CN107597140B - A kind of low-temp desulfurization denitrating catalyst and flue gas low-temperature integration desulfurization denitration method - Google Patents
A kind of low-temp desulfurization denitrating catalyst and flue gas low-temperature integration desulfurization denitration method Download PDFInfo
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Abstract
The present invention relates to a kind of low-temp desulfurization denitrating catalysts and flue gas low-temperature integration desulfurization denitration method, the catalyst to be prepared by following methods：1) semicoke particle is mixed into obtain mixture with calcium oxide micro mist；2) mixture is being continually fed into vapor and CO2Gaseous mixture under the conditions of carry out high-temperature activation obtain activated carrier；3) precursor solution containing copper nitrate, manganese nitrate and sodium chloride is prepared；4) equi-volume impregnating is used to make CuO and MnO with precursor solution impregnating active carrier2Total load quality on activated carrier reach 4.0% 6.0% to get.The present invention is acted synergistically using a variety of activation methods, greatly improves the specific surface area and Kong Rong of semicoke；In the presence of NaCl, Supported CuO and MnO on activated carrier2, adsorption activity and CuO, MnO of active carbocoal2Synergistic effect, gained catalyst have higher denitrification efficiency, Sulfur capacity and longer catalytic activity period.
Description
Technical field
The invention belongs to flue gas integration desulfurization denitration technical fields, and in particular to a kind of low-temp desulfurization denitrating catalyst,
Also relate to a kind of flue gas low-temperature integration desulfurization denitration method using the low-temp desulfurization denitrating catalyst.
Background technology
Coal-smoke pollution is the main feature of China's atmosphere pollution, contains PM, SO in coal-fired flue-gas2、ONX、Hg、CO2Deng more
Kind pollutant, wherein SO2And ONXA large amount of discharges be principal element that acid rain and photochemical fog are formed, not only to ecological environment
Cause serious destruction with social environment, such as cause soil acidification, animal and plant growth slowly, water acidification, Architectural Corrosion,
The health for also greatly endangering the mankind, such as the SO in air2There is strong impulse effect to respiratory mucosa, it can after human body sucking
Cause bronchitis, pneumonia, even pulmonary edema and respiratory paralysis；Human body sucks ONXAfter will produce nitric acid, destroy in blood
Hemoglobin reduces blood oxygen carrying capacity, causes anoxic and nervous centralis is caused to be benumbed.Therefore, cut down and control coal-fired flue-gas
Middle SO2And ONXLargely discharge it is very urgent.
According to removing gas type flue gas desulfurization and denitrification technology can be divided into flue gas desulfurization technique, gas denitrifying technology and
Flue gas integration desulfurization denitration technology.Be most widely used at present and it is ripe be flue gas desulfurization technique, as people live matter
The raising of amount and to ONXThe gradual intensification of cognition is endangered, denitrating flue gas is also concerned.And flue gas integration desulfurization denitration technology
It is sweetening process and denitrification process to be integrated into same set of reaction unit, while realizing SO in flue gas2And ONXRemoving, have
Device configuration is reduced, engineering space is saved, reduces the advantages that investment, operation and maintenance expense, it has also become flue gases purification is sent out
One trend of exhibition.
It is suitble to the flue gas integration desulfurization denitration technology of industrialization large-scale application mainly to have solid absorption catalysis method and urge
Change oxidation-reduction method.Catalytic oxidation-reduction method is metal oxide to be supported on carrier as active constituent, will be in flue gas
SO2Catalysis oxidation is SO3, and sulfate is further generated, under the conditions of spraying ammonia, by ONXSelective reduction is N2, after inhaling sulphur saturation
Catalyst regenerate in reducing atmosphere, and can realize the recycling of sulphur；Current developed catalyst has CuO/SiO2、
CuO/γ-Al2O3Deng.The operation temperature window of this method is generally higher, such as CuO/ γ-Al2O3At 300 DEG C -450 DEG C have compared with
Desulphurization denitration performance while good, but enough catalytic activity, desulfurization and denitrification reaction is not achieved in catalyst when operation temperature is relatively low
It can not carry out, it is therefore desirable to which heating device carries out reheating to flue gas, and cost is higher, and the catalyst Sulfur capacity is smaller, needs
Frequent regeneration also further improves the loss of catalyst, increases cost.The common solid absorbent of solid absorption catalysis method
Active charcoal, molecular sieve, silica gel etc., in flue gas under conditions of aerobic and water, in active carbon desulfurization system spraying into ammonia is
SO can be removed simultaneously2And ONX；The operation temperature window of this method is relatively low, has higher removing when between 120 DEG C -160 DEG C
Efficiency, but since activated carbon price is high, intensity is low, absorption and regenerative process loss are big, and easily by the dioxygen oxidation in flue gas, limit
It has been made to promote the use of.
