CN112387277A - Method for catalytic hydrogenation reduction of algal toxins in water based on supported noble metal catalyst - Google Patents
Method for catalytic hydrogenation reduction of algal toxins in water based on supported noble metal catalyst Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 57
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 24
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- ZYZCGGRZINLQBL-GWRQVWKTSA-N microcystin-LR Chemical compound C([C@H](OC)[C@@H](C)\C=C(/C)\C=C\[C@H]1[C@@H](C(=O)N[C@H](CCC(=O)N(C)C(=C)C(=O)N[C@H](C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@H]([C@H](C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N1)C(O)=O)C(O)=O)C)C1=CC=CC=C1 ZYZCGGRZINLQBL-GWRQVWKTSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a method for catalytic hydrogenation reduction of microcystin in water based on a supported noble metal catalyst, which comprises the steps of adding the supported noble metal catalyst into water containing microcystin, adjusting the pH value of the water to 6.0-9.0, and introducing hydrogen into the water to perform catalytic hydrogenation reduction reaction. After the reaction is completed, the degradation product in the water body has no hepatotoxicity any more, and the effect of detoxification of the product is achieved. Compared with the existing method for degrading MC-LR, the liquid phase catalytic reduction method provided by the invention can selectively reduce Adda toxic groups of MC-LR, has obvious toxicity removal, high MC-LR degradation efficiency and high speed, and has the advantages of technical feasibility, simple operation, easy material acquisition and no secondary pollution of degradation products.
Description
Technical Field
The invention belongs to the field of liquid phase catalysis and environment, and particularly relates to a method for reducing algal toxins in water by catalytic hydrogenation based on a supported noble metal catalyst.
Background
The incidence of algal blooms in surface drinking water resources (lakes, reservoirs and rivers) is increasing, and the global public attention is drawn, wherein Microcystins (MCs) released by various species of blue-green algae (such as microcystins, anabaena, nodulation algae, oscillatoria and the like) are the most common cyanobacterials in eutrophic water bodies, wherein LR type is the most common microcystins and accounts for 46.0-99.8% of the total amount of the microcystins in cyanobacterial blooms. MC-LR is an extremely toxic acute hepatotoxin, the mouse's median Lethal Dose (LD)50) 50 μ g/kg, inhibits protein phosphatases (e.g., PP1 and PP2A), and induces liver cancer by long-term contact with drinking water.
Because of the huge environmental health risk caused by microcystins, the World Health Organization (WHO) sets the drinking water standard of MC-LR to be lower than 1 mug/L, and the domestic Drinking Water quality health Specification (2001) also stipulates that the standard value of MC-LR in domestic water is less than or equal to 1 mug/L.
At present, the common methods for removing algal toxins in water mainly comprise physical and chemical treatment methods. The physical treatment mainly comprises a membrane process and activated carbon adsorption; the chemical method treatment mainly comprises chlorination oxidation, ozone oxidation and photocatalytic oxidation. Physical methods are less efficient and more costly than chemical methods, as membrane treatment also presents membrane fouling. Chemical treatments are currently generally based on oxidative degradation processes. In the chlorination and oxidation process, MC-LR can be removed efficiently under proper conditions, but the greatest defect of the chlorination and oxidation process is that degradation products caused by the formation of disinfection byproducts are possibly more toxic than substances before degradation, trihalomethane is the most common byproduct in the chlorination and oxidation process, and researches show that the concentration of trihalomethane formed by chlorination and oxidation can reach 150 mu g/L and exceeds the European Union directive value (100 mu g/L). The use of the chlorination-oxidation process is also disadvantageous in that it is difficult to operate because it requires optimization of various parameters, such as optimum chlorine dosage, proper contact time and pH, and the large difference in the degradation effect of different kinds of chlorinated oxidants is a problem in the chlorination-oxidation process. The ozone oxidation process has a good MC-LR removal rate, but part of the intermediate by-products formed in the reaction step using the ozone oxidation process have toxic effects and require additional treatment. In addition, natural organic matter present in the water to be treated competitively depletes ozone during the ozonation process, which is also a challenge of the ozonation process. Titanium dioxide is the most commonly used photocatalytic material in photocatalytic oxidation processes. The titanium dioxide-based material can oxidize the algal toxin through hydroxyl radicals formed in the photocatalysis process, so that the degradation effect is achieved. However, the photocatalytic technology has the problems of high energy consumption, strict operating conditions and difficulty in controlling by-products. Therefore, the photocatalytic process is difficult to be a good alternative technology in the water treatment process at present. In summary, the current strategy of removing microcystins based on chemical oxidation methods leads to the generation of toxic by-products, thereby increasing risks and increasing costs. This is a common technical hurdle due to the non-selective nature of the oxidation process. Therefore, there is a need to develop a more efficient and safe method for treating algal toxins in water that is not based on an oxidation process.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a simple and efficient method for removing microcystins in water aiming at the defects of the prior art, and removing the microcystins by a catalytic hydrogenation reduction method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for catalytic hydrogenation reduction of algal toxins in water based on a supported noble metal catalyst comprises the steps of adding the supported noble metal catalyst into water containing microcystins, adjusting the pH value of the water to 6.0-9.0, and introducing hydrogen into the water to perform catalytic hydrogenation reduction reaction. After the reaction is completed, the degradation product in the water body has no hepatotoxicity any more, and the effect of detoxification of the product is achieved.
