WO2015120764A1 - 一种共掺杂TiO2催化剂及其制备方法 - Google Patents

一种共掺杂TiO2催化剂及其制备方法 Download PDF

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WO2015120764A1
WO2015120764A1 PCT/CN2015/071051 CN2015071051W WO2015120764A1 WO 2015120764 A1 WO2015120764 A1 WO 2015120764A1 CN 2015071051 W CN2015071051 W CN 2015071051W WO 2015120764 A1 WO2015120764 A1 WO 2015120764A1
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preparation
catalyst
tio
metal
titanium dioxide
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French (fr)
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曹宏斌
谢勇冰
张懿
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中国科学院过程工程研究所
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    • 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
    • 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
    • B01J21/063—Titanium; 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—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
    • 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
    • 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
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the invention belongs to the technical field of water treatment, in particular to a catalytic material for ozone photocatalytic treatment of organic wastewater and a preparation method thereof, in particular to a co-doped TiO 2 catalyst for photocatalytic treatment of organic wastewater by ozone and a preparation method thereof.
  • Cleaner production includes measures to replace hazardous materials, reduce by-products of reactions, and develop new processes to improve the economics of reaction.
  • End treatment generally utilizes physicochemical methods or biological methods for the decontamination and resource treatment of pollutants.
  • biological methods are most widely used in removing organic pollutants from wastewater.
  • wastewater from coal chemical industry contains a large amount of monophenols and polyphenols, ammonia nitrogen, benzopyrene, polycyclic aromatic hydrocarbons and heterocyclic compounds.
  • the COD in the wastewater is significantly reduced, but only the phenol, ammonia, short-chain fatty acids and other substances in the wastewater are removed, and the toxic substances such as benzene, polycyclic aromatic hydrocarbons and heterocyclic compounds with strong biotoxicity remain. Environmental hazards cannot be ignored, and subsequent deep processing is urgently needed.
  • the advanced oxidation technology utilizes the strong oxidizing hydroxyl radical generated by the process to react with organic matter, which can achieve the effect of deep removal of pollutants, and is widely used in the field of wastewater treatment, including ozone oxidation technology.
  • the standard electrode potential of ozone molecule in acidic environment is 2.076V, which is second only to fluorine (2.866V). It has strong oxidizing property and can decompose and generate a large amount of hydroxyl radical under the action of catalyst. It has the advantages of short reaction time and easy operation. .
  • the ozone utilization rate in the process is low, resulting in high processing costs.
  • the combination of ozone and ultraviolet light can further improve the ozone utilization and oxidation capacity of the process.
  • ozone photocatalytic processes are based on TiO 2 materials with good photocatalytic activity.
  • the ozone photocatalytic-biological activated carbon deep purification water method disclosed in CN1172863A and the ozone-ultraviolet photocatalytic water treatment equipment disclosed in CN200949061Y are based on TiO. 2 Photocatalyst ozone photocatalysis.
  • the hot spot of photocatalysis research is to use a single metal or non-metal doping, metal-metal, metal-nonmetal co-doping method to improve the response of TiO 2 to visible light, so as to effectively utilize solar energy, such as Zhang Xia et al., MnSO4 ⁇ H 2 O and MnC 2 O 4 ⁇ 4H 2 O are manganese sources, and a manganese-doped nano-titanium dioxide photocatalyst prepared by hydrothermal method (J. Phys. Chem. C 2007, 111, 10618-10623).
  • the photocatalyst prepared by the above method is likely to reduce the ultraviolet photocatalytic activity of the material while improving the response of the material to visible light.
  • One of the objects of the present invention is to provide a novel co-doped TiO 2 preparation method, which is co-doped with a transition metal ion and a nitrogen element, thereby not only improving the absorption of visible light by the TiO 2 material, but also improving the ultraviolet photocatalytic activity. .
  • the application of this TiO 2 material to ozone photocatalytic degradation of organic pollutants shows good catalytic activity.
  • the present invention employs the following preparation method:
  • a preparation method of a co-doped TiO 2 catalyst is firstly prepared by a two-layer hydrothermal method for preparing metal ion doped TiO 2 , and then calcining at a high temperature in an ammonia atmosphere for nitrogen doping to obtain metal and nitrogen co-doped TiO. 2 catalyst.
  • the double-layer hydrothermal method heats the inner layer solution through the outer solution medium, and gradually participates in the reaction in the inner layer container by using the water vapor in the hydrothermal reaction, so that the reaction can be uniform and the speed can be controlled.
  • the co-doped metal ions can act as a trapping agent for photogenerated electrons, promoting the separation of photogenerated electrons and hole pairs, facilitating the generation of strongly oxidizing holes and subsequent reaction to generate hydroxyl radicals.
  • TiO 2 itself has very weak absorption of visible light.
