CN109772427B - Catalyst for recycling sulfur and nitrogen in absorption liquid of magnesium-method simultaneous desulfurization and denitrification process and preparation and application thereof - Google Patents
Catalyst for recycling sulfur and nitrogen in absorption liquid of magnesium-method simultaneous desulfurization and denitrification process and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for recycling sulfur and nitrogen in absorption liquid of a magnesium-method simultaneous desulfurization and denitrification process, and a preparation method and application thereof, wherein the catalyst comprises a carrier, and a main active component and a cocatalyst which are loaded on the carrier; the carrier is an SBA-15 molecular sieve; the main active components are transition metals Mn and Co; the cocatalyst is rare earth metal Ce and alkaline earth metal Ca; the loading amount of the main active component is 0.1-10% of the total weight of the catalyst; the load capacity of the cocatalyst is 0.1-1% of the total weight of the catalyst. The invention effectively solves the problems of structure and blockage caused by overhigh concentration of magnesium sulfite in a desulfurization system, can effectively reduce the energy consumption of the traditional desulfurization oxidation system, improves the quality of byproducts, increases the economy, simultaneously solves the problem of secondary pollution of the catalyst, can realize the recycling of the solid-phase catalyst, and greatly reduces the process cost.
Description
Technical Field
The invention relates to the field of environmental catalysis, in particular to a catalyst for efficiently and synergistically recycling sulfur and nitrogen elements in a magnesium method simultaneous desulfurization and denitrification process and a preparation method thereof.
Background
The tail gas of the coal-fired power plant contains a large amount of SO2，NOxAnd pollutants such as heavy metals, which cause serious air pollution problems when discharged into the atmosphere. The magnesium oxide wet flue gas simultaneous desulfurization and denitration process is a flue gas treatment process commonly used by middle and small industrial boilers at present, and the treatment modes of simultaneous desulfurization and denitration slurry and desulfurization and denitration products can be divided into a regeneration method, a disposal method and an oxidation recovery method. The oxidation recovery method is to forcedly oxidize desulfurization and denitrification products of magnesium sulfite and magnesium nitrite into magnesium sulfate and magnesium nitrate, and recover the magnesium sulfate and the magnesium nitrate through evaporation and crystallization.
For example, chinese patent application publication No. CN107866142A discloses a disposal system for dry desulfurization and denitrification by-products in cement industry, which comprises an active coke desulfurization and denitrification reaction tower and a cement kiln decomposition furnace, wherein the active coke desulfurization and denitrification reaction tower is provided with an air outlet and a discharge outlet; the gas outlet is communicated with a tertiary air pipe of the cement kiln decomposing furnace through a gas conveying pipe; the bottom of the activated coke desulfurization and denitrification reaction tower corresponds to the position of the discharge port and is provided with a vibrating screen, and a discharge port of the vibrating screen is communicated with a feeding port of the cement kiln decomposing furnace through a material conveying pipeline.
The chinese utility model patent with publication number CN208465630U discloses a continuous flue gas desulfurization and denitrification slurry regeneration circulation system, which comprises a desulfurization and denitrification reaction tower and a regeneration reaction device communicated with the desulfurization and denitrification reaction tower; the bottom of the desulfurization and denitrification reaction tower is provided with an original flue gas inlet and a saturated slurry outlet, and the top of the desulfurization and denitrification reaction tower is provided with a clean flue gas outlet and a regenerated slurry return port; and the flue gas to be treated enters the desulfurization and denitrification reaction tower through the raw flue gas inlet and reacts with the reaction slurry in the tower, clean flue gas generated by the reaction is discharged from the clean flue gas outlet, saturated slurry generated by the reaction enters the regeneration reaction device through a saturated slurry outlet, and regenerated slurry generated by the reaction in the regeneration reaction device returns to the desulfurization and denitrification reaction tower through the regenerated slurry reflux port.
