WO2012109846A1 - 一种用于肼降解催化剂的制备和应用方法 - Google Patents

一种用于肼降解催化剂的制备和应用方法 Download PDF

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WO2012109846A1
WO2012109846A1 PCT/CN2011/077256 CN2011077256W WO2012109846A1 WO 2012109846 A1 WO2012109846 A1 WO 2012109846A1 CN 2011077256 W CN2011077256 W CN 2011077256W WO 2012109846 A1 WO2012109846 A1 WO 2012109846A1
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catalyst
ruthenium
degradation
hours
solution
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French (fr)
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吴敏
李文利
李春龙
赵一凡
郑颖平
卜长飞
苗春存
王芬
孙岳明
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东南大学
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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
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • B01J21/066—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
    • B01J23/16—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
    • B01J23/28—Molybdenum
    • 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
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/72—Copper
    • 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
    • B01J23/745—Iron
    • 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

Definitions

  • the invention relates to the preparation and application of a catalyst for the degradation of hydrazine and hydrazine hydrate, in particular to the preparation of a composite metal oxide solid acid catalyst and the application of the catalyst to the degradation of hydrazine at normal temperature.
  • Helium is of great significance in spacecraft and is mainly used as a fuel component for rockets and jet engines. At the same time, cockroaches are very toxic, and cockroaches are prone to dripping and sudden leakage during production, transportation and storage. Once the wastewater containing strontium enters the surrounding environment, it will cause pollution to the surrounding environment, including soil and water, and cause harm to surrounding residents and livestock. Therefore, the sewage purification treatment technology is highly valued.
  • the active component which catalyzes the degradation of hydrazine is a supported noble metal ruthenium such as ⁇ 7 ⁇ - ⁇ 1 2 0 3 and a supported amount of 20 to 40% by weight.
  • the cost of precious metal lanthanum is high, so the development of low-cost, high-activity cerium degradation catalyst at room temperature has a good application prospect. It is reported in the literature that transition metal nitrides, carbides, phosphides (CN101380586A, CN101411975A, ZL200410021372.9) show good catalytic activity in the deuterium degradation reaction, but no composite metal oxide solid acid catalyst for deuterium degradation. Patent report.
  • the composite metal oxide solid acid catalyst is an environmentally friendly catalyst with high catalytic activity, mild conditions, no corrosion equipment, simple post-treatment and no pollution to the environment. It is a green catalyst with important application prospects for wastewater purification. .
  • the object of the present invention is to provide a low-cost composite metal oxide solid acid catalyst which can decompose hydrazine and hydrazine hydrate into H 2 , N 2 , NH 3 and the like at a very high temperature, and is a green hydrazine wastewater treatment catalyst.
  • the presence of the catalyst accelerates the degradation of N 2 H 4 , shortens the treatment cycle, and improves the treatment effect.
  • the catalyst-catalyzed hydrazine hydrazine degradation process can replace the hydrogen fuel of the fuel cell to produce a cesium fuel cell (CN1348835, United States Patent 3442711).
  • the technical problem to be solved by the present invention is to provide a composite metal oxide solid acid
  • the preparation method of the catalyst and the application of the catalyst in the hydrazine degradation reaction That is, nanoporous Ti0 2 is used as a carrier, and under the action of a dispersing agent, oxides of manganese, molybdenum, zirconium, iron and copper are mixed, sulfate is supported, and heterogeneous catalytic oxidation technology is used to oxidize and degrade hydrazine and hydrazine hydrate.
  • the catalyst prepared by the invention has high activity at the normal temperature for the hydrazine degradation reaction, has low cost, complete degradation of hydrazine, no pollution to the environment, good stability (reusable), and the preparation method is simpler. , economical, green and efficient treatment.
  • the nanoporous Ti0 2 prepared by the invention is used as a carrier, and under the action of a dispersing agent, composite manganese oxide, molybdenum oxide, zirconium oxide, iron oxide, copper oxide, and sulfate are supported.
  • the catalyst is prepared by sol-gel method, using tetrabutyl titanate and metal salt as raw materials, hydrolyzed, aging, sulfuric acid impregnation, high temperature calcination to obtain a solid acid catalyst.
  • the composition of the catalyst is represented by S0 4 2 7Ti0 2 - M x O y .
  • the catalyst obtained by the invention has low cost and good stability, and can degrade hydrazine very efficiently at normal temperature. It is a green hydrazine wastewater treatment catalyst and has good industrial application prospects.
