CN108993580A - A kind of low temperature SCR denitration catalyst and preparation method thereof of anticalcium poisoning - Google Patents
A kind of low temperature SCR denitration catalyst and preparation method thereof of anticalcium poisoning Download PDFInfo
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- CN108993580A CN108993580A CN201810906669.5A CN201810906669A CN108993580A CN 108993580 A CN108993580 A CN 108993580A CN 201810906669 A CN201810906669 A CN 201810906669A CN 108993580 A CN108993580 A CN 108993580A
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- low temperature
- scr denitration
- catalyst
- anticalcium
- zsm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The invention belongs to technical field of air pollution control, specially a kind of low temperature SCR denitration catalyst and preparation method thereof of anticalcium poisoning.Low temperature SCR denitration catalyst of the invention is using H-ZMS-5 molecular sieve as carrier, using Cu oxide as active component, using Zirconium oxide as auxiliary agent, on the basis of the quality of H-ZSM-5 molecular sieve, copper accounts for the 3.5~4.5% of carrier quality, and zr element accounts for the 0.05%~0.4% of carrier quality.SCR denitration of the invention is prepared using infusion process.The low-temperature denitration activity and anticalcium poisoning performance of anticalcium poisoning low temperature SCR denitration catalyst produced by the present invention are excellent, can be used for the discharged nitrous oxides control of the stationary sources flue gas such as glass, steel, coking coke oven.
Description
Technical field
The invention belongs to technical field of air pollution control, and in particular to a kind of low temperature SCR denitration catalysis of anticalcium poisoning
Agent and preparation method thereof.
Background technique
Nitrogen oxides NOx(NO、NO2And N2O) be atmosphere pollution one of main source, be to cause photochemical fog, acid
The major reason of the environmental problems such as rain, haze and depletion of the ozone layer brings high risks to human habitat and health,
Thus become current environmental problem urgently to be solved.Energy resource structure of the China based on coal cause thermal power station, steel, metallurgy,
The flue gases such as glass, petrochemical industry and coking coke oven contain a large amount of NOx.SCR catalyst (the V of business2O5-WO3/TiO2) require work temperature
Degree, to meet the requirement that catalyst uses temperature, needs for SCR reactor to be placed in front of deduster at 300-450 DEG C.So
And such setting makes catalyst be highly prone to SO2The blocking poisoned with dust, catalyst life reduce, replacement frequency
It is numerous.Therefore, research and development be capable of (150-250 DEG C) of low temperature operation SCR catalyst, enable catalytic reactor be arranged in dedusting and
After desulfurizer, it is of great significance.However, still containing one in flue gas even if low-temperature SCR catalyst is placed in after dedusting
Quantitative alkaline-earth metal Ca, Ca can be adsorbed on catalyst surface, on the one hand can override the active sites of catalyst surface, blocking is urged
Duct in agent；On the other hand neutralization reaction can be carried out with the acidic site of catalyst surface, declines catalyst denitration efficiency
Even inactivate.Therefore the low temperature SCR denitration catalyst of exploitation anticalcium poisoning is of great significance.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of low light-off temperature, high catalytic activity,
The SCR denitration and preparation method thereof of strong anticalcium performance.
Technical solution of the present invention is specifically described as follows.
The present invention provides a kind of low temperature SCR denitration catalyst of anticalcium poisoning, and general formula ZrCu/ZSM-5 is with H-
ZSM-5 molecular sieve is carrier, using Cu oxide as active component, using Zirconium oxide as auxiliary agent；With the quality of H-ZSM-5 molecular sieve
On the basis of, copper accounts for the 3.5~4.5% of carrier quality, and zr element accounts for the 0.05%~0.4% of carrier quality.
In the present invention, on the basis of the quality of H-ZSM-5 molecular sieve, copper accounts for the 3.8~4.2% of carrier quality, zirconium
Element accounts for the 0.05~0.2% of carrier quality.
