CN113318756A - Ammonium molybdate modified catalyst and preparation method and application thereof - Google Patents
Ammonium molybdate modified catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of catalysts. The invention provides an ammonium molybdate modified catalyst, which comprises the following components in a mass ratio of 9.5-10.5: 1.5-2.5 of ammonium molybdate modified ferrous disulfide and molybdenum disulfide. According to the invention, molybdenum disulfide is added into the catalyst, so that sulfur defects, sulfur defects and Fe are easily formed in the hydrogen peroxide solution2+The double active sites promote the decomposition of hydrogen peroxide to oxidize and decompose organic pollutants, and the ammonium molybdate increases the number of active sites of ferrous disulfide and improves the catalytic efficiency; meanwhile, on the basis of self-repairing, the existence of sulfur defects promotes Fe on the surface of the catalyst3+To Fe2+Conversion to achieve the purpose of circulation, so that the whole sewage treatment process can not cause secondary pollutionAnd (6) dyeing. The invention also provides a preparation method of the catalyst, the ammonium molybdate modified ferrous disulfide and molybdenum disulfide are combined by adopting a ball milling process, the process is simple, the technology is mature, and the catalyst is suitable for large-scale popularization.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to an ammonium molybdate modified catalyst, and a preparation method and application thereof.
Background
The treatment of organic wastewater with high concentration, difficult degradation and large toxicity, such as printing and dyeing wastewater, pharmaceutical wastewater, papermaking wastewater, landfill leachate, chemical EDTA plating wastewater in the electronic industry and the like, is a difficult point for industrial wastewater treatment for a long time. The biodegradation of the reactive dye wastewater is the most difficult, more than 10 ten thousand varieties of the reactive dye wastewater exist, more than 2000 varieties of the common dyes exist, and the number of novel dyes artificially synthesized every year is also infinite. Based on ferrous salt decomposition of H2O2Homogeneous Fenton catalysis, which generates strong oxidative hydroxyl free radicals OH, is widely applied to the treatment of various organic wastewater. But the serious problems are: h2O2The decomposition rate is low; the hydroxyl radical OH has short service life (1 microsecond) and low utilization rate; the presence of iron ions results in the production of large amounts of iron sludge in the solution, causing secondary pollution and increasing the cost of disposal. In an alkaline wastewater system, ferrous salt needs to be consumed, and the catalyst is difficult to recycle. Heterogeneous Fenton is a catalyst utilizing the surface active sites of the catalyst to H2O2The activation and decomposition generate hydroxyl free radical and react with substrate molecule. Therefore, increasing the number of active sites on the surface of the fenton catalyst, stably regenerating the active sites, and rapidly reacting hydroxyl radicals (with short lifetime) with the substrate molecules activated by adsorption are key problems of fenton catalysis, and become hot spots and frontiers of current fenton catalytic research. However, the problem that the number of heterogeneous fenton catalytic active sites is limited, the reaction between pollutant molecules and OH is slow due to relatively long distance, and the hydroxyl radical OH has short service life and is easy to 'die' so as to cause low utilization rate is not solved well.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an ammonium molybdate modified catalyst and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an ammonium molybdate modified catalyst, which comprises ammonium molybdate modified ferrous disulfide and molybdenum disulfide;
the mass ratio of the ammonium molybdate modified ferrous disulfide to the molybdenum disulfide is 9.5-10.5: 1.5 to 2.5. Preferably, the preparation method of the ammonium molybdate modified ferrous disulfide comprises the following steps:
(1) dissolving ammonium molybdate, ferrous sulfate heptahydrate, sodium thiosulfate and elemental sulfur to obtain a mixed solution;
(2) heating the mixed solution and centrifuging to obtain a precipitate;
(3) and washing, centrifuging and drying the precipitate in sequence to obtain the ammonium molybdate modified ferrous disulfide.
Preferably, the mass ratio of ammonium molybdate to ferrous sulfate heptahydrate in the step (1) is 0.15-0.2: 7.5 to 7.6;
the mass ratio of the ammonium molybdate to the sodium thiosulfate is 0.15-0.2: 7.5 to 7.6;
the mass ratio of the ammonium molybdate to the elemental sulfur is 0.15-0.2: 0.8 to 0.9;
the reagent for dissolving in the step (1) is water, and the dosage ratio of ammonium molybdate to the reagent is 0.15-0.2 g: 10-50 mL.
