CN104941630A - Low-temperature high-activity flue gas denitrification catalyst and preparation thereof - Google Patents
Low-temperature high-activity flue gas denitrification catalyst and preparation thereof Download PDFInfo
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Abstract
The invention relates to a low-temperature high-activity flue gas denitrification catalyst and preparation thereof. According to the catalyst, a carbon-base material serves as a carrier and carries one or more metal active components of active Al2O3, Mn, Cu and Fe and one or two of rare earth active components of Ce and La. The content of the carbon-base carrier ranges from 35% to 65%, the carrying content of the Al2O3 ranges from 2% to 5% by the content of the aluminum element, the content of the metal active components ranges from 13% to 26% by the content of the metal elements, and the carrying content of the rare earth active components ranges from 20% to 39% by the content of the rare earth elements. According to the catalyst, the carbon-base material is activated through dilute nitric acid and then is coated with aluminum oxide sol, the metal active components and the rare earth active components are carried, then drying and sintering are carried out in the inert atmosphere, and the catalyst is obtained. The catalyst high in flue gas denitrification catalytic efficiently at the low temperature (90-120 DEG C) and not likely to cause poisoning and failures is obtained. The catalyst is low in production cost, simple in production technology and especially suitable for thermal power plants, steel plants, sintering plants and other enterprises with heavy fuel gas emission.
Description
Technical field
The present invention relates to a kind of catalyst of field of Environment Protection, is mainly used in flue gas denitration field, is specifically related to a kind of efficient cryogenic denitrating catalyst and preparation method thereof.
Background technology
Along with the fast development of China's economic, the consumption of Coal Energy Source also grows with each passing day, the sulfur and nitrogen oxides produced in coal burning process is one of primary pollution source causing atmosphere pollution, and therefore, efficient, rational control discharge flue gas becomes the grand strategy of current modernization development.
Flue gas desulfurization (FGD), limestone/gypsum method is because applicable coal is wide, stable operation, operating flexibility are good, desulfurizing agent is easy to get and becomes the flue gas desulfurization technique that current world wide is most widely used, technology is the most ripe.
Denitrating flue gas is NO
xbe reduced to N
2process, mainly contain: selective catalytic reduction, non-selective catalytic reduction, sour absorption process, alkali absorb method, absorption method, gas ions activation method etc.Domestic and international researcher also developed microbiological treatment NO
xmethod.In numerous process, SCR (SCR) is the most effective process route of current denitrating flue gas.
SCR technology is under catalyst action, utilizes reducing agent NH
3(liquefied ammonia, ammoniacal liquor, urea etc.) and the NO in flue gas
xreaction, by the NO in flue gas
xbe reduced to the process of nitrogen and water.But this catalyst needs reactor to be arranged between boiler economizer outlet and air preheater entrance, and the reaction temperature of existing market commercial catalyst is higher, and generally between 320-400 DEG C, denitration efficiency is high, and security of system is stablized, but de-NO
xdevice must before dedusting and desulfurization, and this causes SO in flue gas
xincrease the weight of the poisoning of catalyst and blocking with dust, reduce catalytic activity.
China's SCR technical research is started late, and denitrating flue gas market is almost monopolized by foreign technology.Therefore, research and develop a kind of catalyst that efficiently can play denitration performance at low temperatures and seem particularly important.Efficient cryogenic removes NO
xdevice directly can be positioned over dedusting and de-SO
xafter device.NO is removed at present about low-temperature flue gas
xthe research of catalyst is many, mainly MnO
x/ Al
2o
3, CuO/AC, Fe
2o
3/ AC, Al
2o
3the catalyst such as the metal halogen compound supported, activated coke.Wherein, though activated coke as catalyst research Germany and Japan drop into commercial Application, but mainly under lower than 80 DEG C of conditions, rely on self absorption property to carry out denitration.For in most of boiler export temperature 100 ~ 280 DEG C of temperature ranges, the catalytic activity of activated coke is very low, and is suitable for the little (400h of air speed
-1), operation operating cost is high.
