CN111607099A - Method for rapidly preparing metal organic framework material MIL-53(Cr) by using chromium-containing sludge and application thereof - Google Patents
Method for rapidly preparing metal organic framework material MIL-53(Cr) by using chromium-containing sludge and application thereof Download PDFInfo
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Abstract
The invention relates to a method for rapidly preparing a metal organic framework material MIL-53(Cr) by using chromium-containing sludge and application thereof, wherein the preparation method comprises the following steps: s1: drying, ball-milling and crushing the chromium-containing sludge, and sieving to remove impurities to obtain a chromium source; s2: mixing a chromium source and a mineralizer hydrofluoric acid in deionized water, stirring at room temperature, and uniformly mixing to obtain a solid-liquid mixed solution A; s3: adding terephthalic acid into the solid-liquid mixed solution A, and further uniformly mixing to form a solid-liquid mixed solution B; s4: carrying out hydrothermal reaction on the formed solid-liquid mixed solution B to prepare a crude product; s5: and (5) collecting the crude product obtained in the step S4, washing, drying and activating to obtain a target product. Compared with the prior art, the raw materials are cheap and easily available, and the invention is environment-friendly; the synthesis time is short, and the energy consumption is low; the adsorbent has good adsorption performance on dibenzothiophene, can maintain stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Description
Technical Field
The invention belongs to the technical field of chromium-containing sludge utilization, and relates to a method for quickly preparing a metal organic framework material MIL-53(Cr) by using chromium-containing sludge and application thereof.
Background
The electroplating industry is an important link in the modern industrial chain and is also a high-pollution industry. A large amount of electroplating sludge is generated in the wastewater treatment process of the electroplating industry. The chromium-containing electroplating sludge has high heavy metal content and complex components, mainly exists in the form of metal hydroxides such as chromium, iron, zinc, nickel and the like, and the metals are important strategic resources at the same time. Chromium-containing electroplating sludge contains various heavy metals which can cause serious pollution to soil, water, atmosphere, food and the like and threaten human health, and the chromium-containing electroplating sludge is brought into a dangerous waste management list by countries in the world. At present, the harmless treatment technology is generally adopted for treating the chromium-containing sludge, the harmless treatment of the chromium-containing sludge can be roughly divided into two types, one type is a solidification stabilization technology, chromium-containing waste is solidified in a solidified body by utilizing a curing agent so as to avoid the harm of heavy metal chromium to the environment, and the sludge capacity increase of the method is serious and the metal cannot be recycled; the other type is a recycling technology, a certain leaching agent is used for leaching main target metals for recycling, the recycling of metals, particularly chromium is realized, but the target metals need to be leached first to be used subsequently, and the problems of more waste liquid, complex process and the like exist.
The group of subjects, professor F érey, Versailles France, originally developed a study for the preparation of a metal-organic framework material of the MIL-n (material of institute Lavoiser) series. The metal organic framework material utilizes trivalent metal (such as Cr)3 +、Al3+、V3+、Fe3+Etc.) with terephthalic acid, trimesic acidAcid, etc. to synthesize the complex with stable structure. MIL-53(Cr) is one of the typical representatives of this series of materials and is formed by CrO4(OH)2Octahedron and p-phenyl dicarboxylic acid are bridged in space to form the material with one-dimensional rhombic pore structure. The crystal skeleton of the material has flexibility, the 'breathing' phenomenon can occur under the action of guest molecules, and due to the good thermal and chemical stability, the MIL-53(Cr) has high specific surface area and special pore effect, the material has great potential in the application aspects of catalysis, separation, molecular adsorption and the like. Timofeva et Al studied reactions that catalyze The synthesis of ketals starting from acetone and glycerol in The presence of MIL-53(Cr) (Isotrectural metals MIL-100(M) and MIL-53(M) (M: V, Al, Fe and Cr) as catalysts for condensation of glycerol with acetic acid, Applied Catalysis A: General), Agrawalet et Al reported The use of MIL-53(Cr) to achieve Liquid Phase Multicomponent adsorptive Separation Catalysis of Xylene Mixtures (Liquid-Phase Multicomponent Adsorption and Separation of Xylene Mixtures, General of Physical Chemistry C).
