CN108607574A - A kind of anti-H2O、SO2With the catalyst for denitrating flue gas and preparation method thereof of heavy metal detoxification evil - Google Patents
A kind of anti-H2O、SO2With the catalyst for denitrating flue gas and preparation method thereof of heavy metal detoxification evil Download PDFInfo
- Publication number
- CN108607574A CN108607574A CN201810529011.7A CN201810529011A CN108607574A CN 108607574 A CN108607574 A CN 108607574A CN 201810529011 A CN201810529011 A CN 201810529011A CN 108607574 A CN108607574 A CN 108607574A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- present
- source
- flue gas
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention relates to a kind of anti-H2O、SO2With the catalyst for denitrating flue gas and preparation method thereof of heavy metal detoxification evil, belong to multi-element metal oxide technical field of function materials.The present invention provides a kind of Fe Ce Mn Co/TiO2Five yuan of metal composite oxide catalysts.The polynary denitrating catalyst that the present invention uses has wider denitration temperature window and preferable low-temperature denitration activity, especially anti-H2O、SO2It is stronger with heavy metal detoxification evil ability.
Description
Technical field
The present invention relates to multi-element metal oxide technical field of function materials, and in particular to a kind of anti-H2O、SO2And heavy metal
Catalyst for denitrating flue gas and preparation method thereof of detoxification evil more particularly to a kind of multicomponent catalyst for SCR denitrating flue gas and
Preparation method.
Background technology
Coal, in occupation of absolute leading role, and long-term accounts for China's primary energy consumption in Chinese national economy construction
The ratio of total amount close even higher than 70%.In coal in China consumption, 80% coal is used as steam coal, is directly used in combustion
It burns and generates thermal energy and power.But coal is a kind of low-grade fossil fuel, and there are a large amount of oxysulfides, nitrogen oxygen in combustion product gases
The pollutants such as compound and carbon dioxide.According to statistics:CO, CO of Discharged form Coal Combustion in China2、SO2, NOX and dust account for total fuel combustion
The ratio for burning discharge capacity is followed successively by 71%, 85%, 90%, 70% and 70%.
Although China has obtained significant results to the control of sulfur dioxide and dust, and compared to sulfur dioxide and dust etc.
The reduction of gross contamination emission, discharged nitrous oxides total amount is but quickly increasing, according to scholarly forecast, according to current development
Trend is up to 35,400,000 tons if not taking effective control measure to the year two thousand thirty nitrogen oxide emission, certainly will give China's ecology
Environment and national economy cause huge harm.Meanwhile nitrogen oxides is also in rising trend to the contribution of China's Acid Rain Pollution, acid rain
Middle NO3- concentration obviously increases, and the Acid Rain Pollution of China some areas is just gradually from sulfuric acid type to sulfuric acid, the compound transformation of nitric acid.
Also, nitrogen oxides also has very strong greenhouse effects.Therefore, the discharge for controlling nitrogen oxides, especially controls coal fired thermal power plant
The discharge of nitrogen oxides is trend of the times.
In recent years, in a variety of coal fired thermal power plant denitration technologies, selective catalytic reduction (Selective catalytic
Reduction, SCR), relatively cost-effective because of its denitration efficiency height, oneself becomes the mainstream of current China's coal fired thermal power plant denitration
Technology.Selective catalytic reduction (SCR) denitration is primarily referred to as under the effect of the catalyst, and (coal fired thermal power plant denitration is also for reducing agent
Former agent is mainly urea and NH3, " selective " reacted with NOX in flue gas, generate nontoxic, free of contamination nitrogen and water.
Currently, SCR denitration used in coal-burning power plant of China is vanadium tungsten titanium series, be required for greatly import or
Foreign technology is quoted, therefore first this and the renewal cost dressed up of SCR catalyst is all very high.And due to denitration temperature it is higher (300~
400 DEG C), SCR device can only be arranged between economizer and air preheater.But contain herein there are a large amount of flying dusts in flue gas
There are alkali metal, the substances such as arsenic and mercury inevitably to corrode and poison catalyst, catalyst is caused to be easy inactivation, service life
It does not grow, and complicated component in flue gas, also be easy to cause catalyst poisoning, lead to life time decay；Meanwhile vanadium tungsten titanium series catalyst
Vanadium component is easy to run off in agent, can be caused serious injury to environment and human body.Therefore, catalyst, which has become, restricts China's popularization and application
SCR denitration technology, the principal element for controlling coal fired thermal power plant discharged nitrous oxides.
Therefore, research is nontoxic, denitration performance is good, denitration temperature window mouth width, the SCR denitration of inexpensive, especially
It is that denitration temperature is low, the strong catalyst for denitrating flue gas of anti-poisoning capability, in China there is important practical application to anticipate
Justice, it has also become one of the focus of line research staff's common concern in the industry.
