CN108355680A - A kind of catalyst and preparation method thereof of Collaborative Control stationary source various pollutants in fume - Google Patents

A kind of catalyst and preparation method thereof of Collaborative Control stationary source various pollutants in fume Download PDF

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CN108355680A
CN108355680A CN201810263144.4A CN201810263144A CN108355680A CN 108355680 A CN108355680 A CN 108355680A CN 201810263144 A CN201810263144 A CN 201810263144A CN 108355680 A CN108355680 A CN 108355680A
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catalyst
sulphation
collaborative control
various pollutants
stationary source
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CN108355680B (en
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陈雄波
岑超平
刘莹
方平
唐志雄
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South China Institute of Environmental Science of Ministry of Ecology and Environment
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South China Institute of Environmental Science of Ministry of Ecology and Environment
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract

The invention discloses a kind of catalyst and preparation method thereof of Collaborative Control stationary source various pollutants in fume.The active component of the catalyst is the vanadium cerium composite oxides of sulphation, carrier is the aluminum titanium composite oxide of sulphation, the vanadium cerium composite oxides of sulphation are the complexs that vanadic anhydride, ceria, vanadic sulfate and sulfuric acid are, the aluminum titanium composite oxide of sulphation is the complex of titanium dioxide, aluminium oxide, titanyl sulfate and aluminum sulfate.Under the action of the catalyst, NOx is by NH3It is selectively reduced to nitrogen and water, CO and VOCs are by O2It is oxidized to CO2And water.Smoke gas treatment of the catalyst especially suitable for stationary sources such as fire coal, combustion gas, biomass fired boiler, waste incinerators.

Description

A kind of catalyst of Collaborative Control stationary source various pollutants in fume and its preparation Method
Technical field
The invention belongs to technical field of air pollution control, and in particular to a variety of dirts in a kind of Collaborative Control stationary source flue gas Contaminate the catalyst and preparation method thereof of object.
Background technology
Air emission source is divided into moving source and stationary source, and common moving source includes automobile and ship etc., common fixation Source includes boiler (boiler of power plant and Industrial Boiler), kiln (glass furnace, ceramic kiln, cement kiln), waste incinerator etc.. Stationary atmospheric pollution source can discharged particle, sulfur dioxide (SO2), carbon monoxide (CO), nitrogen oxides (NOx), volatility have Machine object (VOCs).Common particle purifying technology includes electrostatic precipitation, bag-type dust, cyclone dust removal etc., common SO2Purification Technology includes wet method, semidry method, dry method etc., and common NOx purification techniques includes that selective catalytic reduction (SCR), selectivity are non- Catalysis reduction (SNCR), oxidative absorption etc., common VOCs control technologies include combustion method (catalysis burning or flame combustion), inhale Attached method etc., the purification of CO generally use combustion methods.In stationary source smoke gas treatment engineering, it usually needs by various individual event pollutant controls Technology processed is combined series connection, can lead to the drawbacks such as of high cost, occupation of land is big, operation and maintenance difficulty is big, therefore develop multi-pollutant Collaborative Control technology is of great significance.
One of the method that catalysis method can be achieved on multiple pollutant Collaborative Control, using general in purifying vehicle exhaust Time.Hydrocarbon (HC) and CO concentration are higher in tail-gas from gasoline automobiles, and three-way catalyst (noble metal is main active substances) exists Can NOx, HC, CO efficiently be purified simultaneously at 500~850 DEG C, the gaseous matter for participating in reaction is NOx, HC, CO and O2. In diesel car tail gas refining, since HC concentration is relatively much lower, need that ammonia, the catalyst such as vanadium tungsten titanium, molecular sieve, silver-colored aluminium are added Can NOx and CO efficiently be purified simultaneously at 200~450 DEG C, participate in predominantly NOx, CO, NH of reaction3And O2.However, mesh Application of the preceding catalysis method in stationary source multi-pollutant Collaborative Control is few, the main reason is that lacking efficient catalyst.With For biomass boiler, the concentration of NOx, CO, VOCs are all higher in flue gas, but flue-gas temperature usually only 150~450 DEG C, it is unsatisfactory for the Applicable temperature range of ternary catalyst for automobile tail gas, and although all kinds of diesel vehicle catalyst may be implemented NOx's High-efficient purification, but VOCs and CO by ammonia and flue-gas temperature are low due to being influenced, it is difficult to it purifies.G.Busca et al. is even sent out Existing traditional commercial vanadium based denitration catalyst is not under conditions of being passed through ammonia, to the clean-up effect of certain HC and oxygen-containing VOCs It is very limited【Evaluation of V2O5–WO3–TiO2and alternative SCR catalysts in the abatement of VOCs,Catalysis Today 53(1999)525–533】.In addition, being usually contained in stationary source flue gas SO2, the substances such as K, Na, Ca, the poisoning and deactivation of catalyst, patent 201410040277.7 can be caused to find biomass boiler flue gas In catalyst poisoning inactivation be particularly acute.
