Recycling method for denitration and sulfur protection of high-sulfur flue gas and application

Abstract

The invention belongs to the technical field of high-sulfur flue gas treatment, and particularly relates to a high-sulfur flue gas denitration and sulfur protection recycling method and application. The recycling method for denitration and sulfur protection of the high-sulfur flue gas comprises the following steps: carrying out denitration treatment on the high-sulfur flue gas and then carrying out acid making treatment; the denitration treatment comprises the following steps: carrying out spontaneous reaction denitration on the high-sulfur flue gas under a spontaneous reaction condition; the spontaneous reaction condition comprises constant temperature and micro pressure; wherein the constant temperature ranges from 180 DEG C to 450 DEG C; and the pressure of the micro pressure is 1.01 atm to 1.5 atm. According to the recycling method for denitration and sulfur protection of the high-sulfur flue gas, external oxidation / reducing agents such as ammonia and ozone are not introduced in the whole process, and the secondary pollution problems such as ammonium bisulfate blockage, ammonia escape and ozone leakage are avoided from the source.

Description

Technical Field

[0001] This invention belongs to the field of high-sulfur flue gas treatment technology, specifically relating to a resource utilization method and application for high-sulfur flue gas denitrification and sulfur preservation. Background Technology

[0002] Industrial production processes such as non-ferrous metal smelting (e.g., copper, lead, zinc), thermal power generation, and coking generate large quantities of high-sulfur flue gas. This flue gas contains a high concentration of SO2, making it an important sulfur resource for sulfuric acid production. The existing general procedure for producing sulfuric acid from this high-sulfur flue gas involves acid production followed by desulfurization and denitrification to ensure the gas meets emission standards before being discharged as tail gas. A common process is the "two-stage conversion and absorption" process (where SO2 is reacted to produce finished sulfuric acid through two rounds of conversion and absorption reactions).

[0003] However, nitrogen oxides (NOx) also exist in high-sulfur flue gas. x (Mainly NO and NO2), the treatment of these pollutants will lead to the following serious problems: (1) Corrosion of acid production system: It causes severe corrosion of equipment such as heat exchangers, demisters and pipelines in the acid production system, increases system resistance, and seriously affects the continuity and economy of production.

[0004] (2) Affects product purity: NO x Nitric acid is added to sulfuric acid products during the acid production process, reducing product purity. At the same time, nitric acid is volatile and can corrode equipment, posing a health threat to workers' working environment.

[0005] (3) Problem of exhaust gas treatment: NO in the exhaust gas after acid production x Ozone oxidation absorption method for ozone removal has problems such as high ozone preparation cost, secondary pollution caused by ozone release, and high operating cost.

[0006] Therefore, existing technologies lack a method for selectively and efficiently removing NO in a high-concentration SO2 environment. x A targeted solution that does not introduce secondary pollution or affect sulfur resource recovery. Summary of the Invention

[0007] To address the aforementioned problems, this invention provides a resource utilization method and application for denitrification and sulfur retention of high-sulfur flue gas, thereby resolving at least one aspect of the above-mentioned technical problems.

[0008] This invention is achieved through the following technical solution: In a first aspect, the present invention provides a resource recovery method for denitrification and sulfur retention of high-sulfur flue gas, comprising the following steps: High-sulfur flue gas is treated for acid production after denitrification; The denitrification process includes the following steps: High-sulfur flue gas undergoes spontaneous denitrification under spontaneous reaction conditions; The spontaneous reaction conditions include constant temperature and micro-pressure; The constant temperature ranges from 180℃ to 450℃; the micro-pressure ranges from 1.01 atm to 1.5 atm.

