CN107335453A - A kind of board-like catalyst of denitration demercuration and preparation method thereof - Google Patents

A kind of board-like catalyst of denitration demercuration and preparation method thereof Download PDF

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CN107335453A
CN107335453A CN201710551349.8A CN201710551349A CN107335453A CN 107335453 A CN107335453 A CN 107335453A CN 201710551349 A CN201710551349 A CN 201710551349A CN 107335453 A CN107335453 A CN 107335453A
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catalyst
board
tio
copper
sio
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王圣
朱法华
庄柯
金定强
孙雪丽
赵秀勇
李亚春
丁力
周爱奕
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State Power Environmental Protection Research Institute
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • 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
    • 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
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product 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
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates

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  • Environmental & Geological Engineering (AREA)
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Abstract

The invention provides a kind of board-like catalyst of denitration demercuration, include the TiO of halogenation Copper-cladding Aluminum Bar2‑SiO2Composite nanometer particle, potassium halide modified attapulgite, Alumina gel and skeleton；Present invention also offers the preparation method of the board-like catalyst；The present invention has advantages below：Using the TiO of halogenation Copper-cladding Aluminum Bar2‑SiO2Composite nanometer particle makes crystal particle diameter that the activity for below 10nm, the increase of crystal specific surface area, the increase of visible absorption scope, being advantageous to increase catalyst be obviously reduced as active component；Add SiO2The TiO to easy in inactivation, easily condensed2Coated, add its heat endurance and mechanical stability；Using potassium halide modified attapulgite as carrier and adhesive, by strengthening the removing to mercury to the chemisorption of mercury；Using Alumina gel as additional adhesive, while make catalyst quality fine and close, be not easy to split or peel off at high temperature；The board-like composite catalyst improves gas adsorption rate, and denitration demercuration rate reaches more than 92%；The preparation method technique of the present invention is simple.

Description

A kind of board-like catalyst of denitration demercuration and preparation method thereof
Technical field
The invention belongs to smoke comprehensive Treatment process field, and in particular to a kind of board-like catalyst of denitration demercuration and its preparation Method.
Background technology
Coal fire discharged flue gas is the primary pollution source of air, and specific pollutant includes SOX、NOX, mercury etc..In existing skill In art, for NOXThe research and utilization of individual event control technology have reached the level of comparative maturity.But the improvement to mercury is also located The initial stage of starting.Although currently having expanded more extensive research to the emission control technique of mercury both at home and abroad, it is so far Only there is not the technology of maturation yet applied to coal-burning power plant and the mercury control of fire coal boiler fume.
Mercury in fire coal mainly exists in the form of compound state, however, mercury is after burning conversion, final Mercury In Coal Combustion Flue Gas With Hg0、Hg2+、HgpThree kinds of forms are present.Most HgPCan be as flying dust be by electric cleaner and sack cleaner capture；Hg2 +With preferable water solubility, so can be trapped by wet desulphurization device；And for accounting for state total mercury 20-50% Hg0For, no Only there is thermodynamic stability higher under weak oxide activity and the high temperature under low temperature, and be insoluble in water, so existing cigarette Air purifying apparatus is to Hg0Removal efficiency generally than relatively low, most Hg0It will be directly discharged into air.Therefore, Hg0 It is the principal mode of current Mercury In Coal Combustion Flue Gas pollution, studies Hg0Efficient removal method is the key of mercury deep removal.
If by NOX, each pollutant such as mercury carry out classification processing, then can have investment, floor space and operation maintenance expense With it is higher the problem of, comparatively, the integrated treatment of multi-pollutant is more feasible.But prior art is for fume emission Including NOXIntegrated treatment with the multi-pollutant of mercury does not have more ripe technology.
In the prior art either in denitration or demercuration technology using most or cellular catalyst, its have than The advantages such as surface area is big, service life length, but in the coal-fired flue-gas for high fly ash content, easily cause asking for blocking Topic, generally requires setting soot blower；And board-like catalyst need not set soot blower, hole between layers is larger, flue gas Flow resistance is small, and also because it has skeleton structure, bulk strength is higher, and length can reach 1.5m, for grinding for board-like catalyst Study carefully also less.It is also known that TiO2With excellent photocatalysis performance, the caused hole-electron that is excited is to very high oxygen Change ability, but it is only limitted to absorb ultraviolet light, limits the utilization to sunshine, and easy in inactivation, easily cohesion, it is therefore desirable to To TiO2It is modified to improve its utilization scope and its stability of increase to visible ray.
