CN109772427A - It is a kind of for the catalyst of sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid and its preparation and application - Google Patents
It is a kind of for the catalyst of sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid and its preparation and application Download PDFInfo
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Abstract
The invention discloses a kind of catalyst and its preparation method and application for sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid, and catalyst includes main active component and co-catalyst on carrier and load carriers；The carrier is SBA-15 molecular sieve；The main active component is transient metal Mn and Co；The co-catalyst is rare earth metal Ce and alkaline-earth metal Ca；The load capacity of the main active component is the 0.1~10% of total catalyst weight；The load capacity of the co-catalyst is the 0.1~1% of total catalyst weight.The present invention efficiently solves in desulphurization system because of structure and blockage problem caused by magnesium sulfite excessive concentration, the energy consumption of traditional desulfurization oxidation system can be effectively reduced, and improve the quality of by-product, increase its economy, also solves the problems, such as the secondary pollution of catalyst simultaneously, the recycling that can be realized solid-phase catalyst, significantly reduces process costs.
Description
Technical field
The present invention relates to environmental catalysis fields, and in particular to one kind is directed in magnesium processes simultaneous SO_2 and NO removal technique and efficiently cooperates with
The catalyst and preparation method thereof of recycling sulphur nitrogen.
Background technique
Contain a large amount of SO in coal-burning power plant's tail gas2, NOx, the polluters such as heavy metal, these substances are discharged into meeting in atmosphere
Cause extremely serious atmosphere polluting problem.Magnesia wet flue gas simultaneous SO_2 and NO removal technique is current mediumand smallscale industrial boilers
Common flue gas treating process, for the processing mode of simultaneous SO_2 and NO removal slurries and desulphurization denitration product can be divided into method of reproduction,
Abandon method and oxid-reclamatiom method.Wherein oxid-reclamatiom method, which refers to, forces oxygen for desulphurization denitration product magnesium sulfite and magnesium nitrite
It is melted into magnesium sulfate and magnesium nitrate, is recycled by evaporative crystallization.
For example, the Chinese invention patent application document of Publication No. CN107866142A discloses one kind for cement industry
The disposal system of dry desulfurization denitration by-product, including active coke desulphurizing denitration reaction tower and cement kiln dore furnace, activated charcoal
Desulfurization and denitrification reaction tower is provided with gas outlet and discharge port；The gas outlet passes through air shooter and the three of cement kiln dore furnace
Secondary air hose connection；The position that active coke desulphurizing denitration reaction tower bottom corresponds to the discharge port is provided with vibrating screen, vibrating screen
Discharge gate is connected to by feeding pipe with the feeding inlet of the cement kiln dore furnace.
Notification number is that the Chinese utility model patent of CN208465630U discloses a kind of continous way flue gas desulfurization and denitrification slurry
Liquid regeneration cycle system, including desulfurization and denitrification reaction tower and the regenerative response device being connected with the desulfurization and denitrification reaction tower；
The bottom of the desulfurization and denitrification reaction tower offers former gas inlet and saturation serum outlet, and top offers clean flue gas row
Outlet and regeneration rear slurry refluxing opening；Flue gas to be processed through the former gas inlet enter the desulfurization and denitrification reaction tower and with
Reacting slurry reaction in tower, the cleaning flue gases for reacting generation are discharged from the clean flue gas outlet, react the saturation of generation
Slurries enter the regenerative response device through saturation serum outlet, and the regeneration slurries of generation are reacted in the regenerative response device
The desulfurization and denitrification reaction tower is returned through the regeneration rear slurry refluxing opening.
