WO2021043256A1 - 稀土锰/铈锆基复合化合物及其制备方法和应用 - Google Patents

稀土锰/铈锆基复合化合物及其制备方法和应用 Download PDF

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WO2021043256A1
WO2021043256A1 PCT/CN2020/113455 CN2020113455W WO2021043256A1 WO 2021043256 A1 WO2021043256 A1 WO 2021043256A1 CN 2020113455 W CN2020113455 W CN 2020113455W WO 2021043256 A1 WO2021043256 A1 WO 2021043256A1
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Prior art keywords
rare earth
cerium
manganese
zirconium composite
composite compound
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PCT/CN2020/113455
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English (en)
French (fr)
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WO2021043256A8 (zh
Inventor
黄小卫
张永奇
李红卫
翟志哲
钟强
张赫
崔梅生
侯永可
王昊
冯宗玉
Original Assignee
有研稀土高技术有限公司
河北雄安稀土功能材料创新中心有限公司
国科稀土新材料有限公司
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Priority claimed from CN201910833257.8A external-priority patent/CN112439407B/zh
Priority claimed from CN201910845391.XA external-priority patent/CN112439408B/zh
Application filed by 有研稀土高技术有限公司, 河北雄安稀土功能材料创新中心有限公司, 国科稀土新材料有限公司 filed Critical 有研稀土高技术有限公司
Priority to CA3132392A priority Critical patent/CA3132392C/en
Priority to JP2021538818A priority patent/JP7346578B2/ja
Priority to EP20861253.1A priority patent/EP3888787A4/en
Priority to KR1020217020492A priority patent/KR20210094641A/ko
Priority to US17/422,691 priority patent/US20220184583A1/en
Publication of WO2021043256A1 publication Critical patent/WO2021043256A1/zh
Publication of WO2021043256A8 publication Critical patent/WO2021043256A8/zh

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Definitions

  • the embodiment of the present invention relates to the technical field of oxygen storage materials, specifically, to a rare earth manganese/cerium-zirconium-based composite compound and a preparation method thereof, and a catalyst including the composite compound.
  • DOC is a diesel oxidation catalyst used to reduce diesel nitrogen oxides (NO x ), hydrocarbons (HC) and carbon monoxide (CO) gas pollutants.
  • NO x diesel nitrogen oxides
  • HC hydrocarbons
  • CO carbon monoxide
  • NO 2 accounts for a small proportion of the total NOx.
  • a catalyst for highly efficient NO oxidation and a promoter with high oxygen storage capacity are required.
  • the oxygen storage materials commonly used in DOCs generally have an oxygen storage capacity of less than 600umol-O 2 /g.
  • materials with higher oxygen storage performance and low-temperature conversion capabilities are required.
  • a rare earth manganese/cerium-zirconium-based composite compound is provided,
  • the composite compound has a core-shell structure, and its general formula is expressed as: ARE c B a O b -(1-A)Ce x Zr (1-xy) M y O 2-z , where 0.1 ⁇ A ⁇ 0.3, preferably 0.1 ⁇ A ⁇ 0.2;
  • the main component of the shell layer is rare earth manganese oxide, its general formula is RE c B a O b , where RE is a combination of one or more rare earth elements, B is Mn or a combination of Mn and transition metal elements, 1 ⁇ a ⁇ 8, 2 ⁇ b ⁇ 18, 0.25 ⁇ c ⁇ 4;
  • the main component of the core is cerium-zirconium composite oxide, its general formula is Ce x Zr (1-xy) M y O 2-z , and M is at least one of non-cerium rare earth elements and transition metal elements; where 0.1 ⁇ x ⁇ 0.9, 0 ⁇ y ⁇ 0.3, 0.01 ⁇ z ⁇ 0.3.
  • the percentage of the mass of the Mn element in the shell layer to the total mass of the Mn element in the composite compound is 70-98wt%, preferably 90-98wt%.
  • the cerium in the cerium-zirconium composite oxide is a compound valence state of trivalent and tetravalent, and tetravalent cerium accounts for 60-90 wt% of the total cerium, more preferably 70-80 wt%.
  • the shell layer has a mullite structure.
  • the mass percentage of the mass of the Mn element in the shell layer to the total mass of the Mn element in the composite compound is preferably 70-95 wt%, more preferably 80-90%.
  • the rare earth element RE in the rare earth manganese oxide includes one or more of lanthanum, cerium, praseodymium, neodymium, samarium, europium, and yttrium.
  • M in the cerium-zirconium composite oxide is one or more of lanthanum, praseodymium, neodymium, yttrium, samarium, europium, gadolinium, holmium, erbium, thulium, ytterbium, hafnium, aluminum, and barium, preferably One or more of lanthanum, praseodymium, neodymium, yttrium, and samarium.
  • the rare earth manganese oxide is doped with a transition metal element, and the transition metal element is selected from one or more of iron, tungsten, molybdenum, nickel, cobalt, vanadium, and titanium, preferably iron, nickel, One or more of vanadium and titanium;
  • the mass of the transition metal element is 0.01%-10% of the mass of the rare earth manganese oxide, preferably 0.1%-3%, wherein the mass of the transition metal element is calculated by the mass of the transition metal element itself, and the mass of the rare earth manganese oxide is based on the mass of the rare earth manganese oxide.
  • the mass meter of rare earth manganese oxide before the heterotransition metal is 0.01%-10% of the mass of the rare earth manganese oxide, preferably 0.1%-3%, wherein the mass of the transition metal element is calculated by the mass of the transition metal element itself, and the mass of the rare earth manganese oxide is based on the mass of the rare earth manganese oxide.
  • the particle size D50 of the rare earth manganese/cerium-zirconium composite compound is 1-15 ⁇ m, preferably 2-10 ⁇ m, more preferably 3-10 ⁇ m.
  • the shell layer further contains one or more of hydroxide, carbonate, and basic carbonate, and the content is 0.01 to 1 wt%.
  • the second aspect of the present application provides a method for preparing the rare earth manganese/cerium-zirconium composite compound described in any one of the above, including:
  • a mixed raw material containing a divalent manganese source, a rare earth source, and a cerium-zirconium composite oxide is reacted to obtain the rare earth manganese/cerium-zirconium-based composite compound.
  • the reacting the mixed raw materials containing a manganese source, a rare earth source, and a cerium-zirconium composite oxide specifically includes the following steps:
  • the mixed solution containing the divalent manganese source and the rare earth source is added to the cerium-zirconium composite oxide for reaction, and after the reaction is completed, it is dried, calcined, and pulverized to obtain the rare earth manganese/cerium-zirconium composite compound.
  • the concentration of the divalent manganese source in the mixed solution is 2 to 4 mol/L, wherein the molar amount of the divalent manganese source is calculated as the molar amount of manganese;
  • the concentration of the rare earth source in the mixed solution is 0.5-2 mol/L, wherein the molar amount of the rare earth source is based on the molar amount of the rare earth element.
  • the volume of the mixed solution containing the divalent manganese source and the rare earth source is 70-150%, preferably 90-120% of the pore volume of the cerium-zirconium composite oxide.
  • the specific conditions of the reaction include:
  • the reaction temperature is 15 ⁇ 75°C;
  • the reaction time is 5-20min.
  • the reacting the mixed raw materials containing a manganese source, a rare earth source, and a cerium-zirconium composite oxide specifically includes the following steps:
  • the precipitating agent and the oxidizing agent are sequentially added to the mixed slurry containing the divalent manganese source, the rare earth source, and the cerium-zirconium composite oxide to react, and after the reaction is completed, it is washed, dried, calcined, and pulverized to obtain the rare-earth manganese/cerium-zirconium composite compound .
  • the precipitating agent is selected from at least one of sodium hydroxide, ammonia water, ammonium bicarbonate or potassium hydroxide, preferably sodium hydroxide.
  • the amount of the precipitation agent is 5-90% of the stoichiometric amount required for precipitation of manganese and rare earth elements in the slurry.
  • the precipitating agent is added to the mixed slurry in the form of a precipitating agent solution
  • the concentration of the precipitant in the precipitant solution is 0.5-5 mol/L, preferably 1.0-3.0 mol/L.
  • the oxidizing agent is selected from at least one of hydrogen peroxide, oxygen, sodium persulfate, potassium persulfate or ammonium persulfate, preferably hydrogen peroxide.
  • the amount of the oxidizing agent is 0.05-1 times, preferably 0.1-0.5 times, the amount of the Mn 2+ substance contained in the slurry.
  • the specific conditions for washing include:
  • the conductivity of the deionized water at the end of the washing is less than 40 us/cm, preferably less than 20 us/cm.
  • the mixed slurry containing a divalent manganese source, a rare earth source, and a cerium-zirconium composite oxide is prepared by the following method:
  • cerium-zirconium composite oxide Adding cerium-zirconium composite oxide to water to obtain cerium-zirconium composite oxide slurry;
  • the mixed solution containing the divalent manganese source and the rare earth source is mixed with the cerium-zirconium composite oxide slurry to obtain a mixed slurry.
  • the mass concentration of the cerium-zirconium composite oxide in the cerium-zirconium composite oxide slurry is 10-50%.
  • the concentration of the divalent manganese source in the mixed solution is 0.5-2.5 mol/L, wherein the molar amount of the divalent manganese source is calculated as the molar amount of manganese;
  • the concentration of the rare earth source in the mixed solution is 0.5 to 1.5 mol/L, wherein the molar amount of the rare earth source is based on the molar amount of the rare earth element.
  • the divalent manganese source is a soluble metal salt of manganese
  • the soluble metal salt of manganese is selected from at least one of manganese nitrate, manganese acetate, manganese chloride, and manganese sulfate ;
  • the rare earth source is a soluble metal salt of rare earth, and the soluble metal salt of rare earth is selected from at least one of rare earth nitrate, rare earth acetate, rare earth chloride, and rare earth sulfate.
  • the specific conditions for calcination include:
  • the calcination temperature is 500-900°C;
  • the calcination time is 1-6h.
  • the calcination temperature is 700-850°C;
  • the calcination time is 3-5h.
  • a catalyst comprising at least one of the rare earth manganese/cerium zirconium composite compound described in any one of the above and the rare earth manganese/cerium zirconium composite compound prepared by the preparation method described in any one of the above.
  • the fourth aspect of the application provides at least one of the rare earth manganese/cerium-zirconium composite compound described in any one of the above and the rare earth manganese/cerium-zirconium composite compound prepared by the preparation method described in any one of the above as a catalyst.
  • the rare-earth manganese oxide exists on the surface of the cerium-zirconium-based oxide in a single-layer dispersion, and can form a core-shell structure RE c B a O b compound.
  • the rare earth manganese oxide and the cerium-zirconium-based oxide can have a strong interaction, which can change the physical and chemical properties of the two;
  • the single-layer dispersion state can make the surface have more active sites, and the single-layer dispersion can enhance the interface effect;
  • the interface effect can build the oxygen transmission channel and oxygen vacancy between the rare earth manganese oxide and the cerium-zirconium-based oxide, so that Gas-phase oxygen molecules are adsorbed on the oxygen vacancies to replenish the adsorbed oxygen on the surface, thereby greatly enhancing the oxygen storage performance of the cerium-zirconium material;
  • the core-shell structured rare earth manganese/cerium-zirconium composite compound is prepared by the co-precipitation method.
  • the core-shell structured RE C B a O b compound containing mullite structure can be formed on the surface of the cerium-zirconium. Oxygen transport channels and oxygen vacancies between the stone structure oxide and the cerium-zirconium composite oxide make gas-phase oxygen molecules adsorb on the oxygen vacancies to replenish the adsorbed oxygen on the surface, thereby greatly enhancing the oxygen storage performance of the cerium-zirconium material, and further improving the NO Low temperature conversion rate.