Therefore it is a kind of new based on active component TiO there is an urgent need to study2Be used for simultaneously denitration demercuration it is board-like compound Catalyst solves above-mentioned technical problem.
The content of the invention
The present invention is directed to the deficiencies in the prior art, there is provided a kind of board-like catalyst of denitration demercuration and its preparation side Method, solves above-mentioned technical problem.
To achieve these goals, the present invention provides following technical scheme：A kind of board-like catalyst of denitration demercuration, including halogen Change the TiO of Copper-cladding Aluminum Bar2-SiO2Composite nanometer particle, potassium halide modified attapulgite, Alumina gel and skeleton.
It is above-mentioned in photocatalytic activity composition TiO2Middle addition SiO2On the one hand the specific surface area of catalyst can be increased, be advantageous to Catalyst surface generates more hydroxyls, increases acid catalyzed ability；On the other hand the TiO to easy in inactivation, easily condensed2Wrapped Cover, add its heat endurance, mechanical stability.
After the above-mentioned copper halide of doping in the catalyst, copper ion is incorporated into TiO2Lattice structure in, due to copper ion Synergy, copper ion can suppress the rearrangement of titanium ion and oxonium ion in sintering process, so as to suppress anatase particle Growth, is obviously reduced crystal particle diameter；By changing catalyst charge Density Distribution, crystal specific surface area increases, visible ray is inhaled Receive induction enhancing, the increase of visible absorption scope and change lattice types and hinder the physics and chemistry such as transformation of the anatase to rutile Matter is advantageous to increase the activity of catalyst.
Preferably, the TiO of the halogenation Copper-cladding Aluminum Bar2-SiO2Composite nanometer particle particle diameter is 2~8nm, increases specific surface area Add, be more advantageous to fully contacting for composite catalyst and flue gas.
Preferably, with TiO2The molal quantity of middle titanium is calculating benchmark, and the doping of copper ion is 1%~5%, makes catalyst Activity is higher.
Preferably, TiO2And SiO2Mol ratio be 1:2~10, make specific surface area of catalyst and stability more excellent.
Preferably, the copper halide is copper chloride or copper bromide or cupric iodide；More preferably copper chloride, with respect to bromination Copper, cupric iodide, product colour are more shallow.
Cheap and easy to get can be modified itself as the recessed soil of carrier of adhesive in above-mentioned, although recessed soil compares surface Detailed change does not occur for product and pore structure, but modified attapulgite surface generates the chemisorption to mercury, therefore strengthens Removing to mercury.
Preferably, the potassium halide is potassium chloride or KBr or KI；More preferably KI, the removing to mercury Effect is best.
Above-mentioned middle Alumina gel plays further adhesive effect, the TiO with halogenation Copper-cladding Aluminum Bar as adhesive2-SiO2It is compound The composite board type catalyst surface increase that nano particle and potassium halide are mixed with is smooth, has good anti-fouling effect, simultaneously With good water resistance, heat resistance, film forming, antistatic, quality is fine and close, is not easy to split or peel off at high temperature；Alumina gel It can be obtained with metallic aluminium and hydrochloric acid reaction, organo-aluminium hydrolyzes, the direct glue solution of SB powder or inorganic silicon source first alkalize what is be acidified afterwards Method.
Preferably, the pH value of the Alumina gel is 4~6, and its property is more stable, and is avoided that strong caused by strong acid condition Corrosivity.
Preferably, the TiO of halogenation Copper-cladding Aluminum Bar2-SiO2Composite nanometer particle content is 2~20wt%, potassium halide modified attapulgite Content is 80~95wt%, Alumina gel content is 0~3wt%, the catalytic activity of composite catalyst can be made stable, efficiency raising；Its The middle recessed soil of carrier can also be used as adhesive, and Alumina gel can not also add.
In addition, present invention also offers a kind of preparation method of the board-like catalyst of denitration demercuration, comprise the following steps：
（1）Sol-gal process prepares the TiO of halogenation Copper-cladding Aluminum Bar2-SiO2Composite nanometer particle；
（2）Prepare potassium halide modified attapulgite；
（3）Prepare Alumina gel；
（4）By the TiO of halogenation Copper-cladding Aluminum Bar2And SiO2Composite nanometer particle, potassium halide modified attapulgite and Alumina gel are well mixed, system Standby paste, coated on skeleton, high-temperature calcination obtains board-like catalyst.
