CN110354892A - The preparation method of oxide modifying MCM-48 molecular sieve and its application in denitration collaboration demercuration - Google Patents
The preparation method of oxide modifying MCM-48 molecular sieve and its application in denitration collaboration demercuration Download PDFInfo
- Publication number
- CN110354892A CN110354892A CN201910534184.2A CN201910534184A CN110354892A CN 110354892 A CN110354892 A CN 110354892A CN 201910534184 A CN201910534184 A CN 201910534184A CN 110354892 A CN110354892 A CN 110354892A
- Authority
- CN
- China
- Prior art keywords
- mcm
- molecular sieve
- solution
- preparation
- oxide
- 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
- 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
- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/341—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 electric or magnetic fields, wave energy or particle radiation
- B01J37/343—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 electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of preparation method of oxide modifying MCM-48 molecular sieve and its applications in denitration collaboration demercuration, are related to technical field of molecular sieve.It first pre-processes the MCM-48 molecular sieve of non-removed template method；Then using Mn oxide as active material, N oxide synthesizes MnN mixed solution as auxiliary agent；It is added into molecular sieve and carries out impregnation and drying；Molecular sieve after drying is calcined in air；Finally obtain oxide modifying MCM-48 molecular sieve.The preparation-obtained oxide modifying MCM-48 molecular sieve of the present invention is carried out carrying out NOx and Hg under simulated flue gas atmosphere0Removing experiment, and using different mol ratio comparison different manganese lanthanums molar ratio carry out the experiment of denitration demercuration efficiency, be verified by experiments, in low temperature range and high efficiency remove NOx while, have both good demercuration performance.
Description
Technical field
The present invention relates to technical field of molecular sieve, and in particular to a kind of preparation side of the molecular sieve for denitration collaboration demercuration
Method.
Background technique
MCM-48 molecular sieve is the uniform pore size of about 2.6nm or so a kind of, two sets of mutually independent three-dimensional spiral face roads
Structure has preferable hydrothermal stability and thermal stability with good long-range periodicity and the structure feature for stablizing skeleton,
Therefore it is particularly suitable for pyroprocess, it is more likely that is developed to as excellent industrial catalyst.It is in selectivity
Catalysis, macromolecules adsorption separation etc. have very tempting application prospect, can be used as adsorbent and catalysis material in industry
Upper application.Again because its aperture is big, it can adsorb that Hg plasma radius is big, is not easy to be adsorbed by micro porous molecular sieve well from waste water
Heavy metal ion.Thus, and be hopeful to load macromolecular metal, to prepare new catalytic material.MCM-48 molecular sieve
Due to its chemical composition, crystal structure and in terms of have many unique properties, have become at present it is most heavy
One of molecular sieve adsoption catalysis material wanted.
NOx and heavy metal Hg will cause sternly environment and human health as two kinds of typical pollutants in coal-fired flue-gas
It endangers again.NOx emission can generate photochemical fog into atmosphere, acid rain acid mist, destroy ozone layer, and have intoxicating to humans and animals
Effect.The mercury of coal burning release, mainly with Elemental Mercury (Hg0) form presence, in addition to this, there are also the mercury (Hg of compound state+With
Hg2+) and granular mercury.Wherein Hg2+With very high water solubility, and particle mercury can be captured by deduster, therefore easily be removed
It goes.And Hg in flue gas0Removing is not easy to remove, pollution is high, more to the harm of environment and the mankind.And mercury has high toxicity, easily
The characteristics of volatilization, biological concentration, be the most harmful element of human environment, to threaten the health of the mankind.Although current people
The research relative maturity of denitration individual for coal-fired flue-gas and demercuration unit；But in practical engineering applications, if often
Kind pollutant is respectively provided with independent removing facility, not only system complex, but also investment and operating cost greatly increase, therefore available
Existing denitration facility carries out the expansion of mercury contaminants remove, realizes the integrated multi-pollutant Collaborative Control of denitration demercuration.
Currently, selective catalytic reduction (SCR) is considered as one of most effective NOx restoring method.Typical commercialization SCR
Catalyst V2O5-WO3/TiO2The denitration efficiency with higher and to Hg under the conditions of high temperature (300-400 DEG C)0One fixing of removal
It rings.However high temperature not only results in high energy consumption, and the mercury compound to be formed is easy to cause to decompose.In addition, only in power plant
Air pollution control device (APCD) is used alone and removes NO or Hg0Etc. single pollutant, cause investment big, operation cost is high.
Recently, research concentrates on high temperature SCR denitration demercuration integration aspect, and primarily directed to the de- of commercial applications at present
Denox catalyst investigates it to simple substance Hg0Cooperation-removal efficiency, and about low-temperature denitration collaboration demercuration correlative study it is then opposite
It is less.
