WO2012119299A1 - Flue gas denitration catalyst, preparation method and use thereof - Google Patents

Flue gas denitration catalyst, preparation method and use thereof Download PDF

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WO2012119299A1
WO2012119299A1 PCT/CN2011/071563 CN2011071563W WO2012119299A1 WO 2012119299 A1 WO2012119299 A1 WO 2012119299A1 CN 2011071563 W CN2011071563 W CN 2011071563W WO 2012119299 A1 WO2012119299 A1 WO 2012119299A1
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manganese
soluble
cobalt
carrier
salt
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PCT/CN2011/071563
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French (fr)
Chinese (zh)
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祝社民
张舒扬
沈岳松
卫平波
沈树宝
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山东众禾环保科技股份有限公司
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Priority to PCT/CN2011/071563 priority Critical patent/WO2012119299A1/en
Publication of WO2012119299A1 publication Critical patent/WO2012119299A1/en

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    • 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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20746—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • 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

Definitions

  • the present invention relates to a flue gas denitration catalyst and its preparation and use.
  • Nitrogen oxides mainly come from industrially produced fuel combustion (accounting for 90% of total human emissions) and emissions from transportation fuel combustion, and some from the use of nitric acid plants, sulfuric acid plants, nitrogen fertilizer plants, fuel plants, pharmaceutical plants, etc.
  • the emissions of nitric acid enterprises are one of the main sources of pollution caused by air pollution. As China's industrialization process continues to accelerate, the pollution has become increasingly serious.
  • the catalyst disclosed in the Chinese patent (CN 101676019A) is an oxide of cerium as an active component, titanium dioxide as a carrier, two or more variable metals as catalyst assistants, and silicon oxide added to increase the catalyst. strength.
  • the catalyst has a denitration efficiency of more than 90% at 180 °C and an activity of nearly 100% at 200 °C.
  • the catalyst disclosed in the patent (CN 101069855 A) is a mesoporous molecular sieve or the like as a carrier, and a heteropoly compound as an active component.
  • the catalyst prepared by the method can have a denitration rate of more than 92% at 150 °C.
  • the catalyst disclosed in the patent (CN 1724149A) uses manganese oxide as an active component and titanium dioxide as a carrier. Two or more kinds of volatile metal iron or copper or vanadium or an oxide of cerium or chromium are additionally added as a catalyst auxiliary.
  • the catalyst has an SCR activity of 95% or more at 100 ° C and an activity of approximately 100% at 120 ° C.
  • the catalyst disclosed in the patent (CN 101468314 A) uses vanadium oxide as an active component and titanium oxide as a carrier.
  • the catalyst had a NO removal rate of 90% above 200 °C.
  • the catalyst carrier and the active component raw materials described in the patent (CN 101069855A) are relatively expensive; the catalyst described in the patent (CN 1724149A) has good activity but a narrow active temperature window, and it has a good temperature only above 100 ° C. SCR denitrification activity;
  • the catalyst described in the patent (CN 101468314A) is added with the highly toxic component vanadium oxide. The production and recycling links will cause environmental damage.
  • a flue gas denitration catalyst disclosed by the present invention has a different active component from the above catalyst, and a combination of a carrier and a cocatalyst, and has a preparation method as compared with the existing catalyst. Simple, anti-poisoning performance, no secondary pollution to the environment, wide active temperature window and low activity starting temperature.
  • the flue gas denitration catalyst provided by the present invention comprises a carrier and a catalytically active component, wherein the catalytically active component is a manganese cobalt cerium composite oxide, and the molar ratio of manganese, cobalt and cerium in the manganese cobalt cerium composite oxide is 1:0.1 ⁇ 1: 0.1 ⁇ 1.
  • the above carrier is a honeycomb ceramic, a molecular sieve, activated carbon fiber, diatomaceous earth, a ceramic plate or a metal alloy.
  • the mass of the above catalytically active component is from 10% to 25% by mass of the above carrier.
  • the flue gas denitration catalyst further includes a cocatalyst, wherein the cocatalyst is one or a combination of two or more of iron, copper or silicon oxide.
  • the molar ratio of the manganese element to the cocatalyst in the above manganese cobalt cerium composite oxide is 1:0.1-1; the total mass of the above catalytically active component and the above cocatalyst is 15% to 30% of the mass of the carrier.
  • the invention provides a method for preparing the above-mentioned flue gas denitration catalyst, comprising the following steps:
  • the catalyst active component precursor soluble manganese salt, soluble cobalt salt and soluble cerium salt, wherein the molar ratio of manganese, cobalt and lanthanum is 1:0.1 ⁇ 1:0.1 ⁇ 1, uniformly dissolved in the volume equal to the carrier
  • the total pore volume of deionized water adding ammonia water to adjust the solution pH value of 7; (2) immersing the carrier in citric acid, dilute hydrochloric acid or dilute nitric acid aqueous solution at a concentration of 5% to 20% by mass for 24 to 48 hours, taking it out, drying it, and then immersing the carrier in the solution obtained in the step (1). After standing for 24 hours, it is dried;
  • the sample prepared in the step (2) is calcined in the air at a calcination temperature of 500 to 800 ° C, and the calcination time is controlled to 4 to 8 h, and the catalyst is prepared after cooling.
  • the soluble manganese salt in the step (1) is one or a mixture of two or more of manganese nitrate, manganese acetate, manganese phosphate or manganese chloride;
  • the soluble cobalt salt is cobalt nitrate, cobalt acetate, cobalt phosphate or One or a mixture of two or more of cobalt oxalate;
  • the soluble cerium salt is one of cerium nitrate or cerium acetate or a mixture thereof.
  • the invention further provides a method for preparing the above-mentioned flue gas denitration catalyst, comprising the following steps:
  • the carrier is immersed in citric acid, dilute hydrochloric acid or dilute nitric acid aqueous solution having a mass percentage of 5% to 20% for 24 to 48 hours, taken out, dried, and then the carrier is immersed in the solution obtained in the step (1). After standing for 24 ⁇ 48h, dry;
  • step (3) The dried solid in step (2) is calcined in air at a calcination temperature of 500 to 800 ° C, and the calcination time is controlled to 4 to 8 h;
  • soluble manganese salt uniformly dissolved in deionized water having a volume equal to the total pore volume of the carrier, and adjusting the pH of the solution to 5-7 with ammonia water
  • the soluble manganese salt, the soluble cobalt salt and the soluble cerium salt have an elemental molar ratio of manganese/cobalt/strontium 1:0.1-1:0.1-1;
  • the sample prepared in the step (3) is immersed in the solution obtained in the step (4), left to stand for 24 to 48 hours, dried, and calcined in air, the baking temperature is 500 to 800 ° C, and the baking time is controlled to 4 ⁇ At 8 h, a catalyst was obtained.
  • the soluble iron salt in the step (1) is one or a mixture of two or more of ferric nitrate, ferric chloride or iron ammonium diamine tetraacetate, and the soluble copper salt is copper nitrate, copper acetate or chlorine.
  • the above-mentioned soluble silicon source compound is one of orthosilicate or metasilicate; or the above-mentioned soluble manganese salt in step (4) is manganese nitrate or vinegar Any one or a mixture of two or more of manganese sulfate, manganese phosphate or manganese chloride, wherein the soluble cobalt salt is one or a mixture of two or more of cobalt nitrate, cobalt acetate, cobalt phosphate or cobalt oxalate, and the above soluble hydrazine
  • the salt is one of cerium nitrate or cerium acetate or a mixture thereof; the molar ratio of the manganese element in the soluble manganese salt to the promoter precursor in the step (1) in the step (4) is 1: 0.1-1.
  • the invention also provides the use of the above catalyst in flue gas denitration: after heating the catalyst to 80 ⁇ 220 °C, the flue gas to be treated is introduced.
  • the catalyst prepared by the invention has simple preparation method, low activity starting temperature, low cost and easy availability of raw materials and no secondary pollution to the environment. It has a wide active temperature window and good anti-poisoning performance. It can achieve more than 90% SCR denitrification activity at 80 ⁇ 300 °C. And it has good anti-poisoning performance above 220 °C. The 200% S0 2 or 20 vol.% water contained in the flue gas has little effect on its activity, and the NO conversion rate is maintained above 85%.
  • FIG. 1 is a graph showing the denitration activity of a catalyst prepared in Example 1 as a function of temperature.
  • Fig. 2 is a test curve of denitration activity of the catalyst anti-poisoning test prepared in Example 1.
  • the meaning of the curve in Fig. 2 is: 1 220 °C, the simulated denitrification activity of the catalyst anti-poisoning experiment with time curve of 20 vol.% water; 2 220 ° C, the introduction of simulated flue gas containing 200 ppm SO 2 Catalyst anti-poisoning test denitration activity with time curve.
  • Raw material preparation and calculation The mass of the carrier was weighed, and the total pore volume of the carrier was determined. The amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst as 15% of the mass of the carrier.
  • the catalyst precursor is taken according to the molar ratio of Fe/Cu/Si of 1:1:1: ferric nitrate, copper nitrate and orthosilicate, mixed and dissolved in deionized water having a volume equal to the total pore volume of the carrier, using ammonia water Adjusting the pH of the solution to 5;
  • honeycomb ceramic carrier is immersed in a 15% by mass aqueous solution of citric acid for 48 hours, taken out and dried, and then the honeycomb ceramic carrier is immersed in the solution obtained in the step (1), allowed to stand for 48 hours, and then filtered to be air-dried;
  • step (3) The solid obtained in step (2) is calcined at 600 ° C for 5 h;
  • the catalyst active component precursors were respectively taken according to the molar ratio of Mn/Co/Ce of 1:1:1: manganese nitrate, cobalt nitrate and cerium nitrate, wherein the molar ratio of Mn element to promoter precursor was 1: 1 , uniformly dissolved in deionized water having a volume equal to the total pore volume of the carrier, and adding a solution of ammonia water to adjust the pH value of 5;
  • the sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 48 hours, dried, and calcined in air at a calcination temperature of 600 ° C, and the calcination time is controlled. After 5 h, the preparation of the catalyst was completed after cooling.
  • the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is 1:1:1; the promoter is: iron oxide, a copper oxide and a silicon oxide, wherein the molar ratio of the manganese element to the mole of the cocatalyst (the sum of the iron oxide, the copper oxide, and the silicon oxide) is: 1:1; catalytic activity The total mass of the component and cocatalyst is 15% of the mass of the carrier.
  • the activity test method of the catalyst is as follows: The catalyst is charged into a quartz glass tube, and the temperature is controlled by a tubular resistance furnace.
  • the mixed gas simulates the flue gas and is supplied by the corresponding cylinder.
  • the concentration of NO in the inlet and outlet is detected, and the value of the NO concentration at the outlet minus the concentration of the NO at the outlet is divided by the concentration of NO in the inlet, and the obtained result multiplied by 100% is the conversion rate of NO.
  • the specific calculation formula is as follows: N. m -NO. Ut x ro
  • the measured activity results are shown in Figure 1.
  • the NO conversion at 80 ° C can reach more than 90%, and even close to 100% at 110 ° C.
  • Test method for denitrification activity of anti-poisoning experiment 1
  • the catalyst is charged into a quartz glass tube, and the temperature is controlled by a tubular resistance furnace.
  • the mixed gas simulates the flue gas and is supplied by the corresponding cylinder.
  • the catalyst was placed in a quartz glass tube to control the temperature at 220 °C.
  • the mixed gas simulates the flue gas and is supplied by the corresponding cylinder.
  • the simulated nitrogen gas containing simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C maintained a NO conversion rate of more than 85% for a long time.