Preferably, the preparation method of the board-like catalyst of a kind of denitration demercuration, is comprised the following specific steps that：
（1）By TiCl4It is added to tetraethyl orthosilicate in absolute ethyl alcohol, then adds deionized water and acetic acid, dropwise addition are dissolved with The concentrated nitric acid solution of copper halide, 1~2h is reacted in 120~150 DEG C, obtains uniform solvent, be cooled to room temperature and place 10~15h, Gel is formed, filtering, is first washed with acetic acid-ammonium acetate buffer solution, then is washed with ethanol, it is dry that xerogel, grinding obtain The TiO of halogenation Copper-cladding Aluminum Bar2-SiO2Composite nanometer particle, its particle diameter are 2~8nm；
（2）It is 3~5 by mass ratio:50 potassium halide and recessed soil mixing, add deionized water, stirring obtains suspension, Ran Hou 45~90 DEG C of heating evaporating waters obtain pastel, after oven drying to constant weight, are ground to powdery, obtain potassium halide be modified it is recessed Soil；
（3）Aluminium isopropoxide and deionized water are mixed, 60~80 DEG C of addition surfactants is warming up to, reacts 0.5~2h, White precipitate is obtained, is filtered, deionized water is washed 3 times；Then precipitation and nitric acid and deionized water are warming up to 70~90 DEG C instead 1~3h is answered to obtain the transparent Alumina gel that pH value is 4~6；
（4）The TiO for the halogenation Copper-cladding Aluminum Bar that above-mentioned steps are obtained2-SiO2Composite nanometer particle, potassium halide modified attapulgite and aluminium are molten Glue is well mixed, and is added deionized water, is prepared paste, be then coated uniformly on titanium net skeleton, high-temperature calcination obtains board-like Catalyst.
Preferably, the step（1）In with TiO2The molal quantity of middle titanium is calculating benchmark, and the doping of copper ion is 1% ~5%..
Preferably, step（3）Described surfactant is dodecyl benzyl dimethyl ammonium chloride or fatty alcohol polyoxy Vinethene.
Compared with prior art, the present invention has advantages below：Using the TiO of halogenation Copper-cladding Aluminum Bar2-SiO2Composite Nano Grain is used as active component, crystal particle diameter is obviously reduced to below 10nm, the increase of crystal specific surface area, visible absorption scope and increases Add, be advantageous to increase the activity of catalyst；Add SiO2The TiO to easy in inactivation, easily condensed2Coated, add its thermostabilization Property and mechanical stability；Adhesive is also served as simultaneously using potassium halide modified attapulgite as carrier, by making to the chemisorbed of mercury With the removing strengthened to mercury；Using Alumina gel as additional adhesive, while make catalyst quality fine and close, be not easy at high temperature Split or peel off；The board-like composite catalyst can realize while NO_x Reduction by Effective demercuration, improves the adsorption rate to gas, denitration Demercuration rate reaches more than 92%；The preparation method technique of the present invention is simple, and operation is flexible.
Embodiment
With reference to specific embodiment, the present invention is expanded on further, it should be appreciated that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention；In addition, it is to be understood that after present disclosure has been read, those skilled in the art can To be made various changes or modifications to the present invention, these equivalent form of values also fall within appended claims limited range.
