Reactor assembly, sulfur-containing waste treatment system, method for burning sulfur-containing waste, and method for producing sulfuric acid by regenerating sulfur-containing waste

Abstract

The present invention discloses a reactor assembly and a sulfur-containing waste treatment system, the reactor assembly including a cylindrical furnace for a combustion reaction of a sulfur-containing waste mixed solution, a fuel gas inlet and a process gas outlet communicating with the furnace, the fuel gas inlet and the process gas outlet being spaced apart from each other along the axial direction of the furnace at both ends of the furnace, the fuel gas inlet being configured to supply fuel gas flowing along the axial direction of the furnace to the furnace, and the reactor assembly including a combustion supporting air supply mechanism configured to supply combustion supporting air flowing along the circumferential direction of the inner wall of the furnace to the furnace.

Description

Detailed Description of the Invention

[0001] [Cross - Reference to Related Applications] This application claims the benefit of Chinese Patent Applications 202011148953.4, 202011150297.1 filed on October 23, 2020, and Chinese Patent Applications 202110739636.8, 202110736744.X, 202110736751.X, 202110736752.4, 202121481507.5, 202110736743.5 filed on June 30, 2021, the contents of these eight applications are incorporated herein by reference.

[0002] [Technical Field] The present invention relates to the treatment of sulfur - containing waste, specifically to a reactor assembly, a sulfur - containing waste treatment system, a combustion method of sulfur - containing waste, and a sulfuric acid production method by sulfur - containing waste regeneration.

[0003] [Background Art] The petrochemical industry and the organic synthesis industry widely use concentrated sulfuric acid as a catalyst, and a large amount of waste sulfuric acid is generated in this process. Some organic synthesis processes such as the synthesis of methyl methacrylate (MMA) and acrylonitrile (AN) produce about 30 - 45 wt% of ammonium sulfate waste sulfuric acid in addition to waste sulfuric acid. Since these sulfur - containing wastes cause serious environmental pollution, it is necessary to purify and recycle industrial waste acids and sulfur - containing waste liquids to the maximum extent.

[0004] The treatment methods of sulfur - containing waste mainly include high - temperature concentration, solvent extraction, alkali neutralization and chemical oxidation, high - temperature combustion decomposition, etc. Currently, the high - temperature combustion method has the problems of being thorough and environmentally friendly, but having low combustion efficiency, high operation cost, and complex operation.

[0005] [Summary of the Invention] [Problems to be Solved by the Invention] The object of the present invention is to solve the problems existing in the prior art and provide a reactor assembly and a sulfur - containing waste treatment system that can burn sulfur - containing waste and suppress the generation of nitrogen oxides.

[0006] [Means for Solving the Problem] To achieve the above object, the present invention provides a reactor assembly, wherein the reactor assembly includes a furnace for supplying sulfur-containing waste and performing a combustion reaction, a fuel gas inlet and a process gas outlet respectively communicating with the furnace, the fuel gas inlet and the process gas outlet are provided at both ends of the furnace with a space therebetween along the axial direction of the furnace, the fuel gas inlet includes a reactor body having a cylindrical structure configured to supply fuel flowing along the axial direction of the furnace to the furnace, and a combustion air supply mechanism configured to supply combustion air flowing along the circumferential direction of the inner wall of the furnace to the furnace.

[0007] Preferably, the combustion air supply mechanism includes a plurality of groups of combustion air supply ports distributed with a space therebetween along the axial direction of the furnace.

[0008] Preferably, the plurality of groups of combustion air supply ports include a first air supply port group and a second air supply port group, the first air supply port group is provided close to the fuel gas inlet, and the second air supply port group is provided close to the process gas outlet. The reactor assembly includes a control device for controlling the combustion air supply mechanism, which is configured to control air to enter from the first air supply port group and control the oxygen amount at the position of the first air supply port group to be a first oxygen amount, and control air to enter from the second air supply port group and control the oxygen amount at the position of the second air supply port group to be a second oxygen amount which is the theoretical oxygen amount for normal combustion of sulfur-containing waste and is larger than the first oxygen amount, and further control at least two combustions including a first combustion corresponding to the first oxygen amount and a second combustion corresponding to the second oxygen amount of the fuel and the sulfur-containing waste to be combusted, and finally obtain sulfur dioxide-containing gas.

[0009] Preferably, in the first combustion, the oxygen coefficient is X1, the temperature is 1100 - 1250°C, in the last combustion, the oxygen coefficient is X3, the temperature is 1000 - 1100°C, and in the optionally present surplus combustion, the oxygen coefficients are each independently X2, the temperatures are each independently 1100 - 1200°C, and 0.5 ≤ X1 ≤ 0.85, 0.7 ≤ X1 + X2 ≤ 1, 1 ≤ X1 + X2 + X3 ≤ 1.15. The oxygen coefficient is the ratio of the oxygen-containing combustion-supporting gas converted to the oxygen molar content to the oxygen molar content required for the complete combustion of the fuel.

[0010] According to the above technical solution, the fuel gas enters the furnace from the fuel gas inlet and flows along the axial direction of the furnace, and the combustion-supporting air supplied by the combustion-supporting air supply mechanism can flow along the circumferential direction of the inner wall of the furnace. As a result, the mixed gas of the fuel gas and the combustion-supporting air flows spirally to the process gas outlet. Therefore, in the process of flowing spirally, the residence time of the mixed gas in the furnace becomes more sufficient, and it can fully react with the sulfur-containing waste liquid by combustion. Thereby, the combustion efficiency of the reactor assembly is increased. Also, since the mixed gas can stay in the furnace for a longer time, the distance between the fuel gas inlet and the process gas outlet is short, and the reactor assembly of the present invention can be miniaturized.

[0011] The present invention also provides a sulfur-containing waste treatment system including the above reactor assembly for subjecting a sulfur-containing waste to a combustion reaction to obtain a first gas containing sulfur dioxide, a heat energy recovery unit for recovering heat energy from the first gas to obtain a second gas, a purification and cooling unit for purifying and cooling the second gas to obtain a third gas, a drying unit for drying the third gas to obtain a fourth gas, and an oxidation and absorption unit for oxidizing and absorbing the fourth gas to obtain sulfuric acid and an exhaust gas.

[0012] According to the above technical solution, by adopting the sulfur-containing waste treatment system and the reactor assembly according to the present invention, in the reactor, first, oxygen-deficient combustion occurs, reducing the generation of nitrogen oxides. Next, oxygen-enriched combustion occurs at the end, and the desired combustion is carried out. However, since the temperature at the end is low, the generation of nitrogen oxides is also reduced. The reduction of nitrogen oxides improves the sulfur dioxide content in the process gas, and since the desired combustion is carried out, it does not affect the normal process.

[0013] The present invention provides a method for burning sulfur-containing waste based on the above reactor assembly, and a method for producing sulfuric acid by regenerating sulfur-containing waste based on the above sulfur-containing waste treatment system.

[0014] 〔Advantages of the Invention〕 The positive and progressive effects of the present invention are as follows. The present invention provides an optimized and improved mixing treatment process and device for waste sulfuric acid, sulfur-containing solid waste, sulfur-containing waste liquid, and sulfur-containing waste gas, which shortens the process flow as much as possible, reduces the equipment, simplifies the operation, and improves the utilization rate of thermal energy. The sulfur element in the raw material is regenerated into sulfuric acid and fuming sulfuric acid with a concentration of 93-100%.

[0015] 〔Brief Description of the Drawings〕 〔Figure 1〕It is a schematic diagram of the reactor assembly in one embodiment of the present invention.

[0016] 〔Figure 2〕It is a side view of the furnace of the reactor assembly of the present invention.

[0017] 〔Figure 3〕It is a front view of the furnace of the reactor assembly of the present invention.

[0018] 〔Figure 4〕It is a schematic diagram of the heating device of the reactor assembly of the present invention.

[0019] 〔Figure 5〕It is a flowchart of the reactor combustion control method of the sulfur-containing waste treatment system according to one embodiment of the present invention.

[0020] FIG. 6 is a flowchart of a reactor combustion control method for a sulfur-containing waste treatment system according to an embodiment of the present invention.

[0021] FIG. 7 is a schematic diagram of a process flow of a sulfur-containing waste treatment system according to an embodiment of the present invention.

[0022] FIG. 8 is a flowchart of a sulfuric acid production method by regenerating sulfur-containing waste according to the present invention.

[0023] FIG. 9 is a schematic diagram of a dust collection unit and a heat energy recovery unit.

[0024] FIG. 10 is a schematic diagram of a quench humidification tower.

[0025] FIG. 11 is a schematic diagram of a cooling absorption tower.

[0026] FIG. 12 is a schematic diagram of an oxidation absorption unit.

[0027] FIG. 13 is a schematic diagram of a converter.

[0028] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, specific embodiments of the present invention will be described in detail with reference to the drawings. It should be noted that the specific embodiments described herein are merely for explaining and interpreting the present invention and do not limit the present invention.

[0029] As shown in FIGS. 1 to 3, the reactor assembly of the present invention includes a reactor body 100 having a cylindrical furnace 111 for the combustion reaction of sulfur-containing waste. The reactor body 100 is further provided with a fuel gas inlet 112 and a process gas outlet 113 that communicate with the furnace 111. The fuel gas inlet 112 and the process gas outlet 113 are provided at both ends of the furnace 111 with a space along the axial direction of the furnace 111. The fuel gas inlet 112 is configured to supply fuel gas flowing along the axial direction of the furnace 111 to the furnace 111. The reactor assembly 100 further includes a combustion air supply mechanism configured to supply combustion air flowing along the circumferential direction of the inner wall of the furnace 111.