[0009] Secondly, the present invention provides an application of the above-mentioned resource utilization method for denitrification and sulfur preservation of high-sulfur flue gas in the field of flue gas treatment. The resource utilization method for denitrification and sulfur retention of high-sulfur flue gas provided by this invention has at least the following beneficial technical effects compared with the prior art: The present invention provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. In the denitrification process, SO₂ in the high-sulfur flue gas is utilized under specific temperature and pressure conditions. x The concentration was much higher than that of NO. x The characteristics of the concentration make the NO in it x Can be used with SO x It reacts with H2O to produce a solid (NO) x ) a -(SO x ) b -(H2O) c (0 < a ≤ 3; 0 < b ≤ 5; 0 < c ≤ 6), while SO x The relative loss rate can be controlled below 0.1%, thereby removing NO from high-sulfur flue gas. x This process achieves spontaneous denitrification and sulfur retention of high-sulfur flue gas; after spontaneous denitrification, the high-sulfur flue gas undergoes acid production, achieving the dual goals of "denitrification" and "sulfur retention," and the separated solid (NO) x ) a -(SO x ) b -(H2O) c It can also be used as agricultural fertilizer, water purification adsorbent, and crop protection resource, thus realizing the high-level resource utilization of high-sulfur flue gas. Attached Figure Description

[0010] To more clearly illustrate the technical solutions in the embodiments of this drawing or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this drawing. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0011] Figure 1 The solid-state (NO) in Embodiment 1 of the present invention x ) a -(SOx ) b -(H2O) c Infrared spectrum; Figure 2 The solid-state (NO) in Embodiment 1 of the present invention x ) a -(SO x ) b -(H2O) c A picture of the actual product.

[0012] The purpose, features, and advantages of this accompanying drawing will be further explained in conjunction with the embodiments and with reference to the accompanying drawing. Detailed Implementation

[0013] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described and illustrated below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. All other embodiments obtained by those skilled in the art based on the embodiments provided by this invention without inventive effort are within the scope of protection of this invention.

[0014] Obviously, the following description is merely some examples or embodiments of the present invention. Those skilled in the art can apply the present invention to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this invention, modifications to design, manufacturing, or production based on the technical content disclosed in this invention are merely conventional technical means and should not be construed as insufficient disclosure of the present invention.

[0015] However, there may be instances where unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters or repetitive descriptions of essentially the same structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand the invention and is not intended to limit the subject matter of the claims.

[0016] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions, and all technical features and optional technical features of the present invention can be combined with each other to form new technical solutions.

[0017] High-sulfur flue gas contains a high concentration of sulfur (mainly SO2 and SO3), followed by nitrogen oxides. If selective catalytic reduction (SCR) or selective non-catalytic reduction (SNCR) technologies are used before acid production, reducing agents such as ammonia or urea need to be injected. However, in high-oxygen, high-sulfur environments, the consumption of reducing agents is large, and the escaped ammonia and SO3 easily form ammonium bisulfate, which can cause severe blockage and corrosion, resulting in significant sulfur resource loss. Furthermore, to fully utilize the sulfur resources in high-sulfur flue gas, this invention provides a resource utilization method for denitrification and sulfur preservation in high-sulfur flue gas, utilizing the SO2 in the flue gas... x with NO x The reaction between them will cause gaseous NO to... x The gas is converted into easily separable solids, thereby achieving the dual goals of "denitrification" and "sulfur retention". The separated solids can also be used as specific resources, thus realizing the high resource utilization of high-sulfur flue gas.

[0018] The following is a detailed description of a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas provided by an embodiment of the present invention.

[0019] The first aspect of this invention provides a resource recovery method for denitrification and sulfur retention of high-sulfur flue gas, comprising the following steps: S10. High-sulfur flue gas is treated for acid production after denitrification; Denitrification treatment includes the following steps: S101. High-sulfur flue gas undergoes spontaneous denitrification under spontaneous reaction conditions; Spontaneous reaction conditions include constant temperature and low pressure; The constant temperature ranges from 180℃ to 450℃; the micro-pressure ranges from 1.01 atm to 1.5 atm.

[0020] The resource utilization method for denitrification and sulfur retention of high-sulfur flue gas provided in this invention utilizes SO₂ in the high-sulfur flue gas under specific temperature and pressure conditions during the denitrification process. x The concentration was much higher than that of NO. x The characteristics of the concentration make the NO in it x Can be used with SO x It reacts with H2O to produce a solid (NO) x ) a -(SO x ) b -(H2O) c And SO x The relative loss rate can be controlled below 0.1%, thereby removing NO from high-sulfur flue gas. x This process achieves spontaneous denitrification and sulfur retention of high-sulfur flue gas; after spontaneous denitrification, the high-sulfur flue gas undergoes acid production, achieving the dual goals of "denitrification" and "sulfur retention," and the separated solid (NO) x) a -(SO x ) b -(H2O) c It can also be used as agricultural fertilizer, water purification adsorbent, and crop protection resource, thus achieving a high degree of resource utilization of high-sulfur flue gas. The resource utilization method for denitrification and sulfur retention of high-sulfur flue gas provided in this invention embodiment does not introduce external oxidizing / reducing agents such as ammonia and ozone throughout the entire process, thereby avoiding secondary pollution problems such as ammonium bisulfate blockage, ammonia escape, and ozone leakage from the source.

