WO2017025035A1 - 一种非均相催化臭氧化的纳米复合催化剂及其制备方法 - Google Patents

一种非均相催化臭氧化的纳米复合催化剂及其制备方法 Download PDF

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WO2017025035A1
WO2017025035A1 PCT/CN2016/094394 CN2016094394W WO2017025035A1 WO 2017025035 A1 WO2017025035 A1 WO 2017025035A1 CN 2016094394 W CN2016094394 W CN 2016094394W WO 2017025035 A1 WO2017025035 A1 WO 2017025035A1
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zro
carrier
nanocomposite catalyst
catalyst
nanocomposite
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French (fr)
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罗德智
李隽�
赵雪峰
许应玉
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雅本化学股份有限公司
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone

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  • the invention relates to the field of advanced oxidation technology such as catalyst and wastewater treatment, in particular to a nanocomposite catalyst for heterogeneously catalyzed ozonation, in particular to a Ni-ZrO 2 nanocomposite catalyst.
  • the invention further relates to a method of preparing a Ni-ZrO 2 nanocomposite catalyst.
  • catalytic ozonation technology came into being. Catalysts commonly used to catalyze ozonation are transition metal ions, metal oxides, and metal or metal oxides on the support, and transition metal ions are prone to secondary pollution problems.
  • Ni-ZrO 2 nanocomposite catalyst which is heterogeneously catalyzed by ozonation.
  • the present invention also provides a method of preparing a Ni-ZrO 2 nanocomposite catalyst.
  • a nanocomposite catalyst for heterogeneously catalyzed ozonation the catalyst being a Ni-ZrO 2 nanocomposite catalyst.
  • the mass fraction of Ni is 10%-20%.
  • the invention also provides a method for preparing the above nanocomposite catalyst, comprising the steps of:
  • Step (1) Preparation of ZrO 2 carrier by sol-gel method:
  • Step (2) Preparation of Ni-ZrO 2 nanocomposite catalyst by equal volume impregnation method:
  • Step (. 1) ZrO 2 carrier prepared in drying, were weighed volume impregnation of the ZrO 2 carrier, Ni (NO 3) 2 ⁇ 6H 2 O dissolved in deionized water and the like of the ZrO 2 support, impregnating solution adjusted The pH is stirred and the impregnation is completed. The impregnated ZrO 2 carrier is dried and calcined to obtain a surface-agglomerated nickel oxide ZrO 2 composite; then the surface-agglomerated nickel oxide ZrO 2 composite is subjected to high-temperature reduction to finally prepare. Ni-ZrO 2 nanocomposite catalyst.
  • the cetyltrimethylammonium bromide is used in an amount of 1 g to 4 g
  • the deionized water is used in an amount of 50 ml to 200 ml
  • the ZrOCl 2 ⁇ 8H 2 O solution is used in an amount of 25 ml.
  • the pH of the mixture was adjusted to 9-10 using 20% to 30% aqueous ammonia
  • the mixture was aged at 40 ° C - 60 ° C for 20 h - 24 h to obtain a gel.
  • the vacuum dried gel is placed in a muffle furnace and calcined at 500 ° C - 700 ° C for 5 h - 8 h, and the obtained ZrO 2 support is ground into a powder.
  • the ZrO 2 carrier is dried at 200 ° C - 300 ° C for 2 h - 4 h; 10 g - 20 g of the ZrO 2 carrier, 5 g - 15 g of Ni(NO 3 ) 2 ⁇ 6H 2 are weighed, respectively.
  • O is dissolved in 10 ml to 20 ml of deionized water in an equal volume to impregnate the ZrO 2 support, the pH of the impregnation solution is adjusted to 2 by nitric acid, and magnetically stirred at 50 ° C to 80 ° C for 6 h to 12 h to complete the impregnation.
  • the impregnated ZrO 2 carrier is dried at 100 ° C - 120 ° C for 2 h - 6 h, and then calcined in a muffle furnace at 500 ° C - 700 ° C for 5 h - 8 h at a heating rate of 5 ° C / min to obtain a surface attached.
  • ZrO 2 composite of nickel oxide is obtained by calcined in a muffle furnace at 500 ° C - 700 ° C for 5 h - 8 h at a heating rate of 5 ° C / min.
  • the surface-agglomerated nickel oxide ZrO 2 composite is placed in a tube furnace at a high temperature of 300 ° C to 400 ° C for 1 h to 2 h in an Ar/H 2 atmosphere, and the obtained Ni- The ZrO 2 nanocomposite catalyst was ground into a powder.
  • the invention also provides the use of the above nanocomposite catalyst in heterogeneous catalytic ozonation.
  • the beneficial technical effect of the technical solution of the present invention is that the Ni-ZrO 2 nanocomposite catalyst of the invention has high catalytic activity and significantly improves the ozonization efficiency, and the Ni-ZrO 2 nanocomposite catalyst does not contain Transition metal ions, so there is no secondary pollution problem during the treatment of wastewater.
  • the method for preparing the Ni-ZrO 2 nanocomposite catalyst of the invention is simple in process, has no safety hazard in the preparation process, does not generate harmful substances, and thus does not pollute the environment.