In the traditional magnesia simultaneous SO_2 and NO removal technique in China, since the solubility of magnesium sulfate is higher (under the conditions of 40 DEG C
About 44.5g/100g water), cause the Adlerika degree of unsaturation being discharged by absorption tower excessively high, makes traditional evaporation and concentrating technology
Energy consumption is excessively high.The oxidizing reaction rate of slurries by-product magnesium sulfite is relatively slow, causes its residence time longer, required oxidation
Pool area is larger, increases processing cost.Traditional by-product recovery technology only focuses on the recycling in Sulphur ressource, for nitrogen
The recycling concern of resource is simultaneously few.But in Practical Project condition, the presence of magnesium nitrite can influence to a certain extent
The evaporation and concentrating of magnesium sulfate, and disproportionated reaction may occur in the process and generate NO, cause secondary pollution.Furthermore a certain amount of
There is the quality that can be further improved by-product in magnesium nitrate, the economy of sulphur nitrogen recycling is improved, so the oxygen of magnesium nitrite
Change is of great significance for by-product resource.But magnesium nitrite is difficult to oxidation by air, needs a large amount of strong oxidizers will
It is aoxidized, and it is at high cost to result in recovery process.Therefore, develop one kind can simultaneously efficiently catalyzing and oxidizing magnesium sulfite and magnesium nitrite
Catalyst be of great significance.
Summary of the invention
The present invention provides the catalyst and its system for sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid
Preparation Method and application efficiently solve in desulphurization system because of structure and blockage problem caused by magnesium sulfite excessive concentration, energy
The energy consumption of traditional desulfurization oxidation system is enough effectively reduced, and improves the quality of by-product, increases its economy, while also solving
The secondary pollution problem of catalyst, can be realized the recycling of solid-phase catalyst, significantly reduces process costs.
A kind of catalyst for sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid, including carrier and load
Main active component and co-catalyst on carrier；The carrier is SBA-15 molecular sieve；The main active component is transition
Metal Mn and Co；The co-catalyst is rare earth metal Ce and alkaline-earth metal Ca；The load capacity of the main active component is to urge
The 0.1~10% of agent total weight；The load capacity of the co-catalyst is the 0.1~1% of total catalyst weight.
Catalyst of the invention passes through active component Mn and Co activated ozone and oxygen molecule, active component Co enhancing catalysis
Absorption of the agent for magnesium sulfite and magnesium nitrite, at the same introduce rare earth element ce increase catalyst savings oxygen ability and
The electron transport ability of alkaline-earth metal Ca enhancing catalyst.Carrier S BA-15 enhances function using huge specific surface area itself
The dispersibility of component, cellular structure provide the function of nano-reactor, and mutually collaboration promotes between the effect of each component, show
Write the synergistic oxidation rate for improving magnesium sulfite and magnesium nitrite.
Preferably, Mn in the main active component2+With Co2+Molar ratio be (1~10): 1；In the co-catalyst
Ce3+With Ca2+Molar ratio be (1~5): 1.
It is further preferred that it is 2~10% that the main active component gross mass, which accounts for catalyst gross mass percentage, help
It is 0.2~0.8% that catalytic component quality, which accounts for catalyst quality percentage, the Mn2+With Co2+Molar ratio be (2~6): 1,
Ce3+With Ca2+Molar ratio be (1~3): 1.
Still more preferably, it is 2~8% that the main active component gross mass, which accounts for catalyst gross mass percentage, helps and urges
It is 0.2~0.5% that agent constituent mass, which accounts for catalyst quality percentage, the Mn2+With Co2+Molar ratio be (3~5): 1,
Ce3+With Ca2+Molar ratio be (1~2): 1.
Most preferably, it is 5% that the main active component gross mass, which accounts for catalyst gross mass percentage, cocatalyst component matter
It is 0.4% that amount, which accounts for catalyst quality percentage, the Mn2+With Co2+Molar ratio be 4:1, Ce3+With Ca2+Molar ratio be 1:1.