Invention content
The multicomponent catalyst and preparation method thereof that the object of the present invention is to provide a kind of for denitrating flue gas, it is especially a kind of
For the catalyst of SCR denitrating flue gas, the polynary denitrating catalyst that the present invention uses, have wider denitration temperature window and
Preferable low-temperature denitration activity, especially anti-H2O、SO2It is stronger with heavy metal detoxification evil ability.
In order to achieve the above objectives, the present invention provides a kind of multicomponent catalyst for denitrating flue gas, specially a kind of Fe-
Ce-Mn-Co/TiO2Five yuan of metal composite oxide catalysts, wherein
The molar ratio of element of Fe/Ti is (0.3~0.9)：1；
The molar ratio of Elements C e/Ti is (0.3~0.8)：1；
The molar ratio of element M n/Ti is (0.2~0.8)：1；
The molar ratio of Elements C o/Ti is (0.05~0.6)：1.
Preferably, the catalyst has porous structure
Preferably, the granularity of the catalyst is 40~4000 mesh.
Preferably, the porosity of the catalyst is 2.8~1800m2/g。
Preferably, the specific surface area of the catalyst is 0.009~0.42cm3/g。
Invention also provides a kind of preparation methods of above-mentioned multicomponent catalyst for denitrating flue gas, including following step
Suddenly：
A) soluble source of iron, soluble cerium source, soluble manganese source, soluble cobalt source, titanium dioxide and water are mixed, acutely
Dry after stirring, irradiation obtains intermediate powder；
B it) will be ground after intermediate powder calcination that above-mentioned steps obtain, obtain the catalyst for denitrating flue gas.
Preferably, the drying is dried using microwave dryer, and drying time is 5-60 minutes.
Preferably, the irradiation is irradiated using low-energy electronic accelerator irradiation devices, irradiation 0.3-5MeV, spoke
It it is 0.5-2 minutes according to the time.
Preferably, the calcination temperature is 300-600 DEG C, and the time is 1.5-3 hours.
Preferably, the soluble source of iron includes bivalent soluble source of iron and/or trivalent solubility source of iron.
Preferably, the soluble source of iron includes ferric sulfate, ferrous sulfate, iron chloride, frerrous chloride, ferric nitrate and nitric acid
It is one or more in ferrous iron；
The solubility cerium source includes one or more in cerous sulfate, cerium chloride and cerous nitrate；
The solubility manganese source includes one or more in manganese sulfate, manganese chloride and manganese nitrate；
The solubility cobalt source includes one or more in cobaltous sulfate, cobalt chloride and cobalt nitrate.
The present invention provides a kind of multicomponent catalysts for denitrating flue gas, are Fe-Ce-Mn-Co/TiO2Five yuan of metals
Composite oxide catalysts.Compared with prior art, the present invention is toxic for existing vanadium Titanium series catalyst, denitration temperature is high,
The problems such as cost height carry out creative selection and research, it is believed that ferrum-based catalyst has ring in numerous catalyst
The advantages that border is nontoxic, denitration is at low cost is a kind of SCR denitration of great exploitation potential, and is carried out in various metals
Combination, with preferable catalytic performance and on the basis of stability, temperature window is applied in broadening, especially has preferable low temperature
Active and anti-H2O、SO2Ability is done harm to heavy metal detoxification, has finally obtained the Fe-Ce-Mn-Co/TiO of the present invention2Five yuan of metals are multiple
Close oxide catalyst.Fe-Ce-Mn-Co/TiO provided by the invention2Five yuan of metal composite oxide catalysts, can regard as
For iron-based, titanium-based or cerium base catalyst, and the advantages of combine above-mentioned catalyst, each component cooperates, and compensates for original list
The deficiency of one catalyst.The addition of wherein Fe can improve the low temperature active and sulfur poisoning resistance of denitrating catalyst, but flue gas
In SO2It is very big to the activity influence of denitrating catalyst and also different for the influencing mechanism of different catalyst system and catalyzings, and
And middle low-temperature denitration activity is still insufficient, and the multi-element metal oxide of the present invention effectively raises the synthesis energy of antitoxinization
Power；Elements C e is nontoxic, rich reserves, and has excellent redox property, but low temperature active and sulfur poisoning resistance are not
Foot, and the multi-element metal oxide of the present invention effectively compensates for its drawbacks described above.Fe-Ce-Mn-Co/ provided by the invention
TiO2Five yuan of metal composite oxide catalysts have anti-H as SCR catalyst for denitrating flue gas2O、SO2It is done harm to heavy metal detoxification
The advantages that ability is strong, denitration is at low cost also has higher thermal stability, wider temperature window and preferable low-temperature denitration
Activity.The experimental results showed that Fe-Ce-Mn-Co/TiO provided by the invention2Five yuan of metal composite oxide catalysts, catalysis effect
Rate and catalytic activity temperature are adjustable with synthesis component, and water resistant Sulfur tolerance is preferable, in H2O and SO2In existing a certain range, urge
Change stabilised efficiency 92% or more.
