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WO2020093517A1 - Matériau photocatalytique pour une réduction et un retrait efficaces et sélectifs d'azote de nitrate dans de l'eau, et son procédé de préparation - Google Patents

Matériau photocatalytique pour une réduction et un retrait efficaces et sélectifs d'azote de nitrate dans de l'eau, et son procédé de préparation Download PDF

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Publication number
WO2020093517A1
WO2020093517A1 PCT/CN2018/120813 CN2018120813W WO2020093517A1 WO 2020093517 A1 WO2020093517 A1 WO 2020093517A1 CN 2018120813 W CN2018120813 W CN 2018120813W WO 2020093517 A1 WO2020093517 A1 WO 2020093517A1
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WIPO (PCT)
Prior art keywords
gdcro
photocatalytic material
nitrate nitrogen
water
nitrogen
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PCT/CN2018/120813
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English (en)
Chinese (zh)
Inventor
王津南
候志昂
吴超越
Original Assignee
南京大学
南京大学盐城环保技术与工程研究院
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Publication of WO2020093517A1 publication Critical patent/WO2020093517A1/fr

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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
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6522—Chromium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Definitions

  • the invention belongs to the field of environmental functional materials, and in particular relates to a photocatalytic material with high efficiency and selective photocatalytic reduction of nitrate nitrogen in water and a preparation method thereof.
  • Nitrate nitrogen in water will not only cause eutrophication of the water body, but also can be converted into nitrite nitrogen, which seriously threatens human health.
  • Many governments and organizations have adopted more and more stringent standards for the control of nitrate nitrogen concentration in water. In this way, the removal of nitrate nitrogen in water has become a hot and difficult point in the field of water treatment.
  • Traditional methods for removing nitrate nitrogen include ion exchange, reverse osmosis, electrolysis, biological denitrification, and chemical reduction. However, different levels of inefficiency, high cost and complex operating conditions limit the wide application of the above methods.
  • the essence of photocatalysis is that under the excitation condition of light, the "electron-hole pair" produced by the photocatalyst and the target substance undergo redox reactions on the valence band and conduction band of the catalyst, respectively.
  • the photocatalyst represented by titanium dioxide has been widely concerned and developed in the field of environmental protection due to its advantages of good stability, low cost, no toxicity and secondary pollution.
  • the photocatalyst treatment technology of titanium dioxide still has the following defects: (1) the photocatalytic reduction of pure titanium dioxide has a low efficiency of removing nitrate nitrogen; (2) the photocatalytic reduction of pure titanium dioxide photocatalyst has poor selectivity for nitrate, and it is easy to generate nitrous oxide with higher concentration Nitrogen, ammonia nitrogen and other by-products; (3) The method of controlling the morphology of titanium dioxide and exposing its highly catalytically active crystal planes to prepare nano-titanium dioxide is cumbersome and time-consuming, and still has the problem of more by-products.
  • the Chinese patent with the patent application number 2006100461728 discloses a method for photocatalytic removal of nitrogen in water.
  • the patent discloses a method of using metal-supported titanium dioxide nanocatalyst or nitrogen-doped titanium dioxide composite catalyst to remove dissolved oxygen by passing nitrogen or argon Under the conditions, the photocatalytic oxidation of ammonia nitrogen and the photocatalytic reduction of oxidation nitrogen are coupled, with nitrogen as the target product, and the nitrogen-containing components are taken out of the water.
  • the catalytic material disclosed in this patent has a total nitrogen removal rate of only 38% after loading with precious metal silver (ammonia nitrogen and nitrous nitrogen removal rates are 48% and 27%, respectively).
  • the Chinese patent with patent application number 201610891842 discloses a method for photocatalytic reduction of nitrate nitrogen in water.
  • the patent discloses an Ag-Ag 2 O / TiO 2 composite photocatalyst agent, which is used as an electron donor in formic acid In the case of a photocatalytic reduction of nitrate nitrogen in water.
  • the preparation process of the catalytic material involved in this patent is cumbersome, takes a long time (at least 15 hours or more is required), and has low output, making it difficult to prepare and apply it on a large scale.
  • the Chinese patent with the patent application number 2015102738202 discloses a precious metal nanoparticle-selectively modified titanium dioxide material and its preparation method and application.
  • the patent discloses a preparation method and application of a precious metal nanoparticle-selectively modified titanium dioxide-based photocatalytic material The reduction and removal of nitrate nitrogen in water.
  • This material first needs to prepare nano- or micro-scale titanium dioxide crystals with excellent surface growth.
  • the reactants need to be kept at 80-240 ° C for 48-96 hours. After that, the product needs to be washed 5-8 times, dried for 10 hours and then ground. After the precious metal modification, the steps of water washing, drying and grinding are required again.
  • the whole preparation process has complicated steps and takes a long time. Although it has a high catalytic conversion rate, it does not necessarily have a high selectivity, and the stability of the catalyst has not been evaluated.
  • the purpose of the present invention is to solve the problems of low efficiency, poor selectivity and difficulty in controlling the removal of nitrate nitrogen in the current photocatalyst of titanium dioxide, and to provide a high-efficiency selective photocatalytic material for reducing nitrate nitrogen in water and a preparation method thereof .
  • a high-efficiency selective reduction method for preparing photocatalytic material for removing nitrate nitrogen in water includes the following steps:
  • step (3) Place the GdCrO 3 powder prepared in step (3) in a palladium chloride solution, add formic acid and irradiate with ultraviolet light, palladium chloride is reduced to palladium elemental and deposited on the surface of GdCrO 3 , and finally centrifuged, washed, After drying, the photocatalytic material Pd / GdCrO 3 is prepared .
  • the preparation method of the photocatalytic material for efficiently and selectively reducing nitrate nitrogen in water according to the present invention is that the gadolinium nitrate nonahydrate, chromium trioxide and urea in the step (1)
  • the molar ratio is 1: (0.5-1): 4.
  • a method for preparing a photocatalytic material for efficiently and selectively reducing nitrate nitrogen in water according to the present invention is that the volume ratio of anhydrous ethanol to the mixed reactant in the step (1) is 1 :2.
  • the method for preparing a photocatalytic material for efficiently and selectively reducing nitrate nitrogen in water is that the heating temperature of the muffle furnace in the step (2) is 800 ° C, and the heating rate is It is 5-8 °C / min, and the reaction time is 4h.
  • the technical solution for further solving is that the molar ratio of formic acid to palladium chloride in the step (4) is (2- 4): 1.
  • the method for preparing a photocatalytic material for efficiently and selectively reducing nitrate nitrogen in water according to the present invention has a technical solution for further solving that the mass ratio of palladium to GdCrO 3 in the step (4) is (0.5-2 ): 100; the ultraviolet light irradiation time is 100-120 min.
  • the photocatalytic material is Pd nanoparticles and composite GdCrO 3, 3 having an irregular GdCrO nano Plate-like morphology, Pd is attached to the surface of the GdCrO 3 in the form of elemental nanoparticles, and the average diameter of Pd in the photocatalytic material is 5.7 nm.
  • the photocatalytic material prepared above needs to be used in a liquid environment and can be reduced and removed Nitrate nitrogen in water.
  • the invention uses chromium trioxide, gadolinium nitrate, urea, absolute ethanol, palladium chloride, formic acid and the like as raw materials and can be prepared by calcining at high temperature for a short time, because the prepared catalyst has a relatively negative conduction band value (-2.02 V vs NHE), the conduction band electron reduction ability is extremely strong, nitrate nitrogen is mainly reduced by electrons in the conduction band, which improves the efficiency of photocatalytic reduction of nitrate, and the load of Pd not only further improves the photocatalytic efficiency of GdCrO 3 , And it is conducive to the conversion of nitrous nitrogen to nitrogen, which significantly improves the selectivity of photocatalytic reduction of nitrate.
  • the new GdCrO 3 photocatalytic material prepared by the present invention has the following advantages compared with the traditional titanium dioxide-based catalyst:
  • the prepared photocatalytic material has high reduction catalytic activity and has a faster reaction rate.
  • the removal rate of nitrate nitrogen and the selectivity of generating nitrogen are high, and the production of by-products such as nitrous nitrogen and ammonia nitrogen is low.
  • FIG. 1 (a) is an SEM image of GdCrO 3 according to the present invention; (b) is a TEM image of de GdCrO 3 according to the present invention; (c) is a TEM image of Pd / GdCrO 3 according to the present invention ; (d) Pd nanoparticles of the present invention, the particle size distribution; (e) according to the present invention, Pd / GdCrO HRTEM FIG. 3; (f) of the present invention Pd / GdCrO EDS 3 of Figure.
  • FIG. 2 is a GdCrO 3 electron spectrum after Pd loading and a 3d orbit electron spectrum of Pd according to the present invention.
  • FIG. 3 is a schematic diagram of the photocatalytic reaction device of the present invention.
  • FIG. 4 is a graph showing the effect of GdCrO 3 photocatalytic reduction of nitrate nitrogen in water in Comparative Example 1.
  • FIG. 5 is an effect diagram of 0.5% wt Pd / GdCrO 3 photocatalytic reduction of nitrate nitrogen in water in Example 2.
