CN105327614B - SO in joint removing coal-fired flue-gas2、NOXWith the method for Hg pollutants - Google Patents

SO in joint removing coal-fired flue-gas2、NOXWith the method for Hg pollutants Download PDF

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CN105327614B
CN105327614B CN201510745295.XA CN201510745295A CN105327614B CN 105327614 B CN105327614 B CN 105327614B CN 201510745295 A CN201510745295 A CN 201510745295A CN 105327614 B CN105327614 B CN 105327614B
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catalyst
oxidation
solid
flue gas
gas
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CN105327614A (en
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沈伯雄
丝梦
苑鹏
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Hebei University of Technology
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Hebei University of Technology
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    • 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
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

SO in one kind joint removing coal-fired flue-gas2、NOxWith the method for Hg pollutants, strong oxidizer is sprayed into the flue gas before solid catalysis oxidation catalyst, then flue gas is aoxidized by solid catalysis oxidation catalyst bed again；Solid catalysis oxidation catalyst bed is built with solid catalyst, and the solid catalyst is by titania support, major catalyst V2O5And co-catalyst CeO2、Fe2O3And Co2O3One or both of thing arbitrary proportion mixed above mixture composition；This method is to SO in flue gas2, NO and Elemental Mercury oxidation efficiency up to 75 more than 80%.It is an advantage of the invention that：This method utilizes SO in strong oxidizer collaboration heterogeneous catalyst co-oxidation flue gas2, NOxAnd Hg0Multi-pollutant, realizes combined highly effective rate oxidation of the multi-pollutant in a system, so as to provide necessary condition for the removing of follow-up high efficiency.

