CN104984752B - Nitrogen oxide and mercury co-oxidation catalyst and preparation method thereof - Google Patents
Nitrogen oxide and mercury co-oxidation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses nitrogen oxide and mercury co-oxidation catalyst and a preparation method thereof. The catalyst is as shown in the formula: SnaCobGecCudOx, wherein a, b, c, d and x represent the atomic numbers of Sn, Co, Ge, Cu and O respectively; a:b:c:d=(0.40 to 0.65):(0.05 to 0.23):(0.05 to 0.10):(0.50 to 0.02); x depends on the valences of the metallic elements. The preparation method comprises the following steps: (1) adding water into Sn salt, Co salt and meta-germanate, so as to obtain a water solution I; adding ethanol into Cu salt to obtain an alcoholic solution; mixing the water solution I and the alcoholic solution; (2) under an oxygen-free atmosphere, adding an alkaline water solution into the mixed solution obtained in the step (1), stirring to obtain a water solution II; carrying out centrifugation to remove supernate, and carrying out washing and drying; (3) soaking power obtained in the step (2) into an alkaline alcoholic solution, and drying; carrying out calcinations to obtain the catalyst. The catalyst can catalyze NO and Hg<0> in a concerted manner at 200 to 350 DEG C, is high in catalyzing efficiency, and has favorable H2O poisoning and NH3 interference preventing performance.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, more particularly to a kind of metal oxide catalyst and its preparation
Method.
Background technology
Nitrogen oxides (NOx) and hydrargyrum (Hg) be the important atmosphere pollution of China.With developing rapidly for China's economy, with
Energy-consuming based on coal is increased rapidly, and a large amount of Fossil fuel consumptions cause the NO being discharged in airxIt is rapid with Hg discharge capacitys
Increase.They not only cause the environmental problems such as acid rain, photochemical fog, and have high risks to health.Therefore, how
Efficiently control NOxA highly important problem in Chinese national economy development is become with Hg discharges.
At present, ammonia SCR technology (NH3- SCR) it is the widest NO of commercial ApplicationxControl technology, the skill
Art has the applicating history of some time in coal-burning power plant and motor-driven vehicle gas disposal, and its key problem is the development of catalyst.
The NH of industrial applications3- SCR catalyst is usually with TiO2For carrier, V2O5For active component, then load a certain amount of WO3
Or MoO3Deng auxiliary agent, its Applicable temperature scope is 300-400 DEG C.But, this kind of catalyst is still suffered from actual use
Problem：First, in flue gas high level vapor (H2) and sulfur dioxide (SO O2) to catalyst activity and aging effects very
Greatly；Secondly, catalyst activity component V2O5Presoma toxicity it is very big, pollution is produced to human body and ecological environment easily；Again
Secondary, the catalyst system Applicable temperature scope is narrower, relatively low to smog discharge temperature (<250 DEG C) Industrial Boiler/stove be difficult to
Using.Additionally, the catalyst system is expensive, cause NOxControl cost is very high.
SCR catalyst cooperates with demercuration technology by domestic and international researcher extensive concern.The know-why is to utilize SCR catalyst
Nonvalent mercury (HgO) is oxidized to into monovalence or bivalent mercury, then the hydrargyrum after oxidation is removed by dedusting or desulfurization.The technology is solved
HgO is insoluble in the problem of water, with higher demercuration efficiency.But the problem for existing is the NH sprayed into during SCR denitration3Sternly
Suppress the oxidation of HgO again, affect the popularization and application of the technology.Meanwhile, it is narrow that the technology there is also operating temperature range, it is difficult to adapts to
The current demand of Industrial Boiler/stove demercuration.Therefore, develop new type low temperature, efficiently cooperate with the catalyst of denitration demercuration to become me
The urgent needss that state's Industrial Boiler/furnace flue gas are administered.
In recent years, using transition metal and rare-earth oxide exploitation efficient oxidation NO catalyst be NOxControl
One hot subject.Existing document report cobalt oxide has preferable NO oxidation activities, but its vapour resistant poisoning performance
It is poor.The researches of oxidation cobalt oxidation HgO, yet there are no with anti-NH3The cobalt oxide of interference efficient oxidation hydrargyrum synergistic oxidation NO
The report of catalyst.If can develop with the anti-NH of efficient vapour resistant poisoning3The novel nitrogen oxide and hydrargyrum of jamming performance
Synergistic oxidation catalyst, will substantially reduce smoke gas treatment totality cost, promote the acceleration that industrial smoke is administered to implement.