[0030] In the present invention, fuel gas enters the furnace 111 from the fuel gas inlet 112 and flows along the axial direction of the furnace 111. Also, the combustion-supporting air supplied to the furnace 111 by the combustion-supporting air supply mechanism can flow along the circumferential direction of the inner wall of the furnace 111. As a result, the mixed gas of the fuel gas and the combustion-supporting air flows in a spiral shape (see FIG. 2) to the process gas outlet 113. Thus, in the process of flowing in a spiral shape, the residence time of the mixed gas in the furnace 111 becomes more sufficient, and it can fully undergo a combustion reaction with the sulfur-containing waste liquid mixture. As a result, the combustion efficiency of the reactor assembly is increased. Also, since the mixed gas can stay in the furnace 111 for a longer time, the distance between the fuel gas inlet 112 and the process gas outlet 113 is short, and miniaturization of the reactor assembly of the present invention is achieved.

[0031] Note that the combustion-supporting air supply mechanism may be designed in various forms to drive the combustion-supporting air to flow along the circumferential direction of the inner wall of the furnace 111 in the furnace 111. For example, the combustion-supporting air supply mechanism may include a combustion-supporting air nozzle and a guide fan. The combustion-supporting air nozzle is used to supply combustion air to the furnace 111, and the guide fan is provided in the furnace 111 to change the flow direction of the combustion-supporting air, enabling the combustion-supporting air to flow along the circumferential direction of the inner wall of the furnace 111 under the guidance of the guide fan after exiting the combustion-supporting air nozzle. In order to further reduce costs and simplify the structure of the reactor assembly, in one embodiment of the present invention, the combustion-supporting air supply mechanism includes a combustion-supporting air inlet group. The combustion-supporting air inlet group includes a first combustion-supporting air inlet 114 and a second combustion-supporting air inlet 115 that are respectively in communication with the furnace 111. The first combustion-supporting air inlet 114 and the second combustion-supporting air inlet 115 are respectively provided so as to be able to supply combustion-supporting air to the furnace 111 along the tangential direction of the furnace 111, and the flow direction of the combustion-supporting air supplied by the first combustion-supporting air inlet 114 is the same as the flow direction of the combustion-supporting air supplied by the second combustion-supporting air inlet 115. Since both the first combustion-supporting air inlet 114 and the second combustion-supporting air inlet 115 are opened along the tangential direction of the inner wall of the furnace 111, all the combustion-supporting air ejected from the first combustion-supporting air inlet 114 and the second combustion-supporting air inlet 115 can flow in the circumferential direction of the inner wall of the furnace 111. Thereby, other members are omitted, the structure is simplified, and maintenance is facilitated.

[0032] Of course, in addition to the first combustion-supporting air inlet 114 and the second combustion-supporting air inlet 115, the combustion-supporting air inlet group may include a third combustion-supporting air inlet, a fourth combustion-supporting air inlet, etc. All these combustion-supporting air inlets are located in the same radial plane of the furnace 111 and are also provided to open in the same direction (i.e., both clockwise or counterclockwise). In this way, it is possible to realize the spiral flow of the mixed gas in the furnace 111.

[0033] It should be noted that, in one embodiment of the present invention, as shown in FIGS. 2 and 3, the opening directions of both the first combustion-supporting air inlet 114 and the second combustion-supporting air inlet 115 are perpendicular to the axial direction of the furnace 111, that is, the flow direction of the fuel gas is perpendicular to the plane formed by the flow direction of the combustion-supporting air. In another embodiment of the present invention, the opening directions of both the first combustion-supporting air inlet 114 and the second combustion-supporting air inlet 115 are inclined toward the fuel gas inlet 112. According to such a configuration, since the direction in which the combustion-supporting air enters and flows in the furnace 111 is opposite to the flow direction of the fuel gas, the combustion-supporting air and the fuel gas are more sufficiently mixed, the flow rate of the mixed gas decreases, the flow time of the mixed gas in the furnace 111 increases, and the reactor assembly has the advantage of being more miniaturized. Of course, for example, the opening directions of the first combustion-supporting air inlet 114 and the second combustion-supporting air inlet 115 may be slightly inclined toward the fuel gas inlet 112, such as being inclined 20 to 40° toward the fuel gas inlet 112.

[0034] In order to supply the combustion-supporting air more sufficiently, in one embodiment of the present invention, as shown in FIG. 2, the combustion-supporting air supply mechanism includes a plurality of groups of combustion-supporting air supply ports, and the plurality of groups of combustion-supporting air supply ports are distributed at intervals along the axial direction of the furnace 111. In the illustrated preferred embodiment, the reactor body 100 is provided with two aforementioned first combustion-supporting air inlets 114 and second combustion-supporting air inlets 115 respectively. Here, the combustion-supporting air inlets 114a and 115a close to the fuel gas inlet 112 constitute the first air supply port group, and the combustion-supporting air inlets 114b and 115b close to the process gas outlet 113 constitute the second air supply port group. Therefore, the combustion of the sulfur-containing waste can be controlled by the amount of combustion-supporting air introduced into the furnace 111 from the first air supply port group and the second air supply port group.

[0035] Specifically, the flowchart of the reactor combustion control method of the sulfur-containing waste treatment system shown in FIG. 5 includes steps S11 to S13.

[0036] Step S11: Detect the amount of oxygen at the positions of the first air supply port group and the second air supply port group.

[0037] For example, an oxygen sensor for detecting the amount of oxygen may be provided in the first air supply port group and the second air supply port group.

[0038] Step S12: Control such that air enters from the first air supply port group and the amount of oxygen at the position of the first air supply port group becomes a first oxygen amount.

[0039] For example, referring to the amount of oxygen at the position of the first air supply port group, air may be replenished / decreased to the first air supply port group so that the amount of oxygen at the position of the first air supply port group becomes the first oxygen amount. The first oxygen amount is, for example, 60% of the theoretical oxygen amount by normal combustion of sulfur-containing waste. Thereby, the sulfur-containing waste undergoes oxygen-deficient combustion, and when reacting substances containing nitrogen elements contained therein, such as (NH4)2SO4 and / or NH4HSO4, the generation of nitrogen oxides is reduced.

[0040] Step S13: Control such that the air enters from the second air supply port group and the amount of oxygen at the position of the second air supply port group becomes a second oxygen amount that is the theoretical oxygen amount by normal combustion of sulfur-containing waste and is greater than the first oxygen amount.

[0041] For example, in order to achieve normal combustion, air is replenished to the second air supply port group at the end of the reactor so that the amount of oxygen at the position of the second air supply port group becomes the second oxygen amount. The second oxygen amount is, for example, the theoretical oxygen amount by normal combustion of sulfur-containing waste, and the sulfur-containing waste is made to undergo normal combustion. Since the generation amount of nitrogen oxides is related to temperature, that is, it increases as the temperature rises, when the temperature at a position away from the flame center at the end of the reactor is low, although the amount of oxygen is sufficient, the generation amount of nitrogen oxides decreases.

[0042] When the above method is adopted, since nitrogen oxides are reduced, the content of sulfur dioxide in the process gas in the reactor is improved, and since the desired combustion is performed, it does not affect the normal process.

[0043] FIG. 6 is a flowchart of a reactor combustion control method for a sulfur-containing waste treatment system according to another embodiment of the present invention. In this embodiment, the reactor body further includes a third air supply port provided at the central portion of the reactor body, and the method includes steps S21 to S24.

[0044] Step S21: Detect the amount of oxygen at the positions of the first air supply port group and the second air supply port group.

[0045] Step S22: Control so that air enters from the first air supply port group and the amount of oxygen at the position of the first air supply port group becomes a first oxygen amount.

[0046] For example, the embodiments of steps S21 to S22 are similar to the embodiments of steps S11 to S12 described above, and will not be described in detail here.

[0047] Step S23: Control so that the air enters from the third air supply port group and the amount of oxygen at the position of the third air supply port group becomes a third oxygen amount. The third oxygen amount may be, for example, 95% of the second oxygen amount. Also by this, the sulfur-containing waste undergoes oxygen-deficient combustion, and the generation of nitrogen oxides during the reaction of substances containing nitrogen elements contained therein, such as (NH4)2SO4 and / or NH4HSO4, is reduced.

[0048] Step S24: Control so that the air enters from the second air supply port group and the amount of oxygen at the position of the second air supply port group becomes a second oxygen amount that is the theoretical oxygen amount for normal combustion of the sulfur-containing waste, is larger than the first oxygen amount, and is larger than the third oxygen amount.

[0049] For example, similarly, in order to perform normal combustion, air is replenished to the second air supply port group at the end of the reactor, the amount of oxygen at the position of the second air supply port group is made the second oxygen amount, and the sulfur-containing waste is caused to perform normal combustion.

[0050] Note that in the above, only the embodiments having two air supply port groups and three air supply port groups have been described. However, the reactor may have more air supply ports. For example, it may have a plurality of third air supply port groups, and these air supply ports may supply air simultaneously. As long as the amount of oxygen at the position of the terminal air supply port is the theoretical oxygen amount due to the normal combustion of the sulfur-containing waste, and the amount of oxygen at the positions of the remaining air supply ports is all smaller than the theoretical oxygen amount due to the normal combustion of the sulfur-containing waste, it will not be described in detail here.

[0051] In the above process, the fuel and the sulfur-containing waste to be burned are controlled to perform at least two combustions including the first combustion corresponding to the first oxygen amount and the second combustion corresponding to the second oxygen amount, and finally obtain a sulfur dioxide-containing gas.