  • the co-doped nitrogen can promote the absorption of longer wavelength light by TiO 2 material, so it has visible light catalytic activity, that is, the catalyst can be prepared by simultaneously doping metal ions and nitrogen. It has both visible light absorption properties and ultraviolet photocatalytic activity.
  • the TiO 2 material prepared by the double-layer hydrothermal method has small particle size and uniform scale, so the material of the same quality has a higher external specific surface area, which is favorable for the catalytic reaction.
  • the metal content in the co-doped TiO 2 catalyst is 0.01-5 wt%, for example, 0.05 wt%, 0.2 wt%, 0.5 wt%, 0.9 wt%, 1.5 wt%, 2wt%, 3.5wt%, 4wt%, 4.7wt%, etc.
  • nitrogen content is 0.01-5 wt%, for example 0.05 wt%, 0.2 wt%, 0.5 wt%, 0.9 wt%, 1.5 wt%, 2 wt%, 3.5 wt% %, 4 wt%, 4.7 wt%, and the like.
  • the content of metal ions is less than 0.01%, the photocatalytic activity of TiO 2 is almost ineffective. If the content of metal ions is higher than 5%, the activity of the catalyst is not significantly improved, but the catalytic activity decreases as the metal ion content increases.
  • the invention therefore has a metal content of from 0.01 to 5% by weight. If the nitrogen doping amount is less than 0.01%, the visible light absorption performance of TiO 2 is not improved, and when the nitrogen doping amount is higher than 5%, the visible light absorption performance of TiO 2 is decreased, so the nitrogen doping amount of the present invention is also 0.01. -5wt%.
  • the high temperature baking temperature is 400-800 ° C, for example, 440 ° C, 480 ° C, 550 ° C, 600 ° C, 660 ° C, 750 ° C, etc.
  • the high-temperature baking time is 0.5. -10h, for example, 1h, 3h, 5h, 8h, 9.5h, and the like. If the baking temperature is too high or the baking time is too long, it will cause the material Severe agglomeration, reduced activity; and the calcination temperature is too low or the calcination time is too short, which will affect the nitrogen doping effect.
  • the preparation method of the present invention is doped with metal ions in situ when synthesizing TiO 2 , and then subjected to high temperature baking for nitrogen doping;
  • the metal ion doped TiO 2 is spherical or spheroidal nanoparticles
  • the metal ion is one or a combination of two or more of Ni, Co, Mn, Fe, Cu, V or Cr.
  • the preparation method of the present invention is a heterogeneous catalyst comprising the following steps:
  • a uniformly mixed solution of a titanium-containing precursor, ethanol and a metal precursor salt into a container, the outside of which is a mixed solution of ethanol and water, and reacting in a closed state in a hydrothermal reaction to obtain a suspension; a titanium-containing precursor
  • the realization of a homogeneous mixed solution of the ethanol and metal precursor salts can be achieved by stirring, ultrasound or any other suitable method;
  • the titanium-containing precursor in the step (1) is tetrabutyl titanate and/or titanium isopropoxide;
  • the metal precursor salt is one or a combination of two or more of a nitrate, a chloride or a sulfate of Ni, Co, Mn, Fe, Cu, V or Cr, for example, cobalt nitrate, chlorination
  • cobalt nitrate chlorination
  • cobalt nitrate chlorination
  • cobalt nitrate chlorination
  • cobalt nitrate chlorination
  • the molar ratio of the titanium precursor to ethanol is 1:5-20, for example, 1:8, 1:12, 1:15, 1:19, etc., molar ratio of titanium precursor to metal precursor salt It is 1:0.0002-0.08, for example, 1:0.0005, 1:0.002, 1:0.008, 1:0.01, 1:0.04, 1:0.07, and the like.
  • the container is an open polytetrafluoroethylene container.
  • the mass content of water is from 1% to 10%, for example, 1.5%, 2.2%, 5%, 6.5%, 8%, 9.5%, and the like.
  • the hydrolysis rate of the titanium-containing precursor salt can be controlled to obtain TiO 2 with uniform morphology and particle size.
  • the hydrolysis rate of the titanium precursor salt is slow, which will significantly prolong the cycle of the reaction preparation material; if the water content is higher than 10%, the prepared TiO 2 particles are easily agglomerated and the activity is lowered.
  • the temperature of the hydrothermal reaction is 150-200 ° C, for example, 160 ° C, 180 ° C, 185 ° C, 190 ° C, etc.
  • the reaction time is 12-48 h, for example, 15 h, 20 h, 25 h, 30 h, 38h, 46h, etc.
  • the liquid level in the hydrothermal kettle is not more than 2/3, which ensures safe operation.
  • the solid-liquid separation in the step (2) is centrifugal separation and/or suction filtration
  • the washing is washed several times with water until the washing liquid is near neutral.
