WO2021088196A1 - 一种双金属MOFs催化剂及其制备方法和用途 - Google Patents

一种双金属MOFs催化剂及其制备方法和用途 Download PDF

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WO2021088196A1
WO2021088196A1 PCT/CN2019/124442 CN2019124442W WO2021088196A1 WO 2021088196 A1 WO2021088196 A1 WO 2021088196A1 CN 2019124442 W CN2019124442 W CN 2019124442W WO 2021088196 A1 WO2021088196 A1 WO 2021088196A1
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catalyst
manganese
nickel
source
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朱廷钰
徐文青
谢军
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中国科学院过程工程研究所
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/70—Constitutive chemical elements of heterogeneous catalysts of Group VII (VIIB) of the Periodic Table
    • B01J2523/72—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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/84—Metals of the iron group
    • B01J2523/847—Nickel

Definitions

  • This application relates to the field of catalytic materials, for example, to a bimetal MOFs catalyst and its preparation method and application.
  • Nitrogen oxides are a common type of air pollutant that can cause a series of environmental problems such as acid rain, photochemical smog and haze, and also cause harm to humans. With the country in recent years, more and more stringent NO x emission standards, research and efficient removal of nitrogen oxides extrusion technology will be important. At present, the most widely used flue gas denitration technology in industry is Selective Catalysis Reduction (NH 3 -SCR), which uses the reducing agent NH 3 to selectively reduce NO x to N 2 in the presence of a catalyst.
  • NH 3 -SCR Selective Catalysis Reduction
  • the more mature catalysts above are vanadium-titanium-based catalysts, but these catalysts also have some problems in practical applications. For example, the active component of the catalyst, vanadium, is highly toxic and has a high working temperature (generally higher than 300°C). Therefore, the development of new and efficient low-temperature SCR catalysts is a current research hotspot.
  • CN101862651A discloses a V-Sb-Nb/Ti catalyst for selective catalytic reduction of nitrogen oxides and a preparation method thereof.
  • the active components of the catalyst are: 0.1%-5% V 2 O 5 , 0.1% -5% Sb 2 O 3 and 0.1%-15% Nb 2 O 5 , the carrier used is TiO 2 , and the catalyst is prepared by an equal volume impregnation method; the catalyst described in this scheme has poor low-temperature catalytic activity and contains V 2 O 5 easily pollutes the environment.
  • CN107913699A discloses a flue gas denitration catalyst and a preparation method thereof.
  • the specific surface of the catalyst is 50-130m 2 /g, the pore volume is 0.30-0.70cm 3 /g, and the content of TiO 2 is 90-97% by weight.
  • the content of WO 3 is 1-10%, and the content of V 2 O 5 is 0.5-5%.
  • the preparation method is as follows: (1) Form the titanium source precursor into a solution; (2) Dissolve the tungsten source precursor and combine it with (1) (3) Adjust the pH value of the solution obtained in (2), precipitate, filter, and wash; (4) Add water to the filter cake obtained in (3) to make a slurry, add the vanadium source precursor solution, and mix Dry roasting; (5) Mix the solution formed by the precursor of the tungsten source and the powder of (4) into a slurry. After stirring, add a pore-forming assistant to form a denitration catalyst.
  • the above scheme still has a small specific surface area of the catalyst. , The dispersion of active components is low, the catalyst contains toxic components and the low temperature activity of the catalyst is poor.
  • the purpose of this application is to provide a bimetal MOFs catalyst and its preparation method and use.
  • the catalyst contains nickel ions, manganese ions and organic carboxylic acid ligands, and the catalyst has a larger specific surface area and a smaller porosity.
  • the average pore diameter of nickel and manganese ions are highly dispersed in the catalyst, which provides more active sites for the catalyst.
  • the catalyst described in this application has higher catalytic activity at a lower temperature, which is 200-250°C.
  • the conversion rate of the catalytic nitrogen oxides conversion in the temperature range of the catalyst can reach up to 94%, and the preparation process of the catalyst is simple, and it has broad application prospects.
  • the present application provides a bimetal MOFs catalyst.
  • the bimetal MOFs catalyst includes a metal ion and an organic ligand, the metal ion is nickel and manganese, and the organic ligand includes an organic carboxylic acid ligand.
  • MOFs mentioned in this application refer to metal organic framework compounds.
  • the bimetallic MOFs catalysts described in this application include nickel ions, manganese ions and organic carboxylic acid ligands.
  • the above-mentioned substances form metal organic framework compounds, which have larger specific surface area and porosity, and smaller average pore diameter, so that the catalyst is very
  • the reactants have higher adsorption capacity, and nickel ions and manganese ions are highly dispersed in the catalyst, so that the catalyst has more active sites, so that the catalyst described in the present application has higher catalytic activity at lower temperatures.
  • the molar ratio of manganese to nickel in the metal ion is (2-10):1, for example, 2:1, 7:3, 4:1, 6:1, or 9:1, etc., may be ( 4-9):1.
  • the molar ratio of the metal ion to the organic carboxylic acid ligand is 1:(0.1-10), for example, 1:0.15, 1:0.5, 1:0.8, 1:1, 1:2, 1. :5, 1:7 or 1:9, etc., can be 1:(0.1-1).
  • the specific surface area of MOFs bimetallic catalyst is 350-600m 2 / g, for example, 400m 2 / g, 450m 2 / g, 500m 2 / g or 550m 2 / g and the like.