In the prior art in relation to low-temperature denitration demercuration catalyst in terms of research mainly have:
Application number 201210221067.9 discloses a kind of composite catalyst and preparation method thereof of denitration demercuration simultaneously, should
Catalyst includes active component and carrier, and the active component is CeO2And ZrO2, wherein Ce, Zr molar ratio 1:0.1~1, carrier
For one of ceramic honey comb, molecular sieve, ceramic wafer, activated carbon fibre, silica-gel carrier, diatomite, metal alloy, filter bag or more
Kind.On the basis of the quality of carrier, the content of the catalyst activity component is 5%~30%.It further include auxiliary agent, the auxiliary agent
Any combination of one or more of oxide for W, Cu, Fe, Ti, Ni；It is described to help on the basis of the quality of carrier
The content of agent is 0%~15%.To flue gas detected the result shows that: reaction temperature be 300 DEG C when, denitrification rate is
95.6%, the oxygenation efficiency of gaseous elemental mercury is 92.1%.
However, there is also following defects for the above-mentioned prior art:
Once based on dust, SO in high temperature denitrification process2Deng seriously affecting to catalyst activity and selectivity, there is scholar
It proposes for Benitration reactor to be placed in the low temperature SCR denitration arrangement after deduster even desulfurization unit.After desulfurizing tower
Flue gas in SO2Concentration is lower than 50mg/Nm3, dust concentration is lower than 20mg/Nm after dedusting3, the poisoning effect of catalyst is weakened
And reduce the dust stratification of catalyst, abrasion.But " environmental protection product assert the middle-size and small-size fuel-oil or fuel-gas boiler of technical requirements "
(HBC31-2004) it provides, hot-water boiler exhaust gas temperature should be less than 180 DEG C, steam boiler and boiler for domestic should be less than
200℃.And the invention catalyst need to be when reaction temperature be 300 DEG C, denitration demercuration efficiency is up to 90% or more, needs volume at this time
Outer heating device, the investment and operating cost needed are big.
Application number 201610857931.2 discloses a kind of system of efficient cryogenic sulfur resistive water resistant collaboration denitration demercuration catalyst
Preparation Method, this method optimize load various metals salt by catalyst support surface directed modification, with equi-volume impregnating, then
It calcined, be pyrolyzed to obtain high efficient cryogenic denitration demercuration catalyst；Its preparation step are as follows: first by commercial γ-Al2O3Carrier surface
Group is oriented modification, obtains the carrier of catalysis sample；Then by carrier impregnation in the metal salt of certain mass concentration
In solution, low temperature drying after a certain period of time is impregnated；The sample after drying is finally subjected to high-temperature calcination pyrolysis, catalyst is made.
When carrier is successively put in the hydrochloric acid and sodium hydroxide solution of 0.5M respectively, NOx and Hg at 240 DEG C0Conversion ratio be respectively
98% and 92%, but individually it is passed through SO2When, catalyst poisoning can not be restored.
Defect present in the above-mentioned prior art are as follows:
The independent anti-SO of the catalyst2Poisoning performance is poor, SO2It can not restore after poisoning；It needs to use strong acid and strong base in the preparation,
PH must be adjusted during filtration washing, operated more complex.
Since low-temperature denitration is different from the reaction temperature window of high temperature denitration, flue gas composition also has larger difference, for low
Warm (100-280 DEG C) denitration collaboration demercuration mechanism of catalytic reaction lacks system, deep understanding.Research and development have high efficiency, compared with
Low temperature active well, anti-SO2The new catalyst of poisoning, and probe into foreign gas in flue gas, dust composition etc. to catalyst
The affecting laws of denitration demercuration performance and reason etc. need further research.
Summary of the invention
It is assisted the purpose of the present invention is to provide a kind of preparation method of oxide modifying MCM-48 molecular sieve and its in denitration
With the application in demercuration, the oxide modifying MCM-48 molecular sieve that this method is prepared is to Hg0With good removing effect,
And MnN/MCM-48 molecular sieve can in low temperature range (100-280 DEG C) well by NOx conversion be N2, reach preferable denitration
Efficiency.