Preferably, mixing is carried out before dissolution in the step (1), wherein the mixing mode is ball milling, the rotation speed of the ball milling is 350-450 rpm, and the ball milling time is 30-50 min;
the dissolving mode in the step (1) is ultrasonic, the frequency of the ultrasonic is 40-60 kHz, the rotating speed of the ultrasonic is 1200-1400 rpm, and the time of the ultrasonic is 20-40 min;
the heating temperature in the step (2) is 175-185 ℃, and the heating time is 23-25 h;
the rotation speed of centrifugation in the steps (2) and (3) is 1000-1200 rpm independently, and the time of centrifugation is 6-10 min independently;
the drying temperature in the step (3) is 55-65 ℃, and the drying time is 5.5-6.5 h.
Preferably, the preparation method of the molybdenum disulfide comprises the following steps:
(a) refining, dispersing and centrifuging the crude molybdenum disulfide in sequence to obtain molybdenum disulfide supernatant;
(b) and drying the supernatant of the molybdenum disulfide to obtain the molybdenum disulfide.
Preferably, the refining mode in the step (a) is ball milling, the rotation speed of the ball milling is 350-450 rpm, and the ball milling time is 1.8-2.2 h;
the solvent used for dispersing comprises water and ethanol, and the volume ratio of the water to the ethanol is 1: 1.5-2.5; the dosage ratio of the crude molybdenum disulfide to the solvent is 1 g: 3-5 mL;
the dispersion mode is ultrasonic, the frequency of the ultrasonic is 40-60 kHz, the rotating speed of the ultrasonic is 1100-1500 rpm, and the time of the ultrasonic is 1.8-2.3 h.
Preferably, the rotation speed of the centrifugation in the step (a) is 7000-13000 rpm, and the time of the centrifugation is 5-15 min; the centrifugation times are more than or equal to 2;
the drying temperature in the step (b) is 55-65 ℃, and the drying time is 5.5-6.5 h.
The invention also provides a preparation method of the modified catalyst, wherein the ammonium molybdate modified catalyst is obtained by mixing the ammonium molybdate modified ferrous disulfide and molybdenum disulfide;
the mixing mode is ball milling, the rotating speed of the ball milling is 350-450 rpm, and the ball milling time is 1.5-2.5 h.
The invention also provides application of the modified catalyst in organic wastewater degradation.
Preferably, the catalyst degrades methyl orange in the organic wastewater.
The invention provides an ammonium molybdate modified catalyst, which comprises the following components in a mass ratio of 9.5-10.5: 1.5-2.5 of ammonium molybdate modified ferrous disulfide and molybdenum disulfide. The invention adds molybdenum disulfide into the catalyst to form sulfur defects, sulfur defects and sulfur oxides in the hydrogen peroxide solutionFe2+The double active sites promote the decomposition of hydrogen peroxide and generate a large amount of OH with strong oxidizing property to oxidize and decompose organic pollutants; and the existence of sulfur defects can adsorb activated organic pollutants to react with OH at zero distance, thereby greatly improving the degradation efficiency. S dropped after introduction of sulfur vacancy2-Changing free oxygen in water into O by electron donating2-O and2-has strong reducibility, and can convert Fe3+Is reduced to Fe again2+In the invention, the inorganic material ammonium molybdate is added, so that the surface structure of ferrous disulfide is changed, the number of active sites is increased, the cost and the process condition are reduced, and the catalytic efficiency of the catalyst is improved; meanwhile, on the basis of self-repairing, a large amount of Mo is exposed due to the existence of sulfur defects3+Promoting Fe on the surface of the catalyst by taking Mo-Fe bond as a channel for transferring electrons3+To Fe2+The conversion achieves the purpose of circulation, so that the whole sewage treatment process cannot cause secondary pollution. The invention also provides a preparation method of the catalyst, the ammonium molybdate modified ferrous disulfide and molybdenum disulfide are combined by adopting a ball milling process, the process is simple, the technology is mature, and the catalyst is suitable for large-scale popularization.