The following publications and patents report studies on the synthesis of MIL-53 (Cr).
Published Journal of the American Chemical Society,2002,124(45): 13519-13526A method for synthesizing MIL-53(Cr) is reported3)3·9H2O、H2BDC, HF and DI H2Mixing and dissolving O according to the proportion of 1:1:1:280, transferring to a stainless steel reaction kettle, heating to 220 ℃, keeping for 72h, cooling to room temperature, filtering and recovering a light purple solid product, washing the crude product with deionized water, drying at room temperature, and finally calcining at 300 ℃ for 12 h.
Published literature Industrial&Engineering Chemistry Research,2019,58(34),15489-15496, reports a synthesis of MIL-53(Cr), CrCl3·6H2O and H2The molar ratio of BDC is 1:2, transferring the chromium source and the ligand into a mortar, manually grinding for 10min, transferring the mixture into a stainless steel reaction kettle, heating to 220 ℃ for 48h, cooling to room temperature, exchange-washing the crude product with ethanol or N, N-dimethylformamide at 70 ℃, and vacuum-washing at 150 DEG CAnd drying for 12 h.
The publications Dalton Transactions,2016,45(23),9565-9573 reported a synthesis of MIL-53(Cr) using waste PET bottle fragments as H2Ligand source of BDC to synthesize MIL-53(Cr), CrCl3·6H2O, scrap PET bottle scrap, HF and DI H2Mixing O according to the ratio of 1:1:2:280, heating in an autoclave at 160 ℃ for 72h, filtering the crude product to remove unreacted PET, and finally exchanging and washing the product with N, N-dimethylformamide at 200 ℃ for 5 h.
Patent CN 107556488A discloses a method for the synthesis of a metal-organic framework material MIL-53(Cr), CrCl, in a non-solvent phase3·6H2O and H2The molar ratio of BDC is 1:2, CrCl is added3·6H2Introducing O into the reaction kettle, heating at high temperature for 2H, and adding H2BDC, ultrasonic treatment is carried out for 10min, and crystallization is carried out for 48h at 220 ℃. After cooling to room temperature, the crude product is washed with ethanol or N, N-dimethylformamide at 70 ℃ for 12h and dried at 150 ℃ for 12 h. Although the method does not use an organic solvent, the process is complicated and the synthesis time is long.
Disclosure of Invention
At present, the MIL-53(Cr) synthesis method mostly uses pure chromium-containing substances which are mutually soluble with reaction solvents, such as chromium nitrate, chromium chloride and the like, and has the disadvantages of complex synthesis process, harsh conditions, long reaction time, usually 72 hours (which can be reduced to 48 hours after pretreatment), relatively high time and energy consumption cost and difficulty in large-scale production.
The chromium-containing sludge is solid waste generated in the treatment process of chromium-containing wastewater, the chromium content is high, and the chromium-containing sludge is not subjected to high-temperature treatment, the applicant finds that the chromium is mainly in the form of amorphous chromium hydroxide, the water solubility of the chromium hydroxide is poor, and the prior art preferentially adopts a chromium source with better water (solvent) intersolubility to prepare the MIL-53(Cr) material. Therefore, there is no report of using chromium-containing sludge to prepare MIL-53(Cr) material. In addition, the properties of amorphous chromium hydroxide in the chromium-containing sludge are obviously different from those of chromium oxide with higher lattice energy, the amorphous chromium hydroxide has higher reaction activity, and can react with the organic ligand terephthalic acid to synthesize the MIL-53(Cr) material by adding a small amount of mineralizer hydrofluoric acid, the synthesis time is obviously shortened compared with 72 hours in the traditional synthesis method, and a product with good crystallization and higher specific surface can be obtained after reacting for 18 hours. The reason is that Cr ions in amorphous chromium hydroxide in the chromium-containing sludge are mainly in the form of dimer, trimer or multimer formed by hydroxyl and water molecules. The prearranged structure of the polymer is very similar to the basic structural unit-metal-oxygen cluster (metal-oxide cluster) in MIL-53(Cr), the prearranged structure reduces the binding energy of the organic ligand and the metal-oxygen cluster, and the reaction time required at the same reaction temperature as the traditional method is greatly reduced.