Description of the drawings
Fig. 1 is the SEM electromicroscopic photographs of multi-element metal oxide powder prepared by the embodiment of the present invention 1；
Fig. 2 is the EDS energy spectrum diagrams of multi-element metal oxide powder prepared by the embodiment of the present invention 1；
Fig. 3 is the denitration catalyst rate detection figure of multi-element metal oxide powder prepared by the embodiment of the present invention 1.
Specific implementation mode
In order to further appreciate that the present invention, the preferred embodiments of the invention are described with reference to embodiment, but
It is it should be appreciated that these descriptions are only the feature and advantage further illustrated the present invention rather than to patent requirements of the present invention
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to people in the art
It is prepared by conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or metal composite oxygen
The purity of compound field routine.
The present invention provides a kind of multicomponent catalyst for denitrating flue gas, specially a kind of Fe-Ce-Mn-Co/TiO2Five
First metal composite oxide catalyst.
The definition of the multi-element metal oxide is not particularly limited in the present invention, with well known to those skilled in the art more
First metal oxide or composite oxide of metal.The present invention is to the ingredient of the multi-metal oxide catalyst without spy
It does not limit, those skilled in the art can select and adjust according to practical situations, raw material condition and product requirement.
The present invention is to be more advantageous to SCR denitrating flue gas, is especially more advantageous to the middle low temperature SCR denitration of power-plant flue gas, institute
State element of Fe/Ti, i.e., the molar ratio of the described element of Fe and element ti is preferably (0.3~0.9)：1, more preferably (0.4~
0.8)：1, more preferably (0.5~0.7)：1, most preferably (0.55~0.65)：1；The Elements C e/Ti, i.e., the described Elements C e
Molar ratio with element ti is preferably (0.3~0.8)：1, more preferably (0.4~0.8)：1, more preferably (0.5~0.7)：1,
Most preferably (0.55~0.65)：1；The molar ratio of the element M n/Ti, i.e., the described element M n and element ti be preferably (0.2~
0.8)：1, more preferably (0.3~0.6)：1, more preferably (0.4~0.6)：1, most preferably (0.4~0.5)：1；The member
The molar ratio of plain Co/Ti, i.e., the described element Zr and element ti is preferably (0.05~0.6)：1, more preferably (0.1~0.5)：1,
More preferably (0.2~0.4)：1, most preferably (0.3~0.4)：1.
The pattern of the multi-metal oxide catalyst is not particularly limited in the present invention, ripe with those skilled in the art
The pattern for the multi-metal oxide catalyst known is not particularly limited, and those skilled in the art can be according to practical application feelings
Condition, raw material condition and product requirement are selected and are adjusted, and catalyst of the present invention is preferably nano material, the catalysis
The granularity of agent is preferably 40~4000 mesh, more preferably 200~3000 mesh, more preferably 500~3000 mesh, most preferably 1500
~2000 mesh.Catalyst of the present invention preferably has porous structure；The porosity of the catalyst is preferably 2.8~
1800m2/ g, more preferably 15~1000m2/ g, more preferably 150~400m2/ g, most preferably 300~400m2/g；It is described to urge
The specific surface area of agent is preferably 0.009~0.42cm3/ g, more preferably 0.01~0.36cm3/ g, more preferably 0.06~
0.25cm3/ g, most preferably 0.15~0.25cm3/g.Catalyst of the present invention for denitrating flue gas is preferred for SCR cigarettes
The catalyst of qi exhaustion nitre is more preferably used for the catalyst of middle low-temperature smoke air SCR denitration, is more specifically preferred in power-plant flue gas
The catalyst of low temperature SCR denitration.
The present invention is preferably 150~265 DEG C to the temperature in use of the catalyst, more preferably 160~240 DEG C, more excellent
It is selected as 180~220 DEG C, most preferably 190~200 DEG C；Wherein low temperature temperature in use can be 120~180 DEG C, or be 135
~165 DEG C, it is either 140~160 DEG C again or is 150~155 DEG C.
Above-mentioned steps of the present invention provide a kind of Fe-Ce-Mn-Co/TiO2Five yuan of metal composite oxide catalysts, can be with
The advantages of regarding as iron-based, titanium-based or cerium base catalyst, and combining above-mentioned catalyst, each component cooperate, and compensate for original
There is the deficiency of single catalyst.The present invention further optimizes combination to component, with TiO2For carrier, low temperature is urged during Fe is used as
Change doped body, rare earth metal Ce, transient metal Mn and Co are prepared for multicomponent Fe-Ce- as enhancing catalytic performance auxiliary agent
Mn-Co/TiO2Five yuan of metal composite oxide catalysts, each component flexible ratio is adjustable, and not only synthesis cost is relatively low, Er Qiegeng
Add the low temperature SCR denitration suitable for power-plant flue gas.Fe-Ce-Mn-Co/TiO provided by the invention2Five yuan of metal composite oxidations
Object catalyst has anti-H2O、SO2With the advantages that heavy metal detoxification evil ability is strong, denitration is at low cost, also there is higher thermostabilization
Property, wider temperature window and preferable low-temperature denitration activity.
