CN105664978B - Low-temperature denitration of flue gas is acidified the sulfur resistant catalyst molding method for preparing of manganese cobalt cerium with composite carrier load type - Google Patents
Low-temperature denitration of flue gas is acidified the sulfur resistant catalyst molding method for preparing of manganese cobalt cerium with composite carrier load type Download PDFInfo
- Publication number
- CN105664978B CN105664978B CN201510940688.6A CN201510940688A CN105664978B CN 105664978 B CN105664978 B CN 105664978B CN 201510940688 A CN201510940688 A CN 201510940688A CN 105664978 B CN105664978 B CN 105664978B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sio
- tio
- flue gas
- low
- 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.)
- Active
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
Abstract
The present invention relates to a kind of low-temperature denitration of flue gas sulfur resistant catalyst molding method for preparing of composite carrier load type acidification manganese cobalt cerium, specially a kind of low-temperature flue gas NH3The molding method for preparing of SCR denitration acidification catalyst.The catalyst is the TiO for being carried on sol-gal process preparation with infusion process with the nitrate of Mn, Co, Ce metal2/SiO2Complex carrier, then the multicomponent load metal oxide type catalyst roasted after sulphation form powder catalytic using honeycomb moulding preparation method.Catalyst has biggish specific surface area and lower wall thickness, improves resistance to SO_2.The present invention also provides the preparation methods of catalyst.
Description
Technical field
The present invention relates to the sulfur resistant catalyst moldings that a kind of low-temperature denitration of flue gas composite carrier load type is acidified manganese cobalt cerium
Preparation method, specially a kind of low-temperature flue gas NH3SCR denitration is acidified the molding method for preparing of catalyst, and forming technique uses bee
Nest shape forming preparation process, belongs to environmental technology field.
Background technique
The thermal power plant of China is mostly still using coal as fuel, especially northern thermal power plant, coal fuel
Contain a large amount of NO in flamex.SCR method is the most wide and best effect denitration technology of current industrial application.SCR catalyst application
In industrial smoke channel, so that flue gas passes through catalyst, so molded design must be carried out to catalyst, so that catalyst has
Certain shapes, and have certain physical characteristic, chemical characteristic and certain mechanical strength.But current industrial board-like catalyst
Molding method for preparing, corrugated preformed catalyst preparation method increase resistance of the flue gas by catalyst, are in flue gas and flying dust
Washing away under, active component can be lost than more serious, catalyst activity reduce ratio it is very fast, service life substantially reduces, and mentions
High economic cost.
Mn base catalyst is one of current Low-temperature catalyst research hotspot.It is learned both at home and abroad about Mn base catalyst in recent years
Person has carried out a large amount of research work.The d orbital electron of Mn is in underfill state, MnOxWith a variety of oxidation states, in oxygen
Change O that can effectively in activated gas phase in reduction circulation2, therefore there is efficient catalytic activity in SCR reaction.With
MnOxTiO is carried on for active component2、Al2O3On equal carriers, active specy is mainly MnO2And a small amount of Mn2O3.SCR is anti-
The NO answeredxRemoval rate is mainly and MnO2It is related, and to N2Selectivity mainly by Mn2O3It determines.In addition, with Mn for main active group
Point, often the activity or stability of catalyst are improved so as to improve the physical property of catalyst by adding other metal oxides
And resistance to SO_2.Common metal addition auxiliary agent has Cu, Fe, Ce, Ni etc..Ce is common metal promoter, and Ce has stronger storage
The ability of oxygen and release oxygen, the Mn-Ce-O metal composite oxide to be formed is added by Ce or is carried on TiO2Mn- on carrier
Ce loaded catalyst, all to NO under low temperaturexConversion has very high activity.Such as MnOx-CeO2It can be arrived at 200 DEG C to nearly 98%
Denitration effect.In addition, the addition of Fe and Co can also be improved activity of the catalyst at 200 DEG C or so.By the doping of metal,
Specific surface area, Kong Rong, oxygen storage capacity, surface acid center and the acid bit quantity of catalyst all change, to change catalysis
The catalytic activity of agent.