  • the mass of the carrier was weighed, and the total pore volume of the carrier was measured.
  • the amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst of 30% by mass of the carrier.
  • the molecular sieve carrier is immersed in a dilute hydrochloric acid aqueous solution having a mass concentration of 20% for 40 hours, taken out and dried, and then the molecular sieve carrier is immersed in the solution obtained in the step (1), allowed to stand for 48 hours, and then filtered to be air-dried;
  • step (3) The solid obtained in step (2) is calcined at 800 ° C for 4 h;
  • the catalyst precursors were measured according to the molar ratio of Mn/Co/Ce of 1:0.1:0.1: manganese acetate, cobalt phosphate and barium acetate, wherein the molar ratio of manganese to ferric nitrate was 1:0.1, and it was uniformly dissolved in a volume equal to the total pore volume of the carrier in deionized water, adding ammonia to adjust the pH of the solution is 7;
  • the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is: 1:0.1:0.1; the cocatalyst is: iron oxide, The molar ratio of manganese element to iron element is: 1:0.1; the total mass of the catalytically active component and the cocatalyst is 30% of the mass of the carrier.
  • the activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1.
  • the measured activity results in a NO conversion of 80% or more at 80 ° C and nearly 100% at 130 ° C.
  • the simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate over 80% for a long time.
  • the mass of the carrier was weighed, and the total pore volume of the carrier was determined.
  • the amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst of 20% by mass of the carrier.
  • the activated carbon fiber carrier is immersed in a dilute nitric acid aqueous solution having a mass concentration of 15% for 24 hours, taken out and dried, and then the activated carbon fiber carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered to be air-dried;
  • step (3) The solid obtained in step (2) is calcined at 500 ° C for 6 h;
  • the catalyst precursors were measured according to the molar ratio of Mn/Co/Ce of 1:0.5:0.5: manganese phosphate, cobalt oxalate and cerium nitrate, wherein the molar ratio of manganese to copper chloride was 1:0.5, uniformly dissolved.
  • a solution of ammonia water is added dropwise to adjust the pH of the solution to a saturated solution;
  • the sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 24 hours, dried, and calcined in air at a calcination temperature of 500 ° C, and the calcination time is controlled. After 6 h, the preparation of the catalyst was completed after cooling.
  • the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is: 1:0.5:0.5; the promoter is: copper oxide, Wherein the molar ratio of manganese element to copper element is: 1:0.5; the total mass of the catalytically active component and the cocatalyst is 20% of the mass of the carrier.
  • the activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1.
  • the measured activity results in a NO conversion of more than 85% at 80 ° C and nearly 100% at 130 ° C.
  • the simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate over 80% for a long time.
  • the mass of the carrier was weighed, and the total pore volume of the carrier was determined.
  • the amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst as 18% by mass of the carrier.
  • the diatomaceous earth carrier is immersed in a dilute nitric acid aqueous solution having a mass concentration of 5% for 48 hours, taken out and dried, and then the diatomaceous earth carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered off. Air dried
  • step (3) The solid obtained in step (2) is calcined at 700 ° C for 4 h;
  • the catalyst precursors were measured according to the molar ratio of Mn/Co/Ce of 1:0.2:0.6: manganese chloride, cobalt phosphate and barium acetate, wherein the molar ratio of manganese to orthosilicate was 1:0.8, uniform Dissolved in deionized water having a volume equal to the total pore volume of the carrier, adding ammonia water to adjust the pH of the solution to 7;
  • the sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 24 hours, dried, and calcined in air at a calcination temperature of 700 ° C, and the calcination time is controlled. After 4 h, the preparation of the catalyst was completed after cooling.
  • the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is 1:0.2:0.6; the promoter is: silicon oxide, The molar ratio of manganese element to silicon oxide is: 1:0.8; the total mass of catalytically active component and cocatalyst The amount is 18% of the mass of the carrier.
  • the activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1.
  • the measured activity results in a NO conversion of 80% or more at 80 ° C and nearly 100% at 140 ° C.
  • the simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate above 85% for a long time.
  • the mass of the carrier was weighed, and the total pore volume of the carrier was determined.
  • the amount of the promoter precursor and the precursor of the catalytically active component was calculated based on the total mass of the catalytically active component and the cocatalyst as 26% of the mass of the carrier.
  • the ceramic plate carrier is immersed in an aqueous solution of citric acid having a mass concentration of 10% for 40 hours, taken out and dried, and then the ceramic plate carrier is immersed in the solution obtained in the step (1), allowed to stand for 48 hours, and then filtered to be air-dried;
  • step (3) The solid obtained in step (2) is calcined at 600 ° C for 5 h;
  • the catalyst precursors were measured according to the molar ratio of Mn/Co/Ce of 1:0.8:0.2: manganese phosphate, cobalt nitrate and cerium nitrate, wherein the molar ratio of manganese element to promoter precursor was 1:0.3, uniform Dissolved in deionized water having a volume equal to the total pore volume of the carrier, and adding ammonia water to adjust the pH of the solution to 7;
  • the sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 48 hours, dried, and calcined in air at a calcination temperature of 600 ° C, and the calcination time is controlled. After 5 h, the preparation of the catalyst was completed after cooling.
  • the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is: 1:0.8:0.2; the promoter is: iron oxide and The oxide of copper, wherein the molar ratio of the manganese element to the cocatalyst (the sum of the moles of iron oxide and copper oxide) is 1:0.3; the total mass of the catalytically active component and the cocatalyst is the mass of the carrier 26 %. .
  • the activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1.
  • the measured activity results in a NO conversion of more than 90% at 80 ° C and nearly 100% at 110 ° C.
  • the simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate over 80% for a long time.
  • the mass of the carrier was weighed, and the total pore volume of the carrier was measured.
  • the amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst as 21% of the mass of the carrier.
  • the catalyst precursor is taken according to the element molar ratio of Fe/Si of 2:1: iron ferric ammonium iron diamine tetraacetate, metasilicate, mixed in deionized water with a volume equal to the total pore volume of the carrier, using ammonia water Adjusting the pH of the solution to 6;
  • the nickel-aluminum alloy carrier is immersed in a dilute nitric acid aqueous solution having a mass concentration of 15% for 36 hours, taken out and dried, and then the nickel-aluminum alloy carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered off. Air dried
  • Step (2) The obtained solid is calcined at 500 ° C for 4 h;
  • the active component precursors of the catalysts were measured according to the molar ratio of Mn/Co/Ce of 1:0.6:0.6: manganese nitrate, cobalt nitrate and cerium nitrate, wherein the molar ratio of Mn element to promoter precursor was 1: 0.9, uniformly dissolved in deionized water having a volume equal to the total pore volume of the carrier, and adding ammonia water to adjust the pH of the solution to 6;
  • the sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 24 hours, dried, and calcined in air at a calcination temperature of 500 ° C, and the calcination time is controlled. After 4 h, the preparation of the catalyst was completed after cooling.
  • the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is: 1:0.6:0.6; the cocatalyst is: iron oxide and The oxide of silicon, wherein the molar ratio of manganese element to cocatalyst (the sum of the moles of iron oxide and silicon oxide) is 1:0.9; the total mass of catalytically active component and cocatalyst is the mass of the carrier 21 %.
  • the activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1.
  • the measured activity result is that the NO conversion rate can reach 85% or more at 80 ° C, and is connected at 120 ° C. Nearly 100%.
  • the simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate above 85% for a long time.
  • the mass of the carrier was weighed, and the total pore volume of the carrier was measured.
  • the amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst as 25% of the mass of the carrier.
  • the catalyst precursor is taken according to the molar ratio of Fe/Cu/Si of 1:1:1: iron ferric ammonium iron diamine tetraacetate, ferric nitrate, metasilicate, copper nitrate and copper chloride, mixed and dissolved
  • the volume is equal to the total pore volume of the carrier in deionized water, the pH of the solution is adjusted to 5 with ammonia water;
  • the nickel-aluminum alloy carrier is immersed in a dilute nitric acid aqueous solution having a mass concentration of 15% for 24 hours, taken out and dried, and then the nickel-aluminum alloy carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered off. Air dried
  • Step (2) obtained solid, calcined at 600 ° C for 2 h;
  • the catalyst active component precursors are respectively measured according to the molar ratio of Mn/Co/Ce of 1:0.6:0.6: manganese nitrate, manganese acetate, cobalt nitrate, cobalt oxalate, cerium nitrate and cerium acetate, wherein Mn element and The molar ratio of the promoter precursor is 1: 1 , uniformly dissolved in deionized water having a volume equal to the total pore volume of the carrier, and the pH of the solution is adjusted to 5 by adding ammonia water;
  • the sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 24 hours, dried, and calcined in air at a calcination temperature of 600 ° C, and the calcination time is controlled. After 2 h, the preparation of the catalyst was completed after cooling.
  • the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is: 1:0.6:0.6; the promoter is: iron oxide, Copper oxide and silicon oxide, wherein the molar ratio of manganese element to cocatalyst (the sum of iron oxide, copper oxide and silicon oxide) is: 1: 1 ; catalytically active component The total mass of the cocatalyst is 25% of the mass of the carrier.
  • the activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1.
  • the measured activity result is that the NO conversion rate can reach 75% or more at 80 ° C, and is connected at 150 ° C. Nearly 100%.
  • the simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate over 80% for a long time.
  • the mass of the carrier was weighed, the total pore volume of the carrier was measured, and the amount of the precursor of the catalytically active component was calculated based on the mass of the catalytically active component being 10% of the mass of the carrier.
  • the catalyst active component precursors are respectively taken according to the molar ratio of Mn/Co/Ce of 1:1:1: manganese nitrate, cobalt oxalate and cerium acetate, uniformly dissolved in deionized ions having a volume equal to the total pore volume of the carrier. In water, add ammonia to adjust the pH of the solution to 7;
  • the nickel-aluminum alloy carrier is immersed in a 15% by mass aqueous solution of citric acid for 48 hours, taken out and dried, and then the molecular sieve carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered to be air-dried;
  • the sample prepared in the step (2) is calcined in the air at a calcination temperature of 600 ° C, and the calcination time is controlled to 2 h, and the preparation of the catalyst is completed after cooling.
  • the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is 1:1:1; the mass of catalytically active component is carrier mass 10%.
  • the activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1.
  • the measured activity results in a NO conversion of more than 90% at 80 ° C and nearly 100% at 110 ° C.
  • the simulated flue gas containing 200 ppm of S0 2 simulated flue gas or 20 vol.% water at 220 ° C had a NO conversion of about 50%.
  • the mass of the carrier is weighed, the total pore volume of the carrier is determined, and the amount of the precursor of the catalytically active component is calculated according to the mass of the catalytically active component as 25% of the mass of the carrier.
  • the catalyst active component precursors are respectively taken according to the molar ratio of Mn/Co/Ce of 1:0.1:0.1: manganese phosphate, manganese acetate, cobalt acetate and cerium nitrate, uniformly dissolved in the total pore volume equal to the carrier a volume of deionized water, adding a solution of ammonia water to adjust the pH of the solution to a saturated solution;
  • honeycomb ceramic carrier is immersed in an aqueous solution of 15% by mass of nitric acid for 48 hours, taken out and dried, and then the honeycomb ceramic carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered to be air-dried;
  • the sample prepared in the step (2) is calcined in the air at a calcination temperature of 600 ° C, and the calcination time is controlled to 2 h, and the preparation of the catalyst is completed after cooling.
  • the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is 1:1:1; the mass of catalytically active component is carrier mass 25%.