Preferably, the specific surface area of the SBA-15 molecular sieve is 600~800m2/g。
The present invention also provides a kind of preparation methods of solid-phase catalyst, include the following steps:
Manganese nitrate, cobalt nitrate, cerous nitrate and calcium nitrate are dissolved in deionized water and obtain mixed solution, then by SBA-15 points
Son sieve is impregnated in mixed solution, is continuously stirred 6~10h, is calcined after dry to obtain the final product；Manganese nitrate, cobalt nitrate, cerous nitrate, nitric acid
The proportion of calcium and SBA-15 molecular sieve is using the load capacity of transient metal Mn and Co in finished catalyst as total catalyst weight
0.1~10%, the load capacity of rare earth metal Ce and alkaline-earth metal Ca are 0.1~1% meter of total catalyst weight.
Preferably, the proportion of manganese nitrate, cobalt nitrate is by Mn in finished catalyst2+With Co2+Molar ratio be (1~10): 1
Meter；The proportion of cerous nitrate and calcium nitrate is with Ce in finished catalyst3+With Ca2+Molar ratio be (1~5): 1 meter.
The specific surface area of the preferably described SBA-15 molecular sieve is 600~800m2/g。
Preferably, drying condition is 100 DEG C 10~12 hours dry；Calcination condition is 550 DEG C and calcines 4~6 hours.
The present invention also provides a kind of application such as the catalyst in sulphur nitrogen collaboration process for reclaiming, feature exists
In including the following steps:
The solid-phase catalyst is put into the absorbing liquid of magnesium processes simultaneous SO_2 and NO removal system, with air and ozone gaseous mixture
Body is oxidant, in absorbing liquid by-product magnesium sulfite and magnesium nitrite carry out synergistic oxidation reaction.
Preferably, the flow velocity of the mixed gas is 1~10L/min, in mixed gas ozone concentration be 10~
200ppm.Further preferably, air velocity is 1~5L/min, and ozone concentration is 10~100ppm, and catalyst is in absorbing liquid
Concentration is 20g/L~100g/L, and reaction temperature is 20-45 DEG C.
Preferably, concentration of the catalyst in absorbing liquid is 20g/L~100g/L.
Preferably, the concentration ratio of absorbing liquid sulfite magnesium and magnesium nitrite is (1~100): 1, magnesium sulfite and Asia
The total concentration of magnesium nitrate is 20~100g/L.
Compared with prior art, the invention has the following advantages that
(1) the raw materials used in the present invention is common is easy to get, and preparation process is simple.
(2) active component Mn and Co, can as ozone molecule and Activation of Molecular Oxygen substance in catalyst prepared by the present invention
To increase the active oxygen species of catalyst surface, increase the content of hydroxyl radical free radical in solution, active component Co enhances catalysis
Absorption of the agent for magnesium sulfite and magnesium nitrite, while introducing savings oxygen ability and alkali that rare earth element ce increases catalyst
The electron transport ability of earth metal Ca enhancing catalyst.Carrier S BA-15 enhances functional group using huge specific surface area itself
The dispersibility divided, cellular structure provides the function of nano-reactor, so as to enhance catalyst simultaneous oxidation sulfurous acid
The efficiency of magnesium and magnesium nitrite makes the two oxidation efficiency improve 50% or more compared with no catalytic condition, can be efficiently applied to magnesium processes
The optimization of simultaneous SO_2 and NO removal technique oxidative system.
(3) catalyst activity component dosage prepared by the present invention is small, high catalytic efficiency, and active component without leach phenomenon,
Secondary pollution generation is avoided, and solid-phase catalyst is easily recycled, recycling performance is good, greatly reduces operating cost.
Detailed description of the invention
Fig. 1 is the oxygenation efficiency figure of magnesium sulfite and magnesium nitrite under different catalysts dosage in embodiment 1.
Fig. 2 is that matching for main active component compares catalytic effect under catalyst total load amount permanence condition in embodiment 2
Affecting laws.
Fig. 3 is that main active component different loads amount imitates catalysis under co-catalyst load capacity permanence condition in embodiment 3
The affecting laws of fruit.