  • Figure 1 is a flow chart of a method for preparing rare earth manganese/cerium-zirconium-based composite compounds according to a specific embodiment of the present invention
  • FIG. 3 is a flow chart of a method for preparing rare earth manganese/cerium-zirconium-based composite compounds according to another specific embodiment of the present invention.
  • Example 4 is an X-ray diffraction pattern of the rare earth manganese/cerium-zirconium-based composite compound provided in Example 29 of the present invention.
  • a rare earth manganese/cerium zirconium composite compound is provided,
  • the composite compound has a core-shell structure, and its general formula is expressed as: ARE c B a O b -(1-A)Ce x Zr (1-xy) M y O 2-z , where 0.1 ⁇ A ⁇ 0.3, because The most active point is generally near the dispersion threshold.
  • ARE c B a O b -(1-A)Ce x Zr (1-xy) M y O 2-z where 0.1 ⁇ A ⁇ 0.3, because The most active point is generally near the dispersion threshold.
  • the outer layer content of rare earth manganese oxide is near the single-layer dispersion threshold of rare earth manganese on the surface of the cerium-zirconium-based oxide, it is preferably 0.1 ⁇ A ⁇ 0.2;
  • the main component of the shell layer is rare earth manganese oxide, its general formula is RE c B a O b , where RE is a combination of one or more rare earth elements, B is Mn or a combination of Mn and transition metal elements, 1 ⁇ a ⁇ 8, 2 ⁇ b ⁇ 18, 0.25 ⁇ c ⁇ 4; the rare earth manganese oxide containing rare earth elements can form a material with a special phase structure and has a higher oxidation performance for NO.
  • the main component of the core is cerium-zirconium composite oxide, its general formula is Ce x Zr (1-xy) M y O 2-z , and M is at least one of non-cerium rare earth elements and transition metal elements; where 0.1 ⁇ x ⁇ 0.9, 0 ⁇ y ⁇ 0.3, 0.01 ⁇ z ⁇ 0.3.
  • the range of x is 0.2 to 0.7.
  • Cerium-zirconium-based oxide has excellent oxygen storage and release capacity and precious metal dispersion performance.
  • the rare earth manganese oxide has a mullite structure.
  • the mullite structure is AB 2 O 5 , where A is a rare earth element, B is a transition metal element, and the rare earth element may be lanthanum, One or more of cerium, praseodymium, neodymium, samarium, europium, and yttrium; the transition metal element is selected as Mn element.
  • the mullite structure material containing rare earth elements has higher oxidation performance to NO.
  • the mass percentage of the Mn element mass in the shell layer to the total mass of the Mn element in the composite compound is preferably 70-98wt%, more preferably 90-98wt%,
  • the rest are infiltrated cerium or zirconium compounds.
  • tetravalent cerium in cerium-zirconium, can play a role in stabilizing the phase structure, and the presence of part of the trivalent cerium can produce lattice defects and increase the oxygen vacancy concentration.
  • the mutual conversion between trivalent cerium and tetravalent cerium can quickly release/absorb active oxygen atoms, thereby improving the oxygen storage and release capacity.
  • tetravalent cerium accounts for 60-90wt% of the total cerium, preferably, tetravalent cerium accounts for 70-80wt% of the total cerium.
  • the cerium-zirconium composite oxide material is a solid solution of CeO 2 and ZrO 2 and has excellent oxygen storage and release capacity and precious metal dispersion performance.
  • the mass percentage of Mn element in the shell layer is preferably 70-95 wt%, more preferably 80-90%.
  • the rare earth element RE in the rare earth manganese oxide includes one or more of lanthanum, cerium, praseodymium, neodymium, samarium, europium, and yttrium.
  • M in the cerium-zirconium composite oxide is one or more of lanthanum, praseodymium, neodymium, yttrium, samarium, europium, gadolinium, holmium, erbium, thulium, ytterbium, hafnium, aluminum, and barium, preferably One or more of lanthanum, praseodymium, neodymium, yttrium, and samarium.
  • Doping rare earth elements within a certain content can enhance the high temperature sintering resistance of the cerium-zirconium composite oxide and increase the oxygen storage capacity. And the mass percentage of doped rare earth elements does not exceed 30% of the cerium-zirconium composite oxide.
  • the rare earth manganese oxide is doped with a transition metal element, and the transition metal element is selected from one or more of iron, tungsten, molybdenum, nickel, cobalt, vanadium, and titanium, preferably iron, nickel, One or more of vanadium and titanium;
  • the mass of the transition metal element is 0.01%-10% of the mass of the rare earth manganese oxide, preferably 0.1%-3%, wherein the mass of the transition metal element is calculated by the mass of the transition metal element itself, and the mass of the rare earth manganese oxide is based on the mass of the rare earth manganese oxide.
  • the mass meter of rare earth manganese oxide before the heterotransition metal is 0.01%-10% of the mass of the rare earth manganese oxide, preferably 0.1%-3%, wherein the mass of the transition metal element is calculated by the mass of the transition metal element itself, and the mass of the rare earth manganese oxide is based on the mass of the rare earth manganese oxide.
  • the oxygen storage capacity of the cerium-zirconium composite oxide is generally lower than 600umol-O 2 /g
  • the presence of the rare earth manganese oxide in the outer shell increases the surface oxygen vacancy concentration, which increases the oxygen storage capacity.
  • the oxygen storage capacity of the rare earth manganese/cerium-zirconium composite compound is not less than 800umol-O 2 /g.
  • the particle size D50 of the rare earth manganese/cerium-zirconium composite compound is 1-15 ⁇ m, preferably 2-10 ⁇ m, more preferably 3-10 ⁇ m.
  • the shell layer also contains one or more of hydroxide, carbonate, and basic carbonate, with a content of 0.01 to 1 wt%, which can regulate the pore structure to a certain extent.
  • the second aspect of the present application provides a method for preparing the rare earth manganese/cerium-zirconium composite compound described in any one of the above, including:
  • the mixed raw materials containing a divalent manganese source, a rare earth source, and a cerium-zirconium composite oxide are reacted to obtain the rare-earth manganese/cerium-zirconium composite compound.
  • the reacting the mixed raw materials containing a manganese source, a rare earth source, and a cerium-zirconium composite oxide specifically includes the following steps:
  • the mixed solution containing the divalent manganese source and the rare earth source is added to the cerium-zirconium composite oxide for reaction, and after the reaction is completed, it is dried, calcined, and pulverized to obtain the rare earth manganese/cerium-zirconium composite compound.
  • the concentration of the divalent manganese source in the mixed solution is 2 to 4 mol/L, wherein the molar amount of the divalent manganese source is calculated as the molar amount of manganese;
  • the concentration of the rare earth source in the mixed solution is 0.5-2 mol/L, wherein the molar amount of the rare earth source is based on the molar amount of the rare earth element.
  • the volume of the mixed solution containing the divalent manganese source and the rare earth source is 70-150%, preferably 90-120% of the pore volume of the cerium-zirconium composite oxide.
  • the specific conditions of the reaction include:
  • the reaction temperature is 15 ⁇ 45°C;
  • the reaction time is 5-20min.
  • the preparation method of the rare earth manganese/cerium-zirconium composite compound includes:
  • the stoichiometric divalent manganese salt solution and the mixed solution of one or more rare earth metal salt solutions required to configure the final product the solution concentration is 4-6mol/L, preferably 4.5-5.5mol/L; specifically, select soluble The nitrate, acetate, chloride and/or sulfate of as the source of rare earth metal salt and divalent manganese salt, preferably manganese nitrate;
  • the cerium-zirconium-based oxide and the prepared rare earth-manganese mixed solution are mixed to obtain a wet material of the cerium-zirconium composite compound containing rare-earth manganese.
  • the volume of the rare-earth-manganese mixed solution is 70-150% of the pore volume of the cerium-zirconium-based oxide, preferably 90-120%;
  • the wet material of the cerium-zirconium composite compound containing rare earth manganese is dried.
  • the drying process can be carried out in an oxidizing atmosphere to facilitate the oxidation of low-valent manganese into high-valent manganese to form rare earth manganese in the oxidation state of Mn (III, IV, VII) Oxide, the drying temperature is 80-250°C, preferably 150-220°C;
  • the dried cerium-zirconium composite compound containing rare earth manganese is calcined, and the calcining condition is maintained at a temperature in the range of 500-900°C for 1-6 hours, preferably at a temperature in the range of 700°C-850°C for 3-5 hours;
  • the calcined composite compound is pulverized to obtain the rare earth manganese/cerium zirconium composite compound, and the particle size D50 of the rare earth manganese-loaded cerium zirconium composite compound obtained after the pulverization is 1-15um, preferably 2-10um,
  • the selected particle size range facilitates easy coating when making the catalyst.
  • the rare earth manganese-loaded cerium-zirconium composite compound prepared by the above preparation method can form a core-shell structure REMn a O b oxide with the cerium-zirconium-based oxide, and enhance the oxygen storage performance of the cerium-zirconium material through the interface effect, thereby improving the NO oxidation rate.
  • the rare earth manganese oxide in the above-mentioned preparation process of the embodiment of the present invention does not generate waste water, and the preparation process is green and environmentally friendly.
  • the reacting the mixed raw materials containing a manganese source, a rare earth source, and a cerium-zirconium composite oxide specifically includes the following steps:
  • the precipitating agent and the oxidizing agent are sequentially added to the mixed slurry containing the divalent manganese source, the rare earth source, and the cerium-zirconium composite oxide to react, and after the reaction is completed, washing, drying, calcining, and pulverizing, the rare earth manganese/cerium-zirconium composite compound is obtained .
  • the precipitating agent is selected from at least one of sodium hydroxide, ammonia water, ammonium bicarbonate or potassium hydroxide, preferably sodium hydroxide.
  • the amount of the precipitation agent is 5-90% of the stoichiometric amount required for precipitation of manganese and rare earth elements in the slurry.
  • the precipitating agent is added to the mixed slurry in the form of a precipitating agent solution
  • the concentration of the precipitant in the precipitant solution is 0.5-5 mol/L, preferably 1.0-3.0 mol/L.
  • the oxidizing agent is selected from at least one of hydrogen peroxide, oxygen, sodium persulfate, potassium persulfate or ammonium persulfate, preferably hydrogen peroxide.
  • the amount of the oxidizing agent is 0.05-1 times, preferably 0.1-0.5 times, the amount of the Mn 2+ substance contained in the slurry.
  • the specific conditions for washing include:
  • the conductivity of the deionized water at the end of the washing is less than 40 us/cm, preferably less than 20 us/cm.
  • the mixed slurry containing a divalent manganese source, a rare earth source, and a cerium-zirconium composite oxide is prepared by the following method:
  • cerium-zirconium composite oxide Adding cerium-zirconium composite oxide to water to obtain cerium-zirconium composite oxide slurry;
  • the mixed solution containing the divalent manganese source and the rare earth source is mixed with the cerium-zirconium composite oxide slurry to obtain a mixed slurry.
  • the mass concentration of the cerium-zirconium composite oxide in the cerium-zirconium composite oxide slurry is 10-50%.
  • the concentration of the divalent manganese source in the mixed solution is 0.5-2.5 mol/L, wherein the molar amount of the divalent manganese source is calculated as the molar amount of manganese;
  • the concentration of the rare earth source in the mixed solution is 0.5 to 1.5 mol/L, wherein the molar amount of the rare earth source is based on the molar amount of the rare earth element.
  • the divalent manganese source is a soluble metal salt of manganese
  • the soluble metal salt of manganese is selected from at least one of manganese nitrate, manganese acetate, manganese chloride, and manganese sulfate ;
  • the rare earth source is a soluble metal salt of rare earth, and the soluble metal salt of rare earth is selected from at least one of rare earth nitrate, rare earth acetate, rare earth chloride, and rare earth sulfate.
  • the specific conditions for calcination include:
  • the calcination temperature is 500-900°C;
  • the calcination time is 1-6h.
  • the calcination temperature is 700-850°C;
  • the calcination time is 3-5h.