  • the activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1.
  • the measured activity results in a NO conversion of more than 90% at 100 ° C and nearly 100% at 150 ° C.
  • the simulated flue gas containing 200 ppm of S0 2 simulated flue gas or 20 vol.% water at 220 ° C had a NO conversion of about 50%.

Abstract

A flue gas denitration catalyst is provided. The catalyst coprises carrier and active components, wherein the said active components consist of manganese-cobalt-cerium composite oxides,in which the molar ratio of manganese(Mn), cobalt(Co) and cerium(Ce) is 1:0.1-1:0.1-1.The preparation method of said flue gas denitration catalyst comprises: (1) Dissolving soluble Mn salt,soluble Co salt and soluble Ce salt in deionized water, wherein the molar ratio of Mn, Co and Ce is 1:0.1-1:0.1-1, dripping ammonia water to regulate pH to 5-7; (2) Steeping the carrier with citric acid, diluted hydrochloric acid or diluted nitric acid solution for 24-48h, drying, then steeping the carrier with the solution of the step (1), standing for 24h,drying; (3)Roasting the sample prepared by step (2) in the air,cooling. flue gas denitration composite catalyst aforesaid has the characters of simple manufacturing process, strong anti-poisoning capability, no secondary pollution to the environment, extended temperature window of activity and low initial temperature of activity.

Description

一种烟气脱硝催化剂及其制备和应用  Flue gas denitration catalyst and preparation and application thereof
技术领域 本发明涉及一种烟气脱硝催化剂及其制备和应用。 背景技术 氮氧化物主要来自工业生产的燃料燃烧 （占人类总排放量的 90 % )和 交通运输燃料燃烧的排放， 还有部分来自硝酸厂、 硫酸厂、 氮肥厂、 燃料 厂、 药厂等使用硝酸的企业的排放， 是造成大气污染的主要污染源之一。 随着我国工业化进程不断加快， ΝΟχ污染日趋严重。 在 2010年颁布的火电 厂大气污染物排放标准 （征求意见稿） 中， 国家规定对位于重点地区内新 建、 改建和扩建的燃煤电厂， 执行 200mg/m3的排放浓度限值。 同时 "十二 五" 期间我国将加大节能减排力度， 增加脱硝 （ΝΟχ脱除）这一约束性硬 选择性催化还原（SCR )脱硝因效率高、 技术成熟， 是目前国内外应用 最为广泛的技术。 但其所用的催化剂均为剧毒的 V-Ti体系， 且使用温度范 围为 310~410°C。 若低于 310°C , 其还原剂氨 （或尿素） 易与烟气中的 S02 产生硫酸氢铵毒化催化剂、 堵塞管道。 但国内现有锅炉产生的烟气经过省 煤器后， 温度大多降到 130°C以下。 因此，研制国内自主创新的低温、高效、 抗中毒的脱硝催化剂有十分重要的意义。 TECHNICAL FIELD The present invention relates to a flue gas denitration catalyst and its preparation and use. BACKGROUND OF THE INVENTION Nitrogen oxides mainly come from industrially produced fuel combustion (accounting for 90% of total human emissions) and emissions from transportation fuel combustion, and some from the use of nitric acid plants, sulfuric acid plants, nitrogen fertilizer plants, fuel plants, pharmaceutical plants, etc. The emissions of nitric acid enterprises are one of the main sources of pollution caused by air pollution. As China's industrialization process continues to accelerate, the pollution has become increasingly serious. In the 2010 Air Pollutant Emission Standard for Thermal Power Plants (Draft for Comment), the State stipulates that the emission concentration limit of 200mg/m 3 should be implemented for coal-fired power plants built, rebuilt and expanded in key areas. At the same time, during the "Twelfth Five-Year Plan" period, China will increase energy conservation and emission reduction, and increase denitrification (ΝΟχ removal). This binding hard selective catalytic reduction (SCR) denitration has high efficiency and mature technology. Technology. However, the catalysts used are highly toxic V-Ti systems with a temperature range of 310-410 °C. If it is lower than 310 ° C, its reducing agent ammonia (or urea) easily reacts with S0 2 in the flue gas to produce an ammonium hydrogen sulfate poisoning catalyst and block the pipeline. However, after the flue gas generated by the existing domestic boiler passes through the economizer, the temperature is mostly reduced to below 130 °C. Therefore, it is of great significance to develop domestically-innovated low-temperature, high-efficiency, anti-poisoning denitration catalysts.
现有的关于低温烟气脱硝催化剂的专利中， （CN 101676019A )、 ( CN 101069855A )、 ( CN 1724149A ) 以及 ( CN 101468314A )在低温下均具有 很高的脱硝活性。 其中中国专利（CN 101676019A )公开的催化剂是以铈的 氧化物作为活性组分， 以二氧化钛作为载体， 加两种或两种以上变价金属 作为催化剂助剂， 另外加入硅的氧化物来增加催化剂的强度。 该催化剂在 180 °C时脱硝效率为 90%以上， 200 °C时的活性接近 100%。 专利 （ CN 101069855A )公开的催化剂是釆用中孔分子筛等作为载体， 杂多化合物作 为活性组分。该方法制备的催化剂在 150°C时脱硝率可达到 92%以上。 专利 ( CN 1724149A )公开的催化剂以锰的氧化物为活性组分，二氧化钛为载体， 另加入两种或两种以上变价金属铁或铜或钒或铈或铬的氧化物作为催化剂 助剂。该催化剂在 100°C时 SCR活性在 95%以上， 120°C时的活性接近 100%。 专利（ CN 101468314A )公开的催化剂以氧化钒为活性组分、氧化钛为载体。 该催化剂在 200°C以上 NO脱除率为 90%。 其中专利（CN 101069855A )所 述的催化剂载体及活性组分原料价格均较为昂贵； 专利（ CN 1724149A )所 述的催化剂活性好但活性温度窗口较窄， 其只有到 100°C以上才具有好的 SCR脱硝活性； 专利 （CN 101468314A )所述的催化剂添加有剧毒成分氧 化钒， 生产与回收利用环节均会对造成环境造成危害。 发明内容 为了解决上述技术问题， 本发明公开的一种烟气脱硝催化剂因釆用了 与上述催化剂不同的活性组分， 以及载体和助催化剂的组合， 与现有的催 化剂相比， 具有制备方法简单， 抗中毒性能好、 对环境无二次污染， 活性 温度窗口宽且活性起始温度低等优点。 Among the existing patents on low-temperature flue gas denitration catalysts, (CN 101676019A), (CN 101069855A), (CN 1724149A) and (CN 101468314A) have high denitration activity at low temperatures. The catalyst disclosed in the Chinese patent (CN 101676019A) is an oxide of cerium as an active component, titanium dioxide as a carrier, two or more variable metals as catalyst assistants, and silicon oxide added to increase the catalyst. strength. The catalyst has a denitration efficiency of more than 90% at 180 °C and an activity of nearly 100% at 200 °C. The catalyst disclosed in the patent (CN 101069855 A) is a mesoporous molecular sieve or the like as a carrier, and a heteropoly compound as an active component. The catalyst prepared by the method can have a denitration rate of more than 92% at 150 °C. The catalyst disclosed in the patent (CN 1724149A) uses manganese oxide as an active component and titanium dioxide as a carrier. Two or more kinds of volatile metal iron or copper or vanadium or an oxide of cerium or chromium are additionally added as a catalyst auxiliary. The catalyst has an SCR activity of 95% or more at 100 ° C and an activity of approximately 100% at 120 ° C. The catalyst disclosed in the patent (CN 101468314 A) uses vanadium oxide as an active component and titanium oxide as a carrier. The catalyst had a NO removal rate of 90% above 200 °C. The catalyst carrier and the active component raw materials described in the patent (CN 101069855A) are relatively expensive; the catalyst described in the patent (CN 1724149A) has good activity but a narrow active temperature window, and it has a good temperature only above 100 ° C. SCR denitrification activity; The catalyst described in the patent (CN 101468314A) is added with the highly toxic component vanadium oxide. The production and recycling links will cause environmental damage. SUMMARY OF THE INVENTION In order to solve the above technical problems, a flue gas denitration catalyst disclosed by the present invention has a different active component from the above catalyst, and a combination of a carrier and a cocatalyst, and has a preparation method as compared with the existing catalyst. Simple, anti-poisoning performance, no secondary pollution to the environment, wide active temperature window and low activity starting temperature.
本发明提供的烟气脱硝催化剂， 包括载体和催化活性组分， 其中， 上 述催化活性组分为锰钴铈复合氧化物， 上述锰钴铈复合氧化物中锰、 钴和 铈元素的摩尔比为 1:0.1~1:0.1~1。  The flue gas denitration catalyst provided by the present invention comprises a carrier and a catalytically active component, wherein the catalytically active component is a manganese cobalt cerium composite oxide, and the molar ratio of manganese, cobalt and cerium in the manganese cobalt cerium composite oxide is 1:0.1~1: 0.1~1.
优选地， 上述载体为蜂窝陶瓷、 分子筛、 活性碳纤维、 硅藻土、 陶瓷 板或金属合金。  Preferably, the above carrier is a honeycomb ceramic, a molecular sieve, activated carbon fiber, diatomaceous earth, a ceramic plate or a metal alloy.
优选地， 上述催化活性组分的质量为上述载体质量的 10%~25%。  Preferably, the mass of the above catalytically active component is from 10% to 25% by mass of the above carrier.
作为优选的技术方案， 上述的烟气脱硝催化剂， 还包括助催化剂， 上 述助催化剂为铁、 铜或硅的氧化物中的一种或两种以上任意组合。  According to a preferred aspect of the invention, the flue gas denitration catalyst further includes a cocatalyst, wherein the cocatalyst is one or a combination of two or more of iron, copper or silicon oxide.
优选地， 上述锰钴铈复合氧化物中锰元素与助催化剂的摩尔比为 1:0.1-1 ； 上述催化活性组分和上述助催化剂的总质量为载体质量的 15%~30%。  Preferably, the molar ratio of the manganese element to the cocatalyst in the above manganese cobalt cerium composite oxide is 1:0.1-1; the total mass of the above catalytically active component and the above cocatalyst is 15% to 30% of the mass of the carrier.
本发明提供一种制备上述的烟气脱硝催化剂的方法， 包括如下步骤： The invention provides a method for preparing the above-mentioned flue gas denitration catalyst, comprising the following steps:
(1)取催化剂活性组分前驱体： 可溶性锰盐、 可溶性钴盐和可溶性铈盐， 其中锰、钴和铈元素的摩尔比为 1:0.1~1:0.1~1 ,均匀溶解于体积等于载体的 总孔体积的去离子水中， 滴加氨水调节溶液 pH值为 7; (2) 将载体在质量百分比浓度为 5%~20%的柠檬酸、稀盐酸或稀硝酸水 溶液中浸泡 24~48h, 取出后烘干， 然后将载体浸于步骤 (1)得到的溶液中， 静置 24h后， 干燥； (1) Taking the catalyst active component precursor: soluble manganese salt, soluble cobalt salt and soluble cerium salt, wherein the molar ratio of manganese, cobalt and lanthanum is 1:0.1~1:0.1~1, uniformly dissolved in the volume equal to the carrier The total pore volume of deionized water, adding ammonia water to adjust the solution pH value of 7; (2) immersing the carrier in citric acid, dilute hydrochloric acid or dilute nitric acid aqueous solution at a concentration of 5% to 20% by mass for 24 to 48 hours, taking it out, drying it, and then immersing the carrier in the solution obtained in the step (1). After standing for 24 hours, it is dried;
(3)将步骤 (2)制备好的样品在空气中焙烧， 焙烧温度为 500~800°C , 焙 烧时间控制为 4~8h, 冷却后即完成催化剂的制备。  (3) The sample prepared in the step (2) is calcined in the air at a calcination temperature of 500 to 800 ° C, and the calcination time is controlled to 4 to 8 h, and the catalyst is prepared after cooling.