  • the porosity of the bimetal MOFs catalyst is more than 80%, such as 82%, 85%, or 88%.
  • the two metal elements of nickel and manganese in the bimetallic MOFs catalyst are uniformly distributed in the crystal lattice.
  • the specific surface area of the bimetallic MOFs catalyst described in this application can reach 350-600m 2 /g, the porosity is more than 80%, and the average pore diameter is 2-2.15nm, so that the bimetallic MOFs catalyst has a higher adsorption capacity for NO , So that the activity of the catalyst is significantly improved.
  • the nickel element and manganese element in the bimetallic MOFs catalyst described in the present application act as coordination metal atoms at the same time and are uniformly present in the material.
  • the present application provides a method for preparing the bimetal MOFs catalyst as described in the first aspect, and the method includes the following steps:
  • step (1) The product of step (1) is soaked in an alcohol solution and then activated to obtain the bimetal MOFs catalyst.
  • the bimetal MOFs catalyst described in the present application is prepared by a solvothermal reaction method, and the preparation method is simple, and the prepared catalyst has a large specific surface area and a small average pore size, thereby facilitating higher catalytic activity of the catalyst.
  • the reactants and the reaction solvent are evenly mixed, they are placed in a polytetrafluoroethylene-lined reactor and heated at a certain temperature to form a high-temperature and high-pressure environment.
  • Carboxylic acid ligands (2,5-dihydroxybenzoic acid and/or 2,5-dihydroxyterephthalic acid) pair with manganese ions and nickel ions to form bonds, and finally the metal ions are in an octahedral coordination mode
  • Each metal ion is coordinated with six oxygen atoms, three of which are from the carboxyl oxygen atom in the ligand, two are from the hydroxyl oxygen atom in the ligand, and the other is from the solvent (such as dimethylformamide, methanol Or the oxygen atoms in H 2 O) are activated by heating and other means, the solvent is removed to form unsaturated metal sites, resulting in materials with higher gas storage, separation and catalytic capabilities.
  • the solvent such as dimethylformamide, methanol Or the oxygen atoms in H 2 O
  • the manganese source in step (1) includes manganese chloride and/or manganese sulfate.
  • the nickel source in step (1) includes nickel nitrate and/or nickel sulfate.
  • the organic carboxylic acid ligand includes 2,5-dihydroxybenzoic acid and/or 2,5-dihydroxyterephthalic acid.
  • the molar ratio of the manganese source and the nickel source in step (1) is (2-10):1, for example, 3:1, 4:1, 5:1, 6:1, 7:1, 8: 1 or 9:1, etc., can be (4-9):1.
  • the ratio of the sum of the molar amounts of the manganese source and the nickel source to the molar amount of the organic carboxylic acid ligand in step (1) is 1:(0.1-10), for example, 1:0.15, 1:0.5 , 1:0.8, 1:1, 1:2, 1:5, 1:7 or 1:9, etc., can be 1:(0.1-1).
  • the concentration of the organic carboxylic acid ligand in the mixed solution of step (1) is 5-20mmol/L, for example, 7mmol/L, 9mmol/L, 10mmol/L, 11mmol/L, 12mmol/L, 15mmol/L L, 17mmol/L or 19mmol/L, etc., may be 9-13mmol/L, and further may be 11.2mmol/L.
  • the solvent includes any one or a combination of at least two of methanol, ethanol, propanol, dimethylformamide, diethylformamide or water, and the combination exemplarily includes methanol and ethanol.
  • the volume ratio of dimethylformamide, methanol and water in the mixed solution is (12-18):(0.5-2):1, for example, 13:2:1, 15:1:1 or 18 :0.5:1 etc.
  • the temperature of the solvothermal reaction in step (1) is 100-200°C, such as 110°C, 130°C, 150°C, 170°C, or 190°C.
  • the time of the solvothermal reaction in step (1) is 12-72h, such as 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h or 70h.
  • the solvothermal reaction in step (1) further includes solid-liquid separation and washing.
  • the solid-liquid separation method includes filtration and/or centrifugation.
  • the washing detergent includes any one or a combination of at least two of methanol, ethanol, propanol, dimethylformamide or diethylformamide, and the combination exemplarily includes methanol and
  • the combination of ethanol, the combination of propanol and dimethylformamide, or the combination of diethylformamide and methanol, etc. may be dimethylformamide and/or methanol.
  • the alcohol solution in step (2) includes a methanol solution.
  • the immersion method in step (2) includes immersing the product of step (1) in a methanol solution, then changing the methanol solution, continuing the immersion, and repeating the above steps n times.
  • n ⁇ 1 such as 1, 3, 5, 7, or 10, etc.
  • the time interval for changing the methanol solution is 6-12 hours, for example, 7 hours, 8 hours, 9 hours, 10 hours, or 11 hours.
  • the soaking time is 3-7 days, such as 3.5 days, 4 days, 4.5 days, 5 days, 5.5 days, 6 days or 6.5 days.
  • the product prepared by the solvothermal reaction in the alcohol solution immersion step (1) can be used to remove the dimethylformamide solvent with the higher boiling point in the pores of the catalyst material by using a solvent such as methanol with a lower boiling point. Then it can be removed by gentle vacuum or heat treatment without damaging the skeleton structure of the material.
  • the activation method in step (2) includes any one or a combination of at least two of vacuum activation, activation in an air atmosphere, or activation in an inert atmosphere, and activation in an inert atmosphere can be selected.
