One-step synthesis of a multifunctional catalyst for synergistic removal of CO / CH2 by solid-phase high-speed and high-pressure ball milling and its application for heavy metal and sulfur poisoning-resistant denitrification

Abstract

The invention discloses a one-step synthesis of a heavy metal and sulfur poisoning-resistant denitrification synergistic CO / CH removal multifunctional catalyst by solid phase high-speed high-pressure ball milling method and its application. The catalyst is a doped molecular sieve Me1O synthesized by solid phase high-speed high-pressure ball milling method in one step. x ‑Me (Ⅰ) O x ‑R1O2‑Me2O x ‑Me (Ⅱ) O x ‑ZSM‑5, where Me1 is one of V, Ce, and Mn; Me2 is one of Fe, Co, and Cu; (Ⅰ) One of W, Mo, P, S, Me (Ⅱ) is one of La, Pr, Gd and Y, R1 is one of Zr and Ti, and x=1-3. The catalyst of the present invention has the characteristics of large specific surface area, uniform particle size, large number of surface acid sites, small average pore size, multiple redox active centers, high hydrothermal stability, strong resistance to sulfur poisoning and heavy metal poisoning, etc.; its one-step synthesis has the advantages of simplicity, economy and high efficiency.

Description

Technical Field

[0001] The invention belongs to the field of industrial waste gas purification, and particularly relates to a one-step synthesis of a heavy metal and sulfur poisoning-resistant denitration synergistic CO / CH removal multifunctional catalyst by a solid-phase high-speed and high-pressure ball milling method and an application thereof. Background Art

[0002] Pollutants generated by combustion in waste incineration, cement and steel sintering machines mainly include nitrogen oxides (NO x ), CO / CH and dust. Among them, the strong oxidizing (NO x ) is the main factor causing the explosion of PM2.5 and ozone. 3 -SCR denitrification purification technology is to use NH 3 Selectively convert NO x Catalytic reduction to harmless N 2 , the catalyst is the core of this technology. As the most mature commercial denitrification catalyst, vanadium titanium is irreplaceable in the field of denitrification of fixed pollution sources such as thermal power and various industries (the utilization rate has exceeded 98%). CO / CH also leads to the formation of photochemical smog, and the catalytic combustion of CO / CH can not only efficiently eliminate pollutants, but also increase the flue gas temperature, which is conducive to denitrification. However, the widespread application of biomass and solid waste resources in the above industries poses three major challenges to traditional vanadium titanium catalysts: first, its flue gas temperature is lower than that of conventional coal-fired boilers, and the low-temperature denitrification activity of vanadium titanium catalysts (<220 °C) needs to be further improved to improve energy efficiency and reduce carbon emissions; second, the performance of synergistic catalytic oxidation of CO / CH by vanadium titanium catalysts needs to be improved through modification; third, the content of alkali (earth) / heavy metals (K, Na, Ca, Pb, Cd, Tl, etc.) in smoke is high (100-10000 times that of conventional flue gas), which will cause the rapid deactivation of traditional vanadium titanium catalysts.

[0003] By characterizing the adsorption and redox properties of the catalysts, it was found that the catalysts poisoned by heavy metals have two major characteristics: (1) the surface chemical oxygen adsorption capacity is reduced, and the redox performance is greatly weakened; (2) the strength and stability of the acid sites are reduced. Among them, the reduction of the catalyst surface chemical oxygen adsorption capacity and the weakening of the redox performance are the main reasons for catalyst poisoning. Therefore, the development of a multifunctional catalyst for the synergistic removal of CO / CH2 by denitrification with strong redox performance, large specific surface area and more developed pore structure that is resistant to heavy metal poisoning is the key to solving the above problems. Summary of the invention