  • Figure 1a is an XRD image of the ZrO 2 support (a) and the Ni-ZrO 2 nanocomposite catalyst (b) prepared in Example 1.1;
  • Figure 1b is a SEM picture of the ZrO 2 support prepared in Example 1.1;
  • Figure 1c is a SEM image of the Ni-ZrO 2 nanocomposite catalyst prepared in Example 1.1;
  • Figure 2b is a SEM picture of the ZrO 2 support prepared in Example 1.2;
  • Figure 3a is an XRD image of the ZrO 2 support (a) and the Ni-ZrO 2 nanocomposite catalyst (b) prepared in Example 1.3;
  • Figure 3b is a SEM picture of the ZrO 2 support prepared in Example 1.3;
  • Figure 3c is a SEM image of the Ni-ZrO 2 nanocomposite catalyst prepared in Example 1.3;
  • Figure 4a shows the degradation profile of salicylic acid concentration in Example 2.1.1 under ozonation (b) of the ozonated (a) and Ni-ZrO2 nanocomposite catalysts;
  • Figure 4b shows the degradation profile of the salicylic acid concentration in Example 2.1.2 under ozonation (b) of the ozonated (a) and Ni-ZrO 2 nanocomposite catalysts;
  • Figure 4c shows the degradation profile of salicylic acid concentration in Example 2.1.3 under ozonation (b) of the ozonated (a) and Ni-ZrO 2 nanocomposite catalysts;
  • Figure 5a shows the degradation profile of salicylic acid concentration in Example 2.2.1 under ozonation (b) of the ozonated (a) and Ni-ZrO 2 nanocomposite catalysts;
  • Figure 5b shows the degradation profile of salicylic acid concentration in Example 2.2.2 under ozonation (b) of the ozonated (a) and Ni-ZrO 2 nanocomposite catalysts;
  • Figure 5c shows the degradation profile of salicylic acid concentration in Example 2.2.3 under ozonation (b) of the ozonated (a) and Ni-ZrO 2 nanocomposite catalysts;
  • Figure 6a shows the degradation profile of salicylic acid concentration in Example 2.3.1 under ozonation (b) of the ozonated (a) and Ni-ZrO 2 nanocomposite catalysts;
  • Figure 6b shows the degradation profile of salicylic acid concentration in Example 2.3.2 under ozonation (b) of the ozonated (a) and Ni-ZrO 2 nanocomposite catalysts;
  • Figure 6c is a graph showing the degradation of salicylic acid in Example 2.3.3 under ozonation (b) of the ozonated (a) and Ni-ZrO 2 nanocomposite catalysts;
  • the main raw materials used in the present invention are as follows:
  • Vacuum drying oven DZF-6090, Shanghai Qixin Scientific Instrument Co., Ltd.
  • Tube furnace MXG1600-60, Shanghai Chuangsai Scientific Instrument Co., Ltd.
  • the above ZrO 2 carrier was dried at 200 ° C for 4 h, and 10 g of ZrO 2 carrier and 5.4 g of Ni(NO 3 ) 2 ⁇ 6H 2 O were respectively dissolved in 15 ml of deionized water to be impregnated with ZrO 2 carrier, and impregnated by nitric acid.
  • the pH of the liquid was 2, the impregnation liquid was magnetically stirred at 50 ° C for 12 h to completely impregnate, and the impregnated ZrO 2 carrier was dried at 100 ° C for 6 h at a heating rate of 5 ° C / min at 500 ° C in a muffle furnace.
  • Ni-ZrO 2 nanocomposite catalyst was ground into a powder in which the mass fraction of Ni was 10%.
  • Figure 1a is an XRD picture of the ZrO 2 support (a) and the Ni-ZrO 2 nanocomposite catalyst (b) prepared in Example 1.1;
  • Figure 1b is an SEM picture of the ZrO 2 support prepared in Example 1.1;
  • Figure 1c is Example 1.1 SEM picture of the prepared Ni-ZrO 2 nanocomposite catalyst.
  • the invention adopts a sol-gel method to prepare a ZrO 2 carrier, and prepares a Ni-ZrO 2 nanocomposite catalyst by an equal volume dip coating.
  • Ni is uniformly dispersed on the ZrO 2 carrier, and when the 2 ⁇ is 45°, 53°, 76° is the Ni crystal phase; 2 ⁇ is 30°, 50°, 60° is a tetragonal phase ZrO 2 .
  • CAB cetyltrimethylammonium bromide
  • 20 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 100 ml of deionized water, and then 50 ml of a 0.5 M solution of ZrOCl 2 ⁇ 8H 2 O was added and stirred thoroughly to obtain a mixed solution, which was slowly added dropwise.
  • 25% ammonia water was used to adjust the pH of the mixture to 9 to form a sol-gel.
  • the mixture was aged at 50 ° C for 22 h to obtain a gel.
  • the excess chloride ions in the gel were washed by deionized water and dried under vacuum.
  • the inside of the box was dried at 90 ° C for 12 h, and then the vacuum dried gel was placed in a muffle furnace and calcined at 600 ° C for 6 h, and the obtained ZrO 2 support was ground into a powder.
  • the above ZrO 2 carrier was dried at 250 ° C for 3 h, and 10 g of ZrO 2 carrier and 8.7 g of Ni(NO 3 ) 2 ⁇ 6H 2 O were respectively dissolved in 15 ml of deionized water to be impregnated with ZrO 2 carrier, and impregnated by nitric acid.
  • the pH of the liquid was 2, the impregnation liquid was magnetically stirred at 60 ° C for 12 h to completely impregnate, and the impregnated ZrO 2 carrier was dried at 110 ° C for 5 h at a heating rate of 5 ° C / min at 600 ° C in a muffle furnace.
  • Ni-ZrO 2 nanocomposite catalyst was ground into a powder in which the mass fraction of Ni was 15%.
  • FIG. 2a is an XRD picture of the ZrO 2 support (a) and the Ni-ZrO 2 nanocomposite catalyst (b) prepared in Example 1.2;
  • FIG. 2b is an SEM picture of the ZrO 2 support prepared in Example 1.2; and
  • FIG. 2c is Example 1.2. SEM picture of the prepared Ni-ZrO 2 nanocomposite catalyst.
