CN112973770B - Nitrogen oxide methane selective catalytic reduction catalyst and application method thereof - Google Patents
Nitrogen oxide methane selective catalytic reduction catalyst and application method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/40—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
- B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
Abstract
The invention provides a nitrogen oxide methane selective catalytic reduction catalyst and an application method thereof. The catalyst is prepared by taking rare earth Ce and metal Ga as active components and taking molecular sieves (MFI, CHA and BEA) as carriers through an organic acid assisted impregnation method. The catalyst can be used for converting nitrogen oxides into harmless nitrogen under the condition of oxygen enrichment by taking methane as a reducing agent. The reaction conditions are as follows: the reaction temperature is 350-600 ℃, the concentration of nitrogen oxide is 100-2000ppm, the molar ratio of methane to nitrogen oxide is 1-3, and the volume space velocity of the reaction is 1000-100000h ‑1 . The prepared catalyst not only has good activity and hydrothermal stability, but also has the advantages of simple and easy operation of the preparation process, long catalytic life and the like, and the influence of the steam on the reaction activity of the catalyst is reversible, so that the catalyst is suitable for large-scale industrial application and popularization.
Description
Technical Field
The invention belongs to the field of catalysts, and relates to a nitrogen oxide methane selective catalytic reduction catalyst and application thereof, in particular to preparation of a bimetallic molecular sieve catalyst and application thereof in selective catalytic reduction of nitrogen oxide methane.
Background
Nitrogen oxides (NOx) are one of the major atmospheric pollutants and have caused a number of environmental problems. The catalytic reduction (SCR) is a method for reducing nitrogen oxides into harmless nitrogen under the action of a specific catalyst, is a main method for eliminating and purifying nitrogen oxides, and is widely applied. The main reducing agent of the current catalytic reduction process is ammonia (NH) 3 ) I.e. NH 3 -an SCR. However, ammonia has a certain toxicity and a strong corrosivity, and has high storage and transportation costs. Natural gas as a clean fuel contains methane (CH) as the main component 4 ). In the context of the large scale advancement of coal-fired boilers "coal-to-gas", in recent years, CH has been used 4 Selective catalytic reduction of nitrogen oxides (CH) for a reductant 4 -SCR) have received increasing attention. But due to CH 4 High dissociation energy of valence bond, therefore, finding a compound capable of activating CH 4 Catalyst of (2) is CH 4 One difficulty in SCR research. In recent years, zeolite molecular sieve catalysts supported by Co, in and Pd metals have been used on CH 4 Excellent denitration activity is shown in SCR reaction. The applicant discloses In an issued patent (patent number CN 201711315106.0) a molecular sieve catalyst for methane selective catalytic reduction, the main active components of which are bimetallic Cr-In and Ru-In, an H-SSZ-13 molecular sieve is used as a carrier, and the carrier is In CH 4 SCR shows better catalytic performance. However, considering that the metal Cr has certain biotoxicity and is not friendly to the environment, and the metal Ru is a noble metal and has higher price, therefore, the high-CH-content metal Ru has been developed 4 The non-noble metal catalyst with SCR activity and no Cr has very important practical significance and application value.
Disclosure of Invention
The invention aims to provide an environment-friendly catalyst for selective catalytic reduction of nitrogen oxides by methane and an application method thereof. The catalyst takes bimetal Ce-Ga as an active component, does not contain toxic metals such as Cr and the like and noble metals, takes a zeolite molecular sieve as a carrier, and is applied to CH for the first time 4 -in an SCR reaction. The Ce-Ga/molecular sieve catalyst is in CH under the synergistic effect of Ce and Ga species 4 SCR shows high activity and stability. The catalyst has simple preparation process, easy operation and long reaction life, and is suitable for large-scale application in industrial production.