Fig. 4 is the knot that catalyst main component (including main active component and co-catalyst) acts synergistically in embodiment 4
Fruit figure.
Fig. 5 is that main active component and co-catalyst component or load capacity are changed simultaneously in embodiment 5 to catalytic effect shadow
Loud result figure.
Specific embodiment
In order to better illustrate the present invention, following embodiment is enumerated, further the present invention is described in detail.
The test method of the reactivity of magnesium sulfite and magnesium nitrite under catalytic condition is as follows: by catalyst be added to
In the absorbing liquid of magnesium processes simultaneous SO_2 and NO removal system, specific reaction condition are as follows: absorbing liquid volume is 200mL, and reaction temperature is
40 DEG C, magnesium sulfite and magnesium nitrite initial concentration are respectively 20g/L and 1g/L, and pH 6, pressure blasts air 5L/min, smelly
Oxygen concentration is 50ppm.The concentration of sulfate radical and nitrate anion in reactor is measured after reaction 90 minutes, with sulfate radical in 90 minutes and
Nitrate anion production quantity respectively indicates the oxidation efficiency of magnesium sulfite and magnesium nitrite.
Embodiment 1: the catalytic effect of different catalysts dosage
Mn (NO is weighed respectively3)2·6H2O 2.3933g, Co (NO3)2·6H2O 0.6067g, Ce (NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain solid-phase catalyst.
The catalyst being prepared is added in five parallel laboratory test groups, respectively maintain catalyst concn be 20g/L,
40g/L, 60g/L, 80g/L, 100g/L measure its oxidation efficiency under identical reaction conditions.
Experimental result as shown in Figure 1, this catalyst can effectively improve the oxidation rate of magnesium sulfite and magnesium nitrite,
And oxidation rate increases as catalyst amount increases.Catalyst amount is in 20 g/L~100g/L, compared to non-catalytic
90 minutes magnesium sulfite oxygenation efficiency of oxidation system are 67.6%, and magnesium nitrite oxygenation efficiency is 15.8%, magnesium sulfite oxidation rate
0.28~0.46 times is improved, magnesium nitrite oxidation rate improves 1.58~4.88 times.
Embodiment 2: main active component advises with the influence for comparing catalytic effect under catalyst total load amount permanence condition
Rule
Case2:
Mn (NO is weighed respectively3)2·6H2O 1.9907g, Co (NO3)2·6H2O 1.0093g, Ce (NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain main active component Mn2+With Co2+Molar ratio be 2:1 (co-catalyst Ce3+With Ca2+Molar ratio be 1:1) solid phase urge
Agent.Obtained catalyst 8.000g is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, maintenance catalyst concn is 40g/L,
90 minutes internal oxidition rates of magnesium sulfite and magnesium nitrite are respectively 70.7%, 30.2% at this time, and more non-catalytic condition is respectively increased
0.05 times and 0.90 times.
Case3:
Mn (NO is weighed respectively3)2·6H2O 2.2422g, Co (NO3)2·6H2O 0.7578g, Ce(NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain main active component Mn2+With Co2+Molar ratio be 3:1 solid-phase catalyst.Obtained catalyst 8.000g is added
In magnesium processes simultaneous SO_2 and NO removal absorbing liquid, maintenance catalyst concn is 40g/L, at this time in magnesium sulfite and magnesium nitrite 90 minutes
Oxygenation efficiency is respectively 76.8%, 40.6%, and 0.14 times and 1.57 times has been respectively increased in more non-catalytic condition.
Case4:
Mn (NO is weighed respectively3)2·6H2O 2.3933g, Co (NO3)2·6H2O 0.6067g, Ce(NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain main active component Mn2+With Co2+Molar ratio be 4:1 solid-phase catalyst.Obtained catalyst 8.000g is added
In magnesium processes simultaneous SO_2 and NO removal absorbing liquid, maintenance catalyst concn is 40g/L, at this time in magnesium sulfite and magnesium nitrite 90 minutes
Oxygenation efficiency is respectively 91.2%, 80.7%, and 0.35 times and 4.11 times has been respectively increased in more non-catalytic condition.