Liquid-phase catalytic hydrogenation reduction has been attracting attention as a water treatment method, which involves subjecting pollutants to hydrogenation reduction in a water body containing the pollutants by using hydrogen provided by a hydrogen source (hydrogen, formic acid, alcohols, etc.) under the action of a catalyst to convert the pollutants into low-toxicity or non-toxic substances. The invention adopts the supported noble metal catalyst to carry out liquid phase catalytic hydrogenation to reduce the algal toxins in the water, and has the main advantages that firstly, the reduction reaction can be carried out under the action of the catalyst under mild conditions, and the energy consumption is low; secondly, the catalytic hydrogenation reduction method can selectively attack Adda toxic groups of the pollutants and convert the pollutants into low-toxicity or non-toxicity substances, and is an environment-friendly treatment method; and thirdly, the noble metal catalyst has extremely high catalytic activity and is an efficient treatment means compared with other treatment methods.
Specifically, the supported noble metal catalyst comprises a carrier and noble metal particles supported on the carrier;
the carrier is alumina (Al)2O3) Cerium oxide (CeO)2) Titanium oxide (TiO)2) Preferably TiO is used as the binder2；
The noble metal is any one of Pt, Rh or Pd, and is preferably Pd;
the loading amount of the noble metal in the supported noble metal catalyst is 0.1-1 wt.%.
Preferably, the microcystin is LR type microcystin (MC-LR).
The method can directly treat the general environmental water body containing the MC-LR pollutants, wherein the initial concentration of the MC-LR pollutants is about 1-10 ppm, and can ensure that the microcystins in the actual water body are completely removed.
Preferably, the addition amount of the supported noble metal catalyst in a water body is 0.1-0.3 mg/ml.
Specifically, the preparation method of the supported noble metal catalyst comprises the following steps:
(1) placing the carrier in a container, and then adding a salt or acid solution containing the noble metal;
(2) magnetically stirring the mixed solution obtained in the step (1), and adjusting the pH value to 10.5-11;
(3) filtering the solution obtained in the step (2), washing the solution to be neutral, drying the solution, and roasting the dried solution at 300-350 ℃ for 3-5 h;
(4) h, roasting the material obtained in the step (3) at 300-350 DEG C2And reducing for 2-3 h in the atmosphere to obtain the product.
Preferably, in the step (1), the salt or acid solution of the noble metal is any one of chloropalladic acid, chloroplatinic acid or rhodium chloride.
Preferably, in step (2), 1M Na is used for adjusting the pH value2CO3And (3) solution.
Preferably, in the step (2), magnetic stirring is carried out for 1-2 h before the pH value is adjusted, and then the magnetic stirring is carried out for 1-2 h after the pH value is adjusted.
Preferably, in the step (3), the drying temperature is 90-105 ℃.
Preferably, in step (4), H2At 25mL min-1The flow rate of the reaction solution is introduced into a reduction furnace for reduction reaction.