The invention provides a catalyst for selective catalytic reduction of nitrogen oxide methane. The catalyst is prepared by taking soluble gallium salt and soluble cerium salt as raw materials and taking a molecular sieve as a carrier through an organic acid assisted impregnation method. The catalyst comprises the following components in percentage by mass:
2 to 5 percent of metal Ga
1 to 4 percent of metal Ce
91 to 97 percent of molecular sieve
Wherein, the molecular sieve is a silicon-aluminum molecular sieve and a silicon-phosphorus-aluminum molecular sieve with MFI, BEA and CHA structures.
Preferably, the molecular sieve is a ZSM-5 molecular sieve, and Si/Al = 25-35.
The organic acid is any one of citric acid, glutamic acid or salicylic acid, and the molar ratio is that the organic acid: (Ce + Ga) =0 to 1.5.
Preferably, the organic acid is citric acid, and the molar ratio of the organic acid: (Ce + Ga) =1.
Further preferably, H 2 H-ZSM-5=100 mass ratio, ce: H-ZSM-5=0.02 mass ratio, ga: H-ZSM-5=0.04 mass ratio, citric acid (Ga + Ce) =1 molar ratio.
The soluble gallium salt is gallium nitrate and gallium chloride, and the soluble cerium salt is cerium nitrate, cerium chloride, cerium sulfate and cerium acetate.
The invention provides a nitrogen oxide methane selective catalytic reduction catalyst, and a preparation method thereof comprises the following steps:
(1) Dissolving organic acid in measured water, adding measured soluble gallium salt and soluble cerium salt, violently stirring for 0.3-2 hours, adding measured molecular sieve carrier, and continuously stirring for 6-24 hours to obtain uniform mixed slurry.
(2) Evaporating the mixed serous fluid to dryness at low temperature, and drying for 6-20 hours at 80-120 ℃;
(3) Subjecting the product obtained in step (2) to 10% 2 Reduction in Ar at 300-800 ℃ for 0.5-2 hours, then by 10% 2 Oxidizing in Ar for 0.5-2 hours at 200-500 ℃;
(4) And (4) directly extruding and molding the product obtained in the step (3) to obtain a molded catalyst, or coating the molded catalyst on cordierite ceramic or metal corrugated plates with fixed shapes to obtain a monolithic catalyst.
The invention provides a nitrogen oxide methane selective catalytic reduction catalyst, and an application method thereof comprises the following steps:
(1) Placing the shaped catalyst or monolithic catalyst in a fixed bed reactor at 10% 2 Pretreating for 1 hour at 300-400 ℃ in an Ar atmosphere;
(2) Heating the reactor to 300-600 ℃ to perform CH 4 SCR reaction, the concentration of nitrogen oxide at the reaction inlet is 100-2000ppm, the molar ratio of methane to nitrogen oxide is 1-3, and the volume space velocity of the reaction is 1000-100000h -1 。
Preferably, the volume space velocity of the reaction is 40000-60000 h -1 . The methane/nitrogen oxide molar ratio was 1.45.
The catalyst for selective catalytic reduction of nitrogen oxides methane provided by the invention can be used for formula treatment of fixed source nitrogen oxides, such as flue gas denitration processes of boilers in thermal power plants, iron and steel plants, cement plants and the like.
The invention provides a selective catalytic reduction catalyst for nitrogen oxide methane, which is prepared from CH 4 High activity and stability in SCR reactions. The catalyst has simple preparation process, easy operation and long reaction life.
Compared with the prior art, the invention also has the following advantages and effects:
(1) The catalyst shows excellent nitrogen oxide purification effect, and the nitrogen oxide purification efficiency can reach more than 95% at most;
(2) The catalyst component is environment-friendly and does not contain noble metal, and the preparation cost is lower;
(3) The influence of the water vapor on the reaction activity of the catalyst is reversible, and the activity can be recovered after water removal.