Existing catalyst for denitrating flue gas mainly contains CuO/Al
2o
3, V
2o
5/ TiO
2, V
2o
5/ AC etc.CuO as active constituent loading in Al
2o
3on, remove sulfur dioxide in flue gas and nitrogen oxide is furtherd investigate simultaneously, the SO in flue gas can be removed simultaneously
2and NO
x.Between the adsorption temp of this catalyst is 600-750 DEG C, desulphurization denitration rate all can reach more than 90%, does not produce solid-state and liquid secondary pollution, can produce thiamines byproduct, and catalyst can be recycled simultaneously.But after long-play, CuO/Al
2o
3surface can cause SO due to aluminium oxide acidifying
2removal ability decline, during application require temperature higher, need constantly to heat device, process costs is higher.V in addition
2o
5/ TiO
2, V
2o
5the research of the denitrating catalysts such as/AC also receives much concern.Take cordierite honeycomb ceramic as the V that carrier obtains
2o
5/ TiO
2/ cordierite catalyst, the TiO of employing
2easily in preparation process, crystal transfer occur thus reduce yield rate, denitration efficiency reduction, the alkali metal under the condition of denitration simultaneously in flue gas easily makes catalyst poisoning inactivation.
Active carbocoal, as the ideal carrier of low-temperature dry catalyst for denitrating flue gas, as described in CN1475305A, adopts equi-volume impregnating by V
2o
5to be carried on semi-coke forming, and by Catalyst packing in fixed bed reactors, denitration temperature between 150 ~ 250 DEG C, air speed 500 ~ 5000h
-1.V
2o
5/ AC catalyst reduces obviously by the denitration efficiency that affects of desulfurization product in flue gas, is not suitable for industrial applications.Therefore, a kind of low temperature, efficient and the denitrating catalyst of sulfur poisoning-resistant is imperative is studied.
The shortcoming existed about efficient cryogenic denitrating catalyst in prior art mainly has in following 2:
A) denitration activity is low;
B) operating temperature is higher.
The present invention, in order to solve the problems of the technologies described above, this invention exploits a kind of for efficient removal NO under low temperature
xcatalyst.Denitration efficiency is high, not easily there is poison deactivation and technique simple.Specifically, the invention provides following technical scheme.
Containing a catalyst for denitrating flue gas for rare earth, it is characterized in that, take carbon based material as carrier, load has Al
2o
3, any one or the two the active rare-earth component that is selected from one or more metal active constituents in Mn, Cu and Fe and is selected from Ce and La.Wherein, the mass content of each component is as follows: charcoal base carrier content is 35-65%, preferably 40-60%, described Al
2o
3with aluminium element content meter loading content be 2-5%, preferred 3-4%, for described metal active constituent in metal element content loading content be 13-26%, preferred 21-25%, described active rare-earth component in ree content loading content be 20-39%, preferred 30-39%.
Preferably, for described catalyst, wherein, described carbon based material is activation semicoke.
Preferably, for described catalyst, wherein, described activation semicoke hole density is 100-300 hole/inch
2, specific area is 100-500m
2/ g.
In addition, the present invention also provides the preparation method of catalyst described in above-mentioned any one, and it comprises the steps:
A) 10%-25% nitric acid is used to carry out ultrasonic activation, ultrasonic immersing under room temperature, drying the carbon based material after shaping;
B) Al
2o
3the load of colloidal sol: on a) step basis, the ultrasonic load Al of activation half defocused excessive infusion process
2o
3colloidal sol, then carries out drying, calcining is fixing;
C) load of metal active constituent: by for load metal M n/Cu/Fe in one or several metallic compounds be made into metal compound solution, regulate pH to 4-6, b) step basis excessively impregnated in this solution by ultrasonic under active carbocoal room temperature, calcine after suction filtration, freeze-day with constant temperature;
D) load of active rare-earth component: carry out the load of active rare-earth component on c) step basis, active rare-earth component is pre-configured to the aqueous solution, ultrasonic excessive dip loading is also dry;
E) by gained sample in d) process, calcine in an inert atmosphere, inert gas used is N
2or He, calcining heat is 350-500 DEG C.
Preferably, for described preparation method, wherein, step b) in, Al used
2o
3the concentration of sol solution is for containing Al
2o
3quality 1-5%.
Preferably, for described preparation method, wherein, step c) in, metal active constituent used is metallic compound aqueous solution form, contains metal active constituent 5%-10% in this solution of metal active constituent.