Has the advantages that:
compared with the existing method for degrading MC-LR, the liquid phase catalytic reduction method provided by the invention can selectively reduce Adda toxic groups of MC-LR, has obvious toxicity removal, high MC-LR degradation efficiency and high speed, and has the advantages of technical feasibility, simple operation, easy material acquisition and no secondary pollution of degradation products.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a schematic diagram of catalytic hydrogenation reduction of algal toxins in water based on a supported noble metal catalyst.
FIG. 2 shows the effect of different vectors on MC-LR degradation.
FIG. 3 is a graph showing the effect of different metal loading on MC-LR degradation.
FIG. 4 is a graph comparing the effect of different metal loadings on MC-LR degradation.
FIG. 5 is a comparison of MC-LR degradation with different dosages of the preferred materials.
FIG. 6 is a comparison of the degradation of MC-LR by preferred materials at different solution pH.
FIG. 7 shows the toxicity profile during MC-LR degradation.
Detailed Description
The invention will be better understood from the following examples.
Example 1
(1) Respectively weighing 0.5g of titanium oxide, cerium oxide and alumina carriers in small beakers, calculating the volume of the chloropalladic acid required for loading 1 wt.% of Pd according to the mass of the carriers, and adding the chloropalladic acid solution into different carriers by using a pipette according to the calculated volume to obtain 1% Pd/TiO2、1％Pd/Al2O3、1％Pd/CeO2A material.
(2) Magnetically stirring the solution in the beaker of step (1) for 1h and adding 1M Na dropwise2CO3The solution was brought to pH 10.5 and stirring was continued for 1 h.
(3) And (3) washing the solution obtained in the step (2) with deionized water through a 0.45-micron filter membrane until the solution is neutral, drying the solution in a drying oven at 105 ℃, and roasting the solution in a muffle furnace at 300 ℃ for 4 hours.
(4) H, heating the material roasted in the step (3) at 300 DEG C2(25mL min-1) Reducing for 2h in the atmosphere to obtain the Pd materials of different carriers.
(5) Weighing 5mg of Pd materials with different carriers obtained in the step (4), adding into a three-necked bottle, simultaneously adding 40ml of 2ppmMC-LR solution accurately, and then adding for 100ml min-1Introducing nitrogen at the flow rate of (1) for 15min to reach adsorption equilibrium, and introducing nitrogen at the flow rate of (100 ml) for another 100ml min-1Introducing hydrogen gas at the flow rate of 30min, setting four sampling points of 0min, 5min, 10min and 30min, and measuring the concentration of MC-LR by using a high performance liquid chromatograph.
The MC-LR catalytic reduction degradation intermediate product is measured by the optimized catalyst through a high performance liquid chromatography-mass spectrometry combined technology, the following catalytic reduction degradation pathway (figure 1) is obtained, analysis on the degradation pathway shows that the MC-LR reduction product is only a product of Adda group and carbon-carbon double bond which are added to cause toxicity, and other products do not exist, so that the toxic group can be selectively detoxified by using the supported noble metal catalyst to catalyze and reduce microcystin, and the microcystin is prevented from undergoing other chemical transformations, so that the risk of secondary pollution is avoided.
FIG. 2 is a graph showing the comparison of the effect of different carriers on MC-LR degradation, and the comparison shows that TiO2Has better MC-LR degrading effect than other two carriers.
Example 2
(1) Weighing 0.5g of titanium oxide carrier in a small beaker, calculating the volume of palladium chloride acid, chloroplatinic acid and rhodium chloride solution required to be added for loading 0.1 wt.% of Pd, Pt and Rh according to the mass of the carrier, and adding the palladium chloride acid, the chloroplatinic acid and the rhodium chloride solution into the titanium oxide by using a liquid-transferring gun according to the calculated volume to obtain 0.1 percent of Pd/TiO2、0.1％Rh/TiO2、0.1％Pt/TiO2A material.
(2) Magnetically stirring the solution in the beaker of step (1) for 1h and adding 1M Na dropwise2CO3The solution was brought to pH 10.5 and stirring was continued for 1 h.
(3) And (3) washing the solution obtained in the step (2) with deionized water through a 0.45-micron filter membrane until the solution is neutral, drying the solution in a drying oven at 105 ℃, and roasting the solution in a muffle furnace at 300 ℃ for 4 hours.
