CN106238040A - The preparation method of modified fly ash loading Mn Ce bimetallic denitration catalyst - Google Patents
The preparation method of modified fly ash loading Mn Ce bimetallic denitration catalyst Download PDFInfo
- Publication number
- CN106238040A CN106238040A CN201610615259.6A CN201610615259A CN106238040A CN 106238040 A CN106238040 A CN 106238040A CN 201610615259 A CN201610615259 A CN 201610615259A CN 106238040 A CN106238040 A CN 106238040A
- Authority
- CN
- China
- Prior art keywords
- fly ash
- bimetallic
- manganese
- modified
- flyash
- 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.)
- Granted
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
- B01J23/16—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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/048—Treatment with a plasma
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Plasma & Fusion (AREA)
- Biomedical Technology (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention provides the preparation method of a kind of modified fly ash loading Mn Ce bimetallic denitration catalyst, the method comprises the following steps: one, use flyash, bentonite and distilled water through extruding, drying, fly ash grain thing is prepared in shearing；Two, flyash is modified by using plasma；Three, low temperature plasma roasting preparation is used to be loaded with the modified coal ash of manganese；Four, low-temperature ion body roasting is used to prepare modified fly ash loading Mn Ce bimetallic denitration catalyst.The present invention uses low temperature plasma roasting, and roasting time is short, and energy consumption is low, preparation modified fly ash loading Mn Ce bimetallic denitration catalyst good dispersion, crystal grain is uniform, sulfur resistance good, activity and selectivity is strong, can apply in the improvement of denitrating flue gas, and denitration effect is good.
Description
Technical field
The invention belongs to denitrating catalyst preparing technical field, be specifically related to the double gold of a kind of modified fly ash loading Mn-Ce
Belong to the preparation method of denitrating catalyst.
Background technology
The difference of energy state, gas temperature and particle size according to electronics, plasma can be divided into low-temperature plasma
Body and high-temperature plasma, the temperature of high-temperature plasma can reach 106K～108K, is generally used for nuclear technology, for catalyst
Preparation is low temperature plasma with materials synthesis, and low temperature plasma includes again hot plasma and cold plasma, heat etc.
The gas temperature of ion is close with electron temperature (tens electron-volts of eV), and system is in poised state, thus referred to as balance etc.
Gas ions, on the contrary, though cold plasma electron temperature in discharge process the highest (1～10eV), heavy particle temperature is the lowest,
Whole system presents low temperature state, may remain in room temperature, so referred to as cold plasma, is also nonequilibrium state plasma
Body, what current laboratory used is all low temperature plasma.
The method preparing denitrating catalyst at present mainly includes infusion process and sol-gel process, but both approaches is in system
Being directed to long-time high-temperature roasting, i.e. Muffle furnace roasting during Bei, in roasting process, time length and temperature are high, energy consumption
, there is the shortcoming that dispersion is uneven in the easy conglomeration of catalyst after height, and roasting.
Summary of the invention
The technical problem to be solved is for above-mentioned the deficiencies in the prior art, it is provided that a kind of modified fine coal
The preparation method of ash loading Mn-Ce bimetallic denitration catalyst.This preparation method uses low temperature plasma roasting, roasting time
Short, energy consumption is low, and the modified fly ash loading Mn-Ce bimetallic denitration catalyst good dispersion of preparation, crystal grain are uniform, sulfur resistance
Good, activity and selectivity is strong, can apply in the improvement of denitrating flue gas, and denitration effect is good.
For solving above-mentioned technical problem, the technical solution used in the present invention is: the double gold of a kind of modified fly ash loading Mn-Ce
Belong to the preparation method of denitrating catalyst, it is characterised in that comprise the following steps:
Step one, flyash, bentonite are mixed homogeneously with distilled water, be squeezed into bar, more described bar is put
In baking oven, dry under conditions of temperature is 80 DEG C～100 DEG C, then the bar after drying is carried out shear treatment,
To fly ash grain thing；Described flyash and bentonitic mass ratio are (0.5～8): 1, and the quality of described distilled water is described
Flyash and the 50% of bentonite gross mass～80%；
Step 2, fly ash grain thing described in step one is placed in plasma reaction still, then to plasma
Reactor is passed through gas, make fly ash grain thing the power of plasma reaction still be 30W～60W, the flow of gas be
Under conditions of 20mL/min～60mL/min, modification 10min～40min, obtain modified coal ash；Described gas be oxygen,
Argon, nitrogen or nitrogen and the gaseous mixture of hydrocarbon gas；In described gaseous mixture, the percentage by volume of nitrogen is 96.31%；
Soluble manganese salt is loaded to described in step 2 on modified coal ash by step 3, employing equi-volume impregnating,
To containing manganese presoma, then the described presoma containing manganese is placed in plasma reaction still, backward described plasma reaction
Still is passed through oxygen, and to make containing manganese presoma at the power of plasma reaction still be 30W～90W, the gas flow of oxygen is 20mL/
Carry out low-temperature bake process under conditions of min～60mL/min, obtain being loaded with the flyash of manganese；Described low-temperature bake processes
Time is 1min～10min；Described manganese at the described flyash of manganese that is loaded with mainly with MnO2Presented in, described MnO2's
Quality be described in be loaded with manganese flyash quality 4%～16%；
Solubility cerium salt is loaded to be loaded with described in step 3 the flyash of manganese by step 4, employing equi-volume impregnating
On, obtain containing cerium precursor, then will contain cerium precursor and be placed in plasma reaction still, backward described plasma reaction
Still is passed through oxygen, and to make containing cerium precursor at the power of plasma reaction still be 30W～90W, the gas flow of oxygen is 20mL/
Carry out low-temperature bake process under conditions of min～60mL/min, obtain modified fly ash loading Mn-Ce bimetallic denitration catalyst
Agent；The time that described low-temperature bake processes is 1min～10min；Described cerium is at described modified fly ash loading Mn-Ce bimetallic
Mainly with CeO in denitrating catalyst2And Ce2O3Presented in, described CeO2And Ce2O3Quality sum be described modified fine coal
The 1%～12% of ash loading Mn-Ce bimetallic denitration catalyst quality.
The preparation method of above-mentioned modified fly ash loading Mn-Ce bimetallic denitration catalyst, it is characterised in that step one
Described in flyash and bentonitic mass ratio be (1～3): 1, the quality of described distilled water be described flyash and bentonite total
The 60%～70% of quality.
The preparation method of above-mentioned modified fly ash loading Mn-Ce bimetallic denitration catalyst, it is characterised in that step 2
Described in hydrocarbon gas be grouped into by the one-tenth of volumes below percentage ratio: ethane 27%, ethylene 27%, acetylene 13.6%, propane
5.4%, propylene 5.4%, allylene 5.4%, normal butane 5.4%, 1-butylene 5.4%, ethyl acetylene 5.4%.
The preparation method of above-mentioned modified fly ash loading Mn-Ce bimetallic denitration catalyst, it is characterised in that step 2
Described in the power of plasma reaction still be 40W～50W, the flow of gas is 35mL/min～45mL/min, time modified
Between be 20min～30min.
The preparation method of above-mentioned modified fly ash loading Mn-Ce bimetallic denitration catalyst, it is characterised in that step 3
Described in soluble manganese salt be manganese nitrate, manganese chloride or manganese sulfate.
The preparation method of above-mentioned a kind of modified fly ash loading Mn-Ce bimetallic denitration catalyst, it is characterised in that step
The power of plasma reaction still described in rapid three is 50W～70W, and the gas flow of described oxygen is 35mL/min～45mL/
Min, the time that described low-temperature bake processes is 2min～7min；Described MnO2Quality be described in be loaded with the fine coal grey matter of manganese
The 6%～10% of amount.