Low temperature catalyst is placed in after desulfurization and dust removing units, therefore the SO in flue gas2Concentration is lower, but due to SO2Low
It is even more serious to the poisoning effect of SCR catalyst under temperature, therefore the resistance to SO_2 of catalyst is also the problem of must be taken into consideration.Although
TiO2As carrier to SO2With certain resistance, but Mn/TiO2The resistance to SO_2 of catalyst is still lower.Research shows that logical
The resistance to SO_2 of catalyst, such as Ce, Sb, Fe can be improved in the doping for crossing some metallic elements.The addition of Ce metal oxide can be bright
The aobvious resistance to SO_2 for improving catalyst, principle is SO2Cerous sulfate preferentially is formed with Ce, to inhibit catalyst surface ammonium sulfate and sulphur
The generation and deposition of sour hydrogen ammonium.In addition, the geometric configuration of catalyst also has great influence to its resistance to SO_2, studies have shown that logical
SiO is added in passing carrier2Form TiO2-SiO2Composite oxides, the V active constituent catalyst of load is to SO2300~400
DEG C resistance significantly improve.SO2React catalysis while having the influence of positive negative side, on the one hand, SO2It is by catalysis oxidation
SO3, ammonium sulfate is generated with ammonia or ammonium hydrogen sulfate is deposited on catalyst surface, to cover catalytic active site and blocking catalyst
Hole.On the other hand, SO2The Bronsted acidic site of catalyst surface can be improved in processing, to promote NH3Absorption and NOxTurn
Change, therefore, a degree of sulphation can promote NOxThe raising of conversion ratio.
One difficult point of Mn base low-temperature SCR catalyst practical application is that resistance to SO_2 is poor, therefore, improves Mn base catalyst and exists
Resistance to SO_2 under low temperature is very necessary.
Prior art CN104289227A discloses a kind of four component NH of low-temperature denitration of flue gas3- SCR load type metal is urged
Agent and preparation method thereof is to be carried on nanoscale TiO with the nitrate of the elements such as Mn, Co, Ce with infusion process2-P25, pass through
Roasting forms what multicomponent metal composite oxide obtained, and catalyst has acid and oxidisability, is conducive to NH3In catalyst table
Face adsorption activation improves the efficiency of denitration.But resistance to SO_2 effect is poor at low temperature for the catalyst.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of low-temperature denitration of flue gas composite carrier loads
Type is acidified the sulfur resistant catalyst molding method for preparing of manganese cobalt cerium, specially a kind of low-temperature flue gas NH3SCR denitration is acidified catalyst
Molding method for preparing, using transition metal as main component, with composite Ti O2/SiO2As carrier.Using honeycomb moulding technology
Prepare preformed catalyst.
Specifically, the present invention is achieved through the following technical solutions, comprising:
A kind of low-temperature flue gas NH3SCR denitration be acidified shaping of catalyst preparation method, it is characterised in that: using honeycomb at
Type preparation method is to sulphation support type Mn-Co-Ce/TiO2-SiO2Powder catalyst is formed, and is needed in forming process
Addition needs the auxiliary agents such as glass fibre, binder, water, carries out certain temperature drying and roasting extrusion forming.
Wherein, glass fibre addition mass ratio is that the group of 15%, binder becomes the mixture of polyvinyl alcohol and water, bonding
Agent addition mass ratio is 20%, water addition mass ratio is 25%, and surplus is powder catalyst.
The stretching that discovery can promote preformed catalyst by the way that a certain amount of glass fibre is added through a large number of experiments is prolonged
Malleability；Powder catalyst is loose and without mechanical strength, so that catalyst is formed jelly by the way that binder and water is added, is formed
Fine and close and moulding material with good mechanical strength.
Wherein, auxiliary agent further contains glycerol and ammonium hydrogen carbonate, glycerol and ammonium hydrogen carbonate play the role of be respectively: it is sweet
Oil: lubricant, ammonium hydrogen carbonate: pore creating material.
Since the binder of addition cannot be uniformly admixed together with beaded catalyst, preferably further it is added a certain amount of
(glass fiber additive amount is the 15% of catalyst gross mass to extrusion aid, content of binder is the 20% of catalyst gross mass, water adds
Dosage is the 25% of catalyst gross mass, and for the catalyst gross mass plus mass ratio that adds of glycerol is the 5% of catalyst gross mass,
The addition mass ratio of ammonium hydrogen carbonate is the 5% of catalyst gross mass) so that catalyst has certain mechanical strength.
When experiment discovery preformed catalyst goes out mill after being suppressed, catalyst and grinding tool contact surface are bonded, and can be made after depanning
At the breakage of catalyst, being preferably added to lubricant (glycerol: lubricant 5%) makes catalyst smoothly completely go out to grind.
