparation method of hydrothermal carbon and an adsorbent for removing Cr (VI) in water.
Background
Chromium (Cr) is used as redox active metal in water environment and is derived from the chemical processes of leather tanning, textile dyeing, electroplating and the like. Specifically, cr is generally present in both the oxidation state of Cr (VI) and Cr (III). Among them, cr (VI) is identified by the United States Environmental Protection Agency (USEPA) as a "class A" human carcinogen due to its strong toxicity, carcinogenicity, and mutagenicity, while Cr (III) is an essential nutrient for metabolism. The U.S. environmental protection agency requires that the Maximum Contaminant Level (MCL) of drinking water should be controlled to within 100 ug/L; the maximum allowable concentration of the Chinese surface water is 50ug/L. Therefore, it is important to develop a technique for removing Cr (VI) to reduce damage to organisms.
At present, different technical methods for Cr (VI) removal have been explored, such as precipitation, ion exchange, membrane technology and adsorption. Among them, the adsorption technology is receiving extensive attention internationally because of its advantages of low cost, simple operation, environmental protection, etc. Biochar is a carbon-rich solid and has shown great potential in environmental remediation. Biochar can be classified into pyrolytic carbon and hydrothermal carbon according to the preparation conditions.
Pyrolytic carbon is produced from dried biomass under anoxic conditions at a pyrolysis temperature of 300-700 ℃. The Chinese patent application No. 202011479865.2 discloses a method for preparing heavy metal lead and chromium adsorbent by utilizing waste fungus residue, namely, air-drying waste fungus sticks after edible fungus cultivation, mixing the waste fungus sticks with corn stalks, crushing the mixture, placing crushed fungus residue powder into a carbonization furnace, heating to 500 ℃ under the protection of nitrogen, preserving heat for 2 hours, and cooling to obtain fungus residue biochar, namely the adsorbent for heavy metal lead and chromium. The fungus dreg biochar is used for treating heavy metal chromium in wastewater, and when the adding amount of the fungus dreg biochar is 4g/L, cr 6+ The initial concentration is 60mg/L, the pH is 6.0, the oscillation is carried out at 25 ℃ and 150r/min, the removal rate of the heavy metal chromium is increased along with the increase of the oscillation time, and the removal rate of the heavy metal chromium is 20% when the oscillation is carried out for 120 min. The adsorbent is used for removing Cr by adsorption 6+ For Cr 6+ Is poor in the removal effect.
Hydrothermal char is synthesized by direct hydrothermal carbonization of wet biomass at lower temperatures and under autogenous pressure in a milder manner than the vast energy required to produce pyrolytic char. Hydrothermal carbon is sustainable, simple to prepare, economical and innovative. Although the hydrothermal carbon generates a large amount of oxygen-containing functional groups on the surface of the material through a series of reactions such as hydrolysis, polymerization and the like, the adhesion of heavy metals is facilitated, but the heavy metal removal capability is still not satisfied. The Chinese patent No. 202011296386.7, namely, a modified grapefruit Pi Shuire charcoalAdsorption of Cr 6+ The method of (1) discloses a modified grapefruit Pi Shuire carbon adsorption Cr 6+ The method comprises using modified grapefruit Pi Shuire carbon as adsorbent, adding into original Cr 6+ The wastewater with the concentration of 0.4 to 1.2mg/L is filtered after standing and absorbing for 60 to 120 minutes at normal temperature; wherein the dosage of the adsorbent is 6.7-13.3 g/L. The adsorbent is used for removing Cr by adsorption 6+ For Cr 6+ Is poor in the removal effect.
Disclosure of Invention
The invention aims to solve the technical problem that the existing carbon-containing adsorbent has poor Cr & lt6+ & gt removal effect, and provides a preparation method of N, S co-doped hydrothermal carbon and application thereof in removing Cr (VI) in water. The novel adsorbent is prepared by a one-step low-temperature hydrothermal method, and effective active sites such as graphite nitrogen, thiophenic sulfur and the like are introduced into the adsorbent, so that Cr (VI) can be reduced to Cr (III) while adsorption is carried out, and the method has the advantages of simplicity, greenness and high efficiency.
