WO2011127737A1 - 一种对废水中氨氮具有高选择性的改性分子筛及其制备方法 - Google Patents

一种对废水中氨氮具有高选择性的改性分子筛及其制备方法 Download PDF

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WO2011127737A1
WO2011127737A1 PCT/CN2010/079878 CN2010079878W WO2011127737A1 WO 2011127737 A1 WO2011127737 A1 WO 2011127737A1 CN 2010079878 W CN2010079878 W CN 2010079878W WO 2011127737 A1 WO2011127737 A1 WO 2011127737A1
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molecular sieve
magnesium
ammonia nitrogen
modified molecular
high selectivity
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French (fr)
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任洪强
张涛
丁丽丽
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Nanjing University
Nanjing Tech University
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Nanjing University
Nanjing Tech University
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Priority to US13/420,600 priority patent/US8709963B2/en
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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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • 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

  • Modified molecular sieve having high selectivity to ammonia nitrogen in wastewater and preparation method thereof
  • the invention relates to a modified molecular sieve for treating waste water and a preparation method thereof, in particular to a modified molecular sieve for highly selective removal of ammonia nitrogen in waste water and a preparation method thereof.
  • ammonia nitrogen wastewater pollution has become the main source of pollution of surface water in China.
  • Ammonia nitrogen wastewater has many sources of pollution, large emissions, and the concentration of emissions is ever-changing.
  • China's ammonia nitrogen wastewater discharge has far exceeded the capacity of the environment. If the theoretical research and technical application of ammonia nitrogen wastewater treatment technology are not strengthened, the environmental protection situation in China will be more severe.
  • methods for removing ammonia nitrogen in wastewater include biotechnology, air stripping technology, membrane absorption technology, and magnesium ammonium phosphate precipitation technology.
  • the treatment of ammonia nitrogen wastewater by magnesium ammonium phosphate precipitation technology is a hot research technology at home and abroad.
  • the method is to add magnesium salt and phosphate to the wastewater, and chemically react with ammonia nitrogen in the wastewater to form a magnesium ammonium phosphate precipitate (MgNH 4 P0 4 * 63 ⁇ 40) to be removed.
  • the method has simple process flow and is easy to operate and manage, but due to the fluctuation of water quality and quantity of wastewater in the actual treatment process, the quantitative addition of magnesium salt and phosphate is affected. If the dosage of magnesium salt and phosphate is higher than the content of ammonia nitrogen in the wastewater, it is easy to cause waste of chemical precipitation agent; if the dosage of magnesium salt and phosphate is lower than the content of ammonia nitrogen in wastewater, it will affect the treatment of ammonia nitrogen wastewater. effect.
  • the application of fixed bed reactor to treat ammonia nitrogen waste water can effectively solve the problem that magnesium salt and phosphate are difficult to be quantitatively added due to large fluctuations in wastewater quality and quantity. However, the application method of the fixed bed reactor can cause a huge pressure drop when the amount of waste water is large, which is difficult to be practically applied. The above technical difficulties have affected the further research and application of the ammonium magnesium phosphate method.
  • Molecular sieve is a cubic aluminosilicate compound, which is mainly composed of silica-alumina through an oxygen bridge to form an open skeleton structure. In the structure, there are many pores with uniform pores and well-arranged cavities with large internal surface area. Molecular sieves have the advantages of low fluid resistance, high adsorption speed, large adsorption capacity, high selectivity and high mechanical strength. However, pure molecular sieves do not have a highly selective removal effect on ammonia nitrogen. Therefore, how to effectively utilize the structural characteristics of molecular sieves, so that the molecular sieves can retain the advantages of low fluid resistance, stable performance, and high selectivity. The removal of ammonia nitrogen has become an intractable problem. At present, the research and application of molecular sieves using magnesium compounds and phosphorus compounds to remove ammonia nitrogen in wastewater have not been reported in the literature and disclosed in the patent. Summary of the invention
  • the invention discloses a modified molecular sieve having high selectivity to ammonia nitrogen in waste water and a preparation method thereof for removing the problem of ammonia nitrogen in waste water, and adopting a low fluid resistance and high stability.
