CN106076417A - Charcoal base heteropolyacid catalyst and preparation and application method thereof for low-temperature flue gas simultaneous SO_2 and NO removal - Google Patents
Charcoal base heteropolyacid catalyst and preparation and application method thereof for low-temperature flue gas simultaneous SO_2 and NO removal Download PDFInfo
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- CN106076417A CN106076417A CN201610524962.6A CN201610524962A CN106076417A CN 106076417 A CN106076417 A CN 106076417A CN 201610524962 A CN201610524962 A CN 201610524962A CN 106076417 A CN106076417 A CN 106076417A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention discloses a kind of charcoal base heteropolyacid catalyst for low-temperature flue gas simultaneous SO_2 and NO removal and preparation and application method thereof, this catalyst is with activated carbon as carrier, Keggin-type heteropoly acid is active component, and in this catalyst, the parts by weight content of each component is: the activated carbon of 80～85 weight portions, 15～20 Keggin-type heteropoly acids of weight portion.The catalyst that the present invention provides is the highest to the dependence of temperature, still has higher desulphurization denitration activity under cryogenic conditions (80～160 DEG C)；Therefore catalyst can be placed in the afterbody of the relatively low smoke processing system of temperature, after being positioned at dust pelletizing system, dust greatly reduces herein, the alkalies and alkaline earth content being attached on dust also reduces, the toxic action of catalyst is greatly reduced by dust by ponding and the alkali metal of catalyst, reduce the consumption of catalyst in running, extend the service life of catalyst；For a user, it is possible to reduce later maintenance number of times and cost.
Description
Technical field
The present invention relates to catalysis method flue gas desulfurization, denitration field, be specifically related to one and low-temperature flue gas is had desulfurization simultaneously
Catalyst of denitration performance and preparation method thereof.
Background technology
China's atmospheric pollution is extremely serious, and wherein sulfur dioxide and nitrogen oxides are the major pollutants of China's air, also
It is air contaminant treatment and the emphasis of environmental conservation and difficult point.Show according to China Environmental State Bulletin, in China's air in 2014
SO2It is 1974.4 ten thousand tons and 2078.8 ten thousand tons respectively with the total emission volumn of nitrogen oxides.Since " 15 ", along with power plant of China takes off
The construction of sulfur facility, the regulation effect of sulfur dioxide starts to manifest, and nitrogen oxides starts to replace sulfur dioxide and becomes the first big acid
Contact scar gas.Therefore, while flue gas desulfurization, how removing nitrogen oxides therein becomes China's air contaminant treatment urgently
Problem to be solved.
Flue gas desulfurization technique is broadly divided into wet desulphurization and the big class of dry desulfurization two.So-called wet desulphurization, main method
It is to spray lime white to react the calcium sulfate Gypsum Fibrosum generating pulpous state with the sulfur dioxide in flue gas, but this method exists investment greatly, runs
Costly, but also the shortcoming that secondary pollution can be produced.So-called dry flue gas desulphurization, is application powdery or granular absorbent, suction
Attached dose or catalyst remove the SO in flue gas2.Advantage is that technical process is simple, processes problem without sewage, waste acid, and energy consumption is low,
Will not produce " white cigarette " phenomenon, the flue gas after purification need not post bake, and corrosivity is little.Shortcoming is that desulfuration efficiency is relatively low, if
Standby huge, investment is big, floor space is big, operating technology requires height.
Gas denitrifying technology the most industrially apply wider be SCR technology (SCR) and selectivity non-
Catalysis reduction (SNCR) technology.Wherein SCR is the gas denitrifying technology of main flow, and this technology is under an oxygen-containing atmosphere,
Reducing agent is preferential and reaction of nitrogen oxides generation nitrogen and the catalytic reaction process of water under catalyst action.Wherein as reduction
The gas of agent mainly has NH3, CO and Hydrocarbon etc..
At present, the widely used desulfurizing and denitrifying process of China's industrial smoke is traditional desulfurization technology (FGD) Combination selection
Property catalytic reduction technique (SCR) removes SO in flue gas respectively2With the combined desulfurization and denitration technology of nitrogen oxides, such as Calx/Calx
Stone method SCR method process integration.Combined desulfurization and denitrification process typically has higher contaminant removal efficiency, but owing to using two
Covering device carries out desulfurization and denitration respectively, therefore has that floor space is big, flow process is complicated, investment and a shortcoming such as operating cost is high.