One of task of the invention is to provide a kind of preparation method of oxide modifying MCM-48 molecular sieve, which employs
Following technical scheme:
A kind of preparation method of oxide modifying MCM-48 molecular sieve, successively the following steps are included:
A, pretreated step is carried out to the MCM-48 molecular sieve of non-removed template method；
B, using Mn oxide as active material, N oxide is as auxiliary agent, the step of synthesizing MnN mixed solution；Described
N is La, Co or Ce；
C, MnN mixed solution described in the pretreated MCM-48 molecular sieve of step a and step b is sufficiently mixed uniformly,
It is configured to the mixed solution that molar ratio is 2:1, is expressed as Mn2N/MCM-48 solution；
D, to the Mn2N/MCM-48 solution is stirred, and is then placed it in 60-80 DEG C of baking oven and is dried；
E, obtained solid after step d drying is successively fired, after cooled to room temperature, is transferred to vacuum oven
In to get.
As a preferred solution of the present invention, the pre-treatment step of step a includes:
a1, MCM-48 molecular sieve is dissolved in ethyl alcohol, 60-80 DEG C of reflux 10-14h of temperature, be repeated twice after washing is dry；
a2, by step a1MCM-48 molecular sieve that treated, which is dissolved in n-hexane, to be ultrasonically treated；
a3, dropwise be added dropwise a certain amount of 3- aminopropyl triethoxysilane be then sonicated a period of time；
a4, by step a3MCM-48 molecular sieve after sonicated moves into water-bath and is condensed back；
a5, last filtration washing it is dry.
As another preferred embodiment of the invention, in step b, the specific steps of MnN mixed solution are synthesized are as follows:
b1, weigh a certain amount of Mn-based material, and be configured to the Mn (NO of 150mL 0.2mol/L3)2Solution；
b2, weigh a certain amount of lanthanum sill, and be configured to the La (NO of 50mL 0.1mol/L3)2Solution；
b3, weigh a certain amount of cobalt-based material, and be configured to the Co (NO of 50mL 0.1mol/L3)2Solution；
b4, weigh a certain amount of cerium sill, and be configured to the Ce (NO of 50mL 0.1mol/L3)2Solution；
By the Mn (NO3)2Solution and La (NO3)2Solution, Co (NO3)2Solution or Ce (NO3)2Solution mixing to get.
Further, in step d, 10-14h, dry 22-26h are stirred.
Further, in step e, obtained solid is placed in Muffle furnace in 450-500 DEG C of roasting 1-4h after step d is dry.
Further, above-mentioned N is La.After being followed by amido pretreatment to MCM-48 molecular sieve progress stripper plate, use
Infusion process Supported Manganese and lanthanum (when molar ratio is 2:1) have good denitration demercuration efficiency.
Further, step a1In, the quality volume proportion of MCM-48 molecular sieve and ethyl alcohol is 1:20g/mL, step a2In
It is ultrasonically treated 10-20min, step a3Middle ultrasonic treatment 20-40min.
Further, step a4In, the temperature of water-bath is 60-80 DEG C, and the condensing reflux time is 10-14h.
Another task of the invention is to provide a kind of preparation method system of above-mentioned oxide modifying MCM-48 molecular sieve
Application of the standby obtained MCM-48 molecular sieve in denitration collaboration demercuration.
In above-mentioned application, denitration demercuration temperature is set as 100-240 DEG C, when temperature is at 100 DEG C -240 DEG C, MCM-48
The denitration demercuration rate of molecular sieve is 90% or more.
The key reaction principle of the preparation method of oxide modifying MCM-48 molecular sieve of the present invention are as follows:
The MCM-48 molecular sieve of non-removed template method is carried out in pre-treatment step first, by the MCM- of non-removed template method
48 molecular sieves 60-80 DEG C of reflux 12h of water-bath or so in ethanol, is repeated twice and carries out washing drying, to remove molecular sieve
Template does not destroy the hydroxyl of molecular sieve surface, then carries out activation modification to molecular sieve surfaces externally and internally, to introduce amino；It
Active material is evenly spread on MCM-48 molecular sieve afterwards, manganese, lanthanum, cobalt, cerium are specifically evenly spread into MCM-48 molecule
Sieve, specific steps are as follows: the solution that will first contain manganese and lanthanum (cobalt, cerium) is uniformly mixed according to molar ratio Mn:La (Co, Ce)=2:1, then
12h or so is stirred at room temperature after molecular sieve is added, it is therefore an objective to make to prevent active material cluster over a molecular sieve, directly by mixed liquor
It is put into 80 DEG C or so baking ovens and dries, be no wasting phenomenon in order to ensure active material is distributed on molecular sieve；Finally, will bear
The active material being downloaded on molecular sieve becomes oxide, and the solid in step d after drying is put into 450-500 DEG C by specific steps
2h or so is calcined in the Muffle furnace of left and right, and manganese, lanthanum, cobalt, cerium is made all to become its corresponding oxide.