[0004] In order to overcome the shortcomings of the prior art, the present invention aims to provide a one-step synthesis of a multifunctional catalyst for denitration and synergistic removal of CO / CH by a solid phase high-speed and high-pressure ball milling method and its application. The catalyst of the present invention has a large specific surface area (300-700 m 2 / g), uniform particle size (1-7μm), large number of surface acid sites (greater than 60μmol / g), small average pore size (less than 10nm), multiple redox active centers, high hydrothermal stability, strong resistance to sulfur poisoning and heavy metal poisoning, etc., which meet the needs of special SCR catalysts and are particularly suitable for solving the problem of synergistic removal of CO / CH by denitrification of flue gas containing a large amount of heavy metals in cement kilns, biomass boilers and other dusts. Among the corresponding preparation methods, the one-step synthesis has the advantages of simplicity, economy and high efficiency. The solid-phase mixed precursor can effectively reduce the pollution caused by organic solvents and reduce the high cost of using organic solvents.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A one-step synthesis of a heavy metal and sulfur poisoning-resistant denitrification and synergistic removal of CO / CH multifunctional catalyst by solid phase high-speed and high-pressure ball milling, wherein the catalyst is a doped molecular sieve Me synthesized by solid phase high-speed and high-pressure ball milling in one step. 1 O x -Me (Ⅰ) O x -R 1 O 2 -Me 2 O x -Me (Ⅱ) O x -ZSM-5, where Me 1 One of V, Ce, and Mn; Me 2 It is one of Fe, Co, Cu, Me (Ⅰ) One of W, Mo, P, S, Me (Ⅱ) is one of La, Pr, Gd, Y, R 1 It is one of Zr and Ti, and x=1-3.

[0007] Furthermore, the part of the catalyst that performs the denitration function is Me 1 O x -Me (Ⅰ) O x -R 1 O 2 The part that bears the oxidation function is Me 2 O x -Me (Ⅱ) O x -ZSM-5.

[0008] Furthermore, in the part of the catalyst that performs the denitration function, the active ingredient is Me 1 O x , the active ingredient adjuvant is Me (Ⅰ) O x , the carrier is R 1 O 2 ;

[0009] The active component of the catalyst that bears the oxidation function is Me 2 O x , the active ingredient adjuvant is Me (Ⅱ) O x , the carrier is ZSM-5.

[0010] Furthermore, the catalyst is made of raw materials with the following molar ratios: the molar ratios of denitrification active precursor, denitrification partial auxiliary agent, denitrification partial carrier, oxidation active precursor, oxidation partial auxiliary agent, silicon source, aluminum source, alkali source, and template agent are (0.004-0.006): (0.0015-0.003): (0.1-0.2): (0.4-0.7): (1.5-1.9): 27: 1: (0.2-0.4): (1-2).

[0011] Furthermore, the catalyst has a particle size of 1-7 μm and a specific surface area of ​​300-700 m 2 / g, the number of surface acidic sites is greater than 60μmol / g, and the average pore size is less than 10nm.

[0012] Furthermore, the catalyst is obtained by a preparation method comprising the following steps:

[0013] (S1) mixing a denitration active precursor, a denitration auxiliary agent, a denitration partial carrier, an oxidation active precursor, an oxidation auxiliary agent, a silicon source, an aluminum source, an alkali source, and a template agent, adding the mixture to a ball mill for low-speed ball milling to obtain a mixed colloid A;

[0014] (S2) adding the mixed colloid A in step (S1) into a ball mill, subjecting it to high-speed ball milling crystallization under high temperature and high pressure conditions, cooling it to obtain solid B, drying it, calcining it in an air atmosphere, and cooling it to obtain solid B.

[0015] Further, the denitration active precursor is selected from one of ammonium metavanadate, vanadium oxalate, vanadium trichloride, cerium dioxide, cerium nitrate, and manganese nitrate; the denitration auxiliary agent is selected from one of ammonium metatungstate, molybdenum nitrate, phosphoric acid, and thiourea; the denitration carrier is selected from one of titanium dioxide and zirconium dioxide;

[0016] The oxidation active precursor is selected from one of ferric nitrate, ferric chloride, cobalt nitrate, cobalt chloride, copper nitrate and copper chloride; the oxidation part auxiliary agent is one of lanthanum nitrate, praseodymium nitrate, gadolinium nitrate and yttrium nitrate;

[0017] The silicon source is selected from one of tetraethyl orthosilicate, silicic acid, silica sol, and white carbon black; the aluminum source is selected from one of aluminum sulfate, aluminum hydroxide, aluminum oxide, sodium aluminate, and aluminum isopropoxide; the alkali source is selected from one of n-butylamine and urea; and the template agent is selected from one of methanol, ethanol, ethylene glycol, and n-butanol.

[0018] Furthermore, in step (S1), the ball milling speed is controlled at 500-2000 rpm, the ball milling time is 0.5-2h, and the ball milling bead diameter is 20-150mm;

[0019] In step (S2), the ball milling speed is controlled at 50000-100000 rpm, the ball milling bead diameter is 1-10 mm, the ball milling crystallization time is 30 h, the pressure is 1-1.8 MPa, the ball milling crystallization temperature is 100-190° C., and the heating rate is 10° C. / min;

[0020] In step (S2), the calcination temperature is 500-600°C, the heating rate is 2-10°C / min, and the calcination time is 4.0-6.0h.