  • the drying in step (3) is carried out in an oven
  • the drying temperature is 60-110 ° C, for example, 65 ° C, 80 ° C, 95 ° C, 105 ° C, etc.
  • the drying time is 12-24 h, for example, 15 h, 18 h, 20 h, 23 h, and the like.
  • the calcination described in step (4) is carried out in a tube furnace
  • the calcination condition is: heating to 400-800 ° C at a rate of 1-10 ° C / min, for example 3 ° C / min, 5 ° C / min, 7 ° C / min, 9 ° C / min, etc., for example 450 ° C, 500 ° C, 580 ° C, 670 ° C, 750 ° C, etc., maintained for 1-4h, such as 1.2h, 1.6h, 2.5h, 3h, 3.6h and so on.
  • the metal content of the co-doped TiO 2 catalyst is 0.01-5 wt%, and the nitrogen content is 0.01-5 wt%.
  • the amount is TiO 2 .
  • the preparation method of the invention provides a catalytic material for advanced treatment of wastewater, and is a catalytic material for photocatalytic treatment of organic wastewater by ozone.
  • the invention utilizes the photocatalytic activity unique to TiO 2 and the promotion of co-doping of transition metal ions and nitrogen atoms to prepare a co-doped TiO 2 catalyst, which is combined with an ozone generator and an ultraviolet visible light source to utilize ultraviolet light.
  • the combination of light, visible light, ultraviolet light and ozone can achieve faster and more complete removal of organic pollutants in wastewater.
  • the co-doped TiO 2 prepared by the method of the invention can effectively absorb visible light, and the ultraviolet photocatalytic activity is also significantly improved. In the process of ozone photocatalytic treatment of organic wastewater, it has higher catalytic activity than undoped TiO 2 .
  • Figure 1 is an XRD pattern of the product obtained in Example 1;
  • Example 2 is a UV-visible diffuse reflectance spectrum of the product obtained in Example 2.
  • the reactor containing the mixed solution obtained in the step (1) was placed in a 100 ml polytetrafluoro reactor containing 30 ml of a mixed solution of water and ethanol (water to ethanol volume ratio 1:99), sealed and heated to 180. °C, after 12 hours, naturally cool to room temperature.
  • Fig. 1 is an XRD pattern of the product obtained in this example, and it can be seen from the figure that the crystal form of the synthetic material is intact.
  • the solid obtained in the step (4) was subjected to ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS) test, and the visible light absorption was observed in the range of 400-600 nm, while the undoped TiO 2 hardly absorbed visible light.
  • UV-Vis DRS ultraviolet-visible diffuse reflectance spectroscopy
  • the solid obtained in the step (4) was used as a catalyst, and a 500 ml nitrobenzene solution having a concentration of 50 mg/L was subjected to ultraviolet light catalytic treatment.
  • the UV light intensity is 320mW/cm 2
  • the catalyst dosage is 0.2g/L
  • the nitrobenzene removal rate is 52.8% in 120min.
  • the undoped TiO 2 is used as the catalyst.
  • the removal rate of nitrobenzene under the same conditions is only 37.5%.
  • the ozone photocatalytic treatment of the biochemical effluent of a steel plant Under the conditions of ozone concentration 10mg/L, flow rate 100ml/min and liquid surface ultraviolet light intensity 240mW/cm 2 , COD decreased from 200mg/L to 55mg/L in 90min, while undoped TiO 2 was used as catalyst. The lower COD was reduced to 79 mg/L.
  • the reactor containing the mixed solution obtained in the step (1) is placed in a 100 ml polytetrafluoro reactor containing 30 ml of a mixed solution of water and ethanol (volume ratio of 2:98), sealed and heated to 150 ° C to maintain After 48 hours, it was naturally cooled to room temperature.
  • FIG. 2 is a UV-visible diffuse reflection spectrum of the product obtained in the present example. As can be seen from the figure, there is significant visible light absorption in the range of 420-550 nm, while undoped TiO2 absorbs almost no visible light.
  • UV-Vis DRS ultraviolet-visible diffuse reflectance spectroscopy
  • the solid obtained in the step (4) was used as a catalyst, and a 500 ml nitrobenzene solution having a concentration of 50 mg/L was subjected to ultraviolet light catalytic treatment.
  • the UV light intensity is 360mW/cm 2
  • the catalyst dosage is 0.2g/L
  • the nitrobenzene removal rate is 59.8% in 90min.
  • the undoped TiO 2 is used as the catalyst.
  • the removal rate of nitrobenzene under the same conditions is only 43.5%.
  • the ozone photocatalytic treatment of the biochemical effluent of a steel plant Under the conditions of ozone concentration 15mg/L, flow rate 100ml/min and liquid surface ultraviolet light intensity 300mW/cm 2 , COD decreased from 200mg/L to 47mg/L in 90min, while undoped TiO 2 was used as catalyst. The lower COD was reduced to 69 mg/L.