Compared with prior art, present invention offers advantageous effects:
The oxide modifying MCM-48 molecular sieve that the present invention is prepared, it shows uniqueness in physics and chemical aspect
Characteristic, (100-300 DEG C) has good demercuration while high efficiency (75-100%) removes NOx in low temperature range
Energy.
Mesoporous material not only has the characteristics that aperture big, specific surface area and Kong Rong great, but also silicone hydroxyl abundant, exist with
The surfaces externally and internally in duct, the presence of silicone hydroxyl, surface modified etc. for mesoporous material provide good active site；Metal
For oxide as active component, metal source is extensive, cheap, and the method for being converted into oxide is simple.The method of the present invention letter
It is single, it is not high to equipment requirement, it can industrialized production.
Advantageous effects of the invention can also further be embodied from following example, and it is negative that embodiment has studied different metal
It is loaded in the influence on MCM-48 molecular sieve to NOx and mercury removal efficiency, studies have shown that when modified MC M-48 molecular sieve is manganese and lanthanum
When oxide, when the molar ratio of manganese and lanthanum is 2:1, the denitration demercuration rate of oxide modifying MCM-48 molecular sieve 95% with
On.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawing:
Fig. 1 is 1 raw material MnO of the embodiment of the present invention2The MnLa being finally prepared0.5The XRD of/MCM-48 catalyst spreads out
Penetrate figure；
Fig. 2 is 1MnLa of the embodiment of the present invention0.5Denitration demercuration efficiency chart under/MCM-48 catalyst different temperatures.
Specific embodiment
The invention proposes a kind of preparation method of oxide modifying MCM-48 molecular sieve and its in denitration collaboration demercuration
Application the present invention is done combined with specific embodiments below in order to keep advantages of the present invention, technical solution clearer, clear
It is described in detail.
Raw material needed for the present invention can be bought by commercial channel and be obtained.
Catalyst activity of the present invention evaluation method is as follows:
Detection method: fixed bed reactors, the detection architecture of flue gas analyzer and mercury vapourmeter are used.
Adsorbent activity detecting step:
Preparation gained oxide modifying MCM-48 molecular sieve 4cm3Catalyst is placed in the tube furnace of fixed bed reactors, is adopted
The N of air inlet is carried out with mass flowmenter2,NO,NH3,O2Flow control, SCR device is adjusted, using flue gas analyzer
Measure the concentration of NO in flue gas；Mercury generator bath temperature is controlled at 30 DEG C, measures mercury concentration using mercury vapourmeter.
Evaluation method: denitration efficiency can be obtained by the variation of NO concentration in the flue gas of front and back.Calculation method such as formula
(1):
Denitration efficiency is obtained by the variation of NO concentration in the flue gas of front and back.Calculation method such as formula (2):
Embodiment 1:
MCM-48 molecular sieve is dissolved in ethyl alcohol flowing back first by the first step, is repeated twice after washing is dry, then it is dissolved in
Ultrasonic disperse in n-hexane, and 3- aminopropyl triethoxysilane (APTES) is added dropwise dropwise and continues ultrasound 30min；It finally will place
The MCM-48 molecular sieve of reason moves into water-bath reflux 12h, and filtration washing is dry, in case subsequent experimental uses.
Second step pre-processes manganese base and lanthanum sill: weighing 2.5g 50%Mn (NO3)2Solution is matched in beaker
Set 50mL solution；Weigh 1.02g La (NO3)2·6H2O configures 50mL solution in beaker；It will be in two kinds of solution and sufficiently mixed
It closes uniformly, indicates MnLa0.5Solution；
Third step weighs 5g treated MCM-48 molecular sieve, and Mn is added2In the beaker of La solution, it is sufficiently mixed uniformly；
Mixed solution is placed in magnetic stirring apparatus by the 4th step, is at the uniform velocity stirred 12 hours at room temperature, then will mixing
Liquid is put into 80 DEG C of baking ovens 24 hours dry；
5th step, the roasting temperature 5h that the solid after drying is placed in 450 DEG C in Muffle furnace, in horse after the completion of roasting
Not in furnace after cooled to room temperature, it is ground to 80-100 mesh or so and is transferred in vacuum oven to get Mn2La/MCM-
48 catalyst.
The Mn that the present embodiment is prepared2La/MCM-48 catalyst carries out denitration demercuration experiment, experimental result denitration effect
For rate at 140-240 DEG C about 99%, demercuration efficiency is about 96%, sees Fig. 2.MCM-48 molecular sieve is finally prepared
Mn2La/MCM-48 catalyst diffraction pattern is as shown in Figure 1.By comparing two curves, Mn is found2What is occurred on La/MCM-48 is small
Diffraction maximum be Mn oxide and lanthanum-oxides diffraction maximum.