  • the invention relates to the technical field of preparation of green solid acid catalyst and waste water treatment.
  • the composition of the catalyst is as follows: S0 4 2 7Ti0 2 -M x O y (/ distinguishes between the active component and the carrier, - distinguishes between the carrier and the auxiliary, S0 4 2 7Ti0 2 -M x O y represents S0 4 2 - is an active component, Ti0 2 is used as a carrier, and a composite auxiliary oxide M x O y ), wherein M is Mn, Mo, Zr, Fe, Cu.
  • the supported amount of the metal oxide (the weight of the metal oxide as a percentage of the total weight of the catalyst) is from 2.5 to 40% by weight.
  • the above hydrazine degradation catalyst is prepared by a sol-gel method.
  • the specific process is as follows: using tetrabutyl titanate as raw material, dissolving in ethanol solution containing glacial acetic acid, using polyvinylpyrrolidone as dispersing agent, stirring in oil bath of 50 ⁇ 80 ° C for 0.5 ⁇ 2 hours, then dropping into solution Adding a metal salt aqueous solution having a concentration of 1 to 20% by weight, heating and stirring for 1 to 6 hours, allowing the sol to be aged for 10 to 24 hours after hydrolysis, and the obtained gel is dried at 90 to 120 ° C, ground, sieved, The sulfuric acid solution is immersed for 10 to 24 hours, suction-filtered, washed, dried at 90 to 120 ° C, and calcined at 400 to 550 ° C for 3 to 6 hours to prepare a powdery cerium degradation catalyst.
  • the prepared catalyst is tableted, sieved, and used for deuteration degradation at room temperature.
  • the catalyst degrades hydrazine by 98% under the reaction conditions of 70 °C. These catalysts are easy to prepare, have high reactivity, use non-precious metal elements, are low in cost, and have good stability (reusable). It has a very high catalytic activity for the degradation reaction at room temperature, and is especially suitable for the treatment of wastewater.
  • the catalyst preparation method provided by the invention is simple and convenient to operate, and the method adopts non-precious metal elements, has low cost and has good industrial application prospect.
  • the catalyst provided by the invention has high reactivity, good stability and can be reused. 3.
  • the catalyst provided by the invention is used for hydrazine degradation, has very high catalytic activity at normal temperature, has short processing period, fast reaction speed and complete degradation, and the hydrazine degradation is over 98% under the reaction condition of 70 °C.
  • O.lmol tetrabutyl titanate, 0.15 mol glacial acetic acid was dissolved in 100 mL of absolute ethanol, and 50 mL of an anhydrous ethanol solution containing 3 wt% of polyvinylpyrrolidone was added to the mixed solution while stirring, and the oil bath was placed at 60 ° C in an oil bath. After stirring for 1 hour, the mixture was stirred uniformly, and a 5 ⁇ % aqueous solution of metal salt was added dropwise to the mixed solution, and the mixture was further heated and stirred for 3 hours to hydrolyze.
  • the hydrolyzed sol was allowed to stand for aging for 12 hours, and the obtained gel was dried at 90 ° C, ground, and passed through 60 The mesh was immersed in an O.8 mol/L sulfuric acid solution for 24 h, suction filtered, washed, dried at 90 ° C, and calcined at 550 ° C for 3 h.
  • the type and concentration of the metal salt are changed, and a series of different metal oxide supporting amounts of S0 4 2 7Ti0 2 -M x O y catalyst are prepared.
  • M is Mn, Mo, Zr, Fe, or Cu.
  • the catalyst is prepared in the same manner as in the first embodiment. Unlike the first embodiment, the ground sieved sample is directly immersed in a muffle furnace at 550 ° C for 3 hours to obtain a powder Ti0 2 -Mo 2 0 3 without being impregnated with sulfuric acid.
  • the supported amount of the catalyst metal oxide was 20% by weight.
  • the catalyst was prepared in the same manner as in Example 1. The difference from Example 1 was that no polyvinylpyrrolidone was added during the preparation, and the effect of the addition of the dispersant polyvinylpyrrolidone on the particle size distribution of the catalyst was examined.
  • the obtained catalyst was subjected to particle size analysis and N 2 adsorption-desorption ratio surface area.