  • the invention adopts a sol-gel method to prepare a ZrO 2 carrier, and prepares a Ni-ZrO 2 nanocomposite catalyst by an equal volume dip coating.
  • Ni is uniformly dispersed on the ZrO 2 carrier, and when the 2 ⁇ is 45°, 53°, 76° is the Ni crystal phase; 2 ⁇ is 30°, 50°, 60° is a tetragonal phase ZrO 2 .
  • CTAB cetyltrimethylammonium bromide
  • the above ZrO 2 carrier was dried at 200 ° C for 4 h, and 10 g of ZrO 2 carrier and 12.3 g of Ni(NO 3 ) 2 ⁇ 6H 2 O were respectively dissolved in 15 ml of deionized water to be impregnated with ZrO 2 carrier, and impregnated by nitric acid.
  • the pH of the liquid was 2, the impregnation liquid was magnetically stirred at 70 ° C for 10 h to completely impregnate, and the impregnated ZrO 2 carrier was dried at 100 ° C for 6 h at a heating rate of 5 ° C / min at 550 ° C in a muffle furnace.
  • Ni-ZrO 2 nanocomposite catalyst was ground into a powder in which the mass fraction of Ni was 20%.
  • Figure 3a is an XRD picture of the ZrO 2 support (a) and the Ni-ZrO 2 nanocomposite catalyst (b) prepared in Example 1.3;
  • Figure 3b is an SEM picture of the ZrO 2 support prepared in Example 1.3;
  • Figure 3c is Example 1.3 SEM picture of the prepared Ni-ZrO 2 nanocomposite catalyst.
  • the invention adopts a sol-gel method to prepare a ZrO 2 carrier, and prepares a Ni-ZrO 2 nanocomposite catalyst by an equal volume dip coating.
  • Ni is uniformly dispersed on the ZrO 2 carrier, and when the 2 ⁇ is 45°, 53°, 76° is the Ni crystal phase; 2 ⁇ is 30°, 50°, 60° is a tetragonal phase ZrO 2 .
  • Heterogeneous catalytic ozonation treatment of simulated wastewater specifically a Ni-ZrO 2 nanocomposite catalyst for catalytic ozonation, by adding Ni-ZrO2 nanocomposite catalyst to the ozonation unit, thereby enhancing ozonation degradation Simulate salicylic acid in wastewater.
  • the detector is an ultraviolet visible absorption detector (DAD) with a detection wavelength of 296 nm. From the salicylic acid standard curve, the concentration before and after degradation can be calculated, and the degradation rate can be calculated to measure the catalytic ozonation efficiency.
  • DAD ultraviolet visible absorption detector
  • the detector is an ultraviolet visible absorption detector (DAD) with a detection wavelength of 296 nm. From the salicylic acid standard curve, the concentration before and after degradation can be calculated, and the degradation rate can be calculated to measure the catalytic ozonation efficiency.
  • DAD ultraviolet visible absorption detector
  • the detector is an ultraviolet visible absorption detector (DAD) with a detection wavelength of 296 nm. From the salicylic acid standard curve, the concentration before and after degradation can be calculated, and the degradation rate can be calculated to measure the catalytic ozonation efficiency.
  • DAD ultraviolet visible absorption detector
  • Figure 4a shows the degradation profile of salicylic acid concentration in ozonation (a) and o-zrO 2 nanocomposite catalyst ozonation (b) in Example 2.1.1;
  • Figure 4b shows in Example 2.1.2 Degradation profile of salicylic acid concentration under ozonation (b) of ozonated (a) and Ni-ZrO 2 nanocomposite catalysts alone;
  • Figure 4c shows salicylic acid concentration in ozonation alone in Example 2.1.3 (a And the degradation profile of the Ni-ZrO 2 nanocomposite catalyst under ozonation (b).
  • the salicylic acid removal rate increased from 76% to 85%, 91% and 95%, respectively. Increased ozone efficiency.
  • the detector is an ultraviolet visible absorption detector (DAD) with a detection wavelength of 296 nm. From the salicylic acid standard curve, the concentration before and after degradation can be calculated, and the degradation rate can be calculated to measure the catalytic ozonation efficiency.
  • DAD ultraviolet visible absorption detector
  • the detector is an ultraviolet visible absorption detector (DAD) with a detection wavelength of 296 nm. From the salicylic acid standard curve, the concentration before and after degradation can be calculated, and the degradation rate can be calculated to measure the catalytic ozonation efficiency.
  • DAD ultraviolet visible absorption detector
  • the detector is an ultraviolet visible absorption detector (DAD) with a detection wavelength of 296 nm. From the salicylic acid standard curve, the concentration before and after degradation can be calculated, and the degradation rate can be calculated to measure the catalytic ozonation efficiency.
  • DAD ultraviolet visible absorption detector
  • Figure 5a shows the degradation profile of salicylic acid concentration in Example 2.2.1 under ozonation (b) of the ozonated (a) and Ni-ZrO 2 nanocomposite catalysts alone;
  • Figure 5b shows the results in Example 2.2.2.
  • Figure 5c shows salicylic acid concentration in ozonation alone in Example 2.2.3 (a And the degradation profile of the Ni-ZrO 2 nanocomposite catalyst under ozonation (b).
  • the salicylic acid removal rate increased from 76% to 90%, 94% and 98%, respectively. Increased ozone efficiency.
  • the detector is an ultraviolet visible absorption detector (DAD) with a detection wavelength of 296 nm. From the salicylic acid standard curve, the concentration before and after degradation can be calculated, and the degradation rate can be calculated to measure the catalytic ozonation efficiency.
  • DAD ultraviolet visible absorption detector
  • the detector is an ultraviolet visible absorption detector (DAD) with a detection wavelength of 296 nm. From the salicylic acid standard curve, the concentration before and after degradation can be calculated, and the degradation rate can be calculated to measure the catalytic ozonation efficiency.