(4) H, heating the material roasted in the step (3) at 300 DEG C2(25mL min-1) Reducing for 2h in the atmosphere to obtain the titanium oxide material loaded with different metals.
(5) Weighing 2mg of the titanium oxide material loaded with different metals obtained in the step (4), adding the titanium oxide material into a three-necked bottle, simultaneously accurately adding 20ml of 2ppmMC-LR solution, and then performing treatment for 100ml min-1Introducing nitrogen at the flow rate of (1) for 15min to reach adsorption equilibrium, and introducing nitrogen at the flow rate of (100 ml) for another 100ml min-1Introducing hydrogen gas at the flow rate of 30min, setting seven sampling points of 0min, 1min, 2min, 3min, 5min, 10min and 30min, and measuring the concentration of MC-LR by using a high performance liquid chromatograph.
FIG. 3 is a comparison of the MC-LR degradation effect of materials loaded with different noble metals, and the comparison shows that the noble metal Pd has better MC-LR degradation effect than the other two metals.
Example 3
(1) Weighing 0.5g of titanium oxide carrier in a small beaker, calculating the volume of the chloropalladate solution required to be added for loading 0.1 wt.% Pd, 0.2 wt.% Pd and 0.3 wt.% Pd according to the mass of the carrier, and adding the chloropalladate solution into the titanium oxide by using a liquid-transferring gun according to the calculated volume to obtain Pd/TiO with different loading amounts2A material.
(2) Magnetically stirring the solution in the beaker of step (1) for 1h and adding 1M Na dropwise2CO3The solution was brought to pH 10.5 and stirring was continued for 1 h.
(3) And (3) washing the solution obtained in the step (2) with deionized water through a 0.45-micron filter membrane until the solution is neutral, drying the solution in a drying oven at 105 ℃, and roasting the solution in a muffle furnace at 300 ℃ for 4 hours.
(4) H, heating the material roasted in the step (3) at 300 DEG C2(25mL min-1) Reducing for 2h in the atmosphere to obtain the catalyst Pd/TiO with different Pd loading amounts2。
(5) Weighing the Pd/TiO with different Pd loading amounts obtained in the step (4)22mg, added to a three-necked flask with the addition of exactly 20ml of a 2 ppmC-LR solution followed by 100ml min-1Introducing nitrogen at the flow rate of (1) for 15min to reach adsorption equilibrium, and introducing nitrogen at the flow rate of (100 ml) for another 100ml min-1Introducing hydrogen gas at the flow rate of 30min, setting seven sampling points of 0min, 1min, 2min, 3min, 5min, 10min and 30min, and measuring the concentration of MC-LR by using a high performance liquid chromatograph.
FIG. 4 is a comparison of the effect of different metal loading on MC-LR degradation, and it can be seen that the degradation rate of MC-LR is faster with the increase of Pd loading.
Example 4
(1) Weighing 0.5g of titanium oxide carrier in a small beaker, calculating the volume of the chloropalladate solution required to load 0.1 wt.% Pd based on the mass of the carrier, and adding the chloropalladate solution to the titanium oxide by using a pipette according to the calculated volume to obtain 0.1% Pd/TiO2A material.
(2) Magnetically stirring the solution in the beaker of step (1) for 1h and adding 1M Na dropwise2CO3The solution was brought to pH 10.5 and stirring was continued for 1 h.
(3) And (3) washing the solution obtained in the step (2) with deionized water through a 0.45-micron filter membrane until the solution is neutral, drying the solution in a drying oven at 105 ℃, and roasting the solution in a muffle furnace at 300 ℃ for 4 hours.
(4) H, heating the material roasted in the step (3) at 300 DEG C2(25mL min-1) Reducing for 2h in the atmosphere to obtain the titanium oxide material loaded with different metals.
(5) Weighing the 0.1 percent Pd/TiO obtained in the step (4)22mg of material was added to a three-necked flask with the addition of exactly 20ml of a 1ppm, 2ppm, 3ppm, 4ppm MC-LR solution followed by 100ml min-1Introducing nitrogen at the flow rate of (1) for 15min to reach adsorption equilibrium, and introducing nitrogen at the flow rate of (100 ml) for another 100ml min-1Introducing hydrogen gas at the flow rate of 30min, setting seven sampling points of 0min, 1min, 2min, 3min, 5min, 10min and 30min, and measuring the concentration of MC-LR by using a high performance liquid chromatograph.