优选地， 步骤 (1)中上述可溶性锰盐为硝酸锰、 醋酸锰、 磷酸锰或氯化 锰中的一种或两种以上任意混合物； 上述可溶性钴盐为硝酸钴、 醋酸钴、 磷酸钴或草酸钴中的一种或两种以上任意混合物； 可溶性铈盐为硝酸铈或 醋酸铈中的一种或其混合物。  Preferably, the soluble manganese salt in the step (1) is one or a mixture of two or more of manganese nitrate, manganese acetate, manganese phosphate or manganese chloride; the soluble cobalt salt is cobalt nitrate, cobalt acetate, cobalt phosphate or One or a mixture of two or more of cobalt oxalate; the soluble cerium salt is one of cerium nitrate or cerium acetate or a mixture thereof.
本发明另提供一种制备上述的烟气脱硝催化剂的方法， 包括如下步骤: The invention further provides a method for preparing the above-mentioned flue gas denitration catalyst, comprising the following steps:
(1) 取上述助催化剂的前驱体： 可溶性铁盐、 可溶性铜盐或可溶性硅源 化合物中的一种或两种以上任意混合物， 溶于体积等于载体的总孔体积的 去离子水中， 以氨水调节溶液 pH值在 5~7之间； (1) taking the precursor of the above cocatalyst: one or a mixture of two or more of a soluble iron salt, a soluble copper salt or a soluble silicon source compound, dissolved in deionized water having a volume equal to the total pore volume of the carrier, and ammonia water Adjust the pH of the solution between 5 and 7;
(2) 将载体在质量百分比浓度为 5%~20%的柠檬酸、稀盐酸或稀硝酸水 溶液中浸泡 24~48h,取出后烘干，然后将载体浸渍在步骤 (1)所得的溶液中， 静置 24~48h后, 干燥；  (2) The carrier is immersed in citric acid, dilute hydrochloric acid or dilute nitric acid aqueous solution having a mass percentage of 5% to 20% for 24 to 48 hours, taken out, dried, and then the carrier is immersed in the solution obtained in the step (1). After standing for 24~48h, dry;
(3) 将步骤 (2)中干燥后的固体在空气中焙烧， 焙烧温度为 500~800°C , 焙烧时间控制为 4~8h;  (3) The dried solid in step (2) is calcined in air at a calcination temperature of 500 to 800 ° C, and the calcination time is controlled to 4 to 8 h;
(4)取催化活性组分的前驱体： 可溶性锰盐、 可溶性钴盐和可溶性铈盐， 均匀溶解于体积等于载体的总孔体积的去离子水中，以氨水调节溶液 pH值 在 5~7, 其中， 可溶性锰盐、 可溶性钴盐及可溶性铈盐中锰 /钴 /铈的元素摩 尔比 1:0.1-1:0.1-1;  (4) Taking the precursor of the catalytically active component: a soluble manganese salt, a soluble cobalt salt and a soluble cerium salt, uniformly dissolved in deionized water having a volume equal to the total pore volume of the carrier, and adjusting the pH of the solution to 5-7 with ammonia water, Wherein the soluble manganese salt, the soluble cobalt salt and the soluble cerium salt have an elemental molar ratio of manganese/cobalt/strontium 1:0.1-1:0.1-1;
(5) 将步骤 (3)制备的样品浸渍于步骤 (4)所得溶液中， 静置 24~48h后， 干燥， 在空气中焙烧， 焙烧温度为 500~800°C , 焙烧时间控制为 4~8h, 得 到催化剂。  (5) The sample prepared in the step (3) is immersed in the solution obtained in the step (4), left to stand for 24 to 48 hours, dried, and calcined in air, the baking temperature is 500 to 800 ° C, and the baking time is controlled to 4~ At 8 h, a catalyst was obtained.
优选地， 步骤 (1)中上述可溶性铁盐为硝酸铁、 氯化铁或乙二胺四乙酸 铁铵中的一种或两种以上任意混合物， 上述可溶性铜盐为硝酸铜、 醋酸铜 或氯化铜中的一种或两种以上任意混合物， 上述可溶性硅源化合物为正硅 酸或偏硅酸中的一种或其混合物； 步骤 (4)中上述可溶性锰盐为硝酸锰、 醋 酸锰、 磷酸锰或氯化锰中的一种或两种以上任意混合物， 上述可溶性钴盐 为硝酸钴、 醋酸钴、 磷酸钴或草酸钴中的一种或两种以上任意混合物， 上 述可溶性铈盐为硝酸铈或醋酸铈中的一种或其混合物； 步骤 (4)中可溶性锰 盐中锰元素与步骤 (1)中助催化剂前驱体的摩尔比为 1: 0.1~1。 Preferably, the soluble iron salt in the step (1) is one or a mixture of two or more of ferric nitrate, ferric chloride or iron ammonium diamine tetraacetate, and the soluble copper salt is copper nitrate, copper acetate or chlorine. One or a mixture of two or more kinds of copper, the above-mentioned soluble silicon source compound is one of orthosilicate or metasilicate; or the above-mentioned soluble manganese salt in step (4) is manganese nitrate or vinegar Any one or a mixture of two or more of manganese sulfate, manganese phosphate or manganese chloride, wherein the soluble cobalt salt is one or a mixture of two or more of cobalt nitrate, cobalt acetate, cobalt phosphate or cobalt oxalate, and the above soluble hydrazine The salt is one of cerium nitrate or cerium acetate or a mixture thereof; the molar ratio of the manganese element in the soluble manganese salt to the promoter precursor in the step (1) in the step (4) is 1: 0.1-1.
本发明还提供上述催化剂在烟气脱硝中的应用： 将上述催化剂加热至 80~220°C后， 通入待处理烟气。  The invention also provides the use of the above catalyst in flue gas denitration: after heating the catalyst to 80~220 °C, the flue gas to be treated is introduced.
本发明能达到以下技术效果：  The invention can achieve the following technical effects:
本发明制备的催化剂制备方法简单、 活性起始温度低、 原料廉价易得 且对环境不产生二次污染。 活性温度窗口宽、 抗中毒性能好， 在 80~300°C 均可达到 90%以上的 SCR脱硝活性。且在 220 °C以上有很好的抗中毒性能， 通入的烟气中含有 200ppm的 S02或 20 vol.%的水对其活性几乎不产生影 响， NO转化率维持在 85%以上。 附图说明 图 1是实施例 1制得催化剂脱硝活性随温度变化曲线。 The catalyst prepared by the invention has simple preparation method, low activity starting temperature, low cost and easy availability of raw materials and no secondary pollution to the environment. It has a wide active temperature window and good anti-poisoning performance. It can achieve more than 90% SCR denitrification activity at 80~300 °C. And it has good anti-poisoning performance above 220 °C. The 200% S0 2 or 20 vol.% water contained in the flue gas has little effect on its activity, and the NO conversion rate is maintained above 85%. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the denitration activity of a catalyst prepared in Example 1 as a function of temperature.
图 2是实施例 1制得的催化剂抗中毒实验脱硝活性测试曲线。 附图说明：  Fig. 2 is a test curve of denitration activity of the catalyst anti-poisoning test prepared in Example 1. BRIEF DESCRIPTION OF THE DRAWINGS:
图 2中曲线含义： ① 220°C、通入含 20 vol.%水的模拟烟气时催化剂抗 中毒实验脱硝活性随时间变化曲线； ② 220°C、 通入含 200ppm SO2的模拟 烟气时催化剂抗中毒试验脱硝活性随时间变化曲线。 具体实施方式 下面结合附图和具体实施例对本发明作进一步说明， 以使本领域的技 术人员可以更好的理解本发明并能予以实施， 但所举实施例不作为对本发 明的限定。 The meaning of the curve in Fig. 2 is: 1 220 °C, the simulated denitrification activity of the catalyst anti-poisoning experiment with time curve of 20 vol.% water; 2 220 ° C, the introduction of simulated flue gas containing 200 ppm SO 2 Catalyst anti-poisoning test denitration activity with time curve. The present invention will be further described in conjunction with the accompanying drawings and specific embodiments, which are to be understood by those skilled in the art.
实施例 1 :  Example 1
原料准备及计算： 称量载体质量， 测定载体的总孔体积， 根据催化活性组分与助催化剂 的总质量为载体质量的 15%计算助催化剂前驱体和催化活性组分前驱体的 添加量。 Raw material preparation and calculation: The mass of the carrier was weighed, and the total pore volume of the carrier was determined. The amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst as 15% of the mass of the carrier.
具体操作步骤：  Specific steps:
(1)按 Fe/Cu/Si的元素摩尔比 1:1:1取助催化剂前驱体： 硝酸铁、 硝酸 铜和正硅酸， 混合溶于体积等于载体的总孔体积的去离子水中， 用氨水调 节溶液 pH为 5;  (1) The catalyst precursor is taken according to the molar ratio of Fe/Cu/Si of 1:1:1: ferric nitrate, copper nitrate and orthosilicate, mixed and dissolved in deionized water having a volume equal to the total pore volume of the carrier, using ammonia water Adjusting the pH of the solution to 5;
(2) 蜂窝陶瓷载体在质量百分比浓度为 15%的柠檬酸水溶液中浸泡 48h, 取出后烘干， 然后将蜂窝陶瓷载体浸于步骤 (1)得到的溶液中， 静置 48h后滤出风干；  (2) The honeycomb ceramic carrier is immersed in a 15% by mass aqueous solution of citric acid for 48 hours, taken out and dried, and then the honeycomb ceramic carrier is immersed in the solution obtained in the step (1), allowed to stand for 48 hours, and then filtered to be air-dried;
(3)步骤 (2)得到的固体， 在 600°C下焙烧 5h;  (3) The solid obtained in step (2) is calcined at 600 ° C for 5 h;
(4)按 Mn/Co/Ce的元素摩尔比 1:1:1分别量取催化剂活性组分前驱体： 硝酸锰、 硝酸钴及硝酸铈， 其中 Mn元素与助催化剂前驱体的摩尔比 1:1 , 均匀溶解于体积等于载体的总孔体积的去离子水中， 滴加氨水调节溶液 pH 值为 5;  (4) The catalyst active component precursors were respectively taken according to the molar ratio of Mn/Co/Ce of 1:1:1: manganese nitrate, cobalt nitrate and cerium nitrate, wherein the molar ratio of Mn element to promoter precursor was 1: 1 , uniformly dissolved in deionized water having a volume equal to the total pore volume of the carrier, and adding a solution of ammonia water to adjust the pH value of 5;
(5)将步骤 (3)制备好的样品浸渍于步骤 (4)所得催化剂活性组分前驱体 溶液中， 静置 48h后， 干燥， 在空气中焙烧， 焙烧温度为 600°C , 焙烧时间 控制为 5h, 冷却后即完成催化剂的制备。  (5) The sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 48 hours, dried, and calcined in air at a calcination temperature of 600 ° C, and the calcination time is controlled. After 5 h, the preparation of the catalyst was completed after cooling.