The preferred solution of the invention is that (the addition quality of glycerol is that catalyst gross mass is to a certain amount of pore creating material of addition
5%, the addition mass ratio of ammonium hydrogen carbonate is the 5% of total catalyst quality.), greatly increase the specific surface area of molding rear catalyst.
Wherein, drying temperature described in the preferably described drying temperature is 80 DEG C of dry 3h, 100 DEG C of dry 3h, 115 DEG C of dryings
3h, total 12h, maturing temperature is at 300 DEG C after molding.
Catalyst chemical composition of the present invention is SO4 2--Mn-Co-Ce/TiO2/SiO2, the wherein quality of Mn, Ce and Ce
Score be not 5%, 2% and 1%, TiO2/SiO2Middle SiO2Mass fraction be 30~50%, utilization when preparing catalyst
0.1mol/L dilute sulfuric acid impregnates 12h.
Molding method for preparing above-mentioned, more specifically, comprising the following steps:
According to the above ratio after mixing by catalyst and auxiliary agent, it is added to squeeze and carries out honeycomb molding in grinding tool, utilize
Tablet press machine certain pressure carries out squeezing out mold forming, and extrusion time was controlled in 20~30min time.
Sulphation support type Mn-Co-Ce/TiO of the present invention2-SiO2Powder catalyst passes through following preferred system
Preparation Method is prepared, comprising: is carried on sol-gal process preparation with the soluble-salt of Mn, Co and Ce metal with infusion process
TiO2/SiO2Complex carrier, then after sulphation, the multicomponent load metal oxide type catalyst roasted.
More specifically, the preparation method of the specific catalyst, including following preparation step:
(1): by dehydrated alcohol, acetic acid, deionized water 10:2:(0.5~1.0 by volume) mixing, stirs to get solution
A；By butyl titanate and dehydrated alcohol, 5:13 is mixed to get solution B by volume；Then solution B is instilled in solution A dropwise, is used
Magnetic stirrer is initially formed to colloidal sol, then according to SiO2/TiO2Middle SiO2Mass fraction 30~50% weigh centainly
Measure the spherosil SiO of 60~100 mesh2Solution is added, continues stirring to formation gel；
(2): obtained colloidal sol 24~48h of ventilation aging at room temperature forms gel, then in 80~100 DEG C of baking ovens
Interior drying 12h, obtains white powder；
(3): obtained white powder is obtained into TiO in tube furnace with 400~550 DEG C of roasting 2h2/SiO2Complex carrier；
(4): the presoma of a certain amount of Mn, Co and Ce being dissolved in proportion and are uniformly mixed, a certain amount of TiO is added2/SiO2
Carrier continues stirring 1, and the load capacity of active component Mn, Co and Ce are respectively 5%, 2% and 1%, obtains pasty solid；
(5): by obtained pasty solid at room temperature in ventilation aging for 24 hours, then in 90~110 DEG C of drying in oven
8~12h obtains black solid particle with 500 DEG C of roasting 3h in tube furnace；
(6): black solid particle being impregnated into 12h in the sulfuric acid solution of 0.05~0.15mol/L, then in 90~110
Then it is final to obtain 60~100 purposes by screening finally in tube furnace with 300 DEG C of roasting 2h by DEG C 6~12h of drying in oven
SO4 2--Mn-Co-Ce/TiO2/SiO2Solid catalyst.
The present invention compared with the existing technology, the technical effect played, comprising:
The object of the invention is also to provide the preparation methods of above-mentioned catalyst.Carrier is prepared using sol-gal process, living
Property component be carried on complex carrier using infusion process simultaneously, and carry out sulphation, and strict control maturing temperature, obtain height
The excellent catalyst of activity, sulfur resistance.
The present invention has chosen Mn-Co-Ce trimetallic catalyst of the low-temperature space with outstanding catalytic effect as optimization first
Basis, with composite Ti O2/SiO2As carrier, pass through TiO in optimization carrier2With SiO2Ratio, determine TiO2/SiO2In
SiO2Mass fraction be 30~50%.Catalyst 90ppm SO in reaction gas2Have very under existence condition in low-temperature space
Good NOxRemoval rate.Sulphation further is carried out to catalyst, forms SO4 2--Mn-Co-Ce/TiO2/SiO2Catalyst system,
Further improve the resistance to SO_2 of catalyst.