The present invention also provides a kind of preparation methods of above-mentioned multicomponent catalyst for denitrating flue gas, including following step
Suddenly：
A) soluble source of iron, soluble cerium source, soluble manganese source, soluble cobalt source, titanium dioxide and water are mixed, acutely
Dry after stirring, irradiation obtains intermediate powder；
B it) will be ground after intermediate powder calcination that above-mentioned steps obtain, obtain the catalyst for denitrating flue gas.
The present invention especially indicates the range of choice and optimum principle of the poly metal oxide nano material, such as nothing,
It is consistent with the range of choice and optimum principle of the catalyst nano material that is previously used for denitrating flue gas, it no longer goes to live in the household of one's in-laws on getting married one by one herein
It states.
A) soluble source of iron, soluble cerium source, soluble manganese source, soluble cobalt source, titanium dioxide and water are mixed, acutely
Dry after stirring, irradiation obtains intermediate powder；
The soluble source of iron is not particularly limited in the present invention, is with soluble source of iron well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical situations, raw material condition and product requirement
The bright soluble source of iron preferably includes bivalent soluble source of iron and/or trivalent solubility source of iron, more preferably bivalent soluble
Source of iron or trivalent solubility source of iron；It is of the present invention solubility source of iron specifically preferably include ferric sulfate, ferrous sulfate, iron chloride,
It is one or more in frerrous chloride, ferric nitrate and ferrous nitrate, more specifically preferably ferric sulfate, ferrous sulfate, iron chloride, chlorine
Change ferrous, ferric nitrate or ferrous nitrate, most preferably ferric nitrate.The present invention is not special to the addition of the soluble source of iron
Limitation, using the ratio of final products as standard, pilot process consume or practical inventory, those skilled in the art can roots
It is selected and is adjusted according to practical condition, raw material condition and product requirement.
The soluble cerium source is not particularly limited in the present invention, is with soluble cerium source well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical situations, raw material condition and product requirement
The bright soluble cerium source preferably includes one or more in cerous sulfate, cerium chloride and cerous nitrate, more preferably cerous sulfate, chlorine
Change cerium or cerous nitrate, most preferably cerous nitrate.The addition in the soluble cerium source is not particularly limited in the present invention, with final
The ratio of product is standard, and pilot process consume or practical inventory, those skilled in the art can be according to actual productions
Situation, raw material condition and product requirement are selected and are adjusted.
The soluble manganese source is not particularly limited in the present invention, is with soluble manganese source well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical situations, raw material condition and product requirement
The bright soluble manganese source preferably includes one or more in manganese sulfate, manganese chloride and manganese nitrate, more preferably manganese sulfate, chlorine
Change manganese or manganese nitrate, most preferably manganese nitrate.The addition of the soluble manganese source is not particularly limited in the present invention, with final
The ratio of product is standard, and pilot process consume or practical inventory, those skilled in the art can be according to actual productions
Situation, raw material condition and product requirement are selected and are adjusted.
The soluble cobalt source is not particularly limited in the present invention, is with soluble cobalt source well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical situations, raw material condition and product requirement
The bright soluble zirconium source preferably includes one or more in cobaltous sulfate, cobalt chloride and cobalt nitrate, more preferably cobaltous sulfate, chlorine
Change cobalt or cobalt nitrate, most preferably cobalt nitrate.The addition of the soluble cobalt source is not particularly limited in the present invention, with final
The ratio of product is standard, and pilot process consume or practical inventory, those skilled in the art can be according to actual productions
Situation, raw material condition and product requirement are selected and are adjusted.
The addition of the titanium dioxide is not particularly limited in the present invention, using the ratio of final products as standard,
Pilot process consumes or practical inventory, those skilled in the art can be according to practical condition, raw material condition and products
It is required that being selected and being adjusted.Water of the present invention is preferably deionized water；The present invention is not special to the addition of the water
Limitation, using the ratio of final products as standard, pilot process consume or practical inventory, those skilled in the art can roots
It is selected and is adjusted according to practical condition, raw material condition and product requirement.
The mode and condition of the drying is not particularly limited in the present invention, with drying side well known to those skilled in the art
Formula and condition, those skilled in the art can select according to practical condition, raw material condition and product requirement
And adjustment.The mode of drying of the present invention is preferably dried using microwave dryer.Microwave drying is a kind of novel do
Dry mode.When dry, microwave energy directly acts on medium molecule and is converted into thermal energy, since there is microwave penetration performance to make in medium
It heats simultaneously outside, heat transfer is not needed, so heating speed is very fast.Simultaneously regardless of object any shape, due to Jie of object
Matter is inside and outside to be heated simultaneously, and the internal-external temperature difference of material is small, and homogeneous heating makes dry mass greatly improve.The time of the drying is excellent
It is selected as 5~60 minutes, more preferably 10~40 minutes, most preferably 20~30 minutes.