  • the preparation method of the rare earth manganese/cerium-zirconium composite compound includes:
  • the stoichiometric divalent manganese salt solution and the mixed solution of one or more rare earth metal salt solutions required to configure the final product the solution concentration is 2-6mol/L; specifically, soluble nitrate, acetate, and chlorine are selected
  • nitrates and/or sulfates are preferably nitrates.
  • the mixed solution of the manganese salt solution and one or more rare earth metal salt solutions is added to the cerium-zirconium composite oxide to obtain a cerium-zirconium composite oxide slurry containing the mixed solution of manganese and the rare earth salt, the slurry concentration is 5-40%, preferably 10-30%;
  • the rare earth manganese/cerium-zirconium composite compound is obtained.
  • the calcination condition is to maintain the temperature in the range of 500-900°C for 1-6 hours, preferably in the range of 700°C to 850°C for 3-5 hours.
  • the preparation method of the rare earth manganese/cerium-zirconium composite compound includes:
  • the solution concentration is 0.5-4.0 mol/L, preferably 1.0-2.5 mol/L, specifically , Select soluble nitrate, acetate, chloride and/or sulfate as the source of rare earth metal salt and divalent manganese salt, preferably nitrate; add the cerium-zirconium composite oxide to deionized water to make a slurry, and the cerium-zirconium
  • the composite oxide solid powder is uniformly dispersed in water to obtain a cerium-zirconium composite oxide slurry with a slurry concentration of 10-50%, preferably 15-40%.
  • the divalent manganese salt solution and the rare earth metal salt solution can select soluble nitrate, acetate, chloride and/or sulfate as the raw material source; for example, Mn(NO 3 ) 2 , Mn(CH 3 ( COO) 2 ), MnCl 2 , MnSO 4 and so on.
  • the cerium-zirconium composite oxide includes at least one of lanthanum, praseodymium, neodymium, europium, and yttrium.
  • a mixed solution of the manganese salt solution and one or more rare earth metal salt solutions is added to the cerium-zirconium composite oxide slurry to obtain a cerium-zirconium composite oxide slurry containing the mixed solution of manganese and the rare earth salt.
  • the cerium-zirconium slurry and the mixed solution containing manganese and rare earth salt are uniformly dispersed, so that manganese and rare earth can be co-precipitated on the cerium-zirconium composite oxide powder in a uniform phase.
  • an alkali solution is added to the slurry to precipitate a hydroxide containing mullite structure on the cerium-zirconium composite oxide solid powder, and the pH value of the solution is controlled to be greater than 8 to obtain a precipitate.
  • the alkali includes sodium hydroxide, ammonia water, ammonium bicarbonate or potassium hydroxide, and the added amount is in the range of 0.5 mol/L to 5 mol/L, preferably 1.0-3.0 mol/L.
  • the precipitate includes a mixed hydroxide of Mn(OH) 2 and RE(OH) 3 precipitated on the cerium-zirconium composite oxide.
  • the specific reaction formula is:
  • the amount of the oxidizing agent is 0.05-1 times the amount of the Mn 2+ substance, preferably 0.1-0.5 times.
  • the oxidant includes one of hydrogen peroxide, oxygen, ammonium persulfate, sodium persulfate, and potassium persulfate.
  • the reaction formula of hydrogen peroxide is as follows:
  • the precipitate added with the oxidant is filtered and washed with deionized water.
  • the conductivity of the deionized water at the end of the washing is less than 40 us/cm, preferably less than 20 us/cm.
  • the precipitate washed with deionized water is calcined and crushed to obtain the core-shell structure rare earth manganese/cerium zirconium composite compound.
  • the calcination condition is to maintain the temperature in the range of 500-900°C for 1-6 hours, preferably in the range of 700°C to 850°C for 3-5 hours.
  • the particle size D50 of the material is 1-15um, preferably 3-10um.
  • the core-shell structure rare earth manganese/cerium-zirconium composite compound prepared by the above preparation method can form a core-shell structure containing mullite structure RE C B a O b oxide with the cerium-zirconium composite oxide, and strengthen the cerium-zirconium through the interface effect The oxygen storage performance of the material, thereby increasing the oxidation rate of NO.
  • the ratio of RE C B a O b oxide to cerium-zirconium material can be adjusted to meet the requirements of different diesel vehicle DOC catalysts for the oxygen storage capacity and heat resistance of the oxygen storage material.
  • the third aspect of the present application provides at least one of the rare earth manganese/cerium-zirconium composite compound described in any one of the above and the rare earth manganese/cerium-zirconium composite compound prepared by the preparation method described in any one of the above as a catalyst in catalyzing Application in the oxidation of NO.
  • the catalyst is used in the DOC catalyst of diesel vehicles to increase the oxygen storage capacity of the oxygen storage material and help oxidize NO, thereby increasing the conversion rate of NO to NO 2.
  • cerium-zirconium composite oxide used in each embodiment was prepared according to the method described in the patent ZL201010294878.2.
  • the specific method is to purge with He and heat up to 150°C, continue After heating to 800°C, reduce with 10% H 2 /Ar for 1 hour, reduce the temperature of the reactor to 500°C in He gas flow, and purge the residual H 2 , and then pulse into high purity O 2 at 500°C,
  • the total oxygen storage capacity is 821umol O 2 /g calculated by calculating the peak area of O 2 consumption.
  • the total oxygen storage is 857umol O 2 /g calculated by calculating the peak area of O 2 consumption.
  • the total oxygen storage is 894umol O 2 /g calculated by calculating the peak area of O 2 consumption.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 924 umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 957umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 1067umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 847umol O 2 /g.