  • the inert atmosphere includes any one or a combination of at least two of nitrogen, argon, or helium; the combination exemplarily includes a combination of nitrogen and argon, a combination of nitrogen and helium, or helium
  • the combination of gas and argon, etc., can be selected as nitrogen.
  • the activation temperature is 150-350°C, such as 160°C, 200°C, 250°C, 300°C or 330°C, etc., optionally 220-350°C.
  • the activation time is 1-12h, such as 2h, 4h, 6h, 8h or 10h.
  • the method described in the present application can remove residual solvent molecules in the pores of the material through the activation step, thereby exposing more active sites to the catalyst, thereby achieving the purpose of activation.
  • the method includes the following steps:
  • a manganese source, a nickel source and an organic carboxylic acid ligand are dissolved in a solvent to obtain a mixed solution, and then a solvothermal reaction, solid-liquid separation, and washing are performed to obtain a solid product;
  • the manganese source includes manganese chloride and/or Manganese sulfate;
  • the nickel source includes nickel nitrate and/or nickel sulfate;
  • the organic carboxylic acid ligand includes 2,5-dihydroxybenzoic acid and/or 2,5-dihydroxyterephthalic acid;
  • the solvent is A mixed solution of dimethylformamide, methanol and water, the volume ratio of dimethylformamide, methanol and water in the mixed solution is (12-18):(0.5-2):1;
  • the manganese source and The molar ratio of the nickel source is (2-10):1, the molar ratio of the sum of the molar amounts of the manganese source and the nickel source to the organic carboxylic acid ligand is 1:(
  • step (2) Immerse the solid product of step (1) in methanol solution for 3-7 days, separate solid and liquid, activate at 150-350° C. for 1-12 hours in a nitrogen atmosphere, and cool to obtain the bimetal MOFs catalyst.
  • the present application provides the use of the bimetal MOFs catalyst as described in the first aspect, and the bimetal MOFs catalyst is used to catalyze the selective reduction of nitrogen oxides by ammonia.
  • the bimetal MOFs catalyst is used to catalyze the reduction of nitrogen oxides by ammonia at a temperature of 200-250°C, for example, 210°C, 220°C, 240°C, or 250°C.
  • the bimetal MOFs catalyst is used to remove nitrogen oxides from stationary source flue gas or mobile source exhaust gas.
  • the high specific surface of the bimetal MOFs catalyst described in this application cooperates with the highly dispersed manganese ions and nickel ions so that the catalyst has more catalytic active sites, so that the catalyst has higher catalytic activity at lower temperatures In the temperature range of 200-250°C, the catalyst described in the present application has a conversion rate of up to 94% for catalyzing the conversion of nitrogen oxides.
  • the nickel ion and manganese ion in the bimetallic MOFs catalyst described in this application coordinate with the organic carboxylic acid ligand to form a bond, and finally together form an octahedral coordination structure.
  • the manganese catalyst has good denitrification activity. When nickel is used as the central atom, the offensive activity of water on nickel is weak, and the chemical bond stability is better. Therefore, the synergistic effect of manganese and nickel can improve the activity and stability of the catalyst, and at the same time increase the resistance of the catalyst. Water performance. Under the reaction conditions with a moisture content of 5%, the catalyst has high stability in the temperature range of 200-250°C.
  • the bimetallic MOFs catalysts described in this application include nickel ions, manganese ions and organic carboxylic acid ligands, which have a large specific surface area and porosity, so that they have high adsorption capacity for NO and overcome the specific surface area of traditional catalysts. Lower defects, which is conducive to improving the catalytic activity of the catalyst.
  • the catalyst described in the present application exhibits higher low-temperature activity. In the temperature range of 200-250°C, the conversion rate of catalytic nitrogen oxides can reach up to 94 %;
  • the bimetallic MOFs catalyst described in this application has a crystal structure in which manganese ions and nickel ions are evenly distributed, thereby providing more active sites for the reaction;
  • the catalyst is activated through an activation step, so that more active sites are exposed in the catalyst, thereby significantly improving the catalytic activity of the catalyst;
  • the preparation method of bimetallic MOFs catalyst includes the following steps:
  • the solvent is a mixture of N,N-dimethylformamide, methanol and water; the mixture of N,N-dimethylformamide,
  • the volume ratio of methanol and water is 15:1:1, the molar ratio of manganese chloride and nickel nitrate is 9:1; the sum of the molar amounts of manganese chloride and nickel nitrate and 2,5-dihydroxybenzene
  • the molar ratio of formic acid is 3.3:1, and the concentration of 2,5-dihydroxybenzoic acid in the mixed solution is 11.2 mmol/mL;
  • step (2) Soak the solid product of step (1) in methanol solution for 3 days, replace with fresh methanol solution every 12 hours, filter, dry the filtered product at room temperature for 10 minutes, and then place it in a tube furnace under a nitrogen atmosphere 220 Activated at °C for 3 hours, with a heating rate of 2 °C/min, and naturally cooled to room temperature to obtain the bimetallic MOFs catalyst, denoted as Mn/Ni-MOFs.
  • Example 1 Compared with Example 1, the total molar amount of metal ions is unchanged in this example, and the molar ratio of manganese chloride to nickel nitrate is replaced from 9:1 to 4:1. Compared with Example 1, other conditions are completely the same.
  • Example 1 Compared with Example 1, the total molar amount of metal ions is unchanged in this example, and the molar ratio of manganese chloride to nickel nitrate is replaced from 9:1 to 7:3, and other conditions are completely the same as those in Example 1.
