WO2018113004A1 - 一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法 - Google Patents

一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法 Download PDF

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WO2018113004A1
WO2018113004A1 PCT/CN2016/112491 CN2016112491W WO2018113004A1 WO 2018113004 A1 WO2018113004 A1 WO 2018113004A1 CN 2016112491 W CN2016112491 W CN 2016112491W WO 2018113004 A1 WO2018113004 A1 WO 2018113004A1
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molecular sieve
source
denitration catalyst
oxide
solution
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PCT/CN2016/112491
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English (en)
French (fr)
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孙利
徐永贞
李全升
刘晓玲
胡葆华
崔明
唐英杰
王玉昌
周振垒
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中节能万润股份有限公司
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Priority to EP16918110.4A priority Critical patent/EP3363539B1/en
Priority to US16/087,229 priority patent/US10596557B2/en
Priority to JP2018517750A priority patent/JP6603408B2/ja
Publication of WO2018113004A1 publication Critical patent/WO2018113004A1/zh

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Definitions

  • the invention relates to a preparation method of a molecular sieve-multi-oxide composite integrated extrusion denitration catalyst, in particular to a preparation method of a non-vanadium-based, ion exchange molecular sieve-multi-oxide composite denitration catalyst, belonging to air pollution control technology and environmental protection.
  • the field of catalytic materials technology is not limited to catalytic materials technology.
  • Nitrogen oxide (NOx) pollutants are mainly derived from stationary sources such as coal-fired power plants and industrial boilers, as well as mobile sources such as exhaust emissions from motor vehicles. NOx is the basis of nitric acid-type acid rain, and it is one of the main substances that form photochemical smog, cause greenhouse effect and destroy ozone layer. It has strong toxic effects on human body, environment and ecology. With the rapid development of the domestic economy, the coal-based energy structure has led to a rapid increase in the emission of NOx pollutants, which has seriously polluted the ecological environment and has become one of the important factors restricting social and economic development.
  • Ammonia selective catalytic reduction technology (NH 3 -SCR) is currently the most effective NOx pollutant emission control technology, widely used in fixed source flue gas denitration of coal-fired power plants, industrial boilers, etc. This technology has high denitration efficiency and selectivity. It is characterized by good operation, reliable operation and convenient maintenance. It has become one of the most widely used and most mature flue gas denitration technologies in the world.
  • the catalyst is the core of the NH 3 -SCR system and the key to the success of the denitration project.
  • the catalyst system for industrial application is mainly V 2 O 5 -WO 3 (MoO 3 )-TiO 2 , in which anatase titanium dioxide (titanium dioxide) with good sulfur resistance and abundant Lewis acid sites is realized.
  • anatase titanium dioxide titanium dioxide
  • TiO 3 titanium dioxide
  • One of the main raw materials for industrial production of SCR denitration catalysts is also the primary factor in controlling catalyst performance and cost.
  • V 2 O 5 is a highly toxic substance.
  • the large-scale use of such catalysts may endanger human health and cause environmental pollution problems;
  • the mine reserves are small and the price of vanadium oxide is relatively high. Therefore, the development of non-vanadium-based environmentally friendly denitration catalysts with high water and sulfur resistance is a hot topic in academic and industrial circles at home and abroad.
  • the metal-loaded molecular sieve denitration catalyst has become a new hot spot in the research of SCR catalysts due to its wide active temperature window, good high temperature hydrothermal stability and low sulfur dioxide oxidation ability, and has been realized in the mobile source SCR denitration catalyst.
  • Commercialization. Molecular Sieve Denitration Catalysts
  • the metals supported by the ion exchange/impregnation method usually include metal elements such as Mn, Fe, Co, Ni, Cu, and Ce, and the molecular sieve catalysts supported by Mn, Fe, Cu, and Ce metals perform best.
  • the activity of water vapor and sulfur dioxide on the molecular sieve-based denitration catalyst usually has a significant negative effect: the water vapor mainly causes the catalyst to be deactivated by the collapse of the molecular sieve structure and the migration of the active component, and the active metal is sulphated and The ammonium sulfate/ammonium hydrogen sulfate deposition coverage active site is the two main pathways for catalyst poisoning due to sulfur dioxide.
  • the drawbacks of metal-loaded molecular sieves in terms of water and sulfur resistance limit their industrial application in fixed source flue gas denitrification. Therefore, by optimizing the preparation process to improve the water and sulfur resistance of metal-loaded molecular sieve denitration catalysts, the development of non-vanadium-based environmentally friendly denitration catalysts has important practical significance for fixed source flue gas denitrification treatment.
  • the invention constructs an ion exchange molecular sieve-multi-oxide composite active component by using a surfactant-porogen, selects a sulfur-resistant titanium-based carrier, and adds an inorganic binder, thereby reducing the preparation cost of the denitration catalyst and improving the active group.
  • the whole extrusion denitration catalyst prepared according to the invention has wide temperature window, high denitration efficiency and strong resistance to water and sulfur poisoning, and can be used as a fixed source flue gas denitration catalyst for industrial boilers and power plants.
  • the alkaline silicon source is selected to be an alkaline precursor solution, and the acidic precursor solution and the alkaline precursor solution are uniformly mixed to obtain a mixed solution or slurry;
  • step (3) In the mixed solution or slurry obtained in the step (2), adding a basic compound solution to adjust the pH to be alkaline, and then adding a pore former, aging reaction, filtering, washing with water, and discarding the filtrate to obtain a filter cake. That is, a multi-oxide precursor;
  • the ion-exchange molecular sieve slurry obtained in the step (1) is added, stirred and mixed, and then subjected to vacuum dehydration, drying and high-temperature calcination to obtain a molecular sieve-multi-oxide composite.
  • Denitration catalyst active component
  • the present invention can also be improved as follows.
  • the metal salt of manganese, iron, cobalt, nickel, copper, and cerium in the step (1) is one of a soluble metal acetate, a nitrate, a sulfate, and a hydrochloride; the manganese, iron, and cobalt The metal of one or both of nickel, copper and bismuth is added in an amount of 0.5-8% by mass of the molecular sieve; the skeleton topological structure of the molecular sieve is AEI, AFX, BEA, CHA, DDR, ERI , FAU, FER, GIS, KFI, LEV, LTA, MEL, MFI, MOR, PAU, SAS or a mixed structure thereof; the liquid-solid mass ratio of the metal salt solution to the molecular sieve is 2-50:1; The ion exchange temperature is 25-95 ° C, the ion exchange time is 0.5-8 h; the surfactant is a cationic surfactant, an anion a surfactant or
  • a further advantageous effect of the above is that the molecular sieve skeleton topology structure described above conforms to the definition code of the International Zeolite Association (IZA).
  • IZA International Zeolite Association
  • the molar ratio of metal atoms is (0.05-1): (0.05-1).
  • the metal salt is one or two of manganese, iron, copper, and barium metal salts, and the metal of the manganese, iron, copper, and barium metal salts is added in an amount of 2-4% by mass of the molecular sieve;
  • the liquid-solid mass ratio of the metal salt solution to the molecular sieve is 5-10:1;
  • the ion exchange temperature is 50-80 ° C, the ion exchange time is 2-5 h; and the surfactant concentration is 2- 5%.
  • the molecular sieve is an aluminosilicate molecular sieve, a silicoaluminophosphate molecular sieve or an aluminum phosphate molecular sieve; the molecular sieve is of a hydrogen molecular sieve, an ammonium molecular sieve, an alkali metal molecular sieve or an alkaline earth metal molecular sieve.
  • the molecular sieve is of a hydrogen molecular sieve, an ammonium molecular sieve, an alkali metal molecular sieve or an alkaline earth metal molecular sieve.
  • the aluminosilicate molecular sieve has a molar ratio of SiO 2 to Al 2 O 3 of 5-100; the silicon aluminophosphate molecular sieve has a silicon mass fraction of 1-25%; and the molecular sieve type is hydrogen Molecular sieve.
  • the aluminosilicate molecular sieve has a molar ratio of SiO 2 to Al 2 O 3 of 10-40; and the silicon aluminophosphate molecular sieve has a silicon mass fraction of 5-15%.
  • the molecular sieves are SAPO-18, SSZ-39, SAPO-56, SSZ-16, Zeolite Beta, SAPO-34, SSZ-13, SAPO-44, ZSM-58, ZSM-34, Zeolite X, Zeolite Y, SAPO-37, ZSM-35, Zeolite P, SAPO-43, ZK-5, SAPO-35, Zeolite A, ZSM-11, ZSM-5, Zeolite Mordenite, ECR-18, SSZ-73 Or a plurality of; the cationic surfactant is a quaternary ammonium salt; the anionic surfactant is a carboxylic acid, a sulfuric acid, a sulfonic acid or a phosphate; the nonionic surfactant is a long-chain alkane epoxy Vinyl ether, long chain phenolic ethylene vinyl ether or sorbitan ester or polyethylene oxide-polypropylene oxide block copolymer.
  • the molecular sieve is one or both of SSZ-39, SSZ-16, Zeolite Beta, SAPO-34, SSZ-13, Zeolite Y, ZSM-5, Zeolite Mordenite.
  • the mass ratio of the two molecular sieves in the SSZ-39, SSZ-16, Zeolite Beta, SAPO-34, SSZ-13, Zeolite Y, ZSM-5, and Zeolite Mordenite are both (0.1-1): (0.1 -1).
  • the surfactant is cetyltrimethylammonium chloride, hexadecane trimethylammonium bromide, Pluronic P123, Pluronic F127, Pluronic F108, Brij56, Brij 78, Triton X-100, Triton X -114, Tween 20, Tween 40, Tween 60, Tween 80, Span 40 or Span 80.
  • the acidic precursor solution and the alkaline precursor solution in the step (2) are mixed by adding the acidic precursor solution to the alkaline precursor solution, and adding the alkaline precursor solution to the acidic precursor. Mixing in the solution or mixing the acidic precursor solution and the alkaline precursor solution into the same container at the same time; the acidic precursor solution and the alkaline precursor solution have a mass concentration of 5-20%; the manganese, iron, cobalt
  • the metal salt of one or two of nickel, copper, and antimony has an atomic mole fraction of 1 part, and the aluminum source, the titanium source, the zirconium source, and the basic silicon source are aluminum, titanium, zirconium, and silicon.
  • the atomic mole fraction is 0-0.5 parts, 0-0.5 parts, 0-0.5 parts, and 1-2 parts, respectively;
  • the acidic precursor solution further includes a magnesium source, a calcium source, an indium source, a tin source, a germanium source, One or two or three kinds of metal salts of a tungsten source and a molybdenum source; the magnesium source, the calcium source, the indium source, the tin source, the germanium source, the tungsten source, the molybdenum source, magnesium, calcium, indium, tin,
  • the total atomic mole fraction of ruthenium, tungsten and molybdenum is from 0.1 to 0.5 parts.
  • the molar ratio of the metal atoms is (0.05-0.95): (0.05-0.95); the magnesium, In two or three metal salts of calcium, indium, tin, antimony, tungsten and molybdenum, the molar ratio of metal atoms is (0.05-0.45): (0.05-0.45), (0.05-0.45): (0.05- 0.45): (0.05-0.45).
  • the aluminum source is aluminum sol, aluminum chloride, aluminum sulfate or aluminum nitrate;
  • the titanium source is titanium sol, titanium sulfate or titanyl sulfate;
  • the zirconium source is zirconium sol, zirconium oxychloride, sulfuric acid Zirconium, Zirconium nitrate or zirconyl nitrate;
  • the basic silicon source is an alkaline silica sol or a soluble silicate;
  • the magnesium source is a soluble acetate, nitrate, sulfate or hydrochloride;
  • the calcium source is soluble An acetate, a nitrate, a sulfate or a hydrochloride;
  • the source of indium is a soluble acetate, nitrate, sulfate or hydrochloride;
  • the source of tin is a soluble acetate, nitrate, sulfate or a hydrochlor
  • the basic compound in the step (3) is sodium hydroxide, potassium hydroxide, ammonia water, urea, ammonium carbonate, ammonium hydrogencarbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium oxalate, sodium carbonate, sodium hydrogencarbonate or potassium carbonate.
  • the basic compound solution has a mass concentration of 5-30%; the pH is 7.5-9; the pore former is activated carbon, carbon black, nano carbon material or graphite;
  • the temperature is 40-95 ° C, the aging reaction time is 0.5-12 h; the conductivity of the filtrate is less than 500 ⁇ s / cm; the total mass of the multi-oxide calculated based on the mass of the oxide contained in the multi-oxide precursor
  • the mass ratio of the molecular sieve to the molecular sieve in the step (1) is from 0.5 to 1.5:1.
  • the multi-oxide precursor in the step (3) contains MnO, FeO and/or Fe 2 O 3 , CoO, NiO, CuO, CeO 2 , Al 2 O 3 , TiO 2 , ZrO 2 , SiO 2 , An oxide composition of several of MgO, CaO, In 2 O 3 , SnO 2 , La 2 O 3 , WO 3 , and MoO 3 .
  • the pore former is added in an amount of 5 to 50% by mass based on the total mass of the multicomponent oxide.
  • the pore former is added in an amount of 10 to 30% by mass based on the total mass of the multicomponent oxide.
  • the pH is 8-8.5; the aging reaction temperature is 50-80 ° C, and the aging reaction time is 1-6 h.
  • the stirring and mixing time in the step (4) is 0.5-3 h; the vacuum dehydration temperature is 75-85 ° C, the vacuum degree is -0.85-0.95 Mpa; the drying temperature is 100-150 ° C, and the drying time is It is 12-24h; the high temperature baking temperature is 350-450 ° C, and the baking time is 2-6 h.
