CN101791561B - Desulphurization and denitration catalyst and preparation method thereof - Google Patents
Desulphurization and denitration catalyst and preparation method thereof Download PDFInfo
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- CN101791561B CN101791561B CN2010101526374A CN201010152637A CN101791561B CN 101791561 B CN101791561 B CN 101791561B CN 2010101526374 A CN2010101526374 A CN 2010101526374A CN 201010152637 A CN201010152637 A CN 201010152637A CN 101791561 B CN101791561 B CN 101791561B
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Abstract
The invention discloses a low-temperature high-activity desulphurization and denitration catalyst, which comprises the following components in percentage by weight: 5-10% of CuO, 5-10% of Fe2O3, 5-10% of MnO2 and 70-80% of Al2O3. The preparation method of the catalyst comprises the following steps: (1) taking appropriate 95 wt% of Al2O3 particles, drying the particles in a muffle furnace to remove crystal water; (2) preparing copper nitrate, ferric nitrate and manganese acetate impregnating solutions; (3) mixing a carrier and the impregnating solutions, impregnating, heating, decompressing, rotating for evaporation and removing moisture in the mixture; and (4) preparing the carrier via drying, calcination and activation. The prepared catalyst has good activity at low temperature, can desulfurize and denitrate simultaneously, has low material cost and can be recycled, and by-products can be recycled without secondary pollution.
Description
Technical field
The present invention relates to the air contaminant treatment field, particularly relate to a kind ofly under the cryogenic conditions of coal-fired plant flue gas pipe end, remove the SO in the flue gas simultaneously
2With the catalyst and the preparation technology thereof of NOx gas, wherein NOx represents nitrogen oxide.
Background technology
Industries such as the energy, chemical industry, metallurgy, traffic use in the flue gas that fossil fuel (coal, oil, natural gas etc.) discharged and contain a large amount of SO
2And NOx, atmosphere is caused severe contamination.Along with the fast development of Chinese national economy, SO
2Constantly increase with the discharge capacity of NOx, environmental problem has become the key issue that influences the Chinese national economy sustainable development.In recent years, the Chinese government gives great concern to environmental problem, and the Environmental Protection in China method clearly stipulates, uses the coal sulfur content greater than 1% station boiler, must be furnished with the desulfurization facility.And if, only control SO by present emission behaviour
2Discharging, and the discharging of the control NOx that do not adopt an effective measure has the expert to expect 2015～the year two thousand twenty, thermoelectricity industry NOx total emission volumn will surpass SO
2, become the first sour gas pollutant of power industry.
Therefore, under situation with limited economic strength, the pollution prevention technique of greatly developing low expense is the task of top priority.The desulphurization denitration technology has huge advantage economically simultaneously, is a smoke gas treatment technology that tallies with the national condition, and bright development prospect is arranged.At present, common flue gas desulfurization and denitrification technology mainly contains electronic beam method, activated carbon method and aluminium base copper method.Although electronic beam method has been realized industrialization; But because its operating cost is high; Be difficult to large-scale promotion at home, and existing catalyst (comprising active carbon and aluminium base copper), the industrialization because the problem that exists at aspects such as Sulfur capacity, the wear-resisting property of catalyst, preparation technologies is unrealized so far.Infusion process is a kind of method for preparing catalyst of at present comparatively common technical maturity; But for the catalyst that adopts this method preparation; Active component adopts rotary evaporation to combine catalyst prepared to a certain degree to address this problem at carrier inside and outer surface skewness.
The development trend of denitration technology research at present is exactly terminal low temperature (being lower than 250 ℃) SCR (SCR) technology of system, seeks the high-efficiency low-temperature catalysis agent.The low-temperature denitration technology is positioned at after limestone-gypsum wet method fume desulfurizing system (FGD) and the dust arrester owing to it; The characteristic that has low temperature, low-sulfur and low dirt through the flue gas of reactor; Designing requirement meeting for reactor steel construction and soot blower decreases, and can reduce cost to a certain extent.Simultaneously, need not carry out preheating, save the expense that energy consumption and repacking are put flue gas.Therefore, the research and development cost is low, low temperature active is high, the regenerable metal oxide desulphurization denitration catalyst and the preparation technology thereof of non-secondary pollution are significant.
Summary of the invention
The object of the present invention is to provide the high desulphurization denitration catalyst of a kind of low temperature active, cost of material is low, and denitrification efficiency is high, can regeneration cycle use the recyclable utilization of byproduct, non-secondary pollution.
