CN106378145A - Catalyst for gaseous hydrogen peroxide and application thereof - Google Patents
Catalyst for gaseous hydrogen peroxide and application thereof Download PDFInfo
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Abstract
The invention discloses catalyst for gaseous hydrogen peroxide and application thereof. The catalyst for gaseous hydrogen peroxide has active ingredients of manganese copper composite oxides. The invention also provides an integral catalyst prepared from the catalyst, aluminum oxide and honey ceramics, a preparation method of the catalyst and a low-temperature smoke gas denitration method. The catalyst provided by the invention has the advantages that the preparation is simple; the catalyst is suitable for industrial production; the catalyst is mainly applied to the field of smoke gas denitration of nitric oxides in low-temperature smoke gas through gaseous hydrogen peroxide catalytic activation; the catalyst can promote the gaseous hydrogen peroxide to be decomposed into hydroxyl radicals; the hydroxyl radicals have the oxidability higher than that of the hydrogen peroxide. When the catalyst provided by the invention is used, the low-temperature smoke gas can be well denitrified; the consumption of the hydrogen peroxide can be greatly reduced; the denitration efficiency of the hydrogen peroxide can be obviously improved.
Description
Technical field
The present invention relates to a kind of gaseous state hydrogen peroxide catalyst, further relating to one kind gaseous state hydrogen peroxide catalytic decomposition can be
There is the gaseous state hydrogen peroxide integral catalyzer of the hydroxyl radical free radical of strong oxidizing property（Abbreviation integral catalyzer）And low temperature cigarette
The method of denitration of gas.
Technical background
Nitrogen oxides (NO x ) not only form acid rain, it is also to form one of major reason of haze, thus causing huge warp
The life health of Ji loss seriously the threat mankind.Wherein, the nitrogen oxides of industrial discharge occupy very big ratio, according to national ring
Guarantor portion statistics is announced, 2014,2078.0 ten thousand tons of national nitrogen oxides of exhaust gas discharge capacity, and industrial nitrogen oxide emission is
1404.8 ten thousand tons.For increasingly serious atmosphere polluting problem, country increases the renovation dynamics to discharged nitrous oxides.
Gas denitrifying technology mainly selective catalysis reduction（SCR）With oxidative absorption method.Catalysts selective reducing process
（Selective Catalytic Reduction）Abbreviation SCR, is in the presence of uniform temperature and catalyst, with liquefied ammonia or
Carbamide as reducing agent, optionally with flue gas in reaction of nitrogen oxides and generate nitrogen and water.Low-temperature flue gas temperature is most
Below 280 DEG C, but the running temperature of conventional scr denitrating catalyst is 300-400 DEG C, and temperature range is not suitable for, and low
Warm SCR catalyst also haves such problems as sulfur poisoning., typically at 300 DEG C, nitrogen oxides are dense for temperature taking the coking flue gas of low temperature as a example
Degree cyclic fluctuation, according to SCR method, ammonia spraying amount is difficult to control to, and easily causes the secondary pollutions such as NH_3 leakage.In addition, in flue gas
The other components such as coal tar easy blocking catalyst duct, causes catalyst to inactivate.Catalytic reduction method therefore difficult to use is processed
Low-temperature flue gas.
Above-mentioned phenomenon makes oxidative absorption method become the developing direction of low-temperature denitration of flue gas.Oxidative absorption method is using oxidation
Agent becomes the nitrogen oxides of high-valence state oxidation of nitric oxide, by alkali liquor in absorption tower together with other polluters in flue gas
Absorb.Hydrogen peroxide has higher oxidisability, and the by-product reacting only produces oxygen and water, will not produce secondary pollution, claims
For the oxidant of cleaning in the world, in terms of the water pollution controls such as liquid phase oxidation organic contamination, therefore there are a lot of applications.But,
Hydrogen peroxide is used for the research of antioxidant nitroxide and applies then less.Patent CN 105013323A discloses a kind of coke oven flue
Gas energy-saving reduces discharging desulfurization and denitrification integral system, by the way of ozone and liquid hydrogen peroxide combine, flue gas is aoxidized, liquid
State hydrogen peroxide is ejected in gas flue by shower nozzle through overactivation again, but this patent does not disclose how hydrogen peroxide activates, and
And aoxidize using ozone and two kinds of oxidants of liquid hydrogen peroxide, relatively costly, if alone liquid hydrogen peroxide, dioxygen water consumption
Greatly, oxidation efficiency also can reduce.A kind of denitration method for flue gas is disclosed, the method is first using oxidation in patent CN104258701A
Agent aoxidizes to flue gas, is then absorbed with absorbent and water, completes the denitration of flue gas.It is double that oxidant used includes liquid
Oxygen water, liquid hydrogen peroxide spray gun sprays in flue gas, in the case that liquid hydrogen peroxide is 1.7 with nitrogen oxides mol ratio, takes off
Nitre rate is also only 68.75%.