[0021] A one-step synthesis of a multifunctional catalyst for synergistic removal of CO / CH2 by a solid-phase high-speed and high-pressure ball milling method that is resistant to heavy metal and sulfur poisoning and is used in flue gas denitrification.

[0022] The beneficial effects of the present invention are:

[0023] 1. The present invention adopts a one-step method to synthesize the doped molecular sieve Me 1 O x -Me (Ⅰ) O x -R 1 O 2 -Me 2 O x -Me (Ⅱ) O x -ZSM-5 (Me 1 : One of V, Ce, Mn; Me 2 : One of Fe, Co, Cu, Me (Ⅰ) :One of W, Mo, P, S, Me (Ⅱ) :La, Pr, Gd, Y, R 1: one of Zr and Ti), its synthesis method has the advantages of simplicity, economy and high efficiency; and in the mixing process of the precursors, solid phase mixing is adopted without the need to add additional solvents, which effectively reduces the pollution caused by organic solvents and avoids the high cost caused by the use of organic solvents.

[0024] 2. Doped molecular sieve Me synthesized by the present invention 1 O x -Me (Ⅰ) O x -R 1 O 2 -Me 2 O x -Me (Ⅱ) O x -ZSM-5 has the functions of both a denitration catalyst and an oxidation catalyst. It has the characteristics of large specific surface area, uniform particle size, large number of surface acid sites, and small average pore size. It can synergistically remove CO / CH in the denitration process, meeting the requirements of special SCR catalysts.

[0025] 3. The present invention introduces ZSM-5 as a heavy metal scavenger, and utilizes the abundant ion exchange sites of ZSM-5 to enrich heavy metals on the molecular sieve, thereby improving the catalyst's resistance to heavy metal poisoning. 2 The kinetic radius is larger than that of NO x and CO / CH cannot enter the pores of ZSM-5, which can effectively protect the active components and make the catalyst have better resistance to sulfur poisoning.

[0026] The catalyst of the present invention has a large specific surface area (300-700 m 2 / g), uniform particle size (1-7μm), large number of surface acid sites (greater than 60μmol / g), small average pore size (less than 10nm), multiple redox active centers, high hydrothermal stability, strong resistance to sulfur poisoning and heavy metal poisoning, etc., which meet the needs of special SCR catalysts and are particularly suitable for solving the problem of synergistic removal of CO / CH in flue gas denitrification of cement kilns, biomass boilers and other dusts containing a large amount of heavy metals. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a SEM image of the doped molecular sieve synthesized in Example 1;

[0028] Figure 2 This is the XRD phase diagram of the doped molecular sieve synthesized in Example 1;

[0029] Figure 3 This is a comparison chart of the denitration experiments of the doped molecular sieve synthesized in Example 1 and its corresponding hydrothermal aging sample;

[0030] Figure 4 This is a comparison chart of the CO catalytic oxidation experiment of the doped molecular sieve of Example 1 and its corresponding hydrothermal aged sample. DETAILED DESCRIPTION

[0031] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] A one-step synthesis of a heavy metal and sulfur poisoning-resistant denitrification and synergistic removal of CO / CH multifunctional catalyst by solid phase high-speed and high-pressure ball milling, wherein the catalyst is a doped molecular sieve Me synthesized by solid phase high-speed and high-pressure ball milling in one step. 1 O x -Me (Ⅰ) O x -R 1 O 2 -Me 2 O x -Me (Ⅱ) O x -ZSM-5, where Me 1 One of V, Ce, and Mn; Me 2 It is one of Fe, Co, Cu, Me (Ⅰ) One of W, Mo, P, S, Me (Ⅱ) is one of La, Pr, Gd, Y, R 1 It is one of Zr and Ti, and x = 1-3. The part of the catalyst that performs the denitrification function is Me 1 O x -Me (Ⅰ) O x -R 1 O 2 (The active ingredient is Me 1 O x , the active ingredient adjuvant is Me (Ⅰ) O x , the carrier is R 1 O 2 ), the part that bears the oxidation function is Me 2 O x -Me (Ⅱ) O x -ZSM-5 (active ingredient is Me 2 O x , the active ingredient adjuvant is Me (Ⅱ) O x , the carrier is ZSM-5).