Embodiment 2:
Difference from Example 1 is,
Mixed solution is Mn in second step2Co solution.
Selection simulated flue gas NO content is 0.1%, NH3Content 0.12%, O2Content 5%, remaining is N2Balance
Gas, while by changing bath temperature, certain density Hg is obtained in mercury osmos tube0Steam, Hg0The flow velocity of carrier gas is 90mL/
Min, general gas flow 667mL/min, air speed 10000h-1, denitration demercuration experiment is carried out in 100-260 DEG C of temperature range.
For experimental result denitration efficiency at 160-240 DEG C about 95%, demercuration efficiency is about 94%.
Embodiment 3:
Difference from Example 1 is,
Mixed solution is Mn in second step2Ce solution.
Selection simulated flue gas NO content is 0.1%, NH3Content 0.12%, O2Content 5%, remaining is N2Balance
Gas, while by changing bath temperature, certain density Hg is obtained in mercury osmos tube0Steam, Hg0The flow velocity of carrier gas is 90mL/
Min, general gas flow 667mL/min, air speed 10000h-1, denitration demercuration experiment is carried out in 100-260 DEG C of temperature range.
For experimental result denitration efficiency about at 160-240 DEG C about 95%, demercuration efficiency is about 92%.
From above-described embodiment 1- embodiment 3 it is found that denitration demercuration temperature range of the present invention is preferably controlled at 160-240 DEG C,
Middle manganese lanthanum-oxides modified MC M-48 catalyst denitration demercuration efficiency is best, and temperature window is wider.
The difference of air speed size also has an impact to denitration demercuration efficiency,
Research of the present invention prepares manganese lanthanum-oxides modified MC M-48 catalyst in the influence of denitration demercuration performance.
Embodiment 4:
Difference from Example 1 is: the molar ratio of Supported Manganese lanthanum is 2:1.
Selection simulated flue gas NO content is 0.1%, NH3Content 0.12%, O2Content 5%, remaining is N2Balance
Gas, while by changing bath temperature, certain density Hg is obtained in mercury osmos tube0Steam, Hg0The flow velocity of carrier gas is
150mL/min, general gas flow 1000mL/min, air speed 30000h-1, denitration demercuration experiment is carried out, experimental result is denitration
For efficiency at 120-240 DEG C about 100%, demercuration efficiency is about 98%.
Embodiment 5:
The molar ratio of difference from Example 1 Supported Manganese lanthanum is 2:1.
Selection simulated flue gas NO content is 0.1%, NH3Content 0.12%, O2Content 5%, remaining is N2Balance
Gas, while by changing bath temperature, certain density Hg is obtained in mercury osmos tube0Steam, Hg0The flow velocity of carrier gas is
225mL/min, general gas flow 1500mL/min, air speed 45000h-1, it is de- that denitration is carried out in 100-260 DEG C of temperature range
Mercury experiment.Experimental result is denitration efficiency at 140-240 DEG C about 100%, and demercuration efficiency is about 99%.
From above-described embodiment 1, embodiment 4 and embodiment 5 it is found that catalyst of the present invention difference also can be de- to denitration because of air speed
Mercury has certain influence, and air speed is higher, and efficiency is better.
The addition of sulfur dioxide also has an impact to denitration demercuration.
Research of the present invention prepares manganese lanthanum-oxides modified MC M-48 catalyst in the influence of denitration demercuration performance.
Embodiment 6:
Difference from Example 1 is that the molar ratio of Supported Manganese lanthanum is 2:1.
Selection simulated flue gas NO content is 0.1%, NH3Content 0.12%, O2Content 5%, remaining is N2Balance
Gas, while by changing bath temperature, certain density Hg is obtained in mercury osmos tube0Steam, Hg0The flow velocity of carrier gas is 90mL/
Min, general gas flow 667mL/min, air speed 10000h-1, test and be passed through 500ppm SO after first carrying out a period of time2, experiment
After carrying out 30h or so, stopping is passed through SO2, denitration demercuration experiment is carried out in 140 DEG C of temperature ranges.Experimental result is being passed through SO2
Denitration efficiency is about 89% afterwards, and demercuration efficiency is about 88%；Stop logical SO2Denitration efficiency is 95% after 1h, and demercuration efficiency is
93%.
From embodiment 1 and embodiment 6 it is found that the molar ratio of Supported Manganese lanthanum is 2:1, temperature is controlled at 140 DEG C, the present invention
Prepared MnLa0.5/ MCM-48 catalyst sulfur resistance is good.