Therefore, by the SO in flue gas in a system2The desulphurization denitration technology simultaneously removed with nitrogen oxides and its phase
Than having bigger advantage undoubtedly.In recent years, flue gas and desulfurizing and denitrifying technology gradually starts to be subject to people's attention, including:
Plasma method, liquid absorption method and adsoption catalysis method.But a lot of technology of plasma method relies on external import, is difficult in China
Realizing industrial applications, it is perishable to there is equipment in liquid absorption method, and absorbing liquid cost is high, easily cause the shortcomings such as secondary pollution.Inhale
Attached catalysis method overcomes disadvantages mentioned above, is flue gas and desulfurizing and denitrifying technology the most most with prospects.
The Chinese patent literature of Publication No. CN102974359A discloses a kind of simultaneous SO_2 and NO removal catalyst, this catalysis
Agent is with activated carbon (AC) as carrier, and neodymium oxide is active component, and cobalt black is cocatalyst.The quality of described catalyst is divided
Number is the AC of 60～98 weight portions, 2～40 Nd of weight portion2O3, 0～20 cobalt blacks of weight portion.This preparation method is for first to join
Neodymium salt processed and cobalt salt solution, add polyvinyl alcohol, stirring and dissolving wherein, adds activated carbon granule or powder, then heats
It is evaporated to amount of water, uses different forming methods to make granule, column or honeycombed catalyst, the most at last catalysis of molding
Agent is dried, and different temperatures section carries out the finished catalyst that calcining prepares.
Although this catalyst has higher catalysis activity, but neodymium is rare earth metal, expensive, and is listed in hazardous
Learn in the middle of name of an article record；Preparation method operation is numerous and diverse, and catalytic component is more, and technology requires higher, and preparation cost is high.Therefore, it is difficult to
Realize industrial applications and popularization；And reaction temperature is high, under the conditions of 350～500 DEG C, just there is higher SO2With nitrogen oxides
Clearance, must be arranged in high-temperature high dust fragment position, easily causes the poisoning and deactivation of catalyst.
Summary of the invention
For the present situation of flue gas desulfurization and denitrification technology of prior art with not enough, first purpose of the present invention provides one
High activity, low cost, the charcoal base heteropolyacid catalyst for low-temperature flue gas simultaneous SO_2 and NO removal of environmental protection；The of the present invention
Two purposes provide a kind of and prepare this method for the charcoal base heteropolyacid catalyst of low-temperature flue gas simultaneous SO_2 and NO removal；The present invention
The 3rd purpose the method using this for the charcoal base heteropolyacid catalyst of low-temperature flue gas simultaneous SO_2 and NO removal is provided.
For first purpose of the present invention, the charcoal base for low-temperature flue gas simultaneous SO_2 and NO removal that the present invention provides is miscellaneous many
Acid catalyst, with Keggin-type heteropoly acid as active component, activated carbon is as carrier.Keggin-type heteropoly acid has the strongest proton
Transmission with electronics and reserve capabillity, molecular volume is relatively big, has again the strongest oxidation-reduction quality and highly acid, by extensively simultaneously
For catalytic field.But itself there is poor heat stability, specific surface area is little, in the liquid phase the easy problem such as dissolving, this
Again limit its development at catalytic field.Loaded by heteropoly acid on absorbent charcoal carrier, is utilized the ratio that activated carbon is high by the present invention
Surface area, abundant pore structure, good chemical stability, overcome disadvantage mentioned above so that it is reaches stable catalytic effect.
In the charcoal base heteropolyacid catalyst of above-mentioned low-temperature flue gas simultaneous SO_2 and NO removal, the parts by weight content of each component is: 80
～85 activated carbon, 15～20 Keggin-type heteropoly acids of weight portion of weight portion.When Keggin-type heteropoly acid content is less than 15 weights
During amount part, active component is not enough, can directly affect denitrification efficiency；And when Keggin-type heteropoly acid content is more than 20 weight portions
Time, the heteropoly acid being more than can cover activated carbon surface hole, block, reduce specific surface area, make the desulphurization denitration of catalyst on the contrary
Efficiency.