  • the particle size of the screening according to the step (5) is less than 45 ⁇ m;
  • the titanium-based carrier is titanium dioxide powder, titanium silicon powder, titanium tungsten powder or titanium tungsten silicon powder;
  • the inorganic binder is attapulgite clay, bentonite, Mongolia Desiccant or kaolin;
  • the organic binder is aminocarboxymethylcellulose, hydroxypropylmethylcellulose or polyethylene oxide;
  • the structural reinforcing agent is glass fiber, carbon fiber or ceramic fiber;
  • the agent is tianjing powder, wood pulp, activated carbon or carbon black;
  • the lubricant is glycerin, lactic acid or stearic acid;
  • the weight of the composite denitration catalyst active component, the titanium-based carrier, the inorganic binder and the structural reinforcing agent The ratio is (10-40): (40-70): (10-30): (3-8); the weight of the organic binder, the molding pore former, the lubricant and the water are respectively the above composite denitration
  • the invention adopts an ion exchange molecular sieve-multi-oxide composite as an active component, supplements an anti-sulfur titanium-based carrier and an inorganic binder to prepare an integrated extrusion denitration catalyst, and is a low-cost and environment-friendly non-vanadium-based denitration.
  • Catalyst; the integrated extrusion denitration catalyst obtained by the invention has a conversion ratio of nitrogen oxides of more than 80% in the range of 250-420 ° C; the synergistic effect between the ion exchange molecular sieve-multi-oxide-titanium-based carrier makes the catalyst have good Water and sulfur resistance.
  • Example 1 is a graph showing the effect of 10% steam and 1500 ppm of sulfur dioxide on the denitration activity of the honeycomb catalyst of Example 10 at a test temperature of 300 ° C, wherein the abscissa indicates the reaction time / h and the ordinate indicates the nitrogen oxide conversion rate / %.
  • the solution B was added dropwise to the solution A, and after adjusting the pH of the system to 8-8.5 with 25-28% aqueous ammonia, 2.0 g of activated carbon (added amount of 20% of the total mass of the oxide) was added, and then at 55 The reaction was aged for 3 h in a constant temperature water bath.
  • the molar ratio of Fe, Si, Ti, and Zr in the multi-element oxide is 1:1.6:0.4:0.1, and the mass ratio of the multi-oxide to the molecular sieve is 0.5:1.
  • the active component in the step (3) was pulverized by an RT-04SF type high-speed pulverizer and sieved to a particle size of less than 45 ⁇ m (325 mesh).
  • 20.0 g of the pulverized active component 60.0 g of titanium white powder, 17.0 g of attapulgite clay, 1.5 g of aminocarboxymethylcellulose, 3.0 g of glass fiber, 0.4 g of wood pulp, and uniformly mixed with a high-speed pulverizer of RT-04SF type .
  • the material aged in the step (4) is extruded into a strip having a diameter of 2 mm by a TBL-2 type catalyst extruder, and dried and calcined to obtain a molecular sieve-multi-oxide composite integral extrusion type denitration catalyst.
  • the sample was dried in a BPS100CL constant temperature and humidity chamber under the following conditions: 30 ° C humidity 80% dry 4 h, 40 ° C humidity 70% dry 4 h, 50 ° C humidity 60% dry 4 h, 60 ° C humidity 50% dry 1 h, 70 ° C humidity 40% Dry for 1 h, dry at 80 ° C for 35% for 1 h, then oven dry at 100 ° C for 8 h. Finally, it was calcined at 500 ° C for 6 h in a muffle furnace, and the muffle furnace was heated at a rate of 1 ° C/min. The calcined sample was cut into 3-5 mm columnar particles for activity testing.
  • the activity test conditions of the strip catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia gas, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, the reaction equilibrium gas is nitrogen, the catalyst loading is 20 ml, and the reaction is empty.
  • the rate of reduction of nitrogen oxides in the strip catalyst is shown in Table 1 at a rate of 15000 h -1 at eight temperatures of 250 ° C, 270 ° C, 300 ° C, 320 ° C, 350 ° C, 370 ° C, 400 ° C and 420 ° C.
  • Example 1 Compared with Example 1, the difference is that F127 is not added in the first step and the activated carbon is not added in the second step.
  • the conversion rate of the reduced NOx by the strip catalyst is shown in Table 1.
  • Example 1 Compared with Example 1, the difference is that F127 is not added in the first step.
  • the conversion rate of the reduced NOx by the strip catalyst is shown in Table 1.
  • Example 1 Compared with Example 1, the difference is in the molecular sieve used in the step (1), the ion exchange metal and the loading amount, and the silicon source used in the second step is sodium silicate (Na 2 SiO 3 ⁇ 9H 2 O). details as follows:
  • the solution B was added dropwise to the solution A, and after adjusting the pH of the system to 8-8.5 with 25-28% aqueous ammonia, 2.0 g of activated carbon (added amount of 20% of the total mass of the oxide) was added, and then at 55 The reaction was aged for 3 h in a constant temperature water bath.
  • the conversion rate of the reduced NOx by the strip catalyst is shown in Table 1.
  • step (3) The slurry in the step (2) is filtered and washed with water until the filtrate conductivity is less than 500 ⁇ s/cm. Then, the obtained filter cake was added to the molecular sieve slurry obtained in the first step, and stirred and mixed at room temperature for 0.5 h. Then, it was transferred to a rotary evaporator, and the temperature of the water bath was set to 80 ° C. Under the vacuum degree of -0.85 to -0.95 Mpa, most of the water in the material was distilled off until the material was viscous.
  • the obtained product was dried at 100 ° C for 24 h, then calcined at 450 ° C for 2 h in a muffle furnace, and the muffle furnace was heated at a rate of 1 ° C / min.
  • the molecular sieve-multi-oxide composite denitration catalyst active component of the present invention is obtained.
  • the molar ratio of Mn, Ce, Si, Ti, Zr, Al in the multi-element oxide is 0.3:0.7:1.8:0.3:0.5:0.2, and the mass ratio of the multi-oxide to the molecular sieve is 1.1:1.
  • the active component in the step (3) was pulverized by an RT-04SF type high-speed pulverizer and sieved to a particle size of less than 45 ⁇ m (325 mesh).
  • 40.0 g of the pulverized active component 36.0 g of titanium tungsten powder, 20.0 g of bentonite, 1.2 g of hydroxypropylmethylcellulose, 4.0 g of ceramic fiber, 0.5 g of phthalocyanine powder, and mixed with a high-speed pulverizer of RT-04SF type Evenly.
  • glycerin 0.8 g was added to 61.3 g of deionized water and stirred uniformly, and then added to the above mixed materials, and then the material was kneaded into a uniform mud mass, and placed in a ziplock bag to seal the aged for 20 hours.
  • the material aged in the step (4) is extruded into a strip having a diameter of 2 mm by a TBL-2 type catalyst extruder, and dried and calcined to obtain a molecular sieve-multi-oxide composite integral extrusion type denitration catalyst.
  • the sample was dried in a BPS100CL constant temperature and humidity chamber under the following conditions: 30 ° C humidity 80% dry 3 h, 40 ° C humidity 70% dry 3 h, 50 ° C humidity 60% dry 3 h, 60 ° C humidity 50% dry 1 h, 70 ° C humidity 40% Dry for 1 h, dry at 80 ° C for 35% for 1 h, then oven dry at 100 ° C for 8 h.
  • the activity test conditions of the strip catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia gas, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, the reaction equilibrium gas is nitrogen, the catalyst loading is 20 ml, and the reaction is empty.
  • the rate of reduction of nitrogen oxides in the strip catalyst is shown in Table 1 at a rate of 15000 h -1 at eight temperatures of 250 ° C, 270 ° C, 300 ° C, 320 ° C, 350 ° C, 370 ° C, 400 ° C and 420 ° C.
  • the molar ratio of copper to iron in the step (1) can be arbitrarily adjusted within the range of (0.05-1): (0.05-1).
  • the obtained catalyst is The temperature range of 250-350 ° C has good denitration activity; when the molar ratio is 0.05:1, the obtained catalyst has better denitration activity in the temperature range of 350 ⁇ 420 ° C, which is well known to those skilled in the art as iron.
  • the introduction of a temperature window that expands the molecular sieve-based denitration catalyst allows the copper to iron molar ratio to be adjusted depending on the actual application of the final monolithic extruded catalyst.
  • the molar ratio of Mn, Ce, Si, Ti, Zr, and Al is 0.3:0.7:1.8:0.3:0.5:0.2, and the molar ratio of Mn to Ce can be (0.05-0.95):(0.05 -0.95) Any regulation within the range, Mn is mainly used to improve the denitration activity of the catalyst in the low temperature range.
  • the addition of Ce can increase the desulfurization activity of the catalyst while increasing the sulfur resistance of the catalyst; Si, Ti, Zr and Al are mainly in the catalyst. Acting as a carrier for regulating the surface acidity of the molecular sieve-multi-oxide composite catalyst.
  • the preferred range of the atomic mole fraction of silicon in the silicon source is ⁇ 0.2 parts of the total mole fraction of Mn, Ce, Ti, Zr, Al, Ti,
  • the atomic molar ratio of Zr and Al can be arbitrarily regulated in the range of (0.05-0.5):(0.05-0.5):(0.05-0.5), and the addition of Ti, Zr and Al is beneficial to the denitration performance of the whole extruded catalyst.
  • the object of the invention can be achieved by the action and within the molar ratio range.
  • solution B Under stirring, the solution A was added dropwise to the solution B, and after adjusting the pH of the system to 8-8.5 with a 10% Na 2 CO 3 solution, 2.4 g of carbon nanotubes were added (addition amount was 12% of the total mass of the oxide) Then, the reaction was aged for 4 hours in a constant temperature water bath at 70 °C.
  • the molar ratio of Mn, Si, Al, Mg, and Ca in the multi-element oxide is 1:1.8:0.5:0.25:0.15, and the mass ratio of the multi-oxide to the molecular sieve is 1:1.
  • the active component in the step (3) was pulverized by an RT-04SF type high-speed pulverizer and sieved to a particle size of less than 45 ⁇ m (325 mesh).
  • glycerin 1.0 g was added to 58.7 g of deionized water and stirred uniformly, and then added to the above mixed materials, and then the material was kneaded into a uniform mud mass, and placed in a ziplock bag to seal the aged for 17 hours.
  • the material aged in the step (4) is extruded into a strip having a diameter of 2 mm by a TBL-2 type catalyst extruder, and dried and calcined to obtain a molecular sieve-multi-oxide composite integral extrusion type denitration catalyst.
  • the sample was dried in a BPS100CL constant temperature and humidity chamber under the following conditions: 30 ° C humidity 80% dry 5 h, 40 ° C humidity 70% dry 3 h, 50 ° C humidity 60% dry 3 h, 60 ° C humidity 50% dry 1 h, 70 ° C humidity 40% Dry for 1 h, dry at 80 ° C for 35% for 1 h, then oven dry at 100 ° C for 8 h.
  • the activity test conditions of the strip catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia gas, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, the reaction equilibrium gas is nitrogen, the catalyst loading is 20 ml, and the reaction is empty.
  • the rate of reduction of nitrogen oxides in the strip catalyst is shown in Table 1 at a rate of 15000 h -1 at eight temperatures of 250 ° C, 270 ° C, 300 ° C, 320 ° C, 350 ° C, 370 ° C, 400 ° C and 420 ° C.
  • the molar ratio of Mn, Si, Al, Mg, and Ca in the multi-element oxide is 1:1.8:0.5:0.25:0.15, and the present embodiment further proceeds to the acidic precursor solution in the step (2).
  • An alkaline earth metal salt such as Mg or Ca is introduced as a multi-oxide active auxiliary agent, and the atomic molar ratio of the two auxiliary agents can be arbitrarily regulated in the range of (0.05-0.45): (0.05-0.45), and the total atomic molar fraction is 0.1.
  • auxiliaries is mainly used to improve the sulfur resistance of the final integral extrusion denitration catalyst, and the addition of the auxiliaries enriches the technical solution of the present invention, making it easier for the present invention to achieve the technical object of the present invention.
  • step (3) The slurry in the step (2) is filtered and washed with water until the filtrate conductivity is less than 500 ⁇ s/cm.
  • the resulting filter cake was then added to the molecular sieve slurry obtained in the first step, and stirred and mixed at room temperature for 2 hours. Then, it was transferred to a rotary evaporator, and the temperature of the water bath was set to 80 ° C. Under the vacuum degree of -0.85 to -0.95 Mpa, most of the water in the material was distilled off until the material was viscous.
  • the obtained product was dried at 120 ° C for 20 h, then calcined at 400 ° C for 4 h in a muffle furnace, and the muffle furnace was heated at a rate of 1 ° C / min.
  • the molecular sieve-multi-oxide composite denitration catalyst active component of the present invention is obtained.
  • the molar ratio of Ni, Co, Si, Zr, In, Sn, and La in the multi-element oxide is 0.5:0.5:2:0.4:0.2:0.2:0.1, and the mass ratio of the multi-oxide to the molecular sieve is 0.6:1.
  • the active component in the step (3) was pulverized by an RT-04SF type high-speed pulverizer and sieved to a particle size of less than 45 ⁇ m (325 mesh). Take 30.0 g of the pulverized active component, 56.0 g of titanium tungsten silicon powder, 10.0 g of kaolin, 1.5 g of aminocarboxymethylcellulose, 0.9 g of polyethylene oxide, 4.0 g of ceramic fiber, 0.6 g of activated carbon, and the type of RT-04SF The high speed pulverizer is evenly mixed.
  • 1.2 g of lactic acid was added to 60.0 g of deionized water and stirred uniformly, and then added to the above mixed materials, and then the material was kneaded into a uniform mud mass, and placed in a ziplock bag to seal the aged for 18 hours.
  • the material aged in the step (4) is extruded into a strip having a diameter of 2 mm by a TBL-2 type catalyst extruder, and dried and calcined to obtain a molecular sieve-multi-oxide composite integral extrusion type denitration catalyst.
  • the sample was dried in a BPS100CL constant temperature and humidity chamber under the following conditions: 30 ° C humidity 80% dry 6 h, 40 ° C humidity 70% dry 6 h, 50 ° C humidity 60% dry 3 h, 60 ° C humidity 50% dry 1 h, 70 ° C humidity 40% Dry for 1 h, dry at 80 ° C for 35% for 1 h, then oven dry at 100 ° C for 8 h.
  • the activity test conditions of the strip catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia gas, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, the reaction equilibrium gas is nitrogen, the catalyst loading is 20 ml, and the reaction is empty.
  • the rate of reduction of nitrogen oxides in the strip catalyst is shown in Table 1 at a rate of 15000 h -1 at eight temperatures of 250 ° C, 270 ° C, 300 ° C, 320 ° C, 350 ° C, 370 ° C, 400 ° C and 420 ° C.
  • the molar ratio of Ni, Co, Si, Zr, In, Sn, and La atoms in the multi-element oxide is 0.5:0.5:2:0.4:0.2:0.2:0.1
  • the present embodiment is in the step ( 2) Further introducing a metal salt such as In, Sn or La into the acidic precursor solution as a multi-oxide active auxiliary agent, and the atomic molar ratio of the three auxiliary agents may be (0.05-0.45): (0.05-0.45): (0.05 Any adjustment within the range of -0.45), and the total atomic mole fraction is from 0.15 to 0.5 parts.
  • auxiliaries is mainly used to improve the sulfur resistance of the final monolithic extrusion denitration catalyst, and the addition of these auxiliaries enriches the present invention.
  • the technical solution makes it easier for the present invention to achieve the technical object of the present invention.
  • Example 5 Compared with Example 5, the difference lies in the molecular sieve used in the step (4), the ion exchange metal and the loading amount.
  • the silicon source used in the step (2) is solid sodium silicate, and the zirconium source is zirconium oxynitrate. details as follows:
  • the conversion rate of the reduced NOx by the strip catalyst is shown in Table 1.
  • Example 6 it should be noted that the mass ratio of the two molecular sieves of ZSM-5 and SAPO-34 is 1:0.1, and the mass ratio can be arbitrarily regulated within the range of (0.1-1):(0.1-1).
  • the technical object of the present invention can be achieved. It is well known to those skilled in the art that SAPO-34 has better hydrothermal stability and therefore the mass ratio of the two molecular sieves can be adjusted depending on the actual application of the final monolithic extruded catalyst.
  • solution A and solution B were simultaneously added dropwise to the same vessel, and after adjusting the pH of the system to 8-8.5 with 20% NH 4 HCO 3 solution, 108.0 g of activated carbon was added (addition amount was total mass of oxide) 30%), and then aged in a constant temperature water bath at 80 ° C for 1 h.
  • the molar ratio of Ce, Al, Si, and W in the multi-element oxide is 1:0.1:1:0.5, and the mass ratio of the multi-oxide to the molecular sieve is 1.5:1.
  • the active component in the step (3) was pulverized by an RT-04SF type high-speed pulverizer and sieved to a particle size of less than 45 ⁇ m (325 mesh).
  • step (4) Take 200g of the stale material in step (4), and uniformly press it on the stainless steel mesh plate, the thickness of the pressing is 1mm, and then cut into a shape with a width of 10cm ⁇ 3cm, dried, After calcination, a molecular sieve-multi-oxide composite integral extrusion denitration catalyst is obtained.
  • the sample was dried in a BPS100CL constant temperature and humidity chamber under the following conditions: 30 ° C humidity 80% dry 18 h, 40 ° C humidity 70% dry 18 h, 50 ° C humidity 60% dry 12 h, 60 ° C humidity 50% dry 12 h, 70 ° C humidity 40% Dry for 6 h, dry at 80 ° C for 35% for 6 h, then oven dry at 100 ° C for 8 h. Finally, it was calcined at 600 ° C for 3 h in a muffle furnace, and the muffle furnace was heated at a rate of 1 ° C/min. Five calcined plate samples were placed equidistantly in a plate catalyst test mold for activity testing.
  • the aging material in the step (4) is extruded into a 3 cm ⁇ 3 cm (4 ⁇ 4 pore) honeycomb catalyst by a TLJ-40 vacuum kneading extruder, and dried and calcined to obtain a molecular sieve-polyoxide.
  • the drying conditions are the same as in the step (5).
  • the length of the calcined sample was cut to 10 cm for the activity test.
  • the activity test conditions of the flat or honeycomb catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, the reaction equilibrium gas is nitrogen, and the catalyst loading is 90 ml.
  • the reaction space velocity is 6000h -1 .
  • the conversion rate of the nitrogen oxides of the honeycomb catalyst can be seen. Table II.
  • Example 7 Compared with Example 7, the difference is in the molecular sieve used in the step (1), the ion exchange metal and the loading amount, and the silicon source used in the step (2) is solid potassium sodium silicate. details as follows:
  • the activity test conditions of the flat or honeycomb catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, the reaction equilibrium gas is nitrogen, and the catalyst loading is 90 ml.
  • the reaction space velocity is 6000h -1 .
  • the conversion rate of the nitrogen oxides of the honeycomb catalyst can be seen. Table II.
  • step (3) The slurry in the step (2) is filtered and washed with water until the filtrate conductivity is less than 500 ⁇ s/cm. Then, the obtained filter cake was added to the molecular sieve slurry obtained in the first step, and stirred and mixed at room temperature for 3 hours. Then, it was transferred to a rotary evaporator, and the temperature of the water bath was set to 80 ° C. Under the vacuum degree of -0.85 to -0.95 Mpa, most of the water in the material was distilled off until the material was viscous.
  • the obtained product was dried at 120 ° C for 24 h, then calcined at 400 ° C for 5 h in a muffle furnace, and the muffle furnace was heated at a rate of 1 ° C / min.
  • Producing the invention Molecular sieve-multi-oxide composite denitration catalyst active component.
  • the molar ratio of Fe, Si, Ti, Al, and W in the multi-element oxide is 1:1.7:0.2:0.5:0.1, and the mass ratio of the multi-oxide to the molecular sieve is 0.7:1.
  • the active component in the step (3) was pulverized by an RT-04SF type high-speed pulverizer and sieved to a particle size of less than 45 ⁇ m (325 mesh). Take 360.0 g of the pulverized active component, 1128.0 g of titanium tungsten silicon powder, 720.0 g of bentonite, 43.2 g of aminocarboxymethylcellulose, 48.0 g of polyethylene oxide, 3.6 g of stearic acid, and strong blend with QLJ-10L type. The machine was mixed for 30 minutes.
  • step (4) Take 200g of the stale material in step (4), and uniformly press it on the stainless steel mesh plate, the thickness of the pressing is 1mm, and then cut into a shape with a width of 10cm ⁇ 3cm, dried, After calcination, a molecular sieve-multi-oxide composite integral extrusion denitration catalyst is obtained.
  • the sample was dried in a BPS100CL constant temperature and humidity chamber under the following conditions: 30 ° C humidity 80% dry 18 h, 40 ° C humidity 70% dry 18 h, 50 ° C humidity 60% dry 12 h, 60 ° C humidity 50% dry 12 h, 70 ° C humidity 40% Dry for 6 h, dry at 80 ° C for 35% for 6 h, then oven dry at 100 ° C for 8 h. Finally, it was calcined at 600 ° C for 3 h in a muffle furnace, and the muffle furnace was heated at a rate of 1 ° C/min. Five calcined plate samples were placed equidistantly in a plate catalyst test mold for activity testing.
  • the aging material in the step (4) is extruded into a 3 cm ⁇ 3 cm (4 ⁇ 4 pore) honeycomb catalyst by a TLJ-40 vacuum kneading extruder, and dried and calcined to obtain a molecular sieve-polyoxide.
  • the drying conditions are the same as in the step (5).
  • the length of the calcined sample was cut to 10 cm for the activity test.
  • the activity test conditions of the flat or honeycomb catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, the reaction equilibrium gas is nitrogen, and the catalyst loading is 90 ml.
  • the reaction space velocity is 6000h -1 .
  • the conversion rate of the nitrogen oxides of the honeycomb catalyst can be seen. Table II.
  • Example 9 Compared with Example 9, the difference is in the molecular sieve used in the first step, the ion exchange metal and the loading amount, and the silicon source used in the step (2) is solid potassium silicate. details as follows:
  • Tritonx-100 was added, and the mixture was stirred for 40 min using a JRJ300-S type digital shear emulsifier mixer.
  • the mass of copper and cerium in the mixed solution was 2.8% of the mass of the molecular sieve, and the molar ratio of copper to cerium was 1:0.17.
  • the activity test conditions of the flat or honeycomb catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, the reaction equilibrium gas is nitrogen, and the catalyst loading is 90 ml.
  • the reaction space velocity is 6000h -1 .
  • the conversion rate of the nitrogen oxides of the honeycomb catalyst can be seen. Table II.
  • the water and sulfur resistance test conditions of the honeycomb catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia, 1500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, the reaction equilibrium gas is nitrogen, and the catalyst loading is 90 ml, the reaction space velocity was 6000 h -1 , and the denitration efficiency of the honeycomb catalyst was tested with time under the reaction conditions of 300 ° C.
  • the catalyst can maintain a conversion of nitrogen oxides above 90% during the 48 h test period in the presence of 10% steam and 1500 ppm sulfur dioxide, indicating that the catalyst is highly resistant to water. Sulfur performance.
  • Solution B was added dropwise to Solution A, and after adjusting the pH of the system to 8-8.5 with a 15% Na 2 CO 3 solution, 80.0 g of graphite (added amount of 25% of the total mass of the oxide) was added. The reaction was then aged in a constant temperature water bath at 70 ° C for 3 h.
  • the molar ratio of Cu, Si, Ti, and Mo in the multi-element oxide is 1:1.3:0.3:0.15, and the mass ratio of the multi-oxide to the molecular sieve is 0.8:1.
  • the active component in the step (3) was pulverized by an RT-04SF type high-speed pulverizer and sieved to a particle size of less than 45 ⁇ m (325 mesh).
  • 600.0 g of the pulverized active component, 1320.0 g of titanium white powder, 336.0 g of attapulgite clay, 43.2 g of hydroxypropylmethylcellulose, 24.0 g of polyethylene oxide, 14.4 g of phthalocyanine powder and 7.2 g of stearic acid were used.
  • QLJ-10L type strong mixer is mixed for 30min. 36.0 g of glycerin and 1520.0 g of deionized water were stirred uniformly, and then added to the material.
  • the activity test conditions of the honeycomb catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, a reaction equilibrium gas of nitrogen, a catalyst loading of 90 ml, and an empty reaction.
  • the conversion rate of the nitrogen oxides of the honeycomb catalyst is shown in Table 2 at a rate of 6000 h -1 at the temperatures of 250 ° C, 270 ° C, 300 ° C, 320 ° C, 350 ° C, 370 ° C, 400 ° C and 420 ° C.
  • Example 11 Compared with Example 11, the difference lies in the molecular sieve used in the step (1), the ion exchange metal. details as follows:
  • the activity test conditions of the honeycomb catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, a reaction equilibrium gas of nitrogen, a catalyst loading of 90 ml, and an empty reaction.
  • the conversion rate of the nitrogen oxides of the honeycomb catalyst is shown in Table 2 at a rate of 6000 h -1 at the temperatures of 250 ° C, 270 ° C, 300 ° C, 320 ° C, 350 ° C, 370 ° C, 400 ° C and 420 ° C.
  • the difference is that the selected multi-oxide precursor of step (2) comprises a ruthenium source.
  • the molar ratio of Cu, Ce, Si, Ti, Mo in the multi-element oxide is 0.8:0.2:1.3:0.3:0.15, and the mass ratio of the multi-oxide to the molecular sieve is 0.8:1.
  • the activity test conditions of the honeycomb catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, a reaction equilibrium gas of nitrogen, a catalyst loading of 90 ml, and an empty reaction.
  • the conversion rate of the nitrogen oxides of the honeycomb catalyst is shown in Table 2 at a rate of 6000 h -1 at the temperatures of 250 ° C, 270 ° C, 300 ° C, 320 ° C, 350 ° C, 370 ° C, 400 ° C and 420 ° C.
  • the solution A was added dropwise to the solution B, and after adjusting the pH of the system to 8-8.5 with a 30% ammonium carbonate solution, 48.0 g of activated carbon (added in an amount of 10% of the total mass of the oxide) was added, and then The reaction was aged for 3 hours in a constant temperature water bath at 80 °C.
  • the molar ratio of Ce, Al, Ti, Si, and Mo in the multi-element oxide is 1:0.2:0.5:1.2:0.3, and the mass ratio of the multi-oxide to the molecular sieve is 1.2:1.
  • the active component in the step (3) was pulverized by an RT-04SF type high-speed pulverizer and sieved to a particle size of less than 45 ⁇ m (325 mesh).
  • a particle size of less than 45 ⁇ m (325 mesh) Take 840.0 g of the pulverized active component, 1200.0 g of titanium tungsten powder, 240.0 g of kaolin, 28.8 g of hydroxypropyl methylcellulose, 48.0 g of polyethylene oxide, 16.8 g of activated carbon and 6.0 g of stearic acid, using QLJ-10L
  • the type of powerful mixer was mixed for 30 minutes. 42.0 g of glycerin and 1520.0 g of deionized water were stirred uniformly, and then added to the material.
  • the activity test conditions of the honeycomb catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, a reaction equilibrium gas of nitrogen, a catalyst loading of 90 ml, and an empty reaction.
  • the conversion rate of the nitrogen oxides of the honeycomb catalyst is shown in Table 2 at a rate of 6000 h -1 at the temperatures of 250 ° C, 270 ° C, 300 ° C, 320 ° C, 350 ° C, 370 ° C, 400 ° C and 420 ° C.
  • Example 14 The difference from Example 14 is the molecular sieve, ion exchange metal and ratio used in the step (1).
  • the activity test conditions of the honeycomb catalyst are: 500 ppm of nitrogen monoxide, 500 ppm of ammonia, 500 ppm of sulfur dioxide, 10% of water vapor, 10% of oxygen, a reaction equilibrium gas of nitrogen, a catalyst loading of 90 ml, and an empty reaction.
  • the conversion rate of the nitrogen oxides of the honeycomb catalyst is shown in Table 2 at a rate of 6000 h -1 at the temperatures of 250 ° C, 270 ° C, 300 ° C, 320 ° C, 350 ° C, 370 ° C, 400 ° C and 420 ° C.
  • the molecular sieve-multi-oxide composite monolithic extrusion denitration catalyst prepared by the invention has high nitrogen oxide conversion rate in the temperature range of 250-420 ° C in the presence of water and sulfur dioxide. .
  • the molecular sieve-multi-oxide composite denitration catalyst prepared by the preparation method of the invention has good water and sulfur resistance, and is a non-vanadium-based, environmentally-friendly denitration catalyst. It is applied to flue gas denitration of fixed sources such as industrial boilers and power plants.

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Abstract

一种分子筛‑多元氧化物复合整体挤出式脱硝催化剂的制备方法，包括：通过在金属离子交换分子筛表面构筑有机结构涂层、同步添加多元氧化物组分，制备了离子交换分子筛‑多元氧化物复合脱硝催化剂活性组分，经混料、捏合成泥团、陈腐、整体挤压成型、干燥、焙烧后制得了整体挤出式脱硝催化剂。所得催化剂在10％水蒸气和500ppm二氧化硫存在情况下，250‑420℃的温度范围内脱硝效率大于80％。制得的金属负载分子筛脱硝催化剂可以广泛应用于固定源烟气脱硝。

Description

一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法 技术领域
本发明涉及一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，具体涉及一种非钒基、离子交换分子筛-多元氧化物复合脱硝催化剂的制备方法，属于大气污染治理技术和环保催化材料技术领域。
背景技术
氮氧化物(NOx)污染物主要来源于燃煤电厂、工业锅炉等固定发生源以及机动车尾气排放等移动发生源。NOx即是硝酸型酸雨的基础，又是形成光化学烟雾、引发温室效应和破坏臭氧层的主要物质之一，对人体、环境以及生态具有很强的毒害作用。随着国内经济的快速发展，以煤为主的能源结构导致NOx污染物的排放量迅速增加，严重污染了生态环境，已成为制约社会经济发展的重要因素之一。
氨气选择性催化还原技术(NH3-SCR)是目前最有效的NOx污染物排放控制技术，广泛应用于燃煤电厂、工业锅炉等固定源烟气脱硝，该技术具有脱硝效率高、选择性好、运行可靠、维护方便等特点，现已成为世界上应用最多、技术最成熟有效的烟气脱硝技术之一。催化剂是NH3-SCR系统的核心部分，也是脱硝项目成败的关键。目前，工业化应用催化剂体系以V2O5-WO3(MoO3)-TiO2为主，其中具有良好的抗硫性、表面Lewis酸位点丰富的锐钛矿型二氧化钛(钛白粉)是实现SCR脱硝催化剂工业化生产的主要原料之一，也是控制催化剂性能和成本的首要因素。尽管钒基催化剂生产、应用技术成熟，具有良好的中高温活性和抗硫性能，但是V2O5属于高毒性物质，大规模使用该类催化剂有可能危害人体健康和产生环境污染问题；同时钒矿 储量较少，钒氧化物价格相对较高。因此，开发具有高抗水、抗硫性能的非钒基环保型脱硝催化剂是国内外学术界和产业界的一个热点课题。
金属负载分子筛脱硝催化剂由于具有较宽的活性温度窗口、良好的高温水热稳定性以及较低的二氧化硫氧化能力等优点，成为目前SCR催化剂研究的新热点，且已经在移动源SCR脱硝催化剂方面实现了商业化。分子筛脱硝催化剂离子交换/浸渍法负载的金属通常包括Mn、Fe、Co、Ni、Cu、Ce等金属元素，其中又以Mn、Fe、Cu、Ce金属负载的分子筛催化剂活性表现最好。但是，水蒸气和二氧化硫对分子筛基脱硝催化剂的活性通常具有显著的负面影响：水蒸汽主要通过使分子筛结构坍塌脱铝以及活性组分迁移转化而引起催化剂失活，而活性金属的硫酸盐化和硫酸铵/硫酸氢铵沉积覆盖活性位则是催化剂因二氧化硫中毒的两大主要途径。金属负载分子筛在抗水耐硫性能方面的缺陷限制了其在固定源烟气脱硝方面的工业化应用。因此，通过优化制备工艺提高金属负载分子筛脱硝催化剂的抗水抗硫性能，开发非钒基环境友好脱硝催化剂对于固定源烟气脱硝处理具有很重要的现实意义。
发明内容
针对金属负载分子筛脱硝催化剂在固定源烟气脱硝应用方面的现有技术缺陷，本发明的目的在于提供一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法。本发明通过表面活性剂-造孔剂构建离子交换分子筛-多元氧化物复合活性组分、选用抗硫钛基载体、添加无机粘结剂等方式，降低了脱硝催化剂的制备成本，提高了活性组分与载体的协同作用以及整体挤出式催化剂的机械强度。根据本发明制得的整体挤出式脱硝催化剂具有较宽的温度窗口、较高的脱硝效率和较强的抗水耐硫中毒性能，可以作为工业锅炉、电厂等固定源烟气脱硝催化剂。
本发明解决上述技术问题的技术方案如下：一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，包括如下步骤：
(1)取锰、铁、钴、镍、铜、铈中的一种或两种的金属盐溶液，与分子筛混合，经离子交换反应后，再加入表面活性剂，同时进行剪切乳化分散处理，得到离子交换分子筛浆料；
(2)选取锰、铁、钴、镍、铜、铈中的一种或两种的金属盐与铝源、钛源、锆源中的一种或几种的混合物配制成酸性前驱物溶液，选取碱性硅源配制成碱性前驱物溶液，再将上述酸性前驱物溶液和碱性前驱物溶液混合均匀后，得到混合溶液或浆料；
(3)在步骤(2)得到的混合溶液或浆料中，加入碱性化合物溶液调整pH为碱性，然后再加入造孔剂，经老化反应、过滤、水洗，弃滤液，得到滤饼，即为多元氧化物前体；
(4)在步骤(3)得到的多元氧化物前体中，加入步骤(1)得到的离子交换分子筛浆料，搅拌混合后，经真空脱水、干燥和高温焙烧，得到分子筛-多元氧化物复合脱硝催化剂活性组分；
(5)将步骤(4)得到的复合脱硝催化剂活性组分粉碎、筛分后，与钛基载体、无机粘结剂、有机粘结剂、结构增强剂、成型造孔剂、润滑剂和水，经混料、捏合成泥团、陈腐、整体挤压成型、干燥、焙烧后，即得到整体挤出式脱硝催化剂。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，步骤(1)所述锰、铁、钴、镍、铜、铈的金属盐为可溶性金属乙酸盐、硝酸盐、硫酸盐、盐酸盐中的一种；所述锰、铁、钴、镍、铜、铈中的一种或两种的金属盐中金属的加入量为分子筛质量的0.5-8％；所述分子筛的骨架拓扑学结构为AEI、AFX、BEA、CHA、DDR、ERI、FAU、FER、GIS、KFI、LEV、LTA、MEL、MFI、MOR、PAU、SAS或是它们的混合结构；所述金属盐溶液与分子筛的液固质量比为2-50:1；所述离子交换的温度为25-95℃，离子交换为时间为0.5-8h；所述表面活性剂为阳离子型表面活性剂、阴离子 型表面活性剂或非离子型表面活性剂；所述表面活性剂的质量浓度为0.5-10％；所述剪切乳化分散处理时间为10-40min。
采用上述进一步的有益效果是：上述分子筛骨架拓扑学结构符合国际沸石联合会(IZA)定义结构代码。
更进一步，所述锰、铁、钴、镍、铜、铈两种的金属盐溶液中，金属原子的摩尔比均为(0.05-1):(0.05-1)。
更进一步，所述金属盐为锰、铁、铜、铈金属盐中的一种或两种，所述锰、铁、铜、铈金属盐中金属的加入量为分子筛质量的2-4％；所述金属盐溶液与分子筛的液固质量比为5-10:1；所述离子交换的温度为50-80℃，离子交换时间为2-5h；所述表面活性剂的质量浓度为2-5％。
更进一步，所述分子筛为硅铝酸盐分子筛、硅铝磷酸盐分子筛或者磷酸铝盐分子筛；所述分子筛的类型为氢型分子筛、铵型分子筛、碱金属型分子筛或者碱土金属型分子筛中的一种。
更进一步，所述硅铝酸盐分子筛中SiO2与Al2O3摩尔比为5-100；所述硅铝磷酸盐分子筛中的硅质量分数为1-25％；所述分子筛的类型为氢型分子筛。
更进一步，所述硅铝酸盐分子筛中SiO2与Al2O3摩尔比为10-40；所述硅铝磷酸盐分子筛中的硅质量分数为5-15％。
更进一步，所述分子筛为SAPO-18、SSZ-39、SAPO-56、SSZ-16、Zeolite Beta、SAPO-34、SSZ-13、SAPO-44、ZSM-58、ZSM-34、Zeolite X、Zeolite Y、SAPO-37、ZSM-35、Zeolite P、SAPO-43、ZK-5、SAPO-35、Zeolite A、ZSM-11、ZSM-5、Zeolite Mordenite、ECR-18、SSZ-73中的一种或几种；所述阳离子型表面活性剂为季铵盐类；所述阴离子表面活性剂为羧酸、硫酸、磺酸或磷酸盐类；所述非离子表面活性剂为长链烷烃类环氧乙烯醚、长链苯酚类环氧乙烯醚或脱水山梨醇酯或聚环氧乙烷-聚环氧丙烷嵌段共聚物。
更进一步，所述分子筛为SSZ-39、SSZ-16、Zeolite Beta、SAPO-34、SSZ-13、Zeolite Y、ZSM-5、Zeolite Mordenite中的一种或两种。
更进一步，所述SSZ-39、SSZ-16、Zeolite Beta、SAPO-34、SSZ-13、Zeolite Y、ZSM-5、Zeolite Mordenite中两种分子筛的质量比均为(0.1-1):(0.1-1)。
更进一步，所述表面活性剂为十六烷三甲基氯化铵、十六烷三甲基溴化铵、Pluronic P123、Pluronic F127、Pluronic F108、Brij56、Brij 78、Triton X-100、Triton X-114、Tween 20、Tween 40、Tween 60、Tween 80、Span 40或Span 80。
进一步，步骤(2)所述酸性前驱物溶液和碱性前驱物溶液的混合方式为将酸性前驱物溶液滴加到碱性前驱物溶液中混合、将碱性前驱物溶液滴加到酸性前驱物溶液中混合或者将酸性前驱物溶液和碱性前驱物溶液同时加入同一容器中混合；所述酸性前驱物溶液和碱性前驱物溶液的质量浓度为5-20％；所述锰、铁、钴、镍、铜、铈中的一种或两种的金属盐中金属的原子摩尔份数为1份，所述铝源、钛源、锆源以及碱性硅源中铝、钛、锆和硅的原子摩尔份数分别为0-0.5份、0-0.5份、0-0.5份和1-2份；所述酸性前驱物溶液还包括镁源、钙源、铟源、锡源、镧源、钨源、钼源的一种或两种或三种的金属盐；所述镁源、钙源、铟源、锡源、镧源、钨源、钼源中，镁、钙、铟、锡、镧、钨、钼的原子总摩尔份数为0.1-0.5份。
更进一步，步骤(2)所述锰、铁、钴、镍、铜、铈两种的金属盐中，金属原子的摩尔比均为(0.05-0.95):(0.05-0.95)；所述镁、钙、铟、锡、镧、钨、钼的两种或三种金属盐中，金属原子的摩尔比分别均为(0.05-0.45):(0.05-0.45)、(0.05-0.45):(0.05-0.45):(0.05-0.45)。
更进一步，所述铝源为铝溶胶、氯化铝、硫酸铝或者硝酸铝；所述钛源为钛溶胶、硫酸钛或者硫酸氧钛；所述锆源为锆溶胶、氧氯化锆、硫酸锆、 硝酸锆或者硝酸氧锆；所述碱性硅源为碱性硅溶胶或可溶性硅酸盐；所述镁源为可溶性乙酸盐、硝酸盐、硫酸盐或者盐酸盐；所述钙源为可溶性乙酸盐、硝酸盐、硫酸盐或者盐酸盐；所述铟源为可溶性乙酸盐、硝酸盐、硫酸盐或者盐酸盐；所述锡源为可溶性乙酸盐、硝酸盐、硫酸盐或者盐酸盐；所述镧源为可溶性乙酸盐、硝酸盐、硫酸盐或者盐酸盐；所述钨源为钨酸钠或者钨酸铵；所述钼源为钼酸钠或者钼酸铵。