  • the solid obtained in the step (4) was subjected to ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS) test, and the visible light absorption was observed in the range of 400-550 nm, while the undoped TiO 2 hardly absorbed visible light.
  • UV-Vis DRS ultraviolet-visible diffuse reflectance spectroscopy
  • the solid obtained in the step (4) was used as a catalyst, and a 500 ml nitrobenzene solution having a concentration of 50 mg/L was subjected to ultraviolet light catalytic treatment.
  • the UV light intensity is 300mW/cm 2
  • the catalyst dosage is 0.2g/L
  • the nitrobenzene removal rate is 57.8% in 90min.
  • the undoped TiO 2 is used as the catalyst.
  • the removal rate of nitrobenzene under the same conditions is only 44.3%.
  • the ozone photocatalytic treatment of the biochemical effluent of a steel plant Under the conditions of ozone concentration 30mg/L, flow rate 50ml/min and liquid surface ultraviolet light intensity 360mW/cm 2 , COD decreased from 200mg/L to 56mg/L in 90min, while undoped TiO 2 was used as catalyst. The lower COD was reduced to 67 mg/L.
  • the reactor containing the mixed solution obtained in the step (1) was placed in a 100 ml polytetrafluoro reactor containing 30 ml of a mixed solution of water and ethanol (volume ratio of 2:98), sealed and heated to 160 ° C to maintain 18 After a while, it was naturally cooled to room temperature.
  • the solid obtained in the step (4) was subjected to ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS) test, and the visible light absorption was observed in the range of 400-500 nm, while the undoped TiO 2 hardly absorbed visible light.
  • UV-Vis DRS ultraviolet-visible diffuse reflectance spectroscopy
  • the solid obtained in the step (4) was used as a catalyst, and a 500 ml nitrobenzene solution having a concentration of 50 mg/L was subjected to ultraviolet light catalytic treatment.
  • the UV light intensity is 360mW/cm 2
  • the catalyst dosage is 0.2g/L
  • the nitrobenzene removal rate is 52.5% in 90min.
  • the undoped TiO 2 is used as the catalyst.
  • the removal rate of nitrobenzene under the same conditions is only 39.2%.