  • the modified molecular sieve of the magnesium-loaded compound and the phosphorus compound removes the ammonia nitrogen in the wastewater, which can effectively solve the problem of a large pressure drop when the ammonia nitrogen wastewater is treated by the application method of the fixed bed reactor, and the modified molecular sieve can be widely applied. Highly selective removal of ammonia nitrogen from contaminated water.
  • a modified molecular sieve having high selectivity to ammonia nitrogen in wastewater the main structural components thereof include:
  • the basic skeleton is a molecular sieve
  • the functional material supported on the inner surface of the skeleton is a compound of magnesium and a compound of phosphorus.
  • the molecular sieves constituting the basic skeleton described in (1) are common mesoporous molecular sieves of various structures, having a pore diameter of 1. 5 to 10 nm, a BET specific surface area of more than 600 m 2 /g, and a relative crystallinity of more than 90%. There is no specific requirement for the Si/Al of the molecular sieve, and it is greater than 1.
  • the preferred molecular sieve is MCM-41 or SBA-15, most preferably MCM_41.
  • the compound of magnesium in the functional material to be supported as described in (2) is magnesium oxide, magnesium carbonate, magnesium phosphate, magnesium nitrate or the like, and the phosphorus compound is phosphorus pentoxide or magnesium phosphate.
  • the modified molecular sieve has a magnesium content of 5 to 25% by weight and a phosphorus content of 5 to 20% by weight.
  • the invention relates to a preparation method of a modified molecular sieve having high selectivity to ammonia nitrogen in waste water, which mainly comprises the following steps:
  • the magnesium salt used in the step (1) is magnesium nitrate, magnesium carbonate or magnesium oxide.
  • the temperature of the dry dehydration in the step (3) is 100 to 200 ° C, and the time is 4 to 8 h.
  • the temperature of the dry dehydration in the step (4) is 100 to 200 ° C, and the time is 4 to 8 h.
  • the invention provides a modified molecular sieve with high selectivity to ammonia nitrogen in wastewater and a preparation method thereof, and the prepared modified molecular sieve can effectively solve the problem of large pressure drop when the ammonia nitrogen wastewater is treated by the application method of the fixed bed reactor. Problem, high selectivity for the removal of ammonia nitrogen from wastewater.
  • the preparation process of the invention is simple, the material is easy to purchase, and the production is convenient. detailed description
  • a 2 mol/L magnesium salt solution was prepared using magnesium nitrate, and a 2 mol/L phosphoric acid solution was prepared using phosphoric acid.
  • Molecular sieve MCM-41 was added to an equal volume of magnesium salt solution and stirred for 10 min, allowed to stand for 6 h, then dried and dehydrated, and the temperature of drying and dehydration was controlled to be 100 ° C for 8 h, then calcined, and the calcination temperature was adjusted to 500. °C, the time is 6h, that is, the modified molecular sieve of the compound supporting magnesium is obtained.
  • the modified molecular sieve of the magnesium-supporting compound is added to an equal volume of phosphoric acid solution and stirred for 20 minutes, allowed to stand for 1 hour, and then dried and dehydrated, and the temperature of drying and dehydration is controlled to be 100 ° C for 6 hours, and then calcination is carried out to adjust the baking.
  • the temperature was 400 ° C and the time was 4 h, and a modified molecular sieve of a compound supporting magnesium and a compound of phosphorus was obtained.
  • the compound of magnesium was magnesium oxide, and the compound of phosphorus was phosphorus pentoxide.
  • the modified molecular sieve has a pore diameter of 2 to 5 nm, a BET specific surface area of more than 850 m 2 /g, a relative crystallinity of more than 90%, and a molecular sieve Si/Al of more than 1.
  • the modified molecular sieve has a magnesium content of 10% by weight and a phosphorus content of 10% by weight, which can remove ammonia nitrogen in the wastewater with high selectivity, and the adsorption amount of ammonia nitrogen reaches 180 mg/g molecular sieve.