In the traditional magnesium oxide simultaneous desulfurization and denitrification process in China, the magnesium sulfate solution discharged from an absorption tower has overhigh unsaturation degree due to the high solubility of the magnesium sulfate (about 44.5g/100g of water at 40 ℃), so that the energy consumption of the traditional evaporation concentration technology is overhigh. The oxidation reaction rate of the slurry by-product magnesium sulfite is relatively slow, resulting in long retention time, large required oxidation pond area and increased treatment cost. The conventional byproduct recovery technology only focuses on the recovery and utilization of sulfur resources, and the conventional byproduct recovery technology does not pay much attention to the recovery and utilization of nitrogen resources. However, in actual engineering conditions, the existence of magnesium nitrite can affect the evaporation and concentration of magnesium sulfate to a certain extent, and disproportionation reaction can occur in the process to generate NO, so that secondary pollution is caused. In addition, the existence of a certain amount of magnesium nitrate can further improve the quality of the by-product and improve the resource economy of the sulfur and nitrogen, so that the oxidation of the magnesium nitrite has important significance for the resource utilization of the by-product. However, magnesium nitrite is difficult to oxidize by air, and requires a large amount of strong oxidant to oxidize it, resulting in high recovery process cost. Therefore, the development of a catalyst capable of efficiently catalyzing the oxidation of magnesium sulfite and magnesium nitrite simultaneously has important significance.
Disclosure of Invention
The invention provides a catalyst for recycling sulfur and nitrogen in absorption liquid of a magnesium-method simultaneous desulfurization and denitrification process, a preparation method and an application thereof, which effectively solve the problems of structure and blockage caused by overhigh concentration of magnesium sulfite in a desulfurization system, effectively reduce the energy consumption of the traditional desulfurization and oxidation system, improve the quality of byproducts, increase the economy, simultaneously solve the problem of secondary pollution of the catalyst, realize the recycling of a solid-phase catalyst and greatly reduce the process cost.
A catalyst for recycling sulfur and nitrogen in absorption liquid of a magnesium-method simultaneous desulfurization and denitrification process comprises a carrier, and a main active component and a cocatalyst which are loaded on the carrier; the carrier is an SBA-15 molecular sieve; the main active components are transition metals Mn and Co; the cocatalyst is rare earth metal Ce and alkaline earth metal Ca; the loading amount of the main active component is 0.1-10% of the total weight of the catalyst; the load capacity of the cocatalyst is 0.1-1% of the total weight of the catalyst.
The catalyst activates ozone and oxygen molecules through active components Mn and Co, the active component Co enhances the adsorption of the catalyst on magnesium sulfite and magnesium nitrite, and simultaneously, rare earth element Ce is introduced to increase the oxygen storage capacity of the catalyst and the electron transport capacity of the alkaline earth metal Ca enhanced catalyst. The carrier SBA-15 utilizes the huge specific surface area of the carrier SBA-15 to enhance the dispersibility of functional components, the pore structure of the carrier SBA-15 provides the function of a nano reactor, the functions of the components are mutually synergistically promoted, and the synergistic oxidation rate of magnesium sulfite and magnesium nitrite is obviously improved.
Preferably, Mn in the main active component2+And Co2+The molar ratio of (1-10) to (1); ce in the cocatalyst3+With Ca2+The molar ratio of (1-5): 1.
further preferably, the total mass of the main active component accounts for 2-10% of the total mass of the catalyst, the mass of the cocatalyst component accounts for 0.2-0.8% of the mass of the catalyst, and the Mn is2+And Co2+The molar ratio of (2-6): 1, Ce3 +With Ca2+The molar ratio of (1-3): 1.
still further preferably, theThe total mass of the main active components accounts for 2-8% of the total mass of the catalyst, the mass of the cocatalyst components accounts for 0.2-0.5% of the mass of the catalyst, and the Mn2+And Co2+The molar ratio of (3-5): 1, Ce3 +With Ca2+The molar ratio of (1-2): 1.