Flue gas integration desulfurization denitration technology has become the exploitation hot spot of control coal-fired flue-gas disposal of pollutants, how to provide
The desulphurization denitration catalyst being applicable under a kind of small investment, at low cost and low temperature and corresponding flue gas integration desulfurization denitration method,
It is a problem to be solved.
Invention content
The object of the present invention is to provide a kind of low-temp desulfurization denitrating catalyst, it is at low cost and at low temperature have higher cigarette
Desulfurization denitration efficiency.
Second object of the present invention is to provide a kind of flue gas low-temperature integration using the low-temp desulfurization denitrating catalyst
Desulfurization denitration method.
To achieve the goals above, the technical solution adopted in the present invention is：
A kind of low-temp desulfurization denitrating catalyst, is prepared by method comprising the following steps：
1) it is (8-10) according to the mass ratio of semicoke and calcium oxide:1 ratio mixes semicoke particle with calcium oxide micro mist
Uniformly, mixture is obtained；
2) mixture obtained by step 1) is placed in closed container, is being continually fed into vapor and CO2Gaseous mixture item
Under part, 30-40min is kept the temperature at 420-450 DEG C, then is warming up to 800-850 DEG C of heat preservation 2-3h, and postcooling to room temperature is washed, dry
It is dry, obtain activated carrier；
3) it is (7.0-8.0) according to the mass ratio of copper nitrate, manganese nitrate and sodium chloride:(1.5-2.5):0.5 ratio, system
The standby precursor solution containing copper nitrate, manganese nitrate and sodium chloride；
4) equi-volume impregnating is used, the precursor solution impregnation steps 2 obtained by step 3)) gained activated carrier, make CuO
And MnO2Total load quality on activated carrier reaches 4.0%-6.0%；First ultrasonic disperse 30-40min in dipping process, then
Dry after still aging 8-12h, through 400-450 DEG C of roasting 2-2.5h under protective atmosphere, postcooling to room temperature is to get described low
Warm desulphurization denitration catalyst.
In step 1), the granularity of the semicoke particle is 8-16 mesh；The granularity of calcium oxide micro mist is 200-300 mesh.
In the step 2) gaseous mixture, vapor and CO2Volume ratio be (3-4):(6-7).
The rate that is passed through of the step 2) gaseous mixture is：The flow velocity that gaseous mixture is corresponded to per 1g mixtures is 40-60ml/min.
In step 2), mixture is first warming up to 420-450 DEG C with the rate of 5-8 DEG C/min, and (temperature-rise period is using guarantor
Protect atmosphere protection), then start to be continually fed into vapor and CO2Gaseous mixture, at 420-450 DEG C keep the temperature 30-40min after, then with
The rate of 10-15 DEG C/min is warming up to 800-850 DEG C of heat preservation 2-3h.After heat preservation at 800-850 DEG C, gaseous mixture is cut off, is led to
Enter protective atmosphere to be cooled down.
The protective atmosphere is nitrogen or argon gas.
For step 2) with step 4), the temperature of the drying is 105-115 DEG C.
A kind of flue gas low-temperature integration desulfurization denitration method using above-mentioned low-temp desulfurization denitrating catalyst, including it is following
Step：
A) the low-temp desulfurization denitrating catalyst is placed in desulfurization and denitrification reaction device, first sprays into ammonia into pending flue gas
Gas carries the flue gas of ammonia with air speed 4000-5000h-1Flow through from bottom to top catalyst carry out desulphurization denitration, desulphurization denitration it is anti-
It is 130-160 DEG C to answer temperature；
B) the low-temp desulfurization denitrating catalyst of inactivation is sent into regeneration reactor, ammonia is passed through into regeneration reactor,
Catalyst is regenerated under the conditions of 200-240 DEG C；Catalyst circulation after regeneration is used for the desulfurization and denitrification reaction of step a).
In step a), the low-temp desulfurization denitrating catalyst is placed in the fixed bed in desulfurization and denitrification reaction device, it is described
The loading density of catalyst is 540-560kg/m in fixed bed3。
When the desulfuration efficiency of desulfurization and denitrification reaction device is less than 70%, that is, judge low-temp desulfurization Benitration reactor inactivation.
In step b), the air speed of regenerative response is 800-1500h in regeneration reactor-1。
The low-temp desulfurization denitrating catalyst of the present invention, using semicoke as the raw material of catalyst carrier, semicoke is coal partial thermal decomposition
Product, inside contains a large amount of oxygen and hydrogen, itself is easy activation, while its is cheap, and alternative activated carbon is as catalysis
Agent carrier uses；After the present invention mixes semicoke particle with calcium oxide micro mist, in the presence of calcium oxide micro mist, using water
The gaseous mixture of steam and carbon dioxide activates semicoke, and a variety of activation method synergistic effects greatly improve semicoke
Specific surface area and Kong Rong make it have more active adsorption sites, are conducive to the desulphurization denitration performance for improving catalyst.
The low-temp desulfurization denitrating catalyst of the present invention, on the basis of semicoke activated carrier, under the conditions of existing for NaCl,
Using equi-volume impregnating on activated carrier carrying active ingredients CuO and MnO2So that CuO and MnO2On activated carrier
Total load quality reaches 4.0%-6.0%；NaCl can promote CuO and MnO2The surface of active carrier is distributed in single layer state,
Increase the distribution area of active constituent；CuO and MnO simultaneously2Total load amount be less than conventional carrier for metal oxide active
The Monolayer dispersion thresholds of ingredient, so that the active adsorption sites of active carrier are more exposed, the absorption of active carbocoal is lived
Property with CuO, MnO2It simultaneously and deposits, acts synergistically, gained catalyst has higher denitrification efficiency, Sulfur capacity and longer simultaneously
The catalytic activity period.
The flue gas low-temperature integration desulfurization denitration method of the present invention, using above-mentioned low-temp desulfurization denitrating catalyst,
30min is run under the conditions of 130-160 DEG C, desulfurization effect is up to 95% or so, and denitration efficiency is up to 70% or more, when having balance
Between short advantage；For desulfurization and denitrification reaction device after running 1h, desulphurization reaction basically reaches stable state, and desulfuration efficiency reaches
99% or so；After running 2h, denitration reaction basically reaches stable state, and denitration efficiency reaches 95% or more；It is transported in reactor
After row 8h, desulfuration efficiency also has 70%, illustrates that the catalyst has larger Sulfur capacity, simultaneous SO_2 and NO removal effect good.Inactivation
Catalyst afterwards is after 2 regeneration of ammonia, and desulfuration efficiency is still up to 97% or so, and denitration efficiency is basic compared with fresh catalyst
Do not change, shows that the low-temp desulfurization denitrating catalyst has good regenerability；The present invention uses the flue gas one of the catalyst
The method of body desulphurization denitration, running temperature is low, almost the same with boiler emission flue-gas temperature in actual industrial, need not heat
Device, premise cost of investment are low；Sulfur dioxide in flue gas and nitrogen oxides are removed while this method has the effect of good, and
The catalytic cycle of catalyst is long, further reduced the cost of operation and maintenance, saves the use of catalyst, and suitable popularization is answered
With.
Specific implementation mode
The present invention is described further With reference to embodiment.