Invention further provides the preparation side of the above-mentioned charcoal base heteropolyacid catalyst for flue gas and desulfurizing and denitrifying
Method, including following step of preparation process:
(1) under the conditions of 60～65 DEG C, by the salpeter solution pickling that activated carbon granule mass fraction is 28%～32%
Process, then be washed to neutrality, dry (being designated as NAC)；
(2) weigh the heteropoly acid of 15～20 weight portions, soluble in water make mass fraction be 8.9%～12.0% miscellaneous many
Acid solution；Weigh the NAC of 80～85 weight portions again, impregnated in the heteropoly acid solution that above-mentioned mass fraction is 8.9%～12%,
Stand no less than 18 hours, be evaporated at 60～65 DEG C；Then it is dried 10～12h in 100～105 DEG C, prepares complex catalyst precursor
Body；
(3) with N2For protection gas, catalyst precursor is placed in Muffle kiln roasting, heating rate be 4～6 DEG C/min,
Sintering temperature is 200～800 DEG C, roasting time is 2～3h.Then naturally cool to room temperature and i.e. obtain finished catalyst.
Above-mentioned steps (1) is that activated carbon carries out conventional pickling processes, and the activated carbon granule size of employing is at 10～20 mesh
Between.Before activated carbon is carried out pickling, need it is carried out pretreatment, will be immersed in distilled water and boil 1 by activated carbon
～2h, it is subsequently placed in 100～105 DEG C and is dried 10～12h；After pretreatment terminates, then activated carbon is carried out pickling processes, will live
Property charcoal be immersed in the salpeter solution that mass fraction is 28%～32%, at 60～65 DEG C keep 1～2h, then filter off acid
Liquid, carries out filtering and washing with deionized water, until pH is between 6-7, is finally dried 10～12h in 100～105 DEG C, to obtain final product
NAC。
The purpose of above-mentioned steps (2) is to prepare catalyst precursor, uses equi-volume impregnating, and that i.e. makes is miscellaneous many
Acid solution volume is identical with the volume of added activated carbon.By for a long time activated carbon being impregnated in heteropoly acid solution, in conjunction with living
Property the abundant gap structure of charcoal, make heteropoly acid uniform load on activated carbon.
The purpose of above-mentioned steps (3) is to make activation of catalyst, needs control sintering temperature at 200～800 DEG C, sends out after deliberation
Existing, when sintering temperature is too low, the desulfurization effective time of catalyst will shorten；And when sintering temperature is too high, catalyst
Denitration efficiency will reduce；When controlling sintering temperature at 300～500 DEG C, the charcoal base heteropolyacid catalyst that the present invention provides exists
Low temperature has higher desulphurization denitration activity, particularly charcoal base phosphotungstic acid catalyst simultaneously, desulfuration efficiency can reach 98% with
On, denitration efficiency can be up to 82.8%.Additionally, the catalyst that this step obtains is under cryogenic conditions (80～160 DEG C), have
Good heat stability, it is not easily decomposed.
Heteropoly acid is to be passed through the oxygen-containing polyacid of oxygen atom ligand bridging, inventor by hetero atom and polyatom by a fixed structure
Recognize that heteropoly acid has big molecular volume, has excellent transmission and reserve capacity, " brilliant to electronics and proton under study for action
Lattice oxygen " activity, high Bronsted acidity, and be easy to the features such as separation, nontoxic, tasteless, non-volatility, based on above-mentioned spy
Point, is used for preparing the catalyst of flue gas desulfurization and denitrification, for flue gas desulfurization and denitrification by heteropoly acid.
The catalyst that the present invention provides can be simultaneously as flue gas desulfurization and the catalyst of denitration, its desulfurization and denitration mechanism
As follows:
(1) desulphurization mechanism, SO2First catalyst surface it is attracted to, under the catalytic action of active component heteropoly acid,
SO2It is oxidized to SO3, SO simultaneously3Generation sulphuric acid is reacted with the steam in flue gas；The sulphuric acid generated is attached to catalyst surface,
Affect the activity of catalyst, it is therefore desirable to catalyst is carried out desulfurization regeneration, after regeneration, obtain the catalysis of sulphuric acid and activity recovery
Agent.