Description

SO in joint removing coal-fired flue-gas2、NOXWith the method for Hg pollutants
Technical field
The invention belongs to field of environmental technology, and in particular to SO in one kind joint removing coal-fired flue-gas2、NOxWith Hg pollutants Method.
Background technology
The energy resource structure of China is based on coal, and the burning of coal provides about 70% primary energy for China.Coal fires Burning the main gaseous contaminant of discharge includes SO2、NOxWith mercury etc., under conventional fired state, sulphur is mainly with SO2Mode is arranged Put, NOxPrimary discharge mode be NO (NO accounts for more than 90%).Mercury in coal-fired flue-gas has three kinds of forms：Elemental Mercury (Hg0), oxygen Change state mercury (Hg2+) and particle mercury (Hgp), elemental mercury from coal-fired flue gas is the principal mode of gas mercury.Oxidation state mercury (Hg2+) and Particle mercury (Hgp) easily removed by wet method system, but Elemental Mercury (Hg0) due to volatility height, it is difficult to be removed.Current SO2's Processing method is usually the method absorbed using alkaline matter, is divided into wet method and dry desulfurization, and wet desulphurization efficiency is higher than dry method. The processing method of nitrogen oxides has low NOx combustion, selective non-catalytic reduction method (SNCR) and selective catalytic reduction method (SCR), wherein SCR is current denitration efficiency highest method.Generally adsorbed in business using activated carbon is sprayed into flue gas Mercury, but because mercury in flue gas concentration is very low, it is necessary to consume substantial amounts of activated carbon.SO can be made using respective independent alternative2、NOxAnd mercury Gaseous contaminant obtains efficient removal in respective processing system, but one brought significantly has the disadvantage that each system is mutual Independent, whole set process is complicated, floor space is big, once invest and operating cost is high, brings very big to power plant or energy sector Economic pressures.It is achieved that SO2、NOxJoint removing with mercury gaseous contaminant is the development of coal-fired flue-gas pollutant abatement technology field Inexorable trend.
For SO in flue gas2, NOxAnd Hg0Catalysis oxidation there is the principle of general character, the present invention disclose a kind of strong oxygen of utilization Agent (O3And/or H2O2) cooperate with SO in heterogeneous catalyst co-oxidation flue gas (200-300 DEG C)2, NOxAnd Hg0Multi-pollutant Method.The innovative point of the present invention is to utilize strong oxidizer (O3And/or H2O2) collaboration heterogeneous catalyst co-oxidation flue gas (200- 300 DEG C) in SO2, NOxAnd Hg0Multi-pollutant, and traditional method compare, and the invention realizes multi-pollutant in a system Combined highly effective rate oxidation so that for follow-up high efficiency remove provide necessary condition.
The content of the invention
The purpose of the present invention be for it is above-mentioned exist problem there is provided one kind joint removing coal-fired flue-gas in SO2、NOxIt is dirty with Hg The method of thing is contaminated, this method realizes flue gas SO using strong oxidizer coupling solid catalysis oxidation2, NOxAnd Hg0Multi-pollutant is combined Oxidation, necessary condition is provided for the removing of follow-up high efficiency.
Technical scheme：
SO in one kind joint removing coal-fired flue-gas2、NOxWith the method for Hg pollutants, solid catalysis is coupled using strong oxidizer Flue gas SO is realized in oxidation2, NOxAnd Hg0Multi-pollutant co-oxidation, specific method is：Cigarette before solid catalysis oxidation catalyst Strong oxidizer is sprayed into gas, the strong ammoniation dose of penetrating is 0.5-0.9 with the mass ratio of equivalent chemical quantity：1, the strong oxidizer For O3、H2O2Or O3With H2O2Mixed gas, O3With H2O2Mixed gas in O3With H2O2Mol ratio be 1：9-9：1, then Flue gas is aoxidized by solid catalysis oxidation catalyst bed again；Solid catalysis oxidation catalyst bed is built with solid catalysis Agent, the solid catalyst is by titania support, major catalyst V2O5And co-catalyst CeO2、Fe2O3And Co2O3In one kind Or the mixture of two or more mixture arbitrary proportions is constituted, the mass percent of each component is major catalyst in solid catalyst For V2O510-15%, co-catalyst is 5-10%, and titania support is surplus；When catalytic bed interior reaction temperature is 200-300 DEG C when, this method is to SO in flue gas2, NO and Elemental Mercury oxidation efficiency be respectively 80%, 80% and more than 75%.
It is an advantage of the invention that：This method utilizes SO in strong oxidizer collaboration heterogeneous catalyst co-oxidation flue gas2, NOxWith Hg0Multi-pollutant, realizes combined highly effective rate oxidation of the multi-pollutant in a system, so as to be carried for the removing of follow-up high efficiency Necessary condition is supplied.
Embodiment
Embodiment 1：
SO in one kind joint removing coal-fired flue-gas2、NOxWith the method for Hg pollutants, specific method is：In solid catalysis oxygen Change and strong oxidizer O is sprayed into the flue gas before catalyst3Gas, the strong oxidizer O of penetrating3The quality of gas flow and equivalent chemical quantity Than for 0.9：1, then process solid catalysis oxidation catalyst bed is aoxidized flue gas again；Solid catalysis oxidation catalyst bed Built with solid catalyst, the solid catalyst is by titania support, major catalyst V2O5With co-catalyst CeO2、Fe2O3Or Co2O3The mass percent of each component is that major catalyst is V in composition, solid catalyst2O515%, co-catalyst CeO2For 5%, Titania support is 80%；When catalytic bed interior reaction temperature is 200-300 DEG C, this method is to SO in flue gas2, NO and simple substance The oxidation efficiency of mercury is respectively 84%, 85% and 90%.
Embodiment 2：
SO in one kind joint removing coal-fired flue-gas2、NOxWith the method for Hg pollutants, specific method is：In solid catalysis oxygen Change and strong oxidizer H is sprayed into the flue gas before catalyst2O2Gas, the strong oxidizer H of penetrating2O2Gas flow and equivalent chemical quantity Mass ratio is 0.9：1, then process solid catalysis oxidation catalyst bed is aoxidized flue gas again；Solid catalysis oxidation catalyst Bed is built with solid catalyst, and the solid catalyst is by titania support, major catalyst V2O5With co-catalyst CeO2、 Fe2O3Or Co2O3The mass percent of each component is that major catalyst is V in composition, solid catalyst2O515%, co-catalyst CeO2For 10%, titania support is 75%；When catalytic bed interior reaction temperature is 200-300 DEG C, this method is in flue gas SO2, NO and Elemental Mercury oxidation efficiency be respectively 88%, 89% and 85%.
Embodiment 3：
SO in one kind joint removing coal-fired flue-gas2、NOxWith the method for Hg pollutants, specific method is：In solid catalysis oxygen Change and strong oxidizer O is sprayed into the flue gas before catalyst3With H2O2Mixed gas, the strong oxidizer O of penetrating3With H2O2The gaseous mixture scale of construction Mass ratio with equivalent chemical quantity is 0.9：1, O3With H2O2O in mixed gas3With H2O2Mol ratio be 1:1；Then flue gas is again Aoxidized by solid catalysis oxidation catalyst bed；Solid catalysis oxidation catalyst bed, should built with solid catalyst Solid catalyst is by titania support, major catalyst V2O5With co-catalyst CeO2、Fe2O3And Co2O3Composition, solid catalyst The mass percent of middle each component is that major catalyst is V2O515%, co-catalyst CeO2、Fe2O3And Co2O3It is 5%, dioxy It is 70% to change titanium carrier；When catalytic bed interior reaction temperature is 200-300 DEG C, this method is to SO in flue gas2, NO and Elemental Mercury Oxidation efficiency is respectively 91%, 92% and 80%.
Embodiment 4：
SO in one kind joint removing coal-fired flue-gas2、NOxWith the method for Hg pollutants, specific method is：In solid catalysis oxygen Change and strong oxidizer O is sprayed into the flue gas before catalyst3With H2O2Mixed gas, the strong oxidizer O of penetrating3With H2O2The gaseous mixture scale of construction Mass ratio with equivalent chemical quantity is 0.5：1, O3With H2O2O in mixed gas3With H2O2Mol ratio be 1:1；Then flue gas is again Aoxidized by solid catalysis oxidation catalyst bed；Solid catalysis oxidation catalyst bed, should built with solid catalyst Solid catalyst is by titania support, major catalyst V2O5With co-catalyst Fe2O3And Co2O3It is each in composition, solid catalyst The mass percent of component is that major catalyst is V2O510%, co-catalyst Fe2O3For 10%, Co2O3For 5%, TiO 2 carrying Body is 75%；When catalytic bed interior reaction temperature is 200-300 DEG C, this method is to SO in flue gas2, NO and Elemental Mercury oxidation effect Rate is respectively 80%, 81% and 75%.

Claims (1)

1. SO in one kind joint removing coal-fired flue-gas2、NOxWith the method for Hg pollutants, it is characterised in that：Utilize strong oxidizer coupling Close solid catalysis oxidation and realize flue gas SO2, NOxAnd Hg0Multi-pollutant co-oxidation, specific method is：Urged in solid catalysis oxidation Strong oxidizer is sprayed into flue gas before agent, the strong ammoniation dose of penetrating is 0.5-0.9 with the mass ratio of equivalent chemical quantity：1, institute Strong oxidizer is stated for O3、H2O2Or O3With H2O2Mixed gas, O3With H2O2Mixed gas in O3With H2O2Mol ratio be 1： 9-9：1, then process solid catalysis oxidation catalyst bed is aoxidized flue gas again；Solid catalysis oxidation catalyst bed is built-in There is solid catalyst, the solid catalyst is by titania support, major catalyst V2O5And co-catalyst composition, urged wherein helping Agent is CeO2、Fe2O3And Co2O3One or both of any of the above ratio mixture, each component in solid catalyst Mass percent is that major catalyst is V2O510-15%, co-catalyst is 5-10%, and titania support is surplus；Work as catalytic bed When interior reaction temperature is 200-300 DEG C, this method is to SO in flue gas2Oxidation efficiency be that the 80%, oxidation efficiency to NO is 80% and be more than 75% to the oxidation efficiency of Elemental Mercury.
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CN106731803A (en) * 2016-12-27 2017-05-31 西安交通大学 The rotary regenerative air preheater and method of heat accumulating element coupled catalyst oxidation and denitration
CN106861392A (en) * 2017-02-21 2017-06-20 华北电力大学 A kind of nitrogen oxide removal process based on catalytic oxidation of hydrogen peroxide
CN106955589B (en) * 2017-04-11 2020-07-07 中国海洋大学 Boiler flue gas simultaneous desulfurization and denitrification device
CN106984148A (en) * 2017-04-24 2017-07-28 河北工业大学 A kind of method of low-temperature plasma synergistic catalysis oxidation various pollutants in fume
CN109758904A (en) * 2019-01-10 2019-05-17 昆明理工大学 A kind of method of ultraviolet cooperating low-temperature catalytic oxidation processing non-ferrous metal metallurgy flue gas acid preparing tail gas

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