[0033] The catalyst of the present invention is made of raw materials with the following molar ratios: the molar ratios of denitrification active precursor, denitrification partial auxiliary agent, denitrification partial carrier, oxidation active precursor, oxidation partial auxiliary agent, silicon source, aluminum source, alkali source, and template agent are (0.004-0.006): (0.0015-0.003): (0.1-0.2): (0.4-0.7): (1.5-1.9): 27: 1: (0.2-0.4): (1-2). The denitrification active precursor is selected from one of ammonium metavanadate, vanadium oxalate, vanadium trichloride, cerium dioxide, cerium nitrate, and manganese nitrate; the denitrification auxiliary agent is selected from one of ammonium metatungstate, molybdenum nitrate, phosphoric acid, and thiourea; the denitrification partial carrier is selected from one of titanium dioxide and zirconium dioxide; the oxidation active precursor is selected from one of ferric nitrate, ferric chloride, cobalt nitrate, cobalt chloride, copper nitrate, and copper chloride; the oxidation auxiliary agent is one of lanthanum nitrate, praseodymium nitrate, gadolinium nitrate, and yttrium nitrate; the silicon source is selected from one of tetraethyl orthosilicate, silicic acid, silica sol, and white carbon black; the aluminum source is selected from one of aluminum sulfate, aluminum hydroxide, aluminum oxide, sodium aluminate, and aluminum isopropoxide; the alkali source is selected from one of n-butylamine and urea; the template is selected from one of methanol, ethanol, ethylene glycol, and n-butanol.

[0034] The catalyst of the present invention is obtained by a preparation method comprising the following steps:

[0035] (S1) Mixing a denitration active precursor, a denitration auxiliary agent, a denitration partial carrier, an oxidation active precursor, an oxidation auxiliary agent, a silicon source, an aluminum source, an alkali source, and a template agent, and adding the mixture into a ball mill for low-speed ball milling to obtain a mixed colloid A; the ball milling speed is controlled at 500-2000 rpm, the ball milling time is 0.5-2h, and the ball milling bead diameter is 20-150mm.

[0036] (S2) adding the mixed colloid A in step (S1) into a ball mill, subjecting it to high-speed ball milling crystallization under high temperature and high pressure conditions, cooling it to obtain solid B, drying it, calcining it in an air atmosphere, and cooling it to obtain solid B.

[0037] In step (S2), the ball milling speed is controlled at 50000-100000 rpm, the ball milling bead diameter is 1-10 mm, the ball milling crystallization time is 30 h, the pressure is 1-1.8 MPa, the ball milling crystallization temperature is 100-190 ° C, and the heating rate is 10 ° C / min; the calcination temperature is 500-600 ° C, the heating rate is 2-10 ° C / min, and the calcination time is 4.0-6.0 h.

[0038] The catalyst of the present invention has a particle size of 1-7 μm and a specific surface area of ​​300-700 m 2 / g, the number of surface acidic sites is greater than 60μmol / g, and the average pore size is less than 10nm; it can be applied to flue gas denitrification treatment.

[0039] The preferred embodiments are as follows:

[0040] Example 1

[0041] (S1) 0.65 g of ammonium metavanadate, 0.56 g of ammonium metatungstate, 10.59 g of titanium dioxide, 0.625 g of copper nitrate, 1 g of lanthanum nitrate, 30.38 g of tetraethyl orthosilicate, 0.55 g of aluminum oxide, 0.39 g of n-butylamine, and 0.26 g of ethanol were mixed and added to a ball mill for low-speed ball milling for 0.5 h, with the ball milling speed controlled at 2000 rpm and the ball milling bead diameter being 10 mm, to obtain a mixed colloid A;

[0042] (S2) adding the mixed colloid A in step (S1) into a ball mill and subjecting to high-speed ball milling crystallization for 30 hours, wherein the diameter of the ball milling beads is 2 mm, the ball milling speed is controlled at 80,000 rpm, the pressure during the ball milling crystallization process is 1.5 MPa and the temperature is raised to 170°C, the average particle size of the solid after ball milling is 2 microns, and the solid B is obtained after cooling, drying, and then calcining in an air atmosphere, wherein the calcination temperature is 550°C, the heating rate is 10°C / min, and the calcination time is 4 hours, to obtain a doped molecular sieve catalyst, which is named sample 1, and its SEM image is as follows: Figure 1 As shown, the XRD phase diagram is as follows Figure 2 shown.