The invention aims to provide a method for quickly preparing a metal organic framework material MIL-53(Cr) by using chromium-containing sludge and application thereof. The method has the advantages that operations such as leaching or purification of chromium metal are not needed, chromium-containing sludge is directly used, cheap and easily available synthesis sources are utilized, and a metal organic framework material MIL-53(Cr) is quickly, efficiently and simply synthesized, so that the prepared product has good performance, is used for adsorption treatment of sulfur-containing pollutant dibenzothiophene in fuel oil, has ideal effect, and is favorable for realizing industrial production and application of the novel material.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a method for quickly preparing a metal organic framework material MIL-53(Cr) by using chromium-containing sludge, which comprises the following steps:
s1: drying, ball-milling and crushing the chromium-containing sludge, and sieving to remove impurities to obtain a chromium source;
s2: mixing a chromium source and a mineralizer hydrofluoric acid in deionized water, stirring at room temperature, and uniformly mixing to obtain a solid-liquid mixed solution A;
s3: adding terephthalic acid into the solid-liquid mixed solution A obtained in the step S2, and further uniformly mixing to form a solid-liquid mixed solution B;
s4: carrying out hydrothermal reaction on the solid-liquid mixed solution B obtained in the step S3 to obtain a crude product;
s5: and collecting the crude product obtained in the step S4, washing, drying and activating to obtain the metal organic framework material MIL-53 (Cr).
As a preferred technical scheme of the invention, the chromium-containing sludge is derived from residual sludge of electroplating, tanning, chemical industry, pigment and/or metallurgical plant industrial sewage treatment systems.
In the preferable technical scheme of the invention, in the step S1, the drying temperature of the chromium-containing sludge is 80-160 ℃.
As a preferred embodiment of the present invention, in step S1, the conditions for ball milling and pulverization are as follows: selecting steel balls with the diameter of 3-30 mm, and ball-milling for 0.5-1 h at 300-900 rpm according to the ball-to-material ratio of 5: 1-15: 1. Further preferably, steel balls with the diameter of 7mm and the ball-to-material ratio of 10:1 are selected in the process.
In a preferred embodiment of the present invention, the step S1 of sieving is to pass through a 100-mesh sieve.
In a preferred embodiment of the present invention, in step S2, the mass concentration of the mineralizer hydrogen fluoride is 30% to 70%;
as a preferable technical scheme of the invention, in the step S2, the molar ratio of the chromium element in the chromium source, the mineralizer hydrogen fluoride and the deionized water is 1 (0-3) to (100-500). The MIL-53(Cr) material obtained without adding the mineralizer has smaller specific surface area than the material synthesized by adding the mineralizer, and has poor adsorption effect on fuel oil containing dibenzothiophene. Therefore, it is more preferable that the value of the mineralizer is not 0.
As a preferable technical scheme of the invention, in the step S2, ultrasonic mixing is adopted for mixing, and the mixing time is 5-60 min.
In a preferred embodiment of the present invention, in step S3, the molar ratio of terephthalic acid to the chromium element in the chromium source in step S2 is (1-2): 2-1.
As a preferable technical scheme of the invention, in the step S3, ultrasonic mixing is adopted for mixing, and the mixing time is 5-60 min.
As a preferable technical scheme of the invention, in the step S4, the temperature of the hydrothermal reaction is 160-250 ℃, and the reaction time is 12-18 h.
As a preferred technical scheme of the present invention, in step S5, the washing solution used for washing includes at least one of deionized water, methanol, ethanol, and N, N-dimethylformamide, and the washing condition is to centrifugally exchange the crude product with the washing solution for 2 to 6 times.
As a preferable technical scheme of the invention, in the step S5, the drying temperature is 40-120 ℃, and the drying time is 2-24 h.
In a preferable technical scheme of the invention, in the step S5, the activation condition is vacuum drying at 150 ℃ for 6-24 h.
The synthesis method of the metal organic framework material MIL-53(Cr) adopts chromium-containing excess sludge from electroplating and other industrial sewage treatment systems as a chromium source, does not need to purify or leach chromium metal, has cheap and easily obtained reaction raw materials, solves the treatment problem of the chromium-containing sludge, and meets the environmental protection principle of waste utilization.