  • a 4 mol/L magnesium salt solution was prepared using magnesium carbonate, and a 4 mol/L phosphoric acid solution was prepared using phosphoric acid.
  • Molecular sieve MCM-41 was added to an equal volume of magnesium salt solution and stirred for 30 min, allowed to stand for 5 h, then dried and dehydrated, and the temperature of drying and dehydration was controlled to 200 ° C for 4 h, followed by calcination, and the calcination temperature was adjusted to 600. °C, time is 5h, that is, a modified molecular sieve of a compound supporting magnesium is obtained.
  • the modified molecular sieve of the magnesium-supporting compound is added to an equal volume of phosphoric acid solution and stirred for 10 minutes, allowed to stand for 6 hours, and then dried and dehydrated, and the temperature of drying and dehydration is controlled to be 150 ° C for 8 hours, and then calcination is carried out to adjust the baking.
  • the temperature is 500 ° C
  • the time is 3 h
  • a modified molecular sieve of a compound containing magnesium and a compound of phosphorus is obtained, wherein the compound of magnesium is magnesium carbonate, and the combination of phosphorus
  • the substance is phosphorus pentoxide.
  • the modified molecular sieve has a pore diameter of 1.
  • the modified molecular sieve has a magnesium content of 20% by weight and a phosphorus content of 20% by weight, which can remove ammonia nitrogen in the wastewater with high selectivity, and the adsorption amount of ammonia nitrogen reaches 275 mg/g molecular sieve.
  • a magnesium salt solution of 5 mol/L was prepared using magnesium oxide, and a phosphoric acid solution of 4 mol/L was prepared using phosphoric acid.
  • the molecular sieve SBA-15 was added to an equal volume of magnesium salt solution and stirred for 20 min, allowed to stand for 3 h, then dried and dehydrated, and the temperature of drying and dehydration was controlled to be 150 ° C for 6 h, followed by calcination, and the calcination temperature was adjusted to 400. °C, the time is 2h, that is, the modified molecular sieve of the compound supporting magnesium is obtained.
  • the modified molecular sieve of the magnesium-supporting compound is added to an equal volume of phosphoric acid solution and stirred for 30 minutes, and allowed to stand for 2 hours, then dried and dehydrated, and the temperature of drying and dehydration is controlled to be 200 ° C for 4 hours, and then calcination is carried out to adjust the baking.
  • the temperature was 600 ° C and the time was 2 h, and a modified molecular sieve of a compound supporting magnesium and a compound of phosphorus was obtained.
  • the compound of magnesium was a mixture of magnesium nitrate and magnesium phosphate, and the compound of phosphorus was magnesium phosphate.
  • the modified molecular sieve has a pore diameter of 5 to 10 nm, a BET specific surface area of more than 600 m 2 /g, a relative crystallinity of more than 90%, and a molecular sieve Si/Al of more than 1.
  • the modified molecular sieve has a magnesium content of 25% by weight and a phosphorus content of 20% by weight, which can remove ammonia nitrogen in the wastewater with high selectivity, and the adsorption amount of ammonia nitrogen reaches 290 mg/g molecular sieve.
  • a magnesium salt solution of 3 mol/L was prepared using magnesium nitrate, and a phosphoric acid solution of 3 mol/L was prepared using phosphoric acid.
  • the molecular sieve SBA-15 was added to an equal volume of magnesium salt solution and stirred for 10 min, allowed to stand for 4 h, then dried and dehydrated, and the temperature of drying and dehydration was controlled to be 200 ° C for 6 h, followed by calcination, and the calcination temperature was adjusted to 300. °C, the time is 3h, that is, the modified molecular sieve of the compound supporting magnesium is obtained.
  • the modified molecular sieve of the magnesium-supporting compound is added to an equal volume of phosphoric acid solution and stirred for 30 minutes, allowed to stand for 5 hours, then dried and dehydrated, and the temperature of drying and dehydration is controlled to be 200 ° C for 8 hours, and then calcination is carried out to adjust the baking.