(2) denitration mechanism, when flue gas contacts with catalyst, NO thereinx(x=1 or 2) is at active component heteropoly acid
Under effect, with NH3There is reduction reaction, generate N nontoxic, that pollute2And water；Dominant response is as follows:
Owing to heteropoly acid has strong Bronsted acidity, alkaline gas NH3Easily there is adsorption reaction therewith, this enhances
The generation of contacting between reactant with catalyst, beneficially subsequent chemical reaction, thus improve denitration efficiency.
The beneficial effects of the present invention is:
(1) activated carbon wide material sources needed for the present invention, easily obtain, preparation method simple；Preparation cost is cheap, is suitable to advise greatly
Mould produces；Through adjusting, relative to simultaneous SO_2 and NO removal catalysis disclosed in the Chinese patent literature of Publication No. CN102974359A
Agent, the catalyst preparation cost that the present invention provides about can reduce by 110 yuan/Kg；
(2) catalyst that the present invention provides is the highest to the dependence of temperature, still has relatively under cryogenic conditions (80～160 DEG C)
High desulphurization denitration activity；Therefore catalyst can be placed in the afterbody of the relatively low smoke processing system of temperature, be positioned at dedusting herein
After system, dust greatly reduce, the alkalies and alkaline earth content being attached on dust also reduces so that dust is to catalysis
The toxic action of catalyst is greatly reduced by ponding and the alkali metal of agent, reduces the consumption of catalyst in running,
Extend the service life of catalyst；For a user, it is possible to reduce later maintenance number of times and operating cost.
Accompanying drawing explanation
Fig. 1 is that the catalyst using the embodiment of the present invention 5, embodiment 6 and embodiment 7 to obtain carries out desulfurization simulation test,
Desulfuration efficiency is with the change curve of desulphurization reaction time；
Fig. 2 is that the catalyst using the embodiment of the present invention 1, embodiment 2 and embodiment 3 to obtain carries out denitration simulation test,
Denitration efficiency is with the change curve of denitration reaction temperature.
Detailed description of the invention
Below by the drawings and specific embodiments, the invention will be further described, its object is to make the technology of this area
Personnel are better understood from present disclosure, rather than the restriction to present invention.
In order to study the desulphurization denitration performance of the charcoal base heteropolyacid catalyst that the present invention provides, following example are prepared into
To catalyst removal simulated flue gas in SO2Testing with the performance of NO, test condition is: by simulated flue gas with flow be
945mL/min passes through analogue reactor, SO in simulated flue gas2Entrance concentration 1000ppm, NO concentration is 500ppm, oxygen content
Being 10%, Balance Air is nitrogen, and air speed is 5000h-1；Analogue reactor front end carries out desulfurization, and NH is pressed in analogue reactor rear end3/
NO volume ratio is that 1:1 is passed through ammonia and carries out out of stock；Control analogue reactor temperature at 60 DEG C～200 DEG C.
Embodiment 1
Weigh 8g merchandise active carbon, be immersed in distilled water and boil 2h, be subsequently placed in 105 DEG C of thermostatic drying chambers dry
Dry 12h；It is immersed into again in the salpeter solution that mass fraction is 30%, under 60 DEG C of waters bath with thermostatic control, keeps 2h；Filter off acid solution,
Filtering and washing is carried out, until pH is between 6-7 with deionized water；Finally it is placed in 105 DEG C of thermostatic drying chambers and is dried 12h.
Weigh 2g phosphomolybdic acid, be dissolved in 16mL water.Being added by above-mentioned activated carbon in phosphomolybdic acid aqueous solution, hand operated mixing is to mixed
Closing uniformly, sealing and standing 18h, in 60 DEG C of thermostat water baths, water-bath is stirred continuously until being evaporated, and is subsequently placed in 100 DEG C of constant temperature and does
Dry case is dried 12h, prepares catalyst precursor.Above-mentioned presoma is placed in calcination activation in Muffle furnace, with N2For protecting gas,
Gas flow is 200ml/min, and heating rate is 5 DEG C/min, after temperature is raised to 200 DEG C, stops 2h.Naturally cool to room
Temperature, obtains the charcoal base phosphomolybdic acid agent that load capacity is 20%.