The preparation method of above-mentioned modified fly ash loading Mn-Ce bimetallic denitration catalyst, it is characterised in that step 3
Described in solubility cerium salt be cerous nitrate, cerium chloride or cerous sulfate.
The preparation method of above-mentioned modified fly ash loading Mn-Ce bimetallic denitration catalyst, it is characterised in that step 4
Described in the power of plasma reaction still be 50W～70W, the gas flow of described oxygen is 35mL/min～45mL/min,
The time that described low-temperature bake processes is 2min～7min；Described CeO2And Ce2O3Quality sum be described modified coal ash bear
Carry the 2%～6% of Mn-Ce bimetallic denitration catalyst quality.
The present invention compared with prior art has the advantage that
1, the present invention is with flyash as support material, prepares denitrating catalyst and can carry out denitrating flue gas, is solving flyash
While the Heavy environmental pollution that bulk deposition causes, additionally it is possible to reach the purpose of the treatment of wastes with processes of wastes against one another, additionally, due to flyash self
Viscosity poor, it is difficult to molding, the present invention selects the bentonite close with flyash composition mixed as binding agent, makes powder
Coal ash is more easy to extruded.
2, flyash is first modified by using plasma of the present invention, the gas being passed through have oxygen, helium, nitrogen or
Nitrogen and the gaseous mixture of hydrocarbon gas so that it is forming more avtive spot, it is anti-that follow-up load Mn and Ce carries out denitration
Should.
3, the present invention is during carried metal manganese and cerium, manganese metal first loads to the surface of catalyst, then exists
Carried metal cerium on the presoma of manganese.Manganese metal is main with MnO in the catalyst2Presented in, gold-supported on its basis
Belonging to cerium, its principal mode is CeO2And Ce2O3, wherein due to MnO2For P-type semiconductor, Ce3+It is easy to enter MnO2Crystal formation takes
For the Mn in lattice4+, due to Ce3+Valence state compare Mn4+Valence state low, so introduce Ce3+The hole making P-type semiconductor afterwards increases
Adding, make the concentration of free electron in catalyst increase, electric conductivity strengthens, and reduces the energy of reaction, and catalytic effect strengthens.Cause
This, the catalyst using the method for fractional steps to prepare can not only embody two kinds of respective activity of burning, additionally it is possible to forms p-type and partly leads
Body structure, largely strengthens the catalytic effect of catalyst.
4, energy consumption of the present invention is low, and production cost is low, uses low temperature plasma method to prepare modified fly ash loading Mn-Ce double
Metal denitrating catalyst, when catalyst surface is modified by gas with various, promotes catalyst surface to form oxygen-containing functional group
Or nitrogen-containing basic functional group, these functional groups can preferably adsorb the NO in flue gas, provide more for subsequent reactions and live
Property site.
5, the modified fly ash loading Mn-Ce bimetallic denitration catalyst that prepared by the present invention have low-temperature catalytic activity high and
The feature that sulfur resistance is strong.Manganese metal primarily serves the feature improving catalyst low-temperature catalytic activity, and metallic cerium is easily formed Ce3 +/Ce4+Oxidation-reduction pair, and unstable oxygen vacancy and oxygen migration, show excellent storage oxygen-oxygen release ability and unique
Redox property, it is possible to significantly make up the deficiency that manganese metal Process window is narrow.Therefore, when catalyst has loaded 8%
After manganese adds metallic cerium, denitration rate is significantly improved.Therefore, modified fly ash loading Mn-Ce bimetallic denitration catalyst tool
Having efficient low-temperature denitration performance, have preferable sulfur resistance simultaneously, the service life of catalyst is longer.
Below by embodiment, technical scheme is described in further detail.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the modified fly ash loading Mn-Ce bimetallic denitration catalyst of the embodiment of the present invention 1 preparation.
Fig. 2 is the XPS figure of the modified fly ash loading Mn-Ce bimetallic denitration catalyst of the embodiment of the present invention 1 preparation.
Fig. 3 is the XPS of Mn in modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by the embodiment of the present invention 1
Figure.
Fig. 4 is the XPS of Ce in modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by the embodiment of the present invention 1
Figure.
Fig. 5 is the SEM figure of the modified fly ash loading Mn-Ce bimetallic denitration catalyst of the embodiment of the present invention 1 preparation.
Denitration rate when Fig. 6 is to utilize low temperature plasma catalysis simulated flue gas denitration to process, utilize low temperature etc. from
At the modified fly ash loading Mn-Ce bimetallic denitration catalyst concerted catalysis simulated flue gas denitration of daughter and embodiment 1 preparation
Denitration rate during reason, utilize at the modified coal ash concerted catalysis simulated flue gas denitration of low temperature plasma and comparative example 1 preparation
Denitration rate during reason and the fly ash loading Mn denitrating catalyst concerted catalysis mould utilizing low temperature plasma and comparative example 2 to prepare
Intend denitration rate when denitrating flue gas processes.
Fig. 7 is to utilize low temperature plasma and the modified fly ash loading Mn-Ce bimetallic denitration catalyst of embodiment 1 preparation
Agent concerted catalysis contains SO2Simulated flue gas denitration process time denitration rate, utilize low temperature plasma and comparative example 1 preparation change
Property flyash concerted catalysis containing SO2Simulated flue gas denitration process time denitration rate and utilize low temperature plasma and comparative example 2
The fly ash loading Mn denitrating catalyst concerted catalysis of preparation is containing SO2Simulated flue gas denitration process time denitration rate.
Fig. 8 is that the modified fly ash loading Mn-Ce bimetallic utilizing low temperature plasma and the embodiment of the present invention 1 preparation takes off
Denox catalyst concerted catalysis simulated flue gas denitration processes the SEM figure of rear catalyst.
Detailed description of the invention
Embodiment 1
The present embodiment is prepared the method for modified fly ash loading Mn-Ce bimetallic denitration catalyst and is comprised the following steps:
Step one, flyash, bentonite are mixed homogeneously with distilled water, be squeezed into bar, more described bar is put
In baking oven, dry under conditions of temperature is 90 DEG C, then the bar after drying is carried out shear treatment, obtain flyash
Particulate matter；Described flyash and bentonitic mass ratio are 2:1, the quality of described distilled water be described flyash and bentonite total
The 67% of quality；
Step 2, fly ash grain thing described in step one is placed in plasma reaction still, then to described grade from
Daughter reactor is passed through oxygen, make fly ash grain thing the power of plasma reaction still be 45W, the flow of gas be
Modification 25min under conditions of 40mL/min, obtains modified coal ash；
Manganese nitrate is loaded to, described in step 2 on modified coal ash, be contained by step 3, employing equi-volume impregnating
Manganese presoma, is then placed in the described presoma containing manganese in plasma reaction still, backward described plasma reaction still lead to
Entering oxygen, to make containing manganese presoma at the power of plasma reaction still be 60W, the condition that gas flow is 40mL/min of oxygen
Under carry out low-temperature bake process, obtain being loaded with the flyash of manganese；The time that described low-temperature bake processes is 5min；Described manganese exists
The described flyash of manganese that is loaded with is mainly with MnO2Presented in, described MnO2Quality be described in be loaded with the flyash of manganese
The 8% of quality；
Cerous nitrate is loaded to be loaded with described in step 3 on the flyash of manganese by step 4, employing equi-volume impregnating,
Obtain containing cerium precursor, then will contain cerium precursor and be placed in plasma reaction still, backward described plasma reaction still
Being passed through oxygen, to make containing cerium precursor at the power of plasma reaction still be 60W, the bar that gas flow is 40mL/min of oxygen
Carry out low-temperature bake process under part, obtain modified fly ash loading Mn-Ce bimetallic denitration catalyst；Described low-temperature bake processes
Time be 5min；Described cerium is main with CeO in described modified fly ash loading Mn-Ce bimetallic denitration catalyst2With
Ce2O3Presented in, described CeO2For described modified fly ash loading Mn-Ce bimetallic denitration catalyst quality 4%.