[0052] Here, in the first combustion, the oxygen coefficient is X1, the temperature is 1100 - 1250 °C, in the last combustion, the oxygen coefficient is X3, the temperature is 1000 - 1100 °C, in the optionally existing surplus combustion, the oxygen coefficients are each independently X2, the temperatures are each independently 1100 - 1200 °C, and 0.5 ≤ X1 ≤ 0.85, 0.7 ≤ X1 + X2 ≤ 1, 1 ≤ X1 + X2 + X3 ≤ 1.15. The oxygen coefficient is the ratio of the molar amount of the oxygen-containing combustion-supporting gas converted into contained oxygen to the molar amount of oxygen required for the complete combustion of the fuel.

[0053] In the present invention, the oxygen coefficient is the ratio of the molar amount of the oxygen-containing combustion-supporting gas converted into contained oxygen for each combustion to the molar amount of oxygen required for the complete combustion of the fuel. Here, the fuel is the initial total fuel, not the remaining fuel after the previous combustion.

[0054] According to the present invention, in the present invention, the usage amount of the oxygen-containing combustion-supporting gas is controlled for each combustion to adjust the oxygen coefficient for each combustion, and together with other process conditions for each combustion, such as temperature, the sulfur-containing waste is sufficiently burned to obtain a process gas with a high sulfur dioxide content.

[0055] Furthermore, especially in the case of a reaction material containing a nitrogen element, when the method according to the present invention is adopted, without the need for additional denitrification treatment, the content of nitrogen oxides (NO x ) in the obtained process gas can be significantly reduced, which is environmentally friendly, economical and efficient.

[0056] Preferably, in the first combustion, the oxygen coefficient is X1, the temperature is 1150 - 1250 °C, in the last combustion, the oxygen coefficient is X3, the temperature is 1050 - 1100 °C, and in the optionally existing excess combustion, the oxygen coefficients are each independently X2, the temperatures are each independently 1100 - 1200 °C, and 0.7 ≤ X1 ≤ 0.85, 0.8 ≤ X1 + X2 ≤ 1, 1 ≤ X1 + X2 + X3 ≤ 1.15. Therefore, the inventor of the present invention has found that especially when the oxygen coefficient and temperature in the reaction for each combustion are controlled within the aforementioned preferred ranges, by combining both of them, the combustion of the sulfur-containing waste becomes more sufficient, the content of sulfur dioxide in the obtained process gas containing sulfur dioxide is higher, and especially in the case of a reaction material containing a nitrogen element, the content of NO x in the obtained process gas is lower.

[0057] According to the present invention, the at least two combustions may be a plurality of combustions such as two or more times (for example, three times, four times, five times). That is, the optionally existing means that the excess combustion may or may not exist.

[0058] Preferably, the number of combustions is 2 - 3 times.

[0059] According to the present invention, it should be noted that when the combustion is twice, there is only the first combustion and the last combustion, and there is no excess combustion.

[0060] According to one preferred specific embodiment of the present invention, the number of combustions is 2 times, and the method is In the presence of an oxygen-containing combustion-supporting gas, a first combustion and a second combustion are sequentially performed on a fuel and a sulfur-containing waste to be combusted, including the step of obtaining a sulfur dioxide-containing gas.

[0061] Preferably, the conditions for the first combustion include an oxygen coefficient X1 and a temperature of 1150 - 1250 °C, and the conditions for the second combustion include an oxygen coefficient X3, a temperature of 1050 - 1100 °C, and 0.7 ≤ X1 ≤ 0.85, 1 ≤ X1 + X3 ≤ 1.15.

[0062] According to another preferred specific embodiment of the present invention, the number of combustions is three times, and the method In the presence of an oxygen-containing combustion-supporting gas, a first combustion, a second combustion, and a third combustion are sequentially performed on a fuel and a sulfur-containing waste to be combusted, including the step of obtaining a sulfur dioxide-containing gas.

[0063] Preferably, the conditions for the first combustion include an oxygen coefficient X1 and a temperature of 1150 - 1250 °C, the conditions for the second combustion include an oxygen coefficient X2 and a temperature of 1100 - 1200 °C, the conditions for the third combustion include an oxygen coefficient X3 and a temperature of 1050 - 1100 °C, and 0.7 ≤ X1 ≤ 0.85, 0.8 ≤ X1 + X2 ≤ 1, 1 ≤ X1 + X2 + X3 ≤ 1.15.

[0064] Preferably, the oxygen-containing combustion-supporting gas is at least one selected from air (oxygen content 21 mol%), oxygen-enriched air (oxygen content 21 - 40 mol%), pure oxygen, and liquid oxygen. The inventor of the present invention has found that by using oxygen-enriched air or pure oxygen with a high oxygen content as the combustion-supporting gas, the amount of fuel used can be significantly reduced, and in an apparatus of the same scale, a larger amount of sulfur-containing waste can be treated, the investment in the apparatus can be reduced, and the energy consumption and operation cost can be lowered.

[0065] 1] Preferably, the sulfur-containing waste is at least one selected from waste sulfuric acid, sulfur-containing waste liquid, and sulfur-containing waste gas.

[0066] The present invention does not particularly limit the origin and type of the sulfur-containing waste. The sulfur-containing waste liquid may be, for example, liquid sulfur, a sulfur-containing waste liquid containing ammonium sulfate, a sulfur-containing waste liquid containing ammonium bisulfate, a sulfur-containing waste liquid containing iron sulfate, a sulfur-containing waste liquid containing methyl sulfate, a sulfur-containing waste liquid containing gypsum, etc. The sulfur-containing waste gas may be, for example, hydrogen sulfide, sulfur dioxide, and other waste gases containing sulfur components. Preferably, the mass concentration of sulfuric acid in the waste sulfuric acid is 50-99%. Preferably, the water content of the sulfur-containing waste is less than 15 wt%.

[0067] According to one preferred specific embodiment of the present invention, the reactor assembly further includes a liquid spray gun 116 configured to be able to sufficiently atomize the sulfur-containing waste (for example, sulfur-containing waste liquid). The sulfur-containing waste is atomized by high-pressure atomizing air in the liquid spray gun and then sprayed into the furnace, and burns together with the oxygen-containing combustion-supporting gas and the fuel. As a result, the combustion of the sulfur-containing waste becomes more sufficient, and the content of sulfur dioxide in the process gas is improved. Preferably, the pressure of the liquid spray gun is 0.4-0.8 MPa, more preferably 0.5-0.7 MPa.

[0068] According to one preferred specific embodiment of the present invention, the sulfur-containing waste contains sulfur-containing solid waste (for example, sulfur-containing ore sand). The method of the present invention includes performing one combustion on the sulfur-containing solid waste (combustion conditions: temperature 800-1050 °C) to obtain sulfur dioxide-containing gas II, performing at least two combustions on the sulfur-containing waste liquid and / or sulfur-containing waste gas to obtain sulfur dioxide-containing gas I, and combining the sulfur dioxide-containing gas II and the sulfur dioxide-containing gas I to obtain the sulfur dioxide-containing gas of the present invention.

[0069] According to the present invention, the fuel can burn a high-calorific-value combustible material that supplies heat for the combustion of the sulfur-containing waste in the presence of an oxygen-containing combustion-supporting gas. Preferably, the calorific value of the fuel is 500 kcal / Nm 3As described above, for example, the calorific value of natural gas is 9700 kcal / Nm 3 is.

[0070] Preferably, the fuel is at least one selected from natural gas, sulfur, liquefied hydrocarbons, hydrogen sulfide acid gas, and heavy oil organic matter.

[0071] Preferably, the liquefied hydrocarbon is at least one selected from liquefied ethylene, liquefied ethane, liquefied propylene, liquefied propane, liquefied butene, and liquefied butane.

[0072] Preferably, the heavy oil organic matter is at least one selected from gasoline, kerosene, and light oil.

[0073] According to the present invention, the usage amount of the fuel may be reasonably selected and adjusted according to the usage amount of the sulfur-containing waste.

[0074] In addition, according to the present invention, it should be particularly noted that the sulfur-containing waste and the fuel may be the same substance (for example, hydrogen sulfide). As can be understood by those skilled in the art, when the sulfur-containing waste is hydrogen sulfide acid gas, the hydrogen sulfide acid gas itself can function as a fuel, and there is no need to provide additional other fuels. In this case, it is also the inventive concept of the present invention, and those skilled in the art should not understand that this limits the invention.

[0075] Preferably, according to the combustion method of the sulfur-containing waste of the present invention, in the obtained sulfur dioxide-containing gas, the content of sulfur dioxide is 3 to 12 mol%, and the content of NO x is 100 mg / m 3 or less, and the content of oxygen is 0.5 to 5 mol%.

[0076] In the present invention, by controlling the reaction conditions for each combustion, particularly the temperature and oxygen coefficient, the first combustion reaction of the fuel and the sulfur-containing waste to be combusted is carried out under conditions of high temperature and oxygen deficiency. The sulfur-containing waste burns to produce sulfur dioxide, and the nitrogen-containing material produces nitrogen gas under oxygen-deficient conditions. The subsequent combustion is carried out under conditions of low temperature and oxygen enrichment, whereby sufficient combustion of the fuel and sulfur-containing waste is ensured. Moreover, since the nitrogen gas generated by the previous combustion is at a low temperature, it cannot react further to produce nitrogen oxides. Therefore, by combining multiple combustion reactions, a process gas with a high sulfur dioxide content and a low NO x content is obtained, and the obtained sulfur dioxide-containing gas does not contain combustible components.