  • the temperature was 500 ° C and the time was 5 h, and a modified molecular sieve of a compound supporting magnesium and a compound of phosphorus was obtained.
  • the compound of magnesium was magnesium phosphate, and the compound of phosphorus was a mixture of phosphorus pentoxide and magnesium phosphate.
  • the modified molecular sieve has a pore diameter of 6 to 10 nm, a BET specific surface area of more than 650 m 2 /g, a relative crystallinity of more than 90%, and a molecular sieve Si/Al of more than 1.
  • the modified molecular sieve has a weight percentage of magnesium of 15% and a phosphorus content of 15%, which can remove ammonia nitrogen in the wastewater with high selectivity, and the adsorption amount of ammonia nitrogen reaches 235 mg/g molecular sieve.
  • a magnesium salt solution of 1 mol/L was prepared using magnesium oxide, and a phosphoric acid solution of 1 mol/L was prepared using phosphoric acid.
  • Molecular sieve MCM-48 was added to an equal volume of magnesium salt solution and stirred for 20 min, allowed to stand for 1 h, then dried and dehydrated, controlled to dry and dehydrate at a temperature of 100 ° C for 4 h, then calcined to adjust the calcination temperature to 500. °C, the time is 4h, that is, the modified molecular sieve of the compound supporting magnesium is obtained. Then, the modified molecular sieve of the magnesium-supporting compound is added to an equal volume of phosphoric acid solution and stirred for 20 minutes, allowed to stand for 4 hours, then dried and dehydrated, and the temperature of drying and dehydration is controlled to be 150 ° C for 4 hours, and then calcination is carried out to adjust the baking.
  • the temperature was 300 ° C and the time was 2 h, and a modified molecular sieve of a compound supporting magnesium and a compound of phosphorus was obtained.
  • the compound of magnesium was magnesium carbonate, and the compound of phosphorus was phosphorus pentoxide.
  • the modified molecular sieve has a pore diameter of 1. 5 to 5 nm, a BET specific surface area of more than 750 m 2 /g, a relative crystallinity of more than 90%, and a molecular sieve Si/Al of more than 1.
  • the modified molecular sieve has a weight percentage of magnesium of 5% and a phosphorus content of 5% by weight, which can remove ammonia nitrogen in the wastewater with high selectivity, and the adsorption amount of ammonia nitrogen reaches 140 mg/g molecular sieve.
  • a 2 mol/L magnesium salt solution was prepared using magnesium carbonate, and a 2 mol/L phosphoric acid solution was prepared using phosphoric acid.
  • the molecular sieve SBA-3 was added to an equal volume of magnesium salt solution and stirred for 30 min, allowed to stand for 2 h, then dried and dehydrated, and the temperature of drying and dehydration was controlled to be 150 ° C for 8 h, followed by calcination, and the calcination temperature was adjusted to 600. °C, the time is 4h, that is, the modified molecular sieve of the compound supporting magnesium is obtained.
  • the modified molecular sieve of the magnesium-supporting compound is added to an equal volume of phosphoric acid solution and stirred for 10 minutes, allowed to stand for 3 hours, then dried and dehydrated, and the temperature of drying and dehydration is controlled to be 100 ° C for 6 hours, and then calcination is carried out to adjust the baking.
  • the temperature was 400 ° C and the time was 6 h, and a modified molecular sieve of a compound supporting magnesium and a compound of phosphorus was obtained.
  • the compound of magnesium was magnesium oxide, and the compound of phosphorus was phosphorus pentoxide.
  • the modified molecular sieve has a pore diameter of 1.
  • the modified molecular sieve has a magnesium content of 10% by weight and a phosphorus content of 10% by weight, which can remove ammonia nitrogen in the wastewater with high selectivity, and the adsorption amount of ammonia nitrogen reaches 190 mg/g molecular sieve.