The invention provides a metal organic framework material MIL-53(Cr) which is prepared by the method.
As a preferred embodiment of the present invention, the specific surface area of the metal-organic framework material MIL-53(Cr) is 730.27m2Per g, average pore volume 0.33cm3/g。
The third aspect of the invention provides an application of the metal organic framework material MIL-53(Cr) for adsorption treatment of sulfur-containing pollutant dibenzothiophene in fuel oil.
As a preferred technical scheme of the invention, the adsorption treatment comprises the following processes: adding a metal organic framework material MIL-53(Cr) into fuel oil containing dibenzothiophene, stirring, and adsorbing; after adsorption, MIL-53(Cr) is recovered, and then washed by using N, N-dimethylformamide and ethanol sequentially under heating condition to carry out material regeneration treatment.
As a preferable embodiment of the present invention, the adsorption is carried out at normal temperature.
As a preferable technical scheme of the invention, in the washing process, N-dimethylformamide is firstly used for washing for 1-3 times, and then ethanol is used for washing for 1-3 times, so that the material regeneration treatment is carried out.
In a preferred embodiment of the present invention, the heating temperature during washing is 70 ℃.
As a preferred technical scheme of the invention, the optimal dosage of MIL-53(Cr) is 10mg of adsorbent/g of fuel oil.
Sulfur-containing compounds in fuel oil can cause the deactivation of acid rain and engine exhaust three-way catalysts, and are substances which are urgently needed to be removed. The sulfur content is definitely required to be lower than 10ppm in the quality standard of the gasoline for the five automobiles issued by the national Standard Commission of China. The adsorption method can realize the efficient removal of sulfur-containing pollutants in fuel oil, not only can achieve the traditional hydrodesulfurization effect, but also can effectively remove Dibenzothiophene (DBT) and derivatives thereof which are difficult to treat in hydrodesulfurization so as to achieve the ultralow sulfur standard. The MIL-53(Cr) material prepared by the invention can be used for adsorbing sulfur-containing fuel oil pollutants, the adsorbent shows good adsorption performance for removing dibenzothiophene in fuel oil (such as gasoline), and the adsorbent can still maintain good adsorption capacity after regeneration, and the good performance is mainly due to the following factors:
(1) MIL-53(Cr) first physisorbs dibenzothiophene, and the special "breathing" effect allows MIL-53(Cr) to have strong adsorbate-adsorbent interactions with adsorbed dibenzothiophene.
(2) Pollutants are adsorbed into MIL-53(Cr) pore channels, and the metal center of the framework interacts with delocalized pi electrons of dibenzothiophene.
Compared with the prior art, the invention has the following beneficial effects:
(1) the chromium source used for synthesis is the chromium-containing sludge generated by industrial wastewater treatment, does not need to purify or leach chromium metal, is cheap and easy to obtain, has simple process, solves the treatment problem of the chromium-containing sludge, and accords with the environmental protection concept of waste utilization.
(2) Compared with the traditional method, the synthesis time of the method is short, and the time and energy consumption cost are greatly saved.
(3) The MIL-53(Cr) material prepared by the method has good adsorption performance on sulfur-containing pollutant Dibenzothiophene (DBT), still keeps excellent adsorption capacity after regeneration treatment, and can be applied to adsorption treatment of sulfur-containing fuel oil.
Drawings
FIG. 1 is a scanning electron micrograph of chromium-containing sludge.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of MIL-53(Cr) prepared in example 1.
FIG. 3 is an SEM photograph of MIL-53(Cr) prepared in example 2.
FIG. 4 is an X-ray powder diffraction (XRD) pattern of MIL-53(Cr) prepared in example 1, MIL-53(Cr) prepared in example 2, and chromium-containing sludge.
FIG. 5 is a nitrogen adsorption and desorption curve of MIL-53(Cr) prepared in example 1.
FIG. 6 is a thermogravimetric plot of MIL-53(Cr) prepared in example 1.
FIG. 7 is a graph showing comparison of MIL-53(Cr) prepared in example 1 and example 2 in terms of adsorption performance for dibenzothiophene.