  • the total oxygen storage is 857umol O 2 /g calculated by calculating the peak area of O 2 consumption.
  • the total oxygen storage is 928umol O 2 /g calculated by calculating the peak area of O 2 consumption.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 1024umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 897umol O 2 /g.
  • the total oxygen storage is 987umol O 2 /g.
  • the total oxygen storage is 874umol O 2 /g calculated by calculating the peak area of O 2 consumption.
  • the total oxygen storage was calculated to be 994umol O 2 /g by calculating the peak area of O 2 consumption.
  • the composite compound prepared according to the ratio of the rare earth manganese-loaded cerium-zirconium composite compound and the preparation method of the embodiment of the present invention has high oxygen storage performance, and its oxygen storage capacity is not less than 800umol O 2 /g.
  • the specific method is to purge with He and heat up to 150°C, continue After heating to 800°C, reduce with 10% H 2 /Ar for 1 hour, reduce the temperature of the reactor to 500°C in He gas flow, and purge the residual H 2 , and then pulse into high purity O 2 at 500°C,
  • the total oxygen storage capacity is 821umol O 2 /g calculated by calculating the peak area of O 2 consumption.
  • the total oxygen storage is 857umol O 2 /g calculated by calculating the peak area of O 2 consumption.
  • the total oxygen storage is 894umol O 2 /g calculated by calculating the peak area of O 2 consumption.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 924 umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 957umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 997umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 1002umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 921umol O 2 /g.
  • the total oxygen storage is 894umol O 2 /g calculated by calculating the peak area of O 2 consumption.
  • the total oxygen storage is 899 umol O 2 /g calculated by calculating the peak area of O 2 consumption.
  • the total oxygen storage is 987umol O 2 /g.
  • the total oxygen storage was measured to be 1017umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 1067umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 914umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 945umol O 2 /g.
  • Example 2 Using the same oxygen storage test method as in Example 1 for the composite compound prepared above, the total oxygen storage was measured to be 1324 umol O 2 /g.
  • the oxygen storage material prepared according to the ratio of the mullite structure rare earth manganese-cerium zirconium composite compound and the preparation method of the embodiment of the present invention has high oxygen storage performance, and its oxygen storage capacity is not low. At 800umol O 2 /g.
  • Figure 4 shows the X-ray diffraction pattern of 0.3YMn 2 O 5 -0.7Ce 40 Zr 50 La 5 Pr 5 O 1.95 prepared by the method of the present invention. It can be seen from the figure that the inside of the material is a solid solution of cerium and zirconium, and the outside is deposited
  • the YMn 2 O 5 structure compound has a core-shell structure.
  • the total oxygen storage is 693umol O 2 /g calculated by calculating the peak area of O 2 consumption.

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Abstract

一种稀土锰/铈锆基复合化合物及其制备方法和应用，所述复合化合物具有核壳结构，其通式表示为：ARE cB aO b-(1-A)Ce xZr (1-x-y)M yO 2-z，其中0.1≤A≤0.3，优选0.1≤A≤0.2；壳层主成分为稀土锰氧化物，其通式为RE cMn aO b，其中RE为一种或一种以上稀土元素的组合，B为Mn或Mn与过渡金属元素的组合，1≤a≤8，2≤b≤18，0.25≤c≤4；核心主成分为铈锆复合氧化物，其通式为Ce xZr (1-x-y)M yO 2-z，M为一种或一种以上非铈稀土元素；其中0.1≤x≤0.9，0≤y≤0.3，0.01≤z≤0.3。该复合化合物，通过界面效应增强铈锆材料的储氧性能，从而提高对氮氧化物的转化率。

Description

稀土锰/铈锆基复合化合物及其制备方法和应用
本申请要求于2019年9月4日提交中国专利局、申请号为201910833257.8、发明名称为“核壳结构稀土锰/铈锆复合化合物及制备方法和催化剂”及2019年9月4日提交中国专利局、申请号为201910845391.X、发明名称为“负载稀土锰的铈锆复合化合物及制备方法和催化剂”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明实施例涉及储氧材料技术领域，具体而言，涉及一种稀土锰/铈锆基复合化合物及其制备方法，以及包括该复合化合物的催化剂。
背景技术
随着石油资源的日益匮乏与全球气候变暖态势的加剧，稀燃发动机(柴油机和稀燃汽油机)因其较高的燃油经济性和较低的温室气体排放量受到了广泛关注，然而尾气中大量氮氧化物(NO x)不仅能引发光化学烟雾、酸雨等突出环境问题，同时对人类的健康具有严重危害。因此，如何有效去除稀燃发动机尾气中NOx成为当今环境催化的研究热点。现阶段柴油机尾气后处理主要由DOC、SCR、DPF、SCRF/CDPF、ASC构成。DOC是柴油氧化催化剂，用来降低柴油机氮氧化物(NO x)、烃(HC)和一氧化碳(CO)气体污染物。在现有的柴油车尾气中，NO 2占总NOx比重较小，要提高NO 2比重，需要高效氧化NO的催化剂及高储氧能力的助催化剂。目前，DOC通常采用的储氧材料，其储氧量通常低于600umol-O 2/g。但是，为了获得更高的NO氧化性能，需要更高储氧性能的材料及其低温转化能力。
发明内容
根据本申请的一个方面，提供了一种稀土锰/铈锆基复合化合物，
所述复合化合物具有核壳结构，其通式表示为：ARE cB aO b-(1-A)Ce xZr (1-x-y)M yO 2-z，其中0.1≤A≤0.3，优选0.1≤A≤0.2；
壳层主成分为稀土锰氧化物，其通式为RE cB aO b，其中RE为一种或一种以上稀土元素的组合，B为Mn或Mn与过渡金属元素的组合，1≤a≤8，2<b≤18，0.25≤c≤4；
核心主成分为铈锆复合氧化物，其通式为Ce xZr (1-x-y)M yO 2-z，M为非铈稀土元素、过渡金属元素中的至少一种；其中0.1≤x≤0.9，0≤y≤0.3，0.01≤z≤0.3。
在一可选实施例中，壳层中Mn元素的质量与复合化合物中Mn元素的总质量的百分比为70-98wt％，优选90-98wt％。
具体地，所述铈锆复合氧化物中的铈为三价和四价的复合价态，四价铈占铈总量的60-90wt％，更优选70-80wt％。
在一可选实施例中，1≤a≤3，2≤b≤8，优选地，所述壳层为莫来石型结构。相应地，壳层中Mn元素的质量与复合化合物中Mn元素的总质量的质量百分比优选70-95wt％，更优选80～90％。
具体地，所述稀土锰氧化物中稀土元素RE包括镧、铈、镨、钕、钐、铕、钇中的一种或一种以上。
具体地，所述铈锆复合氧化物中M为镧、镨、钕、钇、钐、铕、钆、钬、铒、铥、镱、铪、铝、钡中的一种或一种以上，优选镧、镨、钕、钇、钐的一种或一种以上。
具体地，所述稀土锰氧化物掺杂有过渡金属元素，所述过渡金属元素选自铁、钨、钼、镍、钴、钒、钛中的一种或一种以上，优选铁、镍、钒、钛中的一种或一种以上；
所述过渡金属元素的质量为稀土锰氧化物质量的0.01％-10％，优 选为0.1％-3％，其中过渡金属元素质量以过渡金属元素自身质量计，所述稀土锰氧化物质量以掺杂过渡金属前的稀土锰氧化物的质量计。
具体地，所述的稀土锰/铈锆基复合化合物储氧量不低于800umol-O 2/g。
具体地，所述的稀土锰/铈锆复合化合物粒度D50为1-15μm，优选2～10μm，更优选3～10μm。
进一步地，所述壳层还含有氢氧化物、碳酸盐、碱式碳酸盐中的一种或多种，含量为0.01～1wt％。
本申请的第二方面，提供了上述任一项所述的稀土锰/铈锆复合化合物的制备方法，包括：
对含有二价锰源、稀土源、铈锆复合氧化物的混合原料进行反应，得到所述稀土锰/铈锆基复合化合物。
在一可选实施例中，所述对含有锰源、稀土源、铈锆复合氧化物的混合原料进行反应，具体包括以下步骤：
根据最终产物化学计量比配置二价锰源、稀土源和铈锆复合氧化物；
将含有二价锰源和稀土源的混合溶液加入所述铈锆复合氧化物中进行反应，反应结束后干燥、煅烧、粉碎，得到所述稀土锰/铈锆复合化合物。
具体地，所述二价锰源在所述混合溶液中的浓度为2～4mol/L，其中，所述二价锰源的摩尔量以锰元素摩尔量计；
所述稀土源在所述混合液中的浓度为0.5～2mol/L，其中，所述稀土源的摩尔量以稀土元素摩尔量计。
具体地，所述含有二价锰源和稀土源的混合溶液的体积为所述铈锆复合氧化物孔容积的70～150％，优选90～120％。
具体地，所述反应的具体条件包括：
在搅拌条件下进行；
反应温度为15～75℃；
反应时间为5～20min。
在另一可选实施例中，所述对含有锰源、稀土源、铈锆复合氧化物的混合原料进行反应，具体包括以下步骤：
根据最终产物化学计量比配置二价锰源、稀土源和铈锆复合氧化物；
向含有二价锰源、稀土源、铈锆复合氧化物的混合浆料中依次加入沉淀剂和氧化剂进行反应，反应结束后洗涤、干燥、煅烧、粉碎，得到所述稀土锰/铈锆复合化合物。
具体地，所述沉淀剂选自氢氧化钠、氨水、碳酸氢氨或氢氧化钾中的至少一种，优选氢氧化钠。
具体地，所述沉淀剂的物质的量为沉淀所述浆料中锰元素和稀土元素所需化学计量的5-90％。
具体地，所述沉淀剂以沉淀剂溶液形式加入所述混合浆料中；
所述沉淀剂溶液中沉淀剂浓度为0.5-5mol/L，优选1.0-3.0mol/L。
具体地，所述氧化剂选自过氧化氢、氧气、过硫酸钠、过硫酸钾或过硫酸铵中的至少一种，优选过氧化氢。
具体地，所述氧化剂的物质的量为所述浆料中所含Mn 2+物质的量的0.05-1倍，优选0.1～0.5倍。
具体地，所述洗涤的具体条件包括：
用去离子水进行洗涤，洗涤终点去离子水的电导率小于40us/cm，优选小于20us/cm。
具体地，所述含有二价锰源、稀土源、铈锆复合氧化物的混合浆料，通过以下方法制得：
将铈锆复合氧化物加入水中，得到铈锆复合氧化物浆料；
将含有二价锰源和稀土源的混合溶液与所述铈锆复合氧化物浆料混合，得到混合浆料。