In SO4 2--Mn-Co-Ce/TiO2/SiO2In catalyst, Mn is primary activity component, and the addition of Co and Ce improve
The reactivity of catalyst has simultaneously widened reaction temperature window.TiO2/SiO2In complex carrier, pass through microsphere silica gel SiO2Plus
Enter, improve the specific surface area of catalyst, it is suppressed that the crystal grain of catalyst generates, and is equivalent to the list for reducing active metal component
Elementary volume load capacity, reduces the wall thickness of catalyst, to improve its resistance to SO_2.
Show that glass fibre additive amount 15%, content of binder 20%, water additive amount are by the above experiment of single factor
The mechanical performance of preformed catalyst is best when 25%.
Detailed description of the invention
Fig. 1 is SO4 2--Mn-Co-Ce/TiO2/SiO2The XRD characterization spectrogram of support type preformed catalyst；
Fig. 2 is SO4 2--Mn-Co-Ce/TiO2/SiO2Support type preformed catalyst SCR recycles the active influence of ramp cycle；
Specific embodiment
Realization and possessed beneficial effect of the invention are introduced below by way of specific embodiments and the drawings, but should not be accordingly
Any restriction is constituted to practical range of the invention.
The evaluation method of catalyst activity:
Detection method: fixed-bed micro-reactor-nitrogen-oxide analyzer, detection system is used.Nitrogen-oxide analyzer, is
T200H detects NO, NO using chemoluminescence method2、NOx。
Specific steps: the catalyst sample 100mg weighed up is put into fixed bed reaction pipe, reaction gas, gas are passed through
Flow is 100ml/min.Reaction tube is the quartz ampoule of 9mm internal diameter.Using temperature-programmed reaction, heating rate is 1 DEG C/min.
Evaluation method: the catalytic activity of prepared catalyst can be by NOxReduction rate and corresponding active temperature
It evaluates, reduction conversion ratio calculation method is:
In formula, C0For nitrogen oxides inlet concentration (mL/m3)；C1For nitrogen oxides exit concentration (mL/m3)。
A kind of low-temperature flue gas NH of embodiment 13SCR denitration is acidified catalyst and preparation method thereof
A kind of low-temperature flue gas NH3SCR denitration is acidified catalyst, and the catalyst is the solubility with Mn, Co and Ce metal
Salt is carried on the TiO of sol-gal process preparation with infusion process2/SiO2Complex carrier, then after sulphation, the multiple groups roasted
Divide load metal oxide type catalyst.
The catalyst chemical composition is SO4 2--Mn-Co-Ce/TiO2/SiO2, wherein the mass fraction of Mn, Ce and Ce be
It Wei 5%, 2% and 1%.TiO2/SiO2Middle SiO2Mass fraction be 30%.It is obtained using following preparation method:
(1): by dehydrated alcohol, acetic acid, deionized water, 10:2:0.5 is mixed by volume, stirs to get solution A；By metatitanic acid
5:13 is mixed to get solution B by volume for butyl ester and dehydrated alcohol；Then solution B is instilled in solution A dropwise, uses magnetic agitation
Device is stirred to colloidal sol and initially forms, then according to SiO2/TiO2Middle SiO2Mass fraction 30 weigh a certain amount of 60~100 purpose
Spherosil SiO2Solution is added, continues stirring to formation gel；
(2): ventilation aging for 24 hours, forms gel and obtains then in 80 drying in oven 12h obtained colloidal sol at room temperature
To white powder；
(3): obtained white powder is obtained into TiO in tube furnace with 550 DEG C of roasting 2h2/SiO2Complex carrier；
(4): the presoma of a certain amount of Mn, Co and Ce being dissolved in proportion and are uniformly mixed, a certain amount of TiO is added2/SiO2
Carrier continues to stir 1h, and the load capacity of active component Mn, Co and Ce are respectively 5%, 2% and 1%, obtain pasty solid；
(5): by obtained pasty solid at room temperature in ventilation aging for 24 hours, then in 110 DEG C of drying in oven 12h,
With 500 DEG C of roasting 3h in tube furnace, black solid particle is obtained；
(6): black solid particle being impregnated into 12h in the sulfuric acid solution of 0.10mol/L, is then dried in 110 DEG C of baking ovens
Then dry 12h obtains the final SO of 60~100 purposes by screening finally in tube furnace with 300 DEG C of roasting 2h4 2--Mn-Co-Ce/
TiO2/SiO2Solid catalyst.
Wherein, the presoma of component Mn, Co and Ce of the catalyst are all nitrate.The catalyst is in tube furnace
It is air atmosphere when roasting.