Preferably, for described preparation method, wherein, steps d) in, active rare-earth component used is rare earth compound aqueous solution form, contains metal active constituent 0.5%-2%, the aqueous solution of preferred 1.0-1.5% in this solution of metal active constituent.
Preferably, for described preparation method, wherein, described step b) in, described ultrasonic load time is 2-3h, and described drying is 110 DEG C of conditions, and described calcining heat is 350-450 DEG C.
Preferably, for described preparation method, wherein, described step c) in, by the aqueous solution of metal described in described mixed solution, described condition pH value is regulated by citric acid.
Preferably, for described preparation method, wherein, described steps d) in, also comprise and add acid ligand Isosorbide-5-Nitrae-phthalic acid, the mixed in molar ratio of it being pressed in advance 1:1.0 ~ 2.0, preferably 1:1.0-1.5 with rare earth element is even, ultrasonic load.
Preferably, for described preparation method, wherein, described step e) in, described calcination time 2-4h.
Preferably, for described preparation method, wherein, described step c) in, described metal compound solution refers to manganese nitrate/copper nitrate or iron nitrate aqueous solution form; Described steps d) in, described active rare-earth component is selected from cerous nitrate or cerium oxide, or lanthanum nitrate or lanthana.
Preferably, for described preparation method, wherein, described step c) in, described forging is carried out at temperature 350-500 DEG C.
In addition, the present invention also provides described catalyst for flue gas denitration, or the application in denitration simultaneously and desulfurization.
Preferably, for described application, described denitration is carried out at 90 ~ 120 DEG C.
Preferably, for described application, described denitration rate is greater than 90%.
That is, this catalyst of the present invention is by activating carbon based material with dust technology, and then coating alumina colloidal sol, carried metal active component and active rare-earth component, finally carry out drying under an inert atmosphere, calcining obtains.When present invention obtains a kind of low temperature (90 ~ 120 DEG C), flue gas denitration catalyst efficiency is high and the catalyst of poison deactivation not easily occurs.Production cost is low, production technology is simple, is particularly useful for the large exhaust gas volumn discharge such as thermal power plant, steel plant and sintering plant enterprise.
Specifically, the denitrating catalyst tool prepared by method of the present invention is had the following advantages:
1, denitration activity is high
Conventional commercial denitrating flue gas reaction temperature, generally between 180 DEG C-400 DEG C, obviously reduces lower than denitration efficiency when 180 DEG C, and this denitrating catalyst serviceability temperature is 90 ~ 120 DEG C, and in this temperature range, denitration efficiency can reach more than 93%.Catalyst choice is high, and the tail gas after process can be directly emptying.
2, denitration reaction temperature is low
Conventional commercial denitrating flue gas reaction temperature is generally between 320 DEG C-400 DEG C, and this denitrating catalyst serviceability temperature is 90 ~ 120 DEG C, in this temperature range, and NO
xremoval efficiency can reach more than 93%, and under the condition of temperature lower than 150 DEG C, NO
xremoval efficiency keeps almost constant.
3, technique is simple
Tradition flue gas denitration reactor need be placed between boiler economizer outlet and air preheater entrance, after this denitrating catalyst can be directly used in conventional smoke desulfurization, without the need to heating.Generate without secondary pollutions such as waste water, solid waste, dust.
Summary of the invention
Accompanying drawing explanation
Fig. 1 is the Summarization for Preparation Methods figure of denitrating catalyst of the present invention;
Fig. 2 is the denitrating catalyst preparation flow figure of the preferred embodiment of the invention.
Detailed description of the invention
Denitrating catalyst of the present invention, makes mainly through the technique shown in Fig. 1, namely first activates semicoke, then apply Al
2o
3, then coating active component thereon, carries out drying and calcining and obtains.
For solving the problems of the technologies described above, the preferred embodiment of the invention is specific as follows:
(1) containing the efficient cryogenic catalyst for denitrating flue gas of rare earth, it is characterized in that: be catalyst carrier with carbon based material, load has Al
2o
3, with one or more in metal M n, Cu, Fe for active component, separately add in Rare-Earth Ce, La one or several etc. as active component auxiliary agent, the mass content of each component is as follows: wherein carbon based material 35%-65%, preferably 40-60%, described Al
2o
3with aluminium element content meter loading content be 2-5%, preferred 3-4%, for described metal active constituent in metal element content loading content be 13-26%, preferred 21-25%, described active rare-earth component in ree content loading content be 20-39%, preferred 30-39%.