Comparative example 1:
Difference from Example 1 is:
Second step specific steps are as follows: pre-process to manganese base and lanthanum sill: 2.5g 50%Mn (NO is weighed3)2Solution,
50mL solution is configured in beaker；Weigh 2.04g La (NO3)2·6H2O configures 50mL solution in beaker；By two kinds of solution
It is sufficiently mixed uniformly, indicates MnLa solution；
The MnLa/MCM-48 catalyst that manganese lanthanum molar ratio is 1:1 is finally prepared.
The MnLa/MCM-48 catalyst for being 1:1 to the manganese lanthanum molar ratio that the comparative example is prepared carries out denitration and demercuration
Experiment, selection simulated flue gas NO content are 0.1%, NH3Content 0.12%, O2Content 5%, remaining is N2It carries out doing Balance Air, together
When by change bath temperature, certain density Hg is obtained in mercury osmos tube0Steam, Hg0The flow velocity of carrier gas is 90mL/min,
General gas flow is 667mL/min, air speed 10000h-1, denitration demercuration experiment is carried out in 100-260 DEG C of temperature range.Experiment
As a result for denitration efficiency about at 140-240 DEG C 95%, demercuration efficiency is about 92%.
Comparative example 2:
Difference from Example 1 is:
Second step specific steps are as follows: pre-process to manganese base and lanthanum sill: 2.5g 50%Mn (NO is weighed3)2Solution,
50mL solution is configured in beaker；Weigh 2.04g La (NO3)2·6H2O configures 50mL solution in beaker；By two kinds of solution
It is sufficiently mixed uniformly, indicates Mn0.5La solution；
The Mn that manganese lanthanum molar ratio is 1:2 is finally prepared0.5La/MCM-48 catalyst.
The MnLa for being 1:2 to the manganese lanthanum molar ratio that the comparative example is prepared2/ MCM-48 catalyst carries out denitration and demercuration
Experiment, selection simulated flue gas NO content are 0.1%, NH3Content 0.12%, O2Content 5%, remaining is N2It carries out doing Balance Air, together
When by change bath temperature, certain density Hg is obtained in mercury osmos tube0Steam, Hg0The flow velocity of carrier gas is 90mL/min,
General gas flow is 667mL/min, air speed 10000h-1, denitration demercuration experiment is carried out in 100-260 DEG C of temperature range.Experiment
As a result for denitration efficiency about at 140-240 DEG C 95%, demercuration efficiency is about 91%.
Comparative example 3:
Difference from Example 1 is:
Second step specific steps are as follows: pre-process to manganese base and lanthanum sill: 2.5g 50%Mn (NO is weighed3)2Solution,
50mL solution is configured in beaker；Weigh 2.04g La (NO3)2·6H2O configures 50mL solution in beaker；By two kinds of solution
It is sufficiently mixed uniformly, indicates Mn0.5La solution；
The MnLa that manganese lanthanum molar ratio is 1:3 is finally prepared3/ MCM-48 catalyst.
The MnLa for being 1:3 to the manganese lanthanum molar ratio that the comparative example is prepared3/ MCM-48 catalyst carries out denitration and demercuration
Experiment, selection simulated flue gas NO content are 0.1%, NH3Content 0.12%, O2Content 5%, remaining is N2It carries out doing Balance Air, together
When by change bath temperature, certain density Hg is obtained in mercury osmos tube0Steam, Hg0The flow velocity of carrier gas is 90mL/min,
General gas flow is 667mL/min, air speed 10000h-1, denitration demercuration experiment is carried out in 100-260 DEG C of temperature range.Experiment
As a result for denitration efficiency about at 140-240 DEG C 94%, demercuration efficiency is about 91%.
It uses for reference the prior art and can be realized in the part that do not addressed in the present invention.
It should be noted that any equivalent way that those skilled in the art are made under the introduction of this specification, or
Obvious variant should all be within the scope of the present invention.
Claims (10)
1. a kind of preparation method of oxide modifying MCM-48 molecular sieve, which is characterized in that successively the following steps are included:
A, pretreated step is carried out to the MCM-48 molecular sieve of non-removed template method；
B, using Mn oxide as active material, N oxide is as auxiliary agent, the step of synthesizing MnN mixed solution；The N is
La, Co or Ce；
C, MnN mixed solution described in the pretreated MCM-48 molecular sieve of step a and step b is sufficiently mixed uniformly, configuration
The mixed solution for being 2:1 at molar ratio, is expressed as Mn2N/MCM-48 solution；
D, to the Mn2N/MCM-48 solution is stirred, and is then placed it in 60-80 DEG C of baking oven and is dried；
E, obtained solid after step d drying is successively fired, after cooled to room temperature, is transferred in vacuum oven, i.e.,
?.