Another object of the present invention is to provide a kind of method that is used to prepare above-mentioned desulphurization denitration catalyst, adopt the catalyst sulfur capacity of the method preparation big, wear-resistant, can regeneration cycle use the recyclable utilization of byproduct, non-secondary pollution.
The desulphurization denitration catalyst that a kind of low temperature active is high, according to mass percent by 5～10% CuO, 5～10% Fe
2O
3, 5～10% MnO
2With 70～80% Al
2O
3Form.
A kind of method for preparing said catalyst may further comprise the steps:
(1) choose an amount of activated alumina particle, behind the water that decrystallizes as carrier;
(2) preparation maceration extract: in water, add copper nitrate, ferric nitrate and manganese acetate, the slaine amount of being added should guarantee that the catalyst of processing contains 5～10%CuO, 5～10%Fe
2O
3And 5～10%MnO
2
(3) carrier and maceration extract are mixed, send in the Rotary Evaporators, fully flood a period of time after, heating, decompression, rotary evaporation are removed the moisture in the mixture;
(4) mixture of above-mentioned removal moisture is dry, 450～850 ℃ of following roastings 3～5 hours, catalyst was promptly processed in activation again.
Activated alumina particle of the present invention is γ-Al
2O
3
The physical parameter of catalyst according to the invention is: grain diameter Φ 3～5mm, specific area>=200m
2/ g, pore volume>=0.4ml/g, burning decrement≤7%, breaking strength>=80N/ grain.
The water oven dry completion all night under 200 ℃ in Muffle furnace of decrystallizing of the present invention.
Technique effect of the present invention is embodied in:
(1) to adopt activated alumina particle, copper nitrate and ferric nitrate, manganese acetate be raw material in the present invention, and these raw material sources are extensive, obtain easily, and cost is low.
(2) catalyst activity of preparation is strong, and sulfur capacity is big, and specific area is big, therefore has desulfurization off sulfide effect preferably, and in the simulated flue gas experiment, denitrification efficiency all can reach more than 90%, and is especially better in the low-temperature zone denitration activity.
(3) catalyst is stable, and is wear-resisting, can keep certain activity in a long time.
(4) catalyst is a dry state, does not need the aqueous solution during use, has reduced the water consumption.
(5) in the course of reaction, catalyst at first absorbs SO
2Generate sulfate and reach the desulfurization purpose, under certain reaction temperature and time of staying assurance, remove the SO in the flue gas
2, carry out gas cleaning reaction: MO+SO
2+ 1/2O
2→ MSO
4, the sulfate of generation can also promote NOx and NH
3Reaction is to play denitration.Behind the desulphurization denitration, will contain a large amount of SO
2Catalyst transfer to regenerative system and regenerate, at 450 ℃ of temperature and CH
4Under the gas flow rate, carry out following regenerative response: 2MSO
4→ 2MO+SO
3+ SO
2+ 1/2O
2Catalyst after the regeneration is transferred to reactor with transmission mechanism, continues to participate in desulfurization and denitrification reaction.The SO that regenerative process produces
2, SO
3Mist is sent into the byproduct for treatment part, and through catalysis, conversion and absorption, obtaining concentration is the concentrated sulfuric acid byproduct more than 92%, to reach the purpose of recycling, minimizing secondary pollution.
The specific embodiment
Enumerating embodiment below further specifies the present invention:
Embodiment 1
Get 55～60g activated alumina particle (like γ-Al
2O
3), put under 200 ℃ of the Muffle furnaces water that decrystallizes of oven dry all night, take out the evaporative flask of the Rotary Evaporators of packing into behind the back weighing 50g.The configuration metal salt solution takes by weighing Cu (NO
3)
23H
2O crystal 12.10g, Fe (NO
3)
33H
2O crystal 2 0.20g, (CH
3COO)
2Mn4H
2O crystal 11.26g adds water and stirs and process maceration extract after the mixing.Pour the maceration extract that configures into evaporative flask and mix with activated alumina particle, the rotary dipping certain hour heats, decompression, rotary evaporation water outlet be until the no obvious washmarking in alumina particle surface again.The good aluminium oxide solid of dipping is sent into and is carried out roasting under 500 ℃ of the Muffle furnaces and can obtain desired catalyst in 4 hours in baking oven under 120 ℃ all night after the drying.Catalyst granules particle diameter Φ 3～5mm, specific area>=200m
2/ g, pore volume>=0.4ml/g, burning decrement≤7%, breaking strength>=80N/ grain.
Embodiment 2
Get 55～60g activated alumina particle (like γ-Al
2O
3), put under 200 ℃ of the Muffle furnaces water that decrystallizes of oven dry all night, take out the evaporative flask of the Rotary Evaporators of packing into behind the back weighing 50g.The configuration metal salt solution takes by weighing Cu (NO
3)
23H
2O crystal 6 .05g, Fe (NO
3)
33H
2O crystal 10.10g, (CH
3COO)
2Mn4H
2O crystal 5 .63g adds water and stirs and process maceration extract after the mixing.Pour the maceration extract that configures into evaporative flask and mix with activated alumina particle, the rotary dipping certain hour heats, decompression, rotary evaporation water outlet be until the no obvious washmarking in alumina particle surface again.The good aluminium oxide solid of dipping is sent into and is carried out roasting under 600 ℃ of the Muffle furnaces and can obtain desired catalyst in 3 hours in baking oven under 120 ℃ all night after the drying.Catalyst granules particle diameter Φ 3～5mm, specific area>=200m
2/ g, pore volume>=0.4ml/g, burning decrement≤7%, breaking strength>=80N/ grain.
Embodiment 3
Get 55～60g activated alumina particle (like γ-Al
2O
3), put under 200 ℃ of the Muffle furnaces water that decrystallizes of oven dry all night, take out the evaporative flask of the Rotary Evaporators of packing into behind the back weighing 50g.The configuration metal salt solution takes by weighing Cu (NO
3)
23H
2O crystal 12.10g, Fe (NO
3)
33H
2O crystal 10.10g, (CH
3COO)
2Mn4H
2O crystal 11.26g adds water and stirs and process maceration extract after the mixing.Pour the maceration extract that configures into evaporative flask and mix with activated alumina particle, the rotary dipping certain hour heats, decompression, rotary evaporation water outlet be until the no obvious washmarking in alumina particle surface again.The good aluminium oxide solid of dipping is sent into and is carried out roasting under 450 ℃ of the Muffle furnaces and can obtain desired catalyst in 5 hours in baking oven under 120 ℃ all night after the drying.Catalyst granules particle diameter Φ 3～5mm, specific area>=200m
2/ g, pore volume>=0.4ml/g, burning decrement≤7%, breaking strength>=80N/ grain.
With the chamber small-sized heating furnace simulated flue gas experiment that experimentizes of above-mentioned desulphurization denitration catalyst; Employing is by the applicant's granted patent " regenerable metal oxide desulfur technology and system " technology and equipment (ZL01133521.1); Under normal pressure, operating temperature is the SO that feeds 2000ppm under 80～350 ℃ the condition in the experiment
2, the NO of 750ppm, oxygen are 6%, and with N
2As balance gas, the reactor leading portion carries out desulfurization, and NH is pressed in the reactor rear end
3/ NO mol ratio 1.0～1.2 sprays into NH
3As reducing agent, carry out the while desulphurization denitration.Adopt flue gas analyzer (KM900) and portable infrared radiation detection apparatus (GASMET FT-IR Dx4000) that the smoke components before and after the desulphurization denitration is measured.Desulfurization and denitrification reaction device and regeneration reactor all adopt electrical heating tubular type stove, to keep stable reaction temperature.Experimental result shows:
(1) at 2000ppm inlet SO
2Under the operating temperature of gas concentration and 350 ℃, the desulfurization-regeneration tests in 12 cycles of experience, desulfurization degree still can maintain more than 90%;
(2) at NH
3/ NO mol ratio be 1.0,1.1 and 1.2 3 kind of simulated flue gas situation under; Experience the denitration-regeneration tests in 12 cycles respectively; Can reach more than 90% at 300 ℃ of denitration efficiencies, also can reach more than 80% at 150～200 ℃ of denitration efficiencies, performance obviously is superior to typical catalyst;
(3) specific surface is measured and is shown that the relative fresh catalyst of the specific surface area of catalyst behind the desulphurization denitration reduces (reducing 8～10% approximately) to some extent, and through after the regeneration, specific area is restored basically;
(4) the regeneration rear catalyst can be kept good activity, the lasting life-span;
(5) SO in the regeneration gas
2Concentration can reach 6% (volume ratio), can be to byproduct processing and utilizing in addition, thus avoid secondary pollution;
(6) experiment shows that this desulfurizing agent can reach industrial application requirements.
Claims (3)
1. desulphurization denitration catalyst that low temperature active is high, according to mass percent by 5～10% CuO, 5～10% Fe
2O
3, 5～10% MnO
2With 70～80% Al
2O
3Form, wherein, Al
2O
3Be γ-Al
2O
3Alumina particle.
2. method for preparing the said catalyst of claim 1 may further comprise the steps:
(1) chooses an amount of activated alumina γ-Al
2O
3Particle, in Muffle furnace under 200 ℃ the oven dry water that decrystallizes all night, behind the water that decrystallizes as carrier;
(2) preparation maceration extract: in water, add copper nitrate, ferric nitrate and manganese acetate, the slaine amount of being added should guarantee that the catalyst of processing contains 5～10%CuO, 5～10%Fe
2O
3And 5～10%MnO
2
(3) carrier and maceration extract are mixed, send in the Rotary Evaporators, fully flood a period of time after, heating, decompression, rotary evaporation are removed the moisture in the mixture;
(4) mixture of above-mentioned removal moisture is dry, 450～850 ℃ of following roastings 3～5 hours, activation promptly made said catalyst again.
3. method according to claim 2 is characterized in that, the physical parameter of said catalyst is: grain diameter Φ 3～5mm, specific area>=200m
2/ g, pore volume>=0.4ml/g, burning decrement≤7%, breaking strength>=80N/ grain.
Priority Applications (1)
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|---|---|---|---|
| CN2010101526374A CN101791561B (en) | 2010-04-22 | 2010-04-22 | Desulphurization and denitration catalyst and preparation method thereof |
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|---|---|---|---|
| CN2010101526374A CN101791561B (en) | 2010-04-22 | 2010-04-22 | Desulphurization and denitration catalyst and preparation method thereof |
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| CN101791561B true CN101791561B (en) | 2012-05-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102002402B (en) * | 2010-12-13 | 2013-12-04 | 四川大学 | Preparation method of renewable manganese high-temperature gas desulfurizer |
| CN102631921B (en) * | 2012-03-23 | 2014-04-09 | 华烁科技股份有限公司 | Nitric acid exhaust gas denitration catalyst and preparation method thereof |
| CN102744102B (en) * | 2012-06-14 | 2015-01-21 | 新疆大学 | Metal modified SAPO-34 zeolite catalyst, preparation method thereof and use method thereof |
| CN102886257A (en) * | 2012-10-22 | 2013-01-23 | 安徽工业大学 | Manganese-base catalyst for synthesizing alpha-tetralone from tetrahydronaphthalene and preparation method thereof |
| CN102962064A (en) * | 2012-11-16 | 2013-03-13 | 北京石油化工学院 | Gamma-form alumina loaded metallic oxide catalyst as well as preparation method and application thereof |
| CN103464154A (en) * | 2013-08-29 | 2013-12-25 | 北京石油化工学院 | Catalyst for simultaneous catalytic reduction of both NO and SO2 through CO and preparation method and application of catalyst |
| CN103657737A (en) * | 2013-12-18 | 2014-03-26 | 张继惟 | High-efficiency catalyst carrier for flue gas purification |
| CN104492424B (en) * | 2014-11-19 | 2016-10-19 | 浙江大学 | Ozone coupling MnO2/ Al2o3sO in catalysis oxidation flue gas2the method preparing sulphuric acid |
| CN106492804B (en) * | 2016-11-29 | 2019-02-15 | 西安元创化工科技股份有限公司 | A kind of SCR method treatment of nitric acid tail gas denitrating catalyst |
| CN109420508B (en) * | 2017-08-31 | 2021-04-06 | 中国石油化工股份有限公司 | Denitration catalyst, preparation method and low-temperature denitration process |
| CN112495390A (en) * | 2020-11-22 | 2021-03-16 | 浙江盛旺环境工程有限公司 | Medium-low temperature low-vanadium desulfurization and denitrification catalyst and preparation method thereof |
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| IT1003097B (en) * | 1973-03-28 | 1976-06-10 | Tokyo Electric Co Ltd | CATALYST TO TREAT EXHAUST GASES OF MOTOR VEHICLES |
| DE3641773A1 (en) * | 1986-12-06 | 1988-06-09 | Metallgesellschaft Ag | METHOD FOR CATALYTICALLY REDUCING NO |
| CN100366342C (en) * | 2004-12-17 | 2008-02-06 | 南化集团研究院 | Catalyst for depriving nitrogen oxide under low temperature through reduction and preparation method |
| CN101422736B (en) * | 2007-11-02 | 2011-02-02 | 南化集团研究院 | Catalyst for removing nitrogen oxide in FCC stack gas at low temperature and production method thereof |
| CN101530799B (en) * | 2009-04-16 | 2011-01-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Nitrogen oxide catalyst-sorbent and preparation method |
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