Embodiment 1：
By 9.5gTiCl4Be added to 20.8g tetraethyl orthosilicates in 35ml absolute ethyl alcohols, sequentially add 20ml deionized waters, 15ml acetic acid, the 5ml concentrated nitric acid solutions dissolved with 0.085g copper chlorides are added dropwise, react 1h in 120, obtain uniform colloidal sol, it is cold 10h is placed to room temperature, forms gel, filtering, pH first is 6.0 acetic acid-ammonium acetate buffer solution washing, then uses absolute ethyl alcohol Washing, it is dry that xerogel, grinding obtain the TiO of 9g chlorination Copper-cladding Aluminum Bars2-SiO2Composite nanometer particle, its particle diameter are 2-8nm；
By the recessed soil mixing of 6g potassium chloride and 100g, 250ml deionized waters are added, stirring obtains suspension, then in 45 DEG C of heating Evaporating water obtains pastel, after 80 DEG C of drying to constant weights of baking oven, is ground to powdery, obtains 99g potassium chloride modified attapulgites；
10g aluminium isopropoxides and 25ml deionized waters are mixed, 60 DEG C is warming up to and adds 1g surfactant sodium dodecyls base two Methyl-benzyl ammonium chloride, 0.5h is reacted, obtains white precipitate, filtered, deionized water is washed 3 times；Then will precipitation and 1ml nitric acid 70 DEG C of reaction 1h, which are warming up to, with 10ml deionized waters obtains the transparent Alumina gel that pH value is 4；
Take the TiO for the 9g chlorination Copper-cladding Aluminum Bars that above-mentioned steps obtain2-SiO2Composite nanometer particle, 95g potassium chloride modified attapulgite and 3g Alumina gel is well mixed, and is added 100ml deionized waters, is prepared paste, be then coated uniformly on titanium net skeleton, 450 DEG C of height Temperature calcining obtains board-like catalyst.
Embodiment 2：
By 9.5gTiCl4Be added to 104g tetraethyl orthosilicates in 150ml absolute ethyl alcohols, sequentially add 80ml deionized waters, 75ml acetic acid, the 25ml concentrated nitric acid solutions dissolved with 0.43g copper chlorides are added dropwise, react 2h in 150 DEG C, obtain uniform colloidal sol, It is cooled to room temperature and places 15h, forms gel, filtering, be first that 6.0 acetic acid-ammonium acetate buffer solution washs with pH, then washed with ethanol Wash, it is dry that xerogel, grinding obtain the TiO of 46g chlorination Copper-cladding Aluminum Bars2-SiO2Composite nanometer particle, its particle diameter are 2-8nm；
By the recessed soil mixing of 10g potassium chloride and 100g, 250ml deionized waters are added, stirring obtains suspension, then in 90 DEG C of heating Evaporating water obtains pastel, after 80 DEG C of drying to constant weights of baking oven, is ground to powdery, obtains 105g potassium chloride modified attapulgites；
Take the TiO for the 20g halogenation Copper-cladding Aluminum Bars that above-mentioned steps obtain2-SiO2Composite nanometer particle, 80g potassium halide modified attapulgites mix Close uniformly, add 100ml deionized waters, prepare paste, be then coated uniformly on titanium net skeleton, 450 DEG C of high-temperature calcinations obtain To board-like catalyst.
Embodiment 3：
By 9.5gTiCl4Be added to 62.4g tetraethyl orthosilicates in 100ml absolute ethyl alcohols, sequentially add 60ml deionized waters, 45ml acetic acid, the 15ml concentrated nitric acid solutions dissolved with 0.33g copper bromides are added dropwise, react 1.5h in 145 DEG C, obtain uniform molten Glue, it is cooled to room temperature and places 12h, forms gel, filtering, be first that 6.0 acetic acid-ammonium acetate buffer solution washs with pH, then use ethanol Washing, it is dry that xerogel, grinding obtain the TiO of 28g bromination Copper-cladding Aluminum Bars2-SiO2Composite nanometer particle, its particle diameter are 2~8nm；
By the recessed soil mixing of 8g KBrs and 100g, 250ml deionized waters are added, stirring obtains suspension, then in 70 DEG C of heating Evaporating water obtains pastel, after 80 DEG C of drying to constant weights of baking oven, is ground to powdery, obtains 102g KBr modified attapulgites；
10g aluminium isopropoxides and 25ml deionized waters are mixed, are warming up to 80 DEG C of addition 1g surfactant fatty alcohol polyoxies Vinethene, 2h is reacted, obtains white precipitate, filtered, deionized water is washed 3 times；Then will precipitation and 1ml nitric acid and 10ml go from Sub- water is warming up to 90 DEG C of reaction 3h and obtains the transparent Alumina gel that pH value is 6；
Take the TiO for the 10g bromination Copper-cladding Aluminum Bars that above-mentioned steps obtain2-SiO2Composite nanometer particle, 88g KBrs modified attapulgite and 2g Alumina gels are well mixed, and are added 100ml deionized waters, are prepared paste, be then coated uniformly on titanium net skeleton, 450 DEG C High-temperature calcination obtains board-like catalyst.