Content of the invention
The present invention is directed to the deficiency that liquid hydrogen peroxide oxidation effect is poor, low-temperature denitration of flue gas rate is low, there is provided a kind of gaseous state
Hydrogen peroxide catalyst, this catalyst can carry out catalytic activation to gaseous state hydrogen peroxide, and generation has the hydroxyl of strong oxidizing property certainly
By base, the nitrogen oxides in efficient oxidation low-temperature flue gas, hydrogen peroxide is made still to have higher denitration efficiency under low-temperature flue gas.
Present invention also offers a kind of contain above-mentioned gaseous state hydrogen peroxide integral catalyzer.This integral catalyzer increases
The contact area of catalyst, and can prevent the catalyst from producing fluid resistance in the duct, there is more preferable catalytic effect.
Present invention also offers the preparation method of above two catalyst, the method is easy to industrialized production.
Present invention also offers a kind of method of denitration of low-temperature flue gas, it is oxidant that the method uses gaseous state hydrogen peroxide,
Under catalyst existence condition the nitrogen oxides in flue gas are high-valence state nitrogen oxides soluble in water, are then inhaled with alkalescence
Receive agent to be absorbed the nitrogen oxides in flue gas, you can reach the purpose of denitration.The method is double with the gaseous state of activation of catalyst
Oxygen water is oxidant, significantly improves denitration efficiency it is also possible to reduce the usage amount of hydrogen peroxide.
Concrete technical scheme of the present invention is as follows：
A kind of gaseous state hydrogen peroxide catalyst, this catalyst is copper-manganese composite oxides, and its preparation method comprises the following steps：
（1）Using manganese salt, mantoquita as the presoma of catalyst, use water wiring solution-forming；
（2）The pH of precursor solution is adjusted aging to 8-12 standing, to precipitation by metallic ion completely, then filter, by filter cake
Dry, roasting, obtains gaseous state hydrogen peroxide catalyst.
The present invention prepares gaseous state hydrogen peroxide catalyst using coprecipitation, and the soluble-salt of selection copper and manganese is as catalysis
Agent presoma.These precursor salt are the common metal salt such as nitrate, sulfate, acetate or chloride, with low cost it is easy to
Obtain.The concentration of the solution that presoma is made into does not limit, using the general concentration in the sedimentation method.
Above-mentioned steps（1）In, the mol ratio of the copper ion in mantoquita and the manganese ion in manganese salt is 5:2-5.
Above-mentioned steps（2）In, when adjusting pH value of solution, can be using ammonia, sodium hydroxide or sodium carbonate liquor.
Above-mentioned steps（2）In, after adjustment pH, aging in 20-50 DEG C of standing.Standing is aging to be in order that metal ion is abundant
Precipitation, general 0-24 h ion is precipitable completely, and the concrete time can select according to practical situation.
Above-mentioned steps（2）In, filter cake is generally 7-15 h in 60-120 DEG C of drying, time.
Above-mentioned steps（2）In, roasting is an important step preparing catalyst, the suitable roasting temperature of catalyst of the present invention
Spend for 300-550 DEG C, roasting time is 3-5 h.
Further, present invention also offers a kind of integral catalyzer, this integral catalyzer includes ceramic honey comb,
It is coated with catalyst pulp, described catalyst pulp is mixed by gaseous state hydrogen peroxide catalyst, aluminium oxide and water on ceramic honey comb
Form.
In above-mentioned integral catalyzer, aluminium oxide, as first vector, improves the dispersion of catalyst, and makes catalyst steady
Solid be attached on carrier, it is to avoid catalyst activity component falls off during commercial Application, runs off.Ceramic honey comb conduct
The Second support of catalyst, has abundant pore structure, can load more multiple active components, and substantially reduces catalyst to gaseous state
The fluid resistance of hydrogen peroxide.
In above-mentioned catalyst pulp, catalyst is 1 with the mass ratio of aluminium oxide:4.Gaseous state hydrogen peroxide catalyst is in catalysis
Mass concentration in agent slurry is 30-50%.
In above-mentioned integral catalyzer, active component（Gaseous state hydrogen peroxide catalyst）Load capacity be 25-35 g/L.
In above-mentioned integral catalyzer, the specification of ceramic honey comb and size can be selected according to actual needs.
Present invention also offers the preparation method of above-mentioned integral catalyzer, the method comprises the following steps：
A. gaseous state hydrogen peroxide catalyst, aluminium oxide and the water mixing being obtained according to the method described above, is made into catalyst pulp；
B. above-mentioned catalyst pulp is coated on ceramic honey comb, then dry, roasting, prepared integral catalyzer.
The integral catalyzer of the present invention can carry according to the ceramic honey comb that the use environment of catalyst is coated in different size
On body, catalyst load will not reduce catalyst activity.Ceramic honey comb be integral catalyzer carrier, ceramic honeycomb and
The effect of alumina support mainly has：（1）Catalyst after load will not produce fluid resistance to gaseous state hydrogen peroxide.（2）Enter one
Step improves specific surface area of catalyst.（3）Prevent catalyst loss, improve the utilization rate of catalyst.（4）Carrier can also strengthen catalysis
The catalysis activity of agent.Catalyst load selects manually or automatically coating machine to complete.
In above-mentioned integral catalyzer preparation method, gaseous state hydrogen peroxide catalyst is double with the mass ratio of aluminium oxide, gaseous state
Mass concentration in catalyst pulp for the oxygen water catalyst, the load capacity of gaseous state hydrogen peroxide catalyst and previously mentioned
Cause.
In above-mentioned steps b, the ceramic honey comb being coated with catalyst pulp is dried at 70-120 DEG C.After drying,
300-500 DEG C of roasting 4-6 h.
Present invention also offers a kind of method of denitration of low-temperature flue gas, the method comprises the following steps：
（1）Liquid hydrogen peroxide is gasificated into gaseous state hydrogen peroxide；
（2）Integral catalyzer is obtained according to the method described above, this integral catalyzer is arranged on conveying gaseous state hydrogen peroxide and enters
In the conveyance conduit of flue；
（3）Gaseous state hydrogen peroxide is passed through in flue by conveyance conduit, gaseous state hydrogen peroxide first passes through integral catalyzer and produces more
Many hydroxyl radical free radicals, subsequently into the smoke contacts of flue and 80-150 DEG C, by the NO in flue gas x It is oxidized to soluble in water
Nitrogen oxides；
（4）Flue gas after oxidation enters the absorption tower containing absorbent, completes the denitration of flue gas.
In said method, gaseous state hydrogen peroxide can be obtained by way of liquid hydrogen peroxide is processed, for example, pass through
The mode water to liquid dioxygen obtains, and gasification process using any means disclosed in prior art, but can be considered
Hydrogen peroxide is easily decomposes, therefore gasifies at 60～120 DEG C more suitable.
In the method for denitration of low-temperature flue gas of the present invention, gaseous state hydrogen peroxide is first passed through integral catalyzer, through catalyst
Catalysis make gaseous state hydrogen peroxide produce more hydroxyl radical free radicals, oxidability strengthen, then again can be significantly with smoke contacts
Improve oxidation efficiency and denitration rate.At present, low-temperature flue gas oxidation typically all adopts liquid hydrogen peroxide as oxidant, consumption
Very big.It is oxidant that the present invention uses gaseous state hydrogen peroxide, and gaseous state hydrogen peroxide can be fully contacted with nitrogen oxides, and utilization rate is notable
Improve.Meanwhile, add catalyst to make gaseous state Activation of Hydrogen Peroxide Solution, produce the higher hydroxyl radical free radical of oxidisability, improve double further
Oxygen water oxidation efficiency.
In said method, H2O2With NO in flue gas x Mol ratio be 0.8 ~ 1.7:1, preferably 0.8-1:1, more preferably
0.8-0.9:1.
In said method, described absorbent is the alkaline solution such as ammonia, magnesium hydroxide, sodium hydroxide.
In said method, the direction that gaseous state hydrogen peroxide enters flue is contrary with the flow direction of flue gas.
In said method, integral catalyzer is arranged in the pipeline of conveying gaseous state hydrogen peroxide, the number of its size and installation
Mesh can be adjusted according to the flow of gaseous state hydrogen peroxide, diameter of pipeline etc..
The invention provides a kind of gaseous state hydrogen peroxide catalyst, this catalyst can be at a lower temperature gaseous state dioxygen
Water activates, and produces the higher hydroxyl radical free radical of oxidisability.This catalyst, aluminium oxide and water are configured to slurry and are coated in honeycomb pottery
On ceramic carrier, it is then passed through dry, roasting, the monoblock type gaseous state Activation of Hydrogen Peroxide Solution catalysis with certain mechanical strength can be obtained
Agent, this integral catalyzer has abundant pore structure, gaseous state hydrogen peroxide easily by and by catalytic decomposition become ratio dioxygen water oxygen
The higher hydroxyl radical free radical of the property changed, makes the oxidation and denitration efficiency of hydrogen peroxide greatly promote.The present invention is using the gaseous state dioxygen of activation
Water is oxidant, by oxidative absorption method, low-temperature flue gas is carried out with denitration, the method can be significantly compared with liquid hydrogen peroxide
Reduce dioxygen water consumption, significantly improve hydrogen peroxide denitration efficiency, and integral catalyzer low cost, not easily run off, be easy to back
Receive, practical, it is especially suitable for industrialized production and application.
Brief description
Fig. 1 low-temperature flue gas of the present invention desulfurizing and denitrifying process flow chart.
In figure：1 dioxygen water storage tank, 2 feed pumps, 3 carburator, 4 flues, 5 absorption towers, 6 carrier gas tanks, 7 air intake pumps, 8 preheatings
Device, 9 mixing chambers.
The XRD figure of the catalyst that Fig. 2 embodiment 1 is obtained.
Specific embodiment
For more full and accurate explanation, the description present invention, here enumerates following examples, but described embodiment is not to be regarded as
Limitation of the scope of the invention.
Embodiment 1
Catalyst is prepared using coprecipitation, weighs 1.93 g Cu (NO3)2·3H2O and 1.43 g Mn (NO3)2It is dissolved completely in
In 100 ml deionized waters.After continuously stirred 30 min, it is slowly added dropwise appropriate ammonia to pH=10, generates a large amount of precipitate.Continue
Stir 30 min, gained sediment is stood at normal temperatures aging 12 h.Remove the supernatant, it is heavy that deionized water is repeatedly washed
Forming sediment to solution is in neutrality, puts into 60 DEG C of drying 12 h of baking oven after sucking filtration, and the sample obtaining is placed in Muffle furnace with 5 DEG C/min's
Heating rate rises to 300 DEG C of calcining 3 h, prepared powder catalyst, i.e. gaseous state hydrogen peroxide catalyst.The X of gained catalyst
Ray powder diffraction（XRD）As shown in Fig. 2 result shows, the mainly composition of catalyst is Cu-Mn complex oxide to result, point
Minor is Cu1.5Mn1.5O4.Catalyst is ground, sieves, take the catalyst of particle diameter 0.037 mm -0.045 mm standby.
Embodiment 2
Catalyst is prepared using coprecipitation, weighs 4.83 g Cu (NO3)2 ·3H2O and 1.43 g Mn (NO3)2It is dissolved completely in
In 100 ml deionized waters.After continuously stirred 30 min, it is slowly added dropwise appropriate ammonia to pH=10, generates a large amount of precipitate.Continue
Stir 30 min, gained sediment is stood at normal temperatures aging 12 h.Remove the supernatant, it is heavy that deionized water is repeatedly washed
Forming sediment to solution is in neutrality, puts into 60 DEG C of drying 12 h of baking oven after sucking filtration, and the sample obtaining is placed in Muffle furnace with 5 DEG C/min's
Heating rate rises to 300 DEG C of calcining 3 h, prepared powder catalyst, i.e. gaseous state hydrogen peroxide catalyst.Catalyst is ground,
Sieve, take the catalyst of particle diameter 0.037 mm -0.045 mm standby.
Embodiment 3
Catalyst is prepared using coprecipitation, weighs 3.22 g Cu (NO3)2 ·3H2O and 1.43 g Mn (NO3)2It is dissolved completely in
In 100 ml deionized waters.After continuously stirred 30 min, it is slowly added dropwise appropriate ammonia to pH=10, generates a large amount of precipitate.Continue
Stir 30 min, gained sediment is stood at normal temperatures aging 12 h.Remove the supernatant, it is heavy that deionized water is repeatedly washed
Forming sediment to solution is in neutrality, puts into 60 DEG C of drying 12 h of baking oven after sucking filtration, and the sample obtaining is placed in Muffle furnace with 5 DEG C/min's
Heating rate rises to 300 DEG C of calcining 3 h, prepared powder catalyst, i.e. gaseous state hydrogen peroxide catalyst.Catalyst is ground,
Sieve, take the catalyst of above-mentioned particle diameter 0.037 mm -0.045 mm standby.
Embodiment 4
Catalyst is prepared using coprecipitation, weighs 4.83 g Cu (NO3)2 ·3H2O and 1.43 g Mn (NO3)2It is dissolved completely in
In 100 ml deionized waters.After continuously stirred 30 min, it is slowly added dropwise appropriate ammonia to pH=8, generates a large amount of precipitate.Continue
Stir 30 min, gained sediment is stood at 50 DEG C aging 12 h.Remove the supernatant, it is heavy that deionized water is repeatedly washed
Forming sediment to solution is in neutrality, puts into 120 DEG C of baking oven 7h is dried after sucking filtration, and the sample obtaining is placed in Muffle furnace with 5 DEG C/min's
Heating rate rises to 550 DEG C of calcining 3 h, prepared powder catalyst, i.e. gaseous state hydrogen peroxide catalyst.Catalyst is ground,
Sieve, take the catalyst of above-mentioned particle diameter 0.037 mm -0.045 mm standby.
Comparative example
Weigh ferric nitrate 1.736g, be dissolved in 20mL deionized water, stir to being completely dissolved.Weigh 1.6g aluminium oxide, by nitric acid
Ferrous solution is added dropwise in aluminium oxide, 50 DEG C of stirring in water bath, after being evaporated to solution, 80 DEG C of dryings.Sample grind into powder, puts
In Muffle furnace, 500 DEG C of roasting 6h are risen to 2 DEG C/min heating rate, obtain catalyst sample.
Embodiment 5
The gaseous state hydrogen peroxide of embodiment 1-4 and comparative example is made integral catalyzer with catalyst, step is：Take respectively
The catalyst of 11.1g enforcement 1-4 and comparative example and 44.4g aluminium oxide, add water to be made into slurry, in slurry, the quality of catalyst is dense
Spend for 40%.Using coating machine, slurry being coated in specification is long 200 mm, on the ceramic honey comb of diameter 97 mm, then will coat
Ceramic honey comb afterwards at 70-120 DEG C be dried, then in air atmosphere, the heating rate of 5 DEG C/min rise to 500 DEG C of roastings
5 h, obtain integral catalyzer, and on integral catalyzer, the load capacity of catalyst is 30g/L.
Application examples
Integral catalyzer of the present invention can be used in the desulphurization denitration of low-temperature flue gas, and it can be used as the catalysis of gaseous state hydrogen peroxide
Agent, increases gaseous state hydrogen peroxide oxidation efficiency, and method is as follows：Liquid hydrogen peroxide is gasificated into gaseous state hydrogen peroxide, in conveyance conduit
Integral catalyzer is installed, gaseous state hydrogen peroxide first passes through integral catalyzer in course of conveying and produces more hydroxyl frees
Base, is then mixed with 80-150 DEG C of flue gas again, by the NO in flue gas x It is oxidized to nitrogen oxides soluble in water, after oxidation
Flue gas enters the absorption tower containing absorbent, absorbs the nitrogen oxides in flue gas and oxysulfide, completes the desulphurization denitration of flue gas.
In order to verify each catalyst denitration effect, fume treatment experiment, experiment dress are carried out on pilot plant test device
Put as shown in Figure 1.Experiment process is：Liquid hydrogen peroxide pumps into carburator 3 from dioxygen water storage tank 1 and is gasified, in carrier gas tank 6
Carrier（Nitrogen）Enter preheater 8 by air intake pump 7 to be preheated, the carrier gas after preheating and gaseous state hydrogen peroxide are in mixing chamber 9
Mix homogeneously, is entered flue 4 by pipeline and is mixed with low-temperature flue gas, low-temperature flue gas are aoxidized, integral catalyzer is installed
Enter in the pipeline of flue in conveying gaseous state hydrogen peroxide.Flue gas after oxidation enters absorption tower, and the absorbent in absorption tower can
Soluble components absorb, and the nitrogen oxides in flue gas have obtained effective removing.
Tested according to above-mentioned flow process, detailed process is as follows：
5000 Nm are drawn by coke oven chimney by blower fan3The coking flue gas of/h flow, flue-gas temperature is 120 DEG C.According to inspection
Survey, import NO x Concentration is 300-500 mg/Nm3.Hydrogen peroxide and nitric oxide production mol ratio are 0.8:1.0.Hydrogen peroxide carrier gas stream
Measure 27 m3/ h, hydrogen peroxide feed line diameters 430 mm, integral catalyzer is arranged in pipeline, and catalyst diameter is 97mm,
Length is 600mm, is to be that 97mm, length are the integral catalyzer series connection of 200mm and obtain by three diameters, carrier and gaseous state pair
Oxygen water passes through along catalyst length direction.Mass fraction be 27% hydrogen peroxide gasified by gasification installation after through catalyst live
Change injection flue, the direction that gaseous state hydrogen peroxide enters flue is contrary with the flow direction of low-temperature flue gas.Flue gas after oxidation enters
In absorption tower, in absorption tower, alkali liquor is the ammonia of 2wt.%, and spray measures 5 L/m3.Using Portable smoke analysis instrument
（KM9206, Britain's triumphant grace instrument）Continue 30 min monitoring absorption tower outlet NO x Concentration, calculates the denitration effect of gaseous state hydrogen peroxide
Rate.Gaseous state hydrogen peroxide through the denitration efficiency computing formula after activation of catalyst is：
：Denitration efficiency；[NO]in：Import nitrous oxides concentration；[NO]out：Outlet nitrous oxides concentration.
The integral catalyzer of preparation in each embodiment is carried out denitration experiment, wherein H according to the method described above2O2:NO x
(mol ratio)=0.8:1, denitration efficiency is as shown in table 1 below：
As can be seen from the above table, in the case that gaseous state dioxygen water consumption is relatively low, still can have under activation of catalyst of the present invention
There is higher denitration rate, it can be seen that catalyst of the present invention can reduce the consumption of hydrogen peroxide, greatly improve gaseous state dioxygen
The catalytic effect of water.And the ferriferous oxide catalyst of comparative example is poor to the activation effect of gaseous state hydrogen peroxide.
Comparison study example
（1）5000 Nm are drawn by coke oven chimney by blower fan3The coking flue gas of/h flow, flue-gas temperature is 120 DEG C, import
NO x Concentration is 400-410mg/Nm3.Liquid hydrogen peroxide is gasified by gasification installation, the gaseous state hydrogen peroxide of formation is without catalyst
Catalysis is passed directly into flue, and the direction that gaseous state hydrogen peroxide enters flue is contrary with the flow direction of low-temperature flue gas, H2O2:NO x (rub
You compare)=2：1, the flue gas after oxidation enters in absorption tower, and in absorption tower, alkali liquor is the ammonia of 2wt.%, and spray measures 5 L/m3.
Using Portable smoke analysis instrument（KM9206, Britain's triumphant grace instrument）Monitoring absorption tower outlet NO x Concentration is 320mg/Nm3, gaseous state
Hydrogen peroxide denitration efficiency is 20%.
（2）Liquid hydrogen peroxide is pumped into conveyance conduit, flue is entered by conveyance conduit, pipe diameter 430 mm, whole
Body formula catalyst is installed in the duct, and catalyst diameter is 97mm, and length is 600mm, is to be that 97mm, length are by three diameters
The integral catalyzer of 200mm is connected and is obtained, and liquid hydrogen peroxide passes through along catalyst length direction.Spray is installed in flue
Head, liquid hydrogen peroxide sprays from shower nozzle, and hydrogen peroxide emission direction is in opposite direction with flow of flue gas, H2O2:NO x (mol ratio)=
0.8：1.Flue gas after oxidation enters in absorption tower, and in absorption tower, alkali liquor is the ammonia of 2wt.%, and spray measures 5 L/m3.Using
Portable smoke analysis instrument（KM9206, Britain's triumphant grace instrument）Monitoring absorption tower outlet NO x Concentration, calculates liquid hydrogen peroxide denitration
Efficiency, as shown in table 2 below.