FIG. 8 is a graph showing the adsorption kinetics of MIL-53(Cr) prepared in example 1 at different initial concentrations of dibenzothiophene.
FIG. 9 is a graph showing the adsorption kinetics of MIL-53(Cr) prepared in example 1 under different temperature conditions.
FIG. 10 is a graph showing the effect of regeneration of MIL-53(Cr) prepared in example 1 on the equilibrium adsorption amount of dibenzothiophene.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. It should be noted that the following examples are only for illustrating the technical solutions of the present invention and are not limiting, and that the technical solutions of the present invention are appropriately modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Example 1
Pretreating chromium-containing sludge collected in an electroplating factory, drying at 110 ℃ to constant weight, placing in a ball milling tank, selecting steel balls with the diameter of 7mm, ball milling at 900rpm for 0.5h at a ball-to-material ratio of 10:1, and sieving with a 100-mesh sieve to remove impurities to obtain a chromium source; mixing the dried chromium-containing sludge and mineralizer hydrofluoric acid in deionized water, fully stirring at room temperature, and carrying out ultrasonic treatment for 15min to ensure that the solid-liquid mixed solution is uniform; adding terephthalic acid into the solid-liquid mixed solution, fully stirring at room temperature, and further performing ultrasonic treatment for 15 min; and transferring the solid-liquid mixed solution to a stainless steel high-pressure reaction kettle for synthesis, wherein the reaction temperature is 220 ℃, and the reaction time is 18 hours. Stopping heating, cooling to room temperature, performing solid-liquid separation, collecting, performing centrifugal exchange with N, N-dimethylformamide for 3 times, and performing centrifugal exchange with ethanol for 3 times. Drying the crude product in an oven at 80 ℃; finally, the product is dried in vacuum at 150 ℃ for 12h to obtain the MIL-53(Cr) product.
This example uses chromium-containing sludge collected from electroplating plants (see Table 1 for Energy Dispersive Spectroscopy (EDS) elemental analysis).
TABLE 1 Energy Dispersive Spectroscopy (EDS) elemental analysis of chromium-containing sludge
In the chromium source used in this example, the molar ratio of the chromium element, terephthalic acid, hydrofluoric acid and deionized water was 1:1:1:280, and the mass concentration of hydrofluoric acid was 40%.
FIG. 1 is a scanning electron micrograph of chromium-containing sludge of chromium source from MIL-53(Cr) prepared in example 1; it can be seen from FIG. 1 that the chromium-containing sludge as the chromium source is an amorphous form of particle agglomerates of varying sizes. FIG. 2 is a SEM of MIL-53(Cr) prepared in example 1; from FIG. 2, it can be seen that MIL-53(Cr) synthesized in example 1 exhibited the morphology of elongated triangular prisms with an average size of 1X 8 μm.
Example 2
This example is substantially the same as example 1 except that no mineralizer, hydrofluoric acid, was added.
FIG. 3 is a SEM of MIL-53(Cr) prepared in example 2; from FIG. 3, it can be seen that the MIL-53(Cr) synthesized in example 2 has a shape similar to a narrow triangular prism, but a part of amorphous agglomerates appear in the visual field, indicating that the non-mineralized hydrofluoric acid in example 2 can not completely convert the chromium-containing sludge into the desired MIL-53 (Cr).
FIG. 4 is XRD patterns of chromium-containing sludge, MIL-53(Cr) prepared in example 1, and MIL-53(Cr) prepared in example 2. As can be seen from the map, the chromium-containing sludge of the chromium source shows the map characteristic of amorphous and amorphous,example 1 MIL-53(Cr) prepared with addition of mineralizer hydrofluoric acid and MIL-53(Cr) prepared with no mineralizer hydrofluoric acid in example 2 both showed standard profile characteristics for MIL-53 material, but the peak intensity of the former was significantly higher than the latter. FIG. 5 is a nitrogen adsorption and desorption curve of MIL-53(Cr) prepared in example 1 and MIL-53(Cr) prepared in example 2, according to which the specific surface area of the MIL-53(Cr) material prepared in example 1 reaches 730.27m2(g), the MIL-53(Cr) material obtained in example 2 had a specific surface area of 269.14m2(ii) in terms of/g. FIG. 6 is a thermogravimetric plot of the MIL-53(Cr) material from example 1 and the MIL-53(Cr) material from example 2.