The model that plasma reaction still described in the present embodiment uses Nanjing Suman Plasma Technology Co., Ltd. to produce is
Low temperature plasma atmospheric gas gas, gas-liquid and the gas-solid reactor of DBD-100.
Fig. 1 is the XRD figure of modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by the present embodiment, from Fig. 1
It can be seen that in the modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared of the present embodiment except in flyash itself
There is more SiO2, the most more MnO2And CeO2, and a small amount of Ce2O3, by Fig. 1 can be seen that MnO2、CeO2With
Ce2O3Peak type sharp-pointed, load MnO be described2、CeO2And Ce2O3Modified coal ash is evenly distributed.Manganese first loads to modification
The surface of flyash, mainly with MnO2Form exists, and when the surface carried metal cerium again of modified coal ash carrier, there is Ce2O3
Crystal formation.When both metals load to the surface of modified coal ash simultaneously, under plasma roasting effect, form difference
Crystal formation, interact each other.MnO2For P-type semiconductor, Ce3+Enter into MnO2Crystal formation replaces the Mn in lattice4+, by
In Ce3+Valence state compare Mn4+Valence state low, so introduce Ce3+The hole making P-type semiconductor afterwards increases, and makes in denitrating catalyst
The concentration of free electron increases, and electric conductivity strengthens, and reduces the energy of reaction, and catalytic effect strengthens.
Fig. 2 is the XPS figure of modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by the present embodiment, from Fig. 2
It can be seen that the peak number of catalyst surface manganese metal is two, illustrate to there is the oxide that two kinds of valence states are different.Fig. 3 is this
The XPS figure of Mn in the modified fly ash loading Mn-Ce bimetallic denitration catalyst of inventive embodiments 1 preparation, can from Fig. 3
Going out, the peak of manganese metal is two, and wherein 643eV is Mn4+, 654eV is Mn3+But, Mn3+The ratio shared by oxide few.
Fig. 4 is the XPS figure of Ce in modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by the embodiment of the present invention 1, from Fig. 4
In it can be seen that the peak of metallic cerium is two, illustrate to there is the different oxide of two kinds of valence states, wherein 900eV is Ce4+, 822eV
For Ce3+。
Fig. 5 is the SEM figure of the modified fly ash loading Mn-Ce bimetallic denitration catalyst of the embodiment of the present invention 1 preparation, from
It can be seen that catalyst surface metal oxide dispersion is uniform in Fig. 5, without significantly sintering Cluster Phenomenon, illustrate to use low temperature
Catalyst prepared by plasma method has good dispersibility, contributes to the raising of catalytic effect.Understand in conjunction with Fig. 5 and Fig. 8, de-
Denox catalyst use before and after its configuration of surface have greatly changed, its surface metal oxide cluster together, pore structure
Significantly reduce, cause catalysqt deactivation, cause catalyst effect to reduce.
Comparative example 1
This comparative example is prepared the method for modified coal ash and is comprised the following steps:
Step one, flyash, bentonite are mixed homogeneously with distilled water, be squeezed into bar, more described bar is put
In baking oven, dry under conditions of temperature is 90 DEG C, then the bar after drying is carried out shear treatment, obtain flyash
Particulate matter；Described flyash and bentonitic mass ratio are 2:1, the quality of described distilled water be described flyash and bentonite total
The 67% of quality；
Step 2, fly ash grain thing described in step one is placed in plasma reaction still, then to described grade from
Daughter reactor is passed through oxygen, make fly ash grain thing the power of plasma reaction still be 45W, the flow of gas be
Modification 25min under conditions of 40mL/min, obtains modified coal ash.
Comparative example 2
This comparative example is prepared the method for modified fly ash loading Mn denitrating catalyst and is comprised the following steps:
Step one, flyash, bentonite are mixed homogeneously with distilled water, be squeezed into bar, more described bar is put
In baking oven, dry under conditions of temperature is 90 DEG C, then the bar after drying is carried out shear treatment, obtain flyash
Particulate matter；Described flyash and bentonitic mass ratio are 2:1, the quality of described distilled water be described flyash and bentonite total
The 67% of quality；
Step 2, fly ash grain thing described in step one is placed in plasma reaction still, then to described grade from
Daughter reactor is passed through oxygen, make fly ash grain thing the power of plasma reaction still be 45W, the flow of gas be
Modification 25min under conditions of 40mL/min, obtains modified coal ash；
Manganese nitrate is loaded to, described in step 2 on modified coal ash, be contained by step 3, employing equi-volume impregnating
Manganese presoma, is then placed in the described presoma containing manganese in plasma reaction still, backward described plasma reaction still lead to
Entering oxygen, to make containing manganese presoma at the power of plasma reaction still be 60W, the condition that gas flow is 40mL/min of oxygen
Under carry out low-temperature bake process, obtain modified fly ash loading Mn denitrating catalyst；Described low-temperature bake process time be
5min；Described manganese at the described flyash of manganese that is loaded with mainly with MnO2Presented in, described MnO2Quality be described load
Have manganese flyash quality 8%.
In plasma reactor, simulated flue gas, described simulated flue gas it is passed through under conditions of gas flow is 1L/min
It is grouped into by the one-tenth of volumes below percentage ratio: NO 0.00072%, O26%, surplus is N2, test utilizes low-temperature plasma respectively
Body is catalyzed denitration rate when simulated flue gas denitration processes, utilizes the modified coal ash of low temperature plasma and embodiment 1 preparation to bear
When load Mn-Ce bimetallic denitration catalyst concerted catalysis simulated flue gas denitration processes, (modified fly ash loading Mn-Ce bimetallic takes off
The consumption of denox catalyst is 1g) denitration rate, utilize low temperature plasma and comparative example 1 preparation modified coal ash concerted catalysis
The denitration rate of (consumption of modified coal ash is 1g) and utilize low temperature plasma and comparative example 2 to make when simulated flue gas denitration processes
(fly ash loading Mn denitration catalyst when standby modified fly ash loading Mn denitrating catalyst concerted catalysis simulated flue gas denitration processes
The consumption of agent is 1g) denitration rate, test result is shown in Fig. 6, from fig. 6 it can be seen that add catalysis in low temperature plasma
Agent can substantially increase denitration efficiency.Wherein the modified fly ash loading Mn-Ce bimetallic denitration catalyst of embodiment 1 preparation is de-
Modified coal ash that nitre effect is prepared apparently higher than comparative example 1 and the modified fly ash loading Mn denitration catalyst of comparative example 2 preparation
Agent.Wherein, flyash is modified only with oxygen by comparative example 1, produces oxygen-containing functional group on the surface of flyash, such as carbonyl
Base, carboxyl and hydroxyl, and nitroso-group, positive facilitation is played in denitration by these functional groups.Comparative example 2 is in comparative example 1
On the basis of carried metal manganese, it is possible to the effective catalysis activity improving catalyst, from fig. 6 it can be seen that prepared by comparative example 2
The denitration rate of modified fly ash loading Mn denitrating catalyst more than the denitration rate of modified coal ash of comparative example 1 preparation.Implement
Example 1 is carried metal cerium on the basis of comparative example 2, and its denitration effect is best, and this can provide trivalent oxide mainly due to metallic cerium
Form P-type semiconductor structure to the oxide of 4 valency manganese, improve the catalysis activity of catalyst, additionally 4 valent metal oxide tools of cerium
Having the highest catalysis activity, both act on simultaneously, therefore, it is possible to significantly improve the denitration effect of catalyst.