Drawings
FIG. 1 is a chart of the XED of the ammonium molybdate-modified ferrous disulfide prepared in example 1;
FIG. 2 is an SEM image of ammonium molybdate-modified ferrous disulfide prepared in example 1;
fig. 3 is a graph showing the degradation effect of the ammonium molybdate-modified catalyst prepared in example 1.
Detailed Description
The invention provides an ammonium molybdate modified catalyst, which comprises ammonium molybdate modified ferrous disulfide and molybdenum disulfide;
the mass ratio of the ammonium molybdate modified ferrous disulfide to the molybdenum disulfide is 9.5-10.5: 1.5 to 2.5.
In the invention, the mass ratio of the ammonium molybdate modified ferrous disulfide to the molybdenum disulfide is 9.5-10.5: 1.5-2.5, preferably 9.6-10.4: 1.6 to 2.4, more preferably 9.8 to 10.2: 1.8 to 2.2.
In the invention, the preparation method of the ammonium molybdate modified ferrous disulfide comprises the following steps:
(1) dissolving ammonium molybdate, ferrous sulfate heptahydrate, sodium thiosulfate and elemental sulfur to obtain a mixed solution;
(2) heating the mixed solution and centrifuging to obtain a precipitate;
(3) and washing, centrifuging and drying the precipitate in sequence to obtain the ammonium molybdate modified ferrous disulfide.
In the invention, the mass ratio of ammonium molybdate to ferrous sulfate heptahydrate in the step (1) is preferably 0.15-0.2: 7.5 to 7.6, and more preferably 0.16 to 0.19: 7.52 to 7.58, more preferably 0.17 to 0.18: 7.54 to 7.56.
In the invention, the mass ratio of ammonium molybdate to sodium thiosulfate is preferably 0.15-0.2: 7.5 to 7.6, and more preferably 0.16 to 0.19: 7.52 to 7.58, more preferably 0.17 to 0.18: 7.54 to 7.56.
In the invention, the mass ratio of ammonium molybdate to elemental sulfur is preferably 0.15-0.2: 0.8 to 0.9, and more preferably 0.16 to 0.19: 0.82 to 0.88, more preferably 0.17 to 0.18: 0.84 to 0.86.
In the present invention, the dissolving reagent in the step (1) is preferably water, and the ratio of the ammonium molybdate to the reagent is preferably 0.15 to 0.2 g: 10 to 50mL, more preferably 0.16 to 0.19 g: 20-40 mL, more preferably 0.17-0.18 g: 25-35 mL.
In the invention, mixing is preferably performed before dissolving in the step (1), the mixing mode is preferably ball milling, and the rotation speed of the ball milling is preferably 350-450 rpm, more preferably 360-440 rpm, and more preferably 380-420 rpm; the ball milling time is preferably 30-50 min, more preferably 35-45 min, and even more preferably 38-42 min.
In the invention, the dissolving mode in the step (1) is preferably ultrasonic, and the frequency of the ultrasonic is preferably 40-60 kHz, more preferably 44-56 kHz, and even more preferably 48-52 kHz; the rotation speed of the ultrasonic is preferably 1200-1400 rpm, more preferably 1240-1360 rpm, and more preferably 1260-1340 rpm; the ultrasonic treatment time is preferably 20-40 min, more preferably 22-38 min, and even more preferably 28-32 min.
In the invention, the heating temperature in the step (2) is preferably 175-185 ℃, more preferably 176-184 ℃, and more preferably 178-182 ℃; the heating time is preferably 23-25 h, more preferably 23.5-24.5 h, and even more preferably 23.8-24.2 h.
In the invention, the rotation speed of centrifugation in the steps (2) and (3) is preferably 1000-1200 rpm, more preferably 1040-1160 rpm, and more preferably 1080-1120 rpm independently; the time for centrifugation is preferably 6-10 min, more preferably 7-9 min, and even more preferably 7.5-8.5 min.
In the invention, the precipitate in the step (3) is washed, reagents used for washing are preferably distilled water, carbon tetrachloride and absolute ethyl alcohol sequentially, and the dosage ratio of the elemental sulfur to the reagents used for washing is preferably 0.8-0.9 g: 30 to 50mL, more preferably 0.83 to 0.86 g: 35-45 mL; the number of washing is independently preferably 5 or more, more preferably 6 or more, and still more preferably 7 or more.