  • Example 1 Compared with Example 1, the total molar amount of metal ions is unchanged in this example, and the molar ratio of manganese chloride to nickel nitrate is replaced from 9:1 to 1:2, and other conditions are completely the same as those in Example 1.
  • Example 1 the activation temperature in Example 1 was replaced from 220°C to 150°C, and the other conditions were exactly the same as in Example 1.
  • Example 1 the activation temperature in Example 1 was replaced from 220°C to 350°C, and the other conditions were exactly the same as in Example 1.
  • Example 1 The difference between this comparative example and Example 1 is that the activation step described in step (2) is not performed, that is, the filtered product is dried at room temperature for 10 minutes to obtain a catalyst.
  • the catalysts prepared in Examples 1-6 and Comparative Example 1 were tested for catalytic performance.
  • the test methods are as follows:
  • the composition of the simulated flue gas is: the volume concentration of NO is 500ppm, the volume concentration of ammonia is 500ppm, the volume fraction of oxygen is 5%, N 2 is the balance gas, the catalyst loading in the fixed bed reactor is 0.2g, and the test process is empty.
  • the speed is 60000h -1 , and the test temperature range is 150-300°C; the above test results are shown in Table 1;
  • the bimetal MOFs catalyst described in this application has a nitrogen oxide conversion rate of up to 94% in the temperature range of 200-250°C, and it can be seen from the comparative examples 1-4 that the manganese source is controlled The molar ratio to the nickel source is (4-9):1, and the bimetal MOFs catalyst prepared therefrom has a conversion rate of nitrogen oxides above 80% in the temperature range of 200-250°C. Comparing Examples 1, 5-6, it can be seen that when the activation temperature is controlled in the range of 220-350°C when activated under a nitrogen atmosphere, the obtained bimetal MOFs catalyst has better low-temperature activity.
  • the water resistance test of the catalyst obtained in Example 1 is carried out, and the test method is as follows;
  • Water content in the flue gas The composition of the simulated flue gas is: NO volume concentration is 500ppm, ammonia volume concentration is 500ppm, oxygen volume fraction is 5%, water volume fraction is 5%, N 2 is balance gas, fixed bed reaction
  • the loading of the catalyst is 0.2g
  • the space velocity in the test process is 60000h -1