Therefore, it is the key that catalysis method is used for stationary source flue gas multiple pollutant Collaborative Control to develop applicable catalyst.With Must have running temperature low (150~450 DEG C), pollutant in the catalyst of stationary source various pollutants in fume synergistic purification Purification efficiency high (inhibition for especially avoiding ammonia from aoxidizing VOCs and CO), sulfur resistive alkali resistant metal/alkaline-earth metal are poisoned simultaneously The characteristics such as ability is strong.
Invention content
To solve the disadvantage that the prior art and shortcoming, the primary purpose of the present invention is that it is solid to provide a kind of Collaborative Control Determine the catalyst of source various pollutants in fume.
Another object of the present invention is to provide the above-mentioned catalysis for Collaborative Control stationary source various pollutants in fume The preparation method of agent.
For achieving the above object, the present invention adopts the following technical scheme that：
The active component of a kind of catalyst of Collaborative Control stationary source various pollutants in fume, the catalyst is sulphur The vanadium cerium composite oxides of acidification, carrier are the aluminum titanium composite oxide of sulphation.
The vanadium cerium composite oxides of the sulphation are vanadic anhydride, ceria, vanadic sulfate and cerous sulfate Complex.
The aluminum titanium composite oxide of the sulphation is the compound of titanium dioxide, aluminium oxide, titanyl sulfate and aluminum sulfate Body.
Preferably, the mass fraction of the carrier is 80~99.5%, the mass fraction of the active component is 0.5~ 20%.
The preparation method of the above-mentioned catalyst for Collaborative Control stationary source various pollutants in fume, including following step Suddenly：
(1) cerium precursor and vanadium presoma are weighed, is dissolved in excessive oxalic acid solution, 60~80 DEG C of heating stirrings of water-bath are at breast Turbid, is then added excessive sulfuric acid solution, and 60~80 DEG C of heating stirrings of water-bath obtain sulphur at emulsion, 60~100 DEG C of dryings The vanadium cerium composite oxides of acidification；
(2) titanium dioxide and aluminium oxide are weighed, is immersed in excessive sulfuric acid solution, is stirred 4 hours, is filtered, 60~100 DEG C drying, it is last 500~700 DEG C roast 1~4 hour, obtain the aluminum titanium composite oxide of sulphation；
(3) grind into powder after mixing the vanadium cerium composite oxides of sulphation and the aluminum titanium composite oxide of sulphation, It adds in excessive water, stirs 4 hours, 60~100 DEG C of drying, last 350~550 DEG C roast 2~6 hours.
Preferably, when preparing the vanadium cerium composite oxides of sulphation in step (1), the molar ratio control of V/Ce 0.2~ 5。
Preferably, cerium precursor described in step (1) be cerous nitrate, cerous carbonate, cerium oxalate, one kind in ceria or It is a variety of.
Preferably, vanadium presoma described in step (1) is one or both of ammonium metavanadate or vanadic anhydride.
Preferably, the sulfuric acid solution concentration described in step (1) and (2) is 0.05~2.5mol/L.