[0043] Comparative Example 1

[0044] 35.0 g of deionized water was added to 30.38 g of ethyl orthosilicate, and the solution was stirred for 0.5 h until it was uniform. 2.0 g of n-butylamine was added dropwise at 40° C. and stirred vigorously for 1 h to obtain a pretreated silicon source.

[0045] 0.65g of ammonium metavanadate, 0.56g of ammonium metatungstate, 10.59g of titanium dioxide, 0.625g of copper nitrate, 1g of lanthanum nitrate and 0.55g of aluminum oxide were added to 30.0g of deionized water, and 2.4g of n-butylamine was added dropwise at 25°C. After vigorous stirring for 0.5h, 20.0g of ethanol was added dropwise, and vigorous stirring was performed for 0.5h. The vigorous stirring condition was maintained, and the pretreated silicon source was slowly added to the system. After continuing to vigorously stir for 1h, a crystallized gel was obtained, which was then crystallized at 170°C for 40h. The crystallized product was washed, filtered and dried to obtain a solid, which was then calcined at 550°C in an air atmosphere for 5h to obtain sample 2 synthesized by the hydrothermal method.

[0046] Comparative Example 2

[0047] The difference between this comparative example and Example 1 is that in step (S1), only 0.65 g of ammonium metavanadate, 0.56 g of ammonium metatungstate and 10.59 g of titanium dioxide are added and mixed, and other conditions and operations are the same as those in Example 1. The obtained product is named Sample 3.

[0048] Comparative Example 3

[0049] The difference between this comparative example and Example 1 is that in step (S1), only 0.625 g of copper nitrate, 1 g of lanthanum nitrate, 30.38 g of tetraethyl orthosilicate, 0.55 g of aluminum oxide, 0.39 g of n-butylamine, and 0.18 g of methanol are added, and other conditions and operations are the same as those in Example 1. The obtained product is named Sample 4.

[0050] Comparative Example 4

[0051] The difference between this comparative example and Example 1 is that no molecular sieve is added to S1, and only 0.65g of ammonium metavanadate, 0.56g of ammonium metatungstate, 10.59g of titanium dioxide, 0.625g of copper nitrate, and 1g of lanthanum nitrate are added. Other conditions and operations are the same as those in Example 1. The obtained product is named Sample 5.

[0052] Comparative Example 5

[0053] The sample of Example 1 was aged at 750 °C for 48 h in an atmosphere of air and 10 vol% water vapor, and the obtained product was named Sample 6.

[0054] Application Examples

[0055] The catalysts obtained in the above examples and comparative examples were used to conduct denitration and CO synergistic catalytic experiments. The experimental conditions were as follows: the concentration (vol%) of each gas was controlled by a mass flow meter, NO: 500 ppm, NH 3 : 500ppm, CO: 4000ppm, O 2 :5%,H 2 O: 10%, N 2 For balancing gas, the total gas flow rate is 1000 mL / min, the catalyst dosage is 800 mg, the temperature is 275°C, and the catalysts are fresh catalyst, 100 ppm sulfur poisoned catalyst, and catalyst poisoned with 3 wt% PbO. The results are shown in Table 1 below:

[0056] The formula for calculating denitrification efficiency is η(NO x )=(C1-C2) / C1×100%, the CO degradation efficiency calculation formula is η(CO)=(C3-C4) / C3×100%, where C1 and C3 are NO x and CO inlet concentrations, C2 and C4 are NO x The outlet concentration of CO is measured using a flue gas analyzer.

[0057] Table 1

[0058]

[0059] Table 2

[0060]

[0061] The denitration test comparison of the doped molecular sieve catalyst synthesized in Example 1 and its corresponding hydrothermal aging sample is shown in the figure below: Figure 3 As shown; Example 1 doped molecular sieve catalyst and its corresponding hydrothermal aging sample CO catalytic oxidation experiment comparison diagram as shown Figure 4 shown.