[0021] In this embodiment, the constant temperature is 180℃~450℃. Under these conditions, sufficient reaction kinetic energy can be provided while avoiding overheating and decomposition of reaction products or acid condensation due to excessively low temperatures.

[0022] In this embodiment, the micro-pressure is 1.01 atm to 1.5 atm. In this case, the pressure is higher than atmospheric pressure, which prevents air from entering and diluting the reactants, and facilitates subsequent gas-solid separation. The method of achieving the micro-pressure is conventional in the art and is not particularly limited in this embodiment. However, for illustrative purposes, the micro-pressure can be achieved by using a fan, compressor, or mechanical booster pump with a valve at the reactor outlet for throttling.

[0023] In some embodiments, in step S10 above, the flow rate of the high-sulfur flue gas is 8000 Nm³. 3 / (m 2 ·h)~70000Nm 3 / (m 2 ·h).

[0024] In some specific embodiments, the flow rate of the high-sulfur flue gas is 8000 Nm³. 3 / (m 2 ·h)~20000Nm 3 / (m 2 ·h).

[0025] In some specific embodiments, the flow rate of the high-sulfur flue gas is 8000 Nm³. 3 / (m 2 ·h)~50000Nm 3 / (m 2 ·h).

[0026] In some specific embodiments, the flow rate of the high-sulfur flue gas is 20,000 Nm³. 3 / (m 2 ·h)~50000Nm 3 / (m 2 ·h).

[0027] In some specific embodiments, the flow rate of the high-sulfur flue gas is 50,000 Nm³. 3 / (m 2 ·h)~70000Nm 3 / (m 2 ·h).

[0028] In some embodiments, in step S10 above, NO in the high-sulfur flue gas x The volume fractions of H2O and H2O are respectively: 0.01%~5% NO x 0.3%~8% H2O. Under these conditions, NO x The concentration of NO causes the reaction to spontaneously proceed towards NO. x The reaction proceeds in the correct direction and does not consume excessive amounts of SO. x Adequate amounts of water molecules in flue gas are key components in the formation of many sulfur and nitrate compounds (such as NOHSO4) and can catalyze certain reaction pathways.

[0029] In some specific embodiments, in high-sulfur flue gas, NO x The volume fractions of H2O and H2O are respectively: 0.01%~3% NO x 0.3%~6%H2O.

[0030] In some specific embodiments, in high-sulfur flue gas, NO x The volume fractions of H2O and H2O are respectively: 3%~5% NO x 6%~8%H2O.

[0031] In some embodiments, in step S10 above, SO in the high-sulfur flue gas x The volume fraction is 5%~20%.

[0032] In some specific embodiments, in high-sulfur flue gas, SO x The volume fraction is 5%~15%.

[0033] In some specific embodiments, in high-sulfur flue gas, SO x The volume fraction is 15%~20%.

[0034] In some embodiments, the spontaneous reaction conditions in step S101 above further include catalyst conditions. A catalyst consists of a support and a catalytically active component supported on the support.

[0035] In this case, the catalyst can simultaneously activate SO2 and NO in high-sulfur flue gas. x Molecules significantly reduce the activation energy of the reaction.

[0036] In some embodiments, the carrier includes at least one of TiO2 honeycomb ceramic, Al2O3 honeycomb ceramic, cordierite honeycomb ceramic, mullite honeycomb ceramic, ZrO2 honeycomb ceramic, and cordierite-mullite composite honeycomb ceramic.

[0037] In some embodiments, the catalytically active component includes at least one of Fe2O3, CuO, CeO2, Cr2O3, V2O5 / TiO2, Mn3O4, MnO2, IrO2, RuO2, Pt, perovskite, and spinel.