  • the results showed that the average particle diameter of the catalyst prepared without polyvinylpyrrolidone was 0.639 um, and the specific surface area was 45.36 m 2 /g, plus polyvinylpyrrolidone.
  • the prepared catalyst had a uniform particle size distribution, and the results are shown in Fig. 2A, and the average particle diameter was 0.011 urn, and the specific surface area was 101.95 m 2 /g.
  • polyvinylpyrrolidone is used as a polymer surfactant to generate steric hindrance by polymer coating, which makes the nanoparticles easy to disperse, and improves the agglomeration of Ti0 2 nanoparticles and reduces the particle size.
  • the effect of preparing the catalyst particles with good dispersion and uniform particle size distribution helps to improve the stability of the catalyst.
  • the catalyst preparation was the same as in Example 1.
  • the ruthenium degradation activity of the catalyst was tested in a three-necked flask with a magnetic stirrer, a dropping funnel and a reflux condenser.
  • the reaction raw material was 100 mL of hydrazine solution (1000 mg/L), 2 g of H 2 O 2 was added dropwise, the amount of the catalyst was 0.5 g, the reaction temperature was 70 ° C, and the reaction time was 40 min.
  • the cesium concentration was sampled from the reactor at regular intervals, and dimethylaminobenzaldehyde was used as a color developer, and the spectrophotometric method was used for analysis.
  • the prepared catalysts of different metal salt types were used in the hydrazine degradation experiment, and the obtained hydrazine degradation process curve is shown in Fig. 1.
  • the ⁇ degradation rate is shown in Table 1.
  • the catalyst of the present invention is prepared SO 4 2 7TiO 2 -20wt% Mo 2 O 3 Degradation experiments testing the activity of the comparative catalyst with TiO 2 -20wt% Mo 2 O 3 for the hydrazine reaction conditions as in Example 4. The results showed that the degradation rate of ruthenium was only 43.03% using a blank catalyst which was not impregnated with sulfuric acid. The degradation rate of the catalyst which is also impregnated with sulfuric acid can reach 91.66%. It indicates that the supported sulfuric acid has better catalytic activity.
  • Example 2 In the same manner as in Example 1, a metal complex solid acid catalyst with different manganese oxide loadings was prepared and used in the hydrazine degradation experiment. The reaction conditions were the same as those in Example 4. The ruthenium degradation rate results are shown in Table 2.
  • the ruthenium degradation activity of the catalyst increases with the increase of manganese oxide loading, when the loading reaches 20wt% And above, ⁇ is almost completely degraded.
  • the catalyst is subjected to suction filtration, washing, drying, and regeneration to obtain a catalyst for catalyzing the next deuterium degradation reaction.
  • the catalyst activity test was the same as in Example 4.
  • the deuteration degradation rate of the obtained catalyst is repeated as shown in the table.
  • the catalytic activity was compared for different reaction liquid systems.
  • the reaction raw materials were 100 mL of hydrazine solution (1000 mg/L), H 2 O 2 was added in an amount of 2 g, the amount of the catalyst was 0.5 g, and the reaction temperature was 70 °C.
  • Experimental results show that the presence of 3 ⁇ 40 2 can promote the degradation reaction of hydrazine and increase the reaction rate.
  • the hydrazine solution + catalyst reacts rapidly at normal temperature, and there is obvious gas formation.
  • the reaction needs 2h ⁇ solution + H 2 0 2 + catalyst to react rapidly, and the time required for complete degradation of hydrazine is about 40min.