Drawings
FIG. 1 is an XRD spectrum of a Ce-Ga/H-ZSM-5 catalyst prepared by a citric acid auxiliary impregnation method;
FIG. 2a is an SEM photograph of an H-ZSM-5 catalyst;
FIG. 2b is an SEM photograph of a Ce-Ga/H-ZSM-5 catalyst prepared by a citric acid assisted impregnation method;
FIG. 3 is CH of Ce-Ga/H-ZSM-5 catalyst prepared by citric acid auxiliary impregnation method 4 -SCR reaction activity profile;
FIG. 4 is a drawing showingCatalyst Ce-Ga/H-ZSM-5 in CH 4 -water vapor stability test patterns in SCR reactions;
FIG. 5a is CH for 3% single component Ga/H-ZSM-5 catalyst 4 -SCR reaction activity profile;
FIG. 5b is CH for 4% single component Ga/H-ZSM-5 catalyst 4 -SCR reaction activity profile;
FIG. 5c is CH for 5% single component Ga/H-ZSM-5 catalyst 4 -SCR reaction activity profile.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Technical terms in the present invention are defined in the following, and terms not defined are understood in the ordinary sense in the art.
Example 1:
(1) Preparation of Ce-Ga/H-ZSM-5 catalyst
The raw materials are as follows: h 2 O: H-ZSM-5=100 (mass ratio), ce: H-ZSM-5=0.02 (mass ratio), ga: H-ZSM-5=0.04 (mass ratio), citric acid (Ga + Ce) =1 (molar ratio)
Dissolving metered citric acid in water, adding metered gallium nitrate and cerium nitrate, violently stirring for 0.5 hour, adding H-ZSM-5 (Si/Al = 28) powder, and continuously stirring for 24 hours to obtain uniformly mixed slurry; evaporating the mixed serous fluid to dryness at low temperature, and drying in an oven at 90 ℃ for 15 hours; the dried sample was measured at 10% H 2 Reduction in/Ar at 650 ℃ for 1 hour, at 10% O 2 Oxidizing at 350 deg.C for 1 hr in Ar, coolingAfter cooling to room temperature, the samples were extruded directly.
(2) Catalyst Ce-Ga/H-ZSM-5 in CH 4 Application to SCR reactions
Weighing 0.12g of 20-40 mesh shaped catalyst, placing into fixed bed reactor, and adding into the reactor at a content of 10% 2 After pretreatment for 1 hour at 350 ℃ in the Ar atmosphere, the temperature of the reactor is adjusted to 300 ℃, and reaction mixed gas is introduced, wherein the space velocity of the reaction volume is 60000h -1 The balance gas comprises the following components in percentage by weight: NO =2750ppm, CH 4 =4000ppm, i.e. a methane/nitrogen oxide molar ratio of about 1.45 2 ＝4％，H 2 O =6% and He is balance gas; detecting a data point every 50 deg.C during the reaction, recording the temperature range of 300-550 deg.C, and using NO X The analyzer (Ecotech EC 9841) and the gas chromatograph record the reaction data at different temperatures, and the results are shown in fig. 3.
The catalyst results show that the conversion rate of the nitrogen oxides increases with the increase of the reaction temperature, when the reaction temperature exceeds 450 ℃, the conversion rate of the nitrogen oxides to the nitrogen is close to 90 percent, and when the reaction temperature exceeds 550 ℃, the conversion rate can reach more than 95 percent, as shown in table 1.
Example 2:
the procedure is as for the starting materials and steps in example 1, except that citric acid is used in an amount of 0, i.e. no organic acid is added; the catalyst is in CH as in example 1 4 The results of the application of the SCR reaction show a nitrogen oxide conversion of about 77% at 550 ℃ as shown in Table 1.
Example 3:
the procedure is as in example 1 except that the fixed Ga content is 4% and the modulated Ce metal loading is 1%, and the catalyst is in CH as in example 1 4 The results of the application of the SCR reaction show a conversion of nitrogen oxides to nitrogen of 70% at 550 ℃.