In specific implementation mode, semicoke used is Factory, Shenmu, Shanxi high quality brown coal semicoke, and fixed carbon content 80%, fugitive constituent contains
Amount 7%, content of ashes 6.5%, specific surface area is about 87m2/ g, it is about 0.07cm that hole, which holds,3/g。
Embodiment 1
The low-temp desulfurization denitrating catalyst of the present embodiment, is prepared from the following steps：
1) it is 8 according to the mass ratio of semicoke and calcium oxide:1 ratio, by the semicoke particle and granularity that granularity is 8-16 mesh
It is uniformly mixed for the calcium oxide micro mist of 200-300 mesh, obtains mixture；
2) mixture obtained by step 1) is placed in closed container, under protection of argon gas, is warming up to the rate of 8 DEG C/min
420 DEG C, tripping protection atmosphere；It is being continually fed into vapor and CO2Volume ratio is 3:It (is mixed per 1g under conditions of 7 gaseous mixture
The flow velocity that object corresponds to gaseous mixture is 40ml/min), 40min is kept the temperature at 420 DEG C, then 800 DEG C are warming up to the rate of 15 DEG C/min
3h is kept the temperature, gaseous mixture is cut off afterwards, is cooled to room temperature under protection of argon gas；Product washs repeatedly through deionized water, then in 110 DEG C of items
Dry 4h, obtains activated carrier under part；
3) it is 7.0 according to the mass ratio of copper nitrate, manganese nitrate and sodium chloride:2.5:0.5 ratio, by copper nitrate, chlorination
Sodium is added in manganese nitrate aqueous solution, prepares the precursor solution containing copper nitrate, manganese nitrate and sodium chloride；
4) equi-volume impregnating is used, the precursor solution impregnation steps 2 obtained by step 3)) gained activated carrier, make CuO
And MnO2Total load quality on activated carrier reaches 4.0%；(supersonic frequency is by first ultrasonic disperse 30min in dipping process
30kHz), then at room temperature after still aging 8h, dry 4h, roasts under protective atmosphere (argon gas) through 400 DEG C under the conditions of 110 DEG C
2.5h is burnt, postcooling to room temperature is to get the low-temp desulfurization denitrating catalyst.
Gained low-temp desulfurization denitrating catalyst is sieved into (bulky grain sieves again after can suitably crushing), takes grain size
Particle for 8-16 mesh is spare.
The flue gas low-temperature integration desulfurization denitration method using above-mentioned low-temp desulfurization denitrating catalyst of the present embodiment, including
The following steps：
A) the low-temp desulfurization denitrating catalyst is placed in the fixed bed in desulfurization and denitrification reaction device, in the fixed bed
The loading density of catalyst is 560kg/m3；Ammonia first is sprayed into pending flue gas, carries the flue gas of ammonia with air speed 4000h-1Fixed bed is flowed through from bottom to top and carries out desulphurization denitration, and the reaction temperature of desulphurization denitration is 130 DEG C；
When the desulfuration efficiency of desulfurization and denitrification reaction device is less than 70%, that is, judge low-temp desulfurization Benitration reactor inactivation；
B) the low-temp desulfurization denitrating catalyst of inactivation is sent into regeneration reactor, ammonia is passed through into regeneration reactor,
Catalyst is regenerated under the conditions of 200 DEG C, the air speed of regenerative response is 800h in regeneration reactor-1；Catalyst after regeneration
Desulfurization and denitrification reaction of the cycle for step a).
Embodiment 2
The low-temp desulfurization denitrating catalyst of the present embodiment, is prepared from the following steps：
1) it is 9 according to the mass ratio of semicoke and calcium oxide:1 ratio, by the semicoke particle and granularity that granularity is 8-16 mesh
It is uniformly mixed for the calcium oxide micro mist of 200-300 mesh, obtains mixture；
2) mixture obtained by step 1) is placed in closed container, under protection of argon gas, is warming up to the rate of 8 DEG C/min
450 DEG C, tripping protection atmosphere；It is being continually fed into vapor and CO2Volume ratio is 4:It (is mixed per 1g under conditions of 6 gaseous mixture
The flow velocity that object corresponds to gaseous mixture is 50ml/min), 30min is kept the temperature at 450 DEG C, then 850 DEG C are warming up to the rate of 13 DEG C/min
Keep the temperature 2h, cut off gaseous mixture, after be cooled to room temperature under protection of argon gas；Product washs repeatedly through deionized water, then in 105 DEG C of items
It is dry under part, obtain activated carrier；
3) it is 8.0 according to the mass ratio of copper nitrate, manganese nitrate and sodium chloride:1.5:0.5 ratio, by copper nitrate, chlorination
Sodium is added in manganese nitrate aqueous solution, prepares the precursor solution containing copper nitrate, manganese nitrate and sodium chloride；
4) equi-volume impregnating is used, the precursor solution impregnation steps 2 obtained by step 3)) gained activated carrier, make CuO
And MnO2Total load quality on activated carrier reaches 5.0%；(supersonic frequency is by first ultrasonic disperse 35min in dipping process
30kHz), then at room temperature after still aging 10h, dry 4h under the conditions of 105 DEG C, through 430 DEG C under protective atmosphere (argon gas)
2.5h is roasted, postcooling to room temperature is to get the low-temp desulfurization denitrating catalyst.