The content of the invention
It is an object of the invention to provide a kind of nitrogen oxides and hydrargyrum synergistic oxidation catalyst and preparation method thereof, the catalyst
Can concerted catalysis nitrogen oxides and hydrargyrum, in the wide temperature range more than 200 DEG C have efficiently catalyzing and oxidizing NOxWith HgO's
Performance, while with good vapour resistant poisoning and anti-NH3Jamming performance, can adapt to tightened up emission regulation demands,
Reduce cost and improve the purpose of safety in utilization.
A kind of nitrogen oxides and hydrargyrum synergistic oxidation catalyst that the present invention is provided, the catalyst have below formula：
SnaCobGecCudOx, wherein, a, b, c, d and x represent the atomic number of Sn, Co, Ge, Cu and O, a respectively：b：c：D=(0.40～
0.65)：(0.05～0.23)：(0.05～0.10)：(0.50～0.02), x determine (x=according to the quantivalence of each metallic element
2a+4/3b+2c+d)。
In above-mentioned catalyst, mol ratio Sn of each metallic element in the catalyst：Co：Ge：Cu=a：b：c：D=
(0.40～0.65)：(0.05～0.23)：(0.05～0.10)：(0.50～0.02).
In above-mentioned catalyst, the catalyst concretely following 1) -6) in any one：
1) catalyst with below formula：SnaCobGecCudOx, wherein, a, b, c, d and x represent respectively Sn, Co,
The atomic number of Ge, Cu and O, a：b：c：D=(0.40～0.60)：(0.05～0.15)：(0.05～0.07)：(0.50～
0.25), x is determined according to the valence state taken by the value of a, b, c and d and each metallic element；
2) catalyst with below formula：SnaCobGecCudOx, wherein, a, b, c, d and x represent respectively Sn, Co,
The atomic number of Ge, Cu and O, a：b：c：D=(0.50～0.65)：(0.08～0.23)：(0.07～0.10)：(0.30～
0.02), x is determined according to the valence state taken by the value of a, b, c and d and each metallic element；
3) catalyst has below formula：SnaCobGecCudOx, wherein, a, b, c, d and x represent respectively Sn, Co,
The atomic number of Ge, Cu and O, a：b：c：D=0.4：0.05：0.05：0.50, x determines according to the valence state taken by each metallic element；
4) catalyst has below formula：SnaCobGecCudOx, wherein, a, b, c, d and x represent respectively Sn, Co,
The atomic number of Ge, Cu and O, a：b：c：D=0.65：0.23：0.10：0.02, x is determined by the quantivalence of each metallic element；
5) catalyst has below formula：SnaCobGecCudOx, wherein, a, b, c, d and x represent respectively Sn, Co,
The atomic number of Ge, Cu and O, x are determined by the quantivalence of each metallic element；
6) catalyst has below formula：SnaCobGecCudOx, wherein, a, b, c, d and x represent respectively Sn, Co,
The atomic number of Ge, Cu and O, a：b：c：D=0.60：0.08：0.07：0.25, x is determined by the quantivalence of each metallic element.
In above-mentioned catalyst, in the formula of the catalyst, x by a, b, c, d value and each metallic element taken
Valence state, is determined by chemical equilibrium, and the relational expression of x and a, b, c, d specifically can be as follows：X=2a+4/3b+2c+d.
In above-mentioned catalyst, counted as 100% with the total moles percentage composition of slaine, prepare the slaine of the catalyst
Proportioning can be as follows：Molar content is 50～80% stannic chloride, and molar content is 5～30% cobalt nitrate, is rubbed
Your percentage composition is 5～15% sodium metagermanate, the copper nitrate of surplus.
In above-mentioned catalyst, counted as 100% with the total moles percentage composition of slaine, prepare the slaine of the catalyst
Concretely following 1) -7) in any one：
1) molar content is 50～80% stannic chloride, and molar content is 5～20% cobalt nitrate, moles hundred
Point content is 5～10% sodium metagermanate, the copper nitrate of surplus；
2) molar content is 50～70% stannic chloride, and molar content is 5～10% cobalt nitrate, moles hundred
Point content is 5～10% sodium metagermanate, the copper nitrate of surplus；
3) molar content is 60～80% stannic chloride, and molar content is 10～20% cobalt nitrate, mole
Percentage composition is 5～10% sodium metagermanate, the copper nitrate of surplus；
4) molar content is 50% stannic chloride, and molar content is 5% cobalt nitrate, and molar content is
5% sodium metagermanate, the copper nitrate of surplus；
5) molar content is 80% stannic chloride, and molar content is 10% cobalt nitrate, molar content
For 5% sodium metagermanate, the copper nitrate of surplus；
6) molar content is 60% stannic chloride, and molar content is 20% cobalt nitrate, molar content
For 5% sodium metagermanate, the copper nitrate of surplus；
7) molar content is 70% stannic chloride, and molar content is 10% cobalt nitrate, molar content
For 10% sodium metagermanate, the copper nitrate of surplus.