[0038] In some embodiments, the loading of the catalytically active component is 50 kg / m³. 3 ~360kg / m 3 .

[0039] In some specific embodiments, the loading of the catalytically active component is 80 kg / m³. 3 ~360kg / m 3 .

[0040] In some specific embodiments, the loading of the catalytically active component is 210 kg / m³. 3 ~360kg / m 3 .

[0041] In some specific embodiments, the loading of the catalytically active component is 210 kg / m³. 3 ~300kg / m 3 .

[0042] In some embodiments, the spontaneous reaction conditions in step S101 above further include catalyst promoter conditions; The catalyst promoter includes at least one of Fe-EDTA complex vapor, peracetic acid vapor, and methanol vapor.

[0043] In this case, the catalyst promoter is mixed into the high-sulfur flue gas and evenly distributed in the gas phase, thereby efficiently promoting spontaneous denitrification.

[0044] In some embodiments, the CAS number of the Fe-EDTA complex is 15708-41-5.

[0045] In some embodiments, the flow rate of the catalyst promoter is 0.005% to 1% of the high-sulfur flue gas flow rate.

[0046] In some specific embodiments, the flow rate of the catalyst promoter is 0.05% to 1% of the high-sulfur flue gas flow rate.

[0047] In some embodiments, the spontaneous reaction conditions in step S101 above further include nucleating agent conditions; Nucleating agents include at least one of sodium carbonate, magnesium sulfate, calcium nitrate, calcium hydroxyphosphate, and hydroxyethyl cellulose.

[0048] In this context, nucleating agents guide the rapid nucleation of gas-gas reaction products and the formation of fine particulate matter such as inorganic salts (e.g., carbonates, sulfates, and nitrates) and organic polymers.

[0049] In some embodiments, the amount of nucleating agent used is 5% to 40% of the catalyst mass.

[0050] In some specific embodiments, the amount of nucleating agent used is 10% to 30% of the catalyst mass.

[0051] In some embodiments, the spontaneous reaction condition in step S101 above further includes an external physical field coupling condition. The external physical field includes at least one of the following: ultrasonic field, plasma field, and hypergravity field.

[0052] In this context, the cavitation effect of the ultrasonic field generates localized high temperature and pressure in the high-sulfur flue gas, improving the efficiency of spontaneous denitrification; the plasma field generates highly reactive free radicals in the high-sulfur flue gas, further enhancing the efficiency of spontaneous denitrification; and the hypergravity field can significantly enhance SO2 denitrification. x NO x The microscopic mixing process with H2O promotes gas-solid (solid-state NO) x ) a -(SO x ) b -(H2O) c The separation process of flue gas (after spontaneous reaction).

[0053] In some embodiments, the ultrasonic frequency of the ultrasonic field is 20 kHz to 100 MHz.

[0054] In some specific embodiments, the ultrasonic frequency of the ultrasonic field is 20kHz to 80kHz.

[0055] In some specific embodiments, the ultrasonic frequency of the ultrasonic field is 20MHz to 80MHz.

[0056] In some specific embodiments, the ultrasonic frequency of the ultrasonic field is 80MHz~100MHz.

[0057] In some embodiments, the average electron energy of the plasma field is 1 eV to 40 eV.

[0058] In some specific embodiments, the average electron energy of the plasma field is 1 eV to 8 eV.

[0059] In some specific embodiments, the average electron energy of the plasma field is 8 eV to 20 eV.

[0060] In some specific embodiments, the average electron energy of the plasma field is 20 eV to 40 eV.

[0061] In some embodiments, the hypergravity field is 1g to 5g.

[0062] In some embodiments, the denitrification process in step S10 above further includes the following steps: S102. High-sulfur flue gas undergoes gas-solid separation after spontaneous denitrification.

[0063] In some embodiments, in step S102 above, the gas-solid separation method includes at least one of cyclone separation and filtration separation.

[0064] In some embodiments, in step S10 above, the acid production process includes the following steps: S103. Use the high-sulfur flue gas after denitrification to produce acid.

[0065] It should be noted that the acid production process is a conventional technology in the field and has not been modified in any way in the embodiments of the present invention. Therefore, it is not particularly limited in the embodiments of the present invention.