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Description

一种对废水中氨氮具有高选择性的改性分子筛及其制备方法 技术领域
本发明涉及到一种处理废水的改性分子筛及其制备方法， 具体的说是一种高选择 性去除废水中氨氮的改性分子筛及其制备方法。 背景技术
随着我国经济社会的高速发展， 各种污染物的排放量急剧增加。 其中， 氨氮废水 污染已经成为我国地表水的主要污染来源。 氨氮废水污染来源多， 排放量大， 并且排 放的浓度千变万化。 目前， 我国的氨氮废水排放量已经远远超过了环境所能承受的能 力， 如果不加强对氨氮废水处理技术的理论研究与技术应用， 我国的环境保护形势将 更加严峻。
现有技术中， 去除废水中氨氮的方法有生物技术， 空气吹脱技术， 膜吸收技术， 磷酸铵镁沉淀技术等。 目前， 磷酸铵镁沉淀技术处理氨氮废水是国内外研究的热点技 术。 该方法是向废水中投加镁盐和磷酸盐， 与废水中的氨氮发生化学反应， 生成磷酸 铵镁沉淀 （MgNH4P04* 6¾0) 而被去除。
Mg2+ + H: + P(¾- + 6H20→ Mg H4P04 .6H20 i
该方法工艺流程简单， 易于操作管理， 但是由于在实际处理过程中， 废水的水质 水量波动大， 影响镁盐和磷酸盐的定量投加。 如果镁盐和磷酸盐的投加量高于废水中 氨氮的含量， 容易造成化学沉淀药剂的浪费； 如果镁盐和磷酸盐的投加量低于废水中 氨氮的含量， 会影响氨氮废水的处理效果。 采用固定床反应器的应用方式处理氨氮废 水， 可以有效解决废水水质水量波动大造成的镁盐和磷酸盐难以定量投加的问题。 但 是固定床反应器的应用方式处理废水量大时， 会产生巨大的压力降， 难以实际应用。 上述技术困难， 影响了磷酸铵镁法的进一步研究和应用。
分子筛是一种具有立方晶格的硅铝酸盐化合物， 主要由硅铝通过氧桥连接组成空 旷的骨架结构， 在结构中有很多孔径均匀的孔道和排列整齐、 内表面积很大的空穴。 分子筛具有低流体阻力， 高吸附速度， 吸附容量大， 选择性强， 高机械强度等优点。 但是单纯的分子筛并不能对氨氮具有高选择性的去除效果， 因此如何有效的利用分子 筛的结构特性， 使得既可以保留分子筛低流体阻力、 性能稳定等优点， 又可以高选择 性的去除氨氮， 成为现在一个难以解决的课题。 目前， 使用镁的化合物和磷的化合物 改性分子筛去除废水中氨氮的研究和应用未见文献报道和专利公开。 发明内容
1. 发明要解决的技术问题
针对磷酸铵镁沉淀技术去除废水中氨氮所存在的难题， 本发明公开了一种对废水 中氨氮具有高选择性的改性分子筛及其制备方法， 采用了一种低流体阻力、 高稳定性 的固载镁的化合物和磷的化合物的改性分子筛去除废水中的氨氮， 可以有效解决使用 固定床反应器的应用方式处理氨氮废水时， 产生巨大压力降的问题， 该改性分子筛可 以广泛应用于受污染水体中氨氮的高选择性去除。
2. 本发明的技术方案
本发明的技术方案如下：
一种对废水中氨氮具有高选择性的改性分子筛， 其主要结构组成包括：
(1)基本骨架为分子筛；
(2)骨架内表面固载的功能性材料为镁的化合物和磷的化合物。
组成（1)中所述的基本骨架的分子筛为常见的各种结构的介孔分子筛， 其孔径在 1. 5〜10nm之间， BET比表面积大于 600m2/g， 相对结晶度大于 90%， 分子筛的 Si/Al 并无特定要求，大于 1即可。优选的分子筛为 MCM-41或 SBA-15,最优选使用 MCM_41。