The mode and condition of the irradiation is not particularly limited in the present invention, with irradiation side well known to those skilled in the art
Formula and condition, those skilled in the art can select according to practical condition, raw material condition and product requirement
And adjustment.The mode of irradiation of the present invention is preferably irradiated using low-energy electronic accelerator irradiation devices.Electron accelerator
With room temperature, it is not damaged, without residual hazard, environmental protection, low energy consumption, operation it is easy to operate, high degree of automation, be suitable for large-scale industry
The features such as metaplasia is produced.Ultrasound needs 6 hours, and microwave needs 20min (but in fact not enough uniformly effectively, energy or low).It is described
Irradiation is 0.3-5MeV, more preferably 0.5-4MeV, most preferably 1-3MeV；The irradiation time is 0.5-2 minutes；It is more excellent
It is selected as 1.0-2 minutes, most preferably 1.5-2 minutes.
The present invention will finally be ground after intermediate powder calcination that above-mentioned steps obtain, obtain the catalysis for denitrating flue gas
Agent.
The mode and condition of the calcining is not particularly limited in the present invention, with calcining side well known to those skilled in the art
Formula and condition, those skilled in the art can select according to practical condition, raw material condition and product requirement
And adjustment, the mode of calcining of the present invention is preferably Muffle furnace, is more preferably calcined in air atmosphere；The temperature of the calcining
Preferably 300~600 DEG C of degree, more preferably 400~500 DEG C, most preferably 420~480 DEG C；The time of the calcining is specifically excellent
It is selected as 1.5~3 hours, more preferably 2~2.5 hours, most preferably 2.2~2.5 hours.
The mode and condition of the grinding is not particularly limited in the present invention, with grinding side well known to those skilled in the art
Formula and condition, those skilled in the art can select according to practical condition, raw material condition and product requirement
And adjustment, the granularity of grinding of the present invention is preferably 50~3800 mesh, more preferably 100~3000 mesh, more preferably 500~
2500 mesh, most preferably 1000~2000 mesh.
Above-mentioned steps of the present invention provide a kind of multicomponent catalyst for denitrating flue gas, i.e. Fe-Ce-Mn-Co/TiO2Five
The preparation method of first metal composite oxide catalyst.The present invention particularly prepares the catalyst using hydro-thermal method, Fe, Ce, Mn,
Good interaction occurs for Co and Ti groups branch, and the interworking of catalyst components can be made to reach more preferably effect, improved whole
The redox property of body metal composite oxide catalyst, low-temperature catalytic oxidation NO are NO2Performance, while helping to be catalyzed
The crystal grain refinement of agent, surface area increase, and provide more activity for SCR reactions, finally denitration performance are promoted to be substantially improved, carried simultaneously
High low temperature SCR denitration activity so that denitration temperature window is substantially widened, and is effectively extended to low-temperature space, effective solution
Low-temperature denitration activity is relatively low in existing ferrum-based catalyst, and preparation process is not mature enough, limit its large-scale industry and answer
Inherent shortcoming is more appropriately applied to the removing of the discharged nitrogen oxides of China's coal fired thermal power plant.The experimental results showed that this
The multi-element metal oxide provided is provided, catalytic efficiency and catalytic activity temperature are adjustable with synthesis component, and water resistant Sulfur tolerance compared with
It is good, anti-H2O、SO2It is strong with heavy metal detoxification evil ability, in H2O and SO2In existing a certain range, catalytic efficiency is stablized 92%
More than.
In order to further illustrate the present invention, it a kind of is urged with reference to embodiments for denitrating flue gas to provided by the invention
Agent and preparation method thereof is described in detail, but it is to be understood that these embodiments are before being with technical solution of the present invention
It puts and is implemented, give detailed embodiment and specific operating process, only the spy to further illustrate the present invention
It seeks peace advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following embodiments.
Embodiment 1
It is 0.3 by molar ratio：0.3：0.2：0.05：1 0.32g ferric nitrates, 0.51g cerous nitrates, 0.32g manganese nitrates are water-soluble
Liquid and 0.07g cabaltous nitrate hexahydrates, 0.35g titanium dioxide powders are dissolved in 15mL deionized waters, be vigorously stirred be put into after five minutes it is micro-
Wave drying machine goes water to dry 5 minutes, is then placed in medium energy electrons accelerator irradiation device, and irradiation is set as 0.3MeV, 0.5 point
After clock processing, lower 300 DEG C of air atmosphere is calcined 1.5 hours, grind into powder.Quickly, Fe-Ce-Mn-Co/TiO is efficiently prepared2
Five yuan of metal composite oxide catalysts.