most preferably, the total mass of the main active component accounts for 5 percent of the total mass of the catalyst, the mass of the cocatalyst component accounts for 0.4 percent of the mass of the catalyst, and the Mn is2+And Co2+In a molar ratio of 4: 1, Ce3+With Ca2+In a molar ratio of 1: 1.
preferably, the specific surface area of the SBA-15 molecular sieve is 600-800 m2/g。
The invention also provides a preparation method of the solid-phase catalyst, which comprises the following steps:
dissolving manganese nitrate, cobalt nitrate, cerium nitrate and calcium nitrate in deionized water to obtain a mixed solution, then dipping the SBA-15 molecular sieve in the mixed solution, continuously stirring for 6-10 h, drying and calcining to obtain the catalyst; the proportion of the manganese nitrate, the cobalt nitrate, the cerium nitrate, the calcium nitrate and the SBA-15 molecular sieve is calculated by taking the load of transition metals Mn and Co in a finished catalyst as 0.1-10% of the total weight of the catalyst and taking the load of rare earth metal Ce and alkaline earth metal Ca as 0.1-1% of the total weight of the catalyst.
Preferably, the proportion of the manganese nitrate and the cobalt nitrate is based on Mn in the finished catalyst2+And Co2+The molar ratio of (1-10) to (1); the proportion of cerium nitrate and calcium nitrate is that of Ce in the finished catalyst3+With Ca2+The molar ratio of (1-5): 1 meter.
Preferably, the specific surface area of the SBA-15 molecular sieve is 600-800 m2/g。
Preferably, the drying condition is drying for 10-12 hours at 100 ℃; the calcination condition is calcination at 550 ℃ for 4-6 hours.
The invention also provides application of the catalyst in a sulfur-nitrogen element synergistic recycling process, which is characterized by comprising the following steps of:
and putting the solid-phase catalyst into an absorption liquid of a magnesium method simultaneous desulfurization and denitrification system, and carrying out a synergistic oxidation reaction on by-products of magnesium sulfite and magnesium nitrite in the absorption liquid by taking a mixed gas of air and ozone as an oxidant.
Preferably, the flow rate of the mixed gas is 1-10L/min, and the concentration of ozone in the mixed gas is 10-200 ppm. Further preferably, the air flow rate is 1-5L/min, the ozone concentration is 10-100 ppm, the concentration of the catalyst in the absorption liquid is 20-100 g/L, and the reaction temperature is 20-45 ℃.
Preferably, the concentration of the catalyst in the absorption liquid is 20g/L to 100 g/L.
Preferably, the concentration ratio of the magnesium sulfite to the magnesium nitrite in the absorption liquid is (1-100): 1, and the total concentration of the magnesium sulfite and the magnesium nitrite is 20-100 g/L.
Compared with the prior art, the invention has the following advantages:
(1) the raw materials used in the invention are common and easy to obtain, and the preparation process is simple.
(2) Active components Mn and Co in the catalyst prepared by the invention are used as ozone molecules and oxygen molecule activating substances, active oxygen species on the surface of the catalyst can be increased, the content of hydroxyl free radicals in a solution is increased, the adsorption of the catalyst on magnesium sulfite and magnesium nitrite is enhanced by the active component Co, and meanwhile, the oxygen storage capacity of the catalyst is increased by introducing rare earth element Ce, and the electron transmission capacity of the catalyst is enhanced by alkaline earth metal Ca. The carrier SBA-15 enhances the dispersibility of functional components by utilizing the huge specific surface area per se, and the pore structure provides the function of a nano reactor, so that the efficiency of oxidizing magnesium sulfite and magnesium nitrite by the catalyst at the same time can be enhanced, the oxidation efficiency of the catalyst and the magnesium nitrite is improved by more than 50% compared with the oxidation efficiency without catalysis, and the carrier SBA-15 can be effectively applied to the optimization of an oxidation system of a magnesium method simultaneous desulfurization and denitrification process.