The present invention also provides a kind of preparation method of low temperature SCR denitration catalyst according to claim 1, features
It is, the specific steps are as follows:
(1) mantoquita, zirconates are dissolved in deionized water, are sufficiently stirred to form clear blue mixed solution；
(2) carrier H-ZSM-5 molecular sieve is added into the solution of step (1), room temperature magnetic agitation 0.5~1.5 hour, stirs
After mixing, sample is placed in drying box；
(3) sample after will be dry in step (2) is pulverized, then in Muffle kiln roasting to get into anticalcium
The low temperature SCR denitration catalyst of poison.
In the present invention, in step (1), mantoquita is copper nitrate, and zirconates is zirconium nitrate.
In the present invention, in step (2), the drying temperature of drying box is 115~125 DEG C, and drying time is 10~12 hours.
In the present invention, in step (3), maturing temperature is 540-560 DEG C, and calcining time is 3-5 hours.
Compared to the prior art, the beneficial effects of the present invention are:
The advantages of anticalcium poisoning low temperature SCR denitration catalyst provided by the invention is: preparation method is simple, can be effective gram
Take tradition V2O5-WO3/TiO2The catalyst disadvantage that denitration efficiency is low at low temperature, anticalcium performance is poor.
Low temperature SCR denitration catalyst of the invention is using H-ZMS-5 molecular sieve as carrier, using Cu oxide as active component,
Using Zirconium oxide as auxiliary agent, it is advantageous that improving active component in the dispersion degree of catalyst surface, catalyst is significantly improved
Anticalcium toxicity and low-temperature denitration activity.
Detailed description of the invention
Fig. 1 is the catalyst prepared in embodiment 1, embodiment 2, embodiment 3, embodiment 4 and comparative example 1 and comparative example 2
To NH at a temperature of differential responses3The catalytic activity test curve figure of-SCR reaction.
Specific embodiment
Present invention will be further explained below with reference to specific examples.These embodiments are merely to illustrate the present invention and do not have to
In limiting the scope of the invention.
Embodiment 1
The preparation of anticalcium catalyst: being separately added into 0.456g copper nitrate and 0.007g zirconium nitrate into the deionized water of 6ml,
Magnetic agitation obtains clear blue solution；3.00g H-ZSM-5 molecular sieve is added into above-mentioned solution, it is small to be stirred at room temperature 1
When；Resulting sample is transferred in drying box, maintains 120 DEG C of constant temperature, drying 12 hours；It will be put after solid abrasive to no particle
Enter 550 DEG C of roasting 4h of Muffle furnace.Obtain supported SCR catalyst.
0.222g calcium nitrate is added into the deionized water of 6ml, magnetic agitation obtains clear transparent solutions；To above-mentioned molten
The supported SCR catalyst that 3.00g has been prepared is added in liquid, is stirred at room temperature 1 hour；Resulting sample is transferred to drying box
In, 120 DEG C of constant temperature are maintained, drying 12 hours；550 DEG C of roasting 4h of Muffle furnace will be put into after solid abrasive to no particle.It is granulated, mistake
40-60 mesh obtains the low temperature supported SCR catalyst of anticalcium poisoning, is denoted as Ca/Zr0.05Cu/ZSM-5。
The performance test of anticalcium catalyst:
The catalyst for taking 0.15g tabletting to be sieved is put into fixed bed quartz tube reactor, quartzy bore=0.6cm, mould
Intend flue gas by NO, NH3、O2And N2It forms, wherein NO 500ppm, NH3 500ppm、O25vo1%, air speed 80,000h-1, reaction
Temperature is 100~250 DEG C, reaction end gas NO-NO2-NOxAnalyzer (Testo 340flue gas analyzer) is examined online
It surveys.
The active testing result of catalyst is as shown in figure 1 shown in c.Ca/Zr0.05The catalytic activity of Cu/ZSM-5 catalyst is anti-
When to answer temperature be 160 DEG C, catalytic activity 60%, with the raising of reaction temperature, catalysis work increases, and is in reaction temperature
At 180 DEG C, the high conversion rate of NOx is in 90%, in 200~250 DEG C of temperature ranges, NOxConversion ratio may remain in
100%.