  • DAD ultraviolet visible absorption detector
  • the detector is an ultraviolet visible absorption detector (DAD) with a detection wavelength of 296 nm. From the salicylic acid standard curve, the concentration before and after degradation can be calculated, and the degradation rate can be calculated to measure the catalytic ozonation efficiency.
  • DAD ultraviolet visible absorption detector
  • Figure 6a shows the degradation profile of salicylic acid concentration in Example 2.3.1 under ozonation (b) of the ozonated (a) and Ni-ZrO 2 nanocomposite catalysts alone;
  • Figure 6b shows the example in Example 2.3.2 The degradation profile of salicylic acid concentration under ozonation (b) of ozonized (a) and Ni-ZrO 2 nanocomposite catalysts alone;
  • Figure 6c shows the salicylic acid concentration in ozonation alone in Example 2.3.3 (a And the degradation profile of the Ni-ZrO 2 nanocomposite catalyst under ozonation (b).
  • the salicylic acid removal rate increased from 76% to 92%, 95% and 98%, respectively. Increased ozone efficiency.

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Abstract

一种非均相催化臭氧化的纳米复合催化剂及其制备方法。催化剂为Ni-ZrO 2纳米复合催化剂。先采用溶胶凝胶法制备ZrO 2载体，再采用等体积浸渍法制备Ni-ZrO 2纳米复合催化剂。

Description

一种非均相催化臭氧化的纳米复合催化剂及其制备方法 技术领域
本发明涉及催化剂、废水处理等高级氧化技术领域，尤其涉及一种非均相催化臭氧化的纳米复合催化剂，具体为Ni-ZrO2纳米复合催化剂。本发明还涉及一种制备Ni-ZrO2纳米复合催化剂的方法。
背景技术
臭氧能有效用于废水中有机物的降解和脱色，基于其具有较高的氧化电位(E＝2.08V)，可以对有机物进行直接或间接氧化。然而，由于臭氧在水中的溶解度比较低，在降解芳香类有机物时，不能彻底将其矿化而产生小分子有机物如醛、酮羧酸等，进而抑制臭氧化效率，因而，单独的臭氧化过程难以达到较好的降解效果。为了进一步提高臭氧化效率，催化臭氧化技术应运而生。常用于催化臭氧化的催化剂有过渡金属离子、金属氧化物和载体上的金属或金属氧化物，而过渡金属离子容易造成二次污染问题。
发明内容
针对现有技术的不足，本发明的目的在于提供一种非均相催化臭氧化的Ni-ZrO2纳米复合催化剂。本发明还提供一种制备Ni-ZrO2纳米复合催化剂的方法。
为了实现上述目的，本发明采用以下技术方案：
一种非均相催化臭氧化的纳米复合催化剂，所述催化剂为Ni-ZrO2纳米复合催化剂。
进一步地，Ni的质量分数为10％-20％。
本发明还提供制备上述纳米复合催化剂的方法，包含以下步骤：
步骤(1)：溶胶凝胶法制备ZrO2载体：
将十六烷基三甲基溴化铵溶解于去离子水中，然后加入ZrOCl2·8H2O溶液并不断搅拌使其充分溶解得到混合液，调节所述混合液的pH，然后通过老化、洗涤、烘干、煅烧制备ZrO2载体；
步骤(2)：等体积浸渍法制备Ni-ZrO2纳米复合催化剂：
将步骤(1)中制备的ZrO2载体烘干，分别称取所述ZrO2载体、Ni(NO3)2·6H2O溶于去离子水中等体积浸渍所述ZrO2载体，调节浸渍液的pH并搅拌使得浸渍完全，浸渍后的ZrO2载体通过烘干、煅烧制得表面附聚氧化镍的ZrO2复合物；然后将所述表面附聚氧化镍的ZrO2复合物高温还原最终制备Ni-ZrO2纳米复合催化剂。
进一步地，在步骤(1)中，所述十六烷基三甲基溴化铵的用量为1g-4g，去离子水的用量为50ml-200ml，ZrOCl2·8H2O溶液的用量为25ml-100ml，摩尔浓度为0.5M；使用20％-30％的氨水调节所述混合液的pH为9-10；将所述混合液于40℃-60℃老化20h-24h得到凝胶。
进一步地，通过去离子水洗涤所述凝胶中多余的氯离子，并在真空干燥箱内于80℃-110℃烘干10h-12h。
进一步地，将真空干燥后的凝胶置于马弗炉中于500℃-700℃煅烧5h-8h，并将制得的ZrO2载体研磨成粉。
进一步地，在步骤(2)中，将ZrO2载体于200℃-300℃烘干2h-4h；分别称取10g-20g所述ZrO2载体、5g-15g Ni(NO3)2·6H2O溶于10ml-20ml去离子水中等体积浸渍所述ZrO2载体，通过硝酸调节所述浸渍液的pH为2，并于50℃-80℃磁力搅拌6h-12h以使得浸渍完全。