(3) The catalyst prepared by the invention has the advantages of small using amount of active components, high catalytic efficiency, no leaching phenomenon of the active components, avoidance of secondary pollution, easy recovery of the solid-phase catalyst, good recycling performance and great reduction of the operation cost.
Drawings
FIG. 1 is a graph of the oxidation rates of magnesium sulfite and magnesium nitrite at different catalyst loadings for example 1.
FIG. 2 is the rule of the influence of the ratio of the main active components on the catalytic effect under the condition of the constant total loading of the catalyst in example 2.
FIG. 3 is the effect of different loading of main active components on the catalytic effect under the condition of constant loading of cocatalyst in example 3.
FIG. 4 is a graph showing the results of the synergy between the main components of the catalyst (including the main active component and the cocatalyst) in example 4.
FIG. 5 is a graph showing the effect of varying the main active component and the co-catalyst component or loading amount simultaneously on the catalytic effect in example 5.
Detailed Description
In order to better explain the present invention, the following examples are given to further explain the present invention in detail.
The method for testing the reactivity of the magnesium sulfite and the magnesium nitrite under the catalytic condition is as follows: adding a catalyst into an absorption liquid of a magnesium method simultaneous desulfurization and denitrification system, wherein the specific reaction conditions are as follows: the volume of the absorption liquid is 200mL, the reaction temperature is 40 ℃, the initial concentrations of the magnesium sulfite and the magnesium nitrite are respectively 20g/L and 1g/L, the pH value is 6, air is forcibly blown in for 5L/min, and the ozone concentration is 50 ppm. The concentrations of sulfate and nitrate in the reactor were measured after 90 minutes of reaction, and the oxidation efficiencies of magnesium sulfite and magnesium nitrite were expressed as the amounts of sulfate and nitrate produced in 90 minutes, respectively.
Example 1: catalytic effect of different catalyst dosage
Respectively weighing Mn (NO)3)2·6H2O 2.3933g，Co(NO3)2·6H2O 0.6067g，Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the solid-phase catalyst.
The prepared catalyst was added to five parallel experimental groups, and the oxidation efficiency was measured under the same reaction conditions while maintaining the catalyst concentrations at 20g/L, 40g/L, 60g/L, 80g/L, and 100g/L, respectively.
Experimental results as shown in fig. 1, the present catalyst can effectively increase the oxidation rate of magnesium sulfite and magnesium nitrite, and the oxidation rate increases as the amount of the catalyst increases. When the using amount of the catalyst is 20 g/L-100 g/L, compared with a non-catalytic oxidation system, the oxidation rate of magnesium sulfite is 67.6% in 90 minutes, the oxidation rate of magnesium nitrite is 15.8%, the oxidation rate of magnesium sulfite is improved by 0.28-0.46 times, and the oxidation rate of magnesium nitrite is improved by 1.58-4.88 times.
Example 2: rule of influence of proportion of main active components on catalytic effect under condition of constant total loading of catalyst
case2：
Respectively weighing Mn (NO)3)2·6H2O 1.9907g，Co(NO3)2·6H2O 1.0093g，Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the main active component Mn2+And Co2+In a molar ratio of 2: 1 (cocatalyst Ce)3+With Ca2+In a molar ratio of 1: 1). 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, the oxidation rates of magnesium sulfite and magnesium nitrite in 90 minutes are respectively 70.7 percent and 30.2 percent, and the oxidation rates are respectively improved by 0.05 time and 0.90 time compared with the non-catalytic condition.
case3：
Respectively weighing Mn (NO)3)2·6H2O 2.2422g，Co(NO3)2·6H2O 0.7578g,Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, and placing in a roomContinuously stirring at room temperature for 8 hours, drying at 100 deg.C for 12 hours, calcining at 550 deg.C for 4 hours to obtain main active component Mn2+And Co2+In a molar ratio of 3: 1 in the presence of a solid catalyst. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, the oxidation rates of magnesium sulfite and magnesium nitrite in 90 minutes are respectively 76.8 percent and 40.6 percent, and the oxidation rates are respectively improved by 0.14 time and 1.57 time compared with the non-catalytic condition.