[0077] According to the present invention, preferably, at least one of the oxygen-containing combustion-supporting gas, the fuel, and the sulfur-containing waste contains a nitrogen element. The sulfur-containing waste is, for example, a nitrogen-sulfur-containing substance such as ammonium bisulfate or ammonium sulfate, the fuel is, for example, a combustible material containing nitrogen gas, and the oxygen-containing combustion-supporting gas is, for example, air.

[0078] According to one preferred specific embodiment of the present invention, the method of the present invention further includes the steps of first dehydrating the sulfur-containing waste, and then performing at least two combustions together with the fuel in the presence of an oxygen-containing combustion-supporting gas to obtain a sulfur dioxide-containing gas.

[0079] In the present invention, there are no particular limitations on the specific operation of the dehydration treatment, and it is only necessary to remove at least a part of the moisture in the sulfur-containing waste. For example, it can be carried out by evaporation and concentration.

[0080] In the method according to the present invention, particularly by controlling the combustion conditions of the sulfur-containing waste and combining multiple combustion reactions with each other, the combustion of the sulfur-containing waste is made more sufficient, a process gas with a high sulfur dioxide content is obtained, and the obtained sulfur dioxide-containing gas does not contain combustible components.

[0081] Particularly, in the case of a nitrogen-containing reaction material, when the method according to the present invention is adopted, by controlling the conditions for each combustion in particular, the combustion of the sulfur-containing waste becomes more sufficient, and a process gas with a high sulfur dioxide content and a low NO x content is obtained. The nitrogen element in the nitrogen-containing reaction material is discharged in the form of extremely trace NO x In addition, it is discharged in the form of nitrogen gas. By adopting the method according to the present invention, the content of nitrogen oxides (NO x ) in the obtained process gas can be significantly reduced without the need for additional denitrification treatment.

[0082] Based on the above, the present invention also provides Step (1) of burning a sulfur-containing waste to obtain a sulfur dioxide-containing gas, Step (2) of oxidizing the sulfur dioxide-containing gas to obtain a sulfur trioxide-containing gas, Step (3) of absorbing the sulfur trioxide-containing gas to obtain sulfuric acid, and provides a sulfuric acid production method using a sulfur-containing waste.

[0083] Hereinafter, the present invention will be described in detail with examples.

[0084] Unless otherwise specified, all raw materials used in the following examples are commercially available products.

[0085] Unless otherwise specified, all of the following examples are carried out in the aforementioned reactor assembly. Two sets of combustion-supporting gas inlets are distributed along the axial direction of the reactor (in the axial direction of the reactor, the straight cylindrical section of the furnace has an axial length of L and an aspect ratio of 4 to 10 (for example, an aspect ratio of 5), and two combustion-supporting gas inlets are provided at positions 0.25L away from the fuel inlet side of the furnace and 0.5L away from the gas discharge port side of the furnace respectively). In order to provide the oxygen-containing combustion-supporting gas required for each combustion, the oxygen-containing combustion-supporting gas inlet is configured to supply the oxygen-containing combustion-supporting gas flowing along the tangential direction of the inner wall of the furnace.

[0086] Example 1A The specific compositions of the fuel used in this example and the sulfur-containing waste derived from the chemical fiber industry are shown in Table 1, and the oxygen-containing combustion-supporting gas is air with an oxygen content of 21 mol%.

[0087]

Table 1

[0088] The reactor was heated to 1200 °C, and normal-temperature air was pressurized with an air blower and heated to 630 °C in an electric heating furnace, and then introduced into the reactor through the combustion-supporting gas inlet. The sulfur-containing waste was sprayed into the furnace of the reactor from the sulfur-containing waste inlet with a high-pressure atomizing air of 0.6 MPa by a liquid spray gun. The fuel was introduced into the furnace of the reactor from the fuel inlet.

[0089] The specific process is as follows.

[0090] 38.11 t of sulfur-containing waste (68.22 wt% waste sulfuric acid + 31.78 wt% sulfur-containing waste liquid) and 3990 kg of fuel were introduced into the reactor from the sulfur-containing waste inlet and the fuel inlet respectively. In the axial direction of the furnace, first, the oxygen-containing combustion-supporting gas introduced from the first oxygen-containing combustion-supporting gas inlet was combusted for the first time, and then the oxygen-containing combustion-supporting gas introduced from the second oxygen-containing combustion-supporting gas inlet was combusted for the second time. Here, the conditions for the first combustion included an oxygen coefficient X1 of 0.7 and a temperature of 1200 °C, and the conditions for the second combustion included an oxygen coefficient X3, X1 + X3 = 1.05, and a temperature of 1100 °C. Sulfur dioxide-containing gas was obtained.

[0091] In the sulfur dioxide-containing gas from the furnace, the sulfur dioxide content was 3.8 mol%, the oxygen content was 2 mol%, NO x The content was 100 mg / Nm 3 or less, and the conversion rate of sulfur dioxide was 99 mol%.

[0092] Example 1B A method similar to that of Example 1A was adopted. Except that the oxygen-containing combustion-supporting gas used was oxygen-enriched air with an oxygen content of 40 mol%, the rest was the same as in Example 1.

[0093] In the sulfur dioxide-containing gas from the furnace, the oxygen content was 2 mol%, the sulfur dioxide content was 6 mol%, and the NO x content was 80 mg / Nm 3 or less, and the conversion rate of sulfur dioxide was 99 mol%.

[0094] Example 2 The specific compositions of the chlorine-containing waste sulfuric acid, hydrogen sulfide acid gas, and fuel used in this example are shown in Table 2, and the oxygen-containing combustion-supporting gas was air with an oxygen content of 21 mol%.

[0095] [Table 2]

[0096] The reactor was heated to 1100 °C, and normal-temperature air was introduced into the reactor from the combustion-supporting gas inlet by an air blower. The sulfur-containing waste was sprayed into the furnace of the reactor from the sulfur-containing waste inlet with a high-pressure atomizing air of 0.7 MPa by a liquid spray gun, and the fuel was introduced into the furnace of the reactor from the fuel inlet.

[0097] In this example, the sulfur-containing waste was 7 t (71.43 wt% chlorine-containing waste sulfuric acid + 28.57 wt% hydrogen sulfide acid gas). Here, the chlorine-containing waste sulfuric acid from the polytetrahydrofuran production device had a water content of 48 wt%, a low impurity content, and was evaporated and concentrated to 85 wt% before entering the reactor 9. The hydrogen sulfide acid gas was sulfur-containing waste gas, but only 70 mol% of the heat of the reactor system was supplied, and the remaining 30 mol% of the heat was supplemented by natural gas, which was an auxiliary fuel.

[0098] The specific reaction process is as follows.

[0099] Waste sulfuric acid was introduced from the sulfur-containing waste inlet into the furnace of the reactor, and hydrogen sulfide acidic gas and natural gas were introduced from the fuel inlet into the furnace of the reactor. In the axial direction of the furnace, first, the oxygen-containing combustion-supporting gas introduced from the first oxygen-containing combustion-supporting gas inlet was used for the first combustion, and then, the oxygen-containing combustion-supporting gas introduced from the second oxygen-containing combustion-supporting gas inlet was used for the second combustion. Here, the conditions for the first combustion included an oxygen coefficient X1 of 0.75 and a temperature of 1150 °C, and the conditions for the second combustion included an oxygen coefficient X3, X1 + X3 = 1.05, and a temperature of 1050 °C. Sulfur dioxide-containing gas was obtained.

[0100] In the sulfur dioxide-containing gas from the furnace, the oxygen content was 3 mol%, the sulfur dioxide content was 8.5 mol%, and the NO x content was 100 mg / Nm 3 or less, and the conversion rate of sulfur dioxide was 99 mol%.

[0101] Example 3 The specific compositions of the sulfur-containing waste and fuel used in this example are shown in Table 3, and the oxygen-containing combustion-supporting gas is air with an oxygen content of 21 mol%.

[0102]

Table 3

[0103] The reactor was heated to 1250 °C, normal-temperature air was pressurized with an air blower and heated to 450 °C in an electric heating furnace and then introduced into the reactor. The sulfur-containing waste was sprayed from the sulfur-containing waste inlet into the furnace of the reactor with a high-pressure atomizing air of 0.5 MPa by a liquid spray gun. The fuel was introduced from the fuel inlet into the furnace of the reactor.

[0104] The specific reaction process is as follows.

[0105] 7.5 t of sulfur-containing waste (80 wt% waste sulfuric acid + 20 wt% sulfur-containing ore), and 120 kg of fuel were respectively introduced into the furnace of the reactor from the sulfur-containing waste inlet and the fuel inlet. In the axial direction of the furnace, first, the oxygen-containing combustion-supporting gas introduced from the first oxygen-containing combustion-supporting gas inlet was used for the first combustion, and then the oxygen-containing combustion-supporting gas introduced from the second oxygen-containing combustion-supporting gas inlet was used for the second combustion. Here, the conditions for the first combustion included an oxygen coefficient X1 of 0.85 and a temperature of 1200 °C, and the conditions for the second combustion included an oxygen coefficient X3, X1 + X3 = 1.05, and a temperature of 1050 °C. Sulfur dioxide-containing gas I was obtained. Sulfur-containing ore was burned in another reactor (temperature 800 °C) to produce sulfur dioxide-containing process gas II.