  • the ozone photocatalytic treatment of the biochemical effluent of a steel plant Under the conditions of ozone concentration 20mg/L, flow rate 75ml/min and liquid surface ultraviolet light intensity 300mW/cm 2 , COD decreased from 200mg/L to 53mg/L in 90min, while undoped TiO 2 was used as catalyst. The lower COD dropped to 71 mg/L.
  • the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Abstract

本发明涉及共掺杂TiO2催化剂的制备方法及共掺杂TiO2催化剂。所述制备方法首先通过双层水热法制备金属离子掺杂的TiO2，然后在氨气气氛下高温焙烧进行氮掺杂，得到金属和氮共掺杂的TiO2催化剂。本发明的方法制备的共掺杂TiO2可有效吸收可见光，同时紫外光催化活性也显著提高。在臭氧光催化处理有机废水过程中，比未掺杂TiO2具有更高的催化活性。

Description

一种共掺杂TiO2催化剂及其制备方法 技术领域
本发明属于水处理技术领域，具体地说涉及臭氧光催化处理有机废水的一种催化材料及其制备方法，尤其涉及一种臭氧光催化处理有机废水的共掺杂TiO2催化剂及制备方法。
背景技术
近十年来，我国经济一直保持迅猛发展的势头。在追求GDP快速增长的同时，生产方式和技术水平尚未得到显著提升，整体资源利用效率较低，产生了大量的三废污染物没得到及时有效处理，对生态环境和居民健康造成恶劣影响。全国废水排放总量，一直保持稳步上升的趋势，特别是煤化工、造纸、印染、制药等行业消耗水量大，产生的废水组成复杂、毒害性强，治理难度高，严重影响了行业的持续健康发展。
针对以上重污染行业的排污问题，通常从源头清洁生产和末端污染治理两方面解决。清洁生产包括替换有害原料，减少反应副产物，发展新工艺路线提高反应原子经济性等措施。末端治理一般通过物理化学方法或生物法进行污染物无害化和资源化处理，其中生物法在去除废水中有机污染物中应用最广泛。当前各行业产生废水的组分越来越复杂，如煤化工行业废水中含有大量单元酚及多元酚、氨氮、苯并荜、多环芳烃和杂环化合物等。经过预处理和生化法，废水中COD明显降低，但仅去除废水的酚、氨、短链脂肪酸等物质，剩余生物毒性强的苯系物、多环芳烃和杂环化合物等难降解有机物，对环境危害不容忽视，急需进行后续深度处理。
高级氧化技术利用过程产生的强氧化性羟基自由基与有机物反应，可达到深度去除污染物效果，在废水处理领域应用广泛，其中包括臭氧氧化技术。臭氧分子在酸性环境下标准电极电势为2.076V，仅次于氟(2.866V)，具有很强的氧化性，在催化剂作用下可分解产生大量羟基自由基，具有反应时间短、操作简便等优点。但由于臭氧与有机物反应选择性较强，在较短时间内不可能完全矿化污染物，生成的中间产物无法继续分解，过程中臭氧利用率偏低，导致处理费用偏高。臭氧与紫外光结合后，可进一步提高过程的臭氧利用率和氧化能力。
目前绝大部分臭氧光催化过程均基于光催化活性良好的TiO2材料，如CN1172863A公开的臭氧光催化-生物活性炭深度净化水的方法和CN200949061Y公开的臭氧-紫外线光催化水处理设备均是基于TiO2光催化剂的臭氧光催化。目前光催化研究热点是采用单一金属或非金属掺杂，金属-金属，金属-非金属共掺杂的方法，提高TiO2对可见光响应，以有效利用太阳能，如张霞等人以MnSO4·H2O和MnC2O4·4H2O为锰源，采用水热法制备的锰掺杂纳米二氧化钛光催化剂(J.Phys.Chem.C 2007，111，10618-10623)。上述方法制备的光催化剂在提高材料对可见光响应的同时，材料的紫外光催化活性很可能会降低。
发明内容
本发明的目的之一在于提供一种新的共掺杂TiO2制备方法，采用过渡金属离子和氮元素共掺杂，不但可提高TiO2材料对可见光的吸收，其紫外光催化活性也明显提高。将这种TiO2材料应用于臭氧光催化降解有机污染物，显示出了良好的催化活性。
为了达到上述目的之一，本发明采用如下制备方法：
一种共掺杂TiO2催化剂的制备方法，首先通过双层水热法制备金属离子掺杂的TiO2，然后在氨气气氛下高温焙烧进行氮掺杂，得到金属和氮共掺杂的TiO2催化剂。双层水热法即通过外层溶液介质加热内层溶液，并利用水热反应中的水蒸汽逐步参与内层容器中的反应，可使得反应匀速且速度可控。共掺杂的金属离子可以作为光生电子的捕获剂，促进光生电子和空穴对分离，利于产生强氧化性的空穴及后续反应产生羟基自由基。TiO2本身对可见光吸收能力非常弱，通过共掺杂的氮可促进TiO2材料吸收波长更长的光，因此具有可见光催化活性，即通过同时掺杂金属离子和氮，可使制得的催化剂同时具有可见光吸收性能和紫外光催化剂活性。采用双层水热法制备的TiO2材料粒径小，尺度均一，因此同质量的材料具有更高的外比表面积，有利于催化反应。