Case5:
Mn (NO is weighed respectively3)2·6H2O 2.4942g, Co (NO3)2·6H2O 0.5058g, Ce (NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain main active component Mn2+With Co2+Molar ratio be 5:1 solid-phase catalyst.Obtained catalyst 8.000g is added
In magnesium processes simultaneous SO_2 and NO removal absorbing liquid, maintenance catalyst concn is 40g/L, at this time in magnesium sulfite and magnesium nitrite 90 minutes
Oxygenation efficiency is respectively 84.7%, 67.4%, and 0.25 times and 3.27 times has been respectively increased in more non-catalytic condition.
Case6:
Mn (NO is weighed respectively3)2·6H2O 2.5663g, Co (NO3)2·6H2O 0.4337g, Ce (NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain main active component Mn2+With Co2+Molar ratio be 6:1 solid-phase catalyst.Obtained catalyst 8.000g is added
In magnesium processes simultaneous SO_2 and NO removal absorbing liquid, maintenance catalyst concn is 40g/L, at this time in magnesium sulfite and magnesium nitrite 90 minutes
Oxygenation efficiency is respectively 80.2%, 65.8%, and 0.19 times and 3.16 times has been respectively increased in more non-catalytic condition.
The catalyst 8.000g in case2-case6 is taken respectively, is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, is maintained to urge
Agent concentration is 40g/L, as a result as shown in Fig. 2, magnesium sulfite and magnesium nitrite oxidation under the conditions of wherein case0 indicates non-catalytic
Rate.As can be seen from Figure 2 under conditions of co-catalyst proportion is constant, the Mn of case4 representative2+With Co2+Molar ratio be
The solid-phase catalyst catalytic effect prepared when 4:1 is best.
Embodiment 3: shadow of the main active component different loads amount to catalytic effect under co-catalyst load capacity permanence condition
Ring rule
Case7:
Mn (NO is weighed respectively3)2·6H2O 0.2393g, Co (NO3)2·6H2O 0.0607g, Ce (NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain the solid-phase catalyst that main active component load capacity is 0.5% (co-catalyst load capacity is 0.4%).By obtained catalysis
Agent 8.000g is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, and maintenance catalyst concn is 40g/L, at this time magnesium sulfite and nitrous
90 minutes internal oxidition rates of sour magnesium are respectively 75.7%, 21.2%, and 0.12 times and 0.34 times has been respectively increased in more non-catalytic condition.
Case8:
Mn (NO is weighed respectively3)2·6H2O 0.9573g, Co (NO3)2·6H2O 0.2427g, Ce (NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain the solid-phase catalyst that main active component load capacity is 2%.Magnesium processes desulfurization simultaneously is added in obtained catalyst 8.000g
In denitration absorbing liquor, maintenance catalyst concn is 40g/L, and 90 minutes internal oxidition rates of magnesium sulfite and magnesium nitrite are respectively at this time
85.4%, 42.7%, 0.26 times and 1.70 times has been respectively increased in more non-catalytic condition.
Case9:
Mn (NO is weighed respectively3)2·6H2O 2.3933g, Co (NO3)2·6H2O 0.6067g, Ce (NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain the solid-phase catalyst that main active component load capacity is 5%.Magnesium processes desulfurization simultaneously is added in obtained catalyst 8.000g
In denitration absorbing liquor, maintenance catalyst concn is 40g/L, and 90 minutes internal oxidition rates of magnesium sulfite and magnesium nitrite are respectively at this time
91.2%, 80.7%, 0.35 times and 4.11 times has been respectively increased in more non-catalytic condition.