Present invention provides a kind of preparation method of above-mentioned catalyst, comprises the steps：
(1) add water in pink salt, cobalt salt and inclined germanate, obtain aqueous solution；Ethanol is added in mantoquita, obtains alcoholic solution；It is mixed
Close the aqueous solution and the alcoholic solution；
(2) under oxygen-free atmosphere, in the mixed solution that step (1) is obtained, the aqueous solution of Deca alkali, stirring obtain serosity；
Centrifugation removes supernatant, washs post-drying；
(3) powder infusion after step (2) drying is dried in alkali alcosol；It is fired that the catalyst is obtained.
Above-mentioned preparation method, in step (1), is counted with the total moles percentage composition of slaine as 100%, the pink salt
Molar content can be 50%～80%, concretely 50%～70%, 60%～80%, 50%, 60%, 70% or
80%；The molar content of the cobalt salt can be 5～30%, concretely 5%～20%, 5%～10%, 10%～
20%th, 5%, 10% or 20%；The molar content of the inclined germanate can be 5～15%, concretely 5%～10%,
5% or 10%；The balance of mantoquita.
Above-mentioned preparation method, in step (1), the addition of the water can for the pink salt, the cobalt salt and it is described partially
10～20 times of the quality sum of germanate, concretely 10～15 times, 15～20 times, 10 times, 15 times or 20 times；The pink salt
Can be any one in stannic chloride, stannous chloride and butyl tin trichloride；The cobalt salt can be cobalt nitrate, cobaltous chloride and cobaltous sulfate
In any one；The inclined germanate can be any one in sodium metagermanate, two sodium germanates and lithium germanium oxide；
The addition of the ethanol can be 20～40 times of the mantoquita quality, concretely 20～30 times, 30～40 times,
20 times, 30 times or 40 times；The mantoquita can be any one in copper chloride, copper nitrate and copper sulfate.
In above-mentioned preparation method, in step (2), the addition of the alkali is more than or equal to the pink salt, the cobalt salt, institute
State inclined germanate and the pink salt 2 times of molal quantity sum；
In the aqueous solution of the alkali, alkali is any one in ammonia, ammonium carbonate and sodium hydroxide, and concentration can be 0.5～2mol/
L, concretely 1mol/L.
In above-mentioned preparation method, in step (2), the rate of addition of the aqueous solution of the alkali can be 0.1～2mL/min,
Concretely 1mL/min；
The time of the stirring can be 1～5 hour, concretely 2 hours；
The rotating speed of the centrifugation can be 3000～10000 revs/min, concretely 5000 revs/min；Time can for 2～
10 minutes, concretely 3～10 minutes, 3～5 minutes, 4～10 minutes, 3 minutes, 4 minutes, 5 minutes or 10 minutes；
The temperature of the drying can be 100～120 DEG C, concretely 110 DEG C；Time can be 10～15 hours, specifically may be used
For 12 hours.
In above-mentioned preparation method, in step (3), the powder infusion after step (2) is dried, can in alkali alcosol
Control catalyst surface basic sites intensity and distribution, can remarkably promote catalysis activity；
Can impregnated in alkali alcosol described in 50mL per powder described in 0.5～5g, concretely per 1～5g, 1～2g, 2
Described in～5g, 1g, 2g or 5g, powder infusion is in alkali alcosol described in 50mL；
The alkali alcosol can be to obtain in the dehydrated alcohol of 100 times of quality per 0.2～0.8g alkali solubles, concretely
Per 0.2～0.5g, 0.5～0.8g, 0.2g, 0.5g or 0.8g alkali soluble obtained in the dehydrated alcohol of 100 times of quality；
The alkali can be sodium hydroxide, ammonium carbonate or sodium carbonate；
The time of the dipping can be 1～2 hour, concretely 1 hour；
Then the drying can be dried for first stirring the dipping solution to leather hard；The temperature of the drying is
80～95 DEG C, concretely 90 DEG C；Time can be 10～15 hours, concretely 10～12 hours, 12～15 hours, it is 10 little
When, 12 hours or 15 hours.