进一步地，浸渍后的ZrO2载体于100℃-120℃烘干2h-6h，随后以5℃/min的升温速率于500℃-700℃在马弗炉中煅烧5h-8h，制得表面附聚氧化镍的ZrO2复合物。
进一步地，将所述表面附聚氧化镍的ZrO2复合物置于管式炉中在 Ar/H2气氛中于300℃-400℃下高温还原1h-2h，并将制得的所述Ni-ZrO2纳米复合催化剂研磨成粉。
本发明还提供一种上述纳米复合催化剂在非均相催化臭氧化中的应用。
与现有技术相比，本发明的技术方案的有益技术效果为：本发明的Ni-ZrO2纳米复合催化剂催化活性高，显著提高了臭氧化效率，同时由于Ni-ZrO2纳米复合催化剂不包含过渡金属离子，因而在处理废水过程中不会造成二次污染问题。另外，本发明的制备Ni-ZrO2纳米复合催化剂的方法工艺简单，在制备过程中不存在安全隐患，不会产生有害物质，因而不会对环境造成污染。
附图说明
图1a是实施例1.1制备的ZrO2载体(a)和Ni-ZrO2纳米复合催化剂(b)的XRD图片；
图1b是实施例1.1制备的ZrO2载体的SEM图片；
图1c是实施例1.1制备的Ni-ZrO2纳米复合催化剂的SEM图片；
图2a是实施例1.2制备的ZrO2载体(a)和Ni-ZrO2纳米复合催化剂(b)的XRD图片；
图2b是实施例1.2制备的ZrO2载体的SEM图片；
图2c是实施例1.2制备的Ni-ZrO2纳米复合催化剂的SEM图片；
图3a是实施例1.3制备的ZrO2载体(a)和Ni-ZrO2纳米复合催化剂(b)的XRD图片；
图3b是实施例1.3制备的ZrO2载体的SEM图片；
图3c是实施例1.3制备的Ni-ZrO2纳米复合催化剂的SEM图片；
图4a显示了实施例2.1.1中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；
图4b显示了实施例2.1.2中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2 纳米复合催化剂臭氧化(b)下的降解曲线图；
图4c显示了实施例2.1.3中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；
图5a显示了实施例2.2.1中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；
图5b显示了实施例2.2.2中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；
图5c显示了实施例2.2.3中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；
图6a显示了实施例2.3.1中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；
图6b显示了实施例2.3.2中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；
图6c显示了实施例2.3.3中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，下面结合实施例及附图，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
本发明中所使用的主要原材料如下：
十六烷基三甲基溴化铵：优级纯，Aladdin
ZrOCl2·8H2O：优级纯，Aladdin
氨水：分析纯，Aladdin
Ni(NO3)2·6H2O：分析纯，Aladdin
硝酸：分析纯，Aladdin
真空干燥箱：DZF-6090，上海齐欣科学仪器有限公司
马弗炉：SRJX-4-13，上海合恒仪器设备有限公司
管式炉：MXG1600-60，上海创赛科学仪器有限公司
1、制备实施例
实施例1.1
1.溶胶凝胶法制备ZrO2载体
将1g十六烷基三甲基溴化铵(CTAB)溶解于50ml去离子水中，然后加入25ml、0.5M的ZrOCl2·8H2O溶液并不断搅拌使其充分混合得到混合液，缓慢滴加20％的氨水以调节混合液pH为9，形成溶胶-凝胶，然后将混合液于40℃下老化24h后得到凝胶，通过去离子水清洗凝胶中多余的氯离子，并在真空干燥箱内于80℃下烘干12h，随后将真空干燥后的凝胶置于马弗炉中于500℃煅烧8h，并将制得的ZrO2载体研磨成粉。
2.等体积浸渍法制备Ni-ZrO2纳米复合催化剂
将上述ZrO2载体于200℃下烘干4h，分别称取10g ZrO2载体、5.4g Ni(NO3)2·6H2O溶于15ml去离子水中等体积浸渍ZrO2载体，通过硝酸调节浸渍液的pH为2，将浸渍液置于50℃下磁力搅拌12h以使得完全浸渍，浸渍后的ZrO2载体于100℃烘干6h，以5℃/min的升温速率于500℃在马弗炉中煅烧8h，制得表面附聚氧化镍的ZrO2复合物，随后将表面附聚氧化镍的ZrO2复合物置于管式炉中在Ar/H2气氛中于300℃下高温还原2h，并将制得的Ni-ZrO2纳米复合催化剂研磨成粉，其中Ni的质量分数为10％。
图1a是实施例1.1制备的ZrO2载体(a)和Ni-ZrO2纳米复合催化剂(b)的XRD图片；图1b是实施例1.1制备的ZrO2载体的SEM图片；图1c是实施例1.1制备的Ni-ZrO2纳米复合催化剂的SEM图片。
本发明采用溶胶凝胶法制备ZrO2载体，通过等体积浸渍涂覆制备Ni-ZrO2纳米复合催化剂。本发明所制备的负载型金属催化剂，经SEM和XRD表征可知，Ni在ZrO2载体上均匀分散，当2θ为45°、53°、76°是Ni晶相；2θ为30°、50°、60°是四方晶相ZrO2。