case4：
Respectively weighing Mn (NO)3)2·6H2O 2.3933g，Co(NO3)2·6H2O 0.6067g,Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the main active component Mn2+And Co2+In a molar ratio of 4: 1 in the presence of a solid catalyst. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, the oxidation rates of magnesium sulfite and magnesium nitrite in 90 minutes are respectively 91.2 percent and 80.7 percent, and the oxidation rates are respectively improved by 0.35 time and 4.11 times compared with the non-catalytic condition.
case5：
Respectively weighing Mn (NO)3)2·6H2O 2.4942g，Co(NO3)2·6H2O 0.5058g，Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the main active component Mn2+And Co2+In a molar ratio of 5: 1 in the presence of a solid catalyst. Adding 8.000g of the prepared catalyst into a magnesium method simultaneous desulfurization and denitrification absorption liquid, and maintaining the concentration of the catalyst to be 40g/L, wherein the oxidation rates of magnesium sulfite and magnesium nitrite are 84.7 percent and 67.4 percent respectively in 90 minutes, compared with non-catalysisThe conditions were increased by 0.25 times and 3.27 times, respectively.
case6：
Respectively weighing Mn (NO)3)2·6H2O 2.5663g，Co(NO3)2·6H2O 0.4337g，Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the main active component Mn2+And Co2+In a molar ratio of 6: 1 in the presence of a solid catalyst. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, the oxidation rates of magnesium sulfite and magnesium nitrite in 90 minutes are respectively 80.2 percent and 65.8 percent, and the oxidation rates are respectively improved by 0.19 time and 3.16 times compared with the non-catalytic condition.
8.000g of the catalyst in case2-case6 is respectively taken and added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, and the result is shown in figure 2, wherein case0 represents the oxidation rate of magnesium sulfite and magnesium nitrite under non-catalytic conditions. It can be seen from FIG. 2 that Mn represented by case4 is constant in the cocatalyst ratio2+And Co2+In a molar ratio of 4: the solid phase catalyst prepared by the method 1 has the best catalytic effect.
Example 3: law of influence of different loading amounts of main active components on catalytic effect under condition of unchanged loading amount of cocatalyst
case7：
Respectively weighing Mn (NO)3)2·6H2O 0.2393g，Co(NO3)2·6H2O 0.0607g，Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing the mixture into a uniform aqueous solution, mixing 60.000g of SBA-15 molecular sieve with the prepared nitrate solution, continuously stirring the mixture for 8 hours at room temperature, drying the mixture for 12 hours at 100 ℃, and calcining the mixture for 4 hours at 550 ℃ to obtain the solid-phase catalytic catalyst with the main active component load of 0.5 percent (the cocatalyst load is 0.4 percent)And (3) preparing. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, the oxidation rates of magnesium sulfite and magnesium nitrite in 90 minutes are respectively 75.7 percent and 21.2 percent, and the oxidation rates are respectively improved by 0.12 time and 0.34 time compared with the non-catalytic condition.
case8：
Respectively weighing Mn (NO)3)2·6H2O 0.9573g，Co(NO3)2·6H2O 0.2427g，Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the solid-phase catalyst with the main active component load of 2%. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, the oxidation rates of magnesium sulfite and magnesium nitrite in 90 minutes are 85.4 percent and 42.7 percent respectively, and the oxidation rates are respectively improved by 0.26 time and 1.70 time compared with the non-catalytic condition.