Meanwhile, increasing percentage by volume on the basis of above-mentioned simulated flue gas is the SO of 0.0001%2, analyze denitration catalyst
The sulfur resistance of agent, test utilizes low temperature plasma and the modified fly ash loading Mn-Ce bimetallic of embodiment 1 preparation respectively
Denitrating catalyst concerted catalysis contains SO2Simulated flue gas denitration process time (modified fly ash loading Mn-Ce bimetallic denitration catalyst
The consumption of agent is 1g) denitration rate, utilize the modified coal ash concerted catalysis of low temperature plasma and comparative example 1 preparation containing SO2
Simulated flue gas denitration denitration rate of (consumption of modified coal ash is 1g) and utilize low temperature plasma and comparative example 2 when processing
The modified fly ash loading Mn denitrating catalyst concerted catalysis of preparation is containing SO2Simulated flue gas denitration process time (fly ash loading
The consumption of Mn denitrating catalyst is 1g) denitration rate, test result is shown in Fig. 7, it can be seen from figure 7 that be passed through in simulated flue gas
SO2After, the denitration effect of catalyst substantially reduces.The denitration of the modified fly ash loading Mn denitrating catalyst of comparative example 2 preparation
Rate maintains the time of 35% to be only 5min, and the modified fly ash loading Mn-Ce bimetallic denitration catalyst of embodiment 1 preparation
Denitration rate maintains the time of 35% to be 9mim, and the shortcoming that metallic element cerium can significantly improve manganese metal mithridatism difference is described.
The modified coal ash of comparative example 1 preparation, the denitration rate in the 4min started is less than the catalyst in embodiment 1, but the most again
Higher than the modified fly ash loading Mn-Ce bimetallic denitration catalyst of embodiment 1 preparation, reason is loaded catalyst surface
Containing substantial amounts of metal-oxide, SO2SO it is oxidized to rapidly in plasma reactor3, and anti-with metal-oxide
Should, generating sulfate, cause catalysqt deactivation, denitration rate reduces.If the most inactivations of the metal-oxide contained in catalyst
Speed is the slowest, and the avtive spot finally remained is the fewest, therefore the modified fly ash loading Mn denitration of comparative example 2 preparation
Denitration rate after catalysqt deactivation is higher than the modified fly ash loading Mn-Ce bimetallic denitration catalyst of embodiment 1 preparation.And it is right
The modified coal ash of ratio 1 preparation, tenor is few, so there is not showing of metal-oxide inactivation during whole
As, so to containing SO2Simulated flue gas and without SO2The denitration rate of simulated flue gas the most do not produce impact.
Embodiment 2
The present embodiment is prepared the method for modified fly ash loading Mn-Ce bimetallic denitration catalyst and is comprised the following steps:
Step one, flyash, bentonite are mixed homogeneously with distilled water, be squeezed into bar, more described bar is put
In baking oven, dry under conditions of temperature is 100 DEG C, then the bar after drying is carried out shear treatment, obtain fine coal
Ash particle thing；Described flyash and bentonitic mass ratio are 3:1, and the quality of described distilled water is described flyash and bentonite
The 70% of gross mass；
Step 2, fly ash grain thing described in step one is placed in plasma reaction still, then to described grade from
Daughter reactor is passed through nitrogen, make fly ash grain thing the power of plasma reaction still be 50W, the flow of gas be
Modification 20min under conditions of 45mL/min, obtains modified coal ash；
Manganese chloride is loaded to, described in step 2 on modified coal ash, be contained by step 3, employing equi-volume impregnating
Manganese presoma, is then placed in the described presoma containing manganese in plasma reaction still, backward described plasma reaction still lead to
Entering oxygen, to make containing manganese presoma at the power of plasma reaction still be 70W, the condition that gas flow is 45mL/min of oxygen
Under carry out low-temperature bake process, obtain being loaded with the flyash of manganese；The time that described low-temperature bake processes is 2min；Described manganese exists
The described flyash of manganese that is loaded with is mainly with MnO2Presented in, described MnO2Quality be described in be loaded with the flyash of manganese
The 6% of quality；
Cerium chloride is loaded to be loaded with described in step 3 on the flyash of manganese by step 4, employing equi-volume impregnating,
Obtain containing cerium precursor, then will contain cerium precursor and be placed in plasma reaction still, backward described plasma reaction still
Being passed through oxygen, to make containing cerium precursor at the power of plasma reaction still be 70W, the bar that gas flow is 45mL/min of oxygen
Carry out low-temperature bake process under part, obtain modified fly ash loading Mn-Ce bimetallic denitration catalyst；Described low-temperature bake processes
Time be 2min；Described cerium is main with CeO in described modified fly ash loading Mn-Ce bimetallic denitration catalyst2With
Ce2O3Presented in, described CeO2And Ce2O3Quality sum be that described modified fly ash loading Mn-Ce bimetallic denitration is urged
The 2% of agent quality.
The model that plasma reaction still described in the present embodiment uses Nanjing Suman Plasma Technology Co., Ltd. to produce is
Low temperature plasma atmospheric gas gas, gas-liquid and the gas-solid reactor of DBD-100.
Modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by the present embodiment, catalyst dispersion ratio is more uniform,
Crystal grain is uniform, sulfur resistance good, and intercrystalline exists obvious space, adds the contact surface between NO in catalyst and flue gas
Long-pending, beneficially the carrying out of denitration reaction, utilize modified fly ash loading Mn-Ce bimetallic prepared by plasma and the present embodiment
Denitrating catalyst concerted catalysis simulated flue gas denitration process time, the denitration rate time more than 50% be 3 points 30 seconds, its stable
Nitre rate is about 26.44%.
Embodiment 3
The present embodiment is prepared the method for modified fly ash loading Mn-Ce bimetallic denitration catalyst and is comprised the following steps:
Step one, flyash, bentonite are mixed homogeneously with distilled water, be squeezed into bar, more described bar is put
In baking oven, dry under conditions of temperature is 80 DEG C, then the bar after drying is carried out shear treatment, obtain flyash
Particulate matter；Described flyash and bentonitic mass ratio are 1:1, the quality of described distilled water be described flyash and bentonite total
The 60% of quality；
Step 2, fly ash grain thing described in step one is placed in plasma reaction still, then to described grade from
Daughter reactor is passed through argon, make fly ash grain thing the power of plasma reaction still be 40W, the flow of gas be
Modification 30min under conditions of 35mL/min, obtains modified coal ash；
Manganese sulfate is loaded to, described in step 2 on modified coal ash, be contained by step 3, employing equi-volume impregnating
Manganese presoma, is then placed in the described presoma containing manganese in plasma reaction still, backward described plasma reaction still lead to
Entering oxygen, to make containing manganese presoma at the power of plasma reaction still be 50W, the condition that gas flow is 35mL/min of oxygen
Under carry out low-temperature bake process, obtain being loaded with the flyash of manganese；The time that described low-temperature bake processes is 7min；Described manganese exists
The described flyash of manganese that is loaded with is mainly with MnO2Presented in, described MnO2Quality be described in be loaded with the flyash of manganese
The 10% of quality；
Cerous sulfate is loaded to be loaded with described in step 3 on the flyash of manganese by step 4, employing equi-volume impregnating,
Obtain containing cerium precursor, then will contain cerium precursor and be placed in plasma reaction still, backward described plasma reaction still
Being passed through oxygen, to make containing cerium precursor at the power of plasma reaction still be 50W, the bar that gas flow is 35mL/min of oxygen
Carry out low-temperature bake process under part, obtain modified fly ash loading Mn-Ce bimetallic denitration catalyst；Described low-temperature bake processes
Time be 7min；Described cerium is main with CeO in described modified fly ash loading Mn-Ce bimetallic denitration catalyst2With
Ce2O3Presented in, described CeO2And Ce2O3Quality sum be that described modified fly ash loading Mn-Ce bimetallic denitration is urged
The 6% of agent quality.