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Description

一种用于肼降解催化剂的制备和应用方法 技术领域
本发明涉及一种用于肼、水合肼降解的催化剂的制备及应用， 特别涉及一种 复合金属氧化物固体酸催化剂的制备和该类催化剂在常温下催化肼降解中的应 用。 背景技术
肼在航天飞行器中意义重大， 主要用作火箭和喷气发动机的燃料部分。 同时 肼毒性很大， 肼类燃料在生产、 运输、 贮存等过程中， 易发生滴漏和突发泄漏。 含肼的废水一旦进入周围环境， 将会造成周边环境包括土壤、水质的污染， 对周 边居民、 牲畜产生危害。 因此， 肼污水净化处理技术受到高度重视。
肼具有强还原性， 其可生化性较差。 肼在常温下性质较稳定， 250°C左右可 发生热降解。 肼在催化剂作用下， 如报道担载型 Ιι7γ-Α1203 (Applied Catalysis A:General, 182 (1999) 317-325 ), CuxMg1-xCr204/Y- Al203( Catalysis Today, 75 (2002) 277-285 ) 等催化剂， 能够非常高效地将肼降解为 N2等气体。
催化肼降解的活性组分是担载的贵金属铱，如 Ιι7γ-Α1203，担载量 20〜40wt%。 贵金属铱成本高， 因此研制低成本的、常温下高活性的肼降解催化剂具有良好的 应用前景。 文献中报道了过渡金属氮化物、 碳化物、 磷化物 (CN101380586A,CN101411975A,ZL200410021372.9)在肼降解反应中表现出了 很好的催化活性， 但没有复合金属氧化物固体酸催化剂用于肼降解的专利报道。
复合金属氧化物固体酸催化剂， 是一种环境友好型催化剂， 其催化活性高、 条件温和、 不腐蚀设备、 后处理简单、 对环境无污染， 是一类肼污水净化具有重 要应用前景的绿色催化剂。
本发明的目的是提供一种低成本的复合金属氧化物固体酸催化剂，常温下可 以非常高效地将肼、水合肼降解为 H2、 N2、 NH3等， 是绿色肼废水处理催化剂。 催化剂的存在会加速 N2H4的降解， 縮短处理周期， 提高处理效果。 并且催化剂 催化的水合肼降解过程， 可替代燃料电池的氢燃料， 制作肼燃料电池 (CN1348835 ， United States Patent 3442711 ) 发明内容
技术问题： 本发明要解决的技术问题在于提供一种复合金属氧化物固体酸 催化剂的制备方法和该类催化剂在肼降解反应中的应用。 即应用纳米多孔 Ti02 为载体， 在分散剂的作用下， 复合锰、 钼、 锆、 铁、 铜的氧化物， 负载硫酸根， 采用非均相催化氧化技术， 氧化降解肼以及水合肼。
本发明制备的催化剂在常温下用于肼降解反应具有很高的活性，成本低、对 肼的降解彻底、 对环境无污染， 稳定性好 （可重复使用）， 该制备方法是一种更 简便、 经济、 绿色高效的处理方法。
技术方案： 本发明制备的以纳米多孔 Ti02为载体， 在分散剂的作用下， 复合氧化锰、 氧化钼、 氧化锆、 氧化铁、 氧化铜， 负载硫酸根。 催化剂制备采 用溶胶-凝胶法， 以钛酸四丁酯和金属盐为原料， 经过水解、 陈化， 硫酸浸渍， 高温煅烧而得到固体酸催化剂，该催化剂组成表示方式为 S04 27Ti02-MxOy。该 发明得到的催化剂成本低， 稳定性好， 常温下可以非常高效将肼降解， 是绿色 肼废水处理催化剂， 具有良好的工业应用前景。 本发明是绿色固体酸催化剂制 备与肼废水处理技术领域。
该催化剂的组成如下： S04 27Ti02-MxOy (/ 区分的是活性组分与载体， - 区 分的是载体与助剂， S04 27Ti02-MxOy代表以 S04 2—为活性组分， 以 Ti02为载体， 复合助剂氧化物 MxOy)， 其中， M为 Mn、 Mo、 Zr、 Fe、 Cu。 金属氧化物的担 载量 （金属氧化物重量占催化剂总重量的百分比） 为 2.5〜40wt%。