Wherein the load of each active component is respectively by by Al
2o
3sol solution, metal active constituent solution and active rare-earth component solution are carried in carbon-based supports and make this catalyst carrier.
Wherein, for the base carrier of charcoal described in the present invention, in every this area, the various semicokes from colliery formation of various routine all may be used in the present invention, the semicoke that such as brown coal or anthracite are formed.
Preferably, the concentration of polymer solution (mass fraction) prepared when being carried on carrier and charcoal base carrier content used as follows:
Charcoal base carrier content is 85-90%;
Metal active constituent 5%-10%;
Active rare-earth component auxiliary agent 0.5%-2%;
Al
2o
3the content of solution is 1-5%.
(2) the preferred material feature of above-mentioned (1) described catalyst is as follows:
A) carbon based material described in mainly uses active carbocoal, and specific area is 100-500m
2/ g;
B) slaine described in is solubility manganese nitrate;
C) the active rare-earth auxiliary agent described in is cerous nitrate and lanthanum nitrate;
(3) by (1), preferred catalyst described in (2), concrete preparation process as shown in Figure 1, Fig. 1 is preparation method's summary figure of denitrating catalyst of the present invention, and it comprises semicoke activation, coating alumina solution, load active component and drying and calcining; Specifically details are as follows:
A) the semicoke 10%-25% nitric acid after shaping is carried out ultrasonic activation, ultrasonic immersing 2-4h under room temperature, then constant temperature 110 DEG C of dry 1.5-3h;
B) on a) step basis, the semicoke after activation process carries out excessive dip loading Al
2o
3colloidal sol, institute load Al
2o
3the mass fraction of sol solution is 1-5%, preferably 1.5%-5%, most preferably 1.5-2.5%, dry and calcine (preferred calcination temperature is 350-450 DEG C) 2-3h and fix under 110 DEG C of conditions after ultrasonic load 2-3h;
C) (in Mn element, solution concentration is 5-10%, preferably 7-10% the compound of metal M n used to be made into certain mass mark; Also can with Cu or Fe compound solution) Mn/H
2o mixed solution, lemon acid for adjusting pH, to 4-6, ultrasonic excessive dipping is carried out under room temperature in b) step basis, calcining (preferred calcination temperature is 350-500 DEG C) 1.5-3h after dry under constant temperature 110 DEG C of conditions;
D) on c) step basis, the load of active rare-earth component is carried out.Rare earth adopts rare earth nitrades, is configured to the aqueous solution that mass fraction is 0.5-2%, preferably 0.5-1.5%, through ultrasonic excessive dip loading and drying;
E) selectable, carrying out steps d) in, also preferably add acid ligand, acid ligand used is Isosorbide-5-Nitrae-phthalic acid simultaneously, mixes in advance with active rare-earth component in 1:1.0 ~ 2.0, preferred 1:1.0-1.5 ratio;
F) by gained sample in d) process, carry out calcining 2-4h in an inert atmosphere, inert gas used is N
2or He, calcining heat is 350-500 DEG C.
G) gained catalyst carries out denitrating flue gas Activity determination under 90 ~ 120 DEG C of conditions, NO
xremoval efficiency is greater than 90%.
Illustrate how catalyst of the present invention is prepared below by specific embodiment, as shown in Figure 2, preparation method's flow chart of the denitrating catalyst of embodiments of the invention 1-4; Embodiment that specifically details are as follows:
Embodiment 1:
(purchased from producer: the De Run cleaning unit Co., Ltd in Yulin city, following examples are identical all therewith, and it contains following moisture in mass: 17.96 by mechanical-moulded for commercially available semicoke; Ash content 20.12; Volatile matter 29.19; Fixed carbon 50.69; Full sulphur 1.20), hole density 100-300 holes/inch
2.Get 20% dust technology excessive dipping semicoke carrier, impregnating active 2h, ultrasonic under room temperature (NingBo XinZhi Biology Science Co., Ltd SB-25-12DT, 20-80KHz) floods 2h, then constant temperature 110 DEG C of dry 2h; On this basis, the semicoke after activation process carries out excessive dip loading Al
2o
3pre-configured mass fraction is the Al of 1% by colloidal sol
2o
3the ultrasonic load 2h of solution, 110 DEG C of dryings afterwards are also calcined 3h and are fixed under 400 DEG C of conditions; Soluble M n salt is configured to the aqueous solution that mass fraction is 5% (in Fe content), described soluble M n salt is manganese nitrate.By above-mentioned manganese nitrate solution ultrasonic immersing 2h at 30 DEG C, calcine 3h under constant temperature 110 DEG C of dry 2h 450 DEG C of conditions afterwards; Solubility cerium salt is configured to the aqueous solution that mass fraction is 2%, and described solubility Ce salt is Ce (NO
3)
36H
2o, citric acid adjust ph is 4, and through ultrasonic excessive dip loading 2h, 110 DEG C of dry 2h also calcine 3h under 450 DEG C of conditions; Calcining is at N
2under atmosphere.