The model that plasma reaction still described in the present embodiment uses Nanjing Suman Plasma Technology Co., Ltd. to produce is
Low temperature plasma atmospheric gas gas, gas-liquid and the gas-solid reactor of DBD-100.
Modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by the present embodiment, catalyst dispersion ratio is more uniform,
There is obvious space in intercrystalline, adds entering of the contact area between NO, beneficially denitration reaction in catalyst and flue gas
OK, modified fly ash loading Mn-Ce bimetallic denitration catalyst concerted catalysis mould prepared by plasma and the present embodiment is utilized
Intend denitrating flue gas process time, the denitration rate time more than 50% be 4 points 10 seconds, its stable denitration rate is about 36.47%.
Embodiment 4
The present embodiment is prepared the method for modified fly ash loading Mn-Ce bimetallic denitration catalyst and is comprised the following steps:
Step one, flyash, bentonite are mixed homogeneously with distilled water, be squeezed into bar, more described bar is put
In baking oven, dry under conditions of temperature is 90 DEG C, then the bar after drying is carried out shear treatment, obtain flyash
Particulate matter；Described flyash and bentonitic mass ratio are 0.5:1, and the quality of described distilled water is described flyash and bentonite
The 50% of gross mass；
Step 2, fly ash grain thing described in step one is placed in plasma reaction still, then to described grade from
Daughter reactor is passed through the gaseous mixture of hydrocarbon gas and nitrogen, makes the fly ash grain thing at the power of plasma reaction still be
30W, the flow of gas are modification 40min under conditions of 20mL/min, obtain modified coal ash；Nitrogen in described gaseous mixture
Percentage by volume be 96.31%；Described hydrocarbon gas is grouped into by the one-tenth of volumes below percentage ratio: ethane 0.998%, ethylene
0.997%, acetylene 0.5%, propane 0.2%, propylene 0.199%, allylene 0.198%, normal butane 0.199%, 1-butylene
0.199%, ethyl acetylene 0.2%；
Manganese is loaded to described in step 2 on modified coal ash, before obtaining containing manganese by step 3, employing equi-volume impregnating
Drive body, then the described presoma containing manganese be placed in plasma reaction still, backward described plasma reaction still be passed through oxygen
Gas, to make containing manganese presoma at the power of plasma reaction still be 30W, the gas flow of oxygen enters under conditions of being 20mL/min
Row low-temperature bake processes, and obtains being loaded with the flyash of manganese；The time that described low-temperature bake processes is 10min；Described manganese is in institute
State and be loaded with the flyash of manganese mainly with MnO2Presented in, described MnO2Quality be described in be loaded with the fine coal grey matter of manganese
The 4% of amount；
Cerium is loaded to be loaded with described in step 3 on the flyash of manganese by step 4, employing equi-volume impregnating, obtains
Containing cerium precursor, then will contain cerium precursor and be placed in plasma reaction still, backward described plasma reaction still be passed through
Oxygen, under conditions of to make containing cerium precursor at the power of plasma reaction still be 30W, the gas flow of oxygen is 20mL/min
Carry out low-temperature bake process, obtain modified fly ash loading Mn-Ce bimetallic denitration catalyst；Described low-temperature bake process time
Between be 10min；Described cerium is main with CeO in described modified fly ash loading Mn-Ce bimetallic denitration catalyst2And Ce2O3's
Form exists, described CeO2And Ce2O3Quality sum be described modified fly ash loading Mn-Ce bimetallic denitration catalyst matter
The 1% of amount.
The model that plasma reaction still described in the present embodiment uses Nanjing Suman Plasma Technology Co., Ltd. to produce is
Low temperature plasma atmospheric gas gas, gas-liquid and the gas-solid reactor of DBD-100.
Modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by the present embodiment, catalyst dispersion ratio is more uniform,
Crystal grain is uniform, and intercrystalline exists obvious space, adds the contact area between NO, beneficially denitration in catalyst and flue gas
The carrying out of reaction, utilizes modified fly ash loading Mn-Ce bimetallic denitration catalyst association prepared by plasma and the present embodiment
With catalysis simulated flue gas denitration process time, the denitration rate time more than 50% be 3 points 50 seconds, its stable denitration rate be about
28.56%.
Embodiment 5
The present embodiment is prepared the method for modified fly ash loading Mn-Ce bimetallic denitration catalyst and is comprised the following steps:
Step one, flyash, bentonite are mixed homogeneously with distilled water, be squeezed into bar, more described bar is put
In baking oven, dry under conditions of temperature is 100 DEG C, then the bar after drying is carried out shear treatment, obtain fine coal
Ash particle thing；Described flyash and bentonitic mass ratio are 5:1, and the quality of described distilled water is described flyash and bentonite
The 80% of gross mass；
Step 2, fly ash grain thing described in step one is placed in plasma reaction still, then to described grade from
Daughter reactor is passed through oxygen modified, makes fly ash grain thing at the flow that power is 60W, gas of plasma reaction still
For modification 10min under conditions of 60mL/min, obtain modified coal ash；
Manganese nitrate is loaded to, described in step 2 on modified coal ash, be contained by step 3, employing equi-volume impregnating
Manganese presoma, is then placed in the described presoma containing manganese in plasma reaction still, backward described plasma reaction still lead to
Entering oxygen, to make containing manganese presoma at the power of plasma reaction still be 90W, the condition that gas flow is 60mL/min of oxygen
Under carry out low-temperature bake process, obtain being loaded with the flyash of manganese；The time that described low-temperature bake processes is 1min；Described manganese exists
The described flyash of manganese that is loaded with is mainly with MnO2Presented in, described MnO2Quality be described in be loaded with the flyash of manganese
The 16% of quality；
Cerous nitrate is loaded to be loaded with described in step 3 on the flyash of manganese by step 4, employing equi-volume impregnating,
Obtain containing cerium precursor, then will contain cerium precursor and be placed in plasma reaction still, backward described plasma reaction still
Being passed through oxygen, to make containing cerium precursor at the power of plasma reaction still be 90W, the bar that gas flow is 60mL/min of oxygen
Carry out low-temperature bake process under part, obtain modified fly ash loading Mn-Ce bimetallic denitration catalyst；Described low-temperature bake processes
Time be 1min；Described cerium is main with CeO in described modified fly ash loading Mn-Ce bimetallic denitration catalyst2With
Ce2O3Presented in, described CeO2And Ce2O3Quality sum be that described modified fly ash loading Mn-Ce bimetallic denitration is urged
The 12% of agent quality.
The model that plasma reaction still described in the present embodiment uses Nanjing Suman Plasma Technology Co., Ltd. to produce is
Low temperature plasma atmospheric gas gas, gas-liquid and the gas-solid reactor of DBD-100.
Modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by the present embodiment, catalyst dispersion ratio is more uniform,
Sulfur resistance is good, and intercrystalline exists obvious space, adds the contact area between NO in catalyst and flue gas, is conducive to de-
The carrying out of nitre reaction, utilizes modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by plasma and the present embodiment
Concerted catalysis simulated flue gas denitration process time, the denitration rate time more than 50% be 7 points 55 seconds, its stable denitration rate be about
35.11%.