  • FIG. 5 is an effect diagram of 0.5% wt Pd / GdCrO 3 photocatalytic reduction of nitrate nitrogen in water in Example 2.
  • FIG. 6 is a graph of the effect of 1% wt Pd / GdCrO 3 photocatalytic reduction of nitrate nitrogen in water in Example 3.
  • FIG. 6 is a graph of the effect of 1% wt Pd / GdCrO 3 photocatalytic reduction of nitrate nitrogen in water in Example 3.
  • FIG. 7 is a graph of the effect of 2% wt Pd / GdCrO 3 photocatalytic reduction of nitrate nitrogen in water in Example 4.
  • FIG. 8 is a graph of the effect of recycling 1% wt Pd / GdCrO 3 photocatalytic reduction of nitrate nitrogen in water in Example 5.
  • FIG. 8 is a graph of the effect of recycling 1% wt Pd / GdCrO 3 photocatalytic reduction of nitrate nitrogen in water in Example 5.
  • Example 9 is an XPS diagram of the material in Example 5 before and after the reaction.
  • FIG. 10 is an XRD pattern of the material before and after the reaction in Example 5.
  • a high-efficiency selective reduction method for preparing photocatalytic material for removing nitrate nitrogen in water includes the following steps:
  • step (3) Add 2g of the GdCrO 3 powder prepared in step (3) to the palladium chloride solution, add formic acid as an electron donor to reduce palladium chloride to palladium elemental substance by ultraviolet light and deposit it on the surface of GdCrO 3 to obtain Pd / GdCrO 3 , Finally, Pd / GdCrO 3 photocatalytic material is obtained by centrifugation, washing and drying; the mass ratio of palladium and GdCrO 3 in palladium chloride is 0.5: 100, the molar ratio of formic acid and palladium chloride is 2: 1, and the light time is 120min.
  • the prepared material contains elements such as Gd, Cr, O, Pd, etc.
  • GdCrO 3 has an irregular nano-sheet morphology, Pd
  • the nanoparticles in elemental form are attached to the surface of the GdCrO 3 and the average diameter of Pd is 5.7 nm.
  • a high-efficiency selective reduction method for preparing photocatalytic material for removing nitrate nitrogen in water includes the following steps:
  • step (4) Put the sodium nitrate solution with nitrate concentration of 50mg / L (0.8mmol) in the photoreactor, add 0.5wt% of the Pd / GdCrO3 catalyst prepared in step (4), and the dosage is 0.5g / L. Under the condition of magnetic stirring speed of 350rpm, dark adsorption for 30min, and then add 1mL of formic acid solution, the concentration of the formic acid solution is 1mol / L; turn on the cooling and water bath device to maintain the reaction temperature at 25 °C, turn on the ultraviolet light source of 350W high pressure mercury lamp for photocatalysis Reducing nitrate nitrogen reaction, the time is 100min.
  • the denitrification effect is shown in Figure 5.
  • the removal rate of nitrate by GdCrO 3 loaded with 0.5wt% Pd reached 92.8%, and the ammonia nitrogen produced during the reaction has been maintained at a low level of less than 1 %, The nitrous nitrogen content was also significantly inhibited, and the content was only 5.1%. Due to the selective conversion of nitrous nitrogen to ammonia nitrogen under the catalytic action of Pd, the nitrogen selectivity was greatly increased to 94.1%. It fully shows that the loading of 0.5wt% Pd not only improves the efficiency of photocatalytic reduction of nitrate, but also improves the nitrogen selectivity.
  • step (4) Put the sodium nitrate solution with a nitrate concentration of 50 mg / L (0.8 mmol) in the photoreactor, add 1 wt% of the Pd / GdCrO 3 catalyst prepared in step (4), and the dosage is 0.5 g / L. Under the condition of magnetic stirring speed of 350rpm, dark adsorption for 30min, and then add 1mL of formic acid solution, the concentration of the formic acid solution is 1mol / L; turn on the cooling and water bath device to maintain the reaction temperature at 25 °C, turn on the ultraviolet light source of 350W high pressure mercury lamp for photocatalysis Reducing nitrate nitrogen reaction, the time is 100min.
  • nitrate concentration of 50mg / L (0.8mmol) of sodium nitrate was placed photoreactor, 2wt% added in step (4)
  • step (4) Put the sodium nitrate solution with a nitrate concentration of 50 mg / L (0.8 mmol) in the photoreactor, add the 12 wt% Pd / GdCrO 3 catalyst prepared in step (4), and the dosage is 0.5 g / L. Under the condition of magnetic stirring speed of 350rpm, dark adsorption for 30min, and then add 1mL of formic acid solution, the concentration of the formic acid solution is 1mol / L; turn on the cooling and water bath device to maintain the reaction temperature at 25 °C, turn on the ultraviolet light source of 350W high pressure mercury lamp for photocatalysis Reducing nitrate nitrogen reaction, the time is 100min.
  • a high-efficiency selective reduction method for preparing photocatalytic material for removing nitrate nitrogen in water includes the following steps:
  • the photocatalytic materials prepared by the present invention for high-efficiency selective reduction and removal of nitrate nitrogen in water have simple preparation, high yield, high reduction catalytic activity, and fast reaction rate.
  • the removal rate of nitrate nitrogen and the selectivity of nitrogen reached 98.7% and 100%, respectively, and the effect of 6 cycles of use was not significantly reduced, and it had good catalytic activity and stability.