Desulphurization denitration test result indicate that: in the reaction temperature of 60～140 DEG C, and the desulfuration efficiency of catalyst all can maintain
More than 95%, but 100% can not be reached；After reaction temperature is more than 140 DEG C, desulfuration efficiency begins to decline.The denitration of catalyst
Efficiency first increases with the rising of temperature and declines afterwards, optimal when 140 DEG C, reaches for 66.2% (as shown in Figure 2).
Embodiment 2
Weigh 8g merchandise active carbon, be immersed in distilled water and boil 1.5h, be subsequently placed in 100 DEG C of thermostatic drying chambers
It is dried 12h；It is immersed into again in the salpeter solution that mass fraction is 28%, under 61 DEG C of waters bath with thermostatic control, keeps 1h；Filter off acid
Liquid, carries out filtering and washing with deionized water, until pH is between 6-7；Finally it is placed in 100 DEG C of thermostatic drying chambers and is dried 12h.
Weigh 2g silico-tungstic acid, be dissolved in 16mL water.The activated carbon handled well is added in silicon tungsten acid solution, hand operated mixing
To mix homogeneously, sealing and standing 21h.Being put into by the activated carbon impregnated in 63 DEG C of thermostat water baths is stirred continuously until being evaporated,
It is subsequently placed in 102 DEG C of thermostatic drying chambers and is dried 11h, prepare catalyst precursor.
Above-mentioned presoma is placed in calcination activation in Muffle furnace, with N2For protection gas, gas flow is 200ml/min, with
Ensureing to carry out heat treatment under anaerobic, heating rate is 5 DEG C/min, after temperature is raised to 300 DEG C, stops 2.5h.Natural
It is cooled to room temperature, obtains the charcoal base silicotungstic acid catalyst that load capacity is 20%.
Desulphurization denitration test result indicate that: in the reaction temperature of 80～140 DEG C, and the desulfuration efficiency of catalyst is higher, base
Can maintain more than 98% on Ben, when reaction temperature is 80 DEG C, 100% desulfuration efficiency reaches 60min stabilization time；Temperature reaches
During to 160 DEG C, desulfuration efficiency begins to decline.Denitration efficiency presents with the rising of temperature and first raises the trend reduced afterwards, at 160 DEG C
Time reach maximum, be for 63.2% (as shown in Figure 2) to the maximum.
Embodiment 3
Weigh 8.5g merchandise active carbon, be immersed in distilled water and boil 1h, be subsequently placed in 103 DEG C of thermostatic drying chambers
It is dried 11h；It is immersed into again in the salpeter solution that mass fraction is 32%, under 62 DEG C of waters bath with thermostatic control, keeps 1.5h；Filter off
Acid solution, carries out filtering and washing with deionized water, until pH is between 6-7；Finally it is placed in 103 DEG C of thermostatic drying chambers and is dried 11h.
Weigh 1.5g phosphotungstic acid, be dissolved in 17mL water.The activated carbon handled well is added in phosphotungstic acid aqueous solution, manually stirs
Mix to mix homogeneously, sealing and standing 24h.The activated carbon impregnated is put in 65 DEG C of thermostat water baths and be evaporated, be subsequently placed in 105
DEG C thermostatic drying chamber is dried 10h, prepares catalyst precursor.
Above-mentioned presoma is placed in calcination activation in Muffle furnace, with N2For protection gas, gas flow is 200ml/min, with
Ensureing to carry out heat treatment under anaerobic, heating rate is 6 DEG C/min, after temperature is raised to 500 DEG C, stops 3h.The coldest
But to room temperature, the charcoal base phosphotungstic acid catalyst that load capacity is 15% is obtained.