作为优选技术方案，本发明的制备方法，共掺杂的TiO2催化剂中的金属含量为0.01-5wt％，例如为0.05wt％、0.2wt％、0.5wt％、0.9wt％、1.5wt％、2wt％、3.5wt％、4wt％、4.7wt％等，氮含量为0.01-5wt％，例如为0.05wt％、0.2wt％、0.5wt％、0.9wt％、1.5wt％、2wt％、3.5wt％、4wt％、4.7wt％等。若金属离子的含量低于0.01％，对TiO2光催化活性提高几乎无效果，金属离子的含量高于5％，则催化剂活性无明显提高，反而会随着金属离子含量升高催化活性降低，因此本发明选择金属含量为0.01-5wt％。若氮掺杂量低于0.01％，对TiO2可见光吸收性能无提高效果，而氮掺杂量高于5％，则TiO2可见光吸收性能反而降低，因此本发明选择氮掺杂量也为0.01-5wt％。
作为优选技术方案，本发明的制备方法，所述高温焙烧的温度为400-800℃，例如为440℃、480℃、550℃、600℃、660℃、750℃等，高温焙烧的时间为0.5-10h，例如为1h、3h、5h、8h、9.5h等。焙烧温度太高或焙烧时间太久，会造成材料 严重团聚，活性降低；而焙烧温度太低或焙烧时间太短，会影响掺氮效果。
作为优选技术方案，本发明的制备方法，在合成TiO2时原位掺杂金属离子，然后再进行高温焙烧进行氮掺杂；
优选地，所述金属离子掺杂的TiO2为球形或类球形纳米颗粒；
优选地，所述金属离子为Ni、Co、Mn、Fe、Cu、V或Cr中的1种或2种以上的组合。
作为优选技术方案，本发明的制备方法非均相催化剂，包括如下步骤：
(1)将含钛前驱体、乙醇和金属前驱体盐的均匀混合溶液放入容器中，容器外为乙醇和水混合溶液，整体在密闭容器中水热反应，得到悬浮液；含钛前驱体、乙醇和金属前驱体盐的均匀混合溶液的实现可通过搅拌、超声或任何其他的合适的方法实现；
(2)将步骤(1)得到的悬浮液固液分离，用去离子水洗涤得到的固体；
(3)将步骤(2)分离得到的固体干燥；
(4)将步骤(3)干燥得到的固体在氨气保护下高温焙烧。
优选地，步骤(1)中所述含钛前驱体为钛酸四丁酯和/或异丙醇钛；
优选地，所述金属前驱体盐为Ni、Co、Mn、Fe、Cu、V或Cr的硝酸盐、氯化物或硫酸盐中的1种或2种以上的组合，例如为硝酸钴、氯化钴或硫酸钴中的1种或2中以上的组合，或为硝酸钴与硝酸锰的组合，或为硝酸钴与硫酸钴和氯化铜的组合等等。
优选地，所述钛前驱体与乙醇的摩尔比为1∶5-20，例如为1∶8、1∶12、1∶15、1∶19等，钛前驱体与金属前驱体盐的摩尔比为1∶0.0002-0.08，例如为1∶0.0005、1∶0.002、1∶0.008、1∶0.01、1∶0.04、1∶0.07等。
优选地，所述容器为开口聚四氟容器。
优选地，所述乙醇和水混合溶液中，水的质量含量为1％-10％，例如为1.5％、2.2％、5％、6.5％、8％、9.5％等。当混合溶液中水含量适合时，才可控制含钛前驱体盐水解速度，得到形貌和粒径均一的TiO2。水含量低于1％，钛前驱体盐水解速度慢，会明显延长反应制备材料的周期；水含量高于10％，容易使制备得到的TiO2颗粒团聚，降低活性。
优选地，所述水热反应的温度为150-200℃，例如为160℃、180℃、185℃、190℃等，优选反应的时间为12-48h，例如为15h、20h、25h、30h、38h、46h等。水热反应时控制水热釜中液位高度不超过2/3，保证操作安全即可。
优选地，步骤(2)中所述固液分离为离心分离和/或抽滤；
优选地，所述的洗涤为水洗多次，直至洗涤液接近中性。
优选地，步骤(3)中所述干燥在烘箱中进行；
优选地，所述干燥的温度为60-110℃，例如为65℃、80℃、95℃、105℃等，干燥的时间为12-24h，例如为15h、18h、20h、23h等。
优选地，步骤(4)中所述的焙烧在管式炉中进行；
优选地，所述焙烧条件为：以1-10℃/min，例如为3℃/min、5℃/min、7℃/min、9℃/min等的速度升温到400-800℃，例如为450℃、500℃、580℃、670℃、750℃等，保持1-4h，例如为1.2h、1.6h、2.5h、3h、3.6h等。
本发明的目的之一还在于提供由本发明所述方法制得的共掺杂TiO2催化剂，共掺杂的TiO2催化剂中的金属含量为0.01-5wt％，氮含量为0.01-5wt％，余量为TiO2。
本发明的制备方法提供了一种废水深度处理的催化材料，为一种臭氧光催化处理有机废水的催化材料。本发明利用TiO2自身独有的光催化活性，和过渡金属离子和氮原子共掺杂的促进作用制备共掺杂的TiO2催化剂，经与臭氧发生 器和紫外可见光源等装置组合，利用紫外光、可见光、紫外光与臭氧的结合，可实现对废水中有机污染物更快速彻底去除。