[0106] In the sulfur dioxide-containing mixed gas from the two reactors, the oxygen content was 5 mol%, the sulfur dioxide content was 6 mol%, and the NO x content was 100 mg / Nm 3 or less, and the conversion rate of sulfur dioxide was 99 mol%.

[0107] Comparative Example 1 The method similar to that of Example 1 was adopted, but the difference was that the number of combustions was set to 1 time.

[0108] Specifically, 38.11 t of sulfur-containing waste (68.22 wt% waste sulfuric acid + 31.78% wt% sulfur-containing waste liquid) and 4588 kg of fuel were introduced into the furnace of the reactor from the material inlet, and burned with the oxygen-containing combustion-supporting gas introduced from the first oxygen-containing combustion-supporting gas inlet in the axial direction of the furnace. Here, the combustion conditions included an oxygen coefficient of 1.04 and a temperature of 1150 °C. Sulfur dioxide-containing gas was obtained.

[0109] The temperature of the sulfur dioxide-containing gas from the furnace was 950 - 1000 °C, the oxygen content was 1.8 mol%, the sulfur dioxide content was 3.2 mol%, and the NO x content was about 500 mg / Nm 3 and the conversion rate of sulfur dioxide was 98.8 mol%. In the comparative example, the fuel consumption was 15 wt% more than that in Example 1.

[0110] Comparative Example 2 The method similar to that of Example 1 was adopted, but the oxygen coefficient was different from that of Example 1 in the two combustion decompositions. The oxygen coefficient X1 of the first combustion was 0.9, the oxygen coefficient of the second combustion was X3, and except that X1 + X3 = 1.05, the rest was the same as in Example 1 to obtain a sulfur dioxide-containing gas. In the sulfur dioxide-containing gas from the furnace, the oxygen content was 2 mol%, and the NO x content was about 200 mg / Nm 3 and it was.

[0111] Furthermore, as shown in FIGS. 1 and 4, the combustion air supply mechanism may further include a heating device 120 and a blower 130. The heating device has a heating housing 121 including a heating chamber 123 and a heating mechanism 122 provided in the heating chamber 123. The heating housing 121 is provided with a heating gas inlet 124 and a heating gas outlet 125 that communicate with the heating chamber 123, respectively. The heating gas inlet 124 communicates with the blower 130, and the heating gas outlet 125 communicates with the furnace 111 of the reactor assembly. The heating mechanism 122 is configured to be able to increase the temperature at which the inside of the chamber 123 is heated. Since the heating gas inlet 124 communicates with the blower 130 and the heating gas outlet 125 communicates with the furnace 111 of the reactor assembly, the heating mechanism 122 can improve the internal temperature of the heating chamber 123. Therefore, the temperature of the combustion air from the blower 130 rises when passing through the heating device 120, and the temperature of the combustion air entering the furnace 111 reaches 600 to 650 ° C, increasing the combustion efficiency of the mixed gas of the reactor assembly.

[0112] As shown in FIGS. 7 and 8, the present invention also a reactor assembly 100 that causes a sulfur-containing waste to undergo a combustion reaction to obtain a first gas containing sulfur dioxide, a heat energy recovery unit 300 that recovers heat energy from the first gas to obtain a second gas, a purification cooling unit that purifies and cools the second gas to obtain a third gas, A drying unit 700 that dries the third gas to obtain a fourth gas, and an oxidation absorption unit 800 that oxidizes and absorbs the fourth gas to obtain sulfuric acid and exhaust gas, are provided, and a sulfur-containing waste treatment system is provided.

[0113] Hereinafter, the specific operation process of the treatment system will be exemplarily described by way of examples.

[0114] Although the water content of the sulfur-containing waste (68.22 wt% waste sulfuric acid + 31.78 wt% sulfur-containing waste liquid) containing waste sulfuric acid and sulfur waste liquid is 36 wt%, the waste sulfuric acid and sulfur-containing waste liquid derived from the chemical fiber industry contain a large amount of particles and impurities, so it is difficult to concentrate and dehydrate. Therefore, these were put into the reactor body 110 without dehydration.

[0115] (1) The sulfur-containing waste was atomized with a high-pressure atomizing air of 0.6 MPa by a liquid spray gun and injected into the reactor body 110. The reaction temperature in the furnace was set to 1200 °C, and heat was supplied by fuel (natural gas). Combustion support was carried out using air with an oxygen content of 21 mol%. The normal-temperature combustion-supporting air was pressurized by a blower 130 and then heated to 630 °C by a heating device 120, and the high-temperature combustion-supporting air was introduced into the furnace from different combustion-supporting gas inlets 114, 115. First, the sulfur-containing waste was subjected to a first combustion with the combustion-supporting gas introduced from the first air supply port groups 114a, 115a, and then a second combustion with the combustion-supporting gas introduced from the second air supply port groups 114b, 115b. Here, the conditions for the first combustion include an oxygen coefficient X1 of 0.7 and a temperature of 1200 °C, and the conditions for the second combustion include oxygen coefficients X3, X1 + X3 = 1.05, and a temperature of 1100 °C. The oxygen content remaining in the first gas from the furnace is 2 mol%, and the residence time of the process gas in the furnace is 5 s or more.

[0116] (2) The dust collector unit 200 removes metal dust from the high-temperature process gas from the furnace to obtain the dust-removed high-temperature process gas (the operating conditions of the cyclone dust collector 210 include a supply port temperature of 1100 °C, a supply port pressure of -1 kPa, and an intake air velocity of 30 m / s at the supply port of the cyclone dust collector. The dust collection operating conditions of the ceramic membrane filter 220 include a supply port temperature of 1050 °C, a supply port pressure of -1 kPa, and an intake air velocity of 15 m / s at the supply port of the ceramic membrane filter). Next, the dust-removed high-temperature process gas enters the waste heat boiler 310 to recover heat (the first heat exchange, and the conditions of the first heat exchange include a pressure of -1.5 kPa on the flue gas side of the tube side, a flue gas inlet temperature of 1000 °C of the boiler, a flue gas outlet temperature of 380 °C of the boiler, a pressure of 3.8 MPa on the steam side of the shell side, and a temperature of 249 °C). 31 t of 3.8 MPa saturated steam is generated per hour. The saturated steam exchanges heat with a small amount of high-temperature process gas without solids in the steam superheater 320 (the second heat exchange, and the conditions of the second heat exchange include a pressure of -1.5 kPa on the flue gas side, a flue gas inlet temperature of 1000 °C of the heater, a flue gas outlet temperature of 450 °C of the heater, a steam side pressure of 3.8 MPa, and a temperature of 350 °C). Superheated steam 16 is obtained, and the superheated steam enters the steam turbine, reducing the electrical energy of the device.

[0117] (3) The process gas that has utilized thermal energy enters the quench humidification tower 400, where rapid cooling is performed by adiabatic humidification, and the gas temperature is rapidly cooled from 400 °C to 77 °C. Next, it enters the cooling absorption tower 500 equipped with multi-stage packing, then enters the first absorption layer and is washed by a circulating water cooler, the temperature is reduced to 35 °C. Next, it enters the second absorption layer and is washed, and then washed by a chilled water cooler and the temperature is reduced to 29 °C. The process gas that has undergone two cooling processes enters the electric demister 600 to remove sulfur trioxide mist.

[0118] (4) The process gas from which sulfur trioxide mist has been removed enters the drying unit 700 and is dried with 93 wt% concentrated sulfuric acid.

[0119] (5) The dried process gas has a sulfur dioxide content of 5 mol%, is pressurized to 20 kPa by the main blower 810, then sequentially enters the first external heat exchanger 830 and the second heat exchange pipeline 845b (see Figure 13), and after heat exchange, enters the first conversion chamber. When the temperature of the reaction process gas 37 in the first catalyst layer 844a in the converter 840 reaches 415 ± 5 °C, an oxidation reaction is carried out. When the temperature of the process gas that has completed the reaction reaches 555 ± 5 °C, it exchanges heat with the gas on the tube side of the first heat exchange pipeline 845a of the converter 840. When the temperature of the process gas in the second catalyst layer 844b reaches 455 ± 5 °C, an oxidation reaction is carried out. Thus, the first oxidation reaction is carried out in the first conversion chamber, and the conversion rate of the first oxidation reaction is 96 mol%. The first oxidation reaction process gas 38 exchanges heat through the tube side of the first external heat exchanger 830, and then the temperature is controlled to be 150 °C or higher. It enters the first absorption layer of the multi-stage absorption tower 880 and the first absorption is carried out with 100 wt% sulfuric acid, and the absorption rate is 99.99 wt%.

[0120] The process gas that has completed the first absorption sequentially enters the second external heat exchanger 870 and the first heat exchange pipeline 845a for heat exchange, and then enters the second conversion chamber. When the temperature of the reaction process gas in the third catalyst layer 844c reaches 415 ± 5 °C, the oxidation reaction is started. The sulfur trioxide-containing process gas that has completed the reaction exchanges heat through the second heat exchange pipeline 845b, and then when the temperature of the fourth catalyst layer 844d reaches 415 ± 5 °C, the oxidation reaction is started. The second oxidation reaction is completed in the second conversion chamber, and the total conversion rate of the four catalyst layers after the reaction is 99.92 mol%. Next, the gas temperature of the second oxidation reaction process from the second conversion gas outlet of the converter 840 is controlled to be 130 °C or higher, and it is put into the second absorption layer of the multi-stage absorption tower 880 and the second absorption is carried out with 98 wt% sulfuric acid, and the absorption rate is 99.99 wt%.