Embodiment 4：
By 9.5gTiCl4Be added to 62.4g tetraethyl orthosilicates in 100ml absolute ethyl alcohols, sequentially add 60ml deionized waters, 45ml acetic acid, the 15ml concentrated nitric acid solutions dissolved with 0.48g cupric iodides are added dropwise, react 1.5h in 145 DEG C, obtain uniform molten Glue, it is cooled to room temperature and places 12h, forms gel, filtering, be first that 6.0 acetic acid-ammonium acetate buffer solution washs with pH, then use ethanol Washing, it is dry that xerogel, grinding obtain the TiO of 28g iodate Copper-cladding Aluminum Bars2-SiO2Composite nanometer particle, its particle diameter are 2~8nm；
By the recessed soil mixing of 8g KIs and 100g, 250ml deionized waters are added, stirring obtains suspension, then in 70 DEG C of heating Evaporating water obtains pastel, after 80 DEG C of drying to constant weights of baking oven, is ground to powdery, obtains 102g KI modified attapulgites；
10g aluminium isopropoxides and 25ml deionized waters are mixed, are warming up to 80 DEG C of addition 1g surfactant fatty alcohol polyoxies Vinethene, 2h is reacted, obtains white precipitate, filtered, deionized water is washed 3 times；Then will precipitation and 1ml nitric acid and 10ml go from Sub- water is warming up to 90 DEG C of reaction 3h and obtains the transparent Alumina gel that pH value is 6；
Take the TiO for the 10g iodate Copper-cladding Aluminum Bars that above-mentioned steps obtain2-SiO2Composite nanometer particle, 88g KIs modified attapulgite and 2g Alumina gels are well mixed, and are added 100ml deionized waters, are prepared paste, be then coated uniformly on titanium net skeleton, 450 DEG C High-temperature calcination obtains board-like catalyst.
Comparative example 1：
By 9.5gTiCl4Be added to 20.8g tetraethyl orthosilicates in 35ml absolute ethyl alcohols, sequentially add 20ml deionized waters, 15ml acetic acid, 1h is reacted in 120, obtains uniform colloidal sol, be cooled to room temperature and place 10h, form gel, filtering, pH first is 6.0 acetic acid-ammonium acetate buffer solution washing, then washed with absolute ethyl alcohol, it is dry that xerogel, grinding obtain 9g TiO2-SiO2 Composite nanometer particle, its particle diameter are 2~8nm；
By the recessed soil mixing of 6g potassium chloride and 100g, 250ml deionized waters are added, stirring obtains suspension, then in 45 DEG C of heating Evaporating water obtains pastel, after 80 DEG C of drying to constant weights of baking oven, is ground to powdery, obtains 99g potassium chloride modified attapulgites；
10g aluminium isopropoxides and 25ml deionized waters are mixed, 60 DEG C is warming up to and adds 1g surfactant sodium dodecyls base two Methyl-benzyl ammonium chloride, 0.5h is reacted, obtains white precipitate, filtered, deionized water is washed 3 times；Then will precipitation and 1ml nitric acid 70 DEG C of reaction 1h, which are warming up to, with 10ml deionized waters obtains the transparent Alumina gel that pH value is 4；
Take the 9g TiO that above-mentioned steps obtain2-SiO2Composite nanometer particle, 95g potassium chloride modified attapulgite and the mixing of 3g Alumina gels Uniformly, 100ml deionized waters are added, paste is prepared, is then coated uniformly on titanium net skeleton, 450 DEG C of high-temperature calcinations obtain Board-like catalyst.
Comparative example 2：
By 9.5gTiCl4It is added in 35ml absolute ethyl alcohols, sequentially adds 20ml deionized waters, 15ml acetic acid, dropwise addition is dissolved with The 5ml concentrated nitric acid solutions of 0.085g copper chlorides, 1h is reacted in 120, obtains uniform colloidal sol, be cooled to room temperature and place 10h, formed solidifying Glue, filtering, first pH is 6.0 acetic acid-ammonium acetate buffer solution washing, then is washed with absolute ethyl alcohol, dry xerogel, is ground Mill obtains the TiO of 3.5g chlorination Copper-cladding Aluminum Bars2Nano particle, its particle diameter are 2~8nm；
By the recessed soil mixing of 6g potassium chloride and 100g, 250ml deionized waters are added, stirring obtains suspension, then in 45 DEG C of heating Evaporating water obtains pastel, after 80 DEG C of drying to constant weights of baking oven, is ground to powdery, obtains 99g potassium chloride modified attapulgites；
10g aluminium isopropoxides and 25ml deionized waters are mixed, 60 DEG C is warming up to and adds 1g surfactant sodium dodecyls base two Methyl-benzyl ammonium chloride, 0.5h is reacted, obtains white precipitate, filtered, deionized water is washed 3 times；Then will precipitation and 1ml nitric acid 70 DEG C of reaction 1h, which are warming up to, with 10ml deionized waters obtains the transparent Alumina gel that pH value is 4；
Take the TiO for the 9g chlorination Copper-cladding Aluminum Bars that above-mentioned steps obtain2Nano particle, 95g potassium chloride modified attapulgite and 3g Alumina gels mix Close uniformly, add 100ml deionized waters, prepare paste, be then coated uniformly on titanium net skeleton, 450 DEG C of high-temperature calcinations obtain To board-like catalyst.
