CN111921555B - NO decomposition denitration catalyst and preparation method and application thereof - Google Patents
NO decomposition denitration catalyst and preparation method and application thereof Download PDFInfo
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- 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
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a catalyst for NO decomposition denitration and a preparation method and application thereof, belonging to the technical field of waste gas denitration. The catalyst comprises an active component and a molecular sieve; the active component is at least one of iron, cobalt, nickel, manganese, platinum, rhodium, palladium, ruthenium, iridium, chromium and silver; the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-12, ZSM-35, SSZ-13, SSZ-23, SAPO-34, SAPO-35, AIPO-33 and Beta; the active component accounts for 0.02-10.00wt.% of the weight of the catalyst. The catalyst can provide guarantee for normal operation of ships under the IMO nitrate-limiting command in China, breaks monopoly of European and American high-end ship products, and promotes the development of China to the shipbuilding and strengthening country.
Description
Technical Field
The invention relates to a catalyst for NO decomposition denitration and a preparation method and application thereof, belonging to the technical field of waste gas denitration.
Background
Nitrogen Oxides (NO) x ) Is one of the main atmospheric pollutants seriously harming human health, and mainly comes from fixed sources (power plants, industrial boilers and the like) and mobile sources (ships, motor vehicles and the like). Wherein the fixed source employs ammonia selective catalytic reduction (NH 3 SCR) denitration technology is mature and has been successfully applied. Notably, ocean transportation assumes 90% of the total amount of trade transportation, and its rapid development causes marine exhaust NO x The emission is increased sharply, and the pollution is serious and severe. For this reason, international Maritime Organization (IMO) prescribes the implementation of NO in ship exhaust gas from 1 month 1 day in 2016 x The emission needs to reach the IMO Tier III standard. Forced performance of IMO convention has been irreversible, so experimental screening of dominant denitrification techniques for mobile source vessel denitrification has been urgent.
However, NH employed by the fixed source 3 The SCR denitration technology uses ammonia as a reducing agent, so that the consumption of the ammonia is large, potential safety hazards exist in transportation and storage, the ammonia is easy to produce secondary pollution, and the equipment is huge and the investment and the operation cost are high. Combines the actual working condition of ship exhaust gas and the limitation of the ship use space, and the existing NH 3 The SCR technique is not suitable for diesel exhaust denitration used by mobile sources such as ships.
Ship exhaust gas NO x In which 90-95% is NO, and compared with the existing denitration technology and combined with the actual working condition of the ship, the method directly catalyzes and decomposes NO into N 2 And O 2 The method has the outstanding advantages of no use of reducing agent, small equipment volume, simple process, good economy, no secondary pollution and the like, and is an ideal denitration way for ship waste gas. The NO decomposition reaction is thermodynamically feasible (2 NO- & gt N 2 +O 2 ，△ r G m = -86.6 KJ/mol), but reaction activation energy as high as 364KJ/mol results in kinetic limitation of the reaction, so developing a high-efficiency NO decomposition catalyst is the core of the denitration technology. Hitherto, NO decomposition catalysts have been reported mainly of noble metals, metal oxides, perovskite-type composite oxides and molecular sieves. Wherein, the first three types of catalysts are O generated by NO decomposition 2 Is easy to be adsorbed on the surface of the catalyst to generate oxygen inhibition", prevent NO from further decomposing, so that the catalyst is usually required to have higher activity under the condition of high temperature of 800-900 ℃ in NO decomposition reaction, and the temperature of the tail gas discharged by the ship is usually lower than 400 ℃, so that the noble metal, metal oxide and perovskite type composite oxide catalyst is not suitable for ship waste gas denitration. In contrast, molecular sieve catalysts generally have higher NO decomposition activity at low temperatures of 400-500 ℃.
At present, NO published patent report is made on the use of a molecular sieve catalyst to directly catalyze NO to decompose and denitrate. However, the following publications relate to the catalytic decomposition of NO to N using a molecular sieve catalyst 2 And O 2 . Since Iwamoto et al in 1986 discovered for the first time that Cu-ZSM-5 molecular sieves have NO decomposing activity, subsequent studies have been conducted primarily around Cu-ZSM-5 molecular sieve catalysts, with the focus of the preparation of Cu-ZSM-5 molecular sieve catalysts (mater.sci. -Poland,2016, 34, 177-184), copper precursors (j.chem.technol. Biotechnol,2019, 94, 3356-3366), promoter modification (catalyst.today, 2019, 327, 203-209; appl.catalyst, a: general,2013, 464-465, 61-67; adv.mater.res.,2010, 113-116,1735-1739; catalyst.today, 2007, 126, 284-289), molecular sieve types and properties (chem.rev.. 2016,116,3658-3721; catalyst.com., 2006,7, 705-708, 60; cat.67, B.: 60).