[0066] The following description, in conjunction with specific embodiments, provides further details. Example 1

[0067] Example 1 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas, the steps of which are as follows: E10. Denitrification treatment High-sulfur flue gas undergoes spontaneous denitrification under spontaneous reaction conditions; The conditions for spontaneous reaction are constant temperature and micro-pressure and catalyst conditions; The constant temperature was 310℃; the micro-pressure was 1.3 atm. The flow rate of the high-sulfur flue gas is 20000 Nm³. 3 / (m 2 ·h); In high-sulfur flue gas, NO x , H2O and SO x The volume fractions are as follows: 2% NO x 5% H2O, 10% SO x ; In the catalyst conditions, the catalyst is ZrO2 honeycomb ceramic and V2O5 / TiO2 supported on ZrO2 honeycomb ceramic (V2O5 / TiO2 mass ratio of 3:2), with a loading of 210 kg / m³. 3 .

[0068] E20. Acid production treatment The flue gas obtained after denitrification is then used for acid production. Example 2

[0069] Example 2 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, the constant temperature is 450℃; the micro-pressure is 1.5 atm. The flow rate of the high-sulfur flue gas is 70,000 Nm³. 3 / (m 2 ·h). Example 3

[0070] Example 3 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, the constant temperature is 180℃; the micro-pressure is 1.01 atm. The flow rate of the high-sulfur flue gas is 8000 Nm³. 3 / (m 2 ·h). Example 4

[0071] Example 4 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, in the high-sulfur flue gas, NO x , H2O and SO x The volume fractions are as follows: 0.01% NO x 0.3% H2O, 5% SO x . Example 5

[0072] Example 5 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, in the high-sulfur flue gas, NO x , H2O and SO x The volume fractions are as follows: 3% NO x 6% H2O, 15% SO x . Example 6

[0073] Example 6 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, in the high-sulfur flue gas, NO x , H2O and SO x The volume fractions are as follows: 5% NO x8% H2O, 20% SO x . Example 7

[0074] Example 7 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, the spontaneous reaction conditions are isothermal micro-pressure, catalyst conditions, and nucleating agent conditions; Sodium carbonate is used as the nucleating agent, and its dosage is 17% of the catalyst mass. Example 8

[0075] Example 8 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, the spontaneous reaction conditions are isothermal micro-pressure, catalyst conditions, and nucleating agent conditions; The nucleating agent is sodium carbonate, and its dosage is 5% of the catalyst mass. Example 9

[0076] Example 9 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, the spontaneous reaction conditions are isothermal micro-pressure, catalyst conditions, and nucleating agent conditions; The nucleating agent is sodium carbonate, and its dosage is 10% of the catalyst mass. Example 10

[0077] Example 10 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, the spontaneous reaction conditions are isothermal micro-pressure, catalyst conditions, and nucleating agent conditions; Sodium carbonate is used as the nucleating agent, and its dosage is 30% of the catalyst mass. Example 11

[0078] Example 11 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, the spontaneous reaction conditions are isothermal micro-pressure, catalyst conditions, and nucleating agent conditions; Sodium carbonate is used as the nucleating agent, and its dosage is 40% of the catalyst mass. Example 12

[0079] Example 12 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 7, except that: In step E10, the spontaneous reaction conditions are isothermal micro-pressure, catalyst conditions, nucleating agent conditions, and catalyst promoter conditions; The catalyst promoter is peracetic acid vapor, and its flow rate is 0.05% of the high-sulfur flue gas flow rate. Example 13

[0080] Example 13 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 7, except that: In step E10, the spontaneous reaction conditions are isothermal micro-pressure, catalyst conditions, nucleating agent conditions, and catalyst promoter conditions; The catalyst promoter is peracetic acid vapor, and its flow rate is 0.005% of the high-sulfur flue gas flow rate. Example 14

[0081] Example 14 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 7, except that: In step E10, the spontaneous reaction conditions are isothermal micro-pressure, catalyst conditions, nucleating agent conditions, and catalyst promoter conditions; The catalyst promoter is peracetic acid vapor, and its flow rate is 1% of the high-sulfur flue gas flow rate. Example 15