  • the test temperature range is 150-300°C; the test results show that 5% water is added to the simulated flue gas during the test.
  • the activity decrease is not obvious (the highest decrease value is less than 5% in the test temperature range), indicating that the catalyst described in the present application has good stability and water resistance.
  • the bimetal MOFs catalyst described in this application has a larger specific surface area and a smaller average pore diameter, with an average pore diameter of 2-2.15 nm, so that the bimetal MOFs catalyst has a high adsorption of NO Ability to overcome the shortcomings of low specific surface area of traditional catalysts, thereby helping to improve the catalytic activity of the catalyst.

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Abstract

本文公开了一种双金属MOFs催化剂及其制备方法和用途，所述催化剂包含镍离子、锰离子和有机羧酸配体，所述催化剂具有较大的比表面积和孔隙率，且镍离子、锰离子在催化剂中高度分散，为催化剂提供了更多的活性位点，同时镍锰离子协同作用，可提高催化剂的稳定性和抗水性。本申请所述催化剂在较低温度下具有较高的催化活性，其在200-250℃的温度区间内催化氮氧化物转化的转化率最高可达94％，且催化剂的制备过程简单，具有广阔的应用前景。

Description

一种双金属MOFs催化剂及其制备方法和用途 技术领域
本申请涉及催化材料领域，例如涉及一种双金属MOFs催化剂及其制备方法和用途。
背景技术
氮氧化物是一类常见的大气污染物，会引发酸雨、光化学烟雾及雾霾等一系列环境问题，同时也会对人体造成危害。随着近年来国家对NO x排放标准越来越严格，研究高效脱除氮氧化物脱出技术将具有重要意义。目前工业应用最为广泛的烟气脱硝技术是氨选择性催化还原(Selective Catalysis Reduction,NH 3-SCR)，即在催化剂存在时利用还原剂NH 3将NO x选择性的还原为N 2，目前工业上较为成熟的催化剂是钒钛基催化剂，但这些催化剂在实际应用中也存在一些问题，如：催化剂中的活性组分钒具有较大毒性，且工作温度较高(一般高于300℃)，因此开发新型高效的低温SCR催化剂是目前的一个研究热点。
CN101862651A公开了一种用于选择性催化还原氮氧化物的V-Sb-Nb/Ti催化剂及其制备方法，所述催化剂的活性组分为：0.1％-5％的V 2O 5、0.1％-5％的Sb 2O 3和0.1％-15％的Nb 2O 5，采用的载体为TiO 2，催化剂采用等体积浸渍法制备得到；此方案所述催化剂的低温催化活性较差，且含有V 2O 5，容易对环境造成污染。
CN107913699A公开了一种烟气脱硝催化剂及其制备方法，该催化剂比表面为50～130m 2/g，孔容0.30～0.70cm 3/g，以重量百分比计，含TiO 2为90～97％，含WO 3为1～10％，含V 2O 5为0.5～5％，制备方法为：(1)将钛源前驱体形成溶液；(2)将钨源前驱体溶解，并与(1)的溶液混合；(3)将(2)所得溶液 调节pH值，沉淀，过滤，洗涤；(4)在(3)所得滤饼中加入水，调成浆状，加入钒源前驱体溶液，混合干燥焙烧；(5)将钨源前驱体形成的溶液与(4)的粉状物混合成浆状，搅拌后，加造孔助剂形成脱硝催化剂，上述方案仍存在着催化剂的比表面积较小，活性组分分散度低，催化剂中含有有毒成分及催化剂低温活性较差等问题。
上述文献虽然公开了一些脱硝催化剂及其制备方法，但仍存在着催化剂上活性组分分散度较低，活性不足的问题，因此，开发一种活性组分在催化剂上高度分散，且具有较大的比表面积和较好的低温活性的催化剂仍具有重要意义。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请的目的在于提供一种双金属MOFs催化剂及其制备方法和用途，所述催化剂包含镍离子、锰离子和有机羧酸配体，所述催化剂具有较大的比表面积和孔隙率、较小的平均孔径，且镍离子、锰离子在催化剂中高度分散，为催化剂提供了更多的活性位点，本申请所述催化剂在较低温度下具有较高的催化活性，其在200-250℃的温度区间内催化氮氧化物转化的转化率最高可达94％，且催化剂的制备过程简单，具有广阔的应用前景。
为达此目的，本申请采用以下技术方案：
第一方面，本申请提供了一种双金属MOFs催化剂，所述双金属MOFs催化剂包含金属离子和有机配体，所述金属离子为镍和锰，所述有机配体包括有机羧酸配体。
本申请所述MOFs指的是金属有机骨架化合物。
本申请所述双金属MOFs催化剂包括镍离子、锰离子和有机羧酸配体，上述物质形成金属有机骨架化合物，其具有较大的比表面积和孔隙率、较小的平均孔径，从而使得催化剂对于反应物具有较高的吸附能力，且镍离子和锰离子在催化剂中高度分散，使得催化剂具有更多的活性位点，从而使得本申请所述催化剂在较低温度下具有更高的催化活性。
可选地，所述金属离子中锰和镍的摩尔比为(2-10):1，例如2:1、7:3、4:1、6:1或9:1等，可选为(4-9):1。
可选地，所述金属离子与所述有机羧酸配体的摩尔比为1:(0.1-10)，例如1:0.15、1:0.5、1:0.8、1:1、1:2、1:5、1:7或1:9等，可选为1:(0.1-1)。
可选地，所述双金属MOFs催化剂的比表面积为350-600m 2/g，例如400m 2/g、450m 2/g、500m 2/g或550m 2/g等。
可选地，所述双金属MOFs催化剂的孔隙率为80％以上，例如82％、85％或88％等。
可选地，所述双金属MOFs催化剂中镍和锰两种金属元素均匀分布于晶格中。
本申请所述双金属MOFs催化剂的比表面积可达350-600m 2/g，孔隙率为80％以上，平均孔径为2-2.15nm，使得所述双金属MOFs催化剂对NO具有较高的吸附能力，从而使得催化剂的活性明显提升。
本申请所述双金属MOFs催化剂中镍元素和锰元素同时作为配位金属原子，均匀存在于材料中。
第二方面，本申请提供了如第一方面所述的双金属MOFs催化剂的制备方法，所述方法包括以下步骤：
(1)将锰源、镍源和有机羧酸配体溶于溶剂，得到混合溶液，之后进行溶剂热反应；
(2)将步骤(1)的产物在醇溶液中浸泡，之后活化，得到所述双金属MOFs催化剂。
本申请所述双金属MOFs催化剂通过溶剂热反应的方法制备得到，其制备方法简单，且制备得到的催化剂的比表面积大，平均孔径小，从而有利于催化剂具有更高的催化活性。
本申请所述双金属MOFs催化剂的制备过程中，反应物和反应溶剂混合均匀后，置于聚四氟乙烯内衬的反应釜内，在一定温度下进行加热，形成高温高压的环境，从而有机羧酸配体(2,5-二羟基苯甲酸和/或2,5-二羟基对苯二甲酸)与锰离子和镍离子节点配对成键，最终金属离子处于一种八面体配位模式，每个金属离子与六个氧原子进行配位，其中三个是来自配体中的羧基氧原子，两个来自于配体中羟基氧原子，另一个来自溶剂(例如二甲基甲酰胺、甲醇或H 2O)中的氧原子，经加热等方式活化后，溶剂被移除形成不饱和金属位，导致材料具有较高的气体存储、分离和催化能力。
可选地，步骤(1)所述锰源包括氯化锰和/或硫酸锰。
可选地，步骤(1)所述镍源包括硝酸镍和/或硫酸镍。
可选地，所述有机羧酸配体包括2,5-二羟基苯甲酸和/或2,5-二羟基对苯二甲酸。
可选地，步骤(1)所述锰源和镍源的摩尔比为(2-10):1，例如3:1、4:1、5:1、6:1、7:1、8:1或9:1等，可选为(4-9):1。
可选地，步骤(1)所述锰源和镍源的摩尔量之和与所述有机羧酸配体的摩 尔量之比为1:(0.1-10)，例如1:0.15、1:0.5、1:0.8、1:1、1:2、1:5、1:7或1:9等，可选为1:(0.1-1)。
可选地，步骤(1)所述混合溶液中有机羧酸配体的浓度为5-20mmol/L，例如7mmol/L、9mmol/L、10mmol/L、11mmol/L、12mmol/L、15mmol/L、17mmol/L或19mmol/L等，可选为9-13mmol/L，进一步可选为11.2mmol/L。
可选地，所述溶剂包括甲醇、乙醇、丙醇、二甲基甲酰胺、二乙基甲酰胺或水中的任意一种或至少两种的组合，所述组合示例性的包括甲醇和乙醇的组合、丙醇和二甲基甲酰胺的组合或二乙基甲酰胺和甲醇的组合等；可选为二甲基甲酰胺、甲醇和水的混合液。
可选地，所述混合液中二甲基甲酰胺、甲醇和水的体积比为(12-18):(0.5-2):1，例如13:2:1、15:1:1或18:0.5:1等。
可选地，步骤(1)所述溶剂热反应的温度为100-200℃，例如110℃、130℃、150℃、170℃或190℃等。
可选地，步骤(1)所述溶剂热反应的时间为12-72h，例如15h、20h、25h、30h、35h、40h、45h、50h、55h、60h、65h或70h等。
可选地，步骤(1)所述溶剂热反应之后还包括固液分离，洗涤。
可选地，所述固液分离的方法包括过滤和/或离心。
可选地，所述洗涤的洗涤剂包括甲醇、乙醇、丙醇、二甲基甲酰胺或二乙基甲酰胺中的任意一种或至少两种的组合，所述组合示例性的包括甲醇和乙醇的组合、丙醇和二甲基甲酰胺的组合或二乙基甲酰胺和甲醇的组合等，可选为二甲基甲酰胺和/或甲醇。
可选地，步骤(2)所述醇溶液包括甲醇溶液。
可选地，步骤(2)所述浸泡的方法包括将步骤(1)的产物置于甲醇溶液中浸泡，之后更换甲醇溶液，继续浸泡，重复上述步骤n次。
可选地，n≥1，例如1、3、5、7或10等。
可选地，所述更换甲醇溶液的时间间隔为6-12h，例如7h、8h、9h、10h或11h等。
可选地，所述浸泡的时间为3-7天，例如3.5天、4天、4.5天、5天、5.5天、6天或6.5天等。
本申请所述方法通过醇溶液浸泡步骤(1)中溶剂热反应制备得到的产物，利用沸点较低的甲醇等溶剂可将催化剂材料孔道中的沸点较高的二甲基甲酰胺溶剂移除。而后可利用温和的真空或加热处理将其除去而不破坏材料的骨架结构。
可选地，步骤(2)所述活化的方法包括真空活化、空气气氛下活化或惰性气氛下活化中的任意一种或至少两种的组合，可选为惰性气氛下活化。
可选地，所述惰性气氛包括氮气、氩气或氦气中的任意一种或至少两种的组合；所述组合示例性的包括氮气和氩气的组合、氮气和氦气的组合或氦气和氩气的组合等，可选为氮气。
可选地，所述活化的温度为150-350℃，例如160℃、200℃、250℃、300℃或330℃等，可选为220-350℃。
可选地，所述活化的时间为1-12h，例如2h、4h、6h、8h或10h等。
本申请所述方法通过活化步骤能移除材料孔道中残留的溶剂分子，从而使得催化剂暴露更多的活性位点，从而达到活化的目的。
作为本申请可选的技术方案，所述方法包括以下步骤：
(1)将锰源、镍源和有机羧酸配体溶于溶剂，得到混合溶液，之后进行溶剂热反应，固液分离、洗涤，得到固体产物；所述锰源包括氯化锰和/或硫酸锰；所述镍源包括硝酸镍和/或硫酸镍；所述有机羧酸配体包括2,5-二羟基苯甲酸和/或2,5-二羟基对苯二甲酸；所述溶剂为二甲基甲酰胺、甲醇和水的混合液，所述混合液中二甲基甲酰胺、甲醇和水的体积比为(12-18):(0.5-2):1；所述锰源和镍源的摩尔比为(2-10):1，所述锰源和镍源的摩尔量之和与有机羧酸配体的摩尔比为1:(0.1-10)，所述混合溶液中有机羧酸配体的浓度为9-13mmol/L；
(2)将步骤(1)的固体产物在甲醇溶液中浸泡3-7天，固液分离，在氮气气氛下150-350℃活化1-12h，冷却，得到所述双金属MOFs催化剂。
第三方面，本申请提供了如第一方面所述的双金属MOFs催化剂的用途，所述双金属MOFs催化剂用于催化氨气选择性还原氮氧化物。
可选地，所述双金属MOFs催化剂用于在200-250℃，例如210℃、220℃、240℃或250℃等，的温度下催化氨气还原氮氧化物。
可选地，所述双金属MOFs催化剂用于固定源烟气或移动源尾气中氮氧化物的脱除。
本申请所述双金属MOFs催化剂的高比表面与高度分散的锰离子和镍离子相互配合使得所述催化剂具有更多的催化活性位点，从而使得催化剂在较低温度下具有较高的催化活性，本申请所述催化剂在200-250℃的温度区间内，其催化氮氧化物转化的转化率最高可达94％。
本申请所述双金属MOFs催化剂中镍离子和锰离子与有机羧酸配体配位成键，最终共同构成八面体配位结构。锰催化剂具有较好的脱硝活性，镍做为中心原子时，水对镍的进攻活性较弱，化学键稳定性较好，因此锰镍协同作用能 提高催化剂的活性和稳定性，同时提高催化剂的抗水性能，在水分含量为5％的反应条件下，在200-250℃的温度区间内，催化剂具有较高的稳定性。
相对于现有技术，本申请具有以下有益效果：
(1)本申请所述双金属MOFs催化剂包括镍离子、锰离子和有机羧酸配体，其具有大的比表面积和孔隙率，使得其对NO具有高的吸附能力，克服了传统催化剂比表面积较低的缺陷，从而有利于提高催化剂的催化活性，本申请所述催化剂表现出较高的低温活性，其在200-250℃的温度区间内，催化氮氧化物转化的转化率最高可达94％；
(2)本申请所述双金属MOFs催化剂为晶体结构，所述晶体结构中锰离子和镍离子分布均匀，从而为反应提供了更多的活性位点；
(3)本申请所述双金属MOFs催化剂的制备过程中通过活化步骤进行催化剂的活化，从而使得催化剂中暴露出更多的活性位点，从而使得催化剂的催化活性明显提高；
(4)本申请所述双金属MOFs催化剂的制备过程简单，易于工业化应用。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1
双金属MOFs催化剂的制备方法包括以下步骤：
(1)在室温搅拌的条件下，将氯化锰、硝酸镍和2,5-二羟基苯甲酸溶于溶剂，继续搅拌30min，得到混合溶液，之后在135℃下进行溶剂热反应24h，自 然冷却至室温，固液分离、洗涤，得到固体产物；所述溶剂为N,N-二甲基甲酰胺、甲醇和水的混合液；所述混合液中N,N-二甲基甲酰胺、甲醇和水的体积比为15:1:1，所述氯化锰和硝酸镍的摩尔比为9:1；所述氯化锰和硝酸镍的摩尔量之和与2,5-二羟基苯甲酸的摩尔比为3.3:1，所述混合溶液中2,5-二羟基苯甲酸的浓度为11.2mmol/mL；
(2)将步骤(1)的固体产物在甲醇溶液中浸泡3天，每隔12h更换新鲜甲醇溶液，过滤，将过滤产物在室温下干燥10min，之后置于管式炉中在氮气气氛下220℃活化3h，升温速率为2℃/min，自然降温至室温，得到所述双金属MOFs催化剂，记为Mn/Ni-MOFs。
实施例2
本实施例与实施例1相比，金属离子的总摩尔量不变，将氯化锰与硝酸镍的摩尔比由9:1替换为4:1，其他条件与实施例1相比完全相同。
实施例3
本实施例与实施例1相比，金属离子的总摩尔量不变，将氯化锰与硝酸镍的摩尔比由9:1替换为7:3，其他条件与实施例1相比完全相同。
实施例4
本实施例与实施例1相比，金属离子的总摩尔量不变，将氯化锰与硝酸镍的摩尔比由9:1替换为1:2，其他条件与实施例1相比完全相同。
实施例5
本实施例将实施例1中活化的温度由220℃替换为150℃，其他条件与实施例1完全相同。
实施例6
本实施例将实施例1中活化的温度由220℃替换为350℃，其他条件与实施例1完全相同。
对比例1
本对比例与实施例1的区别在于，不进行步骤(2)所述的活化步骤，即将过滤产物在室温下干燥10min，得到催化剂。
性能测试：
对实施例1-6和对比例1制备得到的催化剂进行催化性能测试，测试方法如下：
模拟烟气组成为：NO的体积浓度为500ppm，氨气体积浓度为500ppm，氧气体积分数为5％，N 2为平衡气，固定床反应器中催化剂的装载量为0.2g，测试过程的空速为60000h -1，测试温度范围为150-300℃；上述测试结果如表1所示；
表1
Figure PCTCN2019124442-appb-000001
由上表可以看出，本申请所述双金属MOFs催化剂在200-250℃的温度区间内其氮氧化物转化率最高可达94％，且对比实施例1-4可以看出，控制锰源和镍源的摩尔比为(4-9):1，其制备得到的双金属MOFs催化剂在200-250℃的温度区间内氮氧化物的转化率均在80％以上。对比实施例1、5-6可以看出，在氮气气氛下活化时，控制活化温度在220-350℃范围内，所得双金属MOFs催化剂具有更优的低温活性。
对实施例1所得催化剂进行抗水性能测试，测试方法如下；
烟气中含水：模拟烟气组成为：NO的体积浓度为500ppm，氨气体积浓度为500ppm，氧气体积分数为5％，水的体积分数为5％，N 2为平衡气，固定床反应其中催化剂的装载量为0.2g，测试过程的空速为60000h -1，测试温度范围为150-300℃；测试结果显示测试过程中在模拟烟气中加入5％的水，实施例1所得催化剂的活性下降不明显(在测试温度区间内最高下降值小于5％)，表明本申请所述催化剂具有较好的稳定性和抗水性。