Gained low-temp desulfurization denitrating catalyst is sieved into (bulky grain sieves again after can suitably crushing), takes grain size
Particle for 8-16 mesh is spare.
The flue gas low-temperature integration desulfurization denitration method using above-mentioned low-temp desulfurization denitrating catalyst of the present embodiment, including
The following steps：
A) the low-temp desulfurization denitrating catalyst is placed in the fixed bed in desulfurization and denitrification reaction device, in the fixed bed
The loading density of catalyst is 550kg/m3；Ammonia first is sprayed into pending flue gas, carries the flue gas of ammonia with air speed 5000h-1Fixed bed is flowed through from bottom to top and carries out desulphurization denitration, and the reaction temperature of desulphurization denitration is 150 DEG C；
When the desulfuration efficiency of desulfurization and denitrification reaction device is less than 70%, that is, judge low-temp desulfurization Benitration reactor inactivation；
B) the low-temp desulfurization denitrating catalyst of inactivation is sent into regeneration reactor, ammonia is passed through into regeneration reactor,
Catalyst is regenerated under the conditions of 220 DEG C, the air speed of regenerative response is 1000h in regeneration reactor-1；Catalyst after regeneration
Desulfurization and denitrification reaction of the cycle for step a).
Embodiment 3
The low-temp desulfurization denitrating catalyst of the present embodiment, is prepared from the following steps：
1) it is 10 according to the mass ratio of semicoke and calcium oxide:1 ratio, by the semicoke particle and granularity that granularity is 8-16 mesh
It is uniformly mixed for the calcium oxide micro mist of 200-300 mesh, obtains mixture；
2) mixture obtained by step 1) is placed in closed container, under protection of argon gas, is warming up to the rate of 6 DEG C/min
435 DEG C, tripping protection atmosphere；It is being continually fed into vapor and CO2Volume ratio is 3.5:(per 1g under conditions of 6.5 gaseous mixture
The flow velocity that mixture corresponds to gaseous mixture is 60ml/min), 35min is kept the temperature at 435 DEG C, then be warming up to the rate of 12 DEG C/min
830 DEG C of heat preservation 2.5h, cut off gaseous mixture, are cooled to room temperature under protection of argon gas afterwards；Product washs repeatedly through deionized water, then
It is dry under the conditions of 115 DEG C, obtain activated carrier；
3) it is 7.5 according to the mass ratio of copper nitrate, manganese nitrate and sodium chloride:2.0:0.5 ratio, by copper nitrate, chlorination
Sodium is added in manganese nitrate aqueous solution, prepares the precursor solution containing copper nitrate, manganese nitrate and sodium chloride；
4) equi-volume impregnating is used, the precursor solution impregnation steps 2 obtained by step 3)) gained activated carrier, make CuO
And MnO2Total load quality on activated carrier reaches 6.0%；(supersonic frequency is by first ultrasonic disperse 40min in dipping process
30kHz), then at room temperature after still aging 12h, dry 4h under the conditions of 115 DEG C, (argon gas) is through 450 DEG C under protective atmosphere
2h is roasted, postcooling to room temperature is to get the low-temp desulfurization denitrating catalyst.
Gained low-temp desulfurization denitrating catalyst is sieved into (bulky grain sieves again after can suitably crushing), takes grain size
Particle for 8-16 mesh is spare.