组成 (2)中所述的固载的功能性材料中镁的化合物为氧化镁， 碳酸镁， 磷酸镁， 硝酸镁等， 磷的化合物为五氧化二磷， 磷酸镁等。 该改性分子筛中镁的重量百分比含 量为 5〜25%， 磷的重量百分比含量为 5〜20%。
一种对废水中氨氮具有高选择性的改性分子筛的制备方法，其主要包括以下步骤:
(1)将镁盐溶解于水中得到 l〜5mol/L的镁盐溶液；
(2)将磷酸溶解于水中得到 l〜4mol/L的磷酸溶液；
(3)将分子筛加入到步骤（1)配制好的镁盐溶液中搅拌 10〜30min，静置 l〜6h，干 燥脱水， 之后在 300〜600°C的温度下焙烧 2〜6h;
(4)将步骤 (3)焙烧后得到的固载镁的化合物的改性分子筛加入到步骤 (2)配制好 的磷酸溶液中搅拌 10〜30min， 静置 l〜6h， 干燥脱水， 之后在 300〜600°C的温度下 焙烧 2〜6h， 即得到对废水中氨氮具有高选择性的改性分子筛。
步骤（1)中使用的镁盐为硝酸镁、 碳酸镁、 氧化镁。 步骤（3)中干燥脱水的温度为 100〜200°C， 时间为 4〜8h。
步骤 (4)中干燥脱水的温度为 100〜200°C， 时间为 4〜8h。
3. 有益效果
本发明提供了一种对废水中氨氮具有高选择性的改性分子筛及其制备方法， 制备 得到的改性分子筛可以有效解决采用固定床反应器的应用方式处理氨氮废水时， 产生 巨大压力降的问题， 高选择性的去除废水中的氨氮。 本发明制备工艺步骤简单， 材料 易购， 便于生产。 具体实施方式
实施例 1
使用硝酸镁配制 2mol/L的镁盐溶液， 使用磷酸配制 2mol/L的磷酸溶液。 将分子 筛 MCM-41加入到等体积的镁盐溶液中搅拌 10min， 静置 6h， 之后进行干燥脱水， 控 制干燥脱水的温度为 100°C， 时间为 8h， 然后进行焙烧， 调节焙烧的温度为 500°C， 时间为 6h， 即得到固载镁的化合物的改性分子筛。然后将固载镁的化合物的改性分子 筛加入到等体积的磷酸溶液中搅拌 20min， 静置 lh， 之后干燥脱水， 控制干燥脱水的 温度为 100°C， 时间为 6h， 然后进行焙烧， 调节焙烧的温度为 400°C， 时间为 4h， 得 到固载镁的化合物和磷的化合物的改性分子筛， 其中镁的化合物为氧化镁， 磷的化合 物为五氧化二磷。 改性分子筛的孔径在 2〜5nm之间， BET比表面积大于 850m2/g， 相 对结晶度大于 90%， 分子筛的 Si/Al大于 1。 该改性分子筛中镁的重量百分比含量为 10%, 磷的重量百分比含量为 10%， 可以高选择性的去除废水中的氨氮， 对氨氮的吸附 量达到 180mg/g分子筛。 实施例 2
使用碳酸镁配制 4mol/L的镁盐溶液， 使用磷酸配制 4mol/L的磷酸溶液。 将分子 筛 MCM-41加入到等体积的镁盐溶液中搅拌 30min， 静置 5h， 之后进行干燥脱水， 控 制干燥脱水的温度为 200°C， 时间为 4h， 然后进行焙烧， 调节焙烧的温度为 600°C， 时间为 5h， 即得到固载镁的化合物的改性分子筛。然后将固载镁的化合物的改性分子 筛加入到等体积的磷酸溶液中搅拌 10min， 静置 6h， 之后干燥脱水， 控制干燥脱水的 温度为 150°C， 时间为 8h， 然后进行焙烧， 调节焙烧的温度为 500°C， 时间为 3h， 得 到固载镁的化合物和磷的化合物的改性分子筛， 其中镁的化合物为碳酸镁， 磷的化合 物为五氧化二磷。 改性分子筛的孔径在 1. 5〜6nm之间， BET比表面积大于 800m2/g， 相对结晶度大于 90%， 分子筛的 Si/Al大于 1。 该改性分子筛中镁的重量百分比含量 为 20%， 磷的重量百分比含量为 20%， 可以高选择性的去除废水中的氨氮， 对氨氮的 吸附量达到 275mg/g分子筛。 实施例 3