实施例1.2
1.溶胶凝胶法制备ZrO2载体
将2g十六烷基三甲基溴化铵(CTAB)溶解于100ml去离子水中，然后加入50ml、0.5M的ZrOCl2·8H2O溶液并不断搅拌使其充分混合得到混合液，缓慢滴加25％的氨水以调节混合液pH为9，形成溶胶-凝胶，然后将混合液于50℃下老化22h后得到凝胶，通过去离子水清洗凝胶中多余的氯离子，并在真空干燥箱内于90℃下烘干12h，随后将真空干燥后的凝胶置于马弗炉中于600℃煅烧6h，并将制得的ZrO2载体研磨成粉。
2.等体积浸渍法制备Ni-ZrO2纳米复合催化剂
将上述ZrO2载体于250℃下烘干3h，分别称取10g ZrO2载体、8.7g Ni(NO3)2·6H2O溶于15ml去离子水中等体积浸渍ZrO2载体，通过硝酸调节浸渍液的pH为2，将浸渍液置于60℃下磁力搅拌12h以使得完全浸渍，浸渍后的ZrO2载体于110℃烘干5h，以5℃/min的升温速率于600℃在马弗炉中煅烧7h，制得表面附聚氧化镍的ZrO2复合物，随后将表面附聚氧化镍的ZrO2复合物置于管式炉中在Ar/H2气氛中于300℃下高温还原2h，并将制得的Ni-ZrO2纳米复合催化剂研磨成粉，其中Ni的质量分数为15％。
图2a是实施例1.2制备的ZrO2载体(a)和Ni-ZrO2纳米复合催化剂(b)的XRD图片；图2b是实施例1.2制备的ZrO2载体的SEM图片；图2c是实施例1.2制备的Ni-ZrO2纳米复合催化剂的SEM图片。
本发明采用溶胶凝胶法制备ZrO2载体，通过等体积浸渍涂覆制备Ni-ZrO2纳米复合催化剂。本发明所制备的负载型金属催化剂，经SEM和XRD表征可知，Ni在ZrO2载体上均匀分散，当2θ为45°、53°、76°是Ni晶相；2θ为30°、50°、60°是四方晶相ZrO2。
实施例1.3
1.溶胶凝胶法制备ZrO2载体
将3g十六烷基三甲基溴化铵(CTAB)溶解于150ml去离子水中，然后加入75ml、0.5M的ZrOCl2·8H2O溶液并不断搅拌使其充分混合得到混 合液，缓慢滴加20％的氨水以调节混合液pH为10，形成溶胶-凝胶，然后将混合液于40℃下老化24h后得到凝胶，通过去离子水清洗凝胶中多余的氯离子，并在真空干燥箱内于100℃下烘干12h，随后将真空干燥后的凝胶置于马弗炉中于550℃煅烧8h，并将制得的ZrO2载体研磨成粉。
2.等体积浸渍法制备Ni-ZrO2纳米复合催化剂
将上述ZrO2载体于200℃下烘干4h，分别称取10g ZrO2载体、12.3g Ni(NO3)2·6H2O溶于15ml去离子水中等体积浸渍ZrO2载体，通过硝酸调节浸渍液的pH为2，将浸渍液置于70℃下磁力搅拌10h以使得完全浸渍，浸渍后的ZrO2载体于100℃烘干6h，以5℃/min的升温速率于550℃在马弗炉中煅烧8h，制得表面附聚氧化镍的ZrO2复合物，随后将表面附聚氧化镍的ZrO2复合物置于管式炉中在Ar/H2气氛中于300℃下高温还原2h，并将制得的Ni-ZrO2纳米复合催化剂研磨成粉，其中Ni的质量分数为20％。
图3a是实施例1.3制备的ZrO2载体(a)和Ni-ZrO2纳米复合催化剂(b)的XRD图片；图3b是实施例1.3制备的ZrO2载体的SEM图片；图3c是实施例1.3制备的Ni-ZrO2纳米复合催化剂的SEM图片。
本发明采用溶胶凝胶法制备ZrO2载体，通过等体积浸渍涂覆制备Ni-ZrO2纳米复合催化剂。本发明所制备的负载型金属催化剂，经SEM和XRD表征可知，Ni在ZrO2载体上均匀分散，当2θ为45°、53°、76°是Ni晶相；2θ为30°、50°、60°是四方晶相ZrO2。
2、应用实施例
非均相催化臭氧化处理模拟废水的工艺，具体来说是一种Ni-ZrO2纳米复合催化剂催化臭氧化的应用，通过向臭氧化装置中加入Ni-ZrO2纳米复合催化剂，进而提高臭氧化降解模拟废水中水杨酸。
实施例2.1
实施例2.1.1
称取500mg水杨酸(分析纯)溶解于1L蒸馏水中，配制成初始浓度为500mg/L的模拟废水；随后分别取两份500ml模拟废水于反应装置中， 一份单独通臭氧，另一份加入0.5g实施例1.1中所制得的Ni-ZrO2纳米复合催化剂，磁力搅拌均匀后通入质量流量为25mg/L的臭氧，并每隔15min取水样分析水中水杨酸含量。水杨酸含量用高效液相色谱(HPLC，Agilent1260)测定，色谱柱为Diamonsil C18(4.6×200mm)，流动相采用乙腈/0.05％的三氟乙酸水溶液＝8/2，流速为1ml/min，检测器为紫外可见吸收检测器(DAD)，检测波长为296nm。由水杨酸标准曲线可计算出降解前后的浓度，从而计算出降解率来衡量催化臭氧化效率。
实施例2.1.2
称取500mg水杨酸(分析纯)溶解于1L蒸馏水中，配制成初始浓度为500mg/L的模拟废水；随后分别取两份500ml模拟废水于反应装置中，一份单独通臭氧，另一份加入1.0g实施例1.1中所制得的Ni-ZrO2纳米复合催化剂，磁力搅拌均匀后通入质量流量为25mg/L的臭氧，并每隔15min取水样分析水中水杨酸含量。水杨酸含量用高效液相色谱(HPLC，Agilent1260)测定，色谱柱为Diamonsil C18(4.6×200mm),流动相采用乙腈/0.05％的三氟乙酸水溶液＝8/2，流速为1ml/min，检测器为紫外可见吸收检测器(DAD)，检测波长为296nm。由水杨酸标准曲线可计算出降解前后的浓度，从而计算出降解率来衡量催化臭氧化效率。
实施例2.1.3