Utilize the specific surface area of low temperature nitrogen adsorption desorption method measurement catalyst, SO4 2--Mn-Co-Ce/TiO2/SiO2Load
The specific surface area of type catalyst is 301m2·g-1.Using the average grain size of X-ray diffraction (XRD) measurement catalyst, it is
9.8nm。
X-ray diffraction characterization, as a result as shown in Figure 1, the corresponding crystal phase of each diffraction maximum and crystal face mark in figure.Detector bar
Part: use Cu target K alpha ray, sweep speed be 6 °/min, scanning 2 θ ranges be 10~80 °, voltage and current be respectively 40kV and
200mA.Titanium dioxide is Anatase, does not detect the crystal phase of Mn, Co, Ce oxide, active component is in catalyst surface
It is dispersed fine.
Various concentration sulfuric acid solution prepared by embodiment is impregnated according to the above-mentioned method to catalyst activity evaluation
SO4 2--Mn-Co-Ce/TiO2/SiO2Catalyst carries out activity rating.The concentration of the sulfuric acid solution of use is respectively 0.05,0.10
And 0.15mol/L, and compared with the catalyst before sulphation.Air inlet SO2Concentration is 50ppm.Catalytic activity such as Fig. 2 institute
Show.In first set reaction, the NO of catalystxMaximum reduction efficiency is 99.5%.Corresponding reaction temperature is 250 DEG C.Implement
The catalyst of example preparation has very high SO at low temperature2Resistance.
To the catalyst SO of embodiment preparation4 2--Mn-Co-Ce/TiO2/SiO2, the sulfuric acid solution concentration that uses for
0.10mol/L, in air inlet SO2Under the conditions of concentration is 90ppm, circulation temperature reaction experiment is carried out, the activity of catalyst is carried out
Evaluation, as shown in Figure 2.In initial program temperature reaction, NOxMaximum reduction efficiency be 98.9%.Corresponding reaction temperature
It is 250 DEG C.After being recycled 8 times, NO of the catalyst at 180~270 DEG C of reaction temperature windowxConversion ratio be maintained at 90% with
On.
A kind of low-temperature flue gas NH of embodiment 23SCR denitration is acidified catalyst and preparation method thereof
On the basis of the scheme of embodiment 1, the sulfuric acid solution that 0.05mol/L is respectively adopted prepares the catalyst.
A kind of low-temperature flue gas NH of embodiment 33SCR denitration is acidified catalyst and preparation method thereof
On the basis of the scheme of embodiment 1, the sulfuric acid solution that 0.15mol/L is respectively adopted prepares the catalyst.
A kind of low-temperature flue gas NH of embodiment 43SCR denitration is acidified catalyst and preparation method thereof
A kind of low-temperature flue gas NH3SCR denitration is acidified catalyst, and the catalyst is the solubility with Mn, Co and Ce metal
Salt is carried on the TiO of sol-gal process preparation with infusion process2/SiO2Complex carrier, then after sulphation, the multiple groups roasted
Divide load metal oxide type catalyst.
The catalyst chemical composition is SO4 2--Mn-Co-Ce/TiO2/SiO2, wherein the mass fraction of Mn, Ce and Ce be
It Wei 5%, 2% and 1%.TiO2/SiO2Middle SiO2Mass fraction be 50%.It is obtained using following preparation method:
(1): by dehydrated alcohol, acetic acid, deionized water, 10:2:1.0 is mixed by volume, stirs to get solution A；By metatitanic acid
5:13 is mixed to get solution B by volume for butyl ester and dehydrated alcohol；Then solution B is instilled in solution A dropwise, uses magnetic agitation
Device is stirred to colloidal sol and initially forms, then according to SiO2/TiO2Middle SiO2Mass fraction 50% weigh a certain amount of 60~100 mesh
Spherosil SiO2Solution is added, continues stirring to formation gel；
(2): obtained colloidal sol ventilation aging 48h at room temperature forms gel, then in 100 DEG C of drying in oven
12h obtains white powder；
(3): obtained white powder is obtained into TiO in tube furnace with 400 DEG C of roasting 2h2/SiO2Complex carrier；
(4): the presoma of a certain amount of Mn, Co and Ce being dissolved in proportion and are uniformly mixed, a certain amount of TiO is added2/SiO2
Carrier continues stirring 1, and the load capacity of active component Mn, Co and Ce are respectively 5%, 2% and 1%, obtains pasty solid；
(5): by obtained pasty solid at room temperature in ventilation aging for 24 hours, then in 90 DEG C of drying in oven 12h,
With 500 DEG C of roasting 3h in tube furnace, black solid particle is obtained；
(6): black solid particle being impregnated into 12h in the sulfuric acid solution of 0.05~0.15mol/L, then in 90~110
Then it is final to obtain 60~100 purposes by screening finally in tube furnace with 300 DEG C of roasting 2h by DEG C 6~12h of drying in oven
SO4 2--Mn-Co-Ce/TiO2/SiO2Solid catalyst.