The flue gas low-temperature integration desulfurization denitration method using above-mentioned low-temp desulfurization denitrating catalyst of the present embodiment, including
The following steps：
A) the low-temp desulfurization denitrating catalyst is placed in the fixed bed in desulfurization and denitrification reaction device, in the fixed bed
The loading density of catalyst is 540kg/m3；Ammonia first is sprayed into pending flue gas, carries the flue gas of ammonia with air speed 6000h-1Fixed bed is flowed through from bottom to top and carries out desulphurization denitration, and the reaction temperature of desulphurization denitration is 140 DEG C；
When the desulfuration efficiency of desulfurization and denitrification reaction device is less than 70%, that is, judge low-temp desulfurization Benitration reactor inactivation；
B) the low-temp desulfurization denitrating catalyst of inactivation is sent into regeneration reactor, ammonia is passed through into regeneration reactor,
Catalyst is regenerated under the conditions of 240 DEG C, the air speed of regenerative response is 1300h in regeneration reactor-1；Catalyst after regeneration
Desulfurization and denitrification reaction of the cycle for step a).
Experimental example 1
This experimental example is respectively detected the specific surface area of activated carrier and Kong Rong obtained by embodiment 1-3, as a result such as table 1
It is shown.Wherein, specific surface area and Kong Rong are measured using Micromeritics ASAP2000 adsorption instruments, and adsorbed gas is nitrogen；
Specific surface area uses BET equation calculations, Kong Rong to be calculated using BJH methods.Test sample is de-gassed before testing.
The specific surface area of activated carrier and hole obtained by 1 embodiment 1-3 of table hold testing result
| Detect object | Specific surface area (m2/g) | Kong Rong (cm3/g) |
| Raw material semicoke | 87.03 | 0.07 |
| Embodiment 1 | 560.74 | 0.85 |
| Embodiment 2 | 554.26 | 0.83 |
| Embodiment 3 | 571.58 | 0.87 |
As it can be seen from table 1 the specific surface area of activated carrier is in 550m obtained by embodiment 1-32/ g or more, Kong Rong exist
0.83cm3/ g or more.Testing result shows the specific surface area of activated carrier and hole obtained by semicoke activation method using the present invention
Appearance is greatly improved, and is conducive to the desulfurization off sulfide effect for improving catalyst.
Experimental example 2
It is pending flue gas respectively to the low-temp desulfurization denitrating catalyst of embodiment 1-3 that this experimental example, which uses simulated flue gas,
Desulphurization denitration performance is detected, and detection method is respectively the flue gas low-temperature integration desulfurization denitration method of embodiment 1-3.
Wherein, the group of simulated flue gas becomes：SO2 6000mg/m3, NO 1000mg/m3, O2For 3% (volume), H2O is
2% (volume), Balance Air are nitrogen.The temperature of simulated flue gas is 130-160 DEG C.Pending flue gas sprays into during ammonia, NO
With NH3Molar ratio be 1:1.2, ammonia is mixed into according to above-mentioned molar ratio.
In experimentation, simulated flue gas is continually fed into desulfurization and denitrification reaction device, and the flue gas of reactor outlet is detected every 1h
Middle SO2With the content of NO (30min is detected for the first time), and removal efficiency is calculated according to pollutant load in import flue gas,
Testing result is as shown in table 2.
The desulphurization denitration performance test results of the low-temp desulfurization denitrating catalyst of 2 embodiment 1-3 of table
From table 2 it can be seen that the low-temp desulfurization denitrating catalyst of the present invention, is used for flue gas integration desulfurization denitration technique
In, after the equilibration time of 30min early period, up to 95% or so, denitration efficiency has desulfurization effect up to 70% or more
The short advantage of equilibration time；For desulfurization and denitrification reaction device after running 1h, desulphurization reaction basically reaches stable state, desulfuration efficiency
Reach 99% or so；After running 2h, denitration reaction basically reaches stable state, and denitration efficiency reaches 95% or more.It is reacting
After device runs 8h, desulfuration efficiency also has 70%, illustrates that the catalyst has larger Sulfur capacity, simultaneous SO_2 and NO removal effect good.
After desulfurization and denitrification reaction device runs 8h, desulfuration efficiency substantially close to or be less than 70%, it is de- to low temperature used
Sulphur denitrating catalyst is regenerated, and technological condition of regeneration is respectively the same as embodiment 1-3.By the low-temp desulfurization denitrating catalyst after regeneration
Desulphurization denitration performance detection is re-started, to simplify experimentation and comparing, only detects the removing after reactor operation 3h and 8h
Rate, the results are shown in Table 3.