进一步，步骤(3)所述碱性化合物为氢氧化钠、氢氧化钾、氨水、尿素、碳酸铵、碳酸氢铵、硫酸铵、硫酸氢铵、草酸铵、碳酸钠、碳酸氢钠、碳酸钾或者碳酸氢钾；所述碱性化合物溶液的质量浓度为5-30％；所述pH为7.5-9；所述造孔剂为活性炭、炭黑、纳米碳材料或者石墨；所述老化反应的温度为40-95℃，老化反应时间为0.5-12h；所述滤液的电导率小于500μs/cm；所述多元氧化物前体中含有的氧化物的质量为基准计算得到的多元氧化物的总质量与步骤(1)中所述分子筛的质量比为0.5-1.5:1。
更进一步，步骤(3)所述多元氧化物前体中含有MnO、FeO和/或Fe2O3、CoO、NiO、CuO、CeO2、Al2O3、TiO2、ZrO2、SiO2、MgO、CaO、In2O3、SnO2、La2O3、WO3、MoO3中的几种的氧化物组合物。
更进一步，所述造孔剂的添加量为所述多元氧化物总质量的5-50％。
更进一步，所述造孔剂的添加量为所述多元氧化物总质量的10-30％。
更进一步，所述pH为8-8.5；所述老化反应温度为50-80℃，老化反应时间为1-6h。
进一步，步骤(4)所述搅拌混合时间为0.5-3h；所述真空脱水的温度为75-85℃，真空度为-0.85-0.95Mpa；所述干燥的温度为100-150℃，干燥时间为12-24h；所述高温焙烧温度为350-450℃，焙烧时间为2-6h。
进一步，步骤(5)所述筛分的粒度小于45μm；所述钛基载体为钛白粉、钛硅粉、钛钨粉或者钛钨硅粉；所述无机粘结剂为凹凸棒粘土、膨润土、蒙 脱土或者高岭土；所述有机粘结剂为氨基羧甲基纤维素、羟丙基甲基纤维素或者聚氧化乙烯；所述结构增强剂为玻璃纤维、碳纤维或者陶瓷纤维；所述成型造孔剂为田菁粉、木浆、活性炭或者炭黑；所述润滑剂为甘油、乳酸或者硬脂酸；所述复合脱硝催化剂活性组分、钛基载体、无机粘结剂、结构增强剂的重量比为(10-40):(40-70):(10-30):(3-8)；所述有机粘结剂、成型造孔剂、润滑剂和水的重量分别为上述复合脱硝催化剂活性组分、钛基载体、无机粘结剂、结构增强剂总重量的1.2-3.8％、0.4-1.0％、0.8-2.5％和51.5-66.7％；所述陈腐为泥团密封放置15-36h；所述催化剂整体挤压成型为粒状、三叶草状、空心圆柱状、整体挤出蜂窝状、整体挤压板状中的一种；所述干燥的温度为35-80℃，干燥的湿度为80-35％，干燥的时间为20-80h；所述焙烧的温度为500-650℃，时间2-6h。
本发明的有益效果是：
本发明以离子交换分子筛-多元氧化物复合物为活性组分，辅以抗硫钛基载体和无机粘结剂制备整体挤出式脱硝催化剂，是一种成本低廉、环境友好的非钒基脱硝催化剂；本发明所得整体挤出式脱硝催化剂在250-420℃范围内，氮氧化物的转化率大于80％；离子交换分子筛-多元氧化物-钛基载体之间的协同作用使得催化剂具有良好的抗水耐硫性能。
附图说明
图1是测试温度300℃时10％水蒸气和1500ppm二氧化硫对实施例10蜂窝式催化剂脱硝活性的影响曲线图，其中，横坐标表示反应时间/h，纵坐标表示氮氧化物转化率/％。
具体实施方式
以下结合具体附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
(1)将1.6g乙酸铜(Cu(CH3COO)2·H2O)加入到100.0g去离子水中，搅拌至完全溶解后，再加入20.0g ZSM-5分子筛(SiO2与Al2O3摩尔比为25)，然后在80℃恒温水浴中搅拌2h，完成后加入2.0g F127，搅拌至完全溶解后，再用JRJ300-S型数显剪切乳化搅拌机搅拌20min。其中铜溶液中铜的质量为分子筛质量的2.5％。
(2)将13.1g硫酸亚铁(FeSO4·7H2O)、3.0g硫酸氧钛(TiOSO4)、1.5g氧氯化锆(ZrOCl2·8H2O)加入到335.0g去离子水中(溶质质量分数为5％)，搅拌至完全溶解，记为溶液A。将15.1g钠型硅溶胶(Na2O<0.4％，30％SiO2)加入到7.6g去离子水中(溶质质量分数为20％)，搅拌混合均匀，记为溶液B。在搅拌条件下，将溶液B滴加到溶液A中，并用25-28％氨水调整体系pH至8-8.5后，加入2.0g活性炭(添加量为氧化物总质量的20％)，然后在55℃恒温水浴中老化反应3h。
(3)将步骤(2)中的浆料过滤、水洗至滤液电导率小于500μs/cm。然后将所得滤饼加入到步骤一所得分子筛浆料中，于室温下搅拌混合1h。然后转移至旋转蒸发仪中，设置水浴温度为75℃，在真空度-0.85～-0.95Mpa下，蒸去物料中的大部分水，至物料呈粘稠状。所得产物于120℃干燥18h，然后于马弗炉中400℃焙烧4h，马弗炉升温速率为1℃/min。制得本发明的分子筛-多元氧化物复合脱硝催化剂活性组分。
本实施例多元氧化物中Fe、Si、Ti、Zr摩尔比为1:1.6:0.4:0.1，多元氧化物与分子筛质量比为0.5:1。
(4)将步骤(3)中的活性组分用RT-04SF型高速粉碎机粉碎、筛分至粒度小于45μm(325目)。取20.0g粉碎后的活性组分、60.0g钛白粉、17.0g凹凸棒粘土、1.5g氨基羧甲基纤维素、3.0g玻璃纤维、0.4g木浆，用RT-04SF型高速粉碎机混合均匀。将1.0g乳酸加入到56.3g去离子水中搅拌均匀后 加入上述混好的物料中，然后将物料捏合成均匀的泥团，放于自封袋中密封陈腐15h。
(5)用TBL-2型催化剂挤出机将步骤(4)中陈腐好的物料挤成直径2mm条状，经干燥、焙烧后得分子筛-多元氧化物复合整体挤出式脱硝催化剂。样品于BPS100CL恒温恒湿箱中干燥，条件为：30℃湿度80％干燥4h，40℃湿度70％干燥4h，50℃湿度60％干燥4h，60℃湿度50％干燥1h，70℃湿度40％干燥1h，80℃湿度35％干燥1h，然后于100℃烘箱干燥8h。最后于马弗炉中500℃焙烧6h，马弗炉升温速率为1℃/min。将焙烧后样品剪切成3-5mm柱状颗粒用于活性测试。
条状催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为20ml，反应空速为15000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，条状催化剂还原氮氧化物的转化率见表一。
实施例1的对比例1
与实施例1相比，不同之处在于步骤一中未添加F127和步骤二中未添加活性炭。条状催化剂还原氮氧化物的转化率见表一。
实施例1的对比例2
与实施例1相比，不同之处在于步骤一中未添加F127。条状催化剂还原氮氧化物的转化率见表一。
实施例2
与实施例1相比，不同之处在于步骤(1)所用分子筛、离子交换金属以及负载量，步骤二所用硅源为硅酸钠(Na2SiO3·9H2O)。具体如下：
(1)将3.3g硫酸亚铁(FeSO4·7H2O)加入到100.0g去离子水中，搅拌至完全溶解后，再加入20.0g Zeolite Mordenite分子筛(SiO2与Al2O3摩尔 比为15)，然后在80℃恒温水浴中搅拌2h，完成后加入2.0g F127，采用JRJ300-S型数显剪切乳化搅拌机搅拌20min。其中铁溶液中铁的质量为分子筛质量的3.2％。
(2)将13.1g硫酸亚铁(FeSO4·7H2O)、3.0g硫酸氧钛(TiOSO4)、1.5g氧氯化锆(ZrOCl2·8H2O)加入到335.0g去离子水中(溶质质量分数为5％)，搅拌至完全溶解，记为溶液A。将21.4g硅酸钠(Na2SiO3·9H2O)加入到85.6g去离子水中(溶质质量分数为20％)，搅拌至完全溶解，记为溶液B。在搅拌条件下，将溶液B滴加到溶液A中，并用25-28％氨水调整体系pH至8-8.5后，加入2.0g活性炭(添加量为氧化物总质量的20％)，然后在55℃恒温水浴中老化反应3h。
条状催化剂还原氮氧化物的转化率见表一。
实施例3
(1)将1.4g硫酸铜(CuSO4·5H2O)、1.6g硫酸亚铁(FeSO4·7H2O)，加入到140.0g去离子水中，搅拌至完全溶解后，再加入20.0g SSZ-13分子筛(SiO2与Al2O3摩尔比为22)，然后在75℃恒温水浴中搅拌2.5h，完成后加入3.5g十六烷三甲基溴化铵，搅拌至完全溶解后，再用JRJ300-S型数显剪切乳化搅拌机搅拌10min。其中混合溶液中铜和铁的质量为分子筛质量的3.3％，铜和铁的摩尔比为1:1。
(2)将3.2g硫酸锰(MnSO4·H2O)、18.0g硫酸铈(Ce(SO4)2·4H2O)、4.6g硫酸钛(Ti(SO4)2)、8.8g硫酸锆(ZrOSO4·4H2O)、8.5g硫酸铝(Al2(SO4)3·18H2O)加入到172.4g去离子水中(溶质质量分数为20％)，搅拌至完全溶解，记为溶液A。将24.2g液体硅酸钠(Na2O：9.0％，SiO2：28.4％，模数：3.1-3.4)加入到156.8g去离子水中(溶质质量分数为5％)，搅拌至混合均匀，记为溶液B。在搅拌条件下，将溶液A滴加到溶液B中，并用30％的NaOH溶液调整体系pH至8-8.5后，加入2.2g炭黑(添加量为氧化物总 质量的10％)，然后在50℃恒温水浴中老化反应6h。
(3)将步骤(2)中的浆料过滤、水洗至滤液电导率小于500μs/cm。然后将所得滤饼加入到步骤一所得分子筛浆料中，于室温下搅拌混合0.5h。然后转移至旋转蒸发仪中，设置水浴温度为80℃，在真空度-0.85～-0.95Mpa下，蒸去物料中的大部分水，至物料呈粘稠状。所得产物于100℃干燥24h，然后于马弗炉中450℃焙烧2h，马弗炉升温速率为1℃/min。制得本发明的分子筛-多元氧化物复合脱硝催化剂活性组分。
本实施例多元氧化物中Mn、Ce、Si、Ti、Zr、Al摩尔比为0.3:0.7:1.8:0.3:0.5:0.2，多元氧化物与分子筛质量比为1.1:1。
(4)将步骤(3)中的活性组分用RT-04SF型高速粉碎机粉碎、筛分至粒度小于45μm(325目)。取40.0g粉碎后的活性组分、36.0g钛钨粉、20.0g膨润土、1.2g羟丙基甲基纤维素、4.0g陶瓷纤维、0.5g田菁粉，用RT-04SF型高速粉碎机混合均匀。将0.8g甘油加入到61.3g去离子水中搅拌均匀后加入上述混好的物料中，然后将物料捏合成均匀的泥团，放于自封袋中密封陈腐20h。
(5)用TBL-2型催化剂挤出机将步骤(4)中陈腐好的物料挤成直径2mm条状，经干燥、焙烧后得分子筛-多元氧化物复合整体挤出式脱硝催化剂。样品于BPS100CL恒温恒湿箱中干燥，条件为：30℃湿度80％干燥3h，40℃湿度70％干燥3h，50℃湿度60％干燥3h，60℃湿度50％干燥1h，70℃湿度40％干燥1h，80℃湿度35％干燥1h，然后于100℃烘箱干燥8h。最后于马弗炉中550℃焙烧4h，马弗炉升温速率为1℃/min。将焙烧后样品剪切成3-5mm柱状颗粒用于活性测试。
条状催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为20ml，反应空速为15000h-1，在250℃、270℃、300℃、320℃、 350℃、370℃、400℃和420℃八个温度条件下，条状催化剂还原氮氧化物的转化率见表一。
关于实施例3，需要说明的是步骤(1)中铜和铁的摩尔比可以在(0.05-1):(0.05-1)范围内任意调控，当摩尔比为1:0.05时，所得催化剂在250-350℃温度段具有较好的脱硝活性；当摩尔比为0.05:1时，所得催化剂在350ˉ420℃温度段具有较好的脱硝活性，对于本领域的技术人员来说所熟知的是铁的引入可以拓展分子筛基脱硝催化剂的温度窗口，因此可以根据最终整体挤出式催化剂的实际应用情况来调整铜和铁的摩尔比。
本实施例中多元氧化物组成Mn、Ce、Si、Ti、Zr、Al摩尔比为0.3:0.7:1.8:0.3:0.5:0.2，Mn和Ce的摩尔比可以在(0.05-0.95):(0.05-0.95)范围内任意调控，Mn主要用于提高催化剂的低温段脱硝活性，Ce的加入在提高催化剂脱硝活性的同时还可以增加催化剂的抗硫性能；Si、Ti、Zr、Al主要在催化剂中起载体作用，用于调控分子筛-多元氧化物复合催化剂表面酸性，硅源中硅的原子摩尔份数的优选范围为Mn、Ce、Ti、Zr、Al的总摩尔份数±0.2份，Ti、Zr、Al的原子摩尔比可以在(0.05-0.5):(0.05-0.5)：(0.05-0.5)范围内任意调控，Ti、Zr、Al的添加对整体挤出式催化剂的脱硝性能均具有有益作用，且在此摩尔比范围内均可以实现本发明的目的。
实施例4
(1)将3.1g硝酸铁(Fe(NO3)3·9H2O)、0.8g乙酸铈(Ce(NO3)3·6H2O)加入到200.0g去离子水中，搅拌至完全溶解后，再加入20.0g SSZ-16分子筛(SiO2与Al2O3摩尔比为10)，然后在70℃恒温水浴中搅拌3.5h，完成后加入10.0g Tween60，采用JRJ300-S型数显剪切乳化搅拌机搅拌20min。其中混合溶液中铁和铈的质量为分子筛质量的4.0％，铁和铈的摩尔比为1:0.3。