However, cu-ZSM-5 molecular sieves have SO resistance, although they have good low temperature activity 2 And O 2 A fatal defect of poor poisoning ability. In one aspect, SO 2 Molecules and O 2 The molecules and NO are subjected to competitive adsorption on the active site of the Cu-ZSM-5 molecular sieve catalyst, so that the adsorption of NO is inhibited, and the NO removal rate is further reduced. On the other hand, SO 2 The copper species of the Cu-ZSM-5 molecular sieve catalyst are easy to generate copper sulfate salt through chemical reaction, so that the Cu-ZSM-5 molecular sieve catalyst is completely poisoned and loses the activity of decomposing NO. To date, no published patent and literature report on SO 2 The NO-decomposing denitration molecular sieve catalyst is preferable in the atmosphere.
Disclosure of Invention
The present invention solves the above-mentioned problems by preparing a novel catalyst.
The invention provides a catalyst for NO decomposition and denitration, which comprises an active component and a molecular sieve; the active component is at least one of iron, cobalt, nickel, manganese, platinum, rhodium, palladium, ruthenium, iridium, chromium and silver; the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-12, ZSM-35, SSZ-13, SSZ-23, SAPO-34, SAPO-35, AIPO-33 and Beta; the active component accounts for 0.02-10.00wt.% of the weight of the catalyst.
The active component is preferably at least one of iron, cobalt and nickel.
The active component is preferably iron, cobalt, nickel or iron-nickel.
Preferably, the molecular sieve is ZSM-5, ZSM-11, SSZ-13, SAPO-34 or Beta.
The invention also aims to provide a preparation method of the catalyst, which comprises the following steps: mixing the baked molecular sieve with nitrate solution containing active components, stirring at 50-80deg.C for 1-3 hr, separating, washing the separated solid to neutrality, drying, and baking at 400-550deg.C for 0.5-3 hr in plasma atmosphere.
The plasma atmosphere is preferably air, N 2 Ar, he and H 2 At least one of them.
It is a further object of the present invention to provide a catalyst as defined above at high SO concentrations 2 And O 2 Application of the following denitration.
The application method of the invention is preferably as follows: SO (SO) 2 Is 300-800ppm, O 2 The concentration of (C) is 5-15vol%, the concentration of NO is 500-1500ppm, and the reaction temperature is 200-450 ℃.
The invention has the beneficial effects that:
the catalyst of the invention can directly decompose NO into N 2 And O 2 The method has the outstanding advantages of no secondary pollution, no use of reducing agent, good economy, simple process and the like, is an ideal denitration way, and is particularly suitable for denitration of tail gas of diesel engines used by mobile sources such as ships and the like.
The catalyst of the invention realizes the reaction of SO 2 Concentration of 500ppm, O 2 The NO removal rate is up to 45.5% in a complex atmosphere with the concentration of 10vol.% and the NO concentration of 1000ppm at the low temperature of 350 ℃; in addition, the catalyst of the invention also has SO removal function 2 Capacity, SO 2 The removal rate is 30%.
The catalyst can provide guarantee for normal operation of ships under the IMO nitrate-limiting command in China, breaks monopoly of European and American high-end ship products, and promotes the development of China to the shipbuilding and strengthening country.
Drawings
In the present invention of figure 1 of the drawings,
FIG. 1 shows NO removal rates of comparative examples 1 to 2 and examples 1 to 3.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The feed gas used in the following comparative examples and examples was simulated marine tail gas atmosphere, and the feed gas had a NO concentration of 1000-1200ppm and SO 2 The concentration is 450-500ppm, O 2 Concentration of 10vol%, N 2 For balancing the gas, the total flow of the raw material gas is 1.0-1.1L/min; the NO decomposition reactor is a continuous flow type fixed bed quartz reactor; the catalyst is filled in the reaction zone of the quartz reactor, the filling amount of the catalyst is 2g, the length of the corresponding reaction zone is 50-65mm, and the space velocity is 15000-20000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature is 300-550 ℃; the NO decomposition denitration effect of the different catalysts was detected and evaluated using a Ma Dugong external flue gas analyzer.
Comparative example 1
The NO decomposition reactor was not filled with a catalyst, and the effect of the reaction temperature on the denitration performance was examined, and the results are shown in table 1 and fig. 1.