Wherein, Al element, metal M n element and the load capacity of Rare-Earth Ce element on carrier are measured (Brooker bruker, signal processing linit) by X-ray energy spectrometer EDS, and three's load capacity is respectively 2.10%, 21.3% and 32.5%.The evaluating catalyst test macro that above-mentioned gained catalyst is built in laboratory is carried out NO_x removal performance test, obtains NO
xconversion ratio is 91%.
Embodiment 2:
By mechanical-moulded for commercially available semicoke, hole density is 100-300 holes/inch
2, through 10% dust technology activation, ultrasonic immersing 4h under room temperature, then constant temperature 110 DEG C of dry 2h; On this basis, the semicoke after activation process carries out excessive dip loading Al
2o
3colloidal sol, Al used
2o
3for mass fraction is 1.5%, dry 2h calcine 2h fix under temperature 400 DEG C of conditions under 110 DEG C of conditions after ultrasonic load 2h; Solubility manganese nitrate is configured in the aqueous solution of its mass fraction 7% of Fe content, carries out ultrasonic immersing 3h on the basis of the above at room temperature 30 DEG C, and constant temperature 110 DEG C of dry 2h also calcine 3h under 450 DEG C of conditions; By Ce (NO
3)
36H
2o and acid ligand used Isosorbide-5-Nitrae-phthalic acid, press 1:1.5 mixed in molar ratio in advance evenly, be configured to containing Ce (NO
3)
3mass fraction be the aqueous solution of 2%, citric acid adjust ph is 6, and through ultrasonic excessive dip loading 2h, 110 DEG C of dry 3h also calcine 2h under 450 DEG C of conditions; Calcining is at N
2carry out under atmosphere;
Wherein, Al element, metal M n element and the load capacity of Rare-Earth Ce element on carrier are measured by EDS, and three's load capacity is respectively 3.05%, 17.6% and 38.4%.The evaluating catalyst test macro that above-mentioned gained catalyst is built in laboratory is carried out NO_x removal performance test, obtains NO
xconversion ratio is 93%.
Embodiment 3:
By mechanical-moulded for commercially available semicoke, hole density is 100-300 hole/inch
2, get the excessive dipping semicoke of 25% dust technology and activate, ultrasonic immersing activation 3h, then constant temperature 110 DEG C of dry 2h under room temperature; Semicoke after activation carries out excessive dip loading Al
2o
3colloidal sol, Al used
2o
3for mass fraction is 2%, dry 3h calcine 3h fix under 450 DEG C of conditions under 110 DEG C of conditions after ultrasonic load 2h; Carrier immerses in solubility manganese nitrate solution, wherein this solution is pre-configured is the aqueous solution of 8% in its mass fraction of Fe content, carry out ultrasonic immersing 2h at room temperature 30 DEG C on the basis of the above, 110 DEG C of freeze-day with constant temperature 3h also calcine 3h and fix under 350 DEG C of conditions; Will in advance by Ce (NO
3)
36H
2o and acid ligand used Isosorbide-5-Nitrae-phthalic acid press 1:2.0 mixed in molar ratio evenly, are configured to containing Ce (NO
3)
3mass fraction be the aqueous solution of 1.5%, citric acid adjust ph is 5; Also under 500 DEG C of conditions, 2h is calcined through ultrasonic excessive dip loading 2h, 110 DEG C of dry 3h; Calcining is at N
2under atmosphere;
Wherein, Al element, metal M n element and the load capacity of Rare-Earth Ce element on carrier are measured by EDS, and three's load capacity is respectively 3.7%, 23.6% and 26.9%.The evaluating catalyst test macro that above-mentioned gained catalyst is built in laboratory is carried out NO_x removal performance test, obtains NO
xconversion ratio is 92%.