Comparative example 3：
By 9.5gTiCl4Be added to 20.8g tetraethyl orthosilicates in 35ml absolute ethyl alcohols, sequentially add 20ml deionized waters, 15ml acetic acid, the 5ml concentrated nitric acid solutions dissolved with 0.085g copper chlorides are added dropwise, react 1h in 120, obtain uniform colloidal sol, it is cold 10h is placed to room temperature, forms gel, filtering, pH first is 6.0 acetic acid-ammonium acetate buffer solution washing, then uses absolute ethyl alcohol Washing, it is dry that xerogel, grinding obtain the TiO of 9g chlorination Copper-cladding Aluminum Bars2-SiO2Composite nanometer particle, its particle diameter are 2-8nm；
10g aluminium isopropoxides and 25ml deionized waters are mixed, 60 DEG C is warming up to and adds 1g surfactant sodium dodecyls base two Methyl-benzyl ammonium chloride, 0.5h is reacted, obtains white precipitate, filtered, deionized water is washed 3 times；Then will precipitation and 1ml nitric acid 70 DEG C of reaction 1h, which are warming up to, with 10ml deionized waters obtains the transparent Alumina gel that pH value is 4；
Take the TiO for the 9g chlorination Copper-cladding Aluminum Bars that above-mentioned steps obtain2-SiO2Composite nanometer particle, 95g potassium chloride modified attapulgite and 3g The recessed soil that Alumina gel and 95g are modified without potassium halide is well mixed, adds 100ml deionized waters, prepares paste, Ran Houjun Even to be coated on titanium net skeleton, 450 DEG C of high-temperature calcinations obtain board-like catalyst.
Using laboratory room small-sized heating furnace simulated flue gas experimental system, above-described embodiment 1-4 and comparative example 1-2 is detected The performance of the denitration demercuration catalyst of preparation.At ambient pressure, operation temperature is passed through 80g/m under conditions of being 100~150 DEG C3 Hg0, 5% O2, 10% CO2, 10ppm HCl, 750ppm NO, 2000ppm SO2, 8% H2O, nitrogen conduct Balance Air, by NH3/ NO mol ratios 1~1.2 spray into NH3As reducing agent, denitration demercuration catalysis prepared by above-described embodiment is added Agent carries out denitration demercuration, using VM3000 mercury vapourmeters, flue gas analyzer (KM950) and portable infrared detector (GASMET FT-IR Dx4000) smoke components before and after denitration demercuration are measured.Tested in laboratory room small-sized heating furnace simulated flue gas Carry out simulating denitration demercuration experiment in system, obtain following experimental result：Embodiment 1 prepare composite catalyst denitration rate be 93.5%, demercuration rate is 94.6%；Composite catalyst denitration rate prepared by embodiment 2 is 94.8%, and demercuration rate is 95.2%；Embodiment The 3 composite catalyst denitration rates prepared are 93.0%, and demercuration rate is 94.1%；Embodiment 4 prepare composite catalyst denitration rate be 92.8%, demercuration rate is 95.8%；Composite catalyst denitration rate prepared by comparative example 1 is 76.8%, and demercuration rate is 78.0%；It is right It is 72.2% than composite catalyst denitration rate prepared by embodiment 2, demercuration rate is 75.1%；Compound the urging of the preparation of comparative example 3 Agent denitration rate is 90.2%, and demercuration rate is 85.1%.