Example 3
This example examines the isothermal adsorption capacity of MIL-53(Cr) materials prepared in examples 1 and 2 for dibenzothiophene. Using normal hexane as a solvent, preparing a dibenzothiophene model fuel oil stock solution with the concentration of 10000ppm, and preparing experimental model oil of example 3 with the dibenzothiophene concentration interval of 500-2000 ppm. In this example, 50mg of the MIL-53(Cr) material synthesized in example 1 and example 2, respectively, was weighed into a model oil of the corresponding dibenzothiophene while controlling the temperature of the adsorption experiment at 25 ℃. Shaking the mixture using a shaker at 200rpm for 24 h. A solution was drawn through a syringe filter (Teflon, hydrophobic, 0.22 μm). The concentration of dibenzothiophene in the model oil after 24h of adsorption was determined using a gas chromatograph. FIG. 7 is a graph comparing MIL-53(Cr) adsorption performance versus dibenzothiophene adsorption performance for examples 1 and 2; it can be seen that MIL-53(Cr) prepared in example 1 has better adsorption capacity for dibenzothiophene than MIL-53(Cr) prepared in example 2, which has reached adsorption saturation in 2000ppm of dibenzothiophene model oil.
Example 4
This example examined the kinetics of adsorption of dibenzothiophene by the MIL-53(Cr) material prepared in example 1. The experimental model oil of example 4 with dibenzothiophene concentrations of 500, 1000 and 1500pm was prepared using n-hexane as a solvent. 50mg each of the MIL-53(Cr) material prepared in example 1 was weighed into solutions of dibenzothiophene concentrations of 500, 1000 and 1500ppm, respectively. Shaking with a shaker at 200rpm, adsorbing at constant temperature of 25 deg.C, and maintaining for 24 hr. A predetermined time is selected and a certain amount of solution is drawn through the syringe filter. The concentration of dibenzothiophene in the model oil was determined using a gas chromatograph for different adsorption times. FIG. 8 is a graph of the adsorption kinetics of MIL-53(Cr) prepared in example 1 at different initial concentrations of dibenzothiophene; it can be seen that the equilibrium adsorption amount of MIL-53(Cr) is increased along with the increase of the initial dibenzothiophene, and the MIL-53(Cr) basically reaches the adsorption equilibrium at the 12 th hour under the condition of different initial concentrations.
Example 5
This example examined the kinetics of adsorption of dibenzothiophene by MIL-53(Cr) material prepared in example 1 under different temperature conditions. 50mg of the MIL-53(Cr) material prepared in example 1 were weighed out into a solution containing 1000ppm of dibenzothiophene. Shaking with a shaker at 200rpm, adsorbing at constant temperature of 25 deg.C, and maintaining for 12 hr. Selecting preset time, extracting a certain solution by using a syringe filter, and measuring the concentration of dibenzothiophene in model oil with different adsorption time by using a gas chromatograph. FIG. 9 is the adsorption kinetics curves of MIL-53(Cr) prepared in example 1 at different temperatures of dibenzothiophene; it can be seen that the equilibrium adsorption amount of MIL-53(Cr) is increased with the increase of the adsorption temperature, which indicates that the reaction of MIL-53(Cr) prepared in example 1 on dibenzothiophene is endothermic, and the adsorption effect can be enhanced by increasing the reaction temperature during the actual treatment of sulfur-containing fuel oil.