Embodiment 6
The present embodiment is prepared the method for modified fly ash loading Mn-Ce bimetallic denitration catalyst and is comprised the following steps:
Step one, flyash, bentonite are mixed homogeneously with distilled water, be squeezed into bar, more described bar is put
In baking oven, dry under conditions of temperature is 90 DEG C, then the bar after drying is carried out shear treatment, obtain flyash
Particulate matter；Described flyash and bentonitic mass ratio are 2.5:1, and the quality of described distilled water is described flyash and bentonite
The 70% of gross mass；
Step 2, fly ash grain thing described in step one is placed in plasma reaction still, then to described grade from
Daughter reactor is passed through oxygen modified, makes fly ash grain thing at the flow that power is 45W, gas of plasma reaction still
For modification 30min under conditions of 30mL/min, obtain modified coal ash；
Manganese nitrate is loaded to, described in step 2 on modified coal ash, be contained by step 3, employing equi-volume impregnating
Manganese presoma, is then placed in the described presoma containing manganese in plasma reaction still, backward described plasma reaction still lead to
Entering oxygen, to make containing manganese presoma at the power of plasma reaction still be 60W, the condition that gas flow is 35mL/min of oxygen
Under carry out low-temperature bake process, obtain being loaded with the flyash of manganese；The time that described low-temperature bake processes is 5min；Described manganese exists
The described flyash of manganese that is loaded with is mainly with MnO2Presented in, described MnO2Quality be described in be loaded with the flyash of manganese
The 12% of quality；
Cerous nitrate is loaded to be loaded with described in step 3 on the flyash of manganese by step 4, employing equi-volume impregnating,
Obtain containing cerium precursor, then will contain cerium precursor and be placed in plasma reaction still, backward described plasma reaction still
Being passed through oxygen, to make containing cerium precursor at the power of plasma reaction still be 50W, the bar that gas flow is 40mL/min of oxygen
Carry out low-temperature bake process under part, obtain modified fly ash loading Mn-Ce bimetallic denitration catalyst；Described low-temperature bake processes
Time be 6min；Described cerium is main with CeO in described modified fly ash loading Mn-Ce bimetallic denitration catalyst2With
Ce2O3Presented in, described CeO2And Ce2O3Quality sum be that described modified fly ash loading Mn-Ce bimetallic denitration is urged
The 8% of agent quality.
The model that plasma reaction still described in the present embodiment uses Nanjing Suman Plasma Technology Co., Ltd. to produce is
Low temperature plasma atmospheric gas gas, gas-liquid and the gas-solid reactor of DBD-100.
Modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by the present embodiment, crystal grain is uniform, sulfur resistance
Good, there is obvious space in intercrystalline, adds the contact area between NO in catalyst and flue gas, beneficially denitration reaction
Carry out, utilize modified fly ash loading Mn-Ce bimetallic denitration catalyst concerted catalysis prepared by plasma and the present embodiment
Simulated flue gas denitration process time, the denitration rate time more than 50% be 9 points 13 seconds, its stable denitration rate is about 38.29%.
Embodiment 7
The present embodiment is prepared the method for modified fly ash loading Mn-Ce bimetallic denitration catalyst and is comprised the following steps:
Step one, flyash, bentonite are mixed homogeneously with distilled water, be squeezed into bar, more described bar is put
In baking oven, dry under conditions of temperature is 80 DEG C, then the bar after drying is carried out shear treatment, obtain flyash
Particulate matter；Described flyash and bentonitic mass ratio are 4:1, the quality of described distilled water be described flyash and bentonite total
The 60% of quality；
Step 2, fly ash grain thing described in step one is placed in plasma reaction still, then to described grade from
Daughter reactor is passed through oxygen modified, makes fly ash grain thing at the flow that power is 50W, gas of plasma reaction still
For modification 25min under conditions of 40mL/min, obtain modified coal ash；
Manganese chloride is loaded to, described in step 2 on modified coal ash, be contained by step 3, employing equi-volume impregnating
Manganese presoma, is then placed in the described presoma containing manganese in plasma reaction still, backward described plasma reaction still lead to
Entering oxygen, to make containing manganese presoma at the power of plasma reaction still be 55W, the condition that gas flow is 40mL/min of oxygen
Under carry out low-temperature bake process, obtain being loaded with the flyash of manganese；The time that described low-temperature bake processes is 8min；Described manganese exists
The described flyash of manganese that is loaded with is mainly with MnO2Presented in, described MnO2Quality be described in be loaded with the flyash of manganese
The 14% of quality；
Cerium chloride is loaded to be loaded with described in step 3 on the flyash of manganese by step 4, employing equi-volume impregnating,
Obtain containing cerium precursor, then will contain cerium precursor and be placed in plasma reaction still, backward described plasma reaction still
Being passed through oxygen, to make containing cerium precursor at the power of plasma reaction still be 65W, the bar that gas flow is 45mL/min of oxygen
Carry out low-temperature bake process under part, obtain modified fly ash loading Mn-Ce bimetallic denitration catalyst；Described low-temperature bake processes
Time be 8min；Described cerium is main with CeO in described modified fly ash loading Mn-Ce bimetallic denitration catalyst2With
Ce2O3Presented in, described CeO2And Ce2O3Quality sum be that described modified fly ash loading Mn-Ce bimetallic denitration is urged
The 10% of agent quality.
The model that plasma reaction still described in the present embodiment uses Nanjing Suman Plasma Technology Co., Ltd. to produce is
Low temperature plasma atmospheric gas gas, gas-liquid and the gas-solid reactor of DBD-100.
Modified fly ash loading Mn-Ce bimetallic denitration catalyst prepared by the present embodiment, catalyst dispersion ratio is more uniform,
Crystal grain is uniform, sulfur resistance good, and intercrystalline exists obvious space, beneficially the carrying out of denitration reaction, utilize plasma with
When modified fly ash loading Mn-Ce bimetallic denitration catalyst concerted catalysis simulated flue gas denitration prepared by the present embodiment processes,
The denitration rate time more than 50% be 8 points 57 seconds, its stable denitration rate is about 37.10%.
The above, be only presently preferred embodiments of the present invention, not impose any restrictions the present invention.Every according to invention skill
Any simple modification, change and the equivalence change that above example is made by art essence, all still falls within technical solution of the present invention
Protection domain in.
Claims (8)
1. the preparation method of a modified fly ash loading Mn-Ce bimetallic denitration catalyst, it is characterised in that include following step
Rapid:
Step one, flyash, bentonite are mixed homogeneously with distilled water after, be squeezed into bar, more described bar be placed in
In baking oven, dry under conditions of temperature is 80 DEG C～100 DEG C, then the bar after drying is carried out shear treatment, obtain
Fly ash grain thing；Described flyash and bentonitic mass ratio are (0.5～8): 1, and the quality of described distilled water is described powder
Coal ash and the 50% of bentonite gross mass～80%；
Step 2, fly ash grain thing described in step one is placed in plasma reaction still, then to plasma reaction
Still is passed through gas, make fly ash grain thing the power of plasma reaction still be 30W～60W, the flow of gas be 20mL/
Under conditions of min～60mL/min, modification 10min～40min, obtain modified coal ash；Described gas be oxygen, argon,
The gaseous mixture of nitrogen or nitrogen and hydrocarbon gas；In described gaseous mixture, the percentage by volume of nitrogen is 96.31%；
Soluble manganese salt is loaded to, described in step 2 on modified coal ash, be contained by step 3, employing equi-volume impregnating
Manganese presoma, is then placed in the described presoma containing manganese in plasma reaction still, backward described plasma reaction still lead to
Entering oxygen, to make containing manganese presoma at the power of plasma reaction still be 30W～90W, the gas flow of oxygen is 20mL/min
～under conditions of 60mL/min, carry out low-temperature bake process, obtain being loaded with the flyash of manganese；Described low-temperature bake process time
Between be 1min～10min；Described manganese at the described flyash of manganese that is loaded with mainly with MnO2Presented in, described MnO2Matter
Amount be described in be loaded with manganese flyash quality 4%～16%；
Solubility cerium salt is loaded to be loaded with described in step 3 on the flyash of manganese by step 4, employing equi-volume impregnating,
Obtain containing cerium precursor, then will contain cerium precursor and be placed in plasma reaction still, backward described plasma reaction still
Being passed through oxygen, to make containing cerium precursor at the power of plasma reaction still be 30W～90W, the gas flow of oxygen is 20mL/
Carry out low-temperature bake process under conditions of min～60mL/min, obtain modified fly ash loading Mn-Ce bimetallic denitration catalyst
Agent；The time that described low-temperature bake processes is 1min～10min；Described cerium is at described modified fly ash loading Mn-Ce bimetallic
Mainly with CeO in denitrating catalyst2And Ce2O3Presented in, described CeO2And Ce2O3Quality sum be described modified fine coal
The 1%～12% of ash loading Mn-Ce bimetallic denitration catalyst quality.