The multi-element metal oxide prepared to the embodiment of the present invention 1 characterizes.Fig. 1 is prepared by the embodiment of the present invention 1
The SEM electromicroscopic photographs of multi-element metal oxide powder.Fig. 2 is multi-element metal oxide powder prepared by the embodiment of the present invention 1
EDS energy spectrum diagrams.Fig. 3 is the XRD spectrum of multi-element metal oxide powder prepared by the embodiment of the present invention 1.Table 1 is multi-element metal oxygen
The atomic percent of each component is corresponded in compound powder.
The atomic percent of each component is corresponded in 1 multi-element metal oxide powder of table
By Fig. 2 and table 1 it is found that the controllable multi-element metal oxide of specific ratio has been prepared in the present invention.
Poly metal oxide nano material prepared by the embodiment of the present invention 1 is carried out using detection.
Test example one
The experimental provision reactor that SCR removes NO uses fixed bed quartz tube reactor, internal diameter 1cm, reaction temperature
By the K-type thermocouple measurement in intercalation reaction device.Simulated flue gas condition is supplied using steel cylinder, flue gas includes Ar (with H2O)、
NO/Ar、O2、SO2/ Ar and NH3The flow of/Ar, gas are controlled and are adjusted by mass flowmenter with composition, steam H2O is by Ar
By being taken out of after steam generating means, react using Ar as balanced gas.In the reaction starting stage, it is real first to carry out saturation absorption
It tests, i.e., is re-introduced into NH after reactor inlet and outlet NO, concentration reach balance3Carry out SCR reactions.The practical typical flue gas of simulation
Distribution composition：500ppmNO/Ar, 500ppmNH3/ Ar, 100ppmSO2/ Ar, 4%O2, Ar is (with H2O(10-30g/m3)) be
Carrier gas.Temperature range is 100-300 DEG C, and reaction pressure is normal pressure, and air speed ratio is 10000/h.Wherein NO and NH3Ratio according to
The mix proportion scheme used when practical power plant's operation is 1:1.The results are shown in Table 2.
2 Fe-Ce-Mn-Co/TiO of table2Five yuan of metal oxides are in different temperatures and SO2NO under concentration restores conversion ratio
By testing result it is found that multi-element metal oxide prepared by the present invention, has wider denitration temperature window (150-
265 DEG C) and preferable low-temperature denitration activity (92% or more).
Test example two
China's fire coal ingredient is extremely complex, present in impurity many heavy metals can be discharged in burning, these a huge sum of money
Category can be enriched to SCR catalyst surface in catalytic process, and catalyst poisoning is caused to inactivate.The present invention is with regard to several typical cases in flue dust
Heavy metal element (Cu, As, Pb) is tested the activity influence of SCR denitration.It is real that this project carries out preventing from heavy metal
Test tries：By incorporation weight percent respectively in CuO, PbO, AS of 0.1%-5%2O3Catalyst afterwards carries out SCR catalyst
The measurement of denitration activity simulates the distribution composition of practical typical flue gas：500ppmNO/Ar, 500ppmNH3/ Ar, 4%O2, Ar (companions
With H2O(10-30g/m3)) it is carrier gas.Reaction pressure is normal pressure, and air speed ratio is 10000/h.Wherein NO and NH3Ratio according to reality
The mix proportion scheme that border power plant uses when running is 1:1.The results are shown in Table 3.
3 Fe-Ce-Mn-Co/TiO of table2NO of five yuan of metal oxides under the incorporation of different weight percentage heavy metal is also
Former conversion ratio
By testing result it is found that by testing result it is found that multi-element metal oxide prepared by the present invention, has stronger anti-
Heavy metal poisons ability.
Embodiment 2
It is 0.9 by molar ratio：0.8：0.8：0.6：1 2.4g iron chloride, 3.69g cerium chlorides, 1.65g manganese chlorides and
2.32g cobalt chloride hexahydrates, 1.3g titanium dioxide powders are dissolved in 100mL deionized waters, are vigorously stirred and are put into microwave after ten minutes
Drying machine goes water to dry 60 minutes, is then placed in medium energy electrons accelerator irradiation device, irradiation is set as 5MeV, at 2 minutes
After reason, lower 600 DEG C of air atmosphere is calcined 3 hours, grind into powder.Quickly, Fe-Ce-Mn-Co/TiO is efficiently prepared2Five yuan of gold
Belong to composite oxide catalysts.
Poly metal oxide nano material prepared by the embodiment of the present invention 2 is carried out using detection.
Method is the same as embodiment 1.
By testing result it is found that multi-element metal oxide prepared by the present invention, anti-H2O、SO2, dust and heavy metal poison energy
Power is strong, also has higher thermal stability, wider temperature window (150-265 DEG C) and preferable low-temperature denitration activity
(92% or more).