Case10:
Mn (NO is weighed respectively3)2·6H2O 3.8293g, Co (NO3)2·6H2O 0.9707g, Ce (NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain the solid-phase catalyst that main active component load capacity is 8%.Magnesium processes desulfurization simultaneously is added in obtained catalyst 8.000g
In denitration absorbing liquor, maintenance catalyst concn is 40g/L, and 90 minutes internal oxidition rates of magnesium sulfite and magnesium nitrite are respectively at this time
81.2%, 52.8%, 0.20 times and 2.34 times has been respectively increased in more non-catalytic condition.
Case11:
Mn (NO is weighed respectively3)2·6H2O 4.7866g, Co (NO3)2·6H2O 1.2134g, Ce (NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain the solid-phase catalyst that main active component load capacity is 10%.Magnesium processes desulfurization simultaneously is added in obtained catalyst 8.000g
In denitration absorbing liquor, maintenance catalyst concn is 40g/L, and 90 minutes internal oxidition rates of magnesium sulfite and magnesium nitrite are respectively at this time
77.8%, 32.7%, 0.15 times and 1.07 times has been respectively increased in more non-catalytic condition.
The catalyst 8.000g in case7~case11 is taken respectively, is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, is maintained
Catalyst concn is 40g/L, magnesium sulfite and magnesium nitrite oxidation rate under the conditions of comparison is non-catalytic, as a result as shown in Figure 3.From
It can be seen that under conditions of co-catalyst load capacity remains unchanged in figure, main active component load capacity that case9 is represented as
5% solid-phase catalyst catalytic effect is best.
Embodiment 4: catalyst main component (including main active component and co-catalyst) synergistic effect.
Case12:
Mn (NO is weighed respectively3)2·6H2O 2.3933g, Co (NO3)2·6H2O 0.6067g, Ce (NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
The solid-phase catalyst of Mn, Co, Ce and Ca are loaded simultaneously.Magnesium processes desulfurization simultaneously is added in obtained catalyst 8.000g
In denitration absorbing liquor, maintenance catalyst concn is 40g/L, at this time 90 minutes internal oxidition rate difference of magnesium sulfite and magnesium nitrite
It is 91.2%, 80.7%.
Case13:
Co (NO is weighed respectively3)2·6H2O 0.6067g, Ce (NO3)3·6H2O 0.1554g, Ca (NO3)2·4H2O
0.0846g is mixed into uniform aqueous solution, SBA-15 molecular sieve 60.000g is mixed with configured nitrate solution, room temperature
Under continuously stir 8 hours, 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C, are obtained while load C o, Ce and Ca
Solid-phase catalyst.Obtained catalyst 8.000g is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, catalyst concn is maintained
For 40g/L, 90 minutes internal oxidition rates of magnesium sulfite and magnesium nitrite are respectively 81.6%, 20.4% at this time.
Case14:
Mn (NO is weighed respectively3)2·6H2O 2.3933g, Ce (NO3)3·6H2O 0.1554g, Ca (NO3)2·4H2O
0.0846g is mixed into uniform aqueous solution, SBA-15 molecular sieve 60.000g is mixed with configured nitrate solution, room temperature
Under continuously stir 8 hours, 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C, are loaded Mn, Ce and Ca simultaneously
Solid-phase catalyst.Obtained catalyst 8.000g is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, catalyst concn is maintained
For 40g/L, 90 minutes internal oxidition rates of magnesium sulfite and magnesium nitrite are respectively 76.7%, 67.1% at this time.
Case15:
Ce (NO is weighed respectively3)3·6H2O 0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform water-soluble
Liquid mixes SBA-15 molecular sieve 60.000g with configured nitrate solution, continuously stirs at room temperature 8 hours, 100 DEG C dry
It after dry 12 hours, calcines 4 hours, obtains while the solid-phase catalyst of load C e and Ca at 550 DEG C.By obtained catalyst
8.000g is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, and maintenance catalyst concn is 40g/L, at this time magnesium sulfite and nitrous acid
90 minutes internal oxidition rates of magnesium are respectively 68.1%, 16.2%.