The preparation method of modified fly ash loading Mn-Ce bimetallic denitration catalyst the most according to claim 1, its feature
Being, flyash described in step one and bentonitic mass ratio are (1～3): 1, and the quality of described distilled water is described fine coal
Ash and the 60%～70% of bentonite gross mass.
The preparation method of modified fly ash loading Mn-Ce bimetallic denitration catalyst the most according to claim 1, its feature
Being, hydrocarbon gas described in step 2 is grouped into by the one-tenth of volumes below percentage ratio: ethane 27%, ethylene 27%, acetylene
13.6%, propane 5.4%, propylene 5.4%, allylene 5.4%, normal butane 5.4%, 1-butylene 5.4%, ethyl acetylene
5.4%.
The preparation method of modified fly ash loading Mn-Ce bimetallic denitration catalyst the most according to claim 1, its feature
Being, the power of plasma reaction still described in step 2 is 40W～50W, and the flow of gas is 35mL/min～45mL/
Min, the modified time is 20min～30min.
The preparation method of modified fly ash loading Mn-Ce bimetallic denitration catalyst the most according to claim 1, its feature
Being, soluble manganese salt described in step 3 is manganese nitrate, manganese chloride or manganese sulfate.
The preparation method of modified fly ash loading Mn-Ce bimetallic denitration catalyst the most according to claim 1, its feature
Being, the power of plasma reaction still described in step 3 is 50W～70W, and the gas flow of described oxygen is 35mL/min
～45mL/min, the time that described low-temperature bake processes is 2min～7min；Described MnO2Quality be described in be loaded with manganese
The 6%～10% of flyash quality.
The preparation method of modified fly ash loading Mn-Ce bimetallic denitration catalyst the most according to claim 1, its feature
Being, the salt of solubility cerium described in step 3 is cerous nitrate, cerium chloride or cerous sulfate.
The preparation method of modified fly ash loading Mn-Ce bimetallic denitration catalyst the most according to claim 1, its feature
Being, the power of plasma reaction still described in step 4 is 50W～70W, and the gas flow of described oxygen is 35mL/min
～45mL/min, the time that described low-temperature bake processes is 2min～7min；Described CeO2And Ce2O3Quality sum be described
The 2%～6% of modified fly ash loading Mn-Ce bimetallic denitration catalyst quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610615259.6A CN106238040B (en) | 2016-07-29 | 2016-07-29 | The preparation method of modified fly ash loading Mn-Ce bimetallic denitration catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610615259.6A CN106238040B (en) | 2016-07-29 | 2016-07-29 | The preparation method of modified fly ash loading Mn-Ce bimetallic denitration catalysts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106238040A true CN106238040A (en) | 2016-12-21 |
| CN106238040B CN106238040B (en) | 2018-05-15 |
Family
ID=57605680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610615259.6A Expired - Fee Related CN106238040B (en) | 2016-07-29 | 2016-07-29 | The preparation method of modified fly ash loading Mn-Ce bimetallic denitration catalysts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106238040B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582606A (en) * | 2016-12-28 | 2017-04-26 | 湖北思搏盈环保科技有限公司 | Non-vanadium-serial low-temperature denitration catalyst and preparation method thereof |
| CN106582596A (en) * | 2016-12-28 | 2017-04-26 | 湖北思搏盈环保科技有限公司 | Method for forming fly-ash-based honeycomb type denitration catalyst ceramic carrier |
| CN107008338A (en) * | 2017-04-05 | 2017-08-04 | 西安科技大学 | A kind of method that plasma method prepares SCO denitration catalyst |
| CN107583417A (en) * | 2017-08-31 | 2018-01-16 | 沈阳三聚凯特催化剂有限公司 | A kind of normal temperature gas phase antichlor and preparation method and application |
| CN107649121A (en) * | 2017-10-24 | 2018-02-02 | 石河子大学 | The method of modifying and modified manganese based denitration catalyst and preparation method of a kind of manganese based denitration catalyst |
| CN107866227A (en) * | 2017-09-16 | 2018-04-03 | 史汉祥 | Prepare the method and denitration method for flue gas of denitration catalyst composition |
| CN107954464A (en) * | 2017-12-11 | 2018-04-24 | 宁夏共宣环保科技有限责任公司 | A kind of method that cupric oxide is recycled from waste methanol catalyst |
| CN108160066A (en) * | 2017-12-29 | 2018-06-15 | 西安科技大学 | A kind of preparation method and application method of lignite tar gas catalytic pyrolysis catalyst |
| CN108435213A (en) * | 2018-05-10 | 2018-08-24 | 钦州学院 | Fly ash loading metal oxide catalyst of starch conversion and preparation method thereof |
| CN109517409A (en) * | 2018-11-12 | 2019-03-26 | 蒋吉平 | Modified medical stone powder and its application in environmental protection coating material |
| CN111185189A (en) * | 2020-01-16 | 2020-05-22 | 中国重型机械研究院股份公司 | Method for preparing yolk-egg white type SCR denitration catalyst and application |
| CN111530279A (en) * | 2020-05-09 | 2020-08-14 | 铭牌精工机械(山东)有限公司 | Ecological environment-friendly treatment method for waste gas |
| CN111530280A (en) * | 2020-05-09 | 2020-08-14 | 铭牌精工机械(山东)有限公司 | Desulfurization and denitrification environment-friendly treatment method |
| CN111701622A (en) * | 2020-06-29 | 2020-09-25 | 西安科技大学 | Preparation method of Cu-MOF-Fe fly ash catalyst for denitration and demercuration |
| CN112221488A (en) * | 2020-11-04 | 2021-01-15 | 西南化工研究设计院有限公司 | Novel core-shell structure catalyst for synergistic denitration and demercuration and preparation method thereof |
| CN114456004A (en) * | 2022-02-21 | 2022-05-10 | 华电电力科学研究院有限公司 | Mineral slow release fertilizer and preparation method thereof |
| CN114797841A (en) * | 2022-03-24 | 2022-07-29 | 绍兴文理学院 | Mn (manganese) 4+ And Ce 3+ Preparation method of enhanced Mn-M-Ti-O ultralow-temperature denitration catalyst |
| CN116328758A (en) * | 2021-12-22 | 2023-06-27 | 中国科学院过程工程研究所 | Fly ash-based manganese catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5353592A (en) * | 1976-10-26 | 1978-05-16 | Mitsubishi Heavy Ind Ltd | Production of exhaust gas denitratin catalyst |
| CN105110566A (en) * | 2015-09-11 | 2015-12-02 | 江苏大学 | Low-pollution type membrane separation device based on low-temperature plasma technology |
-
2016
- 2016-07-29 CN CN201610615259.6A patent/CN106238040B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5353592A (en) * | 1976-10-26 | 1978-05-16 | Mitsubishi Heavy Ind Ltd | Production of exhaust gas denitratin catalyst |
| CN105110566A (en) * | 2015-09-11 | 2015-12-02 | 江苏大学 | Low-pollution type membrane separation device based on low-temperature plasma technology |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582596A (en) * | 2016-12-28 | 2017-04-26 | 湖北思搏盈环保科技有限公司 | Method for forming fly-ash-based honeycomb type denitration catalyst ceramic carrier |