Desulphurization denitration experimental result shows: in the reaction temperature of 60～160 DEG C, and the desulfuration efficiency of catalyst is the highest, energy
Enough stable more than 98%, when reaction temperature is 80 DEG C, 100% desulfuration efficiency reaches 150min stabilization time；Reaction temperature
After 160 DEG C, desulfuration efficiency begins to decline.The denitration efficiency of catalyst first raises with the rising of reaction temperature and reduces afterwards, instead
When to answer temperature be 140 DEG C, denitration efficiency is the highest, reaches for 82.8% (as shown in Figure 2).
Embodiment 4
Weigh 8.5g merchandise active carbon, be immersed in distilled water and boil 1h, be subsequently placed in 105 DEG C of thermostatic drying chambers
It is dried 10h；It is immersed into again in the salpeter solution that mass fraction is 28%, under 63 DEG C of waters bath with thermostatic control, keeps 1h；Filter off acid
Liquid, carries out filtering and washing with deionized water, until pH is between 6-7；Finally it is placed in 105 DEG C of thermostatic drying chambers and is dried 10h.
Weigh 1.5g phosphotungstic acid, be dissolved in 17mL water.The activated carbon handled well is added in phosphotungstic acid aqueous solution, manually stirs
Mix to mix homogeneously, sealing and standing 18h.The activated carbon impregnated is put in 60 DEG C of thermostat water baths and be stirred continuously until steaming
Dry, it is subsequently placed in 100 DEG C of thermostatic drying chambers and is dried 12h, prepare catalyst precursor.
Above-mentioned presoma is placed in calcination activation in Muffle furnace, with N2For protection gas, gas flow is 200ml/min, with
Ensureing to carry out heat treatment under anaerobic, heating rate is 4 DEG C/min, after temperature is raised to 400 DEG C, stops 2h.The coldest
But to room temperature, the charcoal base phosphotungstic acid catalyst that load capacity is 15% is obtained.
Desulphurization denitration experimental result shows: in the reaction temperature of 60～140 DEG C, and the desulfuration efficiency of catalyst is the highest, energy
Enough stable more than 98%, when reaction temperature is 80 DEG C, 100% desulfuration efficiency reaches 120min stabilization time；Reaction temperature
After 140 DEG C, desulfuration efficiency begins to decline.The denitration efficiency of catalyst first raises with the rising of reaction temperature and reduces afterwards, instead
When to answer temperature be 140 DEG C, denitration efficiency is optimal, reaches 68%.
Embodiment 5
Weigh 8g merchandise active carbon, be immersed in distilled water and boil 2h, be subsequently placed in 100 DEG C of thermostatic drying chambers dry
Dry 12h；It is immersed into again in the salpeter solution that mass fraction is 30%, under 64 DEG C of waters bath with thermostatic control, keeps 1.5h；Filter off acid
Liquid, carries out filtering and washing with deionized water, until pH is between 6-7；Finally it is placed in 100 DEG C of thermostatic drying chambers and is dried 12h.
Weigh 2g silico-tungstic acid, be dissolved in 16mL water.The activated carbon handled well is added in silicon tungsten acid solution, hand operated mixing
To mix homogeneously, sealing and standing 21h.Being put into by the activated carbon impregnated in 63 DEG C of thermostat water baths is stirred continuously until being evaporated,
It is subsequently placed in 102 DEG C of thermostatic drying chambers and is dried 11h, prepare catalyst precursor.
Above-mentioned presoma is placed in calcination activation in Muffle furnace, with N2For protection gas, gas flow is 200ml/min, with
Ensureing to carry out heat treatment under anaerobic, heating rate is 5 DEG C/min, after temperature is raised to 600 DEG C, stops 2.5h.Natural
It is cooled to room temperature, obtains the charcoal base silicotungstic acid catalyst that load capacity is 20%.
Desulphurization denitration experimental result shows: in the reaction temperature of 80～160 DEG C, and the desulfuration efficiency of catalyst is the highest, energy
Enough stable more than 98%, when reaction temperature is 80 DEG C, 100% desulfuration efficiency reaches 300min (see Fig. 1 institute stabilization time
Show)；After reaction temperature is more than 160 DEG C, desulfuration efficiency begins to decline.The denitration efficiency of catalyst first rises with the rising of reaction temperature
Reducing after height, when reaction temperature is 160 DEG C, denitration efficiency is optimal, reaches 51%.