In above-mentioned preparation method, in step (3), the roasting is carried out under nitrogen protection, and the temperature of the roasting can
For 450～550 DEG C, concretely 500 DEG C；Time can be 4～6 hours, concretely 4～5 hours, 5～6 hours, 4 hours, 5
Hour or 6 hours.
The present invention has the advantages that：
(1) catalyst of the present invention in the range of 200～350 DEG C, imitate up to the oxidation of 67～90%, HgO by the oxidation efficiency of NO
Rate, can concerted catalysis NO and Hg up to 97～100%0, broad application temperature range, high catalytic efficiency can significantly reduce operating cost.
(2) catalyst of the present invention has good vapour resistant poisoning and anti-NH3Jamming performance.
(3) preparation method of catalyst of the present invention can control catalyst surface basic sites intensity and distribution well, can
Remarkably promote catalysis activity.
Description of the drawings
Fig. 1 is that, under different catalytic temperatures, the catalyst that embodiment 2 is prepared adds 5% water to steam in catalyst system and catalyzing
The variation diagram of the oxygenation efficiency of NO before and after gas.
Fig. 2 is that, under different catalytic temperatures, the catalyst that embodiment 2 is prepared is added in catalyst system and catalyzing
500ppmNH3Hg in front and back0Oxygenation efficiency variation diagram.
Specific embodiment
Experimental technique used in following embodiments if no special instructions, is conventional method.
In following embodiments, material used, reagent etc., if no special instructions, commercially obtain.
Embodiment 1, prepare nitrogen oxides and hydrargyrum synergistic oxidation catalyst
Catalyst is prepared as steps described below：
(1) by stannic chloride, cobalt nitrate and sodium metagermanate normal-temperature dissolution in the water of 10 times of quality, stirring forms aqueous solution；
By copper nitrate normal-temperature dissolution in the ethanol of 30 times of quality, stirring forms ethanol solution；Again above two solution is mixed to form
Clear solution, wherein, is counted with slaine total moles percentage composition as 100%, and the molar content of stannic chloride is 50%, nitric acid
The molar content 5% of cobalt, the molar content 5% of sodium metagermanate, balance of copper nitrate.
(2) by ammonia with 1mol/L ammonia spirit, then dropwise arrive what step one was configured with the speed of 1mL/min
In solution (ammonia spirit addition by ammonia mole more than or equal to step one belong to the twice of salt mole with GOLD FROM PLATING SOLUTION in terms of
Calculate), flocculent deposit is formed, while continuously blasting N2Low-oxygen environment is kept in making mixed liquor, is continued stirring and is obtained serosity in 2 hours.
Gained serosity is placed in a centrifuge, and is centrifuged 5 minutes with 5000 revs/min of rotating speed and is separated, supernatant is poured out, is rejoined
After ionized water vibration is mixed, the process of repeated centrifugation.According to said method eccentric cleaning five times.By the precipitate after cleaning in baking oven
110 DEG C of dryings 12 hours.
(3) take during sodium hydroxide 0.5g is dissolved in the dehydrated alcohol of 100 times of quality and clear solution is obtained.1g steps (2) are obtained
To solidss be put in 50mL clear solutions impregnate 1 hour, make solution gradually be evaporated to leather hard under the conditions of strong agitation,
It is put in baking oven 90 DEG C of dryings 12 hours.Take dried solidss to be put in tube furnace under nitrogen protection in 500 DEG C of roastings 5
Hour, obtain NO and Hg0Synergistic oxidation catalyst SnCoGeCuOx.
In the catalyst that the present embodiment is prepared, the molar ratio of each metallic element is Sn：Co：Ge：Cu=0.4：
0.05：0.05：0.50.
Embodiment 2, prepare nitrogen oxides and hydrargyrum synergistic oxidation catalyst
Catalyst is prepared as steps described below：
(1) by stannic chloride, cobalt nitrate and sodium metagermanate normal-temperature dissolution in the water of 15 times of quality, stirring forms aqueous solution；
By copper nitrate normal-temperature dissolution in the ethanol of 20 times of quality, stirring forms ethanol solution；Again above two solution is mixed to form
Clear solution, wherein, is counted with slaine total moles percentage composition as 100%, and the molar content of stannic chloride is 80%, nitric acid
The molar content 10% of cobalt, the molar content 5% of sodium metagermanate, balance of copper nitrate.