Wherein, the presoma of component Mn, Co and Ce of the catalyst are all nitrate.The catalyst is in tube furnace
It is air atmosphere when roasting.Gained catalyst and aforementioned catalytic agent have consistent NOxRemoval rate and resistance to SO_2.
A kind of low-temperature flue gas NH of embodiment 53SCR denitration is acidified the molding preparation of catalyst
Low-temperature flue gas NH is obtained using embodiment 13SCR denitration is acidified catalyst, and glass fibre addition mass ratio is
15%, the group of binder becomes the mixture of polyvinyl alcohol and water, and binder addition mass ratio is 20%, water addition mass ratio is
25%, surplus is powder catalyst.
Molding preparation is carried out using following technique, according to the above ratio after mixing by catalyst and auxiliary agent, is added and squeezes
Honeycomb molding is carried out in grinding tool, carries out squeezing out mold forming using tablet press machine certain pressure.The drying temperature are as follows: drying temperature
Degree is 80 DEG C of dry 3h, and 100 DEG C of dry 3h, 115 DEG C of dry 3h, total 12h, maturing temperature is at 300 DEG C after molding.
Extrusion time was controlled in the 20min time.
A kind of low-temperature flue gas NH of embodiment 63SCR denitration is acidified the molding preparation of catalyst
Low-temperature flue gas NH is obtained using embodiment 23SCR denitration is acidified catalyst, and glass fibre addition mass ratio is
15%, the group of binder becomes the mixture of polyvinyl alcohol and water, and binder addition mass ratio is 20%, water addition mass ratio is
25%, surplus is powder catalyst.
Auxiliary agent further contains glycerol and ammonium hydrogen carbonate, and it is 5% that the addition quality of glycerol, which is catalyst gross mass, carbonic acid
The addition mass ratio of hydrogen ammonium is the 5% of catalyst gross mass.
Molding preparation is carried out using following technique, according to the above ratio after mixing by catalyst and auxiliary agent, is added and squeezes
Honeycomb molding is carried out in grinding tool, carries out squeezing out mold forming using tablet press machine certain pressure.
Extrusion time was controlled in the 30min time.
A kind of low-temperature flue gas NH of embodiment 73SCR denitration is acidified the molding preparation of catalyst
Low-temperature flue gas NH is obtained using embodiment 33SCR denitration is acidified catalyst, and glass fibre addition mass ratio is
15%, the group of binder becomes polyvinyl alcohol and the mixture binder addition mass ratio of water is 20%, water addition mass ratio is
25%, surplus is powder catalyst.
Auxiliary agent further contains glycerol and ammonium hydrogen carbonate, and it is 5% that the addition quality of glycerol, which is catalyst gross mass, carbonic acid
The addition mass ratio of hydrogen ammonium is the 5% of catalyst gross mass.
Molding preparation is carried out using following technique, according to the above ratio after mixing by catalyst and auxiliary agent, is added and squeezes
Honeycomb molding is carried out in grinding tool, carries out squeezing out mold forming using tablet press machine certain pressure.
Extrusion time was controlled in the 20min time.
A kind of low-temperature flue gas NH of embodiment 83SCR denitration is acidified the molding preparation of catalyst
Low-temperature flue gas NH is obtained using embodiment 43SCR denitration is acidified catalyst, and glass fibre addition mass ratio is
15%, the group of binder becomes the mixture of polyvinyl alcohol and water.Binder addition mass ratio is 20%, water addition mass ratio is
25%, surplus is powder catalyst.
Auxiliary agent further contains glycerol and ammonium hydrogen carbonate, and both glycerol and ammonium hydrogen carbonate are respectively the 5% of catalyst gross mass.
Extrusion aid is further added, and (glass fiber additive amount 15%, content of binder 20%, water additive amount are 25%, sweet
The addition mass ratio of oil is 5%, and the addition mass ratio of ammonium hydrogen carbonate is 5%.), (glycerol, glycerine are respectively catalyst to lubricant
The 3% of gross mass), pore creating material (ammonium hydrogen carbonate is the 5% of total catalyst weight)
Molding preparation is carried out using following technique, according to the above ratio after mixing by catalyst and auxiliary agent, is added and squeezes
Honeycomb molding is carried out in grinding tool, carries out squeezing out mold forming using tablet press machine certain pressure.