The catalyst 8.000g in case12-case15 is taken respectively, is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, is maintained
Catalyst concn is 40g/L, as a result as shown in Figure 4.As can be seen from Figure 4 Mn, Co, Ce are loaded while case12 is represented
And the solid-phase catalyst catalytic effect of Ca is best.Under the same conditions, when lacking Mn or lacking Co, the catalytic effect of catalyst
Decline to a great extent；As catalyst load C e and Ca, do not have the energy of catalysis oxidation magnesium sulfite and magnesium nitrite substantially
Power.This illustrates that main active component Mn and Co have specific interaction on catalyst, and the synergistic effect of the two makes catalyst
Has excellent catalytic performance.
Embodiment 5: influence of the load capacity of main active component and co-catalyst to catalytic effect is changed simultaneously
Case16:
Mn (NO is weighed respectively3)2·6H2O 2.3933g, Co (NO3)2·6H2O 0.6067g, Ce (NO3)3·6H2O
0.1554g, Ca (NO3)2·4H2O 0.0846g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain the solid-phase catalyst that main active component load capacity is 5%, co-catalyst load capacity is 0.4%.By obtained catalyst
8.000g is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, and maintenance catalyst concn is 40g/L, at this time magnesium sulfite and nitrous acid
90 minutes internal oxidition rates of magnesium are respectively 91.2%, 80.7%.
Case17:
Mn (NO is weighed respectively3)2·6H2O 5.7240g, Co (NO3)2·6H2O 1.4560g, Ce (NO3)3·6H2O
0.3886g, Ca (NO3)2·4H2O 0.2114g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain the solid-phase catalyst that main active component load capacity is 12%, co-catalyst load capacity is 1%.By obtained catalyst
8.000g is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, and maintenance catalyst concn is 40g/L, at this time magnesium sulfite and nitrous acid
90 minutes internal oxidition rates of magnesium are respectively 75.6%, 40.3%.
Case18:
Mn (NO is weighed respectively3)2·6H2O 7.1799g, Co (NO3)2·6H2O 1.8201g, Ce (NO3)3·6H2O
0.4663g, Ca (NO3)2·4H2O 0.2537g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain the solid-phase catalyst that main active component load capacity is 15%, co-catalyst load capacity is 1.2%.By obtained catalyst
8.000g is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, and maintenance catalyst concn is 40g/L, at this time magnesium sulfite and nitrous acid
90 minutes internal oxidition rates of magnesium are respectively 72.2%, 30.6%.
Case19:
Mn (NO is weighed respectively3)2·6H2O 9.5733g, Co (NO3)2·6H2O 2.4267g, Ce (NO3)3·6H2O
0.6218g, Ca (NO3)2·4H2O 0.3382g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain the solid-phase catalyst that main active component load capacity is 20%, co-catalyst load capacity is 1.6%.By obtained catalyst
8.000g is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, and maintenance catalyst concn is 40g/L, at this time magnesium sulfite and nitrous acid
90 minutes internal oxidition rates of magnesium are respectively 70.4%, 25.3%.
Case20:
Mn (NO is weighed respectively3)2·6H2O 11.9666g, Co (NO3)2·6H2O 3.0334g, Ce (NO3)3·6H2O
0.7772g, Ca (NO3)2·4H2O 0.4228g is mixed into uniform aqueous solution, by SBA-15 molecular sieve 60.000g and configuration
Good nitrate solution mixing, continuously stirs 8 hours at room temperature, and 100 DEG C after drying 12 hours, are calcined 4 hours at 550 DEG C,
Obtain the solid-phase catalyst that main active component load capacity is 25%, co-catalyst load capacity is 2%.By obtained catalyst
8.000g is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, and maintenance catalyst concn is 40g/L, at this time magnesium sulfite and nitrous acid
90 minutes internal oxidition rates of magnesium are respectively 68.7%, 17.6%.