Preferably, when preparing the aluminum titanium composite oxide of sulphation in step (2), the molar ratio control of Ti/Al 1~ 50。
Preferably, the commercial product of various crystal forms, titanium dioxide can be selected in titanium dioxide and aluminium oxide described in step (2) Specific surface area is not less than 40m2/ g, alumina ratio surface area are not less than 100m2/g。
Catalyst for stationary source various pollutants in fume synergistic purification must still have when flue-gas temperature is relatively low Excellent redox characteristic, need to be in NH3In the presence of can realize the reduction reaction of NOx and the oxygen of CO and VOCs simultaneously Change reaction.Vanadic anhydride, ceria, vanadic sulfate and cerous sulfate form dynamics model in catalyst surface, avoid Competitions of the differential responses to single-activity center.It can be efficiently in the active point of vanadic anhydride, ceria and cerous sulfate It is catalyzed NOx and NH3Between SCR reactions, can efficient catalytic CO and VOCs in the active point of vanadic anhydride and vanadic sulfate Oxidation reaction, and ceria can provide a large amount of chemically adsorbing oxygen for the oxidation reaction of CO and VOCs.
Catalyst for stationary source various pollutants in fume synergistic purification must also have stronger sulfur resistive alkali resistant gold Category/alkaline-earth metal poisoning capability.SO2Caused catalyst poisoning is mostly derived from after active component generates sulfate and inactivates, and SO2With NH3The sulphur ammonium mineralization generated is reacted in catalyst surface, hinders the progress of catalysis reaction.Due to the sulfate of vanadium and cerium Still there is preferable catalytic activity, and cerium oxide can accelerate the decomposition of sulphur ammonium salt, therefore catalyst has excellent resistance to SO_2 Energy.Catalyst poisoning caused by alkali metal/alkaline-earth metal is mostly derived from the destruction of acidic site and changing for active metal component form Become.Since the carrier of catalyst has carried out sulphation processing, surface acidity substantially enhances, and alleviates alkali metal/alkaline-earth metal Destruction to acidity of catalyst position, and the sulfate radical introduced can be combined with alkali metal/alkaline-earth metal, them is prevented to contact activity Metal component, therefore catalyst has excellent alkali resistant metal/alkaline-earth metal poisoning capability.
Compared with prior art, the present invention has the following advantages and beneficial effects：
(1) under the action of catalyst of the present invention, NOx is by NH3It is selectively reduced to nitrogen and water, CO and VOCs are by O2Oxygen Turn to CO2And water；For catalyst of the present invention at 280~450 DEG C, the purification efficiency to NOx is 95%~100%, to the net of CO Change efficiency and be higher than 90%~100%, 85%~100% is higher than to the purification efficiency of VOCs；Catalyst of the present invention is 150~280 DEG C when, be 30%~95% to the purification efficiency of NOx, 20%~90% be higher than to the purification efficiency of CO, the purification of VOCs is imitated Rate is higher than 20%~85%.
(2) catalyst disclosed by the invention can purify multiple pollutant simultaneously, can reduce treatment facility unit, reduce and throw Cost and operating cost are provided, reduces and takes up an area.
(3) catalyst disclosed by the invention has excellent sulfur resistive alkali resistant metal/alkaline-earth metal poisoning capability, service life It is very long.
(4) catalyst disclosed by the invention is solid especially suitable for fire coal, combustion gas, biomass fired boiler, waste incinerator etc. Determine the smoke gas treatment in source.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of catalyst of Collaborative Control stationary source various pollutants in fume, active component are that the vanadium cerium of sulphation is multiple Oxide is closed, carrier is the aluminum titanium composite oxide of sulphation, and preparation method is：
(1) 2.52g cerous nitrates and 0.51g ammonium metavanadates are weighed, is dissolved in excessive oxalic acid solution, 60 DEG C of heating stirrings of water-bath At emulsion, it being then added the sulfuric acid solution of excessive 0.25mol/L, 60 DEG C of heating stirrings of water-bath are at emulsion, 80 DEG C of dryings, Obtain the vanadium cerium composite oxides of sulphation.
(2) 8.516g titanium dioxide and 0.5427g aluminium oxide are weighed, the sulfuric acid solution of excessive 0.25mol/L is immersed in In, it stirs 4 hours, filters, 80 DEG C of drying, last 600 DEG C roast 4 hours, obtain the aluminum titanium composite oxide of sulphation.