称取500mg水杨酸(分析纯)溶解于1L蒸馏水中，配制成初始浓度为500mg/L的模拟废水；随后分别取两份500ml模拟废水于反应装置中，一份单独通臭氧，另一份加入1.5g实施例1.1中所制得的Ni-ZrO2纳米复合催化剂，磁力搅拌均匀后通入质量流量为25mg/L的臭氧，并每隔15min取水样分析水中水杨酸含量。水杨酸含量用高效液相色谱(HPLC，Agilent1260)测定，色谱柱为Diamonsil C18(4.6×200mm),流动相采用乙腈/0.05％的三氟乙酸水溶液＝8/2，流速为1ml/min，检测器为紫外可见吸收检测器(DAD)，检测波长为296nm。由水杨酸标准曲线可计算出降解前后的浓度，从而计算出降解率来衡量催化臭氧化效率。
图4a显示了实施例2.1.1中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2 纳米复合催化剂臭氧化(b)下的降解曲线图；图4b显示了实施例2.1.2中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；图4c显示了实施例2.1.3中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图。
在臭氧化降解模拟废水装置中加入的Ni-ZrO2纳米复合催化剂，在金属Ni表面，臭氧通过羟基自由基的产生将金属氧化，随后有机物分子在催化剂表面吸附后，发生电子迁移而氧化，将电子转移给还原催化剂，有机自由基组分从催化剂上脱附，在水溶液中被HO·或O3氧化。通过对比单独臭氧化和Ni-ZrO2添加量为1～3g/L的催化臭氧化对模拟废水的降解实验可知，水杨酸去除率从76％分别提高到85％、91％和95％，提高了臭氧化效率。
实施例2.2
实施例2.2.1
称取500mg水杨酸(分析纯)溶解于1L蒸馏水中，配制成初始浓度为500mg/L的模拟废水；随后分别取两份500ml模拟废水于反应装置中，一份单独通臭氧，另一份加入0.5g实施例1.2中所制得的Ni-ZrO2纳米复合催化剂，磁力搅拌均匀后通入质量流量为25mg/L的臭氧，并每隔15min取水样分析水中水杨酸含量。水杨酸含量用高效液相色谱(HPLC，Agilent1260)测定，色谱柱为Diamonsil C18(4.6×200mm),流动相采用乙腈/0.05％的三氟乙酸水溶液＝8/2，流速为1ml/min，检测器为紫外可见吸收检测器(DAD)，检测波长为296nm。由水杨酸标准曲线可计算出降解前后的浓度，从而计算出降解率来衡量催化臭氧化效率。
实施例2.2.2
称取500mg水杨酸(分析纯)溶解于1L蒸馏水中，配制成初始浓度为500mg/L的模拟废水；随后分别取两份500ml模拟废水于反应装置中，一份单独通臭氧，另一份加入1.0g实施例1.2中所制得的Ni-ZrO2纳米复合催化剂，磁力搅拌均匀后通入质量流量为25mg/L的臭氧，并每隔15min取水样分析水中水杨酸含量。水杨酸含量用高效液相色谱(HPLC， Agilent1260)测定，色谱柱为Diamonsil C18(4.6×200mm),流动相采用乙腈/0.05％的三氟乙酸水溶液＝8/2，流速为1ml/min，检测器为紫外可见吸收检测器(DAD)，检测波长为296nm。由水杨酸标准曲线可计算出降解前后的浓度，从而计算出降解率来衡量催化臭氧化效率。
实施例2.2.3
称取500mg水杨酸(分析纯)溶解于1L蒸馏水中，配制成初始浓度为500mg/L的模拟废水；随后分别取两份500ml模拟废水于反应装置中，一份单独通臭氧，另一份加入1.5g实施例1.2中所制得的Ni-ZrO2纳米复合催化剂，磁力搅拌均匀后通入质量流量为25mg/L的臭氧，并每隔15min取水样分析水中水杨酸含量。水杨酸含量用高效液相色谱(HPLC，Agilent1260)测定，色谱柱为Diamonsil C18(4.6×200mm),流动相采用乙腈/0.05％的三氟乙酸水溶液＝8/2，流速为1ml/min，检测器为紫外可见吸收检测器(DAD)，检测波长为296nm。由水杨酸标准曲线可计算出降解前后的浓度，从而计算出降解率来衡量催化臭氧化效率。
图5a显示了实施例2.2.1中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；图5b显示了实施例2.2.2中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；图5c显示了实施例2.2.3中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图。
在臭氧化降解模拟废水装置中加入的Ni-ZrO2纳米复合催化剂，在金属Ni表面，臭氧通过羟基自由基的产生将金属氧化，随后有机物分子在催化剂表面吸附后，发生电子迁移而氧化，将电子转移给还原催化剂，有机自由基组分从催化剂上脱附，在水溶液中被HO·或O3氧化。通过对比单独臭氧化和Ni-ZrO2添加量为1～3g/L的催化臭氧化对模拟废水的降解实验可知，水杨酸去除率从76％分别提高到90％、94％和98％，提高了臭氧化效率。
实施例2.3
实施例2.3.1
称取500mg水杨酸(分析纯)溶解于1L蒸馏水中，配制成初始浓度为500mg/L的模拟废水；随后分别取两份500ml模拟废水于反应装置中，一份单独通臭氧，另一份加入0.5g实施例1.3中所制得的Ni-ZrO2纳米复合催化剂，磁力搅拌均匀后通入质量流量为25mg/L的臭氧，并每隔15min取水样分析水中水杨酸含量。水杨酸含量用高效液相色谱(HPLC，Agilent1260)测定，色谱柱为Diamonsil C18(4.6×200mm),流动相采用乙腈/0.05％的三氟乙酸水溶液＝8/2，流速为1ml/min，检测器为紫外可见吸收检测器(DAD)，检测波长为296nm。由水杨酸标准曲线可计算出降解前后的浓度，从而计算出降解率来衡量催化臭氧化效率。