The preparation method of the N, S co-doped hydrothermal carbon comprises the following steps:
1. the mass ratio of the corn stalk powder to the thiourea is 1: (3-4), adding corn stalks and thiourea into water, and stirring for 2-3 hours to obtain a mixture;
2. transferring the mixture into a polytetrafluoroethylene liner of a hydrothermal kettle, and placing the hydrothermal kettle in an oven with the temperature of 240-250 ℃ for 6-10 h; and naturally cooling to room temperature after the reaction is finished, sequentially washing with water and ethanol, and drying to obtain the N, S co-doped hydrothermal carbon, which is expressed by SNHC.
Further, in the first step, the ratio of the mass of the corn stalk to the volume of water is 1g: (25-30) mL.
Further, in the second step, the drying is carried out at a temperature of 50-60 ℃ for 12-24 hours.
The application of the N, S co-doped hydrothermal carbon prepared by the method is to take the N, S co-doped hydrothermal carbon as an adsorbent to remove Cr (VI) in water.
Furthermore, the method for removing Cr (VI) in water by utilizing the N, S co-doped hydrothermal carbon as an adsorbent comprises the following steps:
adding the N, S co-doped hydrothermal carbon into Cr (VI) -containing water, regulating the pH value of the solution to 2-3, stirring and adsorbing for 5-12 hours at the temperature of 293-298K, and filtering the N, S co-doped hydrothermal carbon to finish the treatment of the Cr (VI) -containing water.
The invention prepares a novel adsorbent (SNHC) by a one-step low-temperature hydrothermal method, nitrogen atoms and sulfur atoms are introduced into the surface of a carbon material, a large number of nitrogen-containing functional groups can be formed by introducing the nitrogen atoms, and meanwhile, the electronic state of the material is changed, so that electrons are redistributed, and the affinity to heavy metal anions is enhanced. While sulfur atoms, due to their electronegativity, are similar to carbon atoms, with larger atomic radii leading to defects in the carbon structure and creating more active sites, exhibit excellent physicochemical properties.
The N, S co-doped hydrothermal carbon has the following advantages: 1. introducing N atoms and S atoms into hydrothermal carbon simultaneously by a one-step hydrothermal method under a low-temperature condition to form a large number of functional groups; n, S co-doping to split oxygen-containing functional groups on the surface of the hydrothermal carbon and simultaneously form graphite nitrogen and thiophenic sulfur; 3. graphite nitrogen and thiophenic sulfur are the primary active sites for the reduction of Cr (VI) to Cr (III) as electron donors. The characteristics of the N, S co-doped hydrothermal carbon of the invention enable the Cr (VI) to have a strong adsorption effect on the Cr (VI) and reduce the Cr (VI) into Cr (III) when the Cr (VI) containing wastewater is treated, the adsorption quantity of the N, S co-doped hydrothermal carbon of the invention on the Cr (VI) is 98.84mg/g, and the adsorption equilibrium time is 36h.
The preparation method of the N, S co-doped hydrothermal carbon has the characteristics of simple synthesis method, high efficiency, environmental friendliness and the like. The N, S co-doped hydrothermal carbon can be used in the field of Cr (VI) containing wastewater treatment.
Drawings
FIG. 1 is an SEM image of HC prepared in comparative example 1;
FIG. 2 is an SEM image of SNHC prepared in example 1;
FIG. 3 is XRD spectra of SNHC prepared in example 1 and HC prepared in comparative example 1;
fig. 4 is XPS spectra of SNHC prepared in example 1 and HC prepared in comparative example 1;
FIG. 5 shows the adsorption amount versus adsorption time for SNHC prepared in example 1 and the fitted adsorption profile;
FIG. 6 is a graph showing the adsorption amount of HC prepared in comparative example 1 as a function of adsorption time, and a graph showing the fitted adsorption;
fig. 7 is a graph showing the contents of Cr (VI) and Cr (III) before and after the HC adsorption test of SNHC prepared in example 1 and HC prepared in comparative example 1.
Detailed Description
The following examples are used to demonstrate the benefits of the present invention.
Example 1: the preparation method of the N, S co-doped hydrothermal carbon comprises the following steps:
1.2 g of corn stalk powder and 6g of thiourea are placed in 50mL of deionized water, and magnetically stirred for 2h to obtain a mixture;
2. transferring the mixture into a polytetrafluoroethylene liner of a hydrothermal kettle, and placing the hydrothermal kettle in an oven with the temperature of 240 ℃ for 6 hours; naturally cooling to room temperature after the reaction is finished, washing with deionized water and absolute ethyl alcohol for three times in sequence, and drying in a drying oven at 60 ℃ for 12 hours to obtain black powder which is N, S co-doped hydrothermal carbon and is expressed by SNHC.
Comparative example 1: in the preparation process of the hydrothermal carbon, thiourea is not added, and the specific method comprises the following steps:
1.2 g of corn stalk powder is placed in 50mL of deionized water and magnetically stirred for 2h to obtain a mixture;
2. transferring the mixture into a polytetrafluoroethylene liner of a hydrothermal kettle, and placing the hydrothermal kettle in an oven with the temperature of 240 ℃ for 6 hours; naturally cooling to room temperature after the reaction is finished, washing with deionized water and absolute ethyl alcohol for three times in sequence, and drying in a drying oven at 60 ℃ for 12 hours to obtain black powder which is the hydrothermal carbon and is expressed by HC.
SEM characterization analysis was performed on the SNHC prepared in example 1 and the HC prepared in comparative example 1, with SEM images of HC shown in fig. 1 and SNHC in fig. 2. As can be seen from FIG. 1, a lot of observation was made on the HC surfaceThe more diverse carbon spheres are due to the polysaccharide dehydration reaction during the hydrothermal carbonization process. The larger microsphere diameter is about 600nm and the smallest microsphere diameter is about 10nm. As can be seen from fig. 2, the number of carbon spheres is significantly increased after the thiourea modification, and the size and shape of the carbon spheres are more uniform. Furthermore, it can be observed that SNHC has a pronounced porous structure due to the decomposition of thiourea into slightly corrosive H at high temperatures 2 S and NH 3 . It was determined that the addition of thiourea increased the uniformity of the SNHC carbon sphere and increased the number of porous structures, meaning that the specific surface area could be enlarged.
XRD characterization analysis was performed on SNHC prepared in example 1 and HC prepared in comparative example 1, and the obtained XRD spectra are shown in fig. 3, and it can be seen from fig. 3 that diffraction peaks of HC appear near 14.3 ° and 22.4 °, corresponding to (110), (200) planes of typical cellulose structures, indicating that the raw biomass is not completely decomposed during hydrothermal carbonization. The peak value of SNHC disappears at 14.3 degrees, which indicates that the introduction of N and S has a promoting effect on carbonization of biomass in the hydrothermal process. In addition, it was found that the peak of 22.4 ° shifted to 24.4 °, mainly because N and S atoms introduce a carbon skeleton, N atoms make the interlayer space more narrow, and S atoms further change the degree of lattice defects.
XPS characterization analysis was performed on SNHC prepared in example 1 and HC prepared in comparative example 1, and the obtained XPS spectra are shown in FIG. 4. As can be seen from FIG. 4, C1s in HC and SNHC are separated into 4 peaks (a of FIG. 4) at 284.5eV, 284.8eV, 285.7/285.8eV and 288.5eV, corresponding to C= C, C-C/C-H, C-O/C-N and C=O. Although there was no significant difference between HC and SNHC in C1S, the oxygen-containing functional group was significantly changed in O1S after co-doping of N and S (b of fig. 4). After introducing N and S into the hydrothermal carbon, the peak of SNHC was shifted negatively by 0.7eV. Peaks at 533.5eV, 532.6eV and 531.5eV correspond to C-O, O-c=o and c=o. N and S enter the carbon skeleton, resulting in a reduction of the C-O functionality, and N and S substitution O results in a reduction of the oxygen containing functionality, thereby forming C-S bonds, C-N bonds. In addition, the N1s spectrum was divided into three peaks corresponding to graphite N at 400.22eV, pyrrole N at 399.13eV and pyridine N at 398.00eV (c of fig. 4), respectively. The N distribution of HC is not obvious, and is related to the N content of the original hydrogen coke, while the N1s peak of SNHC is strong, which indicates that a large amount of N exists in the SNHC. The binding energy of S2p divided into three peaks (d of FIG. 4), 163.7eV (C-S-C2 p 1/2) and 164.9eV (C-S-C2 p 3/2) corresponds to thiophene S,168.8eV (-C-SOx-C-) corresponds to oxidized S. Notably, no S was detected in HC, further demonstrating that S was successfully doped in SNHC. Thus, it can be concluded that N, S co-doping results in N and S being present in the form of graphene N and thiophene S, respectively, and that the C-O functionality is reduced. This means that N and S redistribute electrons on the surface of the hydrothermal carbon through a synergistic effect, thereby obtaining more active adsorption sites, and enabling the hydrothermal carbon to have stronger performance for reducing Cr (VI).
The SNHC prepared in example 1 and the HC prepared in comparative example 1 were subjected to adsorption tests, specifically as follows:
three parts of the adsorbent were weighed, 0.04g each, and 1 part of the adsorbent was added to 40mL of Cr (VI) solution, C 0 =100mg·L -1 pH 2, adsorption temperature t=293 k, m/v=1g·l -1 . Adsorption was carried out at 160rpm for 36 hours, and the adsorption amount was measured as a function of adsorption time. The variation curve of the adsorption amount of SNHC along with the adsorption time and the fitted adsorption curve are shown in FIG. 5, and the adsorption amount is calculated to be 98.84mg/g, and the adsorption equilibrium time is calculated to be 36h. The adsorption amount of HC was calculated to be 58.00mg/g by showing the adsorption time-dependent curve and the fitted adsorption curve as shown in FIG. 6.
The amounts of Cr (VI) and Cr (III) before and after the adsorption test were measured simultaneously, and the bar graphs of Cr (VI) and Cr (III) before and after the test were obtained as shown in FIG. 7, and it can be seen from FIG. 7 that the total Cr concentration in the supernatant containing SNHC as the adsorbent was 22.52mg/L, wherein the Cr (VI) concentration was 2.7mg/L and the Cr (III) concentration was 19.82mg/L. In the supernatant liquid with HC as adsorbent, the total Cr concentration is 46.75mg/L, wherein the Cr (VI) concentration is 39.78mg/L, and the Cr (III) concentration is 6.97mg/L. As can be seen by comparison, cr (VI) is converted to Cr (III) in solution with SNHC as an adsorbent.
Claims (5)
1. The preparation method of the N, S co-doped hydrothermal carbon is characterized by comprising the following steps of:
1. the mass ratio of the corn stalk powder to the thiourea is 1: (3-4), adding corn stalks and thiourea into water, and stirring for 2-3 hours to obtain a mixture;
2. transferring the mixture into a polytetrafluoroethylene liner of a hydrothermal kettle, and placing the hydrothermal kettle in an oven with the temperature of 240-250 ℃ for 6-10 h; and naturally cooling to room temperature after the reaction is finished, washing with water and ethanol in sequence, and drying to obtain the N, S co-doped hydrothermal carbon.
2. The method for preparing the N, S co-doped hydrothermal carbon according to claim 1, wherein the ratio of the mass of the corn stalk to the volume of water in the first step is 1g: (25-30) mL.
3. The method for preparing N, S co-doped hydrothermal carbon according to claim 1, wherein the drying in the second step is performed at 50-60 ℃ for 12-24 hours.
4. Use of the N, S co-doped hydrothermal carbon prepared by the method of claim 1, wherein the use is to remove Cr (VI) from water using the N, S co-doped hydrothermal carbon as an adsorbent.
5. The use of the N, S co-doped hydrothermal carbon prepared by the method of claim 1 according to claim 4, wherein the method for removing Cr (VI) in water using the N, S co-doped hydrothermal carbon as an adsorbent is performed by:
adding the N, S co-doped hydrothermal carbon into Cr (VI) -containing water, regulating the pH value of the solution to 2-3, stirring and adsorbing for 5-12 hours at the temperature of 293-298K, and filtering the N, S co-doped hydrothermal carbon to finish the treatment of the Cr (VI) -containing water.
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