[0082] Example 15 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 12, except that: In step E10, the spontaneous reaction conditions are isothermal micro-pressure, catalyst conditions, nucleating agent conditions, catalyst promoter conditions, and ultrasonic field. The ultrasonic frequency of the ultrasonic field is 80 kHz. Example 16

[0083] Example 16 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 12, except that: The ultrasonic frequency of the ultrasonic field is 20MHz. Example 17

[0084] Example 17 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 12, except that: The ultrasonic frequency of the ultrasonic field is 100MHz. Example 18

[0085] Example 18 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 15, except that: In step E10, the spontaneous reaction conditions are isothermal micro-pressure, catalyst conditions, nucleating agent conditions, catalyst promoter conditions, ultrasonic field and plasma field; The average energy of electrons in the plasma field is 12 eV. Example 19

[0086] Example 19 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 15, except that: The average energy of electrons in the plasma field is 1 eV. Example 20

[0087] Example 20 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 15, except that: The average energy of electrons in the plasma field is 25 eV. Example 21

[0088] Example 21 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 15, except that: The average energy of electrons in the plasma field is 40 eV. Example 22

[0089] Example 22 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 18, except that: In step E10, the spontaneous reaction conditions are isothermal micro-pressure, catalyst conditions, nucleating agent conditions, catalyst promoter conditions, ultrasonic field, plasma field, and hypergravity field; The hypergravity field is 3 g.

[0090] Comparative Example 1 Comparative Example 1 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, the denitrification temperature is 230℃, the denitrification pressure is 1 standard atmosphere (1 atm), and the H2O concentration is 0%.

[0091] Comparative Example 2 Comparative Example 2 provides a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas. The steps are basically the same as those in Example 1, except that: In step E10, the denitrification temperature is 100℃ and the denitrification pressure is 1.3 atm.

[0092] To verify the advancement of the resource recovery method for high-sulfur flue gas denitrification and sulfur preservation provided in this embodiment of the invention, the flue gas after denitrification treatment in the resource recovery methods for high-sulfur flue gas denitrification and sulfur preservation in this embodiment and comparative example of the invention was subjected to NO treatment. x and SO x The concentration was detected, and the results are shown in Table 1 below. Infrared spectroscopy was also performed on Example 1, and the results are shown in the appendix. Figure 1 ; Figure 2 This is an appearance diagram of the solid product generated in Example 1.

[0093] Table 1 From Table 1 and the accompanying drawings, at least the following conclusions can be drawn: (1) In the embodiments, the removal effect of nitrogen oxides in Comparative Example 1 under standard atmospheric pressure and a completely dry environment and in Comparative Example 2 at low temperature was very poor, and it can be considered that almost no removal was achieved, and almost no solid matter was generated. Therefore, the resource utilization method for denitrification and sulfur preservation of high-sulfur flue gas provided in this embodiment of the invention can effectively remove low concentrations of NO from high-sulfur flue gas by reasonably controlling the spontaneous denitrification reaction. x and achieve NO x Emissions targets require that the degree of completeness of this spontaneous denitrification reaction be correlated with the reaction's effect on SO2 emissions. x The consumption of nitrogen oxides (NOx) is profoundly affected by temperature, pressure, flow rate, concentration, as well as the catalyst, nucleating agent, and applied physical field. The reaction has a reaction window limited by temperature, pressure, concentration, and flow rate. Optimal catalysts, nucleating agents, and applied physical fields can, within a certain range, enable the spontaneous denitrification reaction to proceed more completely, achieving the best denitrification effect and minimizing SOx emissions. x loss.

[0094] (2) Figure 2 This is an image of the solid product generated in Example 1. Figure 1 In the middle, the characteristics of each absorption peak can be used to identify chemical structures, 3437 cm⁻¹ -1 The absorption peak at 2275 cm⁻¹ usually represents OH or NH; -1 Represents N3 -1 (Azide) or SH vibrational mode; 1631 cm -1 The absorption peak is related to water molecules HOH or NH; 1177 cm⁻¹ -1 The absorption peak at 1069 cm⁻¹ indicates the presence of S=O; -1 It may be related to SO or O=S=O; in addition, 885cm -1 and 852cm -1 This is a typical characteristic absorption of SO; 655 cm⁻¹ -1 Related to NO; 579cm -1 Related to HO; 452cm -1This is formed by metal-N or metal-S, and is usually found in complexes. In summary, the infrared spectral characteristics support the inclusion of SNOH elements in the composition of the solid. It should be noted that this invention is not limited to the above embodiments. The above embodiments are merely examples, and embodiments with essentially the same structure and effect as the technical concept within the scope of this invention are all included within the scope of this invention. Furthermore, various modifications to the embodiments that can be conceived by those skilled in the art, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this invention, are also included within the scope of this invention.