The catalyst 8.000g in case16-case20 is taken respectively, is added in magnesium processes simultaneous SO_2 and NO removal absorbing liquid, is maintained
Catalyst concn is 40g/L, as a result as shown in Figure 5.As can be seen from Figure 5 the main active component load that case16 is represented
The solid-phase catalyst catalytic efficiency that amount is 5%, co-catalyst load capacity is 0.4% is best, when main active component and co-catalysis
When agent load capacity increases, catalyst activity declines to a great extent.
The foregoing is merely the specific implementation cases of the invention patent, but the technical characteristic of the invention patent is not limited to
This, within the field of the present invention, made changes or modifications all cover of the invention special any those skilled in the relevant art
Among sharp range.
Claims (10)
1. a kind of solid-phase catalyst for sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid, including carrier and negative
The main active component and co-catalyst being loaded on carrier；It is characterized in that, the carrier is SBA-15 molecular sieve；It is described main
Active component is transient metal Mn and Co；The co-catalyst is rare earth metal Ce and alkaline-earth metal Ca；The chief active group
The load capacity divided is the 0.1~10% of total catalyst weight；The load capacity of the co-catalyst be total catalyst weight 0.1~
1%.
2. catalyst according to claim 1, which is characterized in that Mn in the main active component2+With Co2+Molar ratio be
(1~10): 1；Ce in the co-catalyst3+With Ca2+Molar ratio be (1~5): 1.
3. catalyst according to claim 1, which is characterized in that the specific surface area of the SBA-15 molecular sieve be 600~
800m2/g。
4. a kind of preparation method for the solid-phase catalyst of sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid,
It is characterized in that, includes the following steps:
Manganese nitrate, cobalt nitrate, cerous nitrate and calcium nitrate are dissolved in deionized water and obtain mixed solution, then by SBA-15 molecular sieve
It is impregnated in mixed solution, continuously stirs 6~10h, calcined after dry to obtain the final product；Manganese nitrate, cobalt nitrate, cerous nitrate, calcium nitrate with
And the proportion of SBA-15 molecular sieve using the load capacity of transient metal Mn in finished catalyst and Co as total catalyst weight 0.1~
10%, the load capacity of rare earth metal Ce and alkaline-earth metal Ca are 0.1~1% meter of total catalyst weight.
5. preparation method according to claim 4, which is characterized in that manganese nitrate, cobalt nitrate proportion by finished catalyst
Mn2+With Co2+Molar ratio be (1~10): 1 meter；The proportion of cerous nitrate and calcium nitrate is with Ce in finished catalyst3+With Ca2+Rub
You are than being (1~5): 1 meter.
6. preparation method according to claim 4, which is characterized in that drying condition is 100 DEG C 10~12 hours dry；Calcining
Condition is 550 DEG C and calcines 4~6 hours.
7. a kind of application of solid-phase catalyst as described in claim 1 in sulphur nitrogen collaboration process for reclaiming, feature exist
In including the following steps:
By in the absorbing liquid of solid-phase catalyst investment magnesium processes simultaneous SO_2 and NO removal system, it is with air and ozone mixed gas
Oxidant, to the by-product magnesium sulfite and magnesium nitrite progress synergistic oxidation in absorbing liquid.
8. applying according to claim 7, which is characterized in that the flow velocity of the mixed gas is 1~10L/min, gaseous mixture
Ozone concentration is 10~200ppm in body.
9. applying according to claim 7, which is characterized in that concentration of the catalyst in absorbing liquid is 20g/L~100g/L.
10. applying according to claim 7, which is characterized in that the concentration ratio of absorbing liquid sulfite magnesium and magnesium nitrite
For (1~100): 1, the total concentration of magnesium sulfite and magnesium nitrite is 20~100g/L.
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| CN116078154A (en) * | 2023-01-17 | 2023-05-09 | 昆明理工大学 | Method for improving oxidation rate of magnesium sulfite |
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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 |