Embodiment 4:
By mechanical-moulded for commercially available semicoke, obtaining hole density is 100-300 hole/inch
2carrier, get the excessive dipping semicoke of 15% dust technology and activate, under room temperature ultrasonic immersing activation 3h, then constant temperature 110 DEG C of dry 2h; Semicoke after activation carries out excessive dip loading Al
2o
3colloidal sol, Al used
2o
3for mass fraction is 2.5%, after ultrasonic load 2h, under 110 DEG C of conditions, dry also 350 DEG C of calcining 3h fix; Carrier immerses in solubility manganese nitrate solution, and wherein this solution is pre-configured is the aqueous solution of 9% in its mass fraction of Fe content.Carry out ultrasonic immersing 3h at room temperature 30 DEG C on the basis of the above, 110 DEG C of freeze-day with constant temperature 3h also calcine 2h and fix under 350 DEG C of conditions; In advance by Ce (NO
3)
36H
2o and acid ligand used Isosorbide-5-Nitrae-phthalic acid press 1:1.0 mixed in molar ratio evenly, are configured to containing Ce (NO
3)
3mass fraction be the aqueous solution of 1.5%, citric acid adjust ph is 4; Through ultrasonic excessive dip loading 2h, 110 DEG C of dry 3h also calcine 2h under 350 DEG C of conditions; Gained carrier is at N
2calcine under gas inert atmosphere;
Wherein, Al element, metal M n element and the load capacity of Rare-Earth Ce element on carrier are measured by EDS, and three's load capacity is respectively 4.26%, 24.8% and 37.9%.The evaluating catalyst test macro that above-mentioned gained catalyst is built in laboratory is carried out NO_x removal performance test, obtains NO
xconversion ratio is 95%.
Embodiment 5:
By mechanical-moulded for commercially available semicoke, hole density is 100-300 holes/inch
2, through 15% dust technology activation, ultrasonic immersing 3h under room temperature, then constant temperature 110 DEG C of dry 2h; On this basis, the semicoke after activation process carries out excessive dip loading Al
2o
3colloidal sol, Al used
2o
3for mass fraction is 3%, dry 2h calcine 2h fix under temperature 400 DEG C of conditions under 110 DEG C of conditions after ultrasonic load 2h; Soluble copper salt is the aqueous solution of mass fraction 5%, and the soluble copper salt of described 5% is copper nitrate, with copper content meter.Carry out ultrasonic immersing 3h at room temperature 30 DEG C on the basis of the above, constant temperature 110 DEG C of dry 2h also calcine 3h under 500 DEG C of conditions; By Ce (NO
3)
36H
2o and acid ligand used Isosorbide-5-Nitrae-phthalic acid, press 1:1.5 mixed in molar ratio in advance evenly, be configured to containing Ce (NO
3)
3mass fraction be the aqueous solution of 1.0%, citric acid adjust ph is 5, and through ultrasonic excessive dip loading 2h, 110 DEG C of dry 3h also calcine 3h under 450 DEG C of conditions; Calcining is at N
2under atmosphere;
Wherein, Al element, Ni metal element and the load capacity of Rare-Earth Ce element on carrier are measured by X-ray energy spectrometer EDS, and three's load capacity is respectively 4.52%, 24.8% and 30.0%.The evaluating catalyst test macro that above-mentioned gained catalyst is built in laboratory is carried out NO_x removal performance test, obtains NO
xconversion ratio is 91%.
Embodiment 6:
By mechanical-moulded for commercially available semicoke, hole density is 100-300 holes/inch
2, through 20% dust technology activation, ultrasonic immersing 4h under room temperature, then constant temperature 110 DEG C of dry 2h; On this basis, the semicoke after activation process carries out excessive dip loading Al
2o
3colloidal sol, Al used
2o
3for mass fraction is 5%, dry 2h calcine 2h fix under temperature 350 DEG C of conditions under 110 DEG C of conditions after ultrasonic load 2h; Solubility ferric nitrate is configured in the aqueous solution of its mass fraction 5% of iron content, carries out ultrasonic immersing 3h on the basis of the above at room temperature 30 DEG C, and constant temperature 110 DEG C of dry 2h also calcine 3h under 450 DEG C of conditions; By Ce (NO
3)
36H
2o and acid ligand used Isosorbide-5-Nitrae-phthalic acid, press 1:1.5 mixed in molar ratio in advance evenly, be configured to containing Ce (NO
3)
3mass fraction be the aqueous solution of 0.5%, citric acid adjust ph is 6, and through ultrasonic excessive dip loading 2h, 110 DEG C of dry 3h also calcine 2h under 450 DEG C of conditions; Calcining is at N
2under atmosphere;
Wherein, Al element, metal Fe element and the load capacity of Rare-Earth Ce element on carrier are measured by X-ray energy spectrometer EDS, and three's load capacity is respectively 5.23%, 14.8% and 27.2%.The evaluating catalyst test macro that above-mentioned gained catalyst is built in laboratory is carried out NO_x removal performance test, obtains NO
xconversion ratio is 90%.
Comparative example
Substantially the same manner as Example 1, difference is only to eliminate active component A l
2o
3load step, obtained catalyst be used for denitration evaluate after, its denitration rate reaches 83%.
Method of evaluating performance:
The catalyst prepared embodiment 1-4 above carries out the evaluation of denitration performance according to following operation:
The catalyst that said process is obtained is placed in fixed bed reactors, is warming up to 90 DEG C and starts ventilation, and be temperature rank with 10 DEG C, determine the NO of this catalyst within the scope of 90 ~ 150 DEG C
xremove performance.Wherein the constituent of normal pressure Imitating flue gas is: 850ppm/min NOx; 950ppm/min NH
3; 30ml/min O
2; N
2968ml/min, N
2for Balance Air.During test, air speed 10000h
-1; Test time 72h, NO
xremoval efficiency > 90% (catalyst of embodiment 1-6 is respectively 91%, 93%, 92%, 95%, 91% and 90%), all non-inactivation of catalyst prepared by embodiment 1-6.
Described analog gas, through mixing chamber before passing into fixed bed reactors, fully mixes and preheats 90 DEG C (temperature identical with reaction system).
Described catalyst n O
xremoval efficiency calculates, and measures NO in inlet flue gas respectively by testo350 flue gas analyzer
xnO in content and exiting flue gas
xcontent, finally obtains transforming NO in process
xamount, i.e. NO
xremoval efficiency (calculating conversion ratio with the change of the content of main component NO contained in nitrogen oxide).
The no catalyst inactivation of described embodiment 1-4, refers to that catalyst activity remains unchanged after 72h test.
The NO of employing and the above catalyst of Evaluation operation example 1-4
xthe identical condition of removal efficiency and device, the activity for the vanadium tungsten titanium catalyst of conventional commercial is evaluated, and result is as follows:
1, catalyst denitration activity of the present invention is high
Conventional commercial denitrating flue gas reaction temperature generally (adopts the model of the tungsten titanium catalyst (anatase thpe white powder) of conventional commercial: PC-200 at 180 DEG C-400 DEG C, sell producer: Shanghai Peng Bo titanium dioxide Co., Ltd) between, obviously reduce lower than denitration efficiency when 180 DEG C, this denitrating catalyst serviceability temperature is 90 ~ 120 DEG C, in this temperature range, denitration efficiency can reach more than 93%.Catalyst choice is high, and the tail gas after process can be directly emptying.
2, the denitration reaction temperature of catalyst of the present invention is low
Conventional commercial denitrating flue gas reaction temperature generally (adopts the model of the vanadium titanium catalyst of conventional commercial: TX100 between 320 DEG C-400 DEG C, sell producer: Shanghai Sha wins chemical industry and sells), this denitrating catalyst serviceability temperature is 90 ~ 120 DEG C, in this temperature range, and NO
xremoval efficiency reaches as high as more than 93%, and under the condition of temperature lower than 150 DEG C, NO
xremoval efficiency keeps almost constant.
3, technique is simple
Tradition flue gas denitration reactor need be placed between boiler economizer outlet and air preheater entrance, after this denitrating catalyst can be directly used in conventional smoke desulfurization, without the need to heating.Generate without secondary pollutions such as waste water, solid waste, dust.
Claims (17)
1., containing a catalyst for denitrating flue gas for rare earth, it is characterized in that, be carrier with carbon based material, load has Al
2o
3, any one or the two the active rare-earth component that is selected from one or more metal active constituents in Mn, Cu and Fe and is selected from Ce and La, wherein, the mass content of each component is as follows: charcoal base carrier content is 35-65%, described Al
2o
3with aluminium element content meter loading content for 2-5%, described metal active constituent in metal element content loading content for 13-26%, described active rare-earth component in ree content loading content for 20-39%.
2. catalyst according to claim 1, wherein, the mass content of each component is as follows: charcoal base carrier content is 40-60%, described Al
2o
3with aluminium element content meter loading content for 3-4%, described metal active constituent in metal element content loading content for 21-25%, described active rare-earth component in ree content loading content for 30-39%.
3. the catalyst according to any one of claim 1-3, wherein, described carbon based material is activation semicoke.
4. catalyst according to claim 3, wherein, described activation semicoke hole density is 100-300 hole/inch
2, specific area is 100-500m
2/ g.
5. the preparation method of the catalyst described in any one of claim 1-4, it comprises the steps:
A) 10%-25% nitric acid is used to carry out ultrasonic activation, ultrasonic immersing under room temperature, drying the carbon based material after shaping;
B) Al
2o
3the load of colloidal sol: on a) step basis, the ultrasonic load Al of activation half defocused excessive infusion process
2o
3colloidal sol, then carries out drying, calcining is fixing;
C) load of metal active constituent: one or several metallic compounds in the metal M n/Cu/Fe of load are made into metal compound solution, regulate pH to 4-6, b) step basis excessively impregnated in this solution by ultrasonic under active carbocoal room temperature, calcine after suction filtration, freeze-day with constant temperature;
D) load of active rare-earth component: carry out the load of active rare-earth component on c) step basis, active rare-earth component is pre-configured to the aqueous solution, ultrasonic excessive dip loading is also dry;
E) by gained sample in d) process, calcine in an inert atmosphere, inert gas used is N
2or He, calcining heat is 350-500 DEG C.
6. preparation method according to claim 5, wherein, step b) in, Al used
2o
3the concentration of sol solution is for containing Al
2o
3quality 1-5%.
7. the preparation method according to claim 5 or 6, wherein, step c) in, metal active constituent used is metallic compound aqueous solution form, contains metal active constituent 5%-10%, preferred 7-10% in this solution of metal active constituent.
8. the preparation method according to any one of claim 5-7, wherein, steps d) in, active rare-earth component used is rare earth compound aqueous solution form, active rare-earth component 0.5%-2% is contained, the aqueous solution of preferred 1.0-1.5% in this solution of active rare-earth component.
9. preparation method according to claim 5, wherein, described step b) in, described ultrasonic load time is 2-3h, and described drying is 110 DEG C of conditions, and described calcining heat is 350-450 DEG C.
10. the preparation method according to claim 5 or 6, wherein, described step c) in, by the aqueous solution of metal described in described mixed solution, described condition pH value is regulated by citric acid.
11. preparation methods according to any one of claim 5-7, wherein, described steps d) in, also comprise and add acid ligand 1,4-phthalic acid, the mixed in molar ratio of it being pressed in advance 1:1.0 ~ 2.0, preferably 1:1.0-1.5 with rare earth element is even, ultrasonic load.
12. preparation methods according to any one of claim 5-8, wherein, described step e) in, described calcination time 2-4h.
13. preparation methods according to any one of claim 5-9, wherein, described step c) in, described metal compound solution refers to manganese nitrate/copper nitrate or iron nitrate aqueous solution form; Described steps d) in, described active rare-earth component is selected from cerous nitrate or cerium oxide, or lanthanum nitrate or lanthana.
14. preparation methods according to any one of claim 5-10, wherein, described step c) in, described forging is carried out at temperature 350-500 DEG C.
The catalyst of 15. any one of claim 1-4 is for flue gas denitration, or the application in denitration simultaneously and desulfurization.
16. application according to claim 12, described denitration is carried out at 90 ~ 120 DEG C.
17. application according to claim 13, described denitration rate is greater than 90%.
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