实施例2.3.2
称取500mg水杨酸(分析纯)溶解于1L蒸馏水中，配制成初始浓度为500mg/L的模拟废水；随后分别取两份500ml模拟废水于反应装置中，一份单独通臭氧，另一份加入1.0g实施例1.3中所制得的Ni-ZrO2纳米复合催化剂，磁力搅拌均匀后通入质量流量为25mg/L的臭氧，并每隔15min取水样分析水中水杨酸含量。水杨酸含量用高效液相色谱(HPLC，Agilent1260)测定，色谱柱为Diamonsil C18(4.6×200mm),流动相采用乙腈/0.05％的三氟乙酸水溶液＝8/2，流速为1ml/min，检测器为紫外可见吸收检测器(DAD)，检测波长为296nm。由水杨酸标准曲线可计算出降解前后的浓度，从而计算出降解率来衡量催化臭氧化效率。
实施例2.3.3
称取500mg水杨酸(分析纯)溶解于1L蒸馏水中，配制成初始浓度为500mg/L的模拟废水；随后分别取两份500ml模拟废水于反应装置中，一份单独通臭氧，另一份加入1.5g实施例1.3中所制得的Ni-ZrO2纳米复合催化剂，磁力搅拌均匀后通入质量流量为25mg/L的臭氧，并每隔15min取水样分析水中水杨酸含量。水杨酸含量用高效液相色谱(HPLC，Agilent1260)测定，色谱柱为Diamonsil C18(4.6×200mm),流动相采用乙腈/0.05％的三氟乙酸水溶液＝8/2，流速为1ml/min，检测器为紫外可见吸收检测器(DAD)，检测波长为296nm。由水杨酸标准曲线可计算出降解 前后的浓度，从而计算出降解率来衡量催化臭氧化效率。
图6a显示了实施例2.3.1中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；图6b显示了实施例2.3.2中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图；图6c显示了实施例2.3.3中水杨酸浓度在单独臭氧化(a)和Ni-ZrO2纳米复合催化剂臭氧化(b)下的降解曲线图。
在臭氧化降解模拟废水装置中加入的Ni-ZrO2纳米复合催化剂，在金属Ni表面，臭氧通过羟基自由基的产生将金属氧化，随后有机物分子在催化剂表面吸附后，发生电子迁移而氧化，将电子转移给还原催化剂，有机自由基组分从催化剂上脱附，在水溶液中被HO·或O3氧化。通过对比单独臭氧化和Ni-ZrO2添加量为1～3g/L的催化臭氧化对模拟废水的降解实验可知，水杨酸去除率从76％分别提高到92％、95％和98％，提高了臭氧化效率。
以上所述实施例仅表达了本发明的实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。

Claims (10)

  1. 一种非均相催化臭氧化的纳米复合催化剂，其特征在于，所述催化剂为Ni-ZrO2纳米复合催化剂。
  2. 根据权利要求1所述的纳米复合催化剂，其特征在于，Ni的质量分数为10％-20％。
  3. 一种制备根据权利要求1-2任一项所述的纳米复合催化剂的方法，其特征在于，包含以下步骤：
    步骤(1)：溶胶凝胶法制备ZrO2载体：
    将十六烷基三甲基溴化铵溶解于去离子水中，然后加入ZrOCl2·8H2O溶液并不断搅拌使其充分溶解得到混合液，调节所述混合液的pH，然后通过老化、洗涤、烘干、煅烧制备ZrO2载体；
    步骤(2)：等体积浸渍法制备Ni-ZrO2纳米复合催化剂：
    将步骤(1)中制备的ZrO2载体烘干，分别称取所述ZrO2载体、Ni(NO3)2·6H2O溶于去离子水中等体积浸渍所述ZrO2载体，调节浸渍液的pH并搅拌使得浸渍完全，浸渍后的ZrO2载体通过烘干、煅烧制得表面附聚氧化镍的ZrO2复合物；然后将所述表面附聚氧化镍的ZrO2复合物高温还原最终制备Ni-ZrO2纳米复合催化剂。
  4. 根据权利要求3所述的方法，其特征在于，在步骤(1)中，所述十六烷基三甲基溴化铵的用量为1g-4g，去离子水的用量为50ml-200ml，ZrOCl2·8H2O溶液的用量为25ml-100ml，摩尔浓度为0.5M；使用20％-30％的氨水调节所述混合液的pH为9-10；将所述混合液于40℃-60℃老化20h-24h得到凝胶。
  5. 根据权利要求4所述的方法，其特征在于，通过去离子水洗涤所述凝胶中多余的氯离子，并在真空干燥箱内于80℃-110℃烘干10h-12h。
  6. 根据权利要求5所述的方法，其特征在于，将真空干燥后的凝胶置于马弗炉中于500℃-700℃煅烧5h-8h，并将制得的ZrO2载体研磨成粉。
  7. 根据权利要求3所述的方法，其特征在于，在步骤(2)中，将ZrO2载体于200℃-300℃烘干2h-4h；分别称取10g-20g所述ZrO2载体、5g-15gNi(NO3)2·6H2O溶于10ml-20ml去离子水中等体积浸渍所述ZrO2载体，通过硝酸调节所述浸渍液的pH为2，并于50℃-80℃磁力搅拌6h-12h以使得浸渍完全。
  8. 根据权利要求7所述的方法，其特征在于，浸渍后的ZrO2载体于100℃-120℃烘干2h-6h，随后以5℃/min的升温速率于500℃-700℃在马弗炉中煅烧5h-8h，制得表面附聚氧化镍的ZrO2复合物。
  9. 根据权利要求8所述的方法，其特征在于，将所述表面附聚氧化镍的ZrO2复合物置于管式炉中在Ar/H2气氛中于300℃-400℃下高温还原1h-2h，并将制得的所述Ni-ZrO2纳米复合催化剂研磨成粉。
  10. 根据权利要求1-2任一项所述的纳米复合催化剂在非均相催化臭氧化中的应用。
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