Extrusion time was controlled in the 30min time.
9 mechanical strength test of embodiment
Test method
It is tested using the moulding material of embodiment 4-8, test result are as follows:
1. radial pressure --- utilize omnipotent pressure testing machine, radial compression catalyst.
2. impact resistance --- vertical lower throwing at 2.5m measures catalyst breakage degree.
Radial pressure: compression strength > 1MPa impact resistance: damaged degree < 15%
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (1)
1. a kind of low-temperature flue gas NH3SCR denitration is acidified shaping of catalyst preparation method, it is characterised in that:
Using honeycomb molding method for preparing to sulphation support type Mn-Co-Ce/TiO2-SiO2Powder catalyst carry out at
Type needs to add glass fibre, binder and water in forming process, carries out certain temperature drying and roasting extrusion forming；
Wherein, the catalyst chemical composition is SO4 2--Mn-Co-Ce/TiO2/SiO2, wherein the mass fraction of Mn, Co and Ce be
It Wei not 5%, 2% and 1%, TiO2/SiO2Middle SiO2Mass fraction be 30%, using following preparation method obtain:
(1): by dehydrated alcohol, acetic acid, deionized water, 10:2:0.5 is mixed by volume, stirs to get solution A；By butyl titanate
And 5:13 is mixed to get solution B to dehydrated alcohol by volume；Then solution B is instilled in solution A dropwise, is stirred with magnetic stirring apparatus
It mixes colloidal sol to initially form, then according to SiO2/TiO2Middle SiO2Mass fraction 30% to weigh a certain amount of 60~100 purpose more
Hole microsphere silica gel SiO2Solution is added, continues stirring to formation gel；
(2): ventilation aging for 24 hours, then in 80 DEG C of drying in oven 12h, obtains white powder to obtained gel at room temperature；
(3): obtained white powder is obtained into TiO in tube furnace with 550 DEG C of roasting 2h2/SiO2Complex carrier；
(4): the presoma of a certain amount of Mn, Co and Ce being dissolved in proportion and are uniformly mixed, a certain amount of TiO is added2/SiO2Carrier,
Continue to stir 1h, the load capacity of active component Mn, Co and Ce are respectively 5%, 2% and 1%, obtain pasty solid；
(5): by obtained pasty solid at room temperature in ventilation aging for 24 hours, then in 110 DEG C of drying in oven 12h, in pipe
With 500 DEG C of roasting 3h in formula furnace, black solid particle is obtained；
(6): black solid particle being impregnated into 12h in the sulfuric acid solution of 0.10mol/L, then in 110 DEG C of drying in oven
Then 12h obtains the final SO of 60~100 purposes by screening finally in tube furnace with 300 DEG C of roasting 2h4 2--Mn-Co-Ce/
TiO2/SiO2Solid catalyst；
Wherein, the presoma of component Mn, Co and Ce of the catalyst are all nitrate, and the catalyst roasts in tube furnace
When be air atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510940688.6A CN105664978B (en) | 2015-12-15 | 2015-12-15 | Low-temperature denitration of flue gas is acidified the sulfur resistant catalyst molding method for preparing of manganese cobalt cerium with composite carrier load type |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510940688.6A CN105664978B (en) | 2015-12-15 | 2015-12-15 | Low-temperature denitration of flue gas is acidified the sulfur resistant catalyst molding method for preparing of manganese cobalt cerium with composite carrier load type |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105664978A CN105664978A (en) | 2016-06-15 |
| CN105664978B true CN105664978B (en) | 2019-06-21 |
Family
ID=56189532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510940688.6A Active CN105664978B (en) | 2015-12-15 | 2015-12-15 | Low-temperature denitration of flue gas is acidified the sulfur resistant catalyst molding method for preparing of manganese cobalt cerium with composite carrier load type |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105664978B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993528A (en) * | 2018-07-25 | 2018-12-14 | 哈尔滨工业大学深圳研究生院 | Modified low-temperature denitration SCR catalyst of a kind of iron and preparation method thereof |
| CN109999829A (en) * | 2019-04-30 | 2019-07-12 | 常州大学 | A kind of bimetallic manganese iron low temperature SCR denitration catalyst, preparation method and applications |