In the invention, after the washing in the step (3) is a single reagent washing, the next reagent is used, each reagent is preferably centrifuged after being washed once, and the rotation speed of the centrifugation is preferably 1000-1200 rpm, more preferably 1040-1160 rpm, and more preferably 1080-1120 rpm; the centrifugation time is preferably 6-10 min, more preferably 7-9 min, and even more preferably 7.5-8.5 min.
In the present invention, the product obtained after the completion of centrifugation is dispersed in anhydrous ethanol and subjected to the next drying.
In the invention, the drying temperature in the step (3) is preferably 55-65 ℃, more preferably 56-64 ℃, and more preferably 58-62 ℃; the drying time is preferably 5.5-6.5 hours, more preferably 5.6-6.4 hours, and even more preferably 5.8-6.2 hours.
In the invention, ammonium molybdate is added during the preparation of ferrous disulfide, and ferric ions are reduced into ferrous ions by utilizing the reduction characteristic of ammonium molybdate in the using process, thereby accelerating the self-repairing speed.
In the invention, the preparation method of the molybdenum disulfide comprises the following steps:
(a) refining, dispersing and centrifuging the crude molybdenum disulfide in sequence to obtain molybdenum disulfide supernatant;
(b) and drying the supernatant of the molybdenum disulfide to obtain the molybdenum disulfide.
In the invention, the refining mode in the step (a) is preferably ball milling, and the rotation speed of the ball milling is preferably 350-450 rpm, more preferably 370-430 rpm, and even more preferably 390-410 rpm; the ball milling time is preferably 1.8-2.2 h, more preferably 1.9-2.1 h, and even more preferably 1.95-2.05 h.
In the present invention, the solvent for dispersion preferably comprises water and ethanol, and the volume ratio of the water to the ethanol is preferably 1: 1.5 to 2.5, and more preferably 1: 1.6-2.4, more preferably 1: 1.8-2.2; the dosage ratio of the crude molybdenum disulfide to the solvent is preferably 1 g: 3-5 mL, more preferably 1 g: 3.4-4.6 mL, more preferably 1 g: 3.8-4.2 mL.
In the invention, the dispersing mode is preferably ultrasonic, and the frequency of the ultrasonic is preferably 40-60 kHz, more preferably 45-55 kHz, and even more preferably 48-52 kHz; the rotation speed of the ultrasonic is preferably 1100-1500 rpm, more preferably 1200-1400 rpm, and even more preferably 1250-1350 rpm; the ultrasonic time is preferably 1.8-2.3 h, more preferably 1.9-2.2 h, and even more preferably 2.0-2.1 h.
In the invention, the rotation speed of centrifugation in the step (a) is preferably 7000-13000 rpm, more preferably 8000-12000 rpm, and more preferably 9000-11000 rpm; the centrifugation time is preferably 5-15 min, more preferably 6-14 min, and even more preferably 8-12 min; the number of times of centrifugation is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more.
In the invention, the drying temperature in the step (b) is preferably 55-65 ℃, more preferably 56-64 ℃, and more preferably 58-62 ℃; the drying time is preferably 5.5-6.5 hours, more preferably 5.6-6.4 hours, and even more preferably 5.8-6.2 hours.
In the invention, the crude molybdenum disulfide is treated in such a way that the multilayer flaky molybdenum disulfide is stripped into a single-layer flaky molybdenum disulfide, so that the molybdenum disulfide is easy to contact with the ammonium molybdate modified ferrous disulfide, and the catalytic efficiency is improved.
The invention also provides a preparation method of the modified catalyst, wherein the ammonium molybdate modified catalyst is obtained by mixing the ammonium molybdate modified ferrous disulfide and molybdenum disulfide;
the mixing mode is ball milling, the rotating speed of the ball milling is 350-450 rpm, and the ball milling time is 1.5-2.5 h.
In the invention, the rotation speed of the ball mill is 350-450 rpm, preferably 360-440 rpm, and more preferably 380-420 rpm.