经 XRD测定， 制得的催化剂中： 催化活性组分为：锰钴铈复合氧化物， 其中锰 /钴 /铈元素的摩尔比为： 1:1:1 ; 助催化剂为： 铁的氧化物、 铜的氧化 物和硅的氧化物， 其中锰元素与助催化剂摩尔数 （铁的氧化物、 铜的氧化 物和硅的氧化物的摩尔数之和） 的摩尔比为： 1:1; 催化活性组分与助催化 剂的总质量为载体质量的 15%。  Determined by XRD, the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is 1:1:1; the promoter is: iron oxide, a copper oxide and a silicon oxide, wherein the molar ratio of the manganese element to the mole of the cocatalyst (the sum of the iron oxide, the copper oxide, and the silicon oxide) is: 1:1; catalytic activity The total mass of the component and cocatalyst is 15% of the mass of the carrier.
催化剂的活性测试方法为： 将催化剂装入石英玻璃管中， 温度由管式 电阻炉进行程序控制。 混合气体模拟烟气， 由相应的钢瓶提供。 相应混合 气体的所占的比例 （体积分数） 为： CNO=CNH3=600ppm, C02=6%, 剩下的 使用 N2作为缓冲气体， 体积空速为 5000h4。 检测进出口的 NO的浓度值， 用进口 NO浓度减掉出口 NO浓度的数值除以进口的 NO浓度，所得的结果 乘以 100%即为 NO的转化率。 具体的计算公式如下： N。m-NO。ut x羅 The activity test method of the catalyst is as follows: The catalyst is charged into a quartz glass tube, and the temperature is controlled by a tubular resistance furnace. The mixed gas simulates the flue gas and is supplied by the corresponding cylinder. The proportion (volume fraction) of the corresponding mixed gas is: C NO = C NH3 = 600 ppm, C 02 = 6%, and the remaining N 2 is used as a buffer gas, and the volume space velocity is 5000 h 4 . The concentration of NO in the inlet and outlet is detected, and the value of the NO concentration at the outlet minus the concentration of the NO at the outlet is divided by the concentration of NO in the inlet, and the obtained result multiplied by 100% is the conversion rate of NO. The specific calculation formula is as follows: N. m -NO. Ut x ro
NOm NO m
测得的活性结果如附图 1所示， 80°C时 NO转化率即可达到 90%以上， 110°C时甚至接近 100%。 抗中毒实验脱硝活性测试方法： ①将催化剂装入石英玻璃管中， 温度 由管式电阻炉进行程序控制。 混合气体模拟烟气， 由相应的钢瓶提供。 相 应混合气体的所占的比例 （体积分数） 为： CNO=CNH3=600ppm, C02=6% , CH2O=20%剩下的使用 N2作为缓冲气体， 体积空速为 5000h4; ②将催化剂 装入石英玻璃管中， 控制温度 220°C。 混合气体模拟烟气， 由相应的钢瓶提 供。相应混合气体的所占的比例（体积分数）为： CNO=CNH3=600ppm, C02=6% , CSO2=200ppm， 剩下的使用 N2作为缓冲气体， 体积空速为 5000h4。 The measured activity results are shown in Figure 1. The NO conversion at 80 ° C can reach more than 90%, and even close to 100% at 110 ° C. Test method for denitrification activity of anti-poisoning experiment: 1 The catalyst is charged into a quartz glass tube, and the temperature is controlled by a tubular resistance furnace. The mixed gas simulates the flue gas and is supplied by the corresponding cylinder. The proportion (volume fraction) of the corresponding mixed gas is: C NO = C NH3 = 600 ppm, C 02 = 6%, C H2O = 20%, and the remaining N 2 is used as a buffer gas, and the volumetric space velocity is 5000 h 4 ; 2 The catalyst was placed in a quartz glass tube to control the temperature at 220 °C. The mixed gas simulates the flue gas and is supplied by the corresponding cylinder. The proportion (volume fraction) of the corresponding mixed gas is: C NO =CNH 3 =600 ppm, C 02 =6%, C SO2 =200 ppm, and the remaining N 2 is used as a buffer gas, and the volume space velocity is 5000 h 4 .
结果如图 2所示，在 220 °C时通入含有 200ppm的 S02的模拟烟气或 20 vol.%的水的模拟烟气其 NO转化率均能长时间保持在 85%以上。 As a result, as shown in Fig. 2 , the simulated nitrogen gas containing simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C maintained a NO conversion rate of more than 85% for a long time.
实施例 2:  Example 2:
原料准备及计算：  Raw material preparation and calculation:
称量载体质量， 测定载体的总孔体积， 根据催化活性组分与助催化剂 的总质量为载体质量的 30%计算助催化剂前驱体和催化活性组分前驱体的 添加量。  The mass of the carrier was weighed, and the total pore volume of the carrier was measured. The amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst of 30% by mass of the carrier.
具体操作步骤：  Specific steps:
(1) 取一定量的助催化剂前驱体： 硝酸铁， 溶于体积等于载体的总孔 体积的去离子水中， 用氨水调节溶液 pH为 7;  (1) taking a certain amount of cocatalyst precursor: ferric nitrate, dissolved in deionized water having a volume equal to the total pore volume of the carrier, adjusting the pH of the solution with ammonia water to 7;
(2) 分子筛载体在质量百分比浓度为 20%的稀盐酸水溶液中浸泡 40h, 取出后烘干， 然后将分子筛载体浸于步骤 (1)得到的溶液中， 静置 48h后滤 出风干；  (2) The molecular sieve carrier is immersed in a dilute hydrochloric acid aqueous solution having a mass concentration of 20% for 40 hours, taken out and dried, and then the molecular sieve carrier is immersed in the solution obtained in the step (1), allowed to stand for 48 hours, and then filtered to be air-dried;
(3) 步骤 (2)得到的固体， 在 800°C下焙烧 4h;  (3) The solid obtained in step (2) is calcined at 800 ° C for 4 h;
(4)按 Mn/Co/Ce的元素摩尔比 1:0.1:0.1分别量取催化剂前驱体： 醋酸 锰、 磷酸钴及醋酸铈， 其中锰元素与硝酸铁的摩尔比 1:0.1 , 均匀溶解于体 积等于载体的总孔体积的去离子水中， 滴加氨水调节溶液 pH值为 7;  (4) The catalyst precursors were measured according to the molar ratio of Mn/Co/Ce of 1:0.1:0.1: manganese acetate, cobalt phosphate and barium acetate, wherein the molar ratio of manganese to ferric nitrate was 1:0.1, and it was uniformly dissolved in a volume equal to the total pore volume of the carrier in deionized water, adding ammonia to adjust the pH of the solution is 7;
(5)将步骤 (3)制备好的样品浸渍于步骤 (4)所得催化剂活性组分前驱体 溶液中， 静置 48h后， 干燥， 在空气中焙烧， 焙烧温度为 800°C , 焙烧时间 控制为 4h, 冷却后即完成催化剂的制备。 (5) immersing the sample prepared in the step (3) in the catalyst active component precursor obtained in the step (4) In the solution, after standing for 48 hours, it was dried, and calcined in air at a calcination temperature of 800 ° C, and the calcination time was controlled to 4 h, and the preparation of the catalyst was completed after cooling.
经 XRD测定， 制得的催化剂中： 催化活性组分为：锰钴铈复合氧化物， 其中锰 /钴 /铈元素的摩尔比为： 1:0.1:0.1 ; 助催化剂为： 铁的氧化物， 其中 锰元素与铁元素的摩尔比为： 1:0.1 ; 催化活性组分与助催化剂的总质量为 载体质量的 30%。  Determined by XRD, the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is: 1:0.1:0.1; the cocatalyst is: iron oxide, The molar ratio of manganese element to iron element is: 1:0.1; the total mass of the catalytically active component and the cocatalyst is 30% of the mass of the carrier.
催化剂的活性测试方法及抗中毒实验脱硝活性测试方法同实施例 1。 测得的活性结果为， 80°C时 NO转化率即可达到 80%以上， 130°C时接 近 100%。 在 220°C时通入含有 200ppm的 S02的模拟烟气或 20 vol.%的水 的模拟烟气其 NO转化率均能长时间保持在 80%以上。 The activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1. The measured activity results in a NO conversion of 80% or more at 80 ° C and nearly 100% at 130 ° C. The simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate over 80% for a long time.
实施例 3:  Example 3:
原料准备及计算：  Raw material preparation and calculation:
称量载体质量， 测定载体的总孔体积， 根据催化活性组分与助催化剂 的总质量为载体质量的 20%计算助催化剂前驱体和催化活性组分前驱体的 添加量。  The mass of the carrier was weighed, and the total pore volume of the carrier was determined. The amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst of 20% by mass of the carrier.
具体操作步骤：  Specific steps:
(1) 取一定量的助催化剂前驱体： 氯化铜， 溶于体积等于载体的总孔体 积的去离子水中， 用氨水调节溶液 pH为 6;  (1) taking a certain amount of promoter precursor: copper chloride, dissolved in deionized water having a volume equal to the total pore volume of the carrier, adjusting the pH of the solution with ammonia water to 6;
(2) 活性碳纤维载体在质量百分比浓度为 15%的稀硝酸水溶液中浸泡 24h, 取出后烘干， 然后将活性碳纤维载体浸于步骤 (1)得到的溶液中， 静置 24h后滤出风干；  (2) The activated carbon fiber carrier is immersed in a dilute nitric acid aqueous solution having a mass concentration of 15% for 24 hours, taken out and dried, and then the activated carbon fiber carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered to be air-dried;
(3) 步骤 (2)得到的固体， 在 500°C下焙烧 6h;  (3) The solid obtained in step (2) is calcined at 500 ° C for 6 h;
(4)按 Mn/Co/Ce的元素摩尔比 1:0.5:0.5分别量取催化剂前驱体： 磷酸 锰、 草酸钴及硝酸铈， 其中锰元素与氯化铜的摩尔比 1:0.5, 均匀溶解于体 积等于载体的总孔体积的去离子水中，滴加氨水调节溶液 pH值为 6配制成 饱和溶液；  (4) The catalyst precursors were measured according to the molar ratio of Mn/Co/Ce of 1:0.5:0.5: manganese phosphate, cobalt oxalate and cerium nitrate, wherein the molar ratio of manganese to copper chloride was 1:0.5, uniformly dissolved. In a deionized water having a volume equal to the total pore volume of the carrier, a solution of ammonia water is added dropwise to adjust the pH of the solution to a saturated solution;
(5)将步骤 (3)制备好的样品浸渍于步骤 (4)所得催化剂活性组分前驱体 溶液中， 静置 24h后， 干燥， 在空气中焙烧， 焙烧温度为 500°C , 焙烧时间 控制为 6h, 冷却后即完成催化剂的制备。 经 XRD测定， 制得的催化剂中： 催化活性组分为：锰钴铈复合氧化物， 其中锰 /钴 /铈元素的摩尔比为： 1:0.5:0.5; 助催化剂为： 铜的氧化物， 其中 锰元素与铜元素的摩尔比为： 1:0.5; 催化活性组分与助催化剂的总质量为 载体质量的 20%。 (5) The sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 24 hours, dried, and calcined in air at a calcination temperature of 500 ° C, and the calcination time is controlled. After 6 h, the preparation of the catalyst was completed after cooling. Determined by XRD, the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is: 1:0.5:0.5; the promoter is: copper oxide, Wherein the molar ratio of manganese element to copper element is: 1:0.5; the total mass of the catalytically active component and the cocatalyst is 20% of the mass of the carrier.
催化剂的活性测试方法及抗中毒实验脱硝活性测试方法同实施例 1。 测得的活性结果为， 80°C时 NO转化率即可达到 85%以上， 130°C时接 近 100%。 在 220°C时通入含有 200ppm的 S02的模拟烟气或 20 vol.%的水 的模拟烟气其 NO转化率均能长时间保持在 80%以上。 The activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1. The measured activity results in a NO conversion of more than 85% at 80 ° C and nearly 100% at 130 ° C. The simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate over 80% for a long time.