本发明的方法制备的共掺杂TiO2可有效吸收可见光，同时紫外光催化活性也显著提高。在臭氧光催化处理有机废水过程中，比未掺杂TiO2具有更高的催化活性。
附图说明
附图1为实施例1中所得产品的XRD图；
附图2为实施例2中所得产品的紫外可见漫反射光谱图。
具体实施方式
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
(1)用双层水热法制备离子掺杂的TiO2。首先将10ml的钛酸四丁酯，乙醇和硝酸镍的混合溶液(钛酸四丁酯和乙醇的体积比1∶5，钛酸四丁酯和硝酸镍摩尔比100∶1)超声10分钟后，置于开口的聚四氟反应容器中。
(2)将步骤(1)得到的含混合溶液的反应器置入内含30ml的水和乙醇混合溶液(水和乙醇体积比1∶99)的100ml聚四氟反应器，密封后加热至180℃，保持12小时后自然冷却至室温。
(3)将步骤(2)反应得到的混合物过滤，用去离子水洗涤，重复过滤和水洗多次，直至洗涤液接近中性。将得到的固体在100℃下干燥12小时。
(4)将步骤(3)干燥得到的固体置于管式炉中，在氨气保护下，以5℃/min的升温速度从室温加热至500℃，保持3小时后自然冷却至室温。
图1是本实施例所得产品的XRD图，从图中可以看出，合成材料晶型完整。
性能测试
取步骤(4)制得的固体进行紫外可见漫反射光谱(UV-Vis DRS)测试，在400-600nm范围内有明显的可见光吸收，而未掺杂TiO2几乎不吸收可见光。
取步骤(4)制得的固体作为催化剂，紫外光催化处理浓度为50mg/L的500ml硝基苯溶液。紫外光强度为320mW/cm2，催化剂用量0.2g/L，120min内硝基苯去除率为52.8％，而采用未掺杂TiO2作为催化剂，相同条件下硝基苯去除率仅37.5％。
取步骤(4)制得的固体作为催化剂，臭氧光催化处理某钢铁厂生化出水。在臭氧浓度10mg/L，流速100ml/min，液面紫外光强度240mW/cm2的条件下，90min内COD从200mg/L降至55mg/L，而采用未掺杂TiO2作为催化剂，相同条件下COD降至79mg/L。
实施例2
(1)用双层水热法制备离子掺杂的TiO2。首先将15ml的钛酸四丁酯，乙醇和硝酸钴的混合溶液(钛酸四丁酯和乙醇的体积比1∶10，钛酸四丁酯和硝酸钴摩尔比50∶1)超声10分钟后，置于开口的聚四氟反应容器中。
(2)将步骤(1)得到的含混合溶液的反应器置入内含30ml的水和乙醇混合溶液(体积比2∶98)的100ml聚四氟反应器，密封后加热至150℃，保持48小时后自然冷却至室温。
(3)将步骤(2)反应得到的混合物过滤，用去离子水洗涤，重复过滤和水洗多次，直至洗涤液接近中性。将得到的固体在105℃下干燥12小时。
(4)将步骤(3)干燥得到的固体置于管式炉中，在氨气保护下，以3℃/min的升温速度从室温加热至600℃，保持2小时后自然冷却至室温。
性能测试
取步骤(4)制得的固体进行紫外可见漫反射光谱(UV-Vis DRS)测试，图2为本实施例所得产品的紫外可见漫反射光谱图。从图中可以看出，在420-550nm范围内有明显的可见光吸收，而未掺杂TiO2几乎不吸收可见光。
取步骤(4)制得的固体作为催化剂，紫外光催化处理浓度为50mg/L的500ml硝基苯溶液。紫外光强度为360mW/cm2，催化剂用量0.2g/L，90min内硝基苯去除率为59.8％，而采用未掺杂TiO2作为催化剂，相同条件下硝基苯去除率仅43.5％。
取步骤(4)制得的固体作为催化剂，臭氧光催化处理某钢铁厂生化出水。在臭氧浓度15mg/L，流速100ml/min，液面紫外光强度300mW/cm2的条件下，90min内COD从200mg/L降至47mg/L，而采用未掺杂TiO2作为催化剂，相同条件下COD降至69mg/L。
实施例3
(1)用双层水热法制备离子掺杂的TiO2。首先将12ml的钛酸四丁酯，乙醇和硫酸锰的混合溶液(钛酸四丁酯和乙醇的体积比1∶10，钛酸四丁酯和硝酸钴摩尔比50∶1)超声10分钟后，置于开口的聚四氟反应容器中。
(2)将步骤(1)得到的含混合溶液的反应器置入内含30ml的水和乙醇混合溶液(体积比2∶98)的100ml聚四氟反应器，密封后加热至200℃，保持12小时后自然冷却至室温。
(3)将步骤(2)反应得到的混合物过滤，用去离子水洗涤，重复过滤和水洗多次，直至洗涤液接近中性。将得到的固体在80℃下干燥16小时。
(4)将步骤(3)干燥得到的固体置于管式炉中，在氨气保护下，以5℃/min的升温速度从室温加热至500℃，保持2.5小时后自然冷却至室温。
性能测试
取步骤(4)制得的固体进行紫外可见漫反射光谱(UV-Vis DRS)测试，在400-550nm范围内有明显的可见光吸收，而未掺杂TiO2几乎不吸收可见光。
取步骤(4)制得的固体作为催化剂，紫外光催化处理浓度为50mg/L的500ml硝基苯溶液。紫外光强度为300mW/cm2，催化剂用量0.2g/L，90min内硝基苯去除率为57.8％，而采用未掺杂TiO2作为催化剂，相同条件下硝基苯去除率仅44.3％。