Example 4:
the starting materials and procedures as in example 1 were followed except that the organic acid to assist in impregnation was changed to glutamic acid and salicylic acid; the catalyst is in CH as in example 1 4 The results of the application of the SCR reaction are shown in Table 1.As can be seen from the table, the catalytic activity of the catalyst can be obviously improved by using the organic acid for auxiliary impregnation, wherein the citric acid has the best effect of improving the citric acid to about 95 percent at 550 ℃ from 77 percent when the organic acid is not added, and the glutamic acid has the effect of reaching 84 percent at most and the salicylic acid has the worst effect of improving the salicylic acid by about 2 percent.
Table 1: organic acid double-metal Ce-Ga/H-ZSM-5 catalyst NO x Effect of conversion
Example 5:
the starting materials and procedure of example 1 were followed except that the citric acid/metal (Ga + Ce) molar ratio was adjusted to 0.5 and 1.5; the catalyst is as in example 1 in CH 4 -method of application of the SCR reaction, results are shown in table 2. When the mole ratio of citric acid to metal (Ga + Ce) is 0.5, the conversion rate of nitrogen oxide to nitrogen at 550 ℃ can reach 83%; when the citric acid/metal (Ga + Ce) molar ratio is 1.5, the conversion rate of nitrogen oxide generating nitrogen at 550 ℃ can also reach 80%. But both are less than conversions with a citric acid/metal (Ga + Ce) molar ratio of 1.
Table 2: citric acid dosage to bimetallic Ce-Ga/H-ZSM-5 catalyst NO x Effect of conversion
Example 6:
the starting material and procedure of example 1 were followed except that the molecular sieve support was changed to a CHA structure molecular sieve, i.e., H-SSZ-13 (Si/Al = 24) molecular sieve; the catalyst is in CH as in example 1 4 The results of the application of the SCR reaction show that the conversion of nitrogen oxides to nitrogen at 550 ℃ is approximately82 percent, which is less than the conversion rate of adopting H-ZSM-5 molecular sieve.
Example 7:
following the raw materials and procedures of example 1, 2% Ce-4% Ga/H-ZSM-5 catalyst was obtained; the catalyst is in CH as in example 1 4 Application method of SCR reaction, except that the space velocity of the reaction volume is respectively adjusted to 40000h -1 And 90000h -1 The results show that the conversion of nitrogen oxides to nitrogen at 550 ℃ is 90% and 72%, respectively.
Example 8:
following the raw materials and procedures of example 1, 2% Ce-4% Ga/H-ZSM-5 catalyst was obtained; the catalyst is as in example 1 in CH 4 Application of the SCR reaction, except that in the reaction mixture, CH 4 The contents of the components were adjusted to 2750ppm and 5500ppm, i.e., the molar ratio of methane to nitrogen oxides was adjusted to 1 and 2, and the results showed that the conversion of nitrogen oxides to nitrogen at 550 ℃ was 85% and 81%, respectively.
Example 9: stability test of catalyst
According to the raw materials and procedures in example 1, 2% Ce-4% of the Ga/H-ZSM-5 catalyst is obtained; the catalyst is in CH as in example 1 4 Application method of the SCR reaction, except that in the reaction mixture, H 2 The content of the O component was adjusted to 0 or 6%, whereby the influence of water vapor on the catalyst performance was examined.
FIG. 4 is a Ce-Ga/H-ZSM-5 catalyst in CH 4 Water vapor stability test in SCR reactions. As can be seen from the figure, when NO water vapor was present in the reaction system, NO was converted to N in the first 30 hours 2 Is maintained at about 92%; when 6% of water vapor is introduced into the reaction system, NO is converted into N 2 The conversion rate of (A) is reduced to only about 89%, and can be maintained for 150 hours; when the water vapor in the mixed gas is removed again, NO is converted into N 2 Can be substantially restored to the level of the anhydrous state. The results show that the effect of water vapor on the reactivity of the catalyst is reversible and the catalyst has excellent stability.