实施例 4:  Example 4:
原料准备及计算：  Raw material preparation and calculation:
称量载体质量， 测定载体的总孔体积， 根据催化活性组分与助催化剂 的总质量为载体质量的 18%计算助催化剂前驱体和催化活性组分前驱体的 添加量。  The mass of the carrier was weighed, and the total pore volume of the carrier was determined. The amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst as 18% by mass of the carrier.
具体操作步骤：  Specific steps:
(1) 取一定量的助催化剂前驱体： 正硅酸， 溶于体积等于载体的总孔体 积的去离子水中， 用氨水调节溶液 pH为 7;  (1) taking a certain amount of promoter precursor: ortho silicic acid, dissolved in deionized water having a volume equal to the total pore volume of the carrier, adjusting the pH of the solution with ammonia water to 7;
(2) 硅藻土载体在质量百分比浓度为 5%的稀硝酸水溶液中浸泡 48h, 取出后烘干， 然后将硅藻土载体浸于步骤 (1)得到的溶液中， 静置 24h后滤 出风干；  (2) The diatomaceous earth carrier is immersed in a dilute nitric acid aqueous solution having a mass concentration of 5% for 48 hours, taken out and dried, and then the diatomaceous earth carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered off. Air dried
(3) 步骤 (2)得到的固体， 在 700°C下焙烧 4h;  (3) The solid obtained in step (2) is calcined at 700 ° C for 4 h;
(4)按 Mn/Co/Ce的元素摩尔比 1:0.2:0.6分别量取催化剂前驱体： 氯化 锰、 磷酸钴及醋酸铈， 其中锰元素与正硅酸的摩尔比 1:0.8, 均匀溶解于体 积等于载体的总孔体积的去离子水中， 滴加氨水调节溶液 pH值为 7;  (4) The catalyst precursors were measured according to the molar ratio of Mn/Co/Ce of 1:0.2:0.6: manganese chloride, cobalt phosphate and barium acetate, wherein the molar ratio of manganese to orthosilicate was 1:0.8, uniform Dissolved in deionized water having a volume equal to the total pore volume of the carrier, adding ammonia water to adjust the pH of the solution to 7;
(5)将步骤 (3)制备好的样品浸渍于步骤 (4)所得催化剂活性组分前驱体 溶液中， 静置 24h后， 干燥， 在空气中焙烧， 焙烧温度为 700°C , 焙烧时间 控制为 4h, 冷却后即完成催化剂的制备。  (5) The sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 24 hours, dried, and calcined in air at a calcination temperature of 700 ° C, and the calcination time is controlled. After 4 h, the preparation of the catalyst was completed after cooling.
经 XRD测定， 制得的催化剂中： 催化活性组分为：锰钴铈复合氧化物， 其中锰 /钴 /铈元素的摩尔比为： 1:0.2:0.6; 助催化剂为： 硅的氧化物， 其中 锰元素与硅的氧化物的摩尔比为： 1:0.8; 催化活性组分与助催化剂的总质 量为载体质量的 18%。 Determined by XRD, the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is 1:0.2:0.6; the promoter is: silicon oxide, The molar ratio of manganese element to silicon oxide is: 1:0.8; the total mass of catalytically active component and cocatalyst The amount is 18% of the mass of the carrier.
催化剂的活性测试方法及抗中毒实验脱硝活性测试方法同实施例 1。 测得的活性结果为， 80°C时 NO转化率即可达到 80%以上， 140°C时接 近 100%。 在 220°C时通入含有 200ppm的 S02的模拟烟气或 20 vol.%的水 的模拟烟气其 NO转化率均能长时间保持在 85%以上。 The activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1. The measured activity results in a NO conversion of 80% or more at 80 ° C and nearly 100% at 140 ° C. The simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate above 85% for a long time.
实施例 5:  Example 5
原料准备及计算：  Raw material preparation and calculation:
称量载体质量， 测定载体的总孔体积， 根据催化活性组分与助催化剂 的总质量为载体质量的 26%计算助催化剂前驱体和催化活性组分前驱体的 添力口量。  The mass of the carrier was weighed, and the total pore volume of the carrier was determined. The amount of the promoter precursor and the precursor of the catalytically active component was calculated based on the total mass of the catalytically active component and the cocatalyst as 26% of the mass of the carrier.
具体操作步骤：  Specific steps:
(1) 按 Fe/Cu的元素摩尔比 2:1取助催化剂前驱体： 氯化铁、 醋酸铜， 混合溶于体积等于载体的总孔体积的去离子水中，用氨水调节溶液 pH为 7;  (1) according to Fe / Cu element molar ratio of 2: 1 to take the promoter precursor: ferric chloride, copper acetate, mixed in a volume equal to the total pore volume of the carrier in deionized water, adjust the pH of the solution with ammonia water of 7;
(2) 陶瓷板载体在质量百分比浓度为 10%的柠檬酸水溶液中浸泡 40h, 取出后烘干， 然后将陶瓷板载体浸于步骤 (1)得到的溶液中， 静置 48h后滤 出风干；  (2) The ceramic plate carrier is immersed in an aqueous solution of citric acid having a mass concentration of 10% for 40 hours, taken out and dried, and then the ceramic plate carrier is immersed in the solution obtained in the step (1), allowed to stand for 48 hours, and then filtered to be air-dried;
(3) 步骤 (2)得到的固体， 在 600°C下焙烧 5h;  (3) The solid obtained in step (2) is calcined at 600 ° C for 5 h;
(4)按 Mn/Co/Ce的元素摩尔比 1:0.8:0.2分别量取催化剂前驱体： 磷酸 锰、 硝酸钴及硝酸铈， 其中锰元素与助催化剂前驱体的摩尔比 1:0.3 , 均匀 溶解于体积等于载体的总孔体积的去离子水中，滴加氨水调节溶液 pH值为 7;  (4) The catalyst precursors were measured according to the molar ratio of Mn/Co/Ce of 1:0.8:0.2: manganese phosphate, cobalt nitrate and cerium nitrate, wherein the molar ratio of manganese element to promoter precursor was 1:0.3, uniform Dissolved in deionized water having a volume equal to the total pore volume of the carrier, and adding ammonia water to adjust the pH of the solution to 7;
(5)将步骤 (3)制备好的样品浸渍于步骤 (4)所得催化剂活性组分前驱体 溶液中， 静置 48h后， 干燥， 在空气中焙烧， 焙烧温度为 600°C , 焙烧时间 控制为 5h, 冷却后即完成催化剂的制备。  (5) The sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 48 hours, dried, and calcined in air at a calcination temperature of 600 ° C, and the calcination time is controlled. After 5 h, the preparation of the catalyst was completed after cooling.
经 XRD测定， 制得的催化剂中： 催化活性组分为：锰钴铈复合氧化物， 其中锰 /钴 /铈元素的摩尔比为： 1:0.8:0.2; 助催化剂为： 铁的氧化物和铜的 氧化物， 其中锰元素与助催化剂 （铁的氧化物和铜的氧化物摩尔数之和） 的摩尔比为： 1:0.3;催化活性组分与助催化剂的总质量为载体质量的 26%。。  Determined by XRD, the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is: 1:0.8:0.2; the promoter is: iron oxide and The oxide of copper, wherein the molar ratio of the manganese element to the cocatalyst (the sum of the moles of iron oxide and copper oxide) is 1:0.3; the total mass of the catalytically active component and the cocatalyst is the mass of the carrier 26 %. .
催化剂的活性测试方法及抗中毒实验脱硝活性测试方法同实施例 1。 测得的活性结果为， 80°C时 NO转化率即可达到 90%以上， 110°C时接 近 100%。 在 220°C时通入含有 200ppm的 S02的模拟烟气或 20 vol.%的水 的模拟烟气其 NO转化率均能长时间保持在 80%以上。 The activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1. The measured activity results in a NO conversion of more than 90% at 80 ° C and nearly 100% at 110 ° C. The simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate over 80% for a long time.
实施例 6:  Example 6:
原料准备及计算：  Raw material preparation and calculation:
称量载体质量， 测定载体的总孔体积， 根据催化活性组分与助催化剂 的总质量为载体质量的 21%计算助催化剂前驱体和催化活性组分前驱体的 添加量。  The mass of the carrier was weighed, and the total pore volume of the carrier was measured. The amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst as 21% of the mass of the carrier.
具体操作步骤：  Specific steps:
(1) 按 Fe/Si的元素摩尔比 2:1取助催化剂前驱体： 乙二胺四乙酸铁铵 铁、 偏硅酸， 混合溶于体积等于载体的总孔体积的去离子水中， 用氨水调 节溶液 pH为 6;  (1) The catalyst precursor is taken according to the element molar ratio of Fe/Si of 2:1: iron ferric ammonium iron diamine tetraacetate, metasilicate, mixed in deionized water with a volume equal to the total pore volume of the carrier, using ammonia water Adjusting the pH of the solution to 6;
(2) 镍铝合金载体在质量百分比浓度为 15%的稀硝酸水溶液中浸泡 36h, 取出后烘干， 然后将镍铝合金载体浸于步骤 (1)得到的溶液中， 静置 24h后滤出风干；  (2) The nickel-aluminum alloy carrier is immersed in a dilute nitric acid aqueous solution having a mass concentration of 15% for 36 hours, taken out and dried, and then the nickel-aluminum alloy carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered off. Air dried
(3)步骤 (2)得到的固体， 在 500°C下焙烧 4h;  (3) Step (2) The obtained solid is calcined at 500 ° C for 4 h;
(4)按 Mn/Co/Ce的元素摩尔比 1:0.6:0.6分别量取催化剂活性组分前驱 体： 硝酸锰、 硝酸钴及硝酸铈， 其中 Mn 元素与助催化剂前驱体的摩尔比 1:0.9, 均匀溶解于体积等于载体的总孔体积的去离子水中， 滴加氨水调节 溶液 pH值为 6;  (4) The active component precursors of the catalysts were measured according to the molar ratio of Mn/Co/Ce of 1:0.6:0.6: manganese nitrate, cobalt nitrate and cerium nitrate, wherein the molar ratio of Mn element to promoter precursor was 1: 0.9, uniformly dissolved in deionized water having a volume equal to the total pore volume of the carrier, and adding ammonia water to adjust the pH of the solution to 6;
(5)将步骤 (3)制备好的样品浸渍于步骤 (4)所得催化剂活性组分前驱体 溶液中， 静置 24h后， 干燥， 在空气中焙烧， 焙烧温度为 500°C , 焙烧时间 控制为 4h, 冷却后即完成催化剂的制备。  (5) The sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 24 hours, dried, and calcined in air at a calcination temperature of 500 ° C, and the calcination time is controlled. After 4 h, the preparation of the catalyst was completed after cooling.
经 XRD测定， 制得的催化剂中： 催化活性组分为：锰钴铈复合氧化物， 其中锰 /钴 /铈元素的摩尔比为： 1:0.6:0.6; 助催化剂为： 铁的氧化物和硅的 氧化物， 其中锰元素与助催化剂 （铁的氧化物和硅的氧化物摩尔数之和） 的摩尔比为： 1:0.9; 催化活性组分与助催化剂的总质量为载体质量的 21%。  Determined by XRD, the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is: 1:0.6:0.6; the cocatalyst is: iron oxide and The oxide of silicon, wherein the molar ratio of manganese element to cocatalyst (the sum of the moles of iron oxide and silicon oxide) is 1:0.9; the total mass of catalytically active component and cocatalyst is the mass of the carrier 21 %.