(2) by ammonia with 1mol/L ammonia spirit, then dropwise arrive what step one was configured with the speed of 1mL/min
In solution (ammonia spirit addition by ammonia mole more than or equal to step one belong to the twice of salt mole with GOLD FROM PLATING SOLUTION in terms of
Calculate), flocculent deposit is formed, while continuously blasting N2Low-oxygen environment is kept in making mixed liquor, is continued stirring and is obtained serosity in 2 hours.
Gained serosity is placed in a centrifuge, and is centrifuged 3 minutes with 5000 revs/min of rotating speed and is separated, supernatant is poured out, is rejoined
After ionized water vibration is mixed, the process of repeated centrifugation.According to said method eccentric cleaning five times.By the precipitate after cleaning in baking oven
110 DEG C of dryings 15 hours.
(3) take during sodium hydroxide 0.2g is dissolved in the dehydrated alcohol of 100 times of quality and clear solution is obtained.2g steps (2) are obtained
To solidss be put in 50mL clear solutions impregnate 1 hour, make solution gradually be evaporated to leather hard under the conditions of strong agitation,
It is put in baking oven 90 DEG C of dryings 10 hours.Take dried solidss to be put in tube furnace under nitrogen protection in 500 DEG C of roastings 6
Hour, obtain NO and Hg0Synergistic oxidation catalyst SnCoGeCuOx.
In the catalyst that the present embodiment is prepared, the molar ratio of each metallic element is Sn：Co：Ge：Cu=0.65：
0.23：0.10：0.02.
Embodiment 3, prepare nitrogen oxides and hydrargyrum synergistic oxidation catalyst
Catalyst is prepared as steps described below：
(1) by stannic chloride, cobalt nitrate and sodium metagermanate normal-temperature dissolution in the water of 20 times of quality, stirring forms aqueous solution；
By copper nitrate normal-temperature dissolution in the ethanol of 20 times of quality, stirring forms ethanol solution；Again above two solution is mixed to form
Clear solution, wherein, is counted with slaine total moles percentage composition as 100%, and the molar content of stannic chloride is 60%, nitric acid
The molar content 20% of cobalt, the molar content 5% of sodium metagermanate, balance of copper nitrate.
(2) by ammonia with 1mol/L ammonia spirit, then dropwise arrive what step one was configured with the speed of 1mL/min
In solution (ammonia spirit addition by ammonia mole more than or equal to step one belong to the twice of salt mole with GOLD FROM PLATING SOLUTION in terms of
Calculate), flocculent deposit is formed, while continuously blasting N2Low-oxygen environment is kept in making mixed liquor, is continued stirring and is obtained serosity in 2 hours.
Gained serosity is placed in a centrifuge, and is centrifuged 4 minutes with 5000 revs/min of rotating speed and is separated, supernatant is poured out, is rejoined
After ionized water vibration is mixed, the process of repeated centrifugation.According to said method eccentric cleaning five times.By the precipitate after cleaning in baking oven
110 DEG C of dryings 12 hours.
(3) take during sodium hydroxide 0.8g is dissolved in the dehydrated alcohol of 100 times of quality and clear solution is obtained.5g steps (2) are obtained
To solidss be put in 100mL clear solutions impregnate 2 hours, make solution gradually be evaporated to leather hard under the conditions of strong agitation
State, is put in baking oven 90 DEG C of dryings 15 hours.Take dried solidss to be put in tube furnace under nitrogen protection in 500 DEG C of roastings
Burn 4 hours, obtain NO and Hg0Synergistic oxidation catalyst SnCoGeCuOx.
It is Sn that the present embodiment prepares the molar ratio of each metallic element in catalyst：Co：Ge：Cu=0.50：0.15：
0.05：0.30.
Embodiment 4, prepare nitrogen oxides and hydrargyrum synergistic oxidation catalyst
Catalyst is prepared as steps described below：
(1) by stannic chloride, cobalt nitrate and sodium metagermanate normal-temperature dissolution in the water of 10 times of quality, stirring forms aqueous solution；
By copper nitrate normal-temperature dissolution in the ethanol of 40 times of quality, stirring forms ethanol solution；Again above two solution is mixed to form
Clear solution, wherein, is counted with slaine total moles percentage composition as 100%, and the molar content of stannic chloride is 70%, nitric acid
The molar content 10% of cobalt, the molar content 10% of sodium metagermanate, balance of copper nitrate.