Claims

1. A resource utilization method for denitrification and sulfur retention of high-sulfur flue gas, characterized in that, Includes the following steps: High-sulfur flue gas is treated for acid production after denitrification; The denitrification process includes the following steps: High-sulfur flue gas undergoes spontaneous denitrification under spontaneous reaction conditions; The spontaneous reaction conditions include constant temperature and micro-pressure; The constant temperature ranges from 180℃ to 450℃; the micro-pressure ranges from 1.01 atm to 1.5 atm.

2. The resource utilization method for denitrification and sulfur retention of high-sulfur flue gas according to claim 1, characterized in that, The spontaneous reaction conditions also include catalyst conditions; A catalyst consists of a support and a catalytically active component supported on the support.

3. The resource utilization method for denitrification and sulfur retention of high-sulfur flue gas according to claim 2, characterized in that, It satisfies at least one of the following characteristics (1) to (3): (1) The carrier includes at least one of TiO2 honeycomb ceramic, Al2O3 honeycomb ceramic, cordierite honeycomb ceramic, mullite honeycomb ceramic, ZrO2 honeycomb ceramic, and cordierite-mullite composite honeycomb ceramic; (2) The catalytically active component includes at least one of Fe2O3, CuO, CeO2, Cr2O3, V2O5 / TiO2, Mn3O4, MnO2, IrO2, RuO2, Pt, perovskite, and spinel; (3) The loading of the catalytically active component is 50 kg / m³. 3 ~360kg / m 3 .

4. The resource utilization method for denitrification and sulfur retention of high-sulfur flue gas according to claim 3, characterized in that, The spontaneous reaction conditions also include catalyst promoter conditions; The catalyst promoter includes at least one of Fe-EDTA complex vapor, peracetic acid vapor, and methanol vapor.

5. The resource utilization method for denitrification and sulfur retention of high-sulfur flue gas according to claim 4, characterized in that, The flow rate of the catalyst promoter is 0.005% to 1% of the flow rate of the high-sulfur flue gas.

6. The resource utilization method for denitrification and sulfur retention of high-sulfur flue gas according to claim 5, characterized in that, The spontaneous reaction conditions also include nucleating agent conditions; Nucleating agents include at least one of sodium carbonate, magnesium sulfate, calcium nitrate, calcium hydroxyphosphate, and hydroxyethyl cellulose.

7. The resource utilization method for denitrification and sulfur retention of high-sulfur flue gas according to claim 6, characterized in that, It satisfies at least one of the following characteristics (1) to (2): (1) The amount of the nucleating agent is 5% to 40% of the catalyst mass; (2) The spontaneous reaction conditions also include the external physical field coupling conditions; The applied physical field includes at least one of ultrasonic field, plasma field, and hypergravity field.

8. The resource utilization method for denitrification and sulfur retention of high-sulfur flue gas according to any one of claims 1 to 7, characterized in that, It satisfies at least one of the following characteristics (1) to (3): (1) The flow rate of the high-sulfur flue gas is 8000 Nm³. 3 / (m 2 ·h)~70000Nm 3 / (m 2 ·h); (2) In the high-sulfur flue gas, NO x The volume fractions of H2O and H2O are respectively: 0.01%~5%NO x 0.3%~8%H2O; (3) In the high-sulfur flue gas, SO x The volume fraction is 5%~20%.

9. The resource utilization method for denitrification and sulfur retention of high-sulfur flue gas according to claim 8, characterized in that, The denitrification process also includes the following steps: High-sulfur flue gas undergoes gas-solid separation after spontaneous denitrification.

10. The application of a resource utilization method for denitrification and sulfur retention of high-sulfur flue gas as described in any one of claims 1 to 9 in the field of flue gas treatment.

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