催化剂的活性测试方法及抗中毒实验脱硝活性测试方法同实施例 1。 测得的活性结果为， 80°C时 NO转化率即可达到 85%以上， 120°C时接 近 100%。 在 220°C时通入含有 200ppm的 S02的模拟烟气或 20 vol.%的水 的模拟烟气其 NO转化率均能长时间保持在 85%以上。 The activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1. The measured activity result is that the NO conversion rate can reach 85% or more at 80 ° C, and is connected at 120 ° C. Nearly 100%. The simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate above 85% for a long time.
实施例 7:  Example 7
原料准备及计算：  Raw material preparation and calculation:
称量载体质量， 测定载体的总孔体积， 根据催化活性组分与助催化剂 的总质量为载体质量的 25%计算助催化剂前驱体和催化活性组分前驱体的 添加量。  The mass of the carrier was weighed, and the total pore volume of the carrier was measured. The amount of the promoter precursor and the catalytically active component precursor was calculated based on the total mass of the catalytically active component and the cocatalyst as 25% of the mass of the carrier.
具体操作步骤：  Specific steps:
(1) 按 Fe/Cu/Si的元素摩尔比 1:1:1取助催化剂前驱体： 乙二胺四乙酸 铁铵铁、 硝酸铁、 偏硅酸、 硝酸铜和氯化铜， 混合溶于体积等于载体的总 孔体积的去离子水中， 用氨水调节溶液 pH为 5;  (1) The catalyst precursor is taken according to the molar ratio of Fe/Cu/Si of 1:1:1: iron ferric ammonium iron diamine tetraacetate, ferric nitrate, metasilicate, copper nitrate and copper chloride, mixed and dissolved The volume is equal to the total pore volume of the carrier in deionized water, the pH of the solution is adjusted to 5 with ammonia water;
(2) 镍铝合金载体在质量百分比浓度为 15%的稀硝酸水溶液中浸泡 24h, 取出后烘干， 然后将镍铝合金载体浸于步骤 (1)得到的溶液中， 静置 24h后滤出风干；  (2) The nickel-aluminum alloy carrier is immersed in a dilute nitric acid aqueous solution having a mass concentration of 15% for 24 hours, taken out and dried, and then the nickel-aluminum alloy carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered off. Air dried
(3)步骤 (2)得到的固体， 在 600°C下焙烧 2h;  (3) Step (2) obtained solid, calcined at 600 ° C for 2 h;
(4)按 Mn/Co/Ce的元素摩尔比 1:0.6:0.6分别量取催化剂活性组分前驱 体： 硝酸锰、 醋酸锰、 硝酸钴、 草酸钴、 硝酸铈和醋酸铈， 其中 Mn元素与 助催化剂前驱体的摩尔比 1: 1 , 均匀溶解于体积等于载体的总孔体积的去离 子水中， 滴加氨水调节溶液 pH值为 5;  (4) The catalyst active component precursors are respectively measured according to the molar ratio of Mn/Co/Ce of 1:0.6:0.6: manganese nitrate, manganese acetate, cobalt nitrate, cobalt oxalate, cerium nitrate and cerium acetate, wherein Mn element and The molar ratio of the promoter precursor is 1: 1 , uniformly dissolved in deionized water having a volume equal to the total pore volume of the carrier, and the pH of the solution is adjusted to 5 by adding ammonia water;
(5)将步骤 (3)制备好的样品浸渍于步骤 (4)所得催化剂活性组分前驱体 溶液中， 静置 24h后， 干燥， 在空气中焙烧， 焙烧温度为 600°C , 焙烧时间 控制为 2h, 冷却后即完成催化剂的制备。  (5) The sample prepared in the step (3) is immersed in the precursor solution of the catalyst active component obtained in the step (4), allowed to stand for 24 hours, dried, and calcined in air at a calcination temperature of 600 ° C, and the calcination time is controlled. After 2 h, the preparation of the catalyst was completed after cooling.
经 XRD测定， 制得的催化剂中： 催化活性组分为：锰钴铈复合氧化物， 其中锰 /钴 /铈元素的摩尔比为： 1:0.6:0.6; 助催化剂为： 铁的氧化物、 铜的 氧化物和硅的氧化物， 其中锰元素与助催化剂 （铁的氧化物、 铜的氧化物 和硅的氧化物摩尔数之和） 的摩尔比为： 1: 1 ; 催化活性组分与助催化剂的 总质量为载体质量的 25%。  Determined by XRD, the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is: 1:0.6:0.6; the promoter is: iron oxide, Copper oxide and silicon oxide, wherein the molar ratio of manganese element to cocatalyst (the sum of iron oxide, copper oxide and silicon oxide) is: 1: 1 ; catalytically active component The total mass of the cocatalyst is 25% of the mass of the carrier.
催化剂的活性测试方法及抗中毒实验脱硝活性测试方法同实施例 1。 测得的活性结果为， 80°C时 NO转化率即可达到 75%以上， 150°C时接 近 100%。 在 220°C时通入含有 200ppm的 S02的模拟烟气或 20 vol.%的水 的模拟烟气其 NO转化率均能长时间保持在 80%以上。 The activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1. The measured activity result is that the NO conversion rate can reach 75% or more at 80 ° C, and is connected at 150 ° C. Nearly 100%. The simulated nitrogen gas with simulated flue gas containing 200 ppm of S0 2 or 20 vol.% of water at 220 ° C can maintain the NO conversion rate over 80% for a long time.
实施例 8:  Example 8
原料准备及计算：  Raw material preparation and calculation:
称量载体质量， 测定载体的总孔体积， 根据催化活性组分质量为载体 质量的 10%计算催化活性组分前驱体的添加量。  The mass of the carrier was weighed, the total pore volume of the carrier was measured, and the amount of the precursor of the catalytically active component was calculated based on the mass of the catalytically active component being 10% of the mass of the carrier.
具体操作步骤：  Specific steps:
(1)按 Mn/Co/Ce的元素摩尔比 1: 1:1分别量取催化剂活性组分前驱体： 硝酸锰、 草酸钴和醋酸铈， 均匀溶解于体积等于载体的总孔体积的去离子 水中， 滴加氨水调节溶液 pH值为 7;  (1) The catalyst active component precursors are respectively taken according to the molar ratio of Mn/Co/Ce of 1:1:1: manganese nitrate, cobalt oxalate and cerium acetate, uniformly dissolved in deionized ions having a volume equal to the total pore volume of the carrier. In water, add ammonia to adjust the pH of the solution to 7;
(2) 镍铝合金载体在质量百分比浓度为 15%的柠檬酸水溶液中浸泡 48h, 取出后烘干， 然后将分子筛载体浸于步骤 (1)得到的溶液中， 静置 24h 后滤出风干；  (2) The nickel-aluminum alloy carrier is immersed in a 15% by mass aqueous solution of citric acid for 48 hours, taken out and dried, and then the molecular sieve carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered to be air-dried;
(3)将步骤 (2)制备好的样品在空气中焙烧， 焙烧温度为 600°C , 焙烧时 间控制为 2h, 冷却后即完成催化剂的制备。  (3) The sample prepared in the step (2) is calcined in the air at a calcination temperature of 600 ° C, and the calcination time is controlled to 2 h, and the preparation of the catalyst is completed after cooling.
经 XRD测定， 制得的催化剂中： 催化活性组分为：锰钴铈复合氧化物， 其中锰 /钴 /铈元素的摩尔比为： 1:1:1 ; 催化活性组分的质量为载体质量的 10%。  Determined by XRD, the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is 1:1:1; the mass of catalytically active component is carrier mass 10%.
催化剂的活性测试方法及抗中毒实验脱硝活性测试方法同实施例 1。 测得的活性结果为， 80°C时 NO转化率即可达到 90%以上， 110°C时接 近 100%。 在 220°C时通入含有 200ppm的 S02的模拟烟气或 20 vol.%的水 的模拟烟气其 NO转化率均为 50%左右。 The activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1. The measured activity results in a NO conversion of more than 90% at 80 ° C and nearly 100% at 110 ° C. The simulated flue gas containing 200 ppm of S0 2 simulated flue gas or 20 vol.% water at 220 ° C had a NO conversion of about 50%.
实施例 9:  Example 9
原料准备及计算：  Raw material preparation and calculation:
称量载体质量， 测定载体的总孔体积， 根据催化活性组分质量为载体 质量的 25%计算催化活性组分前驱体的添加量  The mass of the carrier is weighed, the total pore volume of the carrier is determined, and the amount of the precursor of the catalytically active component is calculated according to the mass of the catalytically active component as 25% of the mass of the carrier.
具体操作步骤：  Specific steps:
(1)按 Mn/Co/Ce的元素摩尔比 1:0.1:0.1分别量取催化剂活性组分前驱 体： 磷酸锰、 醋酸锰、 醋酸钴和硝酸铈， 均匀溶解于体积等于载体的总孔 体积的去离子水中， 滴加氨水调节溶液 pH值为 7配制成饱和溶液； (1) The catalyst active component precursors are respectively taken according to the molar ratio of Mn/Co/Ce of 1:0.1:0.1: manganese phosphate, manganese acetate, cobalt acetate and cerium nitrate, uniformly dissolved in the total pore volume equal to the carrier a volume of deionized water, adding a solution of ammonia water to adjust the pH of the solution to a saturated solution;
(2)蜂窝陶瓷载体在质量百分比浓度为 15%的硝酸水溶液中浸泡 48h, 取出后烘干， 然后将蜂窝陶瓷载体浸于步骤 (1)得到的溶液中， 静置 24h后 滤出风干；  (2) The honeycomb ceramic carrier is immersed in an aqueous solution of 15% by mass of nitric acid for 48 hours, taken out and dried, and then the honeycomb ceramic carrier is immersed in the solution obtained in the step (1), allowed to stand for 24 hours, and then filtered to be air-dried;
(3)将步骤 (2)制备好的样品在空气中焙烧， 焙烧温度为 600°C , 焙烧时 间控制为 2h, 冷却后即完成催化剂的制备。  (3) The sample prepared in the step (2) is calcined in the air at a calcination temperature of 600 ° C, and the calcination time is controlled to 2 h, and the preparation of the catalyst is completed after cooling.
经 XRD测定， 制得的催化剂中： 催化活性组分为：锰钴铈复合氧化物， 其中锰 /钴 /铈元素的摩尔比为： 1:1:1 ; 催化活性组分的质量为载体质量的 25%。  Determined by XRD, the catalytic activity component is: manganese cobalt ruthenium composite oxide, wherein the molar ratio of manganese/cobalt/ruthenium element is 1:1:1; the mass of catalytically active component is carrier mass 25%.
催化剂的活性测试方法及抗中毒实验脱硝活性测试方法同实施例 1。 测得的活性结果为， 100°C时 NO转化率即可达到 90%以上， 150°C时 接近 100%。 在 220°C时通入含有 200ppm的 S02的模拟烟气或 20 vol.%的 水的模拟烟气其 NO转化率均为 50%左右。 以上所述实施例仅是为充分说明本发明而所举的较佳的实施例， 本发 明的保护范围不限于此。 本技术领域的技术人员在本发明基础上所作的等 同替代或变换， 均在本发明的保护范围之内。 本发明的保护范围以权利要 求书为准。 The activity test method of the catalyst and the test method for the denitration activity of the anti-poisoning experiment were the same as those in Example 1. The measured activity results in a NO conversion of more than 90% at 100 ° C and nearly 100% at 150 ° C. The simulated flue gas containing 200 ppm of S0 2 simulated flue gas or 20 vol.% water at 220 ° C had a NO conversion of about 50%. The above-described embodiments are merely preferred embodiments for the purpose of fully illustrating the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are within the scope of the present invention. The scope of the invention is defined by the claims.