When the material is added in a certain amount, the degradation rate is reduced to a certain extent along with the increase of the concentration of MC-LR.
Example 5
(1) Weighing 0.5g of titanium oxide carrier in a small beaker, calculating the volume of the chloropalladate solution required to load 0.1 wt.% Pd based on the mass of the carrier, and adding the chloropalladate solution to the titanium oxide by using a pipette according to the calculated volume to obtain 0.1% Pd/TiO2A material.
(2) Magnetically stirring the solution in the beaker of step (1) for 1h and adding 1M Na dropwise2CO3The solution was brought to pH 10.5 and stirring was continued for 1 h.
(3) And (3) washing the solution obtained in the step (2) with deionized water through a 0.45-micron filter membrane until the solution is neutral, drying the solution in a drying oven at 105 ℃, and roasting the solution in a muffle furnace at 300 ℃ for 4 hours.
(4) H, heating the material roasted in the step (3) at 300 DEG C2(25mL min-1) Reducing for 2h in the atmosphere to obtain the titanium oxide material loaded with different metals.
(5) Weighing the 0.1 percent Pd/TiO obtained in the step (4)22mg, 4mg, 6mg of material were added to a three-necked flask, while exactly 20ml of 2 ppmC-LR solution was added, followed by 100ml min-1Introducing nitrogen at the flow rate of (1) for 15min to reach adsorption equilibrium, and introducing nitrogen at the flow rate of (100 ml) for another 100ml min-1At a flow rate of 30min hydrogen, setting seven sampling points of 0min, 1min, 2min, 3min, 5min, 10min and 30min, and measuring the concentration of MC-LR by using a high performance liquid chromatograph.
FIG. 5 is 0.1% Pd/TiO2Compared with the MC-LR degradation effect, the comparison shows that when the concentration of the microcystin-LR to be degraded is fixed, the larger the material dosage is, the faster the MC-LR degradation speed is.
Example 6
(1) Weighing 0.5g of titanium oxide carrier in a small beaker, calculating the volume of the chloropalladate solution required to load 0.1 wt.% Pd based on the mass of the carrier, and adding the chloropalladate solution to the titanium oxide by using a pipette according to the calculated volume to obtain 0.1% Pd/TiO2A material.
(2) Magnetically stirring the solution in the beaker of step (1) for 1h and adding 1M Na dropwise2CO3The solution was brought to pH 10.5 and stirring was continued for 1 h.
(3) And (3) washing the solution obtained in the step (2) with deionized water through a 0.45-micron filter membrane until the solution is neutral, drying the solution in a drying oven at 105 ℃, and roasting the solution in a muffle furnace at 300 ℃ for 4 hours.
(4) H, heating the material roasted in the step (3) at 300 DEG C2(25mL min-1) Reducing for 2h in the atmosphere to obtain the titanium oxide material loaded with different metals.
(5) Accurately adding 20ml of 2ppmMC-LR solution into a three-necked bottle, adjusting the pH of the solution to 6-9 by using NaOH, and weighing the 0.1% Pd/TiO obtained in the step (4)22mg of material was added to a three-necked flask followed by 100ml min-1Introducing nitrogen at the flow rate of (1) for 15min to reach adsorption equilibrium, and introducing nitrogen at the flow rate of (100 ml) for another 100ml min-1Introducing hydrogen gas at the flow rate of 30min, setting seven sampling points of 0min, 1min, 2min, 3min, 5min, 10min and 30min, and measuring the concentration of MC-LR by using a high performance liquid chromatograph.
FIG. 6 is 0.1% Pd/TiO2The MC-LR degradation reaction can be carried out at pH 6.0-9.0.
Example 7
(1) Weigh 0.5g of titania support in a small beaker and calculate the amount of chloropalladate solution added to load 0.1 wt.% Pd based on the mass of the supportVolume, the chloropalladate solution was added to the titanium oxide using a pipette gun according to the calculated volume to obtain 0.1% Pd/TiO2A material.