The desulphurization denitration performance test results (removal efficiency, %) of 3 regenerated catalyst of table
From table 3 it can be seen that after 2 regeneration, the desulfuration efficiency of the low-temp desulfurization denitrating catalyst of embodiment 1-3
It is still up to 97% or so, denitration efficiency essentially unchangedization compared with fresh catalyst.Above-mentioned testing result shows of the invention low
There is warm desulphurization denitration catalyst good regenerability, the present invention to use the side of the flue gas integration desulfurization denitration of the catalyst
Method has the effect of good removing sulfur dioxide in flue gas and nitrogen oxides, is suitble to promote the use of.
Claims (8)
1. a kind of low-temp desulfurization denitrating catalyst, it is characterised in that：It is prepared by method comprising the following steps：
1) it is (8-10) according to the mass ratio of semicoke and calcium oxide:1 ratio mixes semicoke particle with calcium oxide micro mist
It is even, obtain mixture；
Semicoke used is lignite semi-coke；The granularity of the semicoke particle is 8-16 mesh；The granularity of calcium oxide micro mist is 200-300
Mesh；
2) mixture obtained by step 1) is placed in closed container, is being continually fed into vapor and CO2Gaseous mixture under conditions of,
30-40min is kept the temperature at 420-450 DEG C, then is warming up to 800-850 DEG C of heat preservation 2-3h, and postcooling to room temperature is washed, dry, obtains
Activated carrier；
3) it is (7.0-8.0) according to the mass ratio of copper nitrate, manganese nitrate and sodium chloride:(1.5-2.5):0.5 ratio, preparation contain
The precursor solution of copper nitrate, manganese nitrate and sodium chloride；
4) equi-volume impregnating is used, with precursor solution impregnation steps 2 obtained by step 3)) gained activated carrier, make CuO and
MnO2Total load quality on activated carrier reaches 4.0%-6.0%；First ultrasonic disperse 30-40min in dipping process, then it is quiet
Drying after being aged 8-12h is set, through 400-450 DEG C of roasting 2-2.5h under protective atmosphere, postcooling to room temperature is to get the low temperature
Desulphurization denitration catalyst.
2. low-temp desulfurization denitrating catalyst according to claim 1, it is characterised in that：In the step 2) gaseous mixture, water
Steam and CO2Volume ratio be (3-4):(6-7).
3. low-temp desulfurization denitrating catalyst according to claim 1, it is characterised in that：Step 2) the gaseous mixture is passed through
Rate is：The flow velocity that gaseous mixture is corresponded to per 1g mixtures is 40-60mL/min.
4. low-temp desulfurization denitrating catalyst according to claim 1, it is characterised in that：It is described in step 2) and step 4)
Dry temperature is 105-115 DEG C.
5. a kind of flue gas low-temperature integration desulfurization denitration side using low-temp desulfurization denitrating catalyst as described in claim 1
Method, it is characterised in that：Include the following steps：
A) the low-temp desulfurization denitrating catalyst is placed in desulfurization and denitrification reaction device, first sprays into ammonia into pending flue gas,
The flue gas of ammonia is carried with air speed 4000-5000h-1Catalyst is flowed through from bottom to top carries out desulphurization denitration, the reaction of desulphurization denitration
Temperature is 130-160 DEG C；
B) the low-temp desulfurization denitrating catalyst of inactivation is sent into regeneration reactor, ammonia is passed through into regeneration reactor, in 200-
Catalyst is regenerated under the conditions of 240 DEG C；Catalyst circulation after regeneration is used for the desulfurization and denitrification reaction of step a).
6. flue gas low-temperature integration desulfurization denitration method according to claim 5, it is characterised in that：In step a), by institute
It states low-temp desulfurization denitrating catalyst to be placed in the fixed bed in desulfurization and denitrification reaction device, the filling of catalyst is close in the fixed bed
Degree is 540-560kg/m3。
7. flue gas low-temperature integration desulfurization denitration method according to claim 5, it is characterised in that：Work as desulfurization and denitrification reaction
The desulfuration efficiency of device is less than 70%, that is, judges the low-temp desulfurization Benitration reactor inactivation.
8. flue gas low-temperature integration desulfurization denitration method according to claim 5, it is characterised in that：In step b), regeneration
The air speed of regenerative response is 800-1500h in reactor-1。
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