(3) grind into powder after mixing the vanadium cerium composite oxides of sulphation and the aluminum titanium composite oxide of sulphation, It adds in excessive water, stirs 4 hours, 80 DEG C of drying, last 450 DEG C roast 2 hours.Catalyst activity component quality obtained Score is about 12.5%.
In laboratory simulation coal-burning boiler, the flue gas containing multiple pollutant is generated.Take obtained, 40~60 mesh catalysis Agent 0.5g, is put into fixed bed reactors, then introduces flue gas and ammonia；After catalysis is reacted, NOx, CO and VOCs at 320 DEG C Purification efficiency reach purification efficiency in 100%, 48h and do not decline.
Embodiment 2
A kind of catalyst of Collaborative Control stationary source various pollutants in fume, active component are that the vanadium cerium of sulphation is multiple Oxide is closed, carrier is the aluminum titanium composite oxide of sulphation, and preparation method is：
(1) 2.52g cerium oxide and 0.2667g vanadic anhydrides are weighed, is dissolved in excessive oxalic acid solution, 80 DEG C of heating of water-bath Emulsion is stirred into, is then added the sulfuric acid solution of excessive 0.05mol/L, 80 DEG C of heating stirrings of water-bath are at emulsion, 100 DEG C It is dry, obtain the vanadium cerium composite oxides of sulphation.
(2) 8.516g titanium dioxide and 10.853g aluminium oxide are weighed, the sulfuric acid solution of excessive 0.05mol/L is immersed in In, it stirs 4 hours, filters, 100 DEG C of drying, last 700 DEG C roast 1 hour, obtain the aluminum titanium composite oxide of sulphation.
(3) grind into powder after mixing the vanadium cerium composite oxides of sulphation and the aluminum titanium composite oxide of sulphation, It adds in excessive water, stirs 4 hours, 100 DEG C of drying, last 550 DEG C roast 6 hours.Catalyst activity component matter obtained It is about 9.5% to measure score.
In laboratory simulation biomass boiler, the flue gas containing multiple pollutant is generated.Obtained, 40~60 purposes are taken to urge Agent 0.5g, is put into fixed bed reactors, then introduces flue gas and ammonia；After catalysis is reacted, NOx purifications effect at 250 DEG C Rate, which reaches 85%, CO purification efficiencies and reaches the purification efficiency of 80%, VOCs, to be reached purification efficiency in 65%, 48h and does not decline.
Embodiment 3
A kind of catalyst of Collaborative Control stationary source various pollutants in fume, active component are that the vanadium cerium of sulphation is multiple Oxide is closed, carrier is the aluminum titanium composite oxide of sulphation, and preparation method is：
(1) 2.6g cerium oxalates and 2.79g ammonium metavanadates are weighed, is dissolved in excessive oxalic acid solution, 70 DEG C of heating stirrings of water-bath At emulsion, the sulfuric acid solution of excessive 1mol/L is then added, 70 DEG C of heating stirrings of water-bath are obtained at emulsion, 60 DEG C of dryings To the vanadium cerium composite oxides of sulphation.
(2) 8.5g titanium dioxide and 1g aluminium oxide are weighed, is immersed in the sulfuric acid solution of excessive 1mol/L, stirring 4 is small When, it filters, 60 DEG C of drying, last 500 DEG C roast 2 hours, obtain the aluminum titanium composite oxide of sulphation.
(3) grind into powder after mixing the vanadium cerium composite oxides of sulphation and the aluminum titanium composite oxide of sulphation, It adds in excessive water, stirs 4 hours, 60 DEG C of drying, last 350 DEG C roast 4 hours.Catalyst activity component quality obtained Score is about 20%.
In laboratory simulation waste incineration, the flue gas containing multiple pollutant is generated.Take obtained, 40~60 mesh catalysis Agent 0.5g, is put into fixed bed reactors, then introduces flue gas and ammonia；After catalysis is reacted, NOx purification efficiencies at 200 DEG C Reach 70%, CO purification efficiencies and reach the purification efficiency of 50%, VOCs and reaches purification efficiency in 45%, 48h and do not decline.