| CN106582606A (en) * | 2016-12-28 | 2017-04-26 | 湖北思搏盈环保科技有限公司 | Non-vanadium-serial low-temperature denitration catalyst and preparation method thereof |
| CN106582606B (en) * | 2016-12-28 | 2022-02-08 | 湖北思搏盈环保科技有限公司 | Non-vanadium low-temperature denitration catalyst and preparation method thereof |
| CN107008338B (en) * | 2017-04-05 | 2019-11-26 | 西安科技大学 | A kind of method of plasma method preparation SCO denitration catalyst |
| CN107008338A (en) * | 2017-04-05 | 2017-08-04 | 西安科技大学 | A kind of method that plasma method prepares SCO denitration catalyst |
| CN107583417A (en) * | 2017-08-31 | 2018-01-16 | 沈阳三聚凯特催化剂有限公司 | A kind of normal temperature gas phase antichlor and preparation method and application |
| CN107583417B (en) * | 2017-08-31 | 2019-12-24 | 沈阳三聚凯特催化剂有限公司 | Normal-temperature gas-phase dechlorinating agent and preparation method and application thereof |
| CN107866227A (en) * | 2017-09-16 | 2018-04-03 | 史汉祥 | Prepare the method and denitration method for flue gas of denitration catalyst composition |
| CN107649121A (en) * | 2017-10-24 | 2018-02-02 | 石河子大学 | The method of modifying and modified manganese based denitration catalyst and preparation method of a kind of manganese based denitration catalyst |
| CN107954464A (en) * | 2017-12-11 | 2018-04-24 | 宁夏共宣环保科技有限责任公司 | A kind of method that cupric oxide is recycled from waste methanol catalyst |
| CN108160066A (en) * | 2017-12-29 | 2018-06-15 | 西安科技大学 | A kind of preparation method and application method of lignite tar gas catalytic pyrolysis catalyst |
| CN108160066B (en) * | 2017-12-29 | 2020-09-11 | 西安科技大学 | Preparation method and use method of catalyst for catalytic cracking of lignite tar gas |
| CN108435213A (en) * | 2018-05-10 | 2018-08-24 | 钦州学院 | Fly ash loading metal oxide catalyst of starch conversion and preparation method thereof |
| CN109517409A (en) * | 2018-11-12 | 2019-03-26 | 蒋吉平 | Modified medical stone powder and its application in environmental protection coating material |
| CN111185189A (en) * | 2020-01-16 | 2020-05-22 | 中国重型机械研究院股份公司 | Method for preparing yolk-egg white type SCR denitration catalyst and application |
| CN111530279A (en) * | 2020-05-09 | 2020-08-14 | 铭牌精工机械(山东)有限公司 | Ecological environment-friendly treatment method for waste gas |
| CN111530280A (en) * | 2020-05-09 | 2020-08-14 | 铭牌精工机械(山东)有限公司 | Desulfurization and denitrification environment-friendly treatment method |
| CN111701622A (en) * | 2020-06-29 | 2020-09-25 | 西安科技大学 | Preparation method of Cu-MOF-Fe fly ash catalyst for denitration and demercuration |
| CN112221488A (en) * | 2020-11-04 | 2021-01-15 | 西南化工研究设计院有限公司 | Novel core-shell structure catalyst for synergistic denitration and demercuration and preparation method thereof |
| CN116328758A (en) * | 2021-12-22 | 2023-06-27 | 中国科学院过程工程研究所 | Fly ash-based manganese catalyst and preparation method and application thereof |
| CN114456004A (en) * | 2022-02-21 | 2022-05-10 | 华电电力科学研究院有限公司 | Mineral slow release fertilizer and preparation method thereof |
| CN114456004B (en) * | 2022-02-21 | 2023-03-03 | 华电电力科学研究院有限公司 | Mineral slow release fertilizer and preparation method thereof |
| CN114797841A (en) * | 2022-03-24 | 2022-07-29 | 绍兴文理学院 | Mn (manganese) 4+ And Ce 3+ Preparation method of enhanced Mn-M-Ti-O ultralow-temperature denitration catalyst |
| CN114797841B (en) * | 2022-03-24 | 2024-03-22 | 绍兴文理学院 | Mn (Mn) 4+ And Ce (Ce) 3+ Preparation method of enhanced Mn-M-Ti-O ultralow temperature denitration catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106238040B (en) | 2018-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106238040B (en) | The preparation method of modified fly ash loading Mn-Ce bimetallic denitration catalysts | |
| JP2020082079A (en) | Ruthenium-based catalyst for hydrogen production from ammonia decomposition, preparation method therefor and application thereof | |
| CN104801333A (en) | Preparation method of supported nickel-based catalyst | |
| Qiu et al. | Advancement of modification engineering in lean methane combustion catalysts based on defect chemistry | |
| CN104289242B (en) | Preparation method for the high graphitization degree carbon base catalyst of fuel battery negative pole | |
| CN110372875B (en) | Heteronuclear polymetallic organic framework material and preparation and application thereof in denitration and demercuration | |
| CN113258087B (en) | Preparation method of oxygen reduction and oxygen precipitation dual-function catalyst | |
| CN109331860B (en) | Low-platinum alloy composite nano photocatalyst for air purification and preparation method and application thereof | |
| CN101992089A (en) | Three-dimensional ordered porous-mesoporous iron-based perovskite oxide catalyst and preparation method thereof | |
| CN107511147A (en) | A kind of high stability catalyst for catalytic oxidation and preparation method | |
| CN109772463B (en) | Catalyst ZIF-67-Me/CuO for CO reduction and low-temperature denitrationxAnd preparation method and application thereof | |
| CN104014331A (en) | Preparation method of mesoporous titanium dioxide ball supported Mn-Ce-W compound oxide denitration catalyst | |
| CN104084218B (en) | A kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin | |
| CN110090639A (en) | The method of the one step preparation porous carbon supported catalyst of high dispersive type | |
| Kim et al. | Ag-doped manganese oxide catalyst for gasoline particulate filters: Effect of crystal phase on soot oxidation activity | |
| CN107195914B (en) | Amorphous manganese oxide loaded nitrogen-doped carbon-based catalyst and preparation method thereof | |
| CN106040287A (en) | Exhaust gas purification catalyst | |
| CN103785439B (en) | A kind of bifunctional catalyst ABK/Y and its preparation method and application | |
| CN104971735A (en) | Efficient oxidation catalyst for diesel vehicle tail gas purification and preparation method and application thereof | |
| CN109847745B (en) | Preparation method of ruthenium system ultralow-temperature denitration catalyst | |
| CN107029715B (en) | A kind of rhodium base catalyst and its preparation method and application that polyvinylpyrrolidone PVP is modified | |
| CN106311223A (en) | Preparation method of precious metal/graphene nanocomposite | |
| CN102179252B (en) | Cu/CeOx-TiO2 catalyst for selective catalytic oxidization of ammonia and preparation method thereof | |
| CN104399465A (en) | Core-shell catalyst and preparation method and application thereof | |
| CN106391031A (en) | Methane dry gas reforming catalyst and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180515 Termination date: 20190729 |