Claims

权利要求书 Claim
1、 一种烟气脱硝催化剂， 包括载体和催化活性组分， 其特征在于， 所 述催化活性组分为锰钴铈复合氧化物， 所述锰钴铈复合氧化物中锰、 钴和 铈元素的摩尔比为 1:0.1~1:0.1~1。 A flue gas denitration catalyst comprising a carrier and a catalytically active component, wherein the catalytically active component is a manganese cobalt cerium composite oxide, and the manganese, cobalt and cerium elements in the manganese cobalt cerium composite oxide The molar ratio is 1:0.1~1:0.1~1.
2、 根据权利要求 1 所述的烟气脱硝催化剂， 其特征在于， 所述载体 为蜂窝陶瓷、 分子筛、 活性碳纤维、 硅藻土、 陶瓷板或金属合金。 The flue gas denitration catalyst according to claim 1, wherein the carrier is a honeycomb ceramic, a molecular sieve, an activated carbon fiber, a diatomaceous earth, a ceramic plate or a metal alloy.
3、 根据权利要求 1所述的烟气脱硝催化剂， 其特征在于， 所述催化活 性组分的质量为所述载体质量的 10%~25%。 The flue gas denitration catalyst according to claim 1, wherein the catalytically active component has a mass of 10% to 25% by mass of the carrier.
4、 根据权利要求 1所述的烟气脱硝催化剂， 其特征在于， 还包括助催 化剂， 所述助催化剂为铁、 铜或硅的氧化物中的一种或两种以上任意组合。 The flue gas denitration catalyst according to claim 1, further comprising a cocatalyst which is one or a combination of two or more of iron, copper or silicon oxides.
5、 根据权利要求 4所述的烟气脱硝催化剂， 其特征在于， 所述锰钴铈 复合氧化物中锰元素与助催化剂的摩尔比为 1:0.1~1 ；所述催化活性组分和 所述助催化剂的总质量为载体质量的 15%~30%。 The flue gas denitration catalyst according to claim 4, wherein a molar ratio of manganese element to cocatalyst in the manganese cobalt ruthenium composite oxide is 1:0.1 to 1; the catalytically active component and the The total mass of the cocatalyst is 15% to 30% of the mass of the carrier.
6、 制备权利要求 1~3任一项所述的烟气脱硝催化剂的方法， 其特征在 于， 包括如下步骤： A method of preparing a flue gas denitration catalyst according to any one of claims 1 to 3, characterized by comprising the steps of:
(1)取催化剂活性组分前驱体： 可溶性锰盐、 可溶性钴盐和可溶性铈盐， 其中锰、钴和铈元素的摩尔比为 1:0.1~1:0.1~1 ,均匀溶解于体积等于载体的 总孔体积的去离子水中， 滴加氨水调节溶液 pH值为 5~7；  (1) Taking the catalyst active component precursor: soluble manganese salt, soluble cobalt salt and soluble cerium salt, wherein the molar ratio of manganese, cobalt and lanthanum is 1:0.1~1:0.1~1, uniformly dissolved in the volume equal to the carrier The total pore volume of the deionized water, the aqueous ammonia is adjusted to adjust the pH of the solution to 5~7;
(2) 将载体在质量百分比浓度为 5%~20%的柠檬酸、稀盐酸或稀硝酸水 溶液中浸泡 24~48h, 取出后烘干， 然后将载体浸于步骤 (1)得到的溶液中， 静置 24h后， 干燥；  (2) immersing the carrier in citric acid, dilute hydrochloric acid or dilute nitric acid aqueous solution at a concentration of 5% to 20% by mass for 24 to 48 hours, taking it out, drying it, and then immersing the carrier in the solution obtained in the step (1). After standing for 24 hours, it is dried;
(3)将步骤 (2)制备好的样品在空气中焙烧， 焙烧温度为 500~800°C , 焙 烧时间控制为 4~8h, 冷却后即完成催化剂的制备。  (3) The sample prepared in the step (2) is calcined in the air at a calcination temperature of 500 to 800 ° C, and the calcination time is controlled to 4 to 8 h, and the catalyst is prepared after cooling.
7、 根据权利要求 6所述的方法， 其特征在于， 步骤 (1)中所述可溶性锰 盐为硝酸锰、 醋酸锰、 磷酸锰或氯化锰中的一种或两种以上任意混合物； 所述可溶性钴盐为硝酸钴、 醋酸钴、 磷酸钴或草酸钴中的一种或两种以上 任意混合物； 可溶性铈盐为硝酸铈或醋酸铈中的一种或其混合物。 The method according to claim 6, wherein the soluble manganese salt in the step (1) is one or a mixture of two or more of manganese nitrate, manganese acetate, manganese phosphate or manganese chloride; The soluble cobalt salt is one or more of cobalt nitrate, cobalt acetate, cobalt phosphate or cobalt oxalate. Any mixture; the soluble cerium salt is one of cerium nitrate or cerium acetate or a mixture thereof.
8、 制备权利要求 4或 5所述的烟气脱硝催化剂的方法， 其特征在于， 包括如下步骤：  A method of preparing a flue gas denitration catalyst according to claim 4 or 5, comprising the steps of:
(1) 取所述助催化剂的前驱体： 可溶性铁盐、 可溶性铜盐或可溶性硅源 化合物中的一种或两种以上任意混合物， 溶于体积等于载体的总孔体积的 去离子水中， 以氨水调节溶液 pH值在 5~7之间；  (1) taking the precursor of the cocatalyst: one or a mixture of two or more of a soluble iron salt, a soluble copper salt or a soluble silicon source compound, dissolved in deionized water having a volume equal to the total pore volume of the carrier, The pH of the ammonia water adjustment solution is between 5 and 7;
(2) 将载体在质量百分比浓度为 5%~20%的柠檬酸、稀盐酸或稀硝酸水 溶液中浸泡 24~48h,取出后烘干，然后将载体浸渍在步骤 (1)所得的溶液中， 静置 24~48h后, 干燥；  (2) The carrier is immersed in citric acid, dilute hydrochloric acid or dilute nitric acid aqueous solution having a mass percentage of 5% to 20% for 24 to 48 hours, taken out, dried, and then the carrier is immersed in the solution obtained in the step (1). After standing for 24~48h, dry;
(3) 将步骤 (2)中干燥后的固体在空气中焙烧， 焙烧温度为 500~800°C , 焙烧时间控制为 4~8h;  (3) The dried solid in step (2) is calcined in air at a calcination temperature of 500 to 800 ° C, and the calcination time is controlled to 4 to 8 h;
(4)取催化活性组分的前驱体： 可溶性锰盐、 可溶性钴盐和可溶性铈盐， 均匀溶解于体积等于载体的总孔体积的去离子水中，以氨水调节溶液 pH值 在 5~7, 其中， 可溶性锰盐、 可溶性钴盐及可溶性铈盐中锰 /钴 /铈的元素摩 尔比 1:0.1-1:0.1-1;  (4) Taking the precursor of the catalytically active component: a soluble manganese salt, a soluble cobalt salt and a soluble cerium salt, uniformly dissolved in deionized water having a volume equal to the total pore volume of the carrier, and adjusting the pH of the solution to 5-7 with ammonia water, Wherein the soluble manganese salt, the soluble cobalt salt and the soluble cerium salt have an elemental molar ratio of manganese/cobalt/strontium 1:0.1-1:0.1-1;
(5) 将步骤 (3)制备的样品浸渍于步骤 (4)所得溶液中， 静置 24~48h后， 干燥， 在空气中焙烧， 焙烧温度为 500~800°C , 焙烧时间控制为 4~8h, 得 到催化剂。  (5) The sample prepared in the step (3) is immersed in the solution obtained in the step (4), left to stand for 24 to 48 hours, dried, and calcined in air, the baking temperature is 500 to 800 ° C, and the baking time is controlled to 4~ At 8 h, a catalyst was obtained.
9、 根据权利要求 8所述的方法， 其特征在于， 步骤 (1)中所述可溶性铁 盐为硝酸铁、 氯化铁或乙二胺四乙酸铁铵中的一种或两种以上任意混合物， 所述可溶性铜盐为硝酸铜、 醋酸铜或氯化铜中的一种或两种以上任意混合 物，所述可溶性硅源化合物为正硅酸或偏硅酸中的一种或其混合物；步骤 (4) 中所述可溶性锰盐为硝酸锰、 醋酸锰、 磷酸锰或氯化锰中的一种或两种以 上任意混合物， 所述可溶性钴盐为硝酸钴、 醋酸钴、 磷酸钴或草酸钴中的 一种或两种以上任意混合物， 所述可溶性铈盐为硝酸铈或醋酸铈中的一种 或其混合物； 步骤 (4)中可溶性锰盐中锰元素与步骤 (1)中助催化剂前驱体的 摩尔比为 1: 0.1~1。  The method according to claim 8, wherein the soluble iron salt in the step (1) is one or a mixture of two or more of ferric nitrate, ferric chloride or iron ammonium EDTA. The soluble copper salt is one or a mixture of two or more of copper nitrate, copper acetate or copper chloride, and the soluble silicon source compound is one of orthosilicate or metasilicate; or a mixture thereof; The soluble manganese salt in (4) is one or a mixture of two or more of manganese nitrate, manganese acetate, manganese phosphate or manganese chloride, and the soluble cobalt salt is cobalt nitrate, cobalt acetate, cobalt phosphate or cobalt oxalate. Any one or a mixture of two or more, the soluble cerium salt being one of cerium nitrate or cerium acetate or a mixture thereof; the manganese element in the soluble manganese salt in the step (4) and the promoter precursor in the step (1) The molar ratio of the body is 1: 0.1~1.
10、 权利要求 1~5任一项所述的催化剂在烟气脱硝中的应用， 其特征 在于， 将所述催化剂加热至 80~300°C后， 通入待处理烟气。  The use of the catalyst according to any one of claims 1 to 5 for flue gas denitration, characterized in that the catalyst is heated to 80 to 300 ° C and then introduced into the flue gas to be treated.
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CN114210372A (en) * 2022-01-19 2022-03-22 石河子大学 Fe-based denitration synthetic ammonia catalyst and preparation method and application thereof
CN114210372B (en) * 2022-01-19 2023-11-24 石河子大学 Fe-based denitration ammonia synthesis catalyst and preparation method and application thereof
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CN115106117B (en) * 2022-07-29 2024-02-09 无锡威孚环保催化剂有限公司 Preparation method of catalyst for treating NO
CN115106117A (en) * 2022-07-29 2022-09-27 无锡威孚环保催化剂有限公司 Preparation method of catalyst for treating NO
CN115672310A (en) * 2022-09-28 2023-02-03 合肥工业大学 Low-temperature SCR denitration catalyst with sulfur poisoning resistance and preparation method thereof
CN115445660A (en) * 2022-10-09 2022-12-09 浙江浙能技术研究院有限公司 Preparation method of monolithic catalyst using high molecular polymer as carrier and suitable for ultralow-temperature SCR (selective catalytic reduction) reaction
CN115709062B (en) * 2022-10-11 2024-02-13 清华大学 Denitration catalyst and preparation method thereof
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CN116273197A (en) * 2023-03-23 2023-06-23 山东理工大学 Low-temperature denitration composite material and preparation method and application thereof
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