Example 6
This example examined the effect of the regenerated MIL-53(Cr) material prepared in example 1 on the adsorption capacity of dibenzothiophene. 50mg of the MIL-53(Cr) material prepared in example 1 was weighed into a solution containing 1000ppm dibenzothiophene. Shaking with a shaker at 200rpm, adsorbing at constant temperature of 25 deg.C, and maintaining for 12 hr. A certain amount of the solution was extracted with a syringe filter, and the concentration of dibenzothiophene in the model oil after 12 hours of adsorption was measured with a gas chromatograph. After the completion of the first adsorption, MIL-53(Cr) was recovered by filtration through a filter paper, and subjected to a material regeneration treatment, wherein the used MIL-53(Cr) was washed 3 times each at 70 ℃ in the order of N, N-dimethylformamide and ethanol. And (3) carrying out vacuum drying on the regenerated MIL-53(Cr) at 150 ℃ for 12h, and then carrying out adsorption for the next time. The MIL-53(Cr) adsorption procedure after regeneration was identical to that described above, and was repeated 4 times to determine the dibenzothiophene concentration in the model oil after each adsorption. FIG. 10 is a graph showing the effect of regeneration of MIL-53(Cr) prepared in example 1 on the equilibrium adsorption amount of dibenzothiophene; it can be seen that the MIL-53(Cr) material, after 4 regenerations, still maintained 95% of its initial adsorption capacity, confirming that MIL-53(Cr) prepared in example 1 is a regenerable, recyclable adsorbent for treating sulfur-containing fuel oils.
Example 7
This example is substantially the same as example 1, except that in this example, the molar ratio of the chromium element in the chromium source, terephthalic acid, hydrofluoric acid, and deionized water was 1:2:3: 500. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 8
This example is substantially the same as example 1, except that the molar ratio of the chromium element in the chromium source, terephthalic acid, hydrofluoric acid, and deionized water used in this example was 1:1.5:0.1: 100. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 9
This example is substantially the same as example 1, except that the molar ratio of the chromium element in the chromium source, terephthalic acid, hydrofluoric acid, and deionized water used in this example was 1:0.5:2: 200. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 10
This example is substantially the same as example 1 except that the chromium-containing sludge in this example is derived from excess sludge from a tannery industrial sewage treatment system. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 11
This example is substantially the same as example 1 except that the chromium-containing sludge in this example is derived from excess sludge in an industrial sewage treatment system of a chemical plant. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 12
This example is substantially the same as example 1 except that the chromium-containing sludge in this example is derived from excess sludge from an industrial sewage treatment system of a pigment factory. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 13
This example is substantially the same as example 1 except that the chromium-containing sludge in this example is derived from excess sludge from an industrial sewage treatment system of a metallurgical plant. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 14
This example is essentially the same as example 1, except that in this example, the chromium-containing sludge is a mixture of excess sludge from electroplating and tannery industrial wastewater treatment systems. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 15
This example is substantially the same as example 1 except that the temperature for drying the chromium-containing sludge in this example was 80 ℃. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 16
This example is substantially the same as example 1 except that the temperature for drying the chromium-containing sludge in this example was 160 ℃. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 17
This example is substantially the same as example 1, except that the conditions for the ball milling and pulverizing in this example are as follows: selecting steel balls with the diameter of 3mm, and ball-milling for 1h at 300rpm according to the ball-material ratio of 5: 1. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 18
This example is substantially the same as example 1, except that the conditions for the ball milling and pulverizing in this example are as follows: selecting steel balls with the diameter of 30mm, and ball-milling for 0.6h at 700rpm according to the ball-material ratio of 15: 1. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 19
This example is substantially the same as example 1 except that the mass concentration of the mineralizer, hydrogen fluoride, is 30%. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 20
This example is substantially the same as example 1 except that the mass concentration of the mineralizer, hydrogen fluoride, is 70%. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 21
This example is substantially the same as example 1, except that the two ultrasonic treatments were performed for 5 min. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 22
This example is substantially the same as example 1, except that the two ultrasonic treatments were performed for 60 min. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 23
This example is substantially the same as example 1, except that in this example, the hydrothermal reaction temperature was 160 ℃ and the reaction time was 16 hours. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 24
This example is substantially the same as example 1, except that in this example, the hydrothermal reaction temperature was 250 ℃ and the reaction time was 12 hours. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 25
This example is essentially the same as example 1 except that in this example the crude product was washed 2 times with N, N-dimethylformamide followed by deionized water, or 6 times with N, N-dimethylformamide followed by methanol. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 26
This example is essentially the same as example 1 except that in this example the crude product was dried at 40 ℃ for 24 hours and the activation conditions were 150 ℃ for 24 hours under vacuum. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
Example 27
This example is essentially the same as example 1 except that in this example the crude product was dried at 120 c for 2 hours and the activation conditions were 150 c for 6 hours under vacuum. The MIL-53(Cr) prepared by the embodiment has good adsorption performance on dibenzothiophene, can keep stable adsorption capacity after regeneration, and can be applied to adsorption desulfurization treatment of sulfur-containing fuel oil.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for rapidly preparing a metal organic framework material MIL-53(Cr) by using chromium-containing sludge is characterized by comprising the following steps:
s1: drying, ball-milling and crushing the chromium-containing sludge, and sieving to remove impurities to obtain a chromium source;
s2: mixing a chromium source and a mineralizer hydrofluoric acid in deionized water, stirring at room temperature, and uniformly mixing to obtain a solid-liquid mixed solution A;
s3: adding terephthalic acid into the solid-liquid mixed solution A obtained in the step S2, and further uniformly mixing to form a solid-liquid mixed solution B;
s4: carrying out hydrothermal reaction on the solid-liquid mixed solution B obtained in the step S3 to obtain a crude product;
s5: and collecting the crude product obtained in the step S4, washing, drying and activating to obtain the metal organic framework material MIL-53 (Cr).