上述肼降解催化剂采用溶胶-凝胶法制备。 具体过程为： 以钛酸四丁酯为原 料， 溶于含冰醋酸的乙醇溶液， 以聚乙烯吡咯烷酮为分散剂， 于 50〜80°C油浴下 搅拌 0.5〜2小时， 然后向溶液中滴加浓度为 l〜20wt%的金属盐水溶液， 继续加热 搅拌 1〜6小时， 将水解后溶胶静置陈化 10〜24小时， 所得凝胶于 90〜120°C烘干， 研磨， 过筛， 硫酸溶液浸渍 10〜24小时， 抽滤， 洗涤， 90〜120°C烘干， 400〜550 °C煅烧 3〜6小时， 制成粉状肼降解催化剂。
所制备的催化剂经压片， 过筛， 用于常温下肼降解反应。
所述催化剂在 70°C反应条件下可将肼降解达 98%。 该类催化剂易于制备， 反应活性高， 采用非贵金属元素， 成本低， 稳定性好 （可重复使用）。 常温下用 于肼降解反应有非常高的催化活性， 特别适用于肼废水处理。
有益效果： 本发明的优点为：
1.本发明所提供的催化剂制备方法简单， 便于操作， 且该方法采用非贵金属 元素， 成本低， 具有很好的工业应用前景。
2.本发明所提供的催化剂反应活性高， 稳定性好， 可重复使用。 3.本发明所提供的催化剂用于肼降解， 常温下有非常高的催化活性， 处理周 期短， 反应速度快， 降解彻底， 70°C反应条件下， 肼降解达 98%以上。 附图说明
图 1. 不同种类催化剂的肼降解进程曲线，
图 2. 分散剂对催化剂粒径分布的影响。 具体实施方式
下面通过实施例更好地阐明本催化剂的制备和应用。
实施例 1 溶胶 -凝胶法制备 S04 27Ti02-MxOy催化剂
将 O.lmol钛酸四丁酯， 0.15mol冰醋酸溶于 lOOmL无水乙醇中， 边搅拌边 向混合溶液中加入含有 3wt%聚乙烯吡咯烷酮的无水乙醇溶液 50mL， 于 60°C油 浴下搅拌 lh， 搅拌均匀后向混合溶液中滴加浓度 5^%金属盐水溶液， 继续加热 搅拌 3h水解， 将水解后溶胶静置陈化 12h， 所得凝胶于 90°C烘干， 研磨， 过 60 目筛， 在 O.8mol/L硫酸溶液中浸渍 24h， 抽滤， 洗涤， 90°C干燥， 550°C煅烧 3h。
按上述制备过程， 改变金属盐的种类和浓度， 制备得到一系列不同金属氧化 物担载量的 S04 27Ti02-MxOy催化剂。 其中， M为 Mn、 Mo、 Zr、 Fe、 Cu。
实施例 2 催化剂 Ti02-Mo203的制备
催化剂的制备方法同实施例 1， 与实施例 1不同的是， 研磨过筛后的样品不 经硫酸浸渍， 直接于马弗炉中 550°C煅烧 3h得到粉末 Ti02-Mo203， 该催化剂金 属氧化物的担载量为 20wt%。
实施例 3 分散剂对催化剂粒径分布的影响
催化剂的制备方法同实施例 1， 与实施例 1不同的是在制备过程中不加入聚 乙烯吡咯烷酮， 考察添加分散剂聚乙烯吡咯烷酮对对催化剂粒径分布的影响。
对所得催化剂进行粒度分析和 N2吸附 -脱附测比表面积， 结果表明， 不加聚 乙烯吡咯烷酮所制备的催化剂平均粒径为 0.639 um， 比表面积为 45.36m2/g ， 加 聚乙烯吡咯烷酮所制备的催化剂粒度分布均匀， 结果如图 2A所示， 平均粒径为 0.011 urn, 比表面积为 101.95m2/g。 在催化剂制备过程中， 聚乙烯吡咯烷酮作为 高分子表面活性剂，通过其高分子包覆作用产生空间位阻斥力， 使纳米粒子容易 分散， 对改善 Ti02纳米颗粒团聚、 使粒径减小有明显的作用， 从而制备得到分 散好， 粒度分布均匀的催化剂颗粒， 有助改善催化剂稳定性。 实施例 4 不同金属盐种类催化剂的肼降解实验
催化剂制备同实施例 1。
催化剂活性测试：
催化剂的肼降解活性测试在带有磁力搅拌器、滴液漏斗和回流冷凝管的三颈 烧瓶中进行。 反应原料为 lOOmL肼溶液 （1000mg/L)， 滴加 2g H202， 催化剂用 量为 0.5g， 反应温度为 70°C， 反应时间 40min。定时从反应器中取样进行肼浓度 检测， 以对二甲氨基苯甲醛为显色剂， 采用分光光度法进行分析。
按照上述过程，所制备的不同金属盐种类催化剂用于肼降解实验， 所得的肼 降解进程曲线如图 1， 肼降解率如表 1。
表 1 不同种类催化剂的肼降解率
编 号 1 2 3 4 5