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Abstract

L'invention concerne un procédé de préparation d'un matériau photocatalytique pour une réduction et un retrait efficaces et sélectifs d'azote de nitrate dans de l'eau, comprenant les étapes suivantes : mélanger du nonahydrate de nitrate de gadolinium, du trioxyde de chrome et de l'urée et placer le mélange dans un creuset en alumine, puis ajouter de l'éthanol absolu et agiter le mélange de manière uniforme ; placer le creuset dans un four à moufle pour effectuer une calcination ; broyer le solide obtenu après calcination dans un mortier pour obtenir de la poudre de GdCrO3 ; ajouter la poudre de GdCrO3 obtenue à une solution de chlorure de palladium, puis ajouter de l'acide méthanoïque Et effectuer une irradiation par lumière UV, ce par quoi le chlorure de palladium est réduit à une substance simple de palladium, qui est déposée sur la surface de GdCrO3, obtenir Pd/GdCrO3 ; et enfin, réaliser une centrifugation, le lavage et le séchage.
PCT/CN2018/120813 2018-11-06 2018-12-13 Matériau photocatalytique pour une réduction et un retrait efficaces et sélectifs d'azote de nitrate dans de l'eau, et son procédé de préparation WO2020093517A1 (fr)

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CN201811311199.4A CN109225215A (zh) 2018-11-06 2018-11-06 一种高效选择性光催化还原水中硝态氮的光催化材料及其制备方法
CN201811311199.4 2018-11-06

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CN117511432A (zh) * 2024-01-05 2024-02-06 山东旭贝新材料有限公司 转紫外透明型含氟聚合物膜及其制备方法

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CN110316895B (zh) * 2019-08-06 2021-11-30 东北师范大学 一种含高浓度硝酸盐工业废水的处理方法
CN113198515B (zh) * 2021-05-19 2023-07-28 上海城投原水有限公司 一种三元光催化剂及其制备方法与应用

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CN117511432B (zh) * 2024-01-05 2024-05-07 山东旭贝新材料有限公司 转紫外透明型含氟聚合物膜及其制备方法

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