2. The method for rapidly preparing the metal organic framework material MIL-53(Cr) by using the chromium-containing sludge as claimed in claim 1, wherein the chromium-containing sludge is derived from residual sludge of electroplating, tanning, chemical, pigment and/or metallurgical plant industrial sewage treatment systems.
3. The method for rapidly preparing the metal-organic framework material MIL-53(Cr) by using the chromium-containing sludge as claimed in claim 1, wherein in the step S1, any one or more of the following steps are included:
(a) drying the chromium-containing sludge at the temperature of 80-160 ℃;
(b) the conditions of ball milling and crushing are as follows: selecting steel balls with the diameter of 3-30 mm, and ball-milling for 0.5-1 h at 300-900 rpm according to the ball-to-material ratio of 5: 1-15: 1;
(c) sieving refers to sieving with 100 mesh sieve.
4. The method for rapidly preparing the metal-organic framework material MIL-53(Cr) by using the chromium-containing sludge as claimed in claim 1, wherein in the step S2, any one or more of the following steps are included:
(a) the mass concentration of the mineralizer hydrogen fluoride is 30-70%;
(b) the molar ratio of the chromium element in the chromium source, the mineralizer hydrogen fluoride and the deionized water is 1 (0-3) to (100-500);
(c) ultrasonic mixing is adopted for mixing, and the mixing time is 5-60 min.
5. The method for rapidly preparing the metal-organic framework material MIL-53(Cr) by using the chromium-containing sludge as claimed in claim 1, wherein in the step S3, any one or more of the following steps are included:
(a) the molar ratio of terephthalic acid to the chromium element in the chromium source in the step S2 is (1-2) to (2-1);
(b) ultrasonic mixing is adopted for mixing, and the mixing time is 5-60 min.
6. The method for rapidly preparing the metal-organic framework material MIL-53(Cr) from the chromium-containing sludge as claimed in claim 1, wherein in the step S4, the hydrothermal reaction temperature is 160-250 ℃ and the reaction time is 12-18 h.
7. The method for rapidly preparing the metal-organic framework material MIL-53(Cr) by using the chromium-containing sludge as claimed in claim 1, wherein in the step S5, any one or more of the following steps are included:
(a) washing solution adopted by washing comprises at least one of deionized water, methanol, ethanol and N, N-dimethylformamide, and the washing condition is that the crude product is centrifugally exchanged for 2-6 times by using the washing solution;
(b) the drying temperature is 40-120 ℃, and the drying time is 2-24 hours;
(c) the activation condition is vacuum drying for 6-24 h at 150 ℃.
8. A metal organic framework material MIL-53(Cr), characterized in that it is prepared by the method of any one of claims 1 to 7.
9. Metal-organic framework material MIL-53(Cr) according to claim 8, wherein the metal-organic framework material MIL-53(Cr) has a specific surface area of 730.27m2Per g, average pore volume 0.33cm3/g。
10. Use of the metal organic framework material MIL-53(Cr) according to claim 8 for adsorption treatment of dibenzothiophene, a sulfur-containing contaminant in fuel oil.
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