Conclusion: under different reaction temperatures, the concentration change of NO is not obvious, which indicates that the purpose of removing NO can not be achieved by simply increasing the reaction temperature under the condition of NO participation of a catalyst.
Comparative example 2
A method for preparing a Cu-ZSM-5 catalyst, which comprises the following steps: mixing the roasted ZSM-5 molecular sieve with a copper nitrate solution, stirring at 70 ℃ for 2 hours, separating, washing the solid obtained by separation to be neutral, drying at 120 ℃ for 3 hours, and roasting at 500 ℃ for 3 hours in an air plasma atmosphere to obtain the Cu-ZSM-5 catalyst with copper accounting for 0.51wt.% of the catalyst.
The NO decomposition reactor was filled with Cu-ZSM-5 catalyst, the results of which are shown in Table 1 and FIG. 1.
Example 1
A preparation method of Ni-ZSM-5 catalyst is different from example 1 in that: the calcined ZSM-5 molecular sieve was mixed with a nickel nitrate solution to give a Ni-ZSM-5 catalyst having nickel in an amount of 0.43wt.% based on the weight of the catalyst.
The NO decomposition reactor was filled with Ni-ZSM-5 catalyst, the results of which are shown in Table 1 and FIG. 1.
Example 2
A preparation method of Co-ZSM-5 catalyst is different from example 1 in that: the calcined ZSM-5 molecular sieve was mixed with a cobalt nitrate solution to give a Co-ZSM-5 catalyst having cobalt in an amount of 0.41wt.% based on the weight of the catalyst.
The NO decomposition reactor was filled with Co-ZSM-5 catalyst, the results of which are shown in Table 1 and FIG. 1.
Example 3
A preparation method of the Fe-ZSM-5 catalyst is different from example 1 in that: the calcined ZSM-5 molecular sieve was mixed with an iron nitrate solution to give an Fe-ZSM-5 catalyst having iron in an amount of 0.33wt.% based on the weight of the catalyst.
The NO decomposition reactor was filled with Fe-ZSM-5 catalyst, the results of which are shown in Table 1 and FIG. 1.
Example 4
A preparation method of a Fe-Ni-ZSM-5 catalyst, which comprises the following steps: 1) Mixing the roasted ZSM-5 molecular sieve with nickel nitrate solution, stirring at 70 ℃ for 2 hours, separating, washing the solid obtained by separation to be neutral, drying at 120 ℃ for 3 hours, and roasting at 500 ℃ for 3 hours in an air plasma atmosphere to obtain a Ni-ZSM-5 catalyst; 2) Mixing the Ni-ZSM-5 catalyst with ferric nitrate solution, stirring at 70 ℃ for 2 hours, separating, washing the solid obtained by separation to be neutral, drying at 120 ℃ for 3 hours, and roasting at 500 ℃ for 3 hours in an air plasma atmosphere to obtain the Fe-Ni-ZSM-5 catalyst with iron and nickel accounting for 0.82wt.% of the catalyst.
The NO decomposition reactor was filled with Fe-Ni-ZSM-5 catalyst, and the results are shown in Table 1.
Conclusion: compared with comparative example 1, the filled molecular sieve catalyst remarkably improves the NO removal rate, and the synergistic effect of different metals and ZSM-5 has great influence on the NO denitration effect; in addition, the molecular sieve catalyst also significantly promotes SO 2 And (5) removing. At high concentration SO 2 And high concentration O 2 In the complex atmosphere of (2), the active component Fe has the highest NO removing capability, and then Co and Ni, and Cu has the worst NO removing capability. Notably, the simulated reaction feed gas employed in the molecular sieve catalyst studies reported to date for NO decomposition denitration consisted primarily of NO/N 2 Or NO/O 2 /N 2 Composition, SO-free 2 Research has shown that SO is introduced at a concentration of less than 100ppm during denitration 2 The denitration performance of the molecular sieve catalyst is rapidly reduced. Obviously, simulating the real exhaust gas atmosphere is important to research and develop a preferred NO decomposition denitration catalyst and the practical application of a denitration technology.
Example 5
A process for preparing a Fe-SSZ-13 catalyst differs from example 4 in that: the calcined SSZ-13 molecular sieve was mixed with an iron nitrate solution to give a Fe-SSZ-13 catalyst having iron in an amount of 0.31wt.% based on the weight of the catalyst.
The NO decomposition reactor was filled with Fe-SSZ-13 catalyst, and the results are shown in Table 1.