(2) Magnetically stirring the solution in the beaker of step (1) for 1h and adding 1M Na dropwise2CO3The solution was brought to pH 10.5 and stirring was continued for 1 h.
(3) And (3) washing the solution obtained in the step (2) with deionized water through a 0.45-micron filter membrane until the solution is neutral, drying the solution in a drying oven at 105 ℃, and roasting the solution in a muffle furnace at 300 ℃ for 4 hours.
(4) Then the material calcined in the step (3) is subjected to H treatment at 300 DEG C2(25mL min-1) Reducing for 2h in the atmosphere to obtain the titanium oxide material loaded with different metals.
(5) Accurately adding 20ml of 2ppmMC-LR solution into a three-neck flask, adjusting the pH of the solution to 7, 8 and 9 by using NaOH, and weighing 0.1% Pd/TiO obtained in the step (4)22mg of material was added to a three-necked flask followed by 100ml min-1Introducing nitrogen at the flow rate of (1) for 15min to reach adsorption equilibrium, and introducing nitrogen at the flow rate of (100 ml) for another 100ml min-1Introducing hydrogen gas at the flow rate of 30min, setting seven sampling points of 0min, 1min, 2min, 3min, 5min, 10min and 30min, and collecting fresh solution at each time point.
The toxicity test process adopts MC-LR toxicity test kit, and the specific operation process mainly comprises the following processes:
(1) the fresh solution collected at each time point was diluted 1000-fold so that the solution concentration was in the range of 0.1-2.0ppb and the sample concentration to be tested was in the range of the testability of the kit.
(2) 50. mu.l of the resulting solution and ultrapure water were added to a 96-well plate previously coated with a microcystin antibody.
(3) 70. mu.l of phosphatase solution was added to the corresponding well in step (2).
(4) Add 90. mu.l of chromogenic substrate to the well corresponding to step (3) and shake carefully, cover the gel film and incubate in a shaker at 37 ℃ for 30 minutes.
(5) Adding 70 μ l of stop solution into the corresponding hole in the step (4), carefully shaking, reading out the absorbance values of the blank group and the experimental sample at 405nm, and calculating the toxicity reduction.
As can be seen from toxicity test experiments, when the MC-LR is degraded by the preferred material, not only the microcystins can be degraded with high efficiency, but also the toxicity can be well removed as can be seen from FIG. 7, the toxicity removal rate of the preferred material after degradation for 10 minutes is 76.6% through calculation, and when the material is treated for 30 minutes, the toxicity removal rate can reach 90.8%, which indicates that the method for removing microcystins in water by using the supported noble metal catalyst is a high-efficiency, reliable and feasible method.
The invention provides a method and a thought for a method for catalytic hydrogenation reduction of algal toxins in water based on a supported precious metal catalyst, and a method and a way for realizing the technical scheme are many, the above description is only a preferred embodiment of the invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and embellishments can be made without departing from the principle of the invention, and the improvements and embellishments should also be regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A method for catalytic hydrogenation reduction of algal toxins in water based on a supported noble metal catalyst is characterized in that the supported noble metal catalyst is added into water containing microcystins, the pH value of the water is adjusted to 6.0-9.0, and hydrogen is introduced into the water to perform catalytic hydrogenation reduction reaction.
2. The method for catalytic hydrogenation reduction of algal toxins in water based on the supported noble metal catalyst of claim 1, wherein the supported noble metal catalyst comprises a carrier and noble metal particles supported on the carrier;
the carrier is any one of alumina, cerium oxide or titanium oxide;
the noble metal is any one of Pt, Rh or Pd;
the loading amount of the noble metal in the supported noble metal catalyst is 0.1-1 wt.%.
3. The method for catalytic hydrogenation reduction of algal toxins in water based on the supported noble metal catalyst of claim 1, wherein the microcystins are LR-type microcystins.
4. The method for catalytic hydrogenation reduction of algal toxins in water based on the supported noble metal catalyst as recited in claim 1, wherein the amount of the supported noble metal catalyst added to the water is 0.1-0.3 mg/ml.