(2)将11.4g铝溶胶(Al2O3：20％)加入到166.1g去离子水中，搅拌 均匀后加入17.8g氯化锰(MnCl2·4H2O)、4.6g氯化镁(MgCl2·6H2O)、1.5g氯化钙(CaCl2)，搅拌至完全溶解(溶质质量分数为13％)，记为溶液A。将12.5g固体硅酸钠(SiO2含量为77.8％，Na2O含量为22.2％，模数3.4-3.6)加入到166.1g去离子水中(溶质质量分数为7％)，搅拌至完全溶解，记为溶液B。在搅拌条件下，将溶液A滴加到溶液B中，并用10％Na2CO3溶液调整体系pH至8-8.5后，加入2.4g碳纳米管(添加量为氧化物总质量的12％)，然后在70℃恒温水浴中老化反应4h。
(3)将步骤(2)中的浆料过滤、水洗至滤液电导率小于500μs/cm。然后将所得滤饼加入到步骤一所得分子筛浆料中，于室温下搅拌混合3h。然后转移至旋转蒸发仪中，设置水浴温度为85℃，在真空度-0.85～-0.95Mpa下，蒸去物料中的大部分水，至物料呈粘稠状。所得产物于150℃干燥12h，然后于马弗炉中350℃焙烧6h，马弗炉升温速率为1℃/min。制得本发明的分子筛-多元氧化物复合脱硝催化剂活性组分。
本实施例多元氧化物中Mn、Si、Al、Mg、Ca摩尔比为1:1.8:0.5:0.25:0.15，多元氧化物与分子筛质量比为1:1。
(4)将步骤(3)中的活性组分用RT-04SF型高速粉碎机粉碎、筛分至粒度小于45μm(325目)。取10.0g粉碎后的活性组分、70.0g钛硅粉、15.0g蒙脱土、0.8g氨基羧甲基纤维素、1.3g聚氧化乙烯、5.0g玻璃纤维、0.7g炭黑，用RT-04SF型高速粉碎机混合均匀。将1.0g甘油加入到58.7g去离子水中搅拌均匀后加入上述混好的物料中，然后将物料捏合成均匀的泥团，放于自封袋中密封陈腐17h。
(5)用TBL-2型催化剂挤出机将步骤(4)中陈腐好的物料挤成直径2mm条状，经干燥、焙烧后得分子筛-多元氧化物复合整体挤出式脱硝催化剂。样品于BPS100CL恒温恒湿箱中干燥，条件为：30℃湿度80％干燥5h，40℃湿度70％干燥3h，50℃湿度60％干燥3h，60℃湿度50％干燥1h，70℃湿度40％ 干燥1h，80℃湿度35％干燥1h，然后于100℃烘箱干燥8h。最后于马弗炉中550℃焙烧4h，马弗炉升温速率为1℃/min。将焙烧后样品剪切成3-5mm柱状颗粒用于活性测试。
条状催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为20ml，反应空速为15000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，条状催化剂还原氮氧化物的转化率见表一。
关于实施例4，需要说明的是多元氧化物中Mn、Si、Al、Mg、Ca原子摩尔比为1:1.8:0.5:0.25:0.15，本实施例在步骤(2)酸性前驱物溶液中进一步引入Mg、Ca等碱土金属盐作为多元氧化物活性助剂，两种助剂的原子摩尔比可以在(0.05-0.45)：(0.05-0.45)范围内任意调控，且总原子摩尔份数为0.1-0.5份，这些助剂的添加主要用于提高最终整体挤出式脱硝催化剂的抗硫性能，活性助剂的加入丰富了本发明的技术方案，使本发明更容易实现本发明的技术目的。
实施例5
(1)将1.6g乙酸铈(Ce(CH3COO)3)加入到180.0g去离子水中，搅拌至完全溶解后，再加入20.0g SAPO-34分子筛(P2O5含量47.9％，Al2O3含量38.0％，SiO2含量14.1％)，然后在75℃恒温水浴中搅拌3h，完成后加入4.5g P123，采用JRJ300-S型数显剪切乳化搅拌机搅拌10min。其中混合溶液中铈的质量为分子筛质量的3.5％。
(2)将12.4g锆溶胶(ZrO2含量15％)加入到280.2g去离子水中，然后加入5.5g硝酸镍(Ni(NO3)2·6H2O)、5.5g硝酸钴(Co(NO3)2·6H2O)、2.2g氯化铟(InCl3·4H2O)、2.6g四氯化锡(SnCl4·5H2O)、0.9g氯化镧(LaCl3)，搅拌至完全溶解(溶质质量分数为6％)，记为溶液A。将15.2g液体硅酸钠 (Na2O：11.0％，SiO2：29.7％，模数：2.6-2.9)加入到62.1g去离子水中(溶质质量分数为8％)，搅拌混合均匀，记为溶液B。在搅拌条件下，将溶液A和溶液B同时滴加到同一容器中，并用5％的NaOH溶液调整体系pH至8-8.5后，加入2.2g石墨(添加量为氧化物总质量的18％)，然后在60℃恒温水浴中老化反应5h。
(3)将步骤(2)中的浆料过滤、水洗至滤液电导率小于500μs/cm。然后将所得滤饼加入到步骤一所得分子筛浆料中，于室温下搅拌混合2h。然后转移至旋转蒸发仪中，设置水浴温度为80℃，在真空度-0.85～-0.95Mpa下，蒸去物料中的大部分水，至物料呈粘稠状。所得产物于120℃干燥20h，然后于马弗炉中400℃焙烧4h，马弗炉升温速率为1℃/min。制得本发明的分子筛-多元氧化物复合脱硝催化剂活性组分。
本实施例多元氧化物中Ni、Co、Si、Zr、In、Sn、La摩尔比为0.5:0.5:2:0.4:0.2:0.2:0.1，多元氧化物与分子筛质量比为0.6:1。
(4)将步骤(3)中的活性组分用RT-04SF型高速粉碎机粉碎、筛分至粒度小于45μm(325目)。取30.0g粉碎后的活性组分、56.0g钛钨硅粉、10.0g高岭土、1.5g氨基羧甲基纤维素、0.9g聚氧化乙烯、4.0g陶瓷纤维、0.6g活性炭，用RT-04SF型高速粉碎机混合均匀。将1.2g乳酸加入到60.0g去离子水中搅拌均匀后加入上述混好的物料中，然后将物料捏合成均匀的泥团，放于自封袋中密封陈腐18h。
(5)用TBL-2型催化剂挤出机将步骤(4)中陈腐好的物料挤成直径2mm条状，经干燥、焙烧后得分子筛-多元氧化物复合整体挤出式脱硝催化剂。样品于BPS100CL恒温恒湿箱中干燥，条件为：30℃湿度80％干燥6h，40℃湿度70％干燥6h，50℃湿度60％干燥3h，60℃湿度50％干燥1h，70℃湿度40％干燥1h，80℃湿度35％干燥1h，然后于100℃烘箱干燥8h。最后于马弗炉中650℃焙烧2h，马弗炉升温速率为1℃/min。将焙烧后样品剪切成3-5mm柱 状颗粒用于活性测试。
条状催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为20ml，反应空速为15000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，条状催化剂还原氮氧化物的转化率见表一。
关于实施例5，需要说明的是多元氧化物中Ni、Co、Si、Zr、In、Sn、La原子摩尔比为0.5:0.5:2:0.4:0.2:0.2:0.1，本实施例在步骤(2)酸性前驱物溶液中进一步引入In、Sn、La等金属盐做为多元氧化物活性助剂，三种助剂的原子摩尔比可以在(0.05-0.45)：(0.05-0.45)：(0.05-0.45)范围内任意调控，且总原子摩尔份数为0.15-0.5份，这些助剂的添加主要用于提高最终整体挤出式脱硝催化剂的抗硫性能，这些助剂的加入丰富了本发明的技术方案，使本发明更容易实现本发明的技术目的。
实施例6
与实施例5相比，不同之处在于步骤(4)所用分子筛、离子交换金属以及负载量，步骤(2)所用硅源为固体硅酸钠、锆源为硝酸氧锆。具体如下：
(1)将2.6g乙酸锰(Mn(CH3COO)2·4H2O)加入到180.0g去离子水中，搅拌至完全溶解后，再加入18.2g ZSM-5分子筛(SiO2与Al2O3摩尔比为30)和1.8g SAPO-34分子筛(P2O5含量48.7％，Al2O3含量42.6％，SiO2含量8.7％)，然后在75℃恒温水浴中搅拌3h，完成后加入4.5g P123，采用JRJ300-S型数显剪切乳化搅拌机搅拌10min。其中锰溶液中锰的质量为分子筛质量的2.8％。
(2)将4.0g硝酸氧锆(ZrO(NO3)2·2H2O)加入到324.3g去离子水中，然后加入5.5g硝酸镍(Ni(NO3)2·6H2O)、5.5g硝酸钴(Co(NO3)2·6H2O)、2.2g 氯化铟(InCl3·4H2O)、2.6g四氯化锡(SnCl4·5H2O)、0.9g氯化镧(LaCl3)，搅拌至完全溶解(溶质质量分数为6％)，记为溶液A。将6.5g固体硅酸钠(Na2O：29.9％，SiO2：70.1％，模数：2.2-2.5)加入到74.8g去离子水中(溶质质量分数为8％)，搅拌混合均匀，记为溶液B。在搅拌条件下，将溶液A和溶液B同时滴加到同一容器中，并用5％的NaOH溶液调整体系pH至8-8.5后，加入2.2g石墨(添加量为氧化物总质量的18％)，然后在60℃恒温水浴中老化反应5h。
条状催化剂还原氮氧化物的转化率见表一。
关于实施例6，需要说明的是所述ZSM-5和SAPO-34两种分子筛的质量比为1:0.1，其质量比可以在(0.1-1):(0.1-1)范围内任意调控，均可以实现本发明的技术目的。对于本领域的技术人员来说所熟知的是SAPO-34具有更好的水热稳定性，因此可以根据最终整体挤出式催化剂的实际应用情况来调整两种分子筛的质量比。
实施例7
(1)将31.9g硝酸锰(Mn(NO3)2，50％溶液)，加入到1440.0g去离子水中，搅拌混合均匀后，再加入240.0g SSZ-39分子筛(SiO2与Al2O3摩尔比为20)，然后在55℃恒温水浴中搅拌5h，完成后加入72.0g Tween20，采用JRJ300-S型数显剪切乳化搅拌机搅拌30min。其中锰溶液中锰的质量为分子筛质量的2.0％。
(2)将411.9g硫酸铈(Ce(SO4)2·4H2O)、67.9g硫酸铝(Al2(SO4)3·18H2O)、140.8g偏钨酸铵(WO3含量≥84％)加入到5585.4g去离子水中(溶质质量分数为10％)，搅拌至完全溶解，记为溶液A。将203.9g铵型溶胶(SiO2含量为30％)加入到407.8g去离子水中(溶质质量分数为10％)，搅拌至完全溶解，记为溶液B。在搅拌条件下，将溶液A和溶液B同时滴加到同一容器中，并用20％的NH4HCO3溶液调整体系pH至8-8.5后，加入108.0g活性炭(添加 量为氧化物总质量的30％)，然后在80℃恒温水浴中老化反应1h。
(3)将步骤(2)中的浆料过滤、水洗至滤液电导率小于500μs/cm。然后将所得滤饼加入到步骤一所得分子筛浆料中，于室温下搅拌混合1h。然后转移至旋转蒸发仪中，设置水浴温度为85℃，在真空度-0.85～-0.95Mpa下，蒸去物料中的大部分水，至物料呈粘稠状。所得产物于150℃干燥15h，然后于马弗炉中350℃焙烧6h，马弗炉升温速率为1℃/min。制得本发明的分子筛-多元氧化物复合脱硝催化剂活性组分。
本实施例多元氧化物中Ce、Al、Si、W摩尔比为1:0.1:1:0.5，多元氧化物与分子筛质量比为1.5:1。
(4)将步骤(3)中的活性组分用RT-04SF型高速粉碎机粉碎、筛分至粒度小于45μm(325目)。取480.0g粉碎后的活性组分、1272.0g钛硅粉、480.0g蒙脱土、26.4g氨基羧甲基纤维素、57.6g聚氧化乙烯、19.2g炭黑和4.8g硬脂酸，用QLJ-10L型强力混料机混合30min。然后将48.0g乳酸、1600.0g去离子水搅拌均匀后加入物料中，混合搅拌10min后加入12.0g碳纤维、156.0g陶瓷纤维和80.0g去离子水，混合至纤维完全打碎，物料变成均匀的泥团(泥团最终混炼至含水率为34-35％)，然后将泥团放于自封袋中密封陈腐24h。
(5)取200g步骤(4)中陈腐好的物料，并将其均匀压覆于不锈钢网网板上，压覆厚度为1mm，然后将其剪裁成长宽为10cm×3cm的形状，经干燥、焙烧后得分子筛-多元氧化物复合整体挤出式脱硝催化剂。样品于BPS100CL恒温恒湿箱中干燥，条件为：30℃湿度80％干燥18h，40℃湿度70％干燥18h，50℃湿度60％干燥12h，60℃湿度50％干燥12h，70℃湿度40％干燥6h，80℃湿度35％干燥6h，然后于100℃烘箱干燥8h。最后于马弗炉中600℃焙烧3h，马弗炉升温速率为1℃/min。取5块焙烧后的平板样品等距离放置于板式催化剂测试模具中进行活性测试。
(6)用TLJ-40型真空混炼挤出机将步骤(4)中陈腐好的物料挤成3cm×3cm(4×4孔)蜂窝状催化剂，经干燥、焙烧后得分子筛-多元氧化物复合整体挤出式脱硝催化剂。干燥条件与步骤(5)相同。将焙烧后的样品长度切至10cm用于活性测试。
平板式或蜂窝式催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为90ml，反应空速为6000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，蜂窝式催化剂还原氮氧化物的转化率见表二。
实施例8
与实施例7相比，不同之处在于步骤(1)所用分子筛、离子交换金属以及负载量，步骤(2)所用硅源为固体硅酸钾钠。具体如下：
(1)将25.2g硝酸铜(Cu(NO3)2·3H2O)，加入到1440.0g去离子水中，搅拌混合均匀后，再加入240.0g SSZ-39分子筛(SiO2与Al2O3摩尔比为15)，然后在55℃恒温水浴中搅拌5h，完成后加入72.0g Tween20，采用JRJ300-S型数显剪切乳化搅拌机搅拌30min。其中铜溶液中铜的质量为分子筛质量的2.7％。
(2)将411.9g硫酸铈(Ce(SO4)2·4H2O)、67.9g硫酸铝(Al2(SO4)3·18H2O)、140.8g偏钨酸铵(WO3含量≥84％)加入到5585.4g去离子水中(溶质质量分数为10％)，搅拌至完全溶解，记为溶液A。将92.7g固体硅酸钾钠(SiO2含量为66.0％，Na2O含量为11.5％，K2O含量为22.5％，模数为2.5-2.7)加入到834.3g去离子水中(溶质质量分数为10％)，搅拌至完全溶解，记为溶液B。在搅拌条件下，将溶液A和溶液B同时滴加到同一容器中，并用20％的NH4HCO3溶液调整体系pH至8-8.5后，加入108.0g活性炭(添加量为氧化物总质量的30％)，然后在80℃恒温水浴中老化反应1h。
平板式或蜂窝式催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为90ml，反应空速为6000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，蜂窝式催化剂还原氮氧化物的转化率见表二。
实施例9
(1)将17.5g乙酸铜(Cu(CH3COO)2·H2O)、6.9g乙酸铈(Ce(CH3COO)3)，加入到2400.0g去离子水中，搅拌至完全溶解后，再加入300.0g SSZ-13分子筛(SiO2与Al2O3摩尔比为25)，然后在60℃恒温水浴中搅拌4h，完成后加入72.0g Tritonx-100，采用JRJ300-S型数显剪切乳化搅拌机搅拌40min。其中混合溶液中铜和铈的质量为分子筛质量的2.8％，铜和铈的摩尔比为1:0.25。
(2)将344.0g硝酸铁(Fe(NO3)3·9H2O)、27.2g硫酸氧钛(TiOSO4)、159.6g硝酸铝(Al(NO3)3·9H2O)、28.1g钨酸钠(Na2WO4·2H2O)加入到6427.4g去离子水中(溶质质量分数为8％)，搅拌至完全溶解，记为溶液A。将321.6g液体硅酸钾(K2O含量为18.0％，SiO2含量为27.0％，模数2.2-2.5)加入到884.4g去离子水中(溶质质量分数为12％)，搅拌至完全溶解，记为溶液B。在搅拌条件下，将溶液B滴加到溶液A中，并用15％的KOH溶液调整体系pH至8-8.5后，加入31.5g炭黑(添加量为氧化物总质量的15％)，然后在80℃恒温水浴中老化反应2h。
(3)将步骤(2)中的浆料过滤、水洗至滤液电导率小于500μs/cm。然后将所得滤饼加入到步骤一所得分子筛浆料中，于室温下搅拌混合3h。然后转移至旋转蒸发仪中，设置水浴温度为80℃，在真空度-0.85～-0.95Mpa下，蒸去物料中的大部分水，至物料呈粘稠状。所得产物于120℃干燥24h，然后于马弗炉中400℃焙烧5h，马弗炉升温速率为1℃/min。制得本发明的 分子筛-多元氧化物复合脱硝催化剂活性组分。
本实施例多元氧化物中Fe、Si、Ti、Al、W摩尔比为1:1.7:0.2:0.5:0.1，多元氧化物与分子筛质量比为0.7:1。
(4)将步骤(3)中的活性组分用RT-04SF型高速粉碎机粉碎、筛分至粒度小于45μm(325目)。取360.0g粉碎后的活性组分、1128.0g钛钨硅粉、720.0g膨润土、43.2g氨基羧甲基纤维素、48.0g聚氧化乙烯、3.6g硬脂酸，用QLJ-10L型强力混料机混合30min。然后将56.4g乳酸与1360.0g去离子水搅拌混合均匀后加入混料机中，再混合搅拌10min，然后再将搅拌均匀的24.0g木浆与240.0g去离子水加入混料机中，混合搅拌10min后加入168.0g玻璃纤维、24.0g碳纤维和80.0g去离子水，混合至纤维完全打碎，物料变成均匀的泥团(泥团最终混炼至含水率为34-35％)，放于自封袋中密封陈腐30h。
(5)取200g步骤(4)中陈腐好的物料，并将其均匀压覆于不锈钢网网板上，压覆厚度为1mm，然后将其剪裁成长宽为10cm×3cm的形状，经干燥、焙烧后得分子筛-多元氧化物复合整体挤出式脱硝催化剂。样品于BPS100CL恒温恒湿箱中干燥，条件为：30℃湿度80％干燥18h，40℃湿度70％干燥18h，50℃湿度60％干燥12h，60℃湿度50％干燥12h，70℃湿度40％干燥6h，80℃湿度35％干燥6h，然后于100℃烘箱干燥8h。最后于马弗炉中600℃焙烧3h，马弗炉升温速率为1℃/min。取5块焙烧后的平板样品等距离放置于板式催化剂测试模具中进行活性测试。
(6)用TLJ-40型真空混炼挤出机将步骤(4)中陈腐好的物料挤成3cm×3cm(4×4孔)蜂窝状催化剂，经干燥、焙烧后得分子筛-多元氧化物复合整体挤出式脱硝催化剂。干燥条件与步骤(5)相同。将焙烧后的样品长度切至10cm用于活性测试。
平板式或蜂窝式催化剂的活性测试条件为：500ppm的一氧化氮，500ppm 的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为90ml，反应空速为6000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，蜂窝式催化剂还原氮氧化物的转化率见表二。
实施例10
与实施例9相比，不同之处在于步骤一所用分子筛、离子交换金属以及负载量，步骤(2)所用硅源为固体硅酸钾。具体如下：
(1)将19.8g乙酸铜(Cu(CH3COO)2·H2O)、5.2g乙酸铈(Ce(CH3COO)3)，加入到2400.0g去离子水中，搅拌至完全溶解后，再加入200.0g SSZ-13分子筛(SiO2与Al2O3摩尔比为17)和100.0g Zeolite Beta分子筛(SiO2/Al2O3为40)，然后在60℃恒温水浴中搅拌4h，完成后加入72.0g Tritonx-100，采用JRJ300-S型数显剪切乳化搅拌机搅拌40min。其中混合溶液中铜和铈的质量为分子筛质量的2.8％，铜和铈的摩尔比为1:0.17。
(2)将344.0g硝酸铁(Fe(NO3)3·9H2O)、27.2g硫酸氧钛(TiOSO4)、159.6g硝酸铝(Al(NO3)3·9H2O)、28.1g钨酸钠(Na2WO4·2H2O)加入到6427.4g去离子水中(溶质质量分数为8％)，搅拌至完全溶解，记为溶液A。将128.1g固体硅酸钾(K2O含量为32.2％，SiO2含量为67.8％，模数为3.1-3.4)加入到939.4g去离子水中(溶质质量分数为12％)，搅拌至完全溶解，记为溶液B。在搅拌条件下，将溶液B滴加到溶液A中，并用15％的KOH溶液调整体系pH至8-8.5后，加入31.5g炭黑(添加量为氧化物总质量的15％)，然后在80℃恒温水浴中老化反应2h。
平板式或蜂窝式催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为90ml，反应空速为6000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，蜂窝式催化剂还原氮氧化物 的转化率见表二。
蜂窝式催化剂的抗水抗硫性能测试条件为：500ppm的一氧化氮，500ppm的氨气，1500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为90ml，反应空速为6000h-1，稳定在300℃的反应条件下，测试蜂窝式催化剂的脱硝效率随时间的变化。如图1所示，该催化剂在10％水蒸气和1500ppm二氧化硫存在的情况下，在48h的测试时间内氮氧化物的转化率能够保持在90％以上，表明该催化剂具有很强的抗水耐硫性能。
实施例11
(1)将61.4g硫酸亚铁(FeSO4·7H2O)，加入到2800.0g去离子水中，搅拌至完全溶解后，再加入400.0g Beta分子筛(SiO2与Al2O3摩尔比为28)，然后在60℃恒温水浴中搅拌4.5h，完成后加入84.0g Brij78，采用JRJ300-S型数显剪切乳化搅拌机搅拌40min。其中铁溶液中铁的质量为分子筛质量的3.0％。
(2)将392.9g硫酸铜(CuSO4·5H2O)、75.4g硫酸氧钛(TiOSO4)、41.6g七钼酸铵((NH4)6Mo7O24·4H2O)加入到6774.4g去离子水中(溶质质量分数为7％)，搅拌至完全溶解，记为溶液A。将471.5g液体硅酸钾钠(SiO2含量为26.0％，Na2O含量为6.5％，K2O含量为6.3％，模数为2.5-2.7)加入到748.1g去离子水中(溶质质量分数为15％)，搅拌混合均匀，记为溶液B。在搅拌条件下，将溶液B滴加到溶液A中，并用15％的Na2CO3溶液调整体系pH至8-8.5后，加入80.0g石墨(添加量为氧化物总质量的25％)，然后在70℃恒温水浴中老化反应3h。
(3)将步骤(2)中的浆料过滤、水洗至滤液电导率小于500μs/cm。然后将所得滤饼加入到步骤一所得分子筛浆料中，于室温下搅拌混合2h。然后转移至旋转蒸发仪中，设置水浴温度为80℃，在真空度-0.85～-0.95Mpa下，蒸去物料中的大部分水，至物料呈粘稠状。所得产物于140℃干燥18h， 然后于马弗炉中450℃焙烧3h，马弗炉升温速率为1℃/min。制得本发明的分子筛-多元氧化物复合脱硝催化剂活性组分。
本实施例多元氧化物中Cu、Si、Ti、Mo摩尔比为1:1.3:0.3:0.15，多元氧化物与分子筛质量比为0.8:1。
(4)将步骤(3)中的活性组分用RT-04SF型高速粉碎机粉碎、筛分至粒度小于45μm(325目)。取600.0g粉碎后的活性组分、1320.0g钛白粉、336.0g凹凸棒粘土、43.2g羟丙基甲基纤维素、24.0g聚氧化乙烯、14.4g田菁粉和7.2g硬脂酸，用QLJ-10L型强力混料机混合30min。将36.0g甘油与1520.0g去离子水搅拌均匀后加入物料中，混合搅拌10min后加入144.0g陶瓷纤维和80.0g去离子水，混合至纤维完全打碎，物料变成均匀的泥团(泥团最终混炼至含水率为34-35％)，放于自封袋中密封陈腐36h。
(5)用TLJ-40型真空混炼机将步骤(4)中陈腐好的物料挤成3cm×3cm(4×4孔)蜂窝式催化剂，经干燥、焙烧后得分子筛-多元氧化物复合整体挤出式脱硝催化剂。样品于BPS100CL恒温恒湿箱中干燥，条件为：30℃湿度80％干燥18h，40℃湿度70％干燥12h，50℃湿度60％干燥12h，60℃湿度50％干燥12h，70℃湿度40％干燥6h，80℃湿度35％干燥6h，然后于100℃烘箱干燥8h。最后于马弗炉中550℃焙烧4h，马弗炉升温速率为1℃/min。将焙烧后的样品长度切到10cm用于活性测试。
蜂窝式催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为90ml，反应空速为6000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，蜂窝式催化剂还原氮氧化物的转化率见表二。
实施例12
与实施例11相比，不同之处在于步骤(1)所用分子筛、离子交换金属。 具体如下：
(1)将35.0g乙酸亚铁(Fe(CH3COO)2)、4.92g乙酸锰(Mn(CH3COO)2·4H2O)加入到2800.0g去离子水中，搅拌至完全溶解后，再加入400.0g Beta分子筛(SiO2与Al2O3摩尔比为25)，然后在60℃恒温水浴中搅拌4.5h，完成后加入84.0g Brij78，采用JRJ300-S型数显剪切乳化搅拌机搅拌40min。其中铁和锰溶液中铁和锰的质量为分子筛质量的3.0％，铁和锰的摩尔比为1:0.1。
蜂窝式催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为90ml，反应空速为6000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，蜂窝式催化剂还原氮氧化物的转化率见表二。
实施例13
与实施例11相比，不同之处在于步骤(2)所选多元氧化物前体包含铈源。
(2)将288.3g硫酸铜(CuSO4·5H2O)、404.0g硫酸铈(Ce(SO4)2·4H2O)、69.2g硫酸氧钛(TiOSO4)、38.2g七钼酸铵((NH4)6Mo7O24·4H2O)加入到10624.6g去离子水中(溶质质量分数为7％)，搅拌至完全溶解，记为溶液A。将432.4g液体硅酸钾钠(SiO2含量为26.0％，Na2O含量为6.5％，K2O含量为6.3％，模数为2.5-2.7)加入到686.1g去离子水中(溶质质量分数为15％)，搅拌混合均匀，记为溶液B。在搅拌条件下，将溶液B滴加到溶液A中，并用15％的Na2CO3溶液调整体系pH至8-8.5后，加入80.0g石墨(添加量为氧化物总质量的25％)，然后在70℃恒温水浴中老化反应3h。
本实施例多元氧化物中Cu、Ce、Si、Ti、Mo摩尔比为0.8:0.2:1.3:0.3:0.15，多元氧化物与分子筛质量比为0.8:1。
蜂窝式催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为90ml，反应空速为6000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，蜂窝式催化剂还原氮氧化物的转化率见表二。
实施例14
(1)将36.7g氯化铜(CuCl2·2H2O)、5.3g氯化锰(MnCl2·4H2O)加入到3600.0g去离子水中，搅拌至完全溶解后，再加入200.0g SSZ-39分子筛(SiO2与Al2O3摩尔比为25)、200.0g Zeolite Y分子筛(SiO2与Al2O3摩尔比为12)，然后在70℃恒温水浴中搅拌3h，完成后加入180.0g Span40，采用JRJ300-S型数显剪切乳化搅拌机搅拌30min。其中混合溶液中铜、锰的质量为分子筛质量的3.8％，铜、锰的摩尔比为1:0.13。