Claims (10)

  1. A kind of 1. board-like catalyst of denitration demercuration, it is characterised in that：Include the TiO of halogenation Copper-cladding Aluminum Bar2-SiO2Composite nanometer particle, Potassium halide modified attapulgite, Alumina gel and skeleton.
  2. A kind of 2. board-like catalyst of denitration demercuration according to claim 1, it is characterised in that：The halogenation Copper-cladding Aluminum Bar TiO2-SiO2Composite nanometer particle particle diameter is 2~8nm.
  3. A kind of 3. board-like catalyst of denitration demercuration according to claim 1, it is characterised in that：The copper halide is copper chloride Or copper bromide or cupric iodide, the potassium halide are potassium chloride or KBr or KI.
  4. A kind of 4. board-like catalyst of denitration demercuration according to claim 1, it is characterised in that：With TiO2The molal quantity of middle titanium For calculating benchmark, the doping of copper ion is 1%~5%.
  5. A kind of 5. board-like catalyst of denitration demercuration according to claim 1, it is characterised in that：TiO2And SiO2Mol ratio For 1:2~10.
  6. A kind of 6. board-like catalyst of denitration demercuration according to claim 1, it is characterised in that：The TiO of halogenation Copper-cladding Aluminum Bar2- SiO2Composite nanometer particle content is 2~20wt%, potassium halide modified attapulgite content is 80~95wt%, Alumina gel content be 0~ 3wt%。
  7. A kind of 7. preparation method of the board-like catalyst of denitration demercuration described in claim 1, it is characterised in that：
    （1）Sol-gal process prepares the TiO of halogenation Copper-cladding Aluminum Bar2-SiO2Composite nanometer particle；
    （2）Prepare potassium halide modified attapulgite；
    （3）Prepare Alumina gel；
    （4）By the TiO of halogenation Copper-cladding Aluminum Bar2-SiO2Composite nanometer particle, potassium halide modified attapulgite and Alumina gel are well mixed, and are prepared Paste, coated on skeleton, high-temperature calcination obtains board-like catalyst.
  8. A kind of 8. preparation method of the board-like catalyst of denitration demercuration described in claim 1, it is characterised in that：
    （1）By TiCl4It is added to tetraethyl orthosilicate in absolute ethyl alcohol, then adds deionized water and acetic acid, dropwise addition is dissolved with halogen Change the concentrated nitric acid solution of copper, react 1~2h in 120~150 DEG C, obtain uniform solvent, be cooled to room temperature and place 10~15h, shape Into gel, filtering, first washed with acetic acid-ammonium acetate buffer solution, then washed with ethanol, it is dry that xerogel, grinding obtain halogen Change the TiO of Copper-cladding Aluminum Bar2-SiO2Composite nanometer particle, its particle diameter are 2~8nm；
    （2）It is 3~5 by mass ratio:50 potassium halide and recessed soil mixing, add deionized water, stirring obtains suspension, Ran Hou 45~90 DEG C of heating evaporating waters obtain pastel, after oven drying to constant weight, are ground to powdery, obtain potassium halide be modified it is recessed Soil；
    （3）Aluminium isopropoxide and deionized water are mixed, 60~80 DEG C of addition surfactants is warming up to, reacts 0.5~2h, White precipitate is obtained, is filtered, deionized water is washed 3 times；Then precipitation and nitric acid and deionized water are warming up to 70~90 DEG C instead 1~3h is answered to obtain the transparent Alumina gel that pH value is 4~6；
    （4）The TiO for the halogenation Copper-cladding Aluminum Bar that above-mentioned steps are obtained2-SiO2Composite nanometer particle, potassium halide modified attapulgite and aluminium are molten Glue is well mixed, and is added deionized water, is prepared paste, be then coated uniformly on titanium net skeleton, high-temperature calcination obtains board-like Catalyst.
  9. A kind of 9. preparation method of the board-like catalyst of denitration demercuration according to claim 8, it is characterised in that：Step（1） In with TiO2The molal quantity of middle titanium is calculating benchmark, and the doping of copper ion is 1%~5%.
  10. A kind of 10. preparation method of the board-like catalyst of denitration demercuration according to claim 8, it is characterised in that：Step（3） Described surfactant is dodecyl benzyl dimethyl ammonium chloride or AEO.
CN201710551349.8A 2017-07-07 2017-07-07 A kind of board-like catalyst of denitration demercuration and preparation method thereof Pending CN107335453A (en)

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