As can be seen from the above results, carry out the less efficient of oxidation and denitration using without the gaseous state hydrogen peroxide of catalysis, and
The effect that integral catalyzer is catalyzed gaseous state hydrogen peroxide oxidation denitration is much better than catalysis liquid hydrogen peroxide.
Claims (10)
1. a kind of gaseous state hydrogen peroxide catalyst, is characterized in that：This catalyst is copper-manganese composite oxides, and its preparation method includes
Following steps：
（1）Using manganese salt, mantoquita as the presoma of catalyst, use water wiring solution-forming；
（2）The pH of precursor solution is adjusted aging to 8-12 standing, to precipitation by metallic ion completely, then filter, by filter cake
Dry, roasting, obtains gaseous state hydrogen peroxide catalyst.
2. gaseous state hydrogen peroxide catalyst according to claim 1, is characterized in that：In copper ion in mantoquita and manganese salt
The mol ratio of manganese ion is 5:2-5.
3. gaseous state hydrogen peroxide catalyst according to claim 1 and 2, is characterized in that：Step（1）In, manganese salt, mantoquita are equal
Selected from nitrate, sulfate, acetate or chloride；Step（2）In, after adjustment pH, aging in 20-50 DEG C of standing；Step（2）
In, filter cake roasting 3-5 h at 300-550 DEG C.
4. a kind of gaseous state hydrogen peroxide integral catalyzer, is characterized in that：Including ceramic honey comb, ceramic honey comb is coated with and urges
Agent slurry, gaseous state hydrogen peroxide catalyst described in claim 1,2 or 3 for the described catalyst pulp, aluminium oxide and water mix
Conjunction forms.
5. integral catalyzer according to claim 4, is characterized in that：The load capacity of gaseous state hydrogen peroxide catalyst is
25-35 g/L.
6. a kind of preparation method of integral catalyzer, is characterized in that comprising the following steps：
A. the gaseous state hydrogen peroxide catalyst any one of claim 1-3, aluminium oxide and water are mixed, be made into catalyst
Slurry；
B. above-mentioned catalyst pulp is coated on ceramic honey comb, is then dried, in 300-500 DEG C of roasting, prepared monoblock type is urged
Agent.
7. preparation method according to claim 6, is characterized in that：In step a, gaseous state hydrogen peroxide catalyst and aluminium oxide
Mass ratio be 1:4, mass concentration in catalyst pulp for the gaseous state hydrogen peroxide catalyst is 30-50%；In step b,
300-500 DEG C of roasting 4-6 h.
8. a kind of method of denitration of low-temperature flue gas, is characterized in that comprising the following steps：
（1）Liquid hydrogen peroxide is gasificated into gaseous state hydrogen peroxide；
（2）Preparation method according to the integral catalyzer described in claim 6 or 7 is obtained integral catalyzer, and this is overall
Formula catalyst is arranged on conveying gaseous state hydrogen peroxide and enters in the conveyance conduit of flue；
（3）Gaseous state hydrogen peroxide is passed through in flue by conveyance conduit, gaseous state hydrogen peroxide first passes through integral catalyzer and produces more
Many hydroxyl radical free radicals, subsequently into the smoke contacts of flue and 80-150 DEG C, by the NO in flue gas x It is oxidized to soluble in water
Nitrogen oxides；
（4）Flue gas after oxidation enters the absorption tower containing absorbent, completes the denitration of flue gas.
9. method of denitration according to claim 8, is characterized in that：H2O2With NO in flue gas x Mol ratio be 0.8 ~ 1.7:1；
Described absorbent is alkaline solution, including ammonia, magnesium hydroxide or sodium hydroxide.
10. method according to claim 8 or claim 9, is characterized in that：Gaseous state hydrogen peroxide enters the direction of flue and the stream of flue gas
Dynamic in opposite direction.
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| CN112742378A (en) * | 2021-01-22 | 2021-05-04 | 上海大学 | Melanese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module, preparation method thereof and application of catalyst module in catalytic decomposition of hydrogen peroxide |
| CN114272733A (en) * | 2021-12-31 | 2022-04-05 | 山东正圣环保科技有限公司 | Hydrogen peroxide gasification catalysis increase device |
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| CN112742378A (en) * | 2021-01-22 | 2021-05-04 | 上海大学 | Melanese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module, preparation method thereof and application of catalyst module in catalytic decomposition of hydrogen peroxide |
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