使用氧化镁配制 5mol/L的镁盐溶液， 使用磷酸配制 4mol/L的磷酸溶液。 将分子 筛 SBA-15加入到等体积的镁盐溶液中搅拌 20min， 静置 3h， 之后进行干燥脱水， 控 制干燥脱水的温度为 150°C， 时间为 6h， 然后进行焙烧， 调节焙烧的温度为 400°C， 时间为 2h， 即得到固载镁的化合物的改性分子筛。然后将固载镁的化合物的改性分子 筛加入到等体积的磷酸溶液中搅拌 30min， 静置 2h， 之后干燥脱水， 控制干燥脱水的 温度为 200°C， 时间为 4h， 然后进行焙烧， 调节焙烧的温度为 600°C， 时间为 2h， 得 到固载镁的化合物和磷的化合物的改性分子筛， 其中镁的化合物为硝酸镁和磷酸镁的 混合物， 磷的化合物为磷酸镁。 改性分子筛的孔径在 5〜10nm之间， BET比表面积大 于 600m2/g， 相对结晶度大于 90%， 分子筛的 Si/Al大于 1。 该改性分子筛中镁的重量 百分比含量为 25%， 磷的重量百分比含量为 20%， 可以高选择性的去除废水中的氨氮， 对氨氮的吸附量达到 290mg/g分子筛。 实施例 4
使用硝酸镁配制 3mol/L的镁盐溶液， 使用磷酸配制 3mol/L的磷酸溶液。 将分子 筛 SBA-15加入到等体积的镁盐溶液中搅拌 10min， 静置 4h， 之后进行干燥脱水， 控 制干燥脱水的温度为 200°C， 时间为 6h， 然后进行焙烧， 调节焙烧的温度为 300°C， 时间为 3h， 即得到固载镁的化合物的改性分子筛。然后将固载镁的化合物的改性分子 筛加入到等体积的磷酸溶液中搅拌 30min， 静置 5h， 之后干燥脱水， 控制干燥脱水的 温度为 200°C， 时间为 8h， 然后进行焙烧， 调节焙烧的温度为 500°C， 时间为 5h， 得 到固载镁的化合物和磷的化合物的改性分子筛， 其中镁的化合物为磷酸镁， 磷的化合 物为五氧化二磷和磷酸镁的混合物。 改性分子筛的孔径在 6〜10nm之间， BET比表面 积大于 650m2/g， 相对结晶度大于 90%， 分子筛的 Si/Al大于 1。 该改性分子筛中镁的 重量百分比含量为 15%， 磷的重量百分比含量为 15%， 可以高选择性的去除废水中的 氨氮， 对氨氮的吸附量达到 235mg/g分子筛。 使用氧化镁配制 lmol/L的镁盐溶液， 使用磷酸配制 lmol/L的磷酸溶液。 将分子 筛 MCM-48加入到等体积的镁盐溶液中搅拌 20min， 静置 lh， 之后进行干燥脱水， 控 制干燥脱水的温度为 100°C， 时间为 4h， 然后进行焙烧， 调节焙烧的温度为 500°C， 时间为 4h， 即得到固载镁的化合物的改性分子筛。然后将固载镁的化合物的改性分子 筛加入到等体积的磷酸溶液中搅拌 20min， 静置 4h， 之后干燥脱水， 控制干燥脱水的 温度为 150°C， 时间为 4h， 然后进行焙烧， 调节焙烧的温度为 300°C， 时间为 2h， 得 到固载镁的化合物和磷的化合物的改性分子筛， 其中镁的化合物为碳酸镁， 磷的化合 物为五氧化二磷。 改性分子筛的孔径在 1. 5〜5nm之间， BET比表面积大于 750m2/g， 相对结晶度大于 90%， 分子筛的 Si/Al大于 1。 该改性分子筛中镁的重量百分比含量 为 5%， 磷的重量百分比含量为 5%， 可以高选择性的去除废水中的氨氮， 对氨氮的吸 附量达到 140mg/g分子筛。 实施例 6