[0121] The process gas that has completed the second absorption is discharged to the outside. In the discharged gas, the SO2 concentration is 50 mg / Nm 3 Next, NO x concentration is 50 mg / Nm 3 Next, the concentration of acid mist is 5 mg / Nm 3Hereinafter, the particle concentration is 30 mg / Nm 3 as follows.

[0122] FIG. 9 shows the connection structure between the dust collector unit 200 and the heat energy recovery unit 300 of the sulfur-containing waste treatment system described above. Here, the heat energy recovery unit 300 is connected downstream of the dust collector unit 200. The dust collector unit 200 includes at least two filter groups arranged in parallel, and each filter group includes two filters. The two filters are a cyclone dust collector 210 and a ceramic membrane filter 220, respectively. The ceramic membrane filter 220 is connected in series downstream of the cyclone dust collector 210. The material of the shell of the cyclone dust collector 210 is high alloy steel. An insulating layer and a refractory layer are sequentially provided on the inner wall of the cyclone dust collector 210. The material of the insulating layer is lightweight castable and / or lightweight refractory bricks. The material of the refractory layer is at least one selected from corundum bricks, corundum mullite bricks, chrome corundum bricks, and silicon carbide. The air inlet of the cyclone dust collector has a spiral surface air intake structure. The ash discharge port of the cyclone dust collector adopts a star ash valve structure or an overflow spiral structure. The heat energy recovery unit 300 includes a waste heat boiler 310 and a steam superheater 320. The waste heat boiler 310 and the steam superheater 320 are all communicated with the dust collector unit 200, and the waste heat boiler 310 and the steam superheater 320 are communicated with each other. Thus, the saturated steam obtained in the waste heat boiler 310 can enter the steam superheater 320.

[0123] By combining a specific dust collector unit and a heat energy recovery unit, sequentially providing a specific insulating layer and a refractory layer on the inner wall of the cyclone dust collector, and also adopting a specific device structure and combination form, the requirements for equipment for high-temperature dust-containing flue gas (for example, sulfur dioxide-containing flue gas with a high temperature of 900 - 1200 °C discharged from a high-temperature decomposition furnace in the high-temperature combustion decomposition process of sulfur-containing waste) are met, the dust collection efficiency is high, and the heat loss in the dust collector for dust-containing high-temperature flue gas is significantly reduced.

[0124] The purification and cooling unit of the sulfur-containing waste treatment system described above includes a quenching and humidifying tower 400, a multi-stage cooling and absorption tower 500, and an electric demister 600 that are sequentially connected in communication, and the quenching and humidifying tower 400 and the heat energy recovery unit 300 are in communication.

[0125] FIG. 10 shows a schematic view of the quenching and humidifying tower 400. The quenching and humidifying tower 400 includes a first tower body 410 and a spray assembly 420. The first tower body 410 includes a cooling chamber 411, a chamber inlet 412, and a chamber outlet 413. The chamber inlet 412 and the chamber outlet 413 are respectively provided on the outer wall of the first tower body 410 and communicate with the cooling chamber 411. The chamber inlet 412 is located at the lower part of the tower body 410, and the chamber outlet 413 is located at the upper part of the tower body 410. The spray assembly 420 is provided in the cooling chamber 411. The spray assembly 420 includes a first spray port 421 and a second spray port 422. The first spray port 421 is configured to spray the cooling liquid downward, and the second spray port 422 is configured to spray the cooling liquid upward. The first spray port 421 and the second spray port 422 are provided opposite to each other.

[0126] Since the first spray port 421 of the spray assembly 420 is configured to spray the cooling liquid downward, the second spray port 422 is configured to spray the cooling liquid upward, and the first spray port 421 and the second spray port 422 are provided opposite to each other, when the high-temperature process gas enters the cooling chamber 411 from the chamber inlet 412 and flows to the chamber outlet 130, the cooling liquid sprayed by the first spray port 421 and the second spray port 422 can completely cool and lower the temperature of the high-temperature process gas in two directions, namely upward and downward. In addition, the humidity of the high-temperature process gas can be improved, and the high-temperature process gas can be rapidly cooled from a high temperature of 320 - 350 °C to 75 - 80 °C. Thereby, the temperature of the process gas can be efficiently and effectively reduced, the resistance generated in the system is small, usually 1 Kpa, and thereby, the treatment cycle of the sulfur-containing waste is shortened.

[0127] Furthermore, the rapid cooling and humidifying tower 400 may further include a unidirectional spray 430, the unidirectional spray 430 is provided between the spray assembly 420 and the chamber outlet 413, and the unidirectional spray 430 is configured to spray the cooling liquid downward, thereby enhancing the cooling effect.

[0128] FIG. 11 shows a schematic view of the cooling absorption tower 500. The cooling absorption tower includes a second tower body 510, a first absorption layer, and a second absorption layer. The second tower body 510 is provided along the vertical direction and has a cooling absorption chamber extending in the vertical direction. The second tower body 510 includes a gas supply port and a gas discharge port that communicate with the cooling absorption chamber respectively. The gas supply port is provided at the lower part of the second tower body 510, and the gas discharge port is provided at the upper part of the second tower body 510. The first absorption layer and the second absorption layer are provided in the cooling absorption chamber with a space therebetween along the vertical direction. Here, the first absorption layer includes a first spray mechanism 520 capable of spraying the absorption liquid into the cooling absorption chamber, and the second absorption layer includes a second spray mechanism 530 capable of spraying the absorption liquid into the cooling absorption chamber.

[0129] Since the second tower body 510 is provided along the vertical direction and has a cooling absorption chamber extending in the vertical direction, the occupied area of the cooling absorption tower is reduced and the usage cost is lowered. Also, since the first absorption layer and the second absorption layer are provided in the cooling absorption chamber with a space therebetween along the vertical direction, the first absorption layer includes a first spray mechanism 520 capable of spraying the absorption liquid into the cooling absorption chamber, and the second absorption layer includes a second spray mechanism 530 capable of spraying the absorption liquid into the cooling absorption chamber. Therefore, after the process gas enters the cooling absorption chamber from the gas supply port, it undergoes an absorption reaction with the absorption liquid sprayed by the first spray mechanism 520 and the absorption liquid sprayed by the second spray mechanism 530 respectively. The absorption liquid sufficiently absorbs sulfur trioxide in the process gas, thereby obtaining the effect of washing the process gas.

[0130] Furthermore, a separator 513 may be provided in the cooling absorption chamber of the second tower body 510. The separator 513 divides the cooling absorption chamber into a first chamber and a second chamber from bottom to top. The first absorption layer is provided in the first chamber, and the second absorption layer is provided in the second chamber. The second tower body 510 is provided with an air inlet 511, an exhaust port 512, and a vent hole communicating the first chamber and the second chamber. The air inlet 511 communicates with the first chamber and is located at the lower part of the first chamber and is used to receive the external process gas. The exhaust port 512 communicates with the second chamber and is located at the upper part of the second chamber and is used to discharge the process gas to the downstream process. The first spray mechanism 520 and the second spray mechanism 530 are each configured to be able to spray the absorption liquid and the refrigerant into the first chamber and the second chamber, and the temperature of the refrigerant is lower than the temperature of the coolant. With such a configuration, there is an advantage that the temperature of the process gas can be further reduced by the refrigerant. For example, the temperature of the coolant is 28 to 32 °C, the process gas is washed through the first absorption layer and the temperature is reduced to about 35 °C. Next, after being further cooled by the refrigerant at a temperature of 7 to 10 °C, it can be washed through the second absorption layer and the temperature is reduced to about 15 °C, thereby greatly enhancing the cooling effect.

[0131] In order to improve the utilization efficiency of the coolant, save energy, and reduce production costs, the cooling absorption tower 500 includes a water pump 560 and a cooler 570, whereby the absorption liquid and the refrigerant are cooled and then recycled into the cooling chamber.

[0132] To make the contact between the absorption liquid and the process gas more sufficient, the first absorption layer may include the first packing 540. The first spraying mechanism 520 is configured to be able to spray the absorption liquid downward, and the first packing 540 is provided below the first spraying mechanism 520. The second absorption layer may include the second packing 550. The second spraying mechanism 530 is configured to be able to spray the absorption liquid downward, and the second packing 550 is provided below the second spraying mechanism 530. It should be understood that various materials can be adopted for the packing, as long as the absorption liquid and the process gas can be made to contact more sufficiently. In one embodiment, the first packing 540 and the second packing 550 are polypropylene helical rings.

[0133] After the process gas has been subjected to a drying treatment by the purification cooling and drying unit 700, it is introduced into the oxidation absorption unit 800, where sulfur dioxide therein is converted into sulfur trioxide, and this sulfur trioxide is absorbed to form sulfuric acid. FIG. 12 shows a schematic diagram of the oxidation absorption unit 800, and FIG. 13 is a schematic structural diagram of the converter 840 of the oxidation absorption unit 800.