In the invention, the ball milling time is 1.5-2.5 h, preferably 1.8-2.2 h, and more preferably 1.9-2.1 h.
The invention also provides application of the modified catalyst in organic wastewater degradation.
In the present invention, the catalyst preferably degrades methyl orange in organic wastewater.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparing ammonium molybdate modified ferrous disulfide:
respectively weighing 0.1700g of ammonium molybdate, 7.5955g of ferrous sulfate heptahydrate, 7.9054g of sodium thiosulfate and 0.8016g of elemental sulfur, placing the three substances into a ball mill, carrying out ball milling for 40min at the rotating speed of 400rpm, and mixing with 30mL of deionized water after the ball milling is finished; ultrasonically stirring for 30min under the conditions of 50kHz and 1300rpm to dissolve to obtain a mixed solution;
heating the mixed solution at 180 ℃ for 24h for reaction, cooling to room temperature after heating, placing the reaction system in a centrifuge tube, and centrifuging at 1100rpm for 8min to obtain a precipitate;
washing the precipitate with distilled water for 5 times, wherein the amount of distilled water used for washing each time is 40mL, centrifuging at 1100rpm for 8min after washing each time, and centrifuging for five times; washing with carbon tetrachloride for 5 times after washing with distilled water, wherein the use amount of carbon tetrachloride for washing each time is 40mL, and centrifuging at the rotating speed of 1100rpm for 8min for five times after washing each time; and (3) after the carbon tetrachloride is cleaned, cleaning the carbon tetrachloride for 5 times by using absolute ethyl alcohol, wherein the using amount of the absolute ethyl alcohol for each cleaning is 40mL, centrifuging the carbon tetrachloride for 8min at the rotating speed of 1100rpm after each cleaning, centrifuging the carbon tetrachloride for five times, dispersing the product by using the absolute ethyl alcohol after the centrifuging is finished, and drying the product at the temperature of 60 ℃ for 6h to obtain the ammonium molybdate modified ferrous disulfide.
Preparing molybdenum disulfide:
taking 5g of crude molybdenum disulfide, carrying out ball milling for 2h at the rotating speed of 400rpm, dispersing molybdenum disulfide powder in 20mL of mixed solution after the ball milling is finished, and obtaining a molybdenum disulfide solution, wherein the volume ratio of water to ethanol in the mixed solution is 1: 2, the dispersion condition is ultrasonic stirring for 2 hours under the conditions of 50kHz and 1300 rpm;
centrifuging the molybdenum disulfide solution at 10000rpm for 10min, and repeating twice to obtain a molybdenum disulfide supernatant;
and drying the molybdenum disulfide supernatant at 60 ℃ for 6h to obtain molybdenum disulfide.
Preparing an ammonium molybdate modified catalyst: ammonium molybdate modified ferrous disulfide and molybdenum disulfide were mixed in a ratio of 10: 2, performing ball milling at the rotation speed of 400rpm for 2 hours to obtain the ammonium molybdate modified catalyst.
The XED pattern and the SEM pattern of the ammonium molybdate modified ferrous disulfide prepared in the example are shown in figure 1 and figure 2 respectively.
The catalyst prepared in this example was subjected to a degradation test:
(1) degradation rate at different times:
measuring the pH value of 100ml of 20mg/L methyl orange solution in a beaker; 0.05g of the ammonium molybdate modified catalyst prepared in the embodiment (the concentration of the catalyst in the solution is 0.5g/L) is weighed and placed in 100ml of methyl orange, and the mixture is magnetically stirred for 30min to be adsorbed; after adsorption, taking 1.5mL of solution for centrifugation to obtain stock solution; adding 1mL of 0.1mol/L hydrogen peroxide solution (the concentration of hydrogen peroxide in the solution is 1mmol/L) in a magnetic stirring environment; timing immediately, when the degradation time reaches 0.5min, 1min, 1.5min, 2min and 5min, respectively taking 1.5ml of degradation liquid into a centrifuge tube, and carrying out centrifugal separation; the maximum absorption peaks of the stock solution and the degradation solutions at 0.5min, 1min, 1.5min, 2min, and 5min were measured using a fluorescence spectrophotometer, and the results are recorded in table 1.