Example 6
A preparation method of the Fe-SAPO-34 catalyst is different from example 4 in that: the calcined SAPO-34 molecular sieve was mixed with an iron nitrate solution to obtain an Fe-SAPO-34 catalyst having iron in an amount of 0.33wt.% based on the weight of the catalyst.
The NO decomposition reactor was charged with Fe-SAPO-34 catalyst, and the results are shown in Table 1.
Example 7
A preparation method of the Fe-ZSM-11 catalyst is different from example 4 in that: and mixing the calcined ZSM-11 molecular sieve with an iron nitrate solution to obtain the Fe-ZSM-11 catalyst with iron accounting for 0.35wt.% of the weight of the catalyst.
The NO decomposition reactor was filled with Fe-ZSM-11 catalyst, and the results are shown in Table 1.
Example 8
A preparation method of the Fe-Beta catalyst is different from that of the example 4: the calcined Beta molecular sieve was mixed with an iron nitrate solution to obtain an Fe-Beta catalyst having iron in an amount of 0.42wt.% based on the weight of the catalyst.
The NO decomposition reactor was filled with Fe-Beta catalyst, and the results are shown in Table 1.
Conclusion: at high concentration SO 2 And high concentration O 2 Under the complex atmosphere, the molecular sieve type of the molecular sieve catalyst has a certain influence on the denitration performance of the molecular sieve catalyst, and is mainly reflected in that the acid property and the pore size of the molecular sieve influence the denitration performance of the molecular sieve catalyst. Wherein, the acidity of the molecular sieve directly affects the metal exchange capacity of the molecular sieve catalyst, thereby affecting the NO decomposition performance of the molecular sieve catalyst; while the size of the molecular sieve pores directly affects SO 2 The adsorption performance of the active site of the molecular sieve catalyst metal, the pore size of the SAPO-34 molecular sieve and the SSZ-13 molecular sieve is smaller than
SO inhibition 2 (molecular size->
) Enters into the pore canal of the molecular sieve to prevent SO 2 The catalyst is adsorbed on the metal active site in the pore canal of the molecular sieve, so that the sulfur tolerance of the catalyst is improved.
TABLE 1
| Conversion of NO (%) | Optimum denitration temperature (. Degree. C.) | |
| Comparative example 1 | 0.2 | 400 |
| Comparative example 2 | 14.1 | 350 |
| Example 1 | 23.9 | 400 |
| Example 2 | 31.0 | 350 |
| Example 3 | 36.6 | 400 |
| Example 4 | 40.2 | 400 |
| Example 5 | 45.5 | 350 |
| Example 6 | 41.3 | 400 |
| Example 7 | 42.7 | 350 |
| Example 8 | 24.2 | 400 |
Claims (5)
1. NO decomposition denitration catalyst is in high concentration SO 2 And O 2 The application of the NO decomposition denitration is characterized in that: the catalyst comprises an active component and a molecular sieve;
the active component is at least one of iron, cobalt and nickel;
the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-12, ZSM-35, SSZ-13, SSZ-23, SAPO-34, SAPO-35, AIPO-33 and Beta;
0.02-10.00wt.% of the active component based on the weight of the catalyst;
the SO 2 Is 300-800ppm, O 2 The concentration of (C) is 5-15vol%, the concentration of NO is 500-1500ppm, and the reaction temperature is 200-450 ℃.
2. The catalyst for NO decomposition and denitration according to claim 1 in high-concentration SO 2 And O 2 The application of the NO decomposition denitration is characterized in that: the active component is iron, cobalt, nickel or iron-nickel.
3. The catalyst for NO decomposition and denitration according to claim 1 in high-concentration SO 2 And O 2 The application of the NO decomposition denitration is characterized in that: the molecular sieve is ZSM-5, ZSM-11, SSZ-13, SAPO-34 or Beta.
4. A catalyst for the decomposition and denitration of NO according to claim 1, 2 or 3 in high concentration SO 2 And O 2 The application of the NO decomposition denitration is characterized in that: the preparation method of the catalyst comprises the following steps: mixing the baked molecular sieve with nitrate solution containing active component, stirring at 50-80deg.C for 1-3 hr, separating, washing the separated solid to neutrality, drying, androasting for 0.5-3h at 400-550 ℃ in the plasma atmosphere.
5. The catalyst for NO decomposition denitration according to claim 4 in high-concentration SO 2 And O 2 The application of the NO decomposition denitration is characterized in that: the plasma atmosphere is air, N 2 Ar, he and H 2 At least one of them.
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