[0062] The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. It should be pointed out that for ordinary technicians in this technical field, some improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A one-step synthesis of a multifunctional catalyst for denitrification and synergistic removal of CO / CH by solid phase high-speed and high-pressure ball milling, which is resistant to heavy metal and sulfur poisoning, characterized in that: The catalyst is a doped molecular sieve Me1O synthesized in one step by solid phase high-speed and high-pressure ball milling. x -Me (Ⅰ) O x -R1O2-Me2O x -Me (Ⅱ) O x -ZSM-5, wherein Me1 is one of V, Ce, and Mn; Me2 is one of Fe, Co, and Cu; (Ⅰ) One of W, Mo, P, S, Me (Ⅱ) is one of La, Pr, Gd, and Y, R1 is one of Zr and Ti, x =1-3; The part of the catalyst that bears the denitrification function is Me1O x -Me (Ⅰ) O x -R1O2, the part that takes on the oxidation function is Me2O x -Me (Ⅱ) O x -ZSM-5; The active component of the catalyst that performs the denitration function is Me1O x , the active ingredient adjuvant is Me (Ⅰ) O x , the carrier is R1O2; The active component of the catalyst in the oxidation function is Me2O x , the active ingredient adjuvant is Me (Ⅱ) O x , the carrier is ZSM-5; The catalyst is made of raw materials in the following molar ratios: the molar ratios of denitration active precursor, denitration partial auxiliary agent, denitration partial carrier, oxidation active precursor, oxidation partial auxiliary agent, silicon source, aluminum source, alkali source, and template agent are (0.004-0.006): (0.0015-0.003): (0.1-0.2): (0.4-0.7): (1.5-1.9): 27: 1: (0.2-0.4): (1-2); The catalyst is obtained by a preparation method comprising the following steps: (S1) mixing a denitration active precursor, a denitration auxiliary agent, a denitration partial carrier, an oxidation active precursor, an oxidation auxiliary agent, a silicon source, an aluminum source, an alkali source, and a template agent, adding the mixture to a ball mill for low-speed ball milling to obtain a mixed colloid A; (S2) adding the mixed colloid A in step (S1) into a ball mill, subjecting it to high-speed ball milling crystallization under high temperature and high pressure conditions, cooling it to obtain a solid B, drying it, calcining it in an air atmosphere, and cooling it to obtain a solid B; In step (S1), the ball milling speed is controlled at 500-2000 rpm, the ball milling time is 0.5-2h, and the ball milling bead diameter is 20-150mm; In step (S2), the ball milling speed is controlled at 50000-100000 rpm, the ball milling bead diameter is 1-10 mm, the ball milling crystallization time is 30 h, the pressure is 1-1.8 MPa, the ball milling crystallization temperature is 100-190° C., and the heating rate is 10° C. / min.

2. According to claim 1, a one-step synthesis of a multifunctional catalyst for denitrification and synergistic removal of CO / CH by solid phase high-speed and high-pressure ball milling method resistant to heavy metal and sulfur poisoning, characterized in that: The catalyst has a particle size of 1-7 μm and a specific surface area of ​​300-700 m 2 / g, the number of surface acidic sites is greater than 60μmol / g, and the average pore size is less than 10nm.

3. According to claim 1, a one-step synthesis of a multifunctional catalyst for denitrification and synergistic removal of CO / CH by solid phase high-speed and high-pressure ball milling method resistant to heavy metal and sulfur poisoning, characterized in that: The denitration active precursor is selected from one of ammonium metavanadate, vanadyl oxalate, vanadium trichloride, cerium dioxide, cerium nitrate, and manganese nitrate; the denitration auxiliary agent is selected from one of ammonium metatungstate, molybdenum nitrate, phosphoric acid, and thiourea; the denitration carrier is selected from one of titanium dioxide and zirconium dioxide; The oxidation active precursor is selected from one of ferric nitrate, ferric chloride, cobalt nitrate, cobalt chloride, copper nitrate and copper chloride; the oxidation part auxiliary agent is one of lanthanum nitrate, praseodymium nitrate, gadolinium nitrate and yttrium nitrate; The silicon source is selected from one of tetraethyl orthosilicate, silicic acid, silica sol, and white carbon black; the aluminum source is selected from one of aluminum sulfate, aluminum hydroxide, aluminum oxide, sodium aluminate, and aluminum isopropoxide; the alkali source is selected from one of n-butylamine and urea; and the template agent is selected from one of methanol, ethanol, ethylene glycol, and n-butanol.

4. According to claim 1, a one-step synthesis of a multifunctional catalyst for denitrification and synergistic removal of CO / CH by solid phase high-speed and high-pressure ball milling method resistant to heavy metal and sulfur poisoning, characterized in that: In step (S2), the calcination temperature is 500-600°C, the heating rate is 2-10°C / min, and the calcination time is 4.0-6.0h.

5. Use of a multifunctional catalyst for synergistic removal of CO / CH3 and denitrification resistant to heavy metal and sulfur poisoning synthesized by a one-step solid phase high-speed and high-pressure ball milling method according to any one of claims 1 to 4 in flue gas denitrification.

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