TABLE 1 degradation rates at different times
| Time (min) | Degradation Rate (%) |
| 0.5 | 99.6 |
| 1 | 99.7 |
| 1.5 | 99.8 |
| 2 | 99.8 |
| 5 | 99.8 |
(2) Degradation effect
The catalyst prepared in this example was tested for its degradation effect on methyl orange in the same manner and amount as in (1), as shown in fig. 3. In the figure 3, the effects of degradation for 0min, 0.5min, 1min, 1.5min, 2min and 5min are sequentially performed from left to right; it can be seen that methyl orange was completely degraded after 5min, and the catalyst prepared in this example showed excellent degradation performance.
(3) Degradation rate at different time and pH conditions:
respectively taking 100ml of methyl orange solution and 20mg/L of methyl orange solution, adding acid and alkali into 8 beakers, and respectively adjusting the pH values to 2, 4, 6, 7, 8, 9, 10 and 12;
0.05g of the ammonium molybdate modified catalyst prepared in the example (the concentration of the catalyst in the solution is 0.5g/L) is weighed into 100ml of methyl orange, and the mixture is magnetically stirred for 30min to be adsorbed; after adsorption, taking 1.5mL of solution for centrifugation to obtain stock solution; adding 1mL of 0.1mol/L hydrogen peroxide solution (the concentration of hydrogen peroxide in the solution is 1mmol/L) in a magnetic stirring environment; timing immediately, when the degradation time reaches 0.5min, 1min, 1.5min, 2min and 5min, respectively taking 1.5ml of degradation liquid into a centrifuge tube, and carrying out centrifugal separation; the maximum absorption peaks of the stock solution and the degradation solutions at 0.5min, 1min, 1.5min, 2min, and 5min were measured using a fluorescence spectrophotometer, and the results are recorded in table 2.
TABLE 2 degradation at different pH and time (%)
Example 2
Preparing ammonium molybdate modified ferrous disulfide:
respectively weighing 0.1812g of ammonium molybdate, 7.5623g of ferrous sulfate heptahydrate, 7.5418g of sodium thiosulfate and 0.8283g of elemental sulfur, placing the three substances into a ball mill, carrying out ball milling for 50min at the rotating speed of 450rpm, and mixing with 50mL of deionized water after the ball milling is finished; ultrasonically stirring for 25min at 56kHz and 1360rpm to obtain a mixed solution;
heating the mixed solution at 185 ℃ for 23h for reaction, cooling to room temperature after heating, placing the reaction system in a centrifuge tube, and centrifuging at 1160rpm for 6min to obtain a precipitate;
washing the precipitate with distilled water for 6 times, wherein the amount of distilled water used for washing each time is 30mL, centrifuging at 1160rpm for 6min after washing each time, and centrifuging for six times; cleaning for 6 times by using carbon tetrachloride after the cleaning of distilled water is finished, wherein the use amount of the carbon tetrachloride for cleaning each time is 30mL, and centrifuging for 6min at the rotating speed of 1160rpm after the cleaning of each time is finished for six times; and (3) after the carbon tetrachloride is cleaned, cleaning for 6 times by using absolute ethyl alcohol, wherein the usage amount of the absolute ethyl alcohol for each cleaning is 30mL, centrifuging for 6min at the rotating speed of 1160rpm after each cleaning, centrifuging for six times in total, after the centrifuging is finished, dispersing the product by using the absolute ethyl alcohol, and then drying for 5.5h at the temperature of 65 ℃ to obtain the ammonium molybdate modified ferrous disulfide.
Preparing molybdenum disulfide:
taking 10g of crude molybdenum disulfide, carrying out ball milling for 1.9h at the rotating speed of 430rpm, dispersing molybdenum disulfide powder in 50mL of mixed solution after the ball milling is finished, so as to obtain a molybdenum disulfide solution, wherein the volume ratio of water to ethanol in the mixed solution is 1: 2.5, the dispersion condition is ultrasonic stirring for 2.3h under the conditions of 55kHz and 1200 rpm;
centrifuging the molybdenum disulfide solution for 8min at the rotating speed of 11000rpm, and repeating twice to obtain a molybdenum disulfide supernatant;
and drying the molybdenum disulfide supernatant at 65 ℃ for 5.8h to obtain molybdenum disulfide.