以实施例1-3所述催化剂为例，测试其比表面积和平均孔径如表2所示；
表2
  比表面积，m 2/g 平均孔径，nm
实施例1 545.1 2.03
实施例2 520.2 2.01
实施例3 438.5 2.13
由上表可以看出，本申请所述双金属MOFs催化剂具有较大的比表面积，其平均孔径也较小，其平均孔径为2-2.15nm，从而使得双金属MOFs催化剂对NO具有高的吸附能力，克服了传统催化剂比表面积较低的缺陷，从而有利于提 高催化剂的催化活性。
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此。

Claims (16)

  1. 一种双金属MOFs催化剂，其中，所述双金属MOFs催化剂包含金属离子和有机配体，所述金属离子为镍和锰，所述有机配体包括有机羧酸配体。
  2. 如权利要求1所述的双金属MOFs催化剂，其中，所述金属离子中锰和镍的摩尔比为(2-10):1。
  3. 如权利要求2所述的双金属MOFs催化剂，其中，所述金属离子中锰和镍的摩尔比为(4-9):1。
  4. 如权利要求1-3中任一项所述的双金属MOFs催化剂，其中，所述金属离子的总量与所述有机羧酸配体的摩尔比为1:(0.1-10)，可选为1:(0.1-1)；
    可选地，所述双金属MOFs催化剂的比表面积为350-600m 2/g；
    可选地，所述双金属MOFs催化剂的孔隙率为80％以上。
  5. 一种如权利要求1-4中任一项所述的双金属MOFs催化剂的制备方法，其中，所述方法包括以下步骤：
    (1)将锰源、镍源和有机羧酸配体溶于溶剂，得到混合溶液，之后进行溶剂热反应；
    (2)将步骤(1)的产物在醇溶液中浸泡，之后活化，得到所述双金属MOFs催化剂。
  6. 如权利要求5所述的制备方法，其中，所述活化的温度为150-350℃；
    可选地，所述活化的时间为1-12h。
  7. 如权利要求5或6所述的制备方法，其中，所述活化的温度可选为220-350℃。
  8. 如权利要求5-7中任一项所述的制备方法，其中，步骤(1)所述锰源包括氯化锰和/或硫酸锰；
    可选地，步骤(1)所述镍源包括硝酸镍和/或硫酸镍。
  9. 如权利要求5-8中任一项所述的制备方法，其中，所述有机羧酸配体包括2,5-二羟基苯甲酸和/或2,5-二羟基对苯二甲酸；
    可选地，步骤(1)所述锰源和镍源的摩尔比为(2-10):1，可选为(4-9):1；
    优选地，步骤(1)所述锰源和镍源的摩尔量之和与所述有机羧酸配体的摩尔量之比为1:(0.1-10)，优选为1:(0.1-1)；
    优选可选地，步骤(1)所述混合溶液中有机羧酸配体的浓度为5-20mmol/L，可选为9-13mmol/L，进一步可选为11.2mmol/L。
  10. 如权利要求5-9任一项所述的制备方法，其中，所述溶剂包括甲醇、乙醇、丙醇、二甲基甲酰胺、二乙基甲酰胺或水中的任意一种或至少两种的组合，可选为二甲基甲酰胺、甲醇和水的混合液；
    可选地，所述混合液中二甲基甲酰胺、甲醇和水的体积比为(12-18):(0.5-2):1；
    可选地，步骤(1)所述溶剂热反应的温度为100-200℃；
    可选地，步骤(1)所述溶剂热反应的时间为12-72h。
  11. 如权利要求5-10任一项所述的制备方法，其中，步骤(1)所述溶剂热反应之后还包括固液分离，洗涤；
    可选地，所述固液分离的方法包括过滤和/或离心；
    可选地，所述洗涤的洗涤剂包括甲醇、乙醇、丙醇、二甲基甲酰胺或二乙基甲酰胺中的任意一种或至少两种的组合，可选为二甲基甲酰胺和/或甲醇。
  12. 如权利要求5-11任一项所述的制备方法，其中，步骤(2)所述醇溶液包括甲醇溶液；
    可选地，步骤(2)所述浸泡的方法包括将步骤(1)的产物置于甲醇溶液中浸泡，之后更换甲醇溶液，继续浸泡，重复上述步骤n次；
    可选地，n≥1；
    可选地，所述更换甲醇溶液的时间间隔为6-12h；
    可选地，所述浸泡的时间为3-7天；
    可选地，步骤(2)所述活化的方法包括真空活化、空气气氛下活化或惰性气氛下活化中的任意一种或至少两种的组合，可选为惰性气氛下活化；
    可选地，所述惰性气氛包括氮气、氩气或氦气中的任意一种或至少两种的组合。
  13. 如权利要求5-12任一项所述的制备方法，其中，所述方法包括以下步骤：
    (1)将锰源、镍源和有机羧酸配体溶于溶剂，得到混合溶液，之后进行溶剂热反应，固液分离、洗涤，得到固体产物；所述锰源包括氯化锰和/或硫酸锰；所述镍源包括硝酸镍和/或硫酸镍；所述有机羧酸配体包括2,5-二羟基苯甲酸和/或2,5-二羟基对苯二甲酸，所述溶剂为二甲基甲酰胺、甲醇和水的混合液，所述混合液中二甲基甲酰胺、甲醇和水的体积比为(12-18):(0.5-2):1；所述锰源和镍源的摩尔比为(2-10):1，所述锰源和镍源的摩尔量之和与有机羧酸配体的摩尔比为1:(0.1-10)，所述混合溶液中有机羧酸配体的浓度为9-13mmol/L；
    (2)将步骤(1)的固体产物在甲醇溶液中浸泡3-7天，固液分离，在氮气气氛下150-350℃活化1-12h，冷却，得到所述双金属MOFs催化剂。
  14. 如权利要求1-4中任一项所述的双金属MOFs催化剂的用途，其中，所述双金属MOFs催化剂用于催化氨气选择性还原氮氧化物。
  15. 如权利要求14所述的双金属MOFs催化剂的用途，其中，所述双金属MOFs催化剂用于在200-250℃的温度下催化氨气还原氮氧化物；
  16. 如权利要求14或15所述的双金属MOFs催化剂的用途，其中，所述双金属MOFs催化剂用于固定源烟气或移动源尾气中氮氧化物的脱除。
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