Embodiment 4
A kind of catalyst of Collaborative Control stationary source various pollutants in fume, active component are that the vanadium cerium of sulphation is multiple Oxide is closed, carrier is the aluminum titanium composite oxide of sulphation, and preparation method is：
(1) 2.52g cerous carbonates and 0.51g ammonium metavanadates are weighed, is dissolved in excessive oxalic acid solution, 70 DEG C of heating stirrings of water-bath At emulsion, it being then added the sulfuric acid solution of excessive 0.25mol/L, 70 DEG C of heating stirrings of water-bath are at emulsion, 90 DEG C of dryings, Obtain the vanadium cerium composite oxides of sulphation.
(2) 7g titanium dioxide and 0.38g aluminium oxide are weighed, is immersed in the sulfuric acid solution of excessive 2.5mol/L, stirring 4 Hour, it filters, 90 DEG C of drying, last 600 DEG C roast 4 hours, obtain the aluminum titanium composite oxide of sulphation.
(3) grind into powder after mixing the vanadium cerium composite oxides of sulphation and the aluminum titanium composite oxide of sulphation, It adds in excessive water, stirs 4 hours, 70 DEG C of drying, last 400 DEG C roast 2 hours.Catalyst activity component quality obtained Score is about 14.5%.
In laboratory simulation biomass combustion, the flue gas containing multiple pollutant is generated.Obtained, 40~60 purposes are taken to urge Agent 0.5g, is put into fixed bed reactors, then introduces flue gas and ammonia；After catalysis is reacted, at 320 DEG C NOx, CO and The purification efficiency of VOCs reaches purification efficiency in 100%, 48h and does not decline.
Embodiment 5
A kind of catalyst of Collaborative Control stationary source various pollutants in fume, active component are that the vanadium cerium of sulphation is multiple Oxide is closed, carrier is the aluminum titanium composite oxide of sulphation, and preparation method is：
(1) 0.252g cerous nitrates and 0.12g ammonium metavanadates are weighed, is dissolved in excessive oxalic acid solution, 60 DEG C of heating of water-bath are stirred Emulsion is mixed, the sulfuric acid solution of excessive 0.25mol/L is then added, for 60 DEG C of heating stirrings of water-bath at emulsion, 80 DEG C dry It is dry, obtain the vanadium cerium composite oxides of sulphation.
(2) 35.1g titanium dioxide and 0.96g aluminium oxide are weighed, is immersed in the sulfuric acid solution of excessive 0.5mol/L, stirs It mixes 4 hours, filters, 80 DEG C of drying, last 600 DEG C roast 4 hours, obtain the aluminum titanium composite oxide of sulphation.
(3) grind into powder after mixing the vanadium cerium composite oxides of sulphation and the aluminum titanium composite oxide of sulphation, It adds in excessive water, stirs 4 hours, 80 DEG C of drying, last 450 DEG C roast 5 hours.Catalyst activity component quality obtained Score is about 0.5%.
In laboratory simulation biomass combustion, the flue gas containing multiple pollutant is generated.Obtained, 40~60 purposes are taken to urge Agent 0.5g, is put into fixed bed reactors, then introduces flue gas and ammonia；After catalysis is reacted, at 320 DEG C NOx, CO and The purification efficiency of VOCs reaches purification efficiency in 100%, 48h and does not decline.
Embodiment 6
A kind of catalyst of Collaborative Control stationary source various pollutants in fume, active component are that the vanadium cerium of sulphation is multiple Oxide is closed, carrier is the aluminum titanium composite oxide of sulphation, and preparation method is：
(1) 3g cerous nitrates and 1g ammonium metavanadates are weighed, is dissolved in excessive oxalic acid solution, 60 DEG C of heating stirrings of water-bath are at milkiness Liquid, is then added the sulfuric acid solution of excessive 0.5mol/L, and 60 DEG C of heating stirrings of water-bath obtain sulphur at emulsion, 80 DEG C of dryings The vanadium cerium composite oxides of acidification.
(2) 10g titanium dioxide and 2g aluminium oxide are weighed, is immersed in the sulfuric acid solution of excessive 0.5mol/L, stirring 4 is small When, it filters, 80 DEG C of drying, last 600 DEG C roast 4 hours, obtain the aluminum titanium composite oxide of sulphation.