Embodiment 3
It is 0.2 by molar ratio：0.2：0.2：0.2：1 0.74g iron chloride, 1.278g cerium chlorides, 0.57g manganese chlorides and
1.07g cobalt chloride hexahydrates, 1.8g titanium dioxide powders are dissolved in 50mL deionized waters, and it is dry that microwave is put into after being vigorously stirred 7 minutes
Dry machine goes water to dry 30 minutes, is then placed in medium energy electrons accelerator irradiation device, and irradiation is set as 2.2MeV, 1.3 minutes
After processing, lower 500 DEG C of air atmosphere is calcined 2.3 hours, grind into powder.Quickly, Fe-Ce-Mn-Co/TiO is efficiently prepared2Five
First metal composite oxide catalyst.Poly metal oxide nano material prepared by the embodiment of the present invention 3 is carried out using inspection
It surveys.
Method is the same as embodiment 1.
By testing result it is found that multi-element metal oxide prepared by the present invention, anti-H2O、SO2, dust and heavy metal poison energy
Power is strong, also has higher thermal stability, wider temperature window (150-265 DEG C) and preferable low-temperature denitration activity
(92% or more).
Above to the catalyst provided by the present invention for SCR denitrating flue gas, it to be especially used for low-temperature SCR in power-plant flue gas
Catalyst of denitration and preparation method thereof.It is described in detail, specific case used herein is to the principle of the present invention
And embodiment is expounded, the explanation of above example is only intended to help to understand that the method for the present invention and its core are thought
Think, including best mode, and but also any person skilled in the art can put into practice the present invention, including manufactures and use
Any device or system, and implement the method for any combination.It should be pointed out that coming for those skilled in the art
It says, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention, these improvement and modification
It also falls within the protection scope of the claims of the present invention.The range of patent protection of the present invention is defined by the claims, and can
Including those skilled in the art it is conceivable that other embodiment.It is not different from right if these other embodiments have and wants
The structural element of character express is sought, or if they include and equivalent structure of the character express of claim without essence difference
Element, then these other embodiments should also be included in the scope of the claims.
Claims (8)
1. a kind of multicomponent catalyst for denitrating flue gas, which is characterized in that it is Fe-Ce-Mn-Co/TiO2Five yuan of metal composites
Oxide catalyst.
2. multicomponent catalyst according to claim 1, which is characterized in that wherein,
The molar ratio of element of Fe/Ti is (0.3~0.9)：1；
The molar ratio of Elements C e/Ti is (0.3~0.8)：1；
The molar ratio of element M n/Ti is (0.2~0.8)：1；
The molar ratio of Elements C o/Ti is (0.05~0.6)：1.
3. multicomponent catalyst according to claim 1, which is characterized in that the catalyst has porous structure, described to urge
The granularity of agent is 40~4000 mesh, and the porosity of the catalyst is 2.8~1800m2/ g, the specific surface area of the catalyst
For 0.009~0.42cm3/g。
4. a kind of preparation method of the multicomponent catalyst described in claim 1 for denitrating flue gas, which is characterized in that including with
Lower step：
A) soluble source of iron, soluble cerium source, soluble manganese source, soluble cobalt source, titanium dioxide and water are mixed, are vigorously stirred
After dry, irradiate, obtain intermediate powder；
B it) will be ground after intermediate powder calcination that above-mentioned steps obtain, obtain the catalyst for denitrating flue gas.
5. preparation method according to claim 4, which is characterized in that the drying is dried using microwave dryer,
Drying time is 5-60 minutes.
6. preparation method according to claim 4, which is characterized in that the irradiation is using low-energy electronic accelerator irradiation dress
It sets and is irradiated, irradiation 0.3-5MeV, irradiation time is 0.5-2 minutes.
7. preparation method according to claim 4, which is characterized in that the calcination temperature is 300-600 DEG C, and the time is
1.5-3 hour.