使用碳酸镁配制 2mol/L 的镁盐溶液， 使用磷酸配制 2mol/L 的磷酸溶液。 将分子筛 SBA-3加入到等体积的镁盐溶液中搅拌 30min， 静置 2h， 之后进行干燥脱水， 控制干 燥脱水的温度为 150°C， 时间为 8h， 然后进行焙烧， 调节焙烧的温度为 600°C， 时间 为 4h， 即得到固载镁的化合物的改性分子筛。然后将固载镁的化合物的改性分子筛加 入到等体积的磷酸溶液中搅拌 10min， 静置 3h， 之后干燥脱水， 控制干燥脱水的温度 为 100°C， 时间为 6h， 然后进行焙烧， 调节焙烧的温度为 400°C， 时间为 6h， 得到固 载镁的化合物和磷的化合物的改性分子筛， 其中镁的化合物为氧化镁， 磷的化合物为 五氧化二磷。 改性分子筛的孔径在 1. 5〜4nm之间， BET比表面积大于 1000m2/g， 相对 结晶度大于 90%，分子筛的 Si/Al大于 1。该改性分子筛中镁的重量百分比含量为 10%， 磷的重量百分比含量为 10%， 可以高选择性的去除废水中的氨氮， 对氨氮的吸附量达 到 190mg/g分子筛。

Claims

利 要 求 书
1. 一种对废水中氨氮具有高选择性的改性分子筛， 其主要结构组成包括：
(A)基本骨架为分子筛；
(B)骨架内表面固载的功能性材料为镁的化合物和磷的化合物。
2. 根据权利要求 1所述的一种对废水中氨氮具有高选择性的改性分子筛， 其特征在于
(A)中所述的基本骨架的分子筛为常见的介孔分子筛， 其孔径在 1. 5〜10nm之间， BET 比表面积大于 600m2/g， 相对结晶度大于 90%。
3. 根据权利要求 1所述的一种对废水中氨氮具有高选择性的改性分子筛， 其特征在于
(B)中所述的固载的功能性材料中镁的化合物为氧化镁、 碳酸镁、 磷酸镁或硝酸镁， 磷 的化合物为五氧化二磷或磷酸镁， 其中改性分子筛中镁的重量百分比含量为 5〜25%， 磷的重量百分比含量为 5〜20%。
4. 一种对废水中氨氮具有高选择性的改性分子筛的制备方法， 其步骤为：
(1)将镁盐溶解于水中得到 l〜5mol/L的镁盐溶液；
(2)将磷酸溶解于水中得到 l〜4mol/L的磷酸溶液；
(3)将分子筛加入到步骤（1)配制好的镁盐溶液中搅拌 10〜30min， 静置 l〜6h， 干燥脱 水， 之后在 300〜600°C的温度下焙烧 2〜6h;
(4)将步骤 (3)焙烧后得到的固载镁的化合物的分子筛加入到步骤 (2)配制好的磷酸溶 液中搅拌 10〜30min， 静置 l〜6h， 干燥脱水， 之后在 300〜600°C的温度下焙烧 2〜 6h， 即得到对废水中氨氮具有高选择性的改性分子筛。
5. 根据权利要求 4所述的对废水中氨氮具有高选择性的改性分子筛的制备方法， 其特 征在于步骤（1)中使用的镁盐为硝酸镁、 碳酸镁、 氧化镁。
6. 根据权利要求 4或 5所述的对废水中氨氮具有高选择性的改性分子筛的制备方法， 其特征在于步骤（3)中干燥脱水的温度为 100〜200°C， 时间为 4〜8h。
7. 根据权利要求 4或 5所述的对废水中氨氮具有高选择性的改性分子筛的制备方法， 其特征在于步骤 (4)中干燥脱水的温度为 100〜200°C， 时间为 4〜8h。
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