Embodiment 2
Using the catalyst prepared in embodiment 1, the additive amount of zirconium nitrate in catalyst is improved to 0.014g, catalyst
With embodiment 1, the low temperature supported SCR that the anticalcium of preparation is poisoned is catalyzed for other preparation conditions and catalyst activity evaluation method
Agent is denoted as Ca/Zr0.10Cu/ZSM-5。
The active testing result of catalyst is as shown in figure 1 shown in d.Ca/Zr0.10The catalytic activity of Cu/ZSM-5 catalyst is anti-
When to answer temperature be 160 DEG C, catalytic activity 70%, with the raising of reaction temperature, catalysis work increases, and is in reaction temperature
At 180 DEG C, the conversion ratio of NOx is close to 100%, in 200~250 DEG C of temperature ranges, NOxConversion ratio may remain in
100%.
Embodiment 3
Using the catalyst prepared in embodiment 1, the additive amount of zirconium nitrate in catalyst is improved to 0.028g, catalyst
With embodiment 1, the low temperature supported SCR that the anticalcium of preparation is poisoned is catalyzed for other preparation conditions and catalyst activity evaluation method
Agent is denoted as Ca/Zr0.20Cu/ZSM-5。
The active testing result of catalyst is as shown in figure 1 shown in e.Ca/Zr0.20The catalytic activity of Cu/ZSM-5 catalyst is anti-
When to answer temperature be 160 DEG C, catalytic activity 61%, with the raising of reaction temperature, catalysis work increases, and is in reaction temperature
At 180 DEG C, the conversion ratio of NOx is close to 90%, in 200~250 DEG C of temperature ranges, NOxConversion ratio may remain in
100%.
Embodiment 4
Using the catalyst prepared in embodiment 1, the additive amount of zirconium nitrate in catalyst is improved to 0.056g, catalyst
With embodiment 1, the low temperature supported SCR that the anticalcium of preparation is poisoned is catalyzed for other preparation conditions and catalyst activity evaluation method
Agent is denoted as Ca/Zr0.40Cu/ZSM-5。
The active testing result of catalyst is as shown in figure 1 shown in f.Ca/Zr0.20The catalytic activity of Cu/ZSM-5 catalyst is anti-
When to answer temperature be 160 DEG C, catalytic activity 55%, with the raising of reaction temperature, catalysis work increases, and is in reaction temperature
At 180 DEG C, the conversion ratio of NOx is close to 90%, in 200~250 DEG C of temperature ranges, NOxConversion ratio may remain in
100%.
Comparative example 1
Be not added zirconium nitrate in preparing catalyst process unlike the first embodiment, other preparation conditions of catalyst and
Catalyst activity evaluation method is denoted as Ca/Cu/ZSM- with embodiment 1, by the low temperature supported SCR catalyst of the calcium intoxication of preparation
5。
The active testing result of catalyst is as shown in figure 1 shown in b.The catalytic activity of Ca/Cu/ZSM-5 catalyst is poor, anti-
When to answer temperature be 160 DEG C, catalytic activity is only 55%, and with the raising of reaction temperature, catalysis work increases, in reaction temperature
When being 200 DEG C, NOxConversion ratio close to 100%.
Comparative example 2
Zirconium nitrate and calcium nitrate, other systems of catalyst are not added in preparing catalyst process unlike the first embodiment
The low temperature supported SCR catalyst of preparation is denoted as Cu/ZSM-5 with embodiment 1 by standby condition and catalyst activity evaluation method.
The active testing result of catalyst is as shown in figure 1 shown in a.When reaction temperature is 160 DEG C, Cu/ZSM-5 catalyst
Catalytic activity can achieve 80% or more, in 180~250 DEG C of temperature ranges, NOxConversion ratio may remain in 100%.