(2) by ammonia with 1mol/L ammonia spirit, then dropwise arrive what step one was configured with the speed of 1mL/min
In solution (ammonia spirit addition by ammonia mole more than or equal to step one belong to the twice of salt mole with GOLD FROM PLATING SOLUTION in terms of
Calculate), flocculent deposit is formed, while continuously blasting N2Low-oxygen environment is kept in making mixed liquor, is continued stirring and is obtained serosity in 2 hours.
Gained serosity is placed in a centrifuge, and is centrifuged 10 minutes with 5000 revs/min of rotating speed and is separated, supernatant is poured out, is rejoined
After deionized water vibration is mixed, the process of repeated centrifugation.According to said method eccentric cleaning five times.By the precipitate after cleaning in baking oven
Interior 110 DEG C of dryings 15 hours.
(3) take during sodium hydroxide 0.5g is dissolved in the dehydrated alcohol of 100 times of quality and clear solution is obtained.2g steps (2) are obtained
To solidss be put in 50mL clear solutions impregnate 2 hours, make solution gradually be evaporated to leather hard under the conditions of strong agitation,
It is put in baking oven 90 DEG C of dryings 15 hours.Take dried solidss to be put in tube furnace under nitrogen protection in 500 DEG C of roastings 6
Hour, obtain NO and Hg0Synergistic oxidation catalyst SnCoGeCuOx.
In the catalyst that the present embodiment is prepared, the molar ratio of each metallic element is Sn：Co：Ge：Cu=0.60：
0.08：0.07：0.25.
Embodiment 5, to NO and Hg0The impact to being catalyzed of catalytic effect and water vapour and ammonia
(1) to NO and Hg0Catalytic effect
Matched group：In existing document (Gao Dongmei etc., Co3O4/ MPS catalytic oxidation NO performances. chemical industry is in progress, and 2009,28
(5):A kind of load type Co of report in 805-811)3O4NO oxidation catalysts, its raw material components is：Content is catalyst matter
The cobalt oxide of the 25% of amount percentage composition, remaining is carrier MPS.Its preparation method is comprised the following steps：
Step one, with microemulsion method prepare MPS carriers：By a certain amount of dodecyl amine and tetraethyl orthosilicate in mass ratio 1：
3.8 mixing are dissolved in volume ratio 1：In 1 ethanol solution, temperature constant magnetic stirring 22h so as to microemulsion is presented, sucking filtration uses 1：1
Ethanol solution is washed 2～3 times, is dried 2h, roasting 5h at 600 DEG C of Muffle furnace at 120 DEG C, obtains the MPS of white；
Step 2, catalyst is prepared with equi-volume impregnating：First cobalt nitrate is dissolved in 100mL distilled water, is added
Magnetic agitation 1h after MPS, is dried 4h at 120 DEG C, then the roasting 3h at 300 DEG C, obtains Co3O4/ MPS catalyst.
Co in the catalyst made in above-mentioned matched group3O4Mass fraction be 25%.
The catalytic effect of the catalyst for preparing in above-described embodiment 1-4 and matched group catalyst is tested, is walked
It is rapid as follows：By the nitric oxide (NO) of 500ppm, 80 μ g/m3Nonvalent mercury (Hg0), 5% oxygen (O2) mix, remaining reaction is mixed
Conjunction gas is nitrogen (N2), the useful load of catalyst is 150mg, and reaction velocity is 70000h-1, 200 DEG C, 250 DEG C, 300 DEG C,
Under the conditions of 350 DEG C, 400 DEG C and 450 DEG C equitemperatures, the catalyst prepared in above-described embodiment 1- embodiments 4 and matched group
Catalyst aoxidizes NO and Hg0Conversion ratio see Tables 1 and 2.
The oxygenation efficiency of table 1, each embodiment and matched group catalyst to NO in catalyst system and catalyzing
Table 2, each embodiment and matched group catalyst are to Hg in catalyst system and catalyzing0Oxygenation efficiency
By Tables 1 and 2 as can be seen that catalyst of the present invention is in the range of 200～350 DEG C, the oxidation efficiency of NO up to 67～
, up to 97～100%, temperature applicable range is wide, can concerted catalysis NO and Hg for the oxidation efficiency of 90%, HgO0.Especially embodiment 2
The catalyst Sn for preparing0.65Co0.23Ge0.10Cu0.02Ox, its oxidation efficiency to NO assigns 90% at 300 DEG C, to Hg0's
Oxidation efficiency can reach 100% between 250 DEG C～400 DEG C, high catalytic efficiency.