S04 27Ti02-MxOy Mn Mo Zr Fe Cu 肼降解率 。 94.85 92.76 91.54 91.2 90.20 本发明的低成本的复合金属氧化物固体酸催化剂， 应用于肼降解， 常温下肼 降解率达到 90%以上。
比较例 1
本发明所制备的催化剂 SO4 27TiO2-20wt%Mo2O3同 TiO2-20wt%Mo2O3用于肼 降解实验进行催化剂活性测试对比， 反应条件如实施例 4。 结果显示， 使用未经 硫酸浸渍的空白催化剂， 肼的降解率仅为 43.03%。 同样经硫酸浸渍的催化剂肼 的降解率可达 91.66%。 表明负载硫酸具有更好的催化活性。
实施例 5 不同金属氧化物担载量的催化剂的肼降解实验
同实施例 1， 制备了不同氧化锰担载量的金属复合物固体酸催化剂， 并用于 肼降解实验， 反应条件同实施例 4， 肼降解率结果见表 2。
表 2 不同担载量催化剂的肼降解率 编 号 1 2 3 4 5 氧化锰担载量 /wt% 2.5 10 20 30 40 肼降解率 /% 91.08 94.23 99.84 99.57 99.87
催化剂的肼降解活性随着氧化锰担载量的增加而提高，当担载量达到 20wt% 及以上， 肼几乎完全降解。
实施例 6 重复使用次数对催化剂性能的影响
反应后将催化剂经抽滤， 洗涤， 干燥， 再生得到的催化剂用于催化下一次的 肼降解反应。 催化剂活性测试同实施例 4。 所得催化剂重复使用的肼降解率如表
3。
表 3 重复使用的催化剂的肼降解率
使用次数 1 2 3 4 5 肼降解率 /% 99.84 99.41 98.56 96.38 91.79 由表 3可知， 复合金属氧化物固体酸催化剂用于常温下肼降解实验， 具有较 好的催化稳定性。
实施例 7 催化剂的肼降解实验
针对不同反应液体系， 对比了催化活性。 其中反应原料均为 lOOmL肼溶液 ( 1000mg/L), H202加量 2g， 催化剂用量为 0.5g， 反应温度为 70°C。 实验现象 表明， ¾02的存在可以促进肼降解反应的进行， 提高反应速率。
表 4 不同反应体系的催化剂的肼降解实验
反应体系 M
肼溶液 +¾02 常温下反应缓慢， 观察不到气体的生成
肼溶液 +催化剂 常温下反应较快， 有明显的气体生成， 反应的完成需要 2h 肼溶液 +H202+催化剂 反应迅速， 肼完全降解所需时间约 40min

Claims

权利要求书
1、 一种用于肼降解催化剂的制备方法， 其特征在于： 该催化剂的通式表示 为： S04 27Ti02-MxOy， 其中， M为 Mn、 Mo、 Zr、 Fe、 Cu中的一种， x为 1， 2， y 为 1， 2， 3； 该肼降解催化剂采用溶胶-凝胶法制备， 具体过程为： 以钛酸四丁 酯为原料， 溶于含冰醋酸的乙醇溶液， 以聚乙烯吡咯烷酮为分散剂， 于 50~80°C 油浴下搅拌 0.5~2小时， 然后向溶液中滴加浓度为 l~20wt%的金属盐水溶液， 继 续加热搅拌 1~6小时， 将水解后溶胶静置陈化 10~24小时， 所得凝胶于 90~120 °C烘干， 研磨， 过筛， 硫酸溶液浸渍 10~24小时， 抽滤， 洗涤， 90~120°C烘干， 400~550°C煅烧 3~6小时， 制成粉状肼降解催化剂。
2、 根据权利要求 1所述的一种肼降解催化剂的制备方法， 其特征在于所制 备的粉状肼降解催化剂经压片， 过筛， 制成片状肼降解催化剂， 用于常温下肼降 解反应。
3、 根据权利要求 1或 2所述的一种肼降解催化剂的制备方法， 其特征在于 所制备的肼降解催化剂中， 金属氧化物的担载量为 2.5~40 wt%。
4、根据权利要求 1或 2所述的一种肼降解催化剂的制备方法，其特征在于 所述的硫酸溶液浸渍时， 硫酸溶液浓度为 0.1~1.0 mol/L。
5、根据权利要求 1或 2所述的一种肼降解催化剂的制备方法，其特征在于 以聚乙烯吡咯烷酮为分散剂的加量为 1~5 wt%。
6、 如权利要求 1所述的一种肼降解催化剂用于肼氧化降解的应用方法， 其 特征在于该催化剂用在肼降解中， 反应液温度 10~100°C， pH 5-8
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