8. preparation method according to claim 4, which is characterized in that
The solubility source of iron includes one in ferric sulfate, ferrous sulfate, iron chloride, frerrous chloride, ferric nitrate and ferrous nitrate
Kind is a variety of；
The solubility cerium source includes one or more in cerous sulfate, cerium chloride and cerous nitrate；
The solubility manganese source includes one or more in manganese sulfate, manganese chloride and manganese nitrate；
The solubility cobalt source includes one or more in cobaltous sulfate, cobalt chloride and cobalt nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810529011.7A CN108607574A (en) | 2018-05-29 | 2018-05-29 | A kind of anti-H2O、SO2With the catalyst for denitrating flue gas and preparation method thereof of heavy metal detoxification evil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810529011.7A CN108607574A (en) | 2018-05-29 | 2018-05-29 | A kind of anti-H2O、SO2With the catalyst for denitrating flue gas and preparation method thereof of heavy metal detoxification evil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108607574A true CN108607574A (en) | 2018-10-02 |
Family
ID=63664409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810529011.7A Pending CN108607574A (en) | 2018-05-29 | 2018-05-29 | A kind of anti-H2O、SO2With the catalyst for denitrating flue gas and preparation method thereof of heavy metal detoxification evil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108607574A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112844404A (en) * | 2021-01-29 | 2021-05-28 | 西南化工研究设计院有限公司 | Low-temperature denitration catalyst with TiO2 nanotube as carrier and preparation and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102895872A (en) * | 2011-07-28 | 2013-01-30 | 中国石油化工股份有限公司 | Method for removing sulfur oxides and nitrogen oxides in catalytic cracking regeneration flue gas |
| CN103894185A (en) * | 2014-04-01 | 2014-07-02 | 北京工业大学 | Method for preparing selective catalytic reduction (SCR) denitration catalyst by taking TiO2-ZnO as composite carrier |
| CN106423197A (en) * | 2016-12-05 | 2017-02-22 | 吉林省电力科学研究院有限公司 | Multi-element catalyst for flue gas denitrification and preparation method thereof |
| CN106732624A (en) * | 2016-12-05 | 2017-05-31 | 吉林省电力科学研究院有限公司 | A kind of catalyst for denitrating flue gas and preparation method thereof |
-
2018
- 2018-05-29 CN CN201810529011.7A patent/CN108607574A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102895872A (en) * | 2011-07-28 | 2013-01-30 | 中国石油化工股份有限公司 | Method for removing sulfur oxides and nitrogen oxides in catalytic cracking regeneration flue gas |
| CN103894185A (en) * | 2014-04-01 | 2014-07-02 | 北京工业大学 | Method for preparing selective catalytic reduction (SCR) denitration catalyst by taking TiO2-ZnO as composite carrier |
| CN106423197A (en) * | 2016-12-05 | 2017-02-22 | 吉林省电力科学研究院有限公司 | Multi-element catalyst for flue gas denitrification and preparation method thereof |
| CN106732624A (en) * | 2016-12-05 | 2017-05-31 | 吉林省电力科学研究院有限公司 | A kind of catalyst for denitrating flue gas and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112844404A (en) * | 2021-01-29 | 2021-05-28 | 西南化工研究设计院有限公司 | Low-temperature denitration catalyst with TiO2 nanotube as carrier and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106423197A (en) | Multi-element catalyst for flue gas denitrification and preparation method thereof | |
| CN101920213B (en) | Low temperature SCR denitration catalyst taking organic metal framework as carrier and preparation method thereof | |
| CN106732624A (en) | A kind of catalyst for denitrating flue gas and preparation method thereof | |
| CN104722307A (en) | Iron-based low-temperature SCR denitration catalyst and preparation method thereof | |
| CN101284238B (en) | Catalysts for stationary source ammine selective catalytic reduction for nitrous oxides | |
| CN109569587A (en) | A kind of manganese-based low-temperature catalyst for denitrating flue gas and preparation method thereof | |
| CN109092323A (en) | Low-temperature SCR catalyst for denitrating flue gas and its preparation method and application | |
| CN103752321A (en) | Method for preparing hierarchical bimetallic composite oxide denitrification catalyst | |
| CN106391037B (en) | One kind decomposing N for high-temperature catalytic2The preparation process of the catalyst of O | |
| CN102941083A (en) | Medium/low-temperature core-shell denitration catalyst and preparation method and application thereof | |
| CN108435189B (en) | Samarium-doped iron-based denitration catalyst with water resistance and sulfur resistance and preparation method thereof | |
| CN105879879B (en) | A kind of high sulfur resistive ultralow temperature SCR denitration and preparation method thereof | |
| CN102658155A (en) | Preparation method of supported type denitration catalyst | |
| CN108355662B (en) | The preparation method of nickel load galapectite methylmethane dry reforming catalyst | |
| CN110548518A (en) | Transition metal composite catalyst for purifying coal-fired organic waste gas and preparation method and application thereof | |
| Zhou et al. | NH3 treatment of CeO2 nanorods catalyst for improving NH3-SCR of NO | |
| CN105854894A (en) | Modified iron-ore SCR denitration catalyst and preparing method and application thereof | |
| CN107511160A (en) | A kind of MOX/g C3N4@SiO2The preparation method and applications of catalyst | |
| CN112808277A (en) | Low-temperature SCR denitration catalyst, preparation method and application thereof | |
| CN112138725A (en) | Catalytic decomposition of N2Preparation method of cobalt-based metal organic framework derivative catalyst of O | |
| CN106513005A (en) | A preparing method of an iron-based composite oxide catalyst | |
| CN104437535B (en) | A kind of environmentally friendly manganese cobalt aluminum composite oxide demercuration denitrating catalyst and preparation method thereof | |
| CN105214698B (en) | A kind of phosphorous ceria-based denitration catalyst of wide temperature range type and preparation method thereof | |
| CN112718018B (en) | Lanthanum cobaltite perovskite catalyst treated by acetic acid and preparation method thereof | |
| CN108607574A (en) | A kind of anti-H2O、SO2With the catalyst for denitrating flue gas and preparation method thereof of heavy metal detoxification evil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181002 |