case9：
Respectively weighing Mn (NO)3)2·6H2O 2.3933g，Co(NO3)2·6H2O 0.6067g，Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the solid-phase catalyst with the main active component load of 5%. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, the oxidation rates of magnesium sulfite and magnesium nitrite in 90 minutes are respectively 91.2 percent and 80.7 percent, and the oxidation rates are respectively improved by 0.35 time and 4.11 times compared with the non-catalytic condition.
case10：
Respectively weighing Mn (NO)3)2·6H2O 3.8293g，Co(NO3)2·6H2O 0.9707g，Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the solid-phase catalyst with the main active component load of 8%. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, the oxidation rates of the magnesium sulfite and the magnesium nitrite in 90 minutes are respectively 81.2 percent and 52.8 percent, and the oxidation rates are respectively improved by 0.20 time and 2.34 times compared with the non-catalytic condition.
case11：
Respectively weighing Mn (NO)3)2·6H2O 4.7866g，Co(NO3)2·6H2O 1.2134g，Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the solid-phase catalyst with the main active component load of 10%. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, the oxidation rates of magnesium sulfite and magnesium nitrite in 90 minutes are 77.8 percent and 32.7 percent respectively, and the oxidation rates are respectively improved by 0.15 time and 1.07 time compared with the non-catalytic condition.
8.000g of the catalyst in case 7-case 11 was added to the magnesium process simultaneous desulfurization and denitrification absorption solution, the concentration of the catalyst was maintained at 40g/L, and the results are shown in FIG. 3 comparing the oxidation rates of magnesium sulfite and magnesium nitrite under non-catalytic conditions. It can be seen from the figure that the solid phase catalyst with 5% loading of the main active component represented by case9 has the best catalytic effect under the condition that the loading of the cocatalyst is kept unchanged.
Example 4: the main components of the catalyst (including the main active component and the cocatalyst) act synergistically.
case12：
Respectively weighing Mn (NO)3)2·6H2O 2.3933g，Co(NO3)2·6H2O 0.6067g，Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the solid-phase catalyst simultaneously loaded with Mn, Co, Ce and Ca. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, and the oxidation rates of magnesium sulfite and magnesium nitrite are 91.2 percent and 80.7 percent respectively within 90 minutes.
case13：
Separately weighing Co (NO)3)2·6H2O 0.6067g，Ce(NO3)3·6H2O 0.1554g，Ca(NO3)2·4H2O0.0846g is mixed into a uniform aqueous solution, 60.000g of SBA-15 molecular sieve is mixed with a prepared nitrate solution, the mixture is continuously stirred for 8 hours at room temperature, dried for 12 hours at 100 ℃, and then calcined for 4 hours at 550 ℃, so that the solid-phase catalyst simultaneously loaded with Co, Ce and Ca is obtained. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, and the oxidation rates of the magnesium sulfite and the magnesium nitrite are 81.6 percent and 20.4 percent respectively within 90 minutes.
case14：
Respectively weighing Mn (NO)3)2·6H2O 2.3933g，Ce(NO3)3·6H2O 0.1554g，Ca(NO3)2·4H2O0.0846g is mixed into a uniform aqueous solution, 60.000g of SBA-15 molecular sieve is mixed with a prepared nitrate solution, the mixture is continuously stirred for 8 hours at room temperature, dried for 12 hours at 100 ℃, and then calcined for 4 hours at 550 ℃, so that the solid-phase catalyst simultaneously loaded with Mn, Ce and Ca is obtained. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, and the oxidation rates of magnesium sulfite and magnesium nitrite are 76.7 percent and 67.1 percent respectively within 90 minutes.
case15：
Separately weighing Ce (NO)3)3·6H2O 0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the solid-phase catalyst simultaneously loaded with Ce and Ca. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, and the oxidation rates of magnesium sulfite and magnesium nitrite are 68.1 percent and 16.2 percent respectively within 90 minutes.
8.000g of the catalyst in each of case12-case15 was added to the magnesium method while maintaining the catalyst concentration at 40g/L, as shown in FIG. 4. From FIG. 4, it can be seen that the solid-phase catalyst represented by case12 loaded with Mn, Co, Ce and Ca has the best catalytic effect. Under the same conditions, when Mn is lacked or Co is lacked, the catalytic effect of the catalyst is greatly reduced; when the catalyst is loaded with only Ce and Ca, it has substantially no ability to catalyze the oxidation of magnesium sulfite and magnesium nitrite. This shows that the main active components Mn and Co on the catalyst have specific interaction, and the synergistic effect of the two components enables the catalyst to have excellent catalytic performance.
Example 5: simultaneously changing the influence of the loading of the main active component and the cocatalyst on the catalytic effect
case16：
Respectively weighing Mn (NO)3)2·6H2O 2.3933g，Co(NO3)2·6H2O 0.6067g，Ce(NO3)3·6H2O0.1554g，Ca(NO3)2·4H2O0.0846g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the solid-phase catalyst with 5% of main active component and 0.4% of cocatalyst. Adding 8.000g of the prepared catalyst into a magnesium method and desulfurization and denitrification absorption liquid simultaneously, and maintaining the concentration of the catalyst to be 40g/L, wherein magnesium sulfite and magnesium nitrite are used for 90 minutesThe internal oxidation rates were 91.2% and 80.7%, respectively.
case17：
Respectively weighing Mn (NO)3)2·6H2O 5.7240g，Co(NO3)2·6H2O 1.4560g，Ce(NO3)3·6H2O0.3886g，Ca(NO3)2·4H2O0.2114 g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the solid-phase catalyst with the main active component load of 12% and the cocatalyst load of 1%. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, and the oxidation rates of magnesium sulfite and magnesium nitrite are 75.6 percent and 40.3 percent respectively within 90 minutes.
case18：
Respectively weighing Mn (NO)3)2·6H2O 7.1799g，Co(NO3)2·6H2O 1.8201g，Ce(NO3)3·6H2O0.4663g，Ca(NO3)2·4H2O0.2537 g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the solid-phase catalyst with 15% of main active component load and 1.2% of cocatalyst load. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, and the oxidation rates of magnesium sulfite and magnesium nitrite are 72.2 percent and 30.6 percent respectively within 90 minutes.
case19：
Respectively weighing Mn (NO)3)2·6H2O 9.5733g，Co(NO3)2·6H2O 2.4267g，Ce(NO3)3·6H2O0.6218g，Ca(NO3)2·4H2O0.3382 g, mixing the mixture into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, and continuously stirring for 8 hours at room temperature, 1After drying at 00 ℃ for 12 hours, calcining at 550 ℃ for 4 hours to obtain the solid-phase catalyst with the main active component loading of 20 percent and the cocatalyst loading of 1.6 percent. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, and the oxidation rates of magnesium sulfite and magnesium nitrite are 70.4 percent and 25.3 percent respectively within 90 minutes.
case20：
Respectively weighing Mn (NO)3)2·6H2O 11.9666g，Co(NO3)2·6H2O 3.0334g，Ce(NO3)3·6H2O0.7772g，Ca(NO3)2·4H2O0.4228 g, mixing into a uniform aqueous solution, mixing SBA-15 molecular sieve 60.000g with the prepared nitrate solution, continuously stirring for 8 hours at room temperature, drying for 12 hours at 100 ℃, and calcining for 4 hours at 550 ℃ to obtain the solid-phase catalyst with the main active component load of 25% and the cocatalyst load of 2%. 8.000g of the prepared catalyst is added into a magnesium method and desulfurization and denitrification absorption liquid, the concentration of the catalyst is maintained to be 40g/L, and the oxidation rates of magnesium sulfite and magnesium nitrite are 68.7 percent and 17.6 percent respectively within 90 minutes.
8.000g of the catalyst in each of case16-case20 was added to the magnesium method while maintaining the catalyst concentration at 40g/L, as shown in FIG. 5. From fig. 5, it can be seen that the solid-phase catalyst represented by case16 with 5% loading of the main active component and 0.4% loading of the cocatalyst has the best catalytic efficiency, and the catalyst activity decreases greatly when the main active component and the cocatalyst are loaded.
The above description is only an embodiment of the present invention, but the technical features of the present invention are not limited thereto, and any person skilled in the relevant art can change or modify the present invention within the scope of the present invention.
Claims (8)
1. A solid-phase catalyst for reclaiming S and N in the absorbing liquid of Mg-process desulfurizing-denitrifying process is composed of carrier, and the main active component and cocatalyst carried by said carrierAn oxidizing agent; the method is characterized in that the carrier is an SBA-15 molecular sieve; the main active components are transition metals Mn and Co, and Mn in the main active components2+And Co2+The molar ratio of (1-10) to (1); the catalyst promoter is rare earth metal Ce and alkaline earth metal Ca, and Ce in the catalyst promoter3+With Ca2+The molar ratio of (1-5): 1; the loading amount of the main active component is 0.1-10% of the total weight of the catalyst; the load capacity of the cocatalyst is 0.1-1% of the total weight of the catalyst.
2. The catalyst of claim 1, wherein the SBA-15 molecular sieve has a specific surface area of 600-800 m2/g。
3. A preparation method of a solid-phase catalyst for recycling sulfur and nitrogen in absorption liquid of a magnesium-method simultaneous desulfurization and denitrification process is characterized by comprising the following steps of:
dissolving manganese nitrate, cobalt nitrate, cerium nitrate and calcium nitrate in deionized water to obtain a mixed solution, then dipping the SBA-15 molecular sieve in the mixed solution, continuously stirring for 6-10 h, drying and calcining to obtain the catalyst; the proportion of the manganese nitrate, the cobalt nitrate, the cerium nitrate, the calcium nitrate and the SBA-15 molecular sieve is calculated by taking the load of transition metals Mn and Co in a finished catalyst as 0.1-10% of the total weight of the catalyst and taking the load of rare earth metal Ce and alkaline earth metal Ca as 0.1-1% of the total weight of the catalyst; the proportion of the manganese nitrate and the cobalt nitrate is according to Mn in the finished product catalyst2+And Co2+The molar ratio of (1-10) to (1); the proportion of cerium nitrate and calcium nitrate is that of Ce in the finished catalyst3+With Ca2+The molar ratio of (1-5): 1 meter.
4. The preparation method according to claim 3, wherein the drying is carried out at 100 ℃ for 10 to 12 hours; the calcination condition is calcination at 550 ℃ for 4-6 hours.
5. The application of the solid-phase catalyst according to claim 1 in a sulfur-nitrogen element cooperative recycling process is characterized by comprising the following steps:
and putting the solid-phase catalyst into an absorption liquid of a magnesium method simultaneous desulfurization and denitrification system, and carrying out synergistic oxidation on by-products of magnesium sulfite and magnesium nitrite in the absorption liquid by taking a mixed gas of air and ozone as an oxidant.
6. The use according to claim 5, wherein the flow rate of the mixed gas is 1-10L/min, and the concentration of ozone in the mixed gas is 10-200 ppm.
7. The use according to claim 5, wherein the concentration of the catalyst in the absorption solution is 20g/L to 100 g/L.
8. The use according to claim 5, characterized in that the concentration ratio of magnesium sulfite to magnesium nitrite in the absorption liquid is (1-100): 1, and the total concentration of magnesium sulfite and magnesium nitrite is 20-100 g/L.
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Application publication date: 20190521 Assignee: ZHEJIANG TIANLAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Assignor: ZHEJIANG University Contract record no.: X2022330000787 Denomination of invention: Preparation and application of a catalyst for sulfur and nitrogen recycling in absorption solution of magnesium simultaneous desulfurization and denitrification process Granted publication date: 20200529 License type: Common License Record date: 20221219 |
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