[0134] The oxidation absorption unit 800 includes a conversion device and an absorption device. The conversion device communicates with the drying unit 700 and is used to oxidize sulfur dioxide in the fourth gas obtained in the drying unit 700 to obtain a sulfur trioxide-containing gas. The absorption device communicates with the conversion device and is used to absorb the sulfur trioxide-containing gas to obtain sulfuric acid and exhaust gas. Specifically, in the illustrated preferred embodiment, the oxidation absorption unit 800 includes a first external heat exchanger 830, a second external heat exchanger 870, a multi-stage absorption tower 880, a first heat exchanger 850, a second heat exchanger 860, a sulfuric acid cooler 890, an absorption circulation pump, and a converter 840 provided in a first heat exchange pipeline 845a and a second heat exchange pipeline 845b. The dotted line represents the temperature-rising pipeline, the solid line represents the process pipeline, and the arrow represents the flow direction of the medium during temperature rise. Specifically, the flow is as follows. The process gas is sent by a blower 810 to a temperature-rising furnace 820, then enters the first external heat exchanger 830, then enters the converter 840, then enters the second external heat exchanger 870, and finally returns to the blower 810 through the second heat exchanger 860, thus completing the circulation. In this temperature-rising process, the medium circulates in the blower 810, the temperature-rising furnace 820, and the converter 840 and does not enter the multi-stage absorption tower 880. Although a part of the temperature-rising pipeline and the process pipeline overlap, it does not affect the normal flow of the process.

[0135] The converter 840 shown in FIG. 13 includes a converter housing 841, a catalyst layer assembly, and heat exchange pipelines 845a and 845b. The converter housing 841 has a conversion chamber inside, and the converter housing 841 is provided with a conversion gas inlet 842a, 842b and a conversion gas outlet 843a, 843b that communicate with the conversion chamber respectively. The catalyst layer assembly includes at least two catalyst layers 844a, 844b, 844c, 844d. The plurality of catalyst layers are provided in the conversion chamber and are arranged with spaces in the flow direction of the process gas. The number of the heat exchange pipelines 845a, 845b is the same as the number of the catalyst layers 844a, 844b, 844c, 844d. The heat exchange pipelines are at least partially located in the conversion chamber and are provided between two adjacent catalyst layers. By being configured to be located in the conversion chamber and provided between two adjacent catalyst layers, the occupied space can be significantly reduced and the usage cost can be effectively lowered.

[0136] Specifically, the converter 840 includes a first conversion chamber and a second conversion chamber formed in the converter housing 841, a first catalyst layer 844a, a second catalyst layer 844b, a third catalyst layer 844c, a fourth catalyst layer 844d, a first conversion gas inlet 842a, a second conversion gas inlet 842b, a first conversion gas outlet 843a and a second conversion gas outlet 843b. The first conversion gas inlet 842a and the first conversion gas outlet 843a both communicate with the first conversion chamber. Thereby, the process gas can flow from the first conversion gas inlet 842a to the first conversion gas outlet 843a. The second conversion gas inlet 842b and the second conversion gas outlet 843b both communicate with the second conversion chamber. Thereby, the process gas can flow from the second conversion gas inlet 842b to the second conversion gas outlet 843b. The first catalyst layer 844a and the second catalyst layer 844b are both provided in the first conversion chamber and are provided with spaces in the flow direction of the process gas. The third catalyst layer 844c and the fourth catalyst layer 844d are both provided in the second conversion chamber and are arranged with spaces in the flow direction of the process gas.

[0137] In the present invention, the process gas enters the first conversion chamber from the first conversion gas inlet 842a, first reacts with the first catalyst layer 844a, then reacts with the second catalyst layer 844b. After the reaction is completed, it directly enters an external heat exchanger from the first conversion gas outlet 843a. The sulfur trioxide-containing process gas that has completed the reaction is controlled to a temperature of 150 °C or higher by heat exchange in the external heat exchanger, and then enters the first stage of the multi-stage absorption tower. The conversion rate of the primary conversion is 95-96%. When absorbed with 100 wt% sulfuric acid, the absorption rate is 99.99%. The process gas that has completed the absorption further passes through an external heat exchanger sequentially for heat exchange. After heat exchange, the process gas reaches a temperature of 415-420 °C, enters the second conversion chamber from the second conversion gas inlet 842b, first reacts with the third catalyst layer 844c, and the sulfur trioxide-containing process gas that has completed the reaction is heat-exchanged in the second heat exchange pipeline 845b and then reacts with the fourth catalyst layer 844d. After the reaction, the process gas is controlled to a temperature of 130 °C or higher and enters the second stage of the multi-stage absorption tower from the second conversion gas outlet 843b. The absorption rate is 99.99%. The process gas that has completed the absorption is discharged to the outside, and the SO2 concentration is 50 mg / m 3 Hereinafter, NO x concentration is 100 mg / m 3 Hereinafter, the acid mist is 5 mg / m 3 Hereinafter, the particle concentration is 30 mg / m 3 or less. Therefore, the converter of the present invention has the advantage of high conversion efficiency.

[0138] In order to stably provide each catalyst layer in the conversion chamber, in one embodiment of the present invention, the converter 840 includes a plurality of support assemblies respectively corresponding to a first catalyst layer 844a, a second catalyst layer 844b, a third catalyst layer 844c, and a fourth catalyst layer 844d. The support assembly includes a grid plate 846, and the edge of the grid plate 846 is connected to the inner wall of the converter housing 841 to support the catalyst layer. Further, the support assembly includes heat-resistant ceramic balls 847 provided on the side away from the grid plate 846 of the catalyst layer. In the present invention, the main function of the heat-resistant ceramic balls 847 is to press the catalyst layer and flatly cover the catalyst layer on the grid plate 846 to prevent the catalyst layer from being blown away and scattered by the airflow. In addition, the heat-resistant ceramic balls 847 perform heat exchange with the process gas passing through them, lower the temperature of the process gas to an appropriate temperature for reacting with the catalyst layer, while absorbing impurity particles in the process gas and performing a purification function.

[0139] Based on the above reactor assembly and sulfur-containing waste treatment system, the present invention also provides a method for burning sulfur-containing waste and a method for producing sulfuric acid by regenerating sulfur-containing waste. The sulfur-containing waste to be burned may be waste sulfuric acid, sulfur-containing waste liquid, sulfur-containing waste gas, etc., and the fuel may be at least one selected from natural gas, sulfur, liquefied hydrocarbons, hydrogen sulfide, and heavy oil organic substances. In the process gas by combustion, the sulfur dioxide content is 3 to 12 mol%, and the NO x content is 100 mg / m 3 or less, and the oxygen content is 0.5 to 5 mol%.

[0140] The preferred embodiments of the present invention have been described in detail above with reference to the drawings, but the present invention is not limited thereto. Various simple modifications can be made to the technical solutions of the present invention within the scope of the technical concept of the present invention. In the present invention, various possible combinations are not separately described so as not to cause unnecessary duplication. However, these simple modifications and combinations should also be regarded as the disclosure content of the present invention and all belong to the patent scope of the present invention.

[0141] 〔Explanation of reference numerals〕 100 Reactor Assembly 110 Reactor Body 111 Furnace 112 Fuel Gas Inlet 113 Process Gas Outlet 114 First Combustion Air Inlet 115 Second Combustion Air Inlet 116 Liquid Spray Gun 120 Heating Device 121 Heating Housing 122 Electric Heating Mechanism 123 Heating Chamber 124 Heating Gas Inlet 125 Heating Gas Outlet 130 Blower 200 Dust Collection Unit 210 Cyclone Dust Collector 220 Ceramic Membrane Filter 300 Thermal Energy Recovery Unit 310 Waste Heat Boiler 320 Steam Superheater 400 Quenching and Humidifying Tower 410 First Tower Body 411 Cooling Chamber 412 Chamber Inlet 413 Chamber Outlet 420 Spray Assembly 421 First Spray Port 422 Second Spray Port 430 Unidirectional Spray 500 Cooling Absorption Tower 510 Second Tower Body 511 Air Intake 512 Exhaust Port 513 Separator 520 First Spray Mechanism 530 Second Spray Mechanism 540 First Packing 550 Second Packing 560 Water Pump 570 Cooler 600 Electric Demister 700 Drying Unit 800 Acid Absorption Unit 810 Blower 820 Heating Furnace 830 First External Heat Exchanger 840 Converter 841 Converter Housing 842a First Converter Gas Inlet 842b Second Converter Gas Inlet 843a First Converter Gas Outlet 843b Second Converter Gas Outlet 844a First Catalyst Layer 844b Second Catalyst Layer 844c Third Catalyst Layer 844d Fourth Catalyst Layer 845a First Heat Exchange Pipeline 845b Second Heat Exchange Pipeline 846 Lattice Plate 847 Heat-Resistant Ceramic Balls 850 First Heat Exchanger 860 Second Heat Exchanger 870 Second External Heat Exchanger 880 Multi-Stage Absorption Tower 890 Sulfuric Acid Cooler

Brief Description of the Drawings

[0142]

Figure 1

Figure 2

Figure 3

Figure 4

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Figure 6

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Figure 8

Figure 9

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Figure 13

Claims

1. A reactor assembly comprising: a cylindrical furnace (111) for supplying sulfur-containing waste and performing a combustion reaction; a fuel gas inlet (112) and a process gas outlet (113) respectively communicating with the furnace (111), wherein the fuel gas inlet (112) and the process gas outlet (113) are provided at both ends of the furnace (111) with a space along the axial direction of the furnace (111), and the fuel gas inlet (112) is configured to supply fuel flowing along the axial direction of the furnace (111) to the furnace (111); a reactor body (110); a combustion air supply mechanism configured to supply combustion air flowing along the circumferential direction of the inner wall of the furnace (111) to the furnace (111); the combustion air supply mechanism includes a plurality of combustion air supply port groups distributed with a space along the axial direction of the furnace (111); the plurality of combustion air supply port groups include a first air supply port group (114a, 115a) and a second air supply port group (114b, 115b), the first air supply port group (114a, 115a) is provided close to the fuel gas inlet (112), and the second air supply port group (114b, 115b) is provided close to the process gas outlet (113); the reactor assembly includes a control device for controlling the combustion air supply mechanism, which is configured to control air to enter from the first air supply port group (114a, 115a) and the oxygen amount at the position of the first air supply port group (114a, 115a) to be a first oxygen amount, and control air to enter from the second air supply port group (114b, 115b) and the oxygen amount at the position of the second air supply port group (114b, 115b) to be a second oxygen amount, which is the theoretical oxygen amount for normal combustion of sulfur-containing waste and is greater than the first oxygen amount, and further control at least two combustions including a first combustion corresponding to the first oxygen amount and a second combustion corresponding to the second oxygen amount of the fuel and the sulfur-containing waste to be combusted; at least one third air supply port group is provided between the first air supply port group (114a, 115a) and the second air supply port group (114b, 115b) in the plurality of air supply port groups; The control device is further configured to control such that the air enters from the third air supply port group and the amount of oxygen at the position of the third air supply port group is less than the second oxygen amount. In the first combustion, the oxygen coefficient is X1, the temperature is 1100 - 1250 °C, in the last combustion, the oxygen coefficient is X3, the temperature is 1000 - 1100 °C, and in the excess combustion, the oxygen coefficients are each independently X2, and the temperatures are each independently 1100 - 1200 °C, and 0.5 ≤ X1 ≤ 0.85, 0.7 ≤ X1 + X2 ≤ 1, 1 ≤ X1 + X2 + X3 ≤ 1.