Claims (6)
1. a kind of low temperature SCR denitration catalyst of anticalcium poisoning, which is characterized in that its general formula is ZrCu/ZSM-5, is with H-
ZSM-5 molecular sieve is carrier, using Cu oxide as active component, using Zirconium oxide as auxiliary agent；With the quality of H-ZSM-5 molecular sieve
On the basis of, copper accounts for the 3.5~4.5% of carrier quality, and zr element accounts for the 0.05%~0.4% of carrier quality.
2. low temperature SCR denitration catalyst according to claim 1, which is characterized in that the quality with H-ZSM-5 molecular sieve is
Benchmark, copper account for the 3.8~4.2% of carrier quality, and zr element accounts for the 0.05~0.2% of carrier quality.
3. a kind of preparation method of low temperature SCR denitration catalyst according to claim 1, which is characterized in that specific steps
It is as follows:
(1) mantoquita, zirconates are dissolved in deionized water, are sufficiently stirred to form clear blue mixed solution；
(2) carrier H-ZSM-5 molecular sieve is added into the solution of step (1), room temperature magnetic agitation 0.5~1.5 hour, stirring was tied
Sample is placed in drying box by Shu Hou；
(3) sample after will be dry in step (2) is pulverized, then in Muffle kiln roasting to get to anticalcium poisoning
Low temperature SCR denitration catalyst.
4. preparation method according to claim 3, which is characterized in that in step (1), mantoquita is copper nitrate, and zirconates is nitre
Sour zirconium.
5. preparation method according to claim 3, which is characterized in that in step (2), the drying temperature of drying box is 115
~125 DEG C, drying time is 10~12 hours.
6. preparation method according to claim 3, which is characterized in that in step (3), maturing temperature is 540-560 DEG C, roasting
Burning the time is 3-5 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110170338A (en) * | 2019-05-30 | 2019-08-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of the modified difunctional zeolite ion exchanger of Zr-Cu/ zeolite and products thereof and application |
| CN111389454A (en) * | 2020-04-29 | 2020-07-10 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing p-tolualdehyde from synthesis gas and toluene |
| CN112619693A (en) * | 2021-01-11 | 2021-04-09 | 南京大学 | Low-temperature denitration catalyst and application thereof |
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| CN103599813A (en) * | 2013-12-04 | 2014-02-26 | 北京化工大学 | Molecular sieve based catalyst used for low-temperature SCR denitration and its preparation method |
| CN105597811A (en) * | 2016-01-22 | 2016-05-25 | 柳州市海达新型材料科技有限公司 | Sulfur-tolerance molecular sieve SCR catalyst and preparing method |
| CN105709813A (en) * | 2016-01-22 | 2016-06-29 | 柳州市海达新型材料科技有限公司 | Sulfur-resistant SCR (selective catalytic reduction) catalyst and preparation method thereof |
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2018
- 2018-08-10 CN CN201810906669.5A patent/CN108993580A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103599813A (en) * | 2013-12-04 | 2014-02-26 | 北京化工大学 | Molecular sieve based catalyst used for low-temperature SCR denitration and its preparation method |
| CN105597811A (en) * | 2016-01-22 | 2016-05-25 | 柳州市海达新型材料科技有限公司 | Sulfur-tolerance molecular sieve SCR catalyst and preparing method |
| CN105709813A (en) * | 2016-01-22 | 2016-06-29 | 柳州市海达新型材料科技有限公司 | Sulfur-resistant SCR (selective catalytic reduction) catalyst and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110170338A (en) * | 2019-05-30 | 2019-08-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of the modified difunctional zeolite ion exchanger of Zr-Cu/ zeolite and products thereof and application |
| CN111389454A (en) * | 2020-04-29 | 2020-07-10 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing p-tolualdehyde from synthesis gas and toluene |
| CN111389454B (en) * | 2020-04-29 | 2022-09-20 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing p-tolualdehyde from synthesis gas and toluene |
| CN112619693A (en) * | 2021-01-11 | 2021-04-09 | 南京大学 | Low-temperature denitration catalyst and application thereof |
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Application publication date: 20181214 |