Embodiment 6
Weigh 8g merchandise active carbon, be immersed in distilled water and boil 1.5h, be subsequently placed in 103 DEG C of thermostatic drying chambers
It is dried 12h；It is immersed into again in the salpeter solution that mass fraction is 32%, under 65 DEG C of waters bath with thermostatic control, keeps 2h；Filter off acid
Liquid, carries out filtering and washing with deionized water, until pH is between 6-7；Finally it is placed in 103 DEG C of thermostatic drying chambers and is dried 12h.
Weigh 2g phosphomolybdic acid, be dissolved in 16mL water.The activated carbon handled well is added in phosphomolybdic acid aqueous solution, hand operated mixing
To mix homogeneously, sealing and standing 24h.Being put into by the activated carbon impregnated in 65 DEG C of thermostat water baths is stirred continuously until being evaporated,
It is subsequently placed in 105 DEG C of thermostatic drying chambers and is dried 12h, prepare catalyst precursor.
Above-mentioned presoma is placed in calcination activation in Muffle furnace, with N2For protection gas, gas flow is 200ml/min, with
Ensureing to carry out heat treatment under anaerobic, heating rate is 6 DEG C/min, after temperature is raised to 700 DEG C, stops 3h.The coldest
But to room temperature, the charcoal base phosphomolybdic acid catalyst that load capacity is 20% is obtained.
Desulphurization denitration experimental result shows: in the reaction temperature of 80～160 DEG C, and the desulfuration efficiency of catalyst is the highest, energy
Enough stable more than 98%, when reaction temperature is 80 DEG C, 100% desulfuration efficiency reaches 310min (see Fig. 1 institute stabilization time
Show)；After reaction temperature is more than 160 DEG C, desulfuration efficiency begins to decline.The denitration efficiency of catalyst first rises with the rising of reaction temperature
Reducing after height, when reaction temperature is 160 DEG C, denitration efficiency is optimal, reaches 45%.
Embodiment 7
Weigh 8.5g merchandise active carbon, be immersed in distilled water and boil 1h, be subsequently placed in 100 DEG C of thermostatic drying chambers
It is dried 12h；It is immersed into again in the salpeter solution that mass fraction is 30%, under 63 DEG C of waters bath with thermostatic control, keeps 2h；Filter off acid
Liquid, carries out filtering and washing with deionized water, until pH is between 6-7；Finally it is placed in 105 DEG C of thermostatic drying chambers and is dried 10h.
Weigh 1.5g phosphotungstic acid, be dissolved in 17mL water.The activated carbon handled well is added in phosphotungstic acid aqueous solution, manually stirs
Mix to mix homogeneously, sealing and standing 20h.The activated carbon impregnated is put in 60 DEG C of thermostat water baths and be stirred continuously until steaming
Dry, it is subsequently placed in 105 DEG C of thermostatic drying chambers and is dried 12h, prepare catalyst precursor.
Above-mentioned presoma is placed in calcination activation in Muffle furnace, with N2For protection gas, gas flow is 200ml/min, with
Ensureing to carry out heat treatment under anaerobic, heating rate is 5 DEG C/min, after temperature is raised to 800 DEG C, stops 2h.The coldest
But to room temperature, the charcoal base silicotungstic acid catalyst that load capacity is 15% is obtained.
Desulphurization denitration experimental result shows: in the reaction temperature of 80～140 DEG C, and the desulfuration efficiency of catalyst is the highest, energy
Enough stable more than 98%, when reaction temperature is 80 DEG C, 100% desulfuration efficiency reaches 220min (see Fig. 1 institute stabilization time
Show)；After reaction temperature is more than 140 DEG C, desulfuration efficiency begins to decline.The denitration efficiency of catalyst first rises with the rising of reaction temperature
Reducing after height, when reaction temperature is 160 DEG C, denitration efficiency is optimal, reaches 41%.