(2)将72.6g铝溶胶(Al2O3含量20％)、379.4g钛溶胶(TiO2含量15％)加入到3866.2g去离子水中，然后加入574.7g硫酸铈(Ce(SO4)2·4H2O)、103.3g钼酸钠(Na2MoO4·2H2O)，搅拌混合均匀(溶质质量分数为15％)，记为溶液A。将341.4g钠型硅溶胶(固含量30％)，加入到1707.0g去离子水中(溶质质量分数为5％)，搅拌混合均匀，记为溶液B。在搅拌条件下，将溶液A滴加到溶液B中，并用30％的碳酸铵溶液调整体系pH至8-8.5后，加入48.0g活性炭(添加量为氧化物总质量的10％)，然后在80℃恒温水浴中老化反应3h。
(3)将步骤(2)中的浆料过滤、水洗至滤液电导率小于500μs/cm。然后将所得滤饼加入到步骤一所得分子筛浆料中，于室温下搅拌混合1h。然后转移至旋转蒸发仪中，设置水浴温度为75℃，在真空度-0.85～-0.95Mpa下，蒸去物料中的大部分水，至物料呈粘稠状。所得产物于130℃干燥20h，然后于马弗炉中350℃焙烧5h，马弗炉升温速率为1℃/min。制得本发明的 分子筛-多元氧化物复合脱硝催化剂活性组分。
本实施例多元氧化物中Ce、Al、Ti、Si、Mo摩尔比为1:0.2:0.5:1.2:0.3，多元氧化物与分子筛质量比为1.2:1。
(4)将步骤(3)中的活性组分用RT-04SF型高速粉碎机粉碎、筛分至粒度小于45μm(325目)。取840.0g粉碎后的活性组分、1200.0g钛钨粉、240.0g高岭土、28.8g羟丙基甲基纤维素、48.0g聚氧化乙烯、16.8g活性炭和6.0g硬脂酸，用QLJ-10L型强力混料机混合30min。将42.0g甘油与1520.0g去离子水搅拌均匀后加入物料中，混合搅拌10min后加入120.0g玻璃纤维和80.0g去离子水，混合至纤维完全打碎，物料变成均匀的泥团(泥团最终混炼至含水率为34-35％)，放于自封袋中密封陈腐28h。
(5)用TLJ-40型真空混炼机将步骤四中陈腐好的物料挤成3cm×3cm(4×4孔)蜂窝式催化剂，经干燥、焙烧后得分子筛-多元氧化物复合整体挤出式脱硝催化剂。样品于BPS100CL恒温恒湿箱中干燥，条件为：30℃湿度80％干燥16h，40℃湿度70％干燥12h，50℃湿度60％干燥12h，60℃湿度50％干燥12h，70℃湿度40％干燥6h，80℃湿度35％干燥6h，然后于100℃烘箱干燥8h。最后于马弗炉中550℃焙烧4h，马弗炉升温速率为1℃/min。然后将焙烧后的样品切到10cm用于活性测试。
蜂窝式催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为90ml，反应空速为6000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，蜂窝式催化剂还原氮氧化物的转化率见表二。
实施例15
与实施例14相比，不同之处在于步骤(1)所用分子筛、离子交换金属及比例。
(1)将24.1g氯化锰(MnCl2·4H2O)、22.7g氯化铈(CeCl3·7H2O)，加入到3600.0g去离子水中，搅拌至完全溶解后，再加入300.0g SSZ-16分子筛(SiO2/Al2O3为15)、100.0g Zeolite Y分子筛(SiO2与Al2O3摩尔比为10)，然后在70℃恒温水浴中搅拌3h，完成后加入180.0g Span40，采用JRJ300-S型数显剪切乳化搅拌机搅拌30min。其中混合溶液中锰、铈的质量为分子筛质量的3.8％，锰、铈的摩尔比为1:0.5。
蜂窝式催化剂的活性测试条件为：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，催化剂的装载量为90ml，反应空速为6000h-1，在250℃、270℃、300℃、320℃、350℃、370℃、400℃和420℃八个温度条件下，蜂窝式催化剂还原氮氧化物的转化率见表二。
表一条状催化剂还原氮氧化物的转化率
Figure PCTCN2016112491-appb-000001
表二蜂窝式催化剂还原氮氧化物的转化率
Figure PCTCN2016112491-appb-000002
由表一和表二数据可见，本发明制备的分子筛-多元氧化物复合整体挤出式脱硝催化剂在水和二氧化硫存在情况下，250-420℃的温度范围内具有较高的氮氧化物转化率。
综上所述，与现有技术相比，通过本发明制备方法制备的分子筛-多元氧化物复合脱硝催化剂具有较好的抗水耐硫性能，是一种非钒基、环保型脱硝催化剂，可以应用于工业锅炉、电厂等固定源烟气脱硝。
最后需要说明的是，以上实施例仅用以说明本发明的技术方案而非限制，本领域的技术人员应当理解在本发明的启示下，可以在形式上和细节上对其做出各种各样的改变，而不偏离所附权利要求书所限定的本发明的精神 和范围，这些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。

Claims (10)

  1. 一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，其特征在于，包括如下步骤：
    (1)取锰、铁、钴、镍、铜、铈中的一种或两种的金属盐溶液，与分子筛混合，经离子交换反应后，再加入表面活性剂，同时进行剪切乳化分散处理，得到离子交换分子筛浆料；
    (2)选取锰、铁、钴、镍、铜、铈中的一种或两种的金属盐与铝源、钛源、锆源中的一种或几种的混合物配制成酸性前驱物溶液，选取碱性硅源配制成碱性前驱物溶液，再将上述酸性前驱物溶液和碱性前驱物溶液混合均匀后，得到混合溶液或浆料；
    (3)在步骤(2)得到的混合溶液或浆料中，加入碱性化合物溶液调整pH为碱性，然后再加入造孔剂，经老化反应、过滤、水洗，弃滤液，得到滤饼，即为多元氧化物前体；
    (4)在步骤(3)得到的多元氧化物前体中，加入步骤(1)得到的离子交换分子筛浆料，搅拌混合后，经真空脱水、干燥和高温焙烧，得到分子筛-多元氧化物复合脱硝催化剂活性组分；
    (5)将步骤(4)得到的复合脱硝催化剂活性组分粉碎、筛分后，与钛基载体、无机粘结剂、有机粘结剂、结构增强剂、成型造孔剂、润滑剂和水，经混料、捏合成泥团、陈腐、整体挤压成型、干燥、焙烧后，即得到整体挤出式脱硝催化剂。
  2. 根据权利要求1所述的一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，其特征在于，步骤(1)所述锰、铁、钴、镍、铜、铈的金属盐为可溶性金属乙酸盐、硝酸盐、硫酸盐、盐酸盐中的一种；所述锰、铁、钴、镍、铜、铈中的一种或两种的金属盐中金属的加入量为分子筛质量 的0.5-8％；所述分子筛的骨架拓扑学结构为AEI、AFX、BEA、CHA、DDR、ERI、FAU、FER、GIS、KFI、LEV、LTA、MEL、MFI、MOR、PAU、SAS或是它们的混合结构；所述金属盐溶液与分子筛的液固质量比为2-50:1；所述离子交换的温度为25-95℃，离子交换为时间为0.5-8h；所述表面活性剂为阳离子型表面活性剂、阴离子型表面活性剂或非离子型表面活性剂；所述表面活性剂的质量浓度为0.5-10％；所述剪切乳化分散处理时间为10-40min。
  3. 根据权利要求2所述的一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，其特征在于，所述分子筛为硅铝酸盐分子筛、硅铝磷酸盐分子筛或者磷酸铝盐分子筛；所述分子筛的类型为氢型分子筛、铵型分子筛、碱金属型分子筛或者碱土金属型分子筛中的一种。
  4. 根据权利要求3所述的一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，其特征在于，所述硅铝酸盐分子筛中SiO2与Al2O3摩尔比为5-100；所述硅铝磷酸盐分子筛中的硅质量分数为1-25％；所述分子筛的类型为氢型分子筛。
  5. 根据权利要求2所述的一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，其特征在于，所述分子筛为SAPO-18、SSZ-39、SAPO-56、SSZ-16、Zeolite Beta、SAPO-34、SSZ-13、SAPO-44、ZSM-58、ZSM-34、Zeolite X、Zeolite Y、SAPO-37、ZSM-35、ZeoliteP、SAPO-43、ZK-5、SAPO-35、Zeolite A、ZSM-11、ZSM-5、Zeolite Mordenite、ECR-18、SSZ-73中的一种或几种；所述阳离子型表面活性剂为季铵盐类；所述阴离子表面活性剂为羧酸、硫酸、磺酸或磷酸盐类；所述非离子表面活性剂为长链烷烃类环氧乙烯醚、长链苯酚类环氧乙烯醚或脱水山梨醇酯或聚环氧乙烷-聚环氧丙烷嵌段共聚物。
  6. 根据权利要求1所述的一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，其特征在于，步骤(2)所述酸性前驱物溶液和碱性前 驱物溶液的混合方式为将酸性前驱物溶液滴加到碱性前驱物溶液中混合、将碱性前驱物溶液滴加到酸性前驱物溶液中混合或者将酸性前驱物溶液和碱性前驱物溶液同时加入同一容器中混合；所述酸性前驱物溶液和碱性前驱物溶液的质量浓度为5-20％；所述锰、铁、钴、镍、铜、铈中的一种或两种的金属盐中金属的原子摩尔份数为1份，所述铝源、钛源、锆源以及碱性硅源中铝、钛、锆和硅的原子摩尔份数分别为0-0.5份、0-0.5份、0-0.5份和1-2份；所述酸性前驱物溶液还包括镁源、钙源、铟源、锡源、镧源、钨源、钼源的一种或两种或三种的金属盐；所述镁源、钙源、铟源、锡源、镧源、钨源、钼源中，镁、钙、铟、锡、镧、钨、钼的原子总摩尔份数为0.1-0.5份。
  7. 根据权利要求6所述的一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，其特征在于，所述铝源为铝溶胶、氯化铝、硫酸铝或者硝酸铝；所述钛源为钛溶胶、硫酸钛或者硫酸氧钛；所述锆源为锆溶胶、氧氯化锆、硫酸锆、硝酸锆或者硝酸氧锆；所述碱性硅源为碱性硅溶胶或可溶性硅酸盐；所述镁源为可溶性乙酸盐、硝酸盐、硫酸盐或者盐酸盐；所述钙源为可溶性乙酸盐、硝酸盐、硫酸盐或者盐酸盐；所述铟源为可溶性乙酸盐、硝酸盐、硫酸盐或者盐酸盐；所述锡源为可溶性乙酸盐、硝酸盐、硫酸盐或者盐酸盐；所述镧源为可溶性乙酸盐、硝酸盐、硫酸盐或者盐酸盐；所述钨源为钨酸钠或者钨酸铵；所述钼源为钼酸钠或者钼酸铵。
  8. 根据权利要求1所述的一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，其特征在于，步骤(3)所述碱性化合物为氢氧化钠、氢氧化钾、氨水、尿素、碳酸铵、碳酸氢铵、硫酸铵、硫酸氢铵、草酸铵、碳酸钠、碳酸氢钠、碳酸钾或者碳酸氢钾；所述碱性化合物溶液的质量浓度为5-30％；所述pH为7.5-9；所述造孔剂为活性炭、炭黑、纳米碳材料或者石墨；所述老化反应的温度为40-95℃，老化反应时间为0.5-12h；所述滤 液的电导率小于500μs/cm；所述多元氧化物前体中含有的氧化物的质量为基准计算得到的多元氧化物的总质量与步骤(1)中所述分子筛的质量比为0.5-1.5:1
  9. 根据权利要求1所述的一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，其特征在于，步骤(4)所述搅拌混合时间为0.5-3h；所述真空脱水的温度为75-85℃，真空度为-0.85-0.95Mpa；所述干燥的温度为100-150℃，干燥时间为12-24h；所述高温焙烧温度为350-450℃，焙烧时间为2-6h。
  10. 根据权利要求1所述的一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法，其特征在于，步骤(5)所述筛分的粒度小于45μm；所述钛基载体为钛白粉、钛硅粉、钛钨粉或者钛钨硅粉；所述无机粘结剂为凹凸棒粘土、膨润土、蒙脱土或者高岭土；所述有机粘结剂为氨基羧甲基纤维素、羟丙基甲基纤维素或者聚氧化乙烯；所述结构增强剂为玻璃纤维、碳纤维或者陶瓷纤维；所述成型造孔剂为田菁粉、木浆、活性炭或者炭黑；所述润滑剂为甘油、乳酸或者硬脂酸；所述复合脱硝催化剂活性组分、钛基载体、无机粘结剂、结构增强剂的重量比为(10-40):(40-70):(10-30):(3-8)；所述有机粘结剂、成型造孔剂、润滑剂和水的重量分别为上述复合脱硝催化剂活性组分、钛基载体、无机粘结剂、结构增强剂总重量的1.2-3.8％、0.4-1.0％、0.8-2.5％和51.5-66.7％；所述陈腐为泥团密封放置15-36h；所述催化剂整体挤压成型为为粒状、三叶草状、空心圆柱状、整体挤出蜂窝式、整体挤压板式中的一种；所述干燥的温度为35-80℃，干燥的湿度为80-35％，干燥的时间为20-80h；所述焙烧的温度为500-650℃，时间2-6h。
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