Preparing an ammonium molybdate modified catalyst: ammonium molybdate modified ferrous disulfide and molybdenum disulfide were mixed in a ratio of 10.5: 2.5, the rotation speed of the ball milling is 440rpm, and the ammonium molybdate modified catalyst is obtained after the ball milling is carried out for 1.9 h.
The ammonium molybdate modified catalyst prepared in this example was tested for degradation at various times according to the test method of example 1, and the results are reported in table 3.
TABLE 3 degradation rates at different times
| Time (min) | Degradation Rate (%) |
| 0.5 | 99.9 |
| 1 | 99.6 |
| 1.5 | 99.8 |
| 2 | 99.7 |
| 5 | 99.9 |
Example 3
Preparing ammonium molybdate modified ferrous disulfide:
respectively weighing 0.1658g of ammonium molybdate, 7.5823g of ferrous sulfate heptahydrate, 7.5847g of sodium thiosulfate and 0.8526g of elemental sulfur, placing the three substances into a ball mill, carrying out ball milling for 45min at the rotating speed of 380rpm, and mixing with 25mL of deionized water after the ball milling is finished; ultrasonically stirring for 28min under the conditions of 48kHz and 1260rpm for dissolving to obtain a mixed solution;
heating the mixed solution at 175 ℃ for 25h to react, cooling to room temperature after heating, placing the reaction system in a centrifuge tube, and centrifuging at the rotating speed of 1080rpm for 9min to obtain a precipitate;
washing the precipitate with distilled water for 6 times, wherein the amount of distilled water used for washing each time is 35mL, centrifuging at 1080rpm for 9min after washing each time, and centrifuging for six times; washing with carbon tetrachloride for 6 times after washing with distilled water, wherein the amount of carbon tetrachloride used for washing is 35mL each time, and centrifuging at the rotating speed of 1080rpm for 9min after washing for six times; and (3) after the carbon tetrachloride is cleaned, cleaning for 6 times by using absolute ethyl alcohol, wherein the usage amount of the absolute ethyl alcohol for each cleaning is 35mL, centrifuging for 9min at the rotating speed of 1080rpm after each cleaning, centrifuging for six times totally, after the centrifuging is finished, dispersing the product by using the absolute ethyl alcohol, and then drying for 6.2h at the temperature of 58 ℃ to obtain the ammonium molybdate modified ferrous disulfide.
Preparing molybdenum disulfide:
taking 15g of crude molybdenum disulfide, carrying out ball milling for 2.2h at the rotating speed of 390rpm, dispersing molybdenum disulfide powder in 45mL of mixed solution after the ball milling is finished, so as to obtain a molybdenum disulfide solution, wherein the volume ratio of water to ethanol in the mixed solution is 1: 1.5, the dispersion condition is ultrasonic stirring for 2.3h under the conditions of 48kHz and 1200 rpm;
centrifuging the molybdenum disulfide solution at 9500rpm for 12min, repeating the centrifuging for three times to obtain a molybdenum disulfide supernatant;
and drying the molybdenum disulfide supernatant at 58 ℃ for 6.5h to obtain the molybdenum disulfide.
Preparing an ammonium molybdate modified catalyst: ammonium molybdate modified ferrous disulfide and molybdenum disulfide were mixed in a ratio of 9.5: and ball milling at the mass ratio of 1.5, wherein the rotating speed of the ball milling is 380rpm, and the ammonium molybdate modified catalyst is obtained after ball milling for 2.5 hours.
The ammonium molybdate modified catalyst prepared in this example was tested for degradation at various times according to the test method of example 1 and the results are reported in table 4.
TABLE 4 degradation rates at different times
| Time (min) | Degradation Rate (%) |
| 0.5 | 99.9 |
| 1 | 99.6 |
| 1.5 | 99.5 |
| 2 | 99.8 |
| 5 | 99.6 |
From the above embodiments, the invention provides an ammonium molybdate modified catalyst, and ferrous disulfide is subjected to ammonium molybdate modification treatment, so that ferrous disulfide is introduced into the catalyst, and the catalytic efficiency is improved. According to the results of the embodiment, the catalyst provided by the invention can effectively degrade the organic wastewater, and the highest degradation rate reaches 99.9%; but also can adapt to different pH value environments, thereby reducing the treatment cost.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An ammonium molybdate modified catalyst, which is characterized by comprising ammonium molybdate modified ferrous disulfide and molybdenum disulfide;
the mass ratio of the ammonium molybdate modified ferrous disulfide to the molybdenum disulfide is 9.5-10.5: 1.5 to 2.5.
2. The modified catalyst of claim 1, wherein the process for preparing ammonium molybdate modified ferrous disulfide comprises the steps of:
(1) dissolving ammonium molybdate, ferrous sulfate heptahydrate, sodium thiosulfate and elemental sulfur to obtain a mixed solution;
(2) heating the mixed solution and centrifuging to obtain a precipitate;
(3) and washing, centrifuging and drying the precipitate in sequence to obtain the ammonium molybdate modified ferrous disulfide.
3. The modified catalyst according to claim 2, wherein the mass ratio of ammonium molybdate to ferrous sulfate heptahydrate in the step (1) is 0.15-0.2: 7.5 to 7.6;
the mass ratio of the ammonium molybdate to the sodium thiosulfate is 0.15-0.2: 7.5 to 7.6;
the mass ratio of the ammonium molybdate to the elemental sulfur is 0.15-0.2: 0.8 to 0.9;
the reagent for dissolving in the step (1) is water, and the dosage ratio of ammonium molybdate to the reagent is 0.15-0.2 g: 10-50 mL.
4. The modified catalyst according to any one of claims 1 to 3, wherein the mixing is performed before the dissolution in the step (1), the mixing is performed by ball milling, the rotation speed of the ball milling is 350 to 450rpm, and the ball milling time is 30 to 50 min;
the dissolving mode in the step (1) is ultrasonic, the frequency of the ultrasonic is 40-60 kHz, the rotating speed of the ultrasonic is 1200-1400 rpm, and the time of the ultrasonic is 20-40 min;
the heating temperature in the step (2) is 175-185 ℃, and the heating time is 23-25 h;
the rotation speed of centrifugation in the steps (2) and (3) is 1000-1200 rpm independently, and the time of centrifugation is 6-10 min independently;
the drying temperature in the step (3) is 55-65 ℃, and the drying time is 5.5-6.5 h.
5. The modified catalyst of claim 4, wherein the molybdenum disulfide is prepared by a process comprising the steps of:
(a) refining, dispersing and centrifuging the crude molybdenum disulfide in sequence to obtain molybdenum disulfide supernatant;
(b) and drying the supernatant of the molybdenum disulfide to obtain the molybdenum disulfide.
6. The modified catalyst of claim 5, wherein the refining mode in the step (a) is ball milling, the rotation speed of the ball milling is 350-450 rpm, and the ball milling time is 1.8-2.2 h;
the solvent used for dispersing comprises water and ethanol, and the volume ratio of the water to the ethanol is 1: 1.5-2.5; the dosage ratio of the crude molybdenum disulfide to the solvent is 1 g: 3-5 mL;
the dispersion mode is ultrasonic, the frequency of the ultrasonic is 40-60 kHz, the rotating speed of the ultrasonic is 1100-1500 rpm, and the time of the ultrasonic is 1.8-2.3 h.
7. The modified catalyst according to claim 5 or 6, wherein the rotation speed of the centrifugation in the step (a) is 7000-13000 rpm, and the time of the centrifugation is 5-15 min; the centrifugation times are more than or equal to 2;
the drying temperature in the step (b) is 55-65 ℃, and the drying time is 5.5-6.5 h.
8. The preparation method of the modified catalyst according to any one of claims 1 to 7, characterized in that the ammonium molybdate modified catalyst is obtained by mixing ammonium molybdate modified ferrous disulfide and molybdenum disulfide;
the mixing mode is ball milling, the rotating speed of the ball milling is 350-450 rpm, and the ball milling time is 1.5-2.5 h.
9. Use of the modified catalyst of any one of claims 1 to 7 in the degradation of organic waste water.
10. The use of claim 9, wherein the catalyst degrades methyl orange in organic wastewater.
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