(2) vapour resistant poisoning performance
1) before adding vapor：
By the nitric oxide (NO) of 500ppm, 80 μ g/m3Nonvalent mercury (Hg0) and 5% oxygen (O2) mixing, remaining reaction
Gaseous mixture is nitrogen (N2), by the reaction tube equipped with 2 catalyst of 150mg embodiments, reaction velocity is 70000h-1, temperature model
Enclose for, under the conditions of 200-450 DEG C, the catalyst that catalyst is prepared using embodiment 2 aoxidizes NO and Hg0Conversion ratio see figure
Before adding 5% vapor in 1.
2) after adding vapor：
By the nitric oxide (NO) of 500ppm, 80 μ g/m3Nonvalent mercury (Hg0), 5% oxygen (O2) and 5% vapor mix
Close, remaining reaction gaseous mixture is nitrogen (N2), by the reaction tube equipped with 2 catalyst of 150mg embodiments, reaction velocity is
70000h-1, temperature range be 200-450 DEG C under the conditions of, the catalyst that catalyst is prepared using embodiment 2, oxidation NO and
Hg0Conversion ratio see after.
From figure 1 it appears that the addition of vapor has certain impact to less than 250 DEG C of NO oxygenation efficiency, than anhydrous steaming
Slightly reduce during gas, and the addition of vapor is not almost affected on NO oxygenation efficiency more than 250 DEG C；And the addition of vapor is right
Hg0Oxygenation efficiency affect little.Therefore, catalyst of the present invention has preferable vapour resistant poisoning performance.
(3) anti-NH3Jamming performance
1) add NH3Before：
By the nitric oxide (NO) of 500ppm, 80 μ g/m3Nonvalent mercury (Hg0), 5% oxygen (O2) mix, remaining reaction is mixed
Conjunction gas is nitrogen (N2), by the reaction tube equipped with 2 catalyst of 150mg embodiments, reaction velocity is 70000h-1, temperature range
Under the conditions of 200-450 DEG C, catalyst oxidation Hg0Oxygenation efficiency see3Front curve.
2) add NH3Afterwards：
By the ammonia (NH of 500ppm3), the nitric oxide (NO) of 500ppm, 80 μ g/m3Nonvalent mercury (Hg0), 5% oxygen
(O2) mixing, remaining reaction gaseous mixture is nitrogen (N2), by the reaction tube equipped with 2 catalyst of 150mg embodiments, reaction velocity
For 70000h-1, under the conditions of temperature range is 200-450 DEG C, catalyst oxidation Hg0Oxygenation efficiency see3Song afterwards
Line.
From figure 2 it can be seen that in Range of measuring temp, and NH is not added3When compare, less than 250 DEG C of Hg0Oxygen
Rate reduces larger, temperature Hg in the range of 250-350 DEG C0Oxygenation efficiency remain to be maintained at more than 80%, it is believed that NH3's
Add to Hg0Oxygenation efficiency affects little.Meanwhile, the NO oxygenation efficiency of the catalyst does not receive NH substantially3The impact of addition.As a result show,
Catalyst manufactured in the present embodiment is in Hg0There is stronger anti-NH in oxidizing process3The ability of interference.NH3Addition can pass through
SCR reactions promote the elimination of NO.
Claims (8)
1. a kind of nitrogen oxides and hydrargyrum synergistic oxidation catalyst, it is characterised in that：The catalyst has below formula：
SnaCobGecCudOx, wherein, a, b, c, d and x represent the atomic number of Sn, Co, Ge, Cu and O, a respectively：b：c：D=(0.40～
0.65)：(0.05～0.23)：(0.05～0.10)：(0.50～0.02), x are determined by the quantivalence of each metallic element.
2. catalyst according to claim 1, it is characterised in that：Counted with the total moles percentage composition of slaine as 100%,
The proportioning for preparing the slaine of the catalyst is as follows：Molar content is 50～80% stannic chloride, molar content
For 5～30% cobalt nitrate, molar content is 5～15% sodium metagermanate, the copper nitrate of surplus.