具体地，所述铈锆复合氧化物浆料中铈锆复合氧化物的质量浓度为10-50％。
具体地，所述二价锰源在所述混合溶液中的浓度为0.5～2.5mol/L，其中，所述二价锰源的摩尔量以锰元素摩尔量计；
所述稀土源在所述混合液中的浓度为0.5～1.5mol/L，其中，所述稀土源的摩尔量以稀土元素摩尔量计。
具体地，所述二价锰源为锰的可溶性金属盐，所述锰的可溶性金属盐选自锰的硝酸盐、锰的乙酸盐、锰的氯化物、锰的硫酸盐中的至少一种；
所述稀土源为稀土的可溶性金属盐，所述稀土的可溶性金属盐选自稀土的硝酸盐、稀土的乙酸盐、稀土的氯化物、稀土的硫酸盐中的至少一种。
具体地，所述煅烧的具体条件包括：
煅烧温度为500-900℃；
煅烧时间为1-6h。
优选地，煅烧温度为700-850℃；
煅烧时间为3-5h。
一种催化剂，包括上述任一项所述的稀土锰/铈锆复合化合物、上述任一项所述的制备方法制备的稀土锰/铈锆复合化合物中的至少一种。
本申请的第四方面提供了上述任一项所述的稀土锰/铈锆复合化合物、上述任一项所述的制备方法制备的稀土锰/铈锆复合化合物中的至少一种作为催化剂在机动车尾气NO催化氧化中的应用。
本申请能产生的有益效果包括：
(1)本制备方法得到的稀土锰/铈锆基复合化合物，稀土锰氧化物以单层分散的形式存在于铈锆基氧化物表面，可形成核壳结构的RE cB aO b化合物。稀土锰氧化物与铈锆基氧化物之间可以产生强烈的相互作用，能够改变二者的物理和化学性能；
(2)单层分散状态可使表面拥有更多的活性位点，并且单层分散可增强界面效用；界面效应可以构建稀土锰氧化物与铈锆基氧化物的氧传输通道及氧空位，使得气相氧分子吸附在氧空位上来补给表面吸附的氧，从而大幅增强铈锆材料的储氧性能；
(3)通过共沉淀法制备得到核壳结构稀土锰/铈锆复合化合物，可在铈锆表面形成核壳结构的含有莫来石结构的RE CB aO b化合物，通过界面效应构建了莫来石结构氧化物与铈锆复合氧化物的氧传输通道及氧空位，使得气相氧分子吸附在氧空位上来补给表面吸附的氧，从而大幅增强铈锆材料的储氧性能，进一步地提高对NO的低温转化率。
附图说明
图1为本发明一具体实施例提供的稀土锰/铈锆基复合化合物制备方法流程图；
图2为本发明另一具体实施例提供的稀土锰/铈锆基复合化合物制备方法流程图；
图3为本发明又一具体实施例提供的稀土锰/铈锆基复合化合物制备方法流程图；
图4为本发明实施例29提供的稀土锰/铈锆基复合化合物的X射线衍射图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明了，下面结合具体实施方式并参照附图，对本发明进一步详细说明。应该理解，这些描述只是示例性的，而并非要限制本发明的范围。此外，在以下说明中，省略了对公知结构和技术的描述，以避免不必要地混淆本发明的概念。
根据本申请的一个方面，提供了一种稀土锰/铈锆复合化合物，
所述复合化合物具有核壳结构，其通式表示为：ARE cB aO b-(1-A)Ce xZr (1-x-y)M yO 2-z，其中0.1≤A≤0.3，因为活性最高的点一般在分散阈值附近，为保证稀土锰氧化物的外层含量处于稀土锰在铈锆基氧化物表面的单层分散阈值附近，优选为0.1≤A≤0.2；
壳层主成分为稀土锰氧化物，其通式为RE cB aO b，其中RE为一种或一种以上稀土元素的组合，B为Mn或Mn与过渡金属元素的组合，1≤a≤8，2≤b≤18，0.25≤c≤4；该含有稀土元素的稀土锰氧化物可以形成具有特殊相结构的材料，具有对NO更高的氧化性能。
核心主成分为铈锆复合氧化物，其通式为Ce xZr (1-x-y)M yO 2-z，M为非铈稀土元素、过渡金属元素中的至少一种；其中0.1≤x≤0.9，0≤y≤0.3，0.01≤z≤0.3。优选地，x的范围为0.2～0.7。铈锆基氧化物具有优异的储放氧能力和分散贵金属性能。
在一可选实施例中，稀土锰氧化物为莫来石结构，一般的，莫来石结构为AB 2O 5，其中A是稀土元素，B是过渡金属元素，稀土元素可选择为镧、铈、镨、钕、钐、铕、钇的一种或一种以上；过渡金属元素选择为Mn元素。含有稀土元素的莫来石结构材料具有对NO更高的氧化性能。
壳层Mn含量越高，活性位点越多，催化活性越强，因此壳层中Mn元素质量与复合化合物中Mn元素的总质量的质量百分比优选70-98wt％，更优选90-98wt％，其余为渗透的铈或锆的化合物。
具体地，在铈锆中，四价铈可以起到稳定相结构的作用，部分三价铈的存在可产生晶格缺陷，增加氧空位浓度。三价铈和四价铈之间的相互转换，可迅速释放/吸收活性氧原子，从而提高了储放氧能力。本发明中，四价铈占铈总量的60-90wt％，优选地，四价铈占铈总量的70-80wt％。铈锆复合氧化物材料是CeO 2与ZrO 2的固溶体，具有优异的储放氧能力和分散贵金属性能。
在一可选实施例中，1≤a≤3，2≤b≤8。相应地，Mn元素在壳层的质量百分比优选70-95wt％，更优选80～90％。
具体地，所述稀土锰氧化物中稀土元素RE包括镧、铈、镨、钕、钐、铕、钇中的一种或一种以上。
具体地，所述铈锆复合氧化物中M为镧、镨、钕、钇、钐、铕、钆、钬、铒、铥、镱、铪、铝、钡中的一种或一种以上，优选镧、镨、钕、钇、钐的一种或一种以上。在一定含量内的掺杂稀土元素可增强铈锆复合氧化物的抗高温烧结能力，并提高储氧能力。且掺杂稀土元素质量百分含量不超过铈锆复合氧化物的30％。
具体地，所述稀土锰氧化物掺杂有过渡金属元素，所述过渡金属元素选自铁、钨、钼、镍、钴、钒、钛中的一种或一种以上，优选铁、镍、钒、钛中的一种或一种以上；
所述过渡金属元素的质量为稀土锰氧化物质量的0.01％-10％，优选为0.1％-3％，其中过渡金属元素质量以过渡金属元素自身质量计，所述稀土锰氧化物质量以掺杂过渡金属前的稀土锰氧化物的质量计。
具体地，由于铈锆复合氧化物的储氧量一般低于600umol-O 2/g，由于外层壳层稀土锰氧化物的存在增加了表面氧空位浓度，使得储氧量增加，所述的稀土锰/铈锆复合化合物储氧量不低于800umol-O 2/g。
具体地，所述的稀土锰/铈锆复合化合物粒度D50为1-15μm，优选2～10μm，更优选3～10μm。
进一步地，所述壳层还含有氢氧化物、碳酸盐、碱式碳酸盐中的一种或多种，含量为0.01～1wt％，可以在一定程度上调控孔结构。
本申请的第二方面，提供了上述任一项所述的稀土锰/铈锆复合化合物的制备方法，包括：
对含有二价锰源、稀土源、铈锆复合氧化物的混合原料进行反应，得到所述稀土锰/铈锆复合化合物。
在一可选实施例中，所述对含有锰源、稀土源、铈锆复合氧化物的混合原料进行反应，具体包括以下步骤：
根据最终产物化学计量比配置二价锰源、稀土源和铈锆复合氧化物；
将含有二价锰源和稀土源的混合溶液加入所述铈锆复合氧化物中进行反应，反应结束后干燥、煅烧、粉碎，得到所述稀土锰/铈锆复合化合物。
具体地，所述二价锰源在所述混合溶液中的浓度为2～4mol/L，其中，所述二价锰源的摩尔量以锰元素摩尔量计；
所述稀土源在所述混合液中的浓度为0.5～2mol/L，其中，所述稀土源的摩尔量以稀土元素摩尔量计。
具体地，所述含有二价锰源和稀土源的混合溶液的体积为所述铈锆复合氧化物孔容积的70～150％，优选90～120％。
具体地，所述反应的具体条件包括：
在搅拌条件下进行；
反应温度为15～45℃；
反应时间为5～20min。
如图1所示，在一具体实施例中，所述的稀土锰/铈锆复合化合物的制备方法，包括：
配置最终产物所需化学计量的二价锰盐溶液及一种或多种稀土 金属盐溶液的混合溶液，溶液浓度为4-6mol/L，优选为4.5-5.5mol/L；具体的，选用可溶性的硝酸盐、乙酸盐、氯化物和/或硫酸盐作为稀土金属盐及二价锰盐的来源，优选为硝酸锰；
将铈锆基氧化物和配置好的稀土锰混合溶液进行混合，得到包含稀土锰的铈锆复合化合物湿料,稀土锰混合溶液体积为铈锆基氧化物孔容积的70-150％，优选为90-120％；
将所述包含稀土锰的铈锆复合化合物湿料进行干燥，干燥过程可在氧化气氛中进行，便于将低价锰氧化为高价锰，以形成Mn(Ⅲ,Ⅳ,Ⅶ)氧化态的稀土锰氧化物，干燥温度为80-250℃，优选为150-220℃；
将干燥后的包含稀土锰的铈锆复合化合物进行煅烧，煅烧条件为在温度为500-900℃的范围内保持1-6小时，优选为700℃-850℃范围内保持3-5小时；
将所述煅烧后的复合化合物进行粉碎，即得到所述稀土锰/铈锆复合化合物，所述粉碎后得到负载稀土锰的铈锆复合化合物的粒度D50为1-15um，优选为2-10um，所选粒度范围便于制作催化剂时易于涂覆。
由上述制备方法制备得到的负载稀土锰的铈锆复合化合物，可与铈锆基氧化物形成核壳结构的REMn aO b氧化物，通过界面效应增强铈锆材料的储氧性能，从而提高对NO的氧化率。稀土锰氧化物在本发明实施例的上述制备过程不会产生废水，制备工艺绿色环保。
在另一可选实施例中，所述对含有锰源、稀土源、铈锆复合氧化物的混合原料进行反应，具体包括以下步骤：
根据最终产物化学计量比配置二价锰源、稀土源和铈锆复合氧化物；
向含有二价锰源、稀土源、铈锆复合氧化物的混合浆料中依次加入沉淀剂和氧化剂进行反应，反应结束后洗涤、干燥、煅烧、粉碎， 得到所述稀土锰/铈锆复合化合物。
具体地，所述沉淀剂选自氢氧化钠、氨水、碳酸氢氨或氢氧化钾中的至少一种，优选氢氧化钠。
具体地，所述沉淀剂的物质的量为沉淀所述浆料中锰元素和稀土元素所需化学计量的5-90％。
具体地，所述沉淀剂以沉淀剂溶液形式加入所述混合浆料中；
所述沉淀剂溶液中沉淀剂浓度为0.5-5mol/L，优选1.0-3.0mol/L。
具体地，所述氧化剂选自过氧化氢、氧气、过硫酸钠、过硫酸钾或过硫酸铵中的至少一种，优选过氧化氢。
具体地，所述氧化剂的物质的量为所述浆料中所含Mn 2+物质的量的0.05-1倍，优选0.1～0.5倍。
具体地，所述洗涤的具体条件包括：
用去离子水进行洗涤，洗涤终点去离子水的电导率小于40us/cm，优选小于20us/cm。
具体地，所述含有二价锰源、稀土源、铈锆复合氧化物的混合浆料，通过以下方法制得：
将铈锆复合氧化物加入水中，得到铈锆复合氧化物浆料；
将含有二价锰源和稀土源的混合溶液与所述铈锆复合氧化物浆料混合，得到混合浆料。
具体地，所述铈锆复合氧化物浆料中铈锆复合氧化物的质量浓度为10-50％。
具体地，所述二价锰源在所述混合溶液中的浓度为0.5～2.5mol/L，其中，所述二价锰源的摩尔量以锰元素摩尔量计；
所述稀土源在所述混合液中的浓度为0.5～1.5mol/L，其中，所述稀土源的摩尔量以稀土元素摩尔量计。
具体地，所述二价锰源为锰的可溶性金属盐，所述锰的可溶性金属盐选自锰的硝酸盐、锰的乙酸盐、锰的氯化物、锰的硫酸盐中的至少一种；
所述稀土源为稀土的可溶性金属盐，所述稀土的可溶性金属盐选自稀土的硝酸盐、稀土的乙酸盐、稀土的氯化物、稀土的硫酸盐中的至少一种。
具体地，所述煅烧的具体条件包括：
煅烧温度为500-900℃；
煅烧时间为1-6h。
优选地，煅烧温度为700-850℃；
煅烧时间为3-5h。
如图2所示，在另一具体实施例中，所述的稀土锰/铈锆复合化合物的制备方法，包括：
配置最终产物所需化学计量的二价锰盐溶液及一种或多种稀土金属盐溶液的混合溶液，溶液浓度为2-6mol/L；具体的，选用可溶性的硝酸盐、乙酸盐、氯化物和/或硫酸盐作为稀土金属盐及二价锰盐的来源，优选为硝酸盐。
将所述锰盐溶液及一种或多种稀土金属盐溶液的混合溶液加入所述铈锆复合氧化物中，得到含有锰和稀土盐混合溶液的铈锆复合氧化物浆料，浆料浓度为5-40％，优选为10-30％；
在任选的干燥之后，煅烧、粉碎后即得到所述稀土锰/铈锆复合化合物。煅烧条件为在温度为500-900℃的范围内保持1-6小时，优选为700℃-850℃范围内保持3-5小时。
如图3所示，在又一具体实施例中，所述的稀土锰/铈锆复合化合物的制备方法，包括：
首先，配置最终产物所需化学计量的二价锰盐溶液及一种或多种 稀土金属盐溶液的混合溶液，溶液浓度为0.5-4.0mol/L，优选为1.0-2.5mol/L，具体的，选用可溶性的硝酸盐、乙酸盐、氯化物和/或硫酸盐作为稀土金属盐及二价锰盐的来源，优选为硝酸盐；将铈锆复合氧化物加入去离子水打浆，将铈锆复合氧化物固体粉末均匀分散在水中，得到铈锆复合氧化物浆料,浆料浓度为10-50％，优选为15-40％。具体的，该二价锰盐溶液和稀土金属盐溶液可选择可溶性的硝酸盐、乙酸盐、氯化物和/或硫酸盐作为原料来源；例如，Mn(NO 3) 2、Mn(CH 3(COO) 2)、MnCl 2、MnSO 4等。该铈锆复合氧化物包括镧、镨、钕、铕、钇中的至少一种等。
其次，将锰盐溶液及一种或多种稀土金属盐溶液的混合溶液加入铈锆复合氧化物浆料中，得到含有锰和稀土盐混合溶液的铈锆复合氧化物浆料。使铈锆浆料与含有锰和稀土盐混合溶液分散均匀，便于将锰和稀土以均一相共沉淀在铈锆复合氧化物粉末上。
然后，在上述浆料中加入碱溶液在铈锆复合氧化物固体粉末上沉淀含有莫来石结构氢氧化物，控制溶液pH值大于8以上，得到沉淀物。具体的，碱包括氢氧化钠、氨水、碳酸氢氨或氢氧化钾，加入量在0.5mol/L～5mol/L范围内，优选为1.0-3.0mol/L。该沉淀物包括Mn(OH) 2和RE(OH) 3的混合氢氧化物沉淀在铈锆复合氧化物上。具体反应式为：
RE 3++2Mn 2++7OH ‐＝RE(OH) 3·2Mn(OH) 2
接下来，向沉淀物中加入氧化剂，氧化剂的物质的量为Mn 2+物质的量的0.05-1倍，优选为0.1-0.5倍。具体的，氧化剂包括过氧化氢、氧气、过硫酸铵、过硫酸钠、过硫酸钾中的一种。例如过氧化氢的反应式如下：
Mn(OH) 2+H 2O 2＝MnO(OH) 2+H 2O
过滤该加入氧化剂的沉淀物，并用去离子水洗涤，洗涤终点去离 子水电导率小于40us/cm,优选为小于20us/cm。以将可溶性的阳离子如K +、Na +、NH 4 +及可溶性的阴离子Cl -、SO 4 2-、NO 3 -等杂质离子洗涤干净，杂质离子的存在易造成合成的复合化合物高温烧结，降低比表面积和储氧性能。
在任选的干燥之后，煅烧经过去离子水洗涤的沉淀物，粉碎后即得到该核壳结构稀土锰/铈锆复合化合物。所述煅烧条件为在温度为500-900℃的范围内保持1-6小时，优选为700℃-850℃范围内保持3-5小时。材料的粒度D50为1-15um，优选为3-10um。
由上述制备方法制备得到的核壳结构稀土锰/铈锆复合化合物，可与铈锆复合氧化物形成核壳结构的包含莫来石结构RE CB aO b氧化物，通过界面效应增强铈锆材料的储氧性能，从而提高对NO的氧化率。可通过调控RE CB aO b氧化物与铈锆材料的比例，以满足不同柴油车DOC催化剂对储氧材料储氧量、耐热性能的使用要求。
本申请的第三方面提供了上述任一项所述的稀土锰/铈锆复合化合物、上述任一项所述的制备方法制备的稀土锰/铈锆复合化合物中的至少一种作为催化剂在催化氧化NO中的应用。该催化剂用于柴油车DOC催化剂，提高了储氧材料的储氧量，有助于氧化NO，从而提高NO向NO 2的转化率。
如无特别说明，本申请的实施例中的原料均通过商业途径购买。
其中，各实施例所用铈锆复合氧化物根据专利ZL201010294878.2记载的方法制备而来。
实施例1
0.10CeMn 2O 5-0.90Ce 0.4Zr 0.6O 1.94；
分别量取5mL浓度为3mol/L Ce(NO 3) 3溶液和6mL浓度为5mol/L Mn(NO 3) 2溶液，倒入100mL烧杯中，磁力搅拌10min，得到Ce、Mn混合溶液。称取45g配分为Ce 0.4Zr 0.6O 1.94的铈锆复合氧化物粉末于250mL 烧杯中，将Ce、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在160℃烘箱中干燥24h，然后在马弗炉中750℃煅烧5h后，取出，研磨即得产物，D50＝2um。
将以上制得的复合化合物，取0.1g置于Chembet PULSAR TPR/TPD型化学吸附仪中，通过氧气脉冲法测试样品储放氧性能，具体方法为先用He吹扫并升温至150℃，继续升温至800℃后用10％H 2/Ar还原1h，在He气流中将反应器的温度降至500℃，并将残余的H 2吹扫干净，然后在500℃脉冲进入高纯O 2，通过统计消耗O 2峰面积计算总的储氧量为821umol O 2/g。
实施例2
0.15YMn 2O 5-0.85Ce 0.3Zr 0.6La 0.1O 1.89:
分别量取9mL浓度为3mol/L Y(COOH) 3溶液和12mL浓度为4.5mol/L Mn(COOH) 3溶液，倒入200mL烧杯中，磁力搅拌10min，得到Y、Mn混合溶液。称取42.5g配分为Ce 0.3Zr 0.6La 0.1O 1.89的铈锆复合氧化物粉末于250mL烧杯中，将Y、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在170℃烘箱中干燥24h，然后在马弗炉中770℃煅烧5h后，取出，研磨即得产物，D50＝3.6um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为857umol O 2/g。
实施例3
0.2LaMn 2O 5-0.8Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.92:
分别量取10.5mL浓度为3mol/L La(COOH) 3溶液和14mL浓度为4.5mol/L Mn(COOH) 2溶液，倒入200mL烧杯中，磁力搅拌10min，得到La、Mn混合溶液。称取40g配分为Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.92的铈锆 复合氧化物粉末于250mL烧杯中，将La、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在180℃烘箱中干燥24h，然后在马弗炉中900℃煅烧1h后，取出，研磨即得产物，D50＝15um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为894umol O 2/g。
实施例4
0.25SmMn 2O 5-0.75Ce 0.2Zr 0.7La 0.03Nd 0.07O 1.9
分别量取12.5mL浓度为3mol/L Sm(NO 3) 3溶液和15mL浓度为5mol/L Mn(NO 3) 2溶液，倒入200mL烧杯中，磁力搅拌10min，得到Sm、Mn混合溶液。称取37.5g配分为Ce 0.2Zr 0.7La 0.03Nd 0.07O 1.9的铈锆复合氧化物粉末于250mL烧杯中，将Sm、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在190℃烘箱中干燥24h，然后在马弗炉中500℃煅烧6h后，取出，研磨即得产物，D50＝1.2um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为924umol O 2/g。
实施例5
0.3La 0.33Sm 0.67Mn 2O 5-0.7Ce 0.6Zr 0.3La 0.05Y 0.05O 1.94
分别量取5mL浓度为3mol/L LaNO 3溶液和10mL浓度为3mol/L Sm(NO 3) 3溶液以及18mL浓度为5mol/L Mn(NO 3) 2溶液，倒入200mL烧杯中，磁力搅拌10min，得到La、Sm、Mn混合溶液。称取35g配分为Ce 0.6Zr 0.3La 0.05Y 0.05O 1.94的铈锆复合氧化物粉末于于250mL烧杯中，将La、Sm、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在200℃烘箱中干燥24h，然后在马弗炉中850℃煅烧5h后，取出，研磨即得产物，研磨即得 产物，D50＝9.9um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为957umol O 2/g。
实施例6
0.3La 0.2Ce 0.2Y 0.6Mn 2O 5-0.7Ce 0.4Zr 0.5La 0.02Nd 0.05Y 0.03O 1.95
分别量取4mL浓度为3mol/L LaNO 3溶液和4mL浓度为3mol/L Ce(NO 3) 3溶液以及7mL浓度为5mol/L Mn(NO 3) 2溶液，倒入100mL烧杯中，磁力搅拌10min，得到Ce、Y、Mn混合溶液。称取35g配分为Ce 0.4Zr 0.5La 0.02Nd 0.05Y 0.03O 1.95的铈锆复合氧化物粉末于250mL烧杯中，将Ce、Y、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末，待液体加入完毕后，搅拌10min，取出后在210℃烘箱中干燥24h，然后在马弗炉中810℃煅烧3h后，取出，研磨即得产物，D50＝4.3um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为1067umol O 2/g。
实施例7
0.10Ce 0.25MnO 2-0.90Ce 0.4Zr 0.5Y 0.1O 1.94
分别量取2.5mL浓度为3mol/L Ce(NO 3) 3溶液和6mL浓度为5mol/L Mn(NO 3) 2溶液，倒入100mL烧杯中，磁力搅拌10min，得到Ce、Mn混合溶液。称取45g配分为Ce 0.4Zr 0.5Y 0.1O 1.94的铈锆复合氧化物粉末于250mL烧杯中，将Ce、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在210℃烘箱中干燥24h，然后在马弗炉中820℃煅烧4h后，取出，研磨即得产物，D50＝5.6um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为847umol O 2/g。
实施例8
0.15Y 4Mn 8O 18-0.85Ce 0.3Zr 0.6La 0.1O 1.89:
分别量取9mL浓度为3mol/L Y(COOH) 3溶液和12mL浓度为4.5mol/L Mn(COOH) 3溶液，倒入200mL烧杯中，磁力搅拌10min，得到Y、Mn混合溶液。称取42.5g配分为Ce 0.3Zr 0.6La 0.1O 1.89的铈锆复合氧化物粉末于250mL烧杯中，将Y、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在220℃烘箱中干燥24h，然后在马弗炉中830℃煅烧5h后，取出，研磨即得产物，D50＝3.5um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为857umol O 2/g。
实施例9
0.2LaSmMn 3O 6-0.8Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.92
分别量取7mL浓度为3mol/L La(COOH) 3溶液和7mL浓度为3mol/L的Sm(COOH) 3溶液以及14mL浓度为4.5mol/L Mn(COOH) 2溶液，倒入200mL烧杯中，磁力搅拌10min，得到La、Sm、Mn混合溶液。称取40g配分为Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.92的铈锆复合氧化物粉末于250mL烧杯中，将La、Sm、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在220℃烘箱中干燥24h，然后在马弗炉中840℃煅烧5h后，取出，研磨即得产物，D50＝2.5um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为928umol O 2/g。
实施例10
0.25EuMn 4O 7-0.75Ce 0.2Zr 0.7La 0.03Nd 0.07O 1.9
分别量取6.25mL浓度为3mol/L Eu(NO 3) 2溶液和15mL浓度为5mol/L Mn(NO 3) 2溶液，倒入200mL烧杯中，磁力搅拌10min，得到Sm、 Mn混合溶液。称取37.5g配分为Ce 0.2Zr 0.7La 0.03Nd 0.07O 1.9的铈锆复合氧化物粉末于250mL烧杯中，将Sm、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕5后，搅拌10min，取出后在220℃烘箱中干燥24h，然后在马弗炉中850℃煅烧5h后，取出，研磨即得产物，D50＝6.6um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为1024umol O 2/g。
实施例11
0.3Pr 3Mn 5O 12-0.7Ce 0.6Zr 0.3La 0.05Y 0.05O 1.94
分别量取18mL浓度为3mol/L Pr(NO 3) 3溶液和18mL浓度为5mol/L Mn(NO 3) 2溶液，倒入200mL烧杯中，磁力搅拌10min，得到Pr、Mn混合溶液。称取35g配分为Ce 0.6Zr 0.3La 0.05Y 0.05O 1.94的铈锆复合氧化物粉末于于250mL烧杯中，将Pr、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在200℃烘箱中干燥24h，然后在马弗炉中850℃煅烧4h后，取出，研磨即得产物，研磨即得产物，D50＝4.6um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为897umol O 2/g。
实施例12
0.3LaYCeMn 6O 14-0.7Ce 0.6Zr 0.3La 0.05Y 0.05O 1.94
分别量取5mL浓度为3mol/L La(NO 3) 3溶液、5mL浓度为3mol/L Y(NO 3) 3溶液、5mL浓度为3mol/L Ce(NO 3) 3溶液和18mL浓度为5mol/L Mn(NO 3) 2溶液，倒入200mL烧杯中，磁力搅拌10min，得到La、Y、Ce、Mn混合溶液。称取35g配分为Ce 0.6Zr 0.3La 0.05Y 0.05O 1.94的铈锆复合氧化物粉末于于250mL烧杯中，将La、Y、Ce、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min， 取出后在200℃烘箱中干燥24h，然后在马弗炉中800℃煅烧3h后，取出，研磨即得产物，研磨即得产物，D50＝7.6um。
将以上制得的复合化合物相储氧材料，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为987umol O 2/g。
实施例13
0.2CeY 2Mn 7O 15-0.8Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.92
分别量取3mL浓度为3mol/L Ce(COOH) 3溶液和6mL浓度为3mol/L的Y(COOH) 3溶液以及14mL浓度为4.5mol/L Mn(COOH) 2溶液，倒入200mL烧杯中，磁力搅拌10min，得到Ce、Y、Mn混合溶液。称取40g配分为Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.92的铈锆复合氧化物粉末于250mL烧杯中，将Ce、YMn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在180℃烘箱中干燥24h，然后在马弗炉中790℃煅烧5h后，取出，研磨即得产物，D50＝8.2um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为874umol O 2/g。
实施例14
0.2LaCeNdMn 8O 16-0.8Ce 0.4Zr 0.5La 0.02Y 0.08O 1.97
分别量取2.6mL浓度为3mol/L La(COOH) 3溶液、2.6mL浓度为3mol/L的Ce(COOH) 3溶液、2.6mL浓度3mol/L的Nd(COOH) 3溶液以及14mL浓度为4.5mol/L Mn(COOH) 2溶液，倒入200mL烧杯中，磁力搅拌10min，得到La、Ce、Nd、Mn混合溶液。称取40g配分为Ce 0.4Zr 0.5La 0.02Y 0.08O 1.97的铈锆复合氧化物粉末于250mL烧杯中，将La、Ce、Nd、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，然后在210℃烘箱中干燥24h，然后在马弗炉中780℃煅烧5h后，取出，研磨即得产物，D50＝3.6um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为994umol O 2/g。
由以上实施例可得出，按照本发明实施例的负载稀土锰的铈锆复合化合物的配比及制备方法制备得到的复合化合物具有高储氧性能，其储氧量都不低于800umol O 2/g。
实施例15
0.10CeMn 2O 5-0.90Ce 0.4Zr 0.6O 1.95:
分别量取10mL浓度为1.5mol/L CeCl 3溶液和20mL浓度为1.5mol/L MnCl 2溶液将两溶液倒入100mL烧杯中，磁力搅拌10min混匀。称取45g配分为Ce 0.4Zr 0.6O 1.95的铈锆复合氧化物粉末，将其加入盛有405mL去离子水的烧杯中，磁力搅拌30min，形成分散均匀的浆料。将混合好的铈锰溶液加入到上述浆料中，磁力搅拌10min。量取43mL 2.5mol/L NaOH溶液，逐滴加入上述混有铈锰溶液的浆料中并维持磁力搅拌，时间为1h。NaOH溶液加完后，再继续搅拌10min，然后加入30％的H 2O 2 4mL，继续搅拌30min。过滤上述沉淀物，用去离子水洗涤干净，在160℃烘箱中干燥24h，然后在马弗炉中750℃煅烧5h后，取出，研磨即得产物，D50＝3.2um。
将以上制得的复合化合物，取0.1g置于Chembet PULSAR TPR/TPD型化学吸附仪中，通过氧气脉冲法测试样品储放氧性能，具体方法为先用He吹扫并升温至150℃，继续升温至800℃后用10％H 2/Ar还原1h，在He气流中将反应器的温度降至500℃，并将残余的H 2吹扫干净，然后在500℃脉冲进入高纯O 2，通过统计消耗O 2峰面积计算总的储氧量为821umol O 2/g。
实施例16
0.15YMn 2O 5-0.85Ce 0.3Zr 0.6La 0.1O 1.92:
分别量取18mL浓度为1.5mol/L YCl 3溶液和36mL浓度为 1.5mol/L MnCl 2溶液将两溶液倒入200mL烧杯中，磁力搅拌10min混匀。称取42.5g配分为Ce 0.3Zr 0.6La 0.1O 1.92的铈锆复合氧化物粉末，将其加入盛有240mL去离子水的烧杯中，磁力搅拌30min，形成分散均匀的浆料。将混合好的钇锰溶液加入到上述浆料中，磁力搅拌10min。量取80mL 2mol/L NaOH溶液，逐滴加入上述混有钇锰溶液的浆料中并维持磁力搅拌，时间为1h。NaOH溶液加完后，再继续搅拌10min，然后加入30％的H 2O 2 6mL，继续搅拌30min。过滤上述沉淀物，用去离子水洗涤干净，在170℃烘箱中干燥24h，然后在马弗炉中800℃煅烧5h后，取出，研磨即得产物，D50＝1.3um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为857umol O 2/g。
实施例17
0.2LaMn 2O 5-0.8Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.93:
分别量取21mL浓度为1.5mol/L LaCl 3溶液和42mL浓度为1.5mol/L MnCl 2溶液，将两溶液倒入200mL烧杯中，磁力搅拌10min混匀。称取40g配分为Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.93的铈锆复合氧化物粉末，将其加入盛有160mL去离子水的烧杯中，磁力搅拌30min，形成分散均匀的浆料。将混合好的镧锰溶液加入到上述浆料中，磁力搅拌10min。量取100mL 1.5mol/L NaOH溶液，逐滴加入上述混有镧锰溶液的浆料中并维持磁力搅拌，时间为1h。NaOH溶液加完后，再继续搅拌10min，然后加入30％的H 2O 2 7mL，继续搅拌30min。过滤上述沉淀物，用去离子水洗涤干净，在180℃烘箱中干燥24h，然后在马弗炉中850℃煅烧4h后，取出，研磨即得产物，D50＝4.5um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为894umol O 2/g。
实施例18
0.25SmMn 2O 5-0.75Ce 0.2Zr 0.7La 0.03Nd 0.07O 1.94
分别量取25mL浓度为1.5mol/L SmCl 3溶液和50mL浓度为1.5mol/L MnCl 2溶液，将两溶液倒入200mL烧杯中，磁力搅拌10min混匀。称取37.5g配分为Ce 0.2Zr 0.7La 0.03Nd 0.07O 1.94的铈锆复合氧化物粉末，将其加入盛有115mL去离子水的烧杯中，磁力搅拌30min，形成分散均匀的浆料。将混合好的钐锰溶液加入到上述浆料中，磁力搅拌10min。量取150mL 1mol/L NaOH溶液，逐滴加入上述混有钐锰溶液的浆料中并维持磁力搅拌，时间为1h。NaOH溶液加完后，再继续搅拌10min，然后加入30％的H 2O 2 8mL，继续搅拌30min。过滤上述沉淀物，用去离子水洗涤干净，在180℃烘箱中干燥24h，然后在马弗炉中750℃煅烧3h后，取出，研磨即得产物，D50＝15.0um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为924umol O 2/g。
实施例19
0.3La 0.33Sm 0.67Mn 2O 5-0.7Ce 0.6Zr 0.3La 0.05Y 0.05O 1.96
分别量取10mL浓度为1.5mol/L LaNO 3溶液和20mL浓度为1.5mol/L Sm(NO 3) 3溶液以及60mL浓度为1.5mol/L Mn(NO 3) 2溶液，将三溶液倒入200mL烧杯中，磁力搅拌10min混匀。称取35g配分为Ce 0.6Zr 0.3La 0.05Y 0.05O 1.96的铈锆复合氧化物粉末，将其加入盛有150mL去离子水的烧杯中，磁力搅拌30min，形成分散均匀的浆料。将混合好的镧钐锰溶液加入到上述浆料中，磁力搅拌10min。量取110mL 3mol/L NaOH溶液，逐滴加入上述混有镧钐锰溶液的浆料中并维持磁力搅拌，时间为1h。NaOH溶液加完后，再继续搅拌10min，然后加入30％的H 2O 2 10mL，继续搅拌30min。过滤上述沉淀物，用去离子水洗涤干净，在190℃烘箱中干燥24h，然后在马弗炉中500℃煅烧6h后，取出，研磨即得产物，D50＝10.8um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为957umol O 2/g。
实施例20
0.3La 0.2Ce 0.2Y 0.6Mn 2O 5-0.7Ce 0.4Zr 0.5La 0.02Nd 0.05Y 0.03O 1.97
分别量取8mL浓度为1.5mol/L LaNO 3溶液和8mL浓度为1.5mol/L Ce(NO 3) 3溶液以及24mL浓度为1.5mol/L Mn(NO 3) 2溶液，将三溶液倒入100mL烧杯中，磁力搅拌10min混匀。称取35g配分为Ce 0.4Zr 0.5La 0.02Nd 0.05Y 0.03O 1.97的铈锆复合氧化物粉末，将其加入盛有85mL去离子水的烧杯中，磁力搅拌30min，形成分散均匀的浆料。将混合好的镧铈钇锰溶液加入到上述浆料中，磁力搅拌10min。量取84mL5mol/L氨水，逐滴加入上述混有镧铈钇锰溶液的浆料中并维持磁力搅拌，时间为1h。NaOH溶液加完后，再继续搅拌10min，然后加入30％的H 2O 2 13mL，继续搅拌30min。过滤上述沉淀物，用去离子水洗涤干净，在190℃烘箱中干燥24h，然后在马弗炉中900℃煅烧1h后，取出，研磨即得产物，D50＝4.2um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为997umol O 2/g。
实施例21
0.3Y 0.5MnO 2.5-0.7Ce 0.4Zr 0.5La 0.05Y 0.05O 1.92
分别量取15mL浓度为1.5mol/L YNO 3溶液和24mL浓度为1.5mol/L Mn(NO 3) 2溶液，将三溶液倒入100mL烧杯中，磁力搅拌10min混匀。称取35g配分为Ce 0.4Zr 0.5La 0.05Y 0.05O 1.92的铈锆复合氧化物粉末，将其加入盛有65mL去离子水的烧杯中，磁力搅拌30min，形成分散均匀的浆料。将混合好的钇锰溶液加入到上述浆料中，磁力搅拌10min。量取840mL 0.5mol/L氨水，逐滴加入上述混有钇锰溶液的浆料中并维持磁力搅拌，时间为1h。NaOH溶液加完后，再继续搅拌10min， 然后加入30％的H 2O 2 13mL，继续搅拌30min。过滤上述沉淀物，用去离子水洗涤干净，在200℃烘箱中干燥24h，然后在马弗炉中800℃煅烧5h后，取出，研磨即得产物，D50＝5.3um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为1002umol O 2/g。
实施例22
0.25Ce 0.5YMn 3O 7.5-0.75Ce 0.2Zr 0.7La 0.05Nd 0.05O 1.94
分别量取17mL浓度为1.5mol/L CeCl 3溶液和33mL浓度为1.5mol/L的YCl 3溶液以及50mL浓度为1.5mol/L MnCl 2溶液，将两溶液倒入200mL烧杯中，磁力搅拌10min混匀。称取37.5g配分为Ce 0.2Zr 0.7La 0.05Nd 0.05O 1.94的铈锆复合氧化物粉末，将其加入盛有55mL去离子水的烧杯中，磁力搅拌30min，形成分散均匀的浆料。将混合好的铈钇锰溶液加入到上述浆料中，磁力搅拌10min。量取103mL2.5mol/L NaOH溶液，逐滴加入上述混有铈钇锰溶液的浆料中并维持磁力搅拌，时间为1h。NaOH溶液加完后，再继续搅拌10min，然后加入30％的H 2O 2 8mL，继续搅拌30min。过滤上述沉淀物，用去离子水洗涤干净，在200℃烘箱中干燥24h，然后在马弗炉中810℃煅烧4h后，取出，研磨即得产物，D50＝6.9um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为921umol O 2/g。
实施例23
0.2La 1.25Mn 2.5O 7.25-0.8Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.93:
分别量取21mL浓度为1.5mol/L LaCl 3溶液和42mL浓度为1.5mol/L MnCl 2溶液，将两溶液倒入200mL烧杯中，磁力搅拌10min混匀。称取40g配分为Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.93的铈锆复合氧化物粉末，将其加入盛有45mL去离子水的烧杯中，磁力搅拌30min，形成分散 均匀的浆料。将混合好的镧锰溶液加入到上述浆料中，磁力搅拌10min。量取105mL 2mol/L NaOH溶液，逐滴加入上述混有镧锰溶液的浆料中并维持磁力搅拌，时间为1h。NaOH溶液加完后，再继续搅拌10min，然后加入30％的H 2O 2 7mL，继续搅拌30min。过滤上述沉淀物，用去离子水洗涤干净，在210℃烘箱中干燥24h，然后在马弗炉中820℃煅烧5h后，取出，研磨即得产物，D50＝7.6um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为894umol O 2/g。
实施例24
0.15Ce 0.4Sm 0.4Mn 1.6O 4-0.85Ce 0.3Zr 0.6La 0.1O 1.92:
分别量取9mL浓度为1.5mol/L CeCl 3溶液和9mL浓度为1.5mol/L的SmCl 3溶液以及36mL浓度为1.5mol/L MnCl 2溶液将两溶液倒入200mL烧杯中，磁力搅拌10min混匀。称取42.5g配分为Ce 0.3Zr 0.6La 0.1O 1.92的铈锆复合氧化物粉末，将其加入盛有45mL去离子水的烧杯中，磁力搅拌30min，形成分散均匀的浆料。将混合好的铈钐锰溶液加入到上述浆料中，磁力搅拌10min。量取100mL 1.5mol/L NaOH溶液，逐滴加入上述混有铈钐锰溶液的浆料中并维持磁力搅拌，时间为1h。NaOH溶液加完后，再继续搅拌10min，然后加入30％的H 2O 2 6mL，继续搅拌30min。过滤上述沉淀物，用去离子水洗涤干净，在210℃烘箱中干燥24h，然后在马弗炉中820℃煅烧3h后，取出，研磨即得产物，D50＝8.5um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为899umol O 2/g。
实施例25
0.10Ce 0.5Y 0.5Mn 2O 5-0.90Ce 0.4Zr 0.6O 1.96
分别量取7.5mL浓度为2mol/L Ce(NO 3) 3溶液和7.5mL浓度为 2mol/L的Y(NO 3) 3溶液以及15mL浓度为4.5mol/L Mn(NO 3) 2溶液倒入100mL烧杯中，磁力搅拌10min混匀。称取90g配分为0.90Ce 0.4Zr 0.6O 1.96的铈锆复合氧化物粉末于250mL烧杯中，将Ce、Mn溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，然后在220℃烘箱中干燥24h，然后在马弗炉中850℃煅烧5h后，取出，研磨即得产物，D50＝9.2um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为987umol O 2/g。
实施例26
0.3 La 0.1Ce 0.1Y 0.8Mn 2O 5-Ce 0.4Zr 0.5La 0.05Y 0.05O 1.89
分别量取2.5mL浓度为2mol/L La(NO 3) 3溶液和2.5mL浓度为2mol/L的Ce(NO 3) 3溶液和10mL浓度为4mol/L的Y(NO 3) 3溶液以及23mL浓度为4.5mol/L Mn(NO 3) 2溶液倒入100mL烧杯中，磁力搅拌10min混匀。称取35g配分为Ce 0.4Zr 0.5La 0.05Y 0.05O 1.89的铈锆复合氧化物粉末于250mL烧杯中，将La、Ce、Y、Mn溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，然后在220℃烘箱中干燥24h，然后在马弗炉中850℃煅烧5h后，取出，研磨即得产物，D50＝3.6um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为1017umol O 2/g。
实施例27
0.25Ce 0.5SmMn 3O 7.5-0.75Ce 0.2Zr 0.7La 0.03Nd 0.07O 1.9