2. a kind of preparation method of oxide modifying MCM-48 molecular sieve according to claim 1, which is characterized in that step
The pre-treatment step of a includes:
a1, MCM-48 molecular sieve is dissolved in ethyl alcohol, 60-80 DEG C of reflux 10-14h of temperature, be repeated twice after washing is dry；
a2, by step a1MCM-48 molecular sieve that treated, which is dissolved in n-hexane, to be ultrasonically treated；
a3, dropwise be added dropwise a certain amount of 3- aminopropyl triethoxysilane be then sonicated a period of time；
a4, by step a3MCM-48 molecular sieve after sonicated moves into water-bath and is condensed back；
a5, last filtration washing it is dry.
3. a kind of preparation method of oxide modifying MCM-48 molecular sieve according to claim 2, it is characterised in that: step
In b, the specific steps of MnN mixed solution are synthesized are as follows:
b1, weigh a certain amount of Mn-based material, and be configured to the Mn (NO of 150mL0.2mol/L3)2Solution；
b2, weigh a certain amount of lanthanum sill, and be configured to the La (NO of 50mL0.1mol/L3)2Solution；
b3, weigh a certain amount of cobalt-based material, and be configured to the Co (NO of 50mL0.1mol/L3)2Solution；
b4, weigh a certain amount of cerium sill, and be configured to the Ce (NO of 50mL0.1mol/L3)2Solution；
By the Mn (NO3)2Solution and La (NO3)2Solution, Co (NO3)2Solution or Ce (NO3)2Solution mixing to get.
4. a kind of preparation method of oxide modifying MCM-48 molecular sieve according to claim 3, it is characterised in that: step
In d, 10-14h, dry 22-26h are stirred.
5. a kind of preparation method of oxide modifying MCM-48 molecular sieve according to claim 4, it is characterised in that: step
In e, obtained solid is placed in Muffle furnace in 450-500 DEG C of roasting 1-4h after step d is dry.
6. a kind of preparation method of oxide modifying MCM-48 molecular sieve according to claim 5, it is characterised in that: described
N be La.
7. a kind of preparation method of oxide modifying MCM-48 molecular sieve according to claim 2, which is characterized in that step
a1In, the quality volume proportion of MCM-48 molecular sieve and ethyl alcohol is 1:20g/mL, step a2Middle ultrasonic treatment 10-20min, step
a3Middle ultrasonic treatment 20-40min.
8. a kind of preparation method of oxide modifying MCM-48 molecular sieve according to claim 2, it is characterised in that: step
a4In, the temperature of water-bath is 60-80 DEG C, and the condensing reflux time is 10-14h.
9. a kind of preparation method of oxide modifying MCM-48 molecular sieve according to claim 1-5 is prepared
MCM-48 molecular sieve denitration collaboration demercuration in application.
10. application according to claim 9, it is characterised in that: denitration demercuration temperature is set as 100-260 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910534184.2A CN110354892B (en) | 2019-06-20 | 2019-06-20 | Preparation method of oxide modified MCM-48 molecular sieve and application thereof in denitration and demercuration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910534184.2A CN110354892B (en) | 2019-06-20 | 2019-06-20 | Preparation method of oxide modified MCM-48 molecular sieve and application thereof in denitration and demercuration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110354892A true CN110354892A (en) | 2019-10-22 |
| CN110354892B CN110354892B (en) | 2022-02-22 |
Family
ID=68217509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910534184.2A Active CN110354892B (en) | 2019-06-20 | 2019-06-20 | Preparation method of oxide modified MCM-48 molecular sieve and application thereof in denitration and demercuration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110354892B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111215124A (en) * | 2020-03-12 | 2020-06-02 | 青岛理工大学 | Preparation method of catalyst for synergistically removing hydrogen sulfide and elemental mercury in garbage gasification pollutants |
| CN113209979A (en) * | 2021-05-18 | 2021-08-06 | 重庆大学 | Novel coal-fired flue gas demercuration catalyst and preparation method thereof |
| CN116059955A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | EVS-10-based manganese-loaded catalytic adsorbent for flue gas mercury removal and denitration, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070297975A1 (en) * | 2006-06-23 | 2007-12-27 | Janssen Marcel J | Metal loading of molecular sieves using organic carriers with limited water content |
| CN102423685A (en) * | 2011-10-27 | 2012-04-25 | 浙江师范大学 | Method for preparing amino functional MCM-48 mesoporous material |
-
2019
- 2019-06-20 CN CN201910534184.2A patent/CN110354892B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070297975A1 (en) * | 2006-06-23 | 2007-12-27 | Janssen Marcel J | Metal loading of molecular sieves using organic carriers with limited water content |