3. the preparation method of the catalyst described in claim 1 or 2, comprises the steps：
(1) add water in pink salt, cobalt salt and inclined germanate, obtain aqueous solution；Ethanol is added in mantoquita, obtains alcoholic solution；Mixing institute
State aqueous solution and the alcoholic solution；
(2) under oxygen-free atmosphere, in the mixed solution that step (1) is obtained, the aqueous solution of Deca alkali, stirring obtain serosity；Centrifugation
Supernatant is removed, post-drying is washed；
(3) powder infusion after step (2) drying is dried in alkali alcosol；It is fired that the catalyst is obtained.
4. preparation method according to claim 3, it is characterised in that：In step (1), contained with the total moles percentage of slaine
Measure and count for 100%, the molar content of the pink salt is 50%～80%；The molar content of the cobalt salt be 5～
30%；The molar content of the inclined germanate is 5～15%；The balance of mantoquita.
5. the preparation method according to claim 3 or 4, it is characterised in that：In step (1), the addition of the water is institute
State pink salt, the cobalt salt and the inclined germanate 10～20 times of quality sum；The pink salt be stannic chloride, stannous chloride and
Any one in butyl tin trichloride；The cobalt salt is any one in cobalt nitrate, cobaltous chloride and cobaltous sulfate；The inclined germanate
For any one in sodium metagermanate, two sodium germanates and lithium germanium oxide；
The addition of the ethanol is 20～40 times of the mantoquita quality；The mantoquita is copper chloride, copper nitrate and copper sulfate
In any one.
6. preparation method according to claim 5, it is characterised in that：In step (2), the addition of the alkali is more than or equal to
2 times of the molal quantity sum of the pink salt, the cobalt salt, the inclined germanate and the mantoquita；
In the aqueous solution of the alkali, alkali is any one in ammonia, ammonium carbonate and sodium hydroxide, and concentration is 0.5～2mol/L；
The rate of addition of the aqueous solution of the alkali is 0.1～2mL/min；
The time of the stirring is 1～5 hour；
The rotating speed of the centrifugation is 3000～10000 revs/min, and the time is 2～10 minutes；
The temperature of the drying is 100～120 DEG C, and the time is 10～15 hours.
7. preparation method according to claim 6, it is characterised in that：Step (3), per powder infusion described in 0.5～5g in
In alkali alcosol described in 50mL；
The alkali alcosol is to obtain in the dehydrated alcohol of 100 times of quality per 0.2～0.8g alkali solubles, and the alkali is hydroxide
Sodium, ammonium carbonate or sodium carbonate；
The time of the dipping is 1～2 hour；
Then the drying is dried for first stirring the dipping solution to leather hard；The temperature of the drying is 80～95
DEG C, the time is 10～15 hours.
8. preparation method according to claim 7, it is characterised in that：Step (3), the roasting are entered under nitrogen protection
OK, the temperature of the roasting is 450～550 DEG C, and the time is 4～6 hours.
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| CN1239444A (en) * | 1997-10-14 | 1999-12-22 | 株式会社五十铃陶瓷研究所 | Catalyst for exhaust gas purification |
| CN1280036A (en) * | 1999-05-13 | 2001-01-17 | 株式会社日本触媒 | Catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid and its use |
| JP2008194684A (en) * | 2007-01-18 | 2008-08-28 | Shiga Univ Of Medical Science | Treatment method of exhaust material, and method for recovering rare metal |
| CN102292156A (en) * | 2009-01-22 | 2011-12-21 | 三菱树脂株式会社 | Catalyst for removing nitrogen oxides and method for producing same |
| CN103648641A (en) * | 2011-01-28 | 2014-03-19 | 日本化药株式会社 | Catalyst for selectively reducing saturated aldehyde, and production method thereof |
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| CN1239444A (en) * | 1997-10-14 | 1999-12-22 | 株式会社五十铃陶瓷研究所 | Catalyst for exhaust gas purification |
| CN1280036A (en) * | 1999-05-13 | 2001-01-17 | 株式会社日本触媒 | Catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid and its use |
| JP2008194684A (en) * | 2007-01-18 | 2008-08-28 | Shiga Univ Of Medical Science | Treatment method of exhaust material, and method for recovering rare metal |
| CN102292156A (en) * | 2009-01-22 | 2011-12-21 | 三菱树脂株式会社 | Catalyst for removing nitrogen oxides and method for producing same |
| CN103648641A (en) * | 2011-01-28 | 2014-03-19 | 日本化药株式会社 | Catalyst for selectively reducing saturated aldehyde, and production method thereof |
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