Fig. 1 gives the catalyst using the embodiment of the present invention 5, embodiment 6 and embodiment 7 to obtain and carries out desulfurization simulation survey
In examination, desulfuration efficiency is with the curve chart of desulphurization reaction time, it can be seen that the catalyst that the present invention provides is in desulfurization side
Face, it is possible in the case of low-temperature flue gas, the desulfuration efficiency of long-time maintenance 100%, thus illustrate that this catalyst has stable
Catalytic effect.
Fig. 2 gives the catalyst using the embodiment of the present invention 1, embodiment 2 and embodiment 3 to obtain and carries out denitration simulation survey
In examination, denitration efficiency is with the curve chart of denitration reaction temperature, it can be seen that the catalyst that the present invention provides is at low temperature cigarette
Gas still has higher denitration efficiency.
Can be seen that what the present invention provided catalyst can be under the conditions of low-temp reaction from above-described embodiment 1-embodiment 7
Realize desulphurization denitration simultaneously；Especially when catalyst activation temperature is at 300～500 DEG C, the charcoal base heteropoly acid that the present invention provides
Catalyst has higher desulphurization denitration activity simultaneously, and the charcoal base phosphotungstic acid catalyst that embodiment 3 is given, desulfuration efficiency can reach
To 100%, denitration efficiency can be up to 82.8%.
Those of ordinary skill in the art it will be appreciated that embodiment described here be to aid in reader understanding this
Bright principle, it should be understood that protection scope of the present invention is not limited to such special statement and embodiment.This area
It is each that those of ordinary skill can make various other without departing from essence of the present invention according to these technology disclosed by the invention enlightenment
Planting concrete deformation and combination, these deform and combine the most within the scope of the present invention.
Claims (6)
1. the charcoal base heteropolyacid catalyst for low-temperature flue gas simultaneous SO_2 and NO removal, it is characterised in that with activated carbon for carrying
Body, Keggin-type heteropoly acid is active component, and in this catalyst, the parts by weight content of each component is: the work of 80～85 weight portions
Property charcoal, 15～20 Keggin-type heteropoly acids of weight portion.
Charcoal base heteropolyacid catalyst for low-temperature flue gas simultaneous SO_2 and NO removal the most according to claim 1, its feature exists
It is the one in phosphomolybdic acid, phosphotungstic acid and silico-tungstic acid in being carried on the described Keggin-type heteropoly acid of activated carbon.
3. described in claim 1 or 2, it is used for the preparation method of the charcoal base heteropolyacid catalyst of low-temperature flue gas simultaneous SO_2 and NO removal, its
It is characterised by mainly including following step of preparation process:
(1) under the conditions of 60～65 DEG C, by the salpeter solution pickling processes that activated carbon granule weight fraction is 28%～32%,
It is washed to neutrality again, dries, be designated as NAC；
(2) weigh the heteropoly acid of 15～20 weight portions, soluble in water to make the heteropoly acid that weight fraction is 8.9%～12.0% molten
Liquid；Weigh the NAC of 80～85 weight portions again, impregnated in the heteropoly acid solution that above-mentioned weight fraction is 8.9%～12%, stand
No less than 18 hours, it is evaporated at 60～65 DEG C；Then it is dried 10～12h in 100～105 DEG C, prepares catalyst precursor；
(3) with N2For protection gas, catalyst precursor being placed in Muffle kiln roasting, heating rate is not higher than 6 DEG C/min, roasting
Burn temperature be 200～800 DEG C, roasting time be 2～3h, then naturally cool to room temperature and i.e. obtain finished catalyst.
It is used for the preparation method of the charcoal base heteropolyacid catalyst of low-temperature flue gas simultaneous SO_2 and NO removal the most according to claim 3,
It is characterized in that activated carbon granule size is between 10～20 mesh.
It is used for the preparation method of the charcoal base heteropolyacid catalyst of low-temperature flue gas simultaneous SO_2 and NO removal the most according to claim 3,
It is characterized in that described heteropoly acid liquor capacity is identical with the volume of added activated carbon.
6. the charcoal base heteropolyacid catalyst for low-temperature flue gas simultaneous SO_2 and NO removal described in claim 1 or 2 is applied, its feature
It is, the flue gases of 80～160 DEG C are carried out desulphurization denitration simultaneously.
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