5. The method for catalytic hydrogenation reduction of algal toxins in water based on the supported noble metal catalyst of claim 1, wherein the supported noble metal catalyst is prepared by the following steps:
(1) placing the carrier in a container, and then adding a salt or acid solution containing the noble metal;
(2) magnetically stirring the mixed solution obtained in the step (1), and adjusting the pH value to 10.5-11;
(3) filtering the solution obtained in the step (2), washing the solution to be neutral, drying the solution, and roasting the dried solution at 300-350 ℃ for 3-5 h;
(4) h, roasting the material obtained in the step (3) at 300-350 DEG C2And reducing for 2-3 h in the atmosphere to obtain the product.
6. The method for catalytic hydrogenation reduction of algal toxins in water based on the supported noble metal catalyst according to claim 5, wherein in the step (1), the salt or the acid solution of the noble metal is any one of chloropalladic acid, chloroplatinic acid or rhodium chloride.
7. The method for catalytic hydrogenation reduction of algal toxins in water based on the supported noble metal catalyst as claimed in claim 5, wherein in the step (2), 1M Na is adopted for pH adjustment2CO3And (3) solution.
8. The method for catalytic hydrogenation reduction of algal toxins in water based on the supported noble metal catalyst according to claim 5, wherein in the step (2), the stirring is performed for 1-2 hours before the pH value is adjusted, and the stirring is continued for 1-2 hours after the pH value is adjusted.
9. The method for catalytic hydrogenation reduction of algal toxins in water based on the supported noble metal catalyst as claimed in claim 5, wherein the drying temperature in the step (3) is 90-105 ℃.
10. The method for catalytic hydrogenation reduction of algal toxins in water based on the supported noble metal catalyst according to claim 5, wherein in the step (4), H is performed under normal pressure2At 25mLmin-1The flow rate of the reaction solution is introduced into a reduction furnace for reduction reaction.
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| CN113511765A (en) * | 2021-07-22 | 2021-10-19 | 杭州千岛湖丹然饮用水有限公司 | Drinking water filtering method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648057A (en) * | 2005-01-07 | 2005-08-03 | 南京大学 | Method for degradating microcystein -LR in water using radiation |
| WO2010104908A1 (en) * | 2009-03-11 | 2010-09-16 | LiveFuels, Inc. | Systems and methods for regulating algal biomass |
| CN101891295A (en) * | 2010-04-30 | 2010-11-24 | 南京大学 | Liquid-phase catalytical processing method for hexavalent chromium in water |
| WO2015108608A4 (en) * | 2013-11-04 | 2016-01-14 | Portland State University | Method of making a metallic composite and use thereof |
| CN105854900A (en) * | 2016-04-27 | 2016-08-17 | 厦门大学 | Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof |
-
2020
- 2020-12-11 CN CN202011457668.0A patent/CN112387277A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648057A (en) * | 2005-01-07 | 2005-08-03 | 南京大学 | Method for degradating microcystein -LR in water using radiation |
| WO2010104908A1 (en) * | 2009-03-11 | 2010-09-16 | LiveFuels, Inc. | Systems and methods for regulating algal biomass |
| CN101891295A (en) * | 2010-04-30 | 2010-11-24 | 南京大学 | Liquid-phase catalytical processing method for hexavalent chromium in water |
| WO2015108608A4 (en) * | 2013-11-04 | 2016-01-14 | Portland State University | Method of making a metallic composite and use thereof |
| CN105854900A (en) * | 2016-04-27 | 2016-08-17 | 厦门大学 | Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| WEERACHAWANASAK, P ET AL.: ""Effect of strong metal-support interaction on the catalytic performance of Pd/TiO2 in the liquid-phase semihydrogenation of phenylacetylene"", 《JOURNAL OF CATALYSIS》 * |
| YINGGAO ET AL.: ""Comparison of degradation mechanisms of microcystin-LR using nanoscale zero-valent iron (nZVI) and bimetallic Fe/Ni and Fe/Pd nanoparticles"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 周军燕等: ""Al2O3负载Pd催化剂对溴氯代乙酸的催化加氢脱卤研究"", 《环境化学》 * |
| 陶善倩: ""Pd/TiO2催化剂对水体中三氯生和么2,2，,4,4，-四溴联苯醚的催化加氢研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113511765A (en) * | 2021-07-22 | 2021-10-19 | 杭州千岛湖丹然饮用水有限公司 | Drinking water filtering method |
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