分别量取4mL浓度为3mol/L的Ce(NO 3) 3溶液和8mL浓度为3mol/L Sm(NO 3) 3溶液以及15mL浓度为5mol/L Mn(NO 3) 2溶液，倒入200mL烧杯中，磁力搅拌10min。称取37.5g配分为Ce 0.2Zr 0.7La 0.03Nd 0.07O 1.9的铈锆复合氧化物粉末于250mL烧杯中，将Sm、Mn混合溶液逐滴加入到 搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，在180℃烘箱中干燥24h，然后在马弗炉中750℃煅烧5h后，取出，研磨即得产物，D50＝3.9um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为1067umol O 2/g。
实施例28
0.3Pr 3Mn 5O 12-0.7Ce 0.6Zr 0.3La 0.05Y 0.05O 1.98
分别量取18mL浓度为3mol/L Pr(NO 3) 3溶液和18mL浓度为5mol/L Mn(NO 3) 2溶液，倒入200mL烧杯中，磁力搅拌10min混匀。称取35g配分为Ce 0.6Zr 0.3La 0.05Y 0.05O 1.98的铈锆复合氧化物粉末于250mL烧杯中，将Pr、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在200℃烘箱中干燥24h，然后在马弗炉中850℃煅烧5h后，取出，研磨即得产物，研磨即得产物，D50＝4.6um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为914umol O 2/g。
实施例29
分别量取18mL浓度为3mol/L Y(NO 3) 3溶液和18mL浓度为5mol/L Mn(NO 3) 2溶液，倒入200mL烧杯中，磁力搅拌10min混匀。称取35g配分为Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.95的铈锆复合氧化物粉末于250mL烧杯中，将Y、Mn混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在200℃烘箱中干燥24h，然后在马弗炉中850℃煅烧5h后，取出，研磨即得产物，研磨即得产物，D50＝4.8um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为945umol O 2/g。
实施例30
分别量取18mL浓度为3mol/L Y(NO 3) 3溶液和17mL浓度为5mol/L Mn(NO 3) 2溶液，1mL 5mol/L Fe(NO 3) 2溶液倒入200mL烧杯中，磁力搅拌10min混匀。称取35g配分为Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.95的铈锆复合氧化物粉末于250mL烧杯中，将Y、Mn、Fe混合溶液逐滴加入到搅拌状态的铈锆复合氧化物粉末里，待液体加入完毕后，搅拌10min，取出后在200℃烘箱中干燥24h，然后在马弗炉中850℃煅烧5h后，取出，研磨即得产物，研磨即得产物，D50＝4.7um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，测得总的储氧量为1324umol O 2/g。
由以上实施例可得出，按照本发明实施例的莫来石结构稀土锰-铈锆复合化合物的配比及制备方法制备得到的储氧材料具有高储氧性能，其储氧量都不低于800umol O 2/g。
实施例31
如图4为采用本发明方法制备得到的0.3YMn 2O 5-0.7Ce 40Zr 50La 5Pr 5O 1.95的X射线衍射图，从图中可以看出，材料内部是铈锆固溶体，外部沉积YMn 2O 5结构化合物，为核壳结构。
其他实施例所得产物均具有类似复合结构。
对比例1
Ce 0.4Zr 0.5La 0.05Pr 0.05O 1.95，采用与实施例1同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为498umol O 2/g。
对比例2
LaMnO 3
分别量取18mL浓度为3mol/L La(NO 3) 3溶液和18mL浓度为5mol/L Mn(NO 3) 2溶液，将两溶液倒入200mL烧杯中，磁力搅拌10min混匀。量取100mL 1.5mol/L NaOH溶液，逐滴加入上述钇锰溶液中并维持磁 力搅拌，时间为1h。NaOH溶液加完后，再继续搅拌10min，然后加入30％的H 2O 22mL，继续搅拌30min。过滤上述沉淀物，用去离子水洗涤干净，在210℃烘箱中干燥24h，然后在马弗炉中820℃煅烧3h后，取出，研磨即得产物，D50＝8.5um。
将以上制得的复合化合物，采用与实施例1中同样的储氧量测试方法，通过统计消耗O 2峰面积计算总的储氧量为693umol O 2/g。
实施例31
分别取各实施例制得的复合化合物50mg，置于微反应器中进行催化剂活性评价试验，通过红外气体分析仪(MKS)记录对应温度下NO、NO 2及NO x的含量，从而计算出NO的转化率。具体试验条件如下：反应气体的体积组成：氧气10％、一氧化氮100ppm；平衡气为氮气：总流量为150mL/min。反应温度设置：以20℃/min的速度从室温升至400℃，反应时间为20min。测试结果参见表1：
表1 各实施例催化性能参数表
Figure PCTCN2020113455-appb-000001
Figure PCTCN2020113455-appb-000002
由表1可见，本申请实施例提供的复合化合物催化氧化NO时， NO的最高转化率可达88，较对比例1提高了78％，较对比例2提高了30％。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (29)

  1. 一种稀土锰/铈锆基复合化合物，其特征在于：
    所述复合化合物具有核壳结构，其通式表示为：A RE cB aO b-(1-A)Ce xZr (1-x-y)M yO 2-z，其中0.1≤A≤0.3；
    壳层主成分为稀土锰氧化物，其通式为RE cB aO b，其中RE为一种或一种以上稀土元素的组合，B为Mn或Mn与过渡金属元素的组合，1≤a≤8，2<b≤18，0.25≤c≤4；
    核心主成分为铈锆复合氧化物，其通式为Ce xZr (1-x-y)M yO 2-z，M为非铈稀土元素、过渡金属元素中的至少一种；其中0.1≤x≤0.9，0≤y≤0.3，0.01≤z≤0.3。
  2. 根据权利要求1所述的稀土锰/铈锆复合化合物，其特征在于：壳层中Mn元素质量与稀土锰/铈锆复合化合物中Mn元素的总质量的质量百分比为70-98wt％。
  3. 根据权利要求1或2所述的稀土锰/铈锆复合化合物，其特征在于：所述铈锆复合氧化物中的铈为三价和四价的复合价态，四价铈占铈总量的60-90wt％。
  4. 根据权利要求1～3任一项所述的稀土锰/铈锆复合化合物，其特征在于：1≤a≤3，2≤b≤8，优选地，所述壳层为莫来石型结构化合物。
  5. 根据权利要求4所述的稀土锰/铈锆复合化合物，其特征在于：壳层中Mn元素质量与稀土锰/铈锆复合化合物中Mn元素的总质量的质量百分比为70-95wt％。
  6. 根据权利要求1～5任一项所述的稀土锰/铈锆复合化合物，其特征在于：
    所述稀土锰氧化物中稀土元素RE包括镧、铈、镨、钕、钐、铕、钆、钇中的一种或一种以上；
    所述铈锆复合氧化物中M为镧、镨、钕、钇、钐、铕、钆、钬、铒、铥、镱、铪、铝、钡中的一种或一种以上。
  7. 根据权利要求1～6任一项所述的稀土锰/铈锆复合化合物，其特征在于：所述壳层还含有氢氧化物、碳酸盐、碱式碳酸盐中的一种或多种，含量为0.01～1wt％。
  8. 根据权利要求1～7任一项所述的稀土锰/铈锆复合化合物，其特征在于：
    所述稀土锰氧化物掺杂有过渡金属元素，所述过渡金属元素选自铁、钨、钼、镍、钴、钒、钛中的一种或一种以上；
    所述过渡金属元素的质量为稀土锰氧化物质量的0.01％-10％，其中过渡金属元素质量以过渡金属元素自身质量计，所述稀土锰氧化物质量以掺杂过渡金属前的稀土锰氧化物的质量计。
  9. 根据权利要求1～8任一项所述的稀土锰/铈锆复合化合物，其特征在于：所述的稀土锰/铈锆复合化合物储氧量不低于800umol-O 2/g。
  10. 根据权利要求1～8任一项所述的稀土锰/铈锆复合化合物，其特征在于：粒度D50为1-15um。
  11. 权利要求1～10任一项所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，包括：
    对含有二价锰源、稀土源、铈锆复合氧化物的混合原料进行反应，得到所述稀土锰/铈锆复合化合物。
  12. 根据权利要求11所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述对含有锰源、稀土源、铈锆复合氧化物的混合原料进行反应，具体包括以下步骤：
    根据最终产物化学计量比配置二价锰源、稀土源和铈锆复合氧化物；
    将含有二价锰源和稀土源的混合溶液加入所述铈锆复合氧化物中进行反应，反应结束后干燥、煅烧、粉碎，得到所述稀土锰/铈锆复合化合物。
  13. 根据权利要求12所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述二价锰源在所述混合溶液中的浓度为2～4mol/L，其中，所述二价锰源的摩尔量以锰元素摩尔量计；
    所述稀土源在所述混合液中的浓度为0.5～2mol/L，其中，所述稀土源的摩尔量以稀土元素摩尔量计。
  14. 根据权利要求12或13所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述含有二价锰源和稀土源的混合溶液的体积为所述铈锆复合氧化物孔容积的70～150％。
  15. 根据权利要求12～14任一项所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述反应的具体条件包括：
    在搅拌条件下进行；
    反应温度为15～45℃；
    反应时间为5～20min。
  16. 根据权利要求11所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述对含有锰源、稀土源、铈锆复合氧化物的混合原料进行反应，具体包括以下步骤：
    根据最终产物化学计量比配置二价锰源、稀土源和铈锆复合氧化物；
    向含有二价锰源、稀土源、铈锆复合氧化物的混合浆料中依次加入沉淀剂和氧化剂进行反应，反应结束后洗涤、干燥、煅烧、粉碎，得到所述稀土锰/铈锆复合化合物。
  17. 根据权利要求16所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述沉淀剂选自氢氧化钠、氨水、碳酸氢氨或氢氧化钾 中的至少一种。
  18. 根据权利要求16或17所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述沉淀剂的物质的量为沉淀所述浆料中锰元素和稀土元素所需化学计量的5-90％。
  19. 根据权利要求16～18任一项所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述沉淀剂以沉淀剂溶液形式加入所述混合浆料中；
    所述沉淀剂溶液中沉淀剂浓度为0.5-5mol/L。
  20. 根据权利要求16～18任一项所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述氧化剂选自过氧化氢、氧气、过硫酸钠、过硫酸钾或过硫酸铵中的至少一种。
  21. 根据权利要求16～10任一项所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述氧化剂的物质的量为所述浆料中所含Mn 2+物质的量的0.05-1倍。
  22. 根据权利要求16～21任一项所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述洗涤的具体条件包括：
    用去离子水进行洗涤，洗涤终点去离子水的电导率小于40us/cm。
  23. 根据权利要求16～22任一项所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述含有二价锰源、稀土源、铈锆复合氧化物的混合浆料，通过以下方法制得：
    将铈锆复合氧化物加入水中，得到铈锆复合氧化物浆料；
    将含有二价锰源和稀土源的混合溶液与所述铈锆复合氧化物浆料混合，得到混合浆料。
  24. 根据权利要求23任一项所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述铈锆复合氧化物浆料中铈锆复合氧化物的质量浓度为10-50％。
  25. 根据权利要求23任一项所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述二价锰源在所述混合溶液中的浓度为0.5～2.5mol/L，其中，所述二价锰源的摩尔量以锰元素摩尔量计；
    所述稀土源在所述混合液中的浓度为0.5～1.5mol/L，其中，所述稀土源的摩尔量以稀土元素摩尔量计。
  26. 根据权利要求11所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述二价锰源为锰的可溶性金属盐，所述锰的可溶性金属盐选自锰的硝酸盐、锰的乙酸盐、锰的氯化物、锰的硫酸盐中的至少一种；
    所述稀土源为稀土的可溶性金属盐，所述稀土的可溶性金属盐选自稀土的硝酸盐、稀土的乙酸盐、稀土的氯化物、稀土的硫酸盐中的至少一种。
  27. 根据权利要求16～25任一项所述的稀土锰/铈锆复合化合物的制备方法，其特征在于，所述煅烧的具体条件包括：
    煅烧温度为500-900℃；
    煅烧时间为1-6h。
  28. 一种催化剂，包括权利要求1～10任一项所述的稀土锰/铈锆复合化合物、权利要求11～27任一项所述的制备方法制备的稀土锰/铈锆复合化合物中的至少一种。
  29. 权利要求28所述的催化剂在机动车尾气N0催化氧化中的应用。
PCT/CN2020/113455 2019-09-04 2020-09-04 稀土锰/铈锆基复合化合物及其制备方法和应用 WO2021043256A1 (zh)

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