Comparative example 1: CH of single-component Ga/H-ZSM-5 catalyst 4 -SCR Activity
Single-component Ga/H-ZSM-5 catalysts having metal Ga loadings of 3%, 4% and 5% were prepared according to the raw materials and procedures of example 1 except that metal Ga was added without metal Ce and Ga: H-ZSM-5= (0.03), 0.04 and 0.05 (mass ratio); the catalyst is as in example 1 in CH 4 The results of the application of the SCR reaction are shown in FIG. 5, and it can be seen that NO is converted into N 2 The highest conversions of 59%, 49% and 52%, respectively, are much lower than those of the bicomponent Ce-Ga/H-ZSM-5 catalyst.
Claims (7)
1. A nitrogen oxide methane selective catalytic reduction catalyst is characterized in that: the catalyst is prepared by taking soluble gallium salt and soluble cerium salt as raw materials and a molecular sieve as a carrier through an organic acid assisted impregnation method, and comprises the following components in percentage by mass:
metal Ce 1 to 4%
Metal Ga 2 to 5%
Molecular sieves 91 to 97%
Wherein the molecular sieve is a ZSM-5 molecular sieve;
the organic acid is any one of citric acid, glutamic acid or salicylic acid, and the molar ratio is that the organic acid: (Ce + Ga) =0.5 to 1.5;
the soluble gallium salt is one or a mixture of more than two of gallium nitrate and gallium chloride; the soluble cerium salt is one or a mixture of more than two of cerium nitrate, cerium chloride, cerium sulfate and cerium acetate;
the preparation method comprises the following steps:
(1) Adding soluble gallium salt and soluble cerium salt into an organic acid aqueous solution according to the measurement, violently stirring for 0.3 to 2 hours, adding a molecular sieve carrier, and continuously stirring for 6 to 24 hours to obtain uniform mixed slurry;
(2) Evaporating the mixed serous fluid to dryness at low temperature, and drying for 6-20 hours at 80-120 ℃;
(3) The product obtained in the step (2) is mixed with 10% H 2 Reduction in Ar at 300 to 800 ℃ for 0.5 to 2 hours, and then 10% O 2 Oxidizing in Ar at 200-500 ℃ for 0.5-2 hours;
(4) And (4) directly extruding and molding the product obtained in the step (3) to obtain a molded catalyst, or coating the molded catalyst on cordierite ceramic or metal corrugated plates with fixed shapes to obtain a monolithic catalyst.
2. The catalyst of claim 1, wherein: the organic acid is citric acid, and the molar ratio is that the organic acid: (Ce + Ga) =1.
3. The catalyst of claim 1, wherein: the molecular sieve is a ZSM-5 molecular sieve, and Si/Al =25 to 35.
4. The catalyst of claim 3, wherein: the molecular sieve is H-ZSM-5 molecular sieve with the mass ratio of H 2 H-ZSM-5=100, ce: H-ZSM-5=0.02, ga: H-ZSM-5=0.04, and citric acid (Ga + Ce) =1.
5. The method for using the catalyst according to claim 1, wherein: the method comprises the following steps: placing the formed catalyst or monolithic catalyst into a fixed bed reactor, and using 10% of O 2 Pretreating Ar for 1 hour at 300-400 ℃, and then carrying out CH 4 -an SCR reaction; the reaction temperature is 300 to 600 ℃, the concentration of nitrogen oxide at the reaction inlet is 100 to 2000ppm, the molar ratio of methane to nitrogen oxide is 1 to 3, and the volume space velocity of the reaction is 1000 to 100000h -1 。
6. The method for using the catalyst according to claim 5, wherein: the volume space velocity of the reaction is 40000 to 60000h -1 。
7. The method for using the catalyst according to claim 6, wherein: the methane/nitrogen oxide molar ratio was 1.45.
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