| CN102423685A (en) * | 2011-10-27 | 2012-04-25 | 浙江师范大学 | Method for preparing amino functional MCM-48 mesoporous material |
Non-Patent Citations (5)
| Title |
|---|
| JEA-HUN JANG ET AL.: "Characterization of Pt-impregnated MCM-41 and MCM-48 and their catalytic performances in selective catalytic reduction for NOx", 《APPLIED CATALYSIS A: GENERAL》 * |
| 吴一楠等(著): "《具有多层次结构环境功能材料的制备及性能研究》", 31 August 2017, 同济大学出版社 * |
| 张安超等: "Mn-Co/MCM-41吸附剂表征及脱除烟气中单质汞研究", 《中国环境科学》 * |
| 李学峰著: "《环氧化催化剂：过渡金属掺杂的介孔分子筛》", 31 March 2017, 武汉大学出版社 * |
| 游华伟: "MnOx-CeO2/γ-Al2O3催化剂脱硝脱汞的实验研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111215124A (en) * | 2020-03-12 | 2020-06-02 | 青岛理工大学 | Preparation method of catalyst for synergistically removing hydrogen sulfide and elemental mercury in garbage gasification pollutants |
| CN113209979A (en) * | 2021-05-18 | 2021-08-06 | 重庆大学 | Novel coal-fired flue gas demercuration catalyst and preparation method thereof |
| CN116059955A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | EVS-10-based manganese-loaded catalytic adsorbent for flue gas mercury removal and denitration, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110354892B (en) | 2022-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104888806B (en) | A kind of regeneration method that inactivation vanadium titanium-based Faveolate denitration catalyst combined denitration demercuration is modified | |
| CN110354892A (en) | The preparation method of oxide modifying MCM-48 molecular sieve and its application in denitration collaboration demercuration | |
| Lan et al. | Unraveling the promotion effects of dynamically constructed CuO x-OH interfacial sites in the selective catalytic oxidation of ammonia | |
| CN105032403A (en) | Catalyst used for low temperature desulphurization and denitration of flue gas and preparation method thereof | |
| CN104785302B (en) | Denitrifying catalyst with selective catalytic reduction and its preparation method and application | |
| CN106731226B (en) | The method that one step in-situ synthesis prepares binary denitration sulfur resistant catalyst load filtrate | |
| CN105214670B (en) | Preparation and method of testing using former iron ore as the middle low temperature support type denitrating catalyst of carrier | |
| CN103212245B (en) | Dedusting filter material containing MnO2 catalyst, and preparation method and application thereof | |
| CN107185493A (en) | The composite mesopore carbosphere air purifying preparation preparation method that graphene is modified | |
| JPH01218635A (en) | Deodorizing agent, its manufacturing method, deodorizing method, deodorizing apparatus and refrigeration cycle apparatus with said deodorizing apparatus | |
| Yang et al. | Reducing the competitive adsorption between SO2 and NO by Al2O3@ TiO2 core-shell structure adsorbent | |
| Yang et al. | Mn-Ce-Nb-Ox/P84 catalytic filters prepared by a novel method for simultaneous removal of particulates and NO | |
| CN111420660A (en) | Precious metal composite vanadium-titanium catalyst for purifying organic waste gas in coal-fired flue gas and preparation method and application thereof | |
| CN112657541A (en) | Preparation method of molecular sieve based low-temperature environment-friendly SCR denitration catalyst | |
| Hao et al. | Constructing and synthesizing optimal Cu-BTC and its application in low-temperature denitration | |
| Jung et al. | Pilot-scale evaluation of a novel TiO2-supported V2O5 catalyst for DeNOx at low temperatures at a waste incinerator | |
| Cui et al. | Preparation of copper-based biochar adsorbent with outstanding H2S adsorption capacity and study on H2S removal | |
| CN103372373A (en) | Method for denitration and purification of catalytic cracking regeneration flue gas | |
| CN101733111A (en) | Perovskite/cerium dioxide composite catalyst and preparation method thereof and catalytic combustion on soot | |
| CN106925034B (en) | A kind of preparation method of denitration function polyphenylene sulfide composite filtering material | |
| CN102698740A (en) | Bag-type NOx removal catalyst and preparation method thereof | |
| Huang et al. | Mercury removal over Ce-doped LaCoO3 supported on CeO2 at low temperatures from coal combustion flue gas | |
| CN109876824A (en) | A kind of MnO2- NiO activated coke low-temperature denitration catalyst and preparation method thereof | |
| CN101357238A (en) | Normal-pressure low-temperature plasma catalysis method for removing benzene, toluene and xylene from air in door (car) | |
| CN104707618B (en) | A kind of substep zontation Preparation Method of NOx absorbing and reducing bifunctional catalyst |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |