CN115672056A - NH (hydrogen sulfide) 2 -MIL/biochar composite membrane and preparation method and application thereof - Google Patents
NH (hydrogen sulfide) 2 -MIL/biochar composite membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of wastewater treatment, and relates to NH 2 -MIL/biochar composite membrane and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) Preparing the biochar; 2) And preparing Al by adopting a vacuum impregnation method 2 O 3 A biochar composite; 3) Preparation of NH 2 -MIL/biochar composite membranes. The NH 2 The MIL/biochar composite membrane has good nuclide removal effect, and has the advantages of low cost, simple preparation process, high adsorption efficiency, good repeatability and the like.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and relates to NH 2 -MIL/biochar composite membrane and preparation thereofPreparation method and application.
Background
The rapid development of the nuclear industry has raised a high level of concern for radioactive waste. Uranium is one of the most common natural radioactive elements and poses a potential threat to the biosphere. Technetium-99 ( 99 Tc) is a nuclear fission product of 235U. In aqueous solutions containing oxygen, tc is usually pertechnetate anion (TcO) 4 - ) Exist in the form of (1). ReO 4 - And TcO 4 - Have similar chemical properties and are used as non-radioactive substitutes. The removal of radionuclides from water is a major concern of research. Thus, preparation of a Radioactive cation UO 2 2+ And the radioactive anion ReO 4 - While efficient material removal remains a challenge.
Owing to the characteristics of specific surface area, exchangeable ligand part and active metal site, metal-organic framework Materials (MOFs) are widely applied to radioactive wastewater removal. However, MOFs are usually present in the form of dispersed nanopowders, making their recovery difficult.
In view of the above-mentioned shortcomings of the prior art, it is desirable to provide a new material capable of removing radionuclides in water.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide NH 2 The MIL/biochar composite membrane and the preparation method and application thereof have the advantages of low cost, simple preparation process, high adsorption efficiency, good repeatability and the like.
In order to achieve the above purpose, the invention provides the following technical scheme:
NH (hydrogen sulfide) 2 -a method for preparing an MIL/biochar composite membrane, characterized by comprising the steps of:
1) And preparing the biochar: stabilizing the pine cylinder piece at 250 deg.C for 1h, heating to 600 deg.C at a heating rate of 2 deg.C/min, and heating to 600 deg.C under N 2 Carbonizing and preserving heat for 2 hours in the protection process to prepare biochar;
2) And preparing Al by adopting a vacuum impregnation method 2 O 3 Biochar composite: impregnating the whole of the biochar in Al (NO) 3 ) 3 ·H 2 Keeping the saturated solution in vacuum at 0.01MPa for 24 hr to form Al-rich solution 3+ Ionic biochar; enriching the Al 3+ Drying the ionic biochar at 60 ℃ for 24 hours; calcining at 120 ℃ for 4 hours after drying to form the Al 2 O 3 A biochar composite;
3) Preparation of NH 2 -MIL/biochar composite membrane: adding the Al 2 O 3 Putting the biochar composite material and 2-amino terephthalic acid aqueous solution into a high-pressure kettle for ultrasonic treatment for 30min; taking out the Al after ultrasonic treatment 2 O 3 Heating the biochar composite material at 110 ℃ for 6h; heating and then alternately washing with ethanol and deionized water; washing and freeze drying to obtain NH 2 -MIL/biochar composite membranes.
Preferably, in the step 1), the diameter of the pine cylinder piece is 3cm, and the height of the pine cylinder piece is 1cm.
Preferably, in the step 2), the Al (NO) is 3 ) 3 ·H 2 Al (NO) in O saturated solution 3 ) 3 ·H 2 The O content was 25g/L.
Preferably, in the step 3), the Al is 2 O 3 The ratio of the biochar composite to the 2-amino terephthalic acid aqueous solution is 0.2g:10mL.
Preferably, in the step 3), the mass concentration of the 2-aminoterephthalic acid aqueous solution is 1.0% w/V.
In addition, the invention also provides NH 2 -MIL/biochar composite membrane, characterized in that it is prepared by the above-mentioned preparation method.
Moreover, the invention also provides a method for preparing the NH 2 -MIL/biochar composite membrane for radionuclide removal in water, characterized in that the NH is used 2 -MIL/charcoal composite membrane adsorbing the radionuclide in the water body.
Preferably, the pH of the body of water is adjusted to 5 prior to adsorption.
Finally, the present invention provides a process for the preparation of the above NH 2 -method for desorption of MIL/biochar composite membranes, characterized in that the NH is subjected to a solution of ethanol and 10% hydrochloric acid 2 Soaking and washing the MIL/biochar composite membrane.
Preferably, the ratio of ethanol to 10% hydrochloric acid solution is 5:1: .
Compared with the prior art, the NH of the invention 2 The MIL/biochar composite membrane and the preparation method and application thereof have one or more of the following beneficial technical effects:
1. the cost is low, and the preparation process is simple.
2. The adsorption efficiency of the adsorbent to the radioactive nuclide in the water body is high, and the experimental result shows that the adsorbent can adsorb the radioactive cation UO 2 2+ And the radioactive anion ReO 4 - All show the characteristic of quick removal, and the removal rate can reach 86 percent and 73 percent respectively.
3. The method has wide application range and low requirement on water flow flux.
4. It can be recycled and has high reusability.
Drawings
FIG. 1 is NH of the present invention 2 -flow diagram of a process for the preparation of an MIL/biochar composite membrane.
FIG. 2 shows NW and NH 2 Morphology and SEM of MIL-W.
FIG. 3 is NW and NH 2 XRD spectrum of MIL-W.
FIG. 4 is NW and NH 2 -infrared spectrum of MIL-W.
FIG. 5 is NW and NH 2 Nitrogen adsorption-desorption curve of MIL-W.
FIG. 6 is NW and NH 2 The pore size distribution plot of MIL-W.
FIG. 7 is NW and NH 2 -MIL-W vs. UO 2 2+ Adsorption isotherm model of (1).
FIG. 8 is NW and NH 2 -MIL-W vs. ReO 4- Adsorption isotherm model of (1).
FIG. 9 is NW and NH 2 -MIL-W vs. UO 2 2+ Is suckedAttaching a kinetic model.
FIG. 10 is NW and NH 2 -MIL-W vs. ReO 4- Adsorption kinetics model of (2).
FIG. 11 shows water flux vs. UO 2 2+ The effect of removal rate.
FIG. 12 shows water flux vs. ReO 4- The effect of removal rate.
FIG. 13 is NW and NH 2 -multiplex evaluation graph of MIL-W.
Detailed Description
The present invention is further described with reference to the following drawings and examples, which are not intended to limit the scope of the present invention.
The wood is widely available, and the wood is rich in polar functional groups, so that an anchoring position is provided for the loading of the metal precursor. The wood has a large number of 3D open and low tortuosity channels in the growth direction, and cellulose in the internal channels, as the main component of the wood cell wall, contains a large number of hydroxyl groups. The wood porous carbon gene has hierarchical porous structure, flexibility, excellent mechanical property and active material loaded surface mouldability, and is beneficial to recovery and regeneration. Therefore, in the invention, the MOFs material is constructed in situ in the internal channel to prepare the MOFs wood film tool with high migration and adsorption performance by combining the structural characteristics of wood.
Meanwhile, considering that the direct loading of the MOFs crystals can generate an agglomeration phenomenon in a solution, the realization of uniform loading of the crystals on the surface of the substrate is a difficult point. In the present invention, al is used 2 O 3 The self-sacrifice template method, pre-deposited metal oxide is used as MOFs structure precursor, and Al is prefabricated 2 O 3 The released metal ions are beneficial to the uniform distribution of MOFs on the surface of the substrate, and further the agglomeration and crystallization are inhibited.
FIG. 1 shows NH of the present invention 2 -flow diagram of a process for the preparation of an MIL/biochar composite membrane. As shown in fig. 1, NH of the present invention 2 The preparation method of the-MIL/biochar composite membrane comprises the following steps:
1. preparing the biochar.
Pine cylinder pieces were stabilized at a temperature of 250 ℃ for 1h.
Then, the temperature is raised to 600 ℃ at the temperature rise rate of 2 ℃/min, and N is added at the temperature of 600 DEG C 2 Carbonizing and preserving heat for 2h in the protection process to prepare charcoal (WC).
Preferably, the pine cylinder piece has a diameter of 3cm and a height of 1cm.
2. Preparation of Al by vacuum impregnation method 2 O 3 A biochar composite material.
Impregnating the whole of the biochar in Al (NO) 3 ) 3 ·H 2 Keeping the O saturated solution in vacuum with absolute pressure of 0.01MPa for 24 hours to form Al-rich solution 3+ Ionic biochar.
Then, enriching the Al 3+ The ionic biochar is dried for 24 hours at 60 ℃.
Calcining at 120 ℃ for 4 hours after drying to form the Al 2 O 3 A biochar composite material.
In the present invention, al can be ensured by vacuum impregnation 3+ Ions are fully diffused in the porous wood structure of the biochar.
Preferably, the Al (NO) 3 ) 3 ·H 2 Al (NO) in O saturated solution 3 ) 3 ·H 2 The O content was 25g/L.
More preferably, the drying is performed in a drying oven and the calcining is performed in a muffle furnace.
3. Preparation of NH 2 -MIL/biochar composite membranes.
Adding the Al 2 O 3 Biochar composite and 2-amino terephthalic acid aqueous solution (NH) 2 -BDC) was placed in a Teflon liner of an autoclave for sonication for 30min.
Preferably, the temperature is 25 ℃ during ultrasonic treatment, the time is 30min, the ultrasonic frequency is 40Kh, and the ultrasonic power is 600W.
Taking out the Al after ultrasonic treatment 2 O 3 The biochar composite material is heated for 6 hours at 110 ℃.
Preferably, the heating is carried out by using an oven.
After heating, the mixture was washed alternately with ethanol and deionized water.
Preferably, the washing is carried out 5 times alternately with ethanol and deionized water
Washing and freeze drying to obtain NH 2 -MIL/biochar composite membrane (NH for short) 2 -MIL-W)。
Preferably, the temperature of the freeze-drying is-40 ℃ and the time is 24h.
Further, in the present invention, preferably, the Al is 2 O 3 The ratio of the biochar composite to the 2-amino terephthalic acid aqueous solution is 0.2g:10mL. That is, 0.2g of the Al 2 O 3 The/biochar composite was added to the autoclave with 10mL of the aqueous 2-aminoterephthalic acid solution for sonication.
More preferably, the 2-amino terephthalic acid aqueous solution has a mass concentration of 1.0% by weight in terms of W/V.
Next, we verified the NH prepared by the above preparation method through various experiments and the like 2 Various properties of MIL/biochar composite membranes.
Description of the drawings: all batch adsorption experiments in the present invention were performed in 10.0mL polyethylene tubes. Before the experiment, by adding trace amount of HNO 3 Or NaOH solution, wherein the pH value of the water body is adjusted to be 5. Wherein, for the water body, the water body is stirred in a water bath constant temperature oscillator, after stirring for 18h, the polyethylene pipe is centrifuged for 10 minutes at 8000rpm, and the solid phase is separated from the solution phase. The concentration of the contaminant in the supernatant, the amount of adsorbed contaminant (qe, mg g) was measured by an ultraviolet spectrophotometer -1 ) And the adsorption percentages (R%) are respectively:
in the formula (I), the compound is shown in the specification,C 0 (mg L -1 )、C e (mg L -1 ) V (L), m (g) represent the initial concentration of the contaminant, the final concentration, the volume of the adsorption solution, and the mass of the adsorbent, respectively.
The water flux is used as an important influence factor for influencing the water purification efficiency of the circulating flow device, and the calculation mode refers to the following steps: w = V/S, where V is the solution flow rate of the peristaltic pump (L · h) -1 ) S is NH 2 Water flow contact area (m) of MIL-W 2 ) W is the water flux (L.m) -2 ·h -1 )。
FIG. 2 shows NW and NH 2 Morphology and SEM of MIL-W. Wherein NW is raw pine chips, NH 2 -MIL-W is NH of the invention 2 -MIL/biochar composite membranes.
FIGS. 2a and 2d are respectively raw pine pieces (NW) and NH of the present invention 2 Macro-image of MIL/biochar composite membrane (NH 2-MIL-W). From fig. 2a it can be seen that the NW takes on the original wood color, and from fig. 2d it can be seen that NH 2 -MIL-W is grey black.
And further using a Scanning Electron Microscope (SEM) to characterize the microstructure and the morphology of the two. Fig. 2b and 2c are SEM images of NWs. As can be seen from fig. 2b and 2c, the NWs have an interconnected porous network structure. In longitudinal section, the tubular channels are partially aligned, and the side wall has a large number of radially distributed rays and fiber tracheids with a diameter of a few micrometers.
FIG. 2e and FIG. 2f are NH 2 SEM picture of MIL-W. As can be seen from fig. 2e and 2f, NH is formed after a second hydrothermal growth in solution, unlike the smooth surface of NW 2 The surface of-MIL-W became very rough, indicating NH 2 -payload of MIL crystals on NW substrate. And NH generated 2 The stereo multichannel structural features in MIL-W are well preserved.
For NW and NH by X-ray diffraction (XRD) 2 The crystal structure of MIL-W is further characterized. As shown in fig. 3, for NW, the broad peaks at 2 θ =23 ° and 35 ° correspond to the (002) and (100) crystalline phases of graphitic carbon reflection, respectively. Two very sharp sets of peaks appear at the loaded NH 2 NH of crystals of-MIL-W 2 -MIL-W wood film.Characteristic peak and NH 2 Simulated diffraction pattern of MIL-53 (Al) coincides, lying at 2 θ =10.3 ° and 18.1 ° respectively corresponding to NH 2 MIL-53 (020) and (200). The above results illustrate that Al is transferred to NW 2 O 3 Successfully use NH as a sacrificial template 2 MIL-53 was loaded onto a wood substrate.
In the present invention, the surface functionality profile of NW and NH2-MIL-W was further determined by FT-IR (Fourier-Infrared Spectroscopy). As shown in FIG. 4, the absorption peak was approximately 1577cm for NW -1 Belonging to the stretching vibration of aromatic C ═ C or carboxyl C ═ O; and a peak value of 1420cm -1 Due to the-OH groups contained in the phenolic resin. On the other hand, at 1031cm -1 And 876cm -1 Can be classified as C-O stretching vibration and C-OH stretching vibration respectively. The above results indicate that the presence of oxygen-containing functional groups in NW can act as immobilized Al 3+ The site of the ion. And for NH 2 MIL-W, observable from the spectrum at 740cm -1 The absorption band corresponding to its tetrahedral coordination Al-O bond appeared, indicating that the MIL crystals were successfully immobilized on the wood substrate surface. At 3440cm -1 The typical vibration band of (A) can be attributed to NH 2 Stretching and vibrating of the group; and 1383cm -1 The presence of amino or aromatic amine was confirmed by the stretching vibration of the C-N bond. At 1577cm -1 The weak absorption peak at (A) is the tensile vibration corresponding to the coordinated carboxyl group, indicating that the NH is synthesized 2 -carboxylic acid ligands are present in the MIL-W composite. By analyzing the above characteristic peaks, NH can be confirmed 2 Al in the structural skeleton of-MIL-W 3+ And the coordination bond between the O atoms being via NH 2 -carboxyl groups in BDC linker.
To study NW and NH 2 The specific surface area and the pore diameter of-MIL-W and the like, and the nitrogen adsorption-desorption test is also carried out. As shown in fig. 5 and 6, the NW channels are predominantly mesoporous, NH 2 MIL-W retains mesoporous characteristics (pore size of 3.74 nm) and exhibits a larger specific surface area (17.3423 m) 2 g -1 ). The result is loaded NH 2 Due to the abundant pore structure on MILs. The appearance of hysteresis loop in FIG. 5 is due to the occurrence of mesopores in NW channelsIs caused by capillary condensation. In summary, the NH of the present invention 2 MIL-W has large porosity and specific surface area, and has a unique three-dimensional layered multi-channel microstructure of a wood material. These characteristics, while enhancing water transport capacity, also ensure adequate contact and interaction between the active adsorption sites and the target contaminants, helping to further enhance their removal capacity.
For NW and NH 2 The adsorption isotherms and adsorption kinetics of MIL-W were studied. As shown in fig. 7 and 8, the equilibrium adsorption capacity (Qe) increases significantly with increasing radionuclide concentration in the initial body of water and approaches saturation values, indicating that all potential active sites are fully occupied and removal reaches equilibrium. NH compared to NW 2 -MIL-W vs. UO 2 2+ And ReO 4- Has higher adsorption efficiency.
In addition, the present invention further uses a representative Langmuir, freundlich model to fit the experimental data, and the results are shown in table 1.
TABLE 1 NW and NH 2 Adsorption of UO by-MIL-W 2 2+ And ReO 4- Langmuir and Freundlich model parameters
The results in Table 1 show that the Freundlich isotherm model more closely conforms to the description of UO 2 2+ And ReO 4 - At NH 2 Adsorption on MIL-W, correlation coefficient up to R, respectively 2 =0.986 and R 2 =0.975. According to model calculation, NH at pH =5.0, t =25 ℃ 2 -MIL-W vs. UO 2 2+ And ReO 4- The removal rate of the product can reach 86 percent and 73 percent respectively, and the result is far higher than that of the NW to UO 2 2+ And ReO 4- Removal of (2%) was performed (41% and 32%).
At the same time, NH was studied by adsorption kinetics 2 -MIL-W vs. UO 2 2+ And ReO 4- The time of adsorption affects the adsorption behavior. As shown in fig. 9 and 10, NH 2 -MIL-W vs. UO 2 2+ And ReO 4- The adsorption of (a) was very rapid within the first 30 minutes and then stabilized within 50 minutes. At equilibrium, NH 2 -MIL-W vs. UO 2 2+ And ReO 4- The removal efficiency of the method is as high as 86% and 72%; and for NW, UO 2 2+ And ReO 4- The final removal rates of (a) and (b) were only 22% and 26%, respectively. NH (NH) 2 The improved efficiency of MIL-W removal is attributable to the unique internal channel structure of wood, significantly promoting the rate of contaminant conduction, increasing the active sites and UO 2 2+ And ReO 4- Thereby achieving rapid and effective contaminant removal.
To show the NH of the invention 2 MIL-W for nuclide removal in water, NH has been studied extensively in the present invention with the aid of a circulating flow device 2 Dynamic UO removal from bodies of water by MIL-W 2 2+ And ReO 4- The use of (1). Wherein the flux vs. UO was sought in order to further evaluate the performance of the circulating flow device 2 2+ And ReO 4- The effect of efficiency is removed.
As shown in FIGS. 11 and 12, the water flux was 20X 10 3 L·m -2 ·h -1 All can maintain more than 80% of UO 2 2+ Removal rate and ReO of more than 75% 4- And (4) removing rate. The results show NH 2 MIL-W maintains stable contaminant removal efficiency, whether under high-flux or low-flux conditions. NH (NH) 2 The excellent and stable removal performance of MIL-W is benefited by NH with high specific surface area in the wood channels 2 -a uniform distribution of MIL particles, which greatly improves the utilization of the space in the wood passage. Secondly, the elongated and irregular multiple channels in the wood contribute to the NH 2 Sufficient contact between the MIL particles and the contaminants in the water is established. Finally, the direct-flow channel with good hydrophilicity can promote the rapid delivery of the sewage, thereby improving the removal efficiency.
Finally, the NH after the experiment was adsorbed 2 the-MIL-W is recycled by soaking and washing with ethanol and 10% hydrochloric acid solution (the proportion of the two is 5:1). As shown in fig. 13, even inAfter 5 times of adsorption-desorption, NH 2 -MIL-W vs. UO 2 2+ And ReO 4- Still over 70% and 60% removal efficiency. The results show that NH 2 The MIL-W has good reusability, and also proves that the MIL-W has practical application prospect in the field of radioactive wastewater.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. Obvious changes and modifications of the technical scheme of the invention are included in the protection scope of the invention.
Claims (10)
1. NH (hydrogen sulfide) 2 -a method for preparing an MIL/biochar composite membrane, comprising the steps of:
1) And preparing the biochar: stabilizing the pine cylinder piece at 250 deg.C for 1h, heating to 600 deg.C at a heating rate of 2 deg.C/min, and heating at 600 deg.C under N 2 Carbonizing and preserving heat for 2 hours in the protection process to prepare biochar;
2) Preparing Al by adopting a vacuum impregnation method 2 O 3 Biochar composite: impregnating the whole of the biochar in Al (NO) 3 ) 3 ·H 2 Keeping the saturated solution in vacuum at 0.01MPa for 24 hr to form Al-rich solution 3+ Ionic biochar; enriching the Al 3+ Drying the ionic biochar for 24 hours at 60 ℃; calcining at 120 ℃ for 4 hours after drying to form the Al 2 O 3 A biochar composite;
3) Preparation of NH 2 -MIL/biochar composite membrane: mixing the Al 2 O 3 Putting the biochar composite material and 2-amino terephthalic acid aqueous solution into a high-pressure kettle for ultrasonic treatment for 30min; taking out the Al after ultrasonic treatment 2 O 3 Heating the biochar composite material at 110 ℃ for 6h; heating, washing with ethanol and deionized water alternately(ii) a Washing and freeze drying to obtain NH 2 -MIL/biochar composite membranes.
2. NH according to claim 1 2 The preparation method of the MIL/biochar composite membrane is characterized in that in the step 1), the diameter of the pine cylinder piece is 3cm, and the height of the pine cylinder piece is 1cm.
3. NH according to claim 1 2 -MIL/biochar composite membrane, characterized in that, in step 2), the Al (NO) is added 3 ) 3 ·H 2 Al (NO) in O saturated solution 3 ) 3 ·H 2 The O content was 25g/L.
4. NH according to claim 1 2 -MIL/biochar composite membrane, characterized in that, in step 3), the Al is 2 O 3 The ratio of the biochar composite to the 2-amino terephthalic acid aqueous solution is 0.2g:10mL.
5. NH according to claim 4 2 A method for preparing the MIL/biochar composite membrane, wherein the mass concentration of the 2-aminoterephthalic acid aqueous solution in the step 3) is 1.0% by weight w/V.
6. NH (hydrogen sulfide) 2 -MIL/biochar composite membranes, characterized in that they are prepared using the preparation method according to any one of claims 1 to 5.
7. Use of NH according to claim 6 2 -MIL/biochar composite membrane for radionuclide removal in water, characterized in that the NH is used 2 -MIL/charcoal composite membrane adsorbing the radionuclides in the water body.
8. The method of claim 7, wherein the pH of the body of water is adjusted to 5 prior to adsorption.
9. NH as defined in claim 6 2 -method for desorption of MIL/biochar composite membranes, characterized in that the NH is subjected to a solution of ethanol and 10% hydrochloric acid 2 -soaking and washing the MIL/charcoal composite membrane.
10. The method according to claim 9, characterized in that the ratio of ethanol to 10% hydrochloric acid solution is 5:1: .
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| CN116850949A (en) * | 2023-05-26 | 2023-10-10 | 安徽农业大学 | UiO-W composite wood film and preparation method and application thereof |
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| CN116850949A (en) * | 2023-05-26 | 2023-10-10 | 安徽农业大学 | UiO-W composite wood film and preparation method and application thereof |
| CN116850949B (en) * | 2023-05-26 | 2024-05-07 | 安徽农业大学 | UiO-W composite wood film and preparation method and application thereof |
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