取步骤(4)制得的固体作为催化剂，臭氧光催化处理某钢铁厂生化出水。在臭氧浓度30mg/L，流速50ml/min，液面紫外光强度360mW/cm2的条件下，90min内COD从200mg/L降至56mg/L，而采用未掺杂TiO2作为催化剂，相同条件下COD降至67mg/L。
实施例4
(1)用双层水热法制备离子掺杂的TiO2。首先将10ml的钛酸四丁酯，乙醇和氯化铜的混合溶液(钛酸四丁酯和乙醇的体积比1∶10，钛酸四丁酯和硝酸钴摩尔比150∶1)超声10分钟后，置于开口的聚四氟反应容器中。
(2)将步骤(1)得到的含混合溶液的反应器置入内含30ml水和乙醇混合溶液(体积比2∶98)的100ml聚四氟反应器，密封后加热至160℃，保持18小时后自然冷却至室温。
(3)将步骤(2)反应得到的混合物过滤，用去离子水洗涤，重复过滤和水洗多次，直至洗涤液接近中性。将得到的固体在105℃下干燥18小时。
(4)将步骤(3)干燥得到的固体置于管式炉中，在氨气保护下，以5℃/min的升温速度从室温加热至600℃，保持1.5小时后自然冷却至室温。
性能测试
取步骤(4)制得的固体进行紫外可见漫反射光谱(UV-Vis DRS)测试，在400-500nm范围内有明显的可见光吸收，而未掺杂TiO2几乎不吸收可见光。
取步骤(4)制得的固体作为催化剂，紫外光催化处理浓度为50mg/L的500ml硝基苯溶液。紫外光强度为360mW/cm2，催化剂用量0.2g/L，90min内硝基苯去除率为52.5％，而采用未掺杂TiO2作为催化剂，相同条件下硝基苯去除率仅39.2％。
取步骤(4)制得的固体作为催化剂，臭氧光催化处理某钢铁厂生化出水。在臭氧浓度20mg/L，流速75ml/min，液面紫外光强度300mW/cm2的条件下，90min内COD从200mg/L降至53mg/L，而采用未掺杂TiO2作为催化剂，相同条件下COD降至71mg/L。
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种共掺杂TiO2催化剂的制备方法，其特征在于，首先通过双层水热法制备金属离子掺杂的TiO2，然后在氨气气氛下高温焙烧进行氮掺杂，得到金属和氮共掺杂的TiO2催化剂。
  2. 根据权利要求1所述的制备方法，其特征在于，共掺杂的TiO2催化剂中的金属含量为0.01-5wt％，氮含量为0.01-5wt％。
  3. 根据权利要求1所述的制备方法，其特征在于，所述高温焙烧的温度为400-800℃，高温焙烧的时间为0.5-10h。
  4. 根据权利要求1所述的制备方法，其特征在于，在合成TiO2时原位掺杂金属离子，然后再进行高温焙烧进行氮掺杂；
    优选地，所述金属离子掺杂的TiO2为球形或类球形纳米颗粒；
    优选地，所述金属离子为Ni、Co、Mn、Fe、Cu、V或Cr中的1种或2种以上的组合。
  5. 根据权利要求1-4任一项所述的制备方法，其特征在于，包括如下步骤：
    (1)将含钛前驱体、乙醇和金属前驱体盐的均匀混合溶液放入容器中，容器外为乙醇和水混合溶液，整体在密闭容器中水热反应，得到悬浮液；
    (2)将步骤(1)得到的悬浮液固液分离，用去离子水洗涤得到的固体；
    (3)将步骤(2)分离得到的固体干燥；
    (4)将步骤(3)干燥得到的固体在氨气保护下高温焙烧。
  6. 根据权利要求5所述的制备方法，其特征在于，步骤(1)中所述含钛前驱体为钛酸四丁酯和/或异丙醇钛；
    优选地，所述金属前驱体盐为Ni、Co、Mn、Fe、Cu、V或Cr的硝酸盐、氯化物或硫酸盐中的1种或2种以上的组合；
    优选地，所述钛前驱体与乙醇的摩尔比为1∶5-20，钛前驱体与金属前驱体盐 的摩尔比为1∶0.0002-0.08；
    优选地，所述容器为开口聚四氟容器；
    优选地，所述乙醇和水混合溶液中，水的质量含量为1％-10％；
    优选地，所述水热反应的温度为150-200℃，优选反应的时间为12-48h。
  7. 根据权利要求5所述的制备方法，其特征在于，步骤(2)中所述固液分离为离心分离和/或抽滤；
    优选地，所述的洗涤为水洗多次，直至洗涤液接近中性。
  8. 根据权利要求5所述的制备方法，其特征在于，步骤(3)中所述干燥在烘箱中进行；
    优选地，所述干燥的温度为60-110℃，干燥的时间为12-24h。
  9. 根据权利要求5所述的制备方法，其特征在于，步骤(4)中所述的焙烧在管式炉中进行；
    优选地，所述焙烧条件为：以1-10℃/min的速度升温到400-800℃，保持1-4h。
  10. 一种权利要求1-9任一项所述方法制得的共掺杂TiO2催化剂，其特征在于，共掺杂的TiO2催化剂中的金属含量为0.01-5wt％，氮含量为0.01-5wt％，余量为TiO2。
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