15. The oxygen coefficient is a ratio of the oxygen-containing combustion-supporting gas converted to the oxygen molar content to the oxygen molar content required for the complete combustion of the fuel, and is characterized by the reactor assembly.

2. The combustion-supporting air supply mechanism includes a first combustion-supporting air inlet (114) and a second combustion-supporting air inlet (115) that are opened in the reactor body (110) and communicate with the furnace (111) respectively. The first combustion-supporting air inlet (114) and the second combustion-supporting air inlet (115) are configured to supply combustion-supporting air to the furnace (111) along the tangential direction of the furnace (111) at various positions in the circumferential direction of the furnace (111). The flow direction of the combustion-supporting air supplied by the first combustion-supporting air inlet (114) is the same as the flow direction of the combustion-supporting air supplied by the second combustion-supporting air inlet (115). The reactor assembly according to claim 1 is characterized by this.

3. The first oxygen amount is 60% of the second oxygen amount, and the reactor assembly according to claim 1 is characterized by this.

4. The combustion-supporting air supply mechanism includes a heating device (120) including a heating housing (121) and an electric heating mechanism (122). The heating housing (121) has a heating chamber (123) inside. A heating gas inlet (124) and a heating gas outlet (125) that communicate with the heating chamber (123) are respectively opened in the heating housing (121). The heating gas inlet (124) communicates with an external gas source, and the heating gas outlet (125) communicates with the furnace (111) to supply the combustion-supporting air to the furnace (111). The electric heating mechanism (122) is configured to be able to raise the temperature inside the heating chamber (123), and the reactor assembly according to claim 1 is characterized by this.

5. A sulfur-containing waste treatment system, comprising: a reactor assembly (100) according to any one of claims 1 to 4, which causes a sulfur-containing waste to undergo a combustion reaction to obtain a first gas containing sulfur dioxide; a heat energy recovery unit (300) that recovers heat energy from the first gas to obtain a second gas; a purification and cooling unit that purifies and cools the second gas to obtain a third gas; a drying unit (700) that dries the third gas to obtain a fourth gas; an oxidation absorption unit (800) that oxidizes and absorbs the fourth gas to obtain sulfuric acid and an exhaust gas. **Claim 6** The sulfur-containing waste treatment system according to claim 5, further comprising a dust collection unit (200) provided between the reactor assembly (100) and the heat energy recovery unit (300), wherein the first gas obtained by the reactor assembly (100) first enters the dust collection unit (200) for dust collection treatment, and then enters the heat energy recovery unit (300) to recover the heat energy and obtain the second gas. **Claim 7** The sulfur-containing waste treatment system according to claim 6, wherein the dust collection unit (200) includes at least two filter groups arranged in parallel, and each filter group includes at least one filter. **Claim 8** The sulfur-containing waste treatment system according to claim 6, wherein the heat energy recovery unit (300) includes a waste heat boiler (310) and a steam superheater (320), and both the waste heat boiler (310) and the steam superheater (320) communicate with the dust collection unit (200) such that the process gas obtained by the dust collection unit (200) enters the waste heat boiler (310) and the steam superheater (320) respectively, and the waste heat boiler (310) and the steam superheater (320) communicate with each other such that the saturated steam obtained by the waste heat boiler (310) enters the steam superheater (320). **Claim 9** The sulfur-containing waste treatment system according to claim 5, wherein the purification and cooling unit includes a quenching and humidifying tower (400), a multi-stage cooling and absorption tower (500), and an electric demister (600) that are sequentially communicated, and the quenching and humidifying tower (400) communicates with the heat energy recovery unit (300).

10. The quenching and humidifying tower (400) includes a first tower body (410) and a spray assembly (420), The first tower body (410) includes a cooling chamber (411), a chamber inlet (412), and a chamber outlet (413). The chamber inlet (412) and the chamber outlet (413) are respectively opened on the outer wall of the first tower body (410) and communicate with the cooling chamber (411). The chamber inlet (412) is located at the lower part of the first tower body (410) and receives the process gas from the process gas outlet (113) of the reactor assembly (100). The chamber outlet (413) is located at the upper part of the first tower body (410), The spray assembly (420) is provided in the cooling chamber (411). The spray assembly (420) includes a first spray port (421) and a second spray port (422). The first spray port (421) is configured to spray the cooling liquid downward, and the second spray port (422) is configured to spray the cooling liquid upward. The first spray port (421) and the second spray port (422) are provided opposite to each other. The sulfur-containing waste treatment system according to claim 9, wherein

11. The cooling and absorption tower (500) includes a second tower body (510), a first absorption layer, and a second absorption layer, The second tower body (510) is provided along the vertical direction and has a cooling and absorption chamber extending along the vertical direction. The second tower body (510) includes a gas supply port and a gas discharge port that respectively communicate with the cooling and absorption chamber. The gas supply port is provided at the lower part of the second tower body and receives the process gas from the process gas outlet (113) of the reactor assembly (100). The gas discharge port is provided at the upper part of the second tower body (510), The first absorption layer and the second absorption layer are provided with spaces in the cooling and absorption chamber along the vertical direction. The first absorption layer includes a first spray mechanism (520) capable of spraying the absorption liquid in the cooling and absorption chamber. The second absorption layer includes a second spray mechanism (530) capable of spraying the absorption liquid in the cooling and absorption chamber. The sulfur-containing waste treatment system according to claim 9, wherein

12. The oxidation and absorption unit (800) includes a conversion device and an absorption device, The conversion device communicates with the drying unit (700) and is used to oxidize the fourth gas obtained by the drying unit (700) to obtain a sulfur trioxide-containing gas. The absorption device communicates with the conversion device and is used to absorb the sulfur trioxide-containing gas to obtain the sulfuric acid and the exhaust gas. The sulfur-containing waste treatment system according to claim 5 is characterized by this.

13. The conversion device includes a converter (840), and the converter includes a converter housing (841), a catalyst layer assembly, and heat exchange pipelines (845a, 845b). The inside of the converter housing (841) has a conversion chamber, and the converter housing (841) is provided with a conversion gas inlet (842a, 842b) and a conversion gas outlet (843a, 843b) that communicate with the conversion chamber respectively. The conversion gas inlet (842a, 842b) is used to receive the process gas from the process gas outlet (113) of the reactor assembly (100). The catalyst layer assembly includes at least two catalyst layers (844a, 844b, 844c, 844d). The plurality of catalyst layers (844a, 844b, 844c, 844d) are provided in the conversion chamber and are arranged with a space along the flow direction of the process gas. The number of the heat exchange pipelines (845a, 845b) is adapted to the number of the catalyst layers (844a, 844b, 844c, 844d). The heat exchange pipelines (845a, 845b) are at least partially located in the conversion chamber and are provided between two adjacent catalyst layers (844a, 844b, 844c, 844d). The sulfur-containing waste treatment system according to claim 12 is characterized by this.

14. A method for burning sulfur-containing waste using the reactor assembly according to any one of claims 1 to 4.

15. A method for producing sulfuric acid by regenerating sulfur-containing waste, In the presence of an oxygen-containing combustion-supporting gas, introducing the fuel and the sulfur-containing waste into the reactor assembly by the method according to claim 14 to perform at least two combustions to obtain a first gas containing sulfur dioxide (step (1)); Introducing the first gas into a heat energy recovery unit to recover heat energy to obtain superheated steam and a second gas (step (2)); Step (3) of introducing the second gas into a purification and cooling unit for purification and cooling to obtain a third gas; Step (4) of introducing the third gas into a drying unit for drying to obtain a fourth gas; Step (5) of introducing the fourth gas into an oxidation and absorption unit for oxidation and absorption to obtain sulfuric acid and an exhaust gas, the method being characterized by including these steps.

16. The sulfur-containing waste is at least one selected from waste sulfuric acid, sulfur-containing waste liquid, and sulfur-containing waste gas; The fuel is at least one selected from natural gas, sulfur, liquefied hydrocarbons, hydrogen sulfide, and heavy oil organic matter. The first gas contains 3 to 12 mol% sulfur dioxide and 2 to 12 mol% NO ｘ The content is 100 mg / Nm ３ 16. The method according to claim 15, wherein the oxygen content is 0.5 to 5 mol%.

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