(3) grind into powder after mixing the vanadium cerium composite oxides of sulphation and the aluminum titanium composite oxide of sulphation, It adds in excessive water, stirs 4 hours, 80 DEG C of drying, last 450 DEG C roast 2 hours.Catalyst activity component quality obtained Score is about 12.5%.
In laboratory simulation biomass combustion, the flue gas containing multiple pollutant is generated.Obtained, 40~60 purposes are taken to urge Agent 0.5g, is put into fixed bed reactors, then introduces flue gas and ammonia；After catalysis is reacted, at 320 DEG C NOx, CO and The purification efficiency of VOCs reaches purification efficiency in 100%, 48h and does not decline.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications, Equivalent substitute mode is should be, is included within the scope of the present invention.

Claims (9)

1. a kind of catalyst of Collaborative Control stationary source various pollutants in fume, which is characterized in that the work of the catalyst Property group be divided into the vanadium cerium composite oxides of sulphation, carrier is the aluminum titanium composite oxide of sulphation, the vanadium of the sulphation Cerium composite oxides are the complex of vanadic anhydride, ceria, vanadic sulfate and cerous sulfate, the titanium aluminium of the sulphation Composite oxides are the complexs of titanium dioxide, aluminium oxide, titanyl sulfate and aluminum sulfate.
2. the catalyst of Collaborative Control stationary source various pollutants in fume according to claim 1, which is characterized in that institute The mass fraction for stating carrier is 80~99.5%, and the mass fraction of the active component is 0.5~20%.
3. the preparation method of the catalyst of Collaborative Control stationary source various pollutants in fume as claimed in claim 1 or 2, special Sign is, includes the following steps：
(1) cerium precursor and vanadium presoma are weighed, is dissolved in excessive oxalic acid solution, 60~80 DEG C of heating stirrings of water-bath are at milkiness Liquid, is then added excessive sulfuric acid solution, and 60~80 DEG C of heating stirrings of water-bath obtain sulfuric acid at emulsion, 60~100 DEG C of dryings The vanadium cerium composite oxides of change；
(2) titanium dioxide and aluminium oxide are weighed, is immersed in excessive sulfuric acid solution, is stirred 4 hours, is filtered, 60~100 DEG C of bakings Dry, last 500~700 DEG C roast 1~4 hour, obtain the aluminum titanium composite oxide of sulphation；
(3) grind into powder after mixing the vanadium cerium composite oxides of sulphation and the aluminum titanium composite oxide of sulphation, then add Enter in excessive water, stirs 4 hours, 60~100 DEG C of drying, last 350~550 DEG C roast 2~6 hours.
4. the preparation method of the catalyst of Collaborative Control stationary source various pollutants in fume according to claim 3, It is characterized in that, when preparing the vanadium cerium composite oxides of sulphation in step (1), the molar ratio of V/Ce is controlled 0.2~5.
5. the preparation method of the catalyst of Collaborative Control stationary source various pollutants in fume according to claim 3, It is characterized in that, cerium precursor described in step (1) is one or more in cerous nitrate, cerous carbonate, cerium oxalate, ceria.
6. the preparation method of the catalyst of Collaborative Control stationary source various pollutants in fume according to claim 3, It is characterized in that, vanadium presoma described in step (1) is one or both of ammonium metavanadate or vanadic anhydride.
7. the preparation method of the catalyst of Collaborative Control stationary source various pollutants in fume according to claim 3, It is characterized in that, the sulfuric acid solution concentration described in step (1) and (2) is 0.05~2.5mol/L.
8. the preparation method of the catalyst of Collaborative Control stationary source various pollutants in fume according to claim 3, It is characterized in that, when preparing the aluminum titanium composite oxide of sulphation in step (2), the molar ratio of Ti/Al is controlled 1~50.
9. the preparation method of the catalyst of Collaborative Control stationary source various pollutants in fume according to claim 3, It is characterized in that, titanium dioxide specific surface area described in step (2) is 40m2/ g or more, alumina ratio surface area are 100m2/ g with On.
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