| CN111841614B (en) * | 2020-08-18 | 2021-10-29 | 福州大学 | Nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0415145A1 (en) * | 1989-08-09 | 1991-03-06 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Catalyst for removal of nitrogen oxides and method for removal of nitrogen oxides by use of the catalyst |
| CN102658173A (en) * | 2012-04-25 | 2012-09-12 | 吉林大学 | MnOx/TiO2 ammonia denitration catalyst improved by utilizing H2SO4 and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4508584B2 (en) * | 2003-09-05 | 2010-07-21 | 三菱重工業株式会社 | Denitration catalyst for high temperature exhaust gas |
-
2015
- 2015-12-15 CN CN201510940688.6A patent/CN105664978B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0415145A1 (en) * | 1989-08-09 | 1991-03-06 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Catalyst for removal of nitrogen oxides and method for removal of nitrogen oxides by use of the catalyst |
| CN102658173A (en) * | 2012-04-25 | 2012-09-12 | 吉林大学 | MnOx/TiO2 ammonia denitration catalyst improved by utilizing H2SO4 and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Silica supported SO42- /TiO2for photocatalytic decomposition of acrylonitrile under simulant solar light irradiation";D. Pang et al.;《Chemical Engineering Journal》;20150221;第270卷;第590–596页 |
| "酸改性 Mn-Co-Ce/TiO2-SiO2低温SCR 催化剂抗硫性能及成型的研究";张长亮;《哈尔滨工业大学-硕士》;20151201;摘要第8、11、14-15、21-23、25、33、37-40页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105664978A (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105413715B (en) | Low-temperature denitration of flue gas is acidified the sulfur resistant catalyst and preparation method thereof of manganese cobalt cerium with composite carrier load type | |
| CN102861595B (en) | Honeycombed SCR (selective catalytic reduction) denitrification catalyst for low-temperature flue gas denitrification and preparation method thereof | |
| CN105126827B (en) | A kind of coating type low-temperature denitration of flue gas catalyst and its preparation method and application | |
| CN102553574B (en) | Method for preparing flue gas SCR (Selective Catalytic Reduction) denitration catalyst | |
| CN101947443B (en) | Cellular Mn-Ti-based catalyst for low-temperature selective catalytic reduction denitration reaction and preparation method and using method | |
| CN102441396B (en) | The application of double perovskite type oxide oxygen carrier in hydrogen production of chemical chain and preparation method | |
| CN101480611B (en) | Vanadium-doped titanium-base flue gas denitration catalyst material and preparation method thereof | |
| CN103143345B (en) | Composite catalyst for catalytically oxidizing nitrogen oxide and preparation method of composite catalyst | |
| CN103861591B (en) | Selective oxidation removes load type nano gold catalyst and the Synthesis and applications thereof of CO | |
| CN102489294B (en) | Low-temperature SCR catalyst prepared by extrusion molding, and preparation method thereof | |
| CN101773837A (en) | Supported SCR denitration catalyst of medium and low temperature flue gas and preparation method and application thereof | |
| CN104475122A (en) | Forming SCR catalyst with both water resistance and sulphur resistance and preparation method thereof | |
| CN105664978B (en) | Low-temperature denitration of flue gas is acidified the sulfur resistant catalyst molding method for preparing of manganese cobalt cerium with composite carrier load type | |
| CN102861565A (en) | Aluminum oxide-loaded cerium oxide catalyst and preparation method and application thereof | |
| CN112742413A (en) | Low-temperature SCR denitration catalyst and preparation method and application thereof | |
| CN104014332A (en) | Preparation method for Mn-Ce-W compound oxide integral type denitration catalyst based on titanium wire net | |
| CN108479845B (en) | Denitration catalyst and preparation method thereof | |
| CN102443454B (en) | Oxygen carrier of chemical-looping combustion and preparation method and application thereof | |
| CN104437653A (en) | Bio-based rubble paper-like catalyst for low-temperature synchronous denitration and desulfurization and preparation method thereof | |
| CN104874394A (en) | Cheap low-temperature SCR catalyst with sulfur resistance and preparation method thereof | |
| CN103263911B (en) | Preparation method of denitration catalyst with nanoscale ordered honeycomb structure | |
| CN111111647B (en) | Niobite type manganese-niobium-based SCR denitration catalyst and preparation method thereof | |
| CN107185523B (en) | Preparation method of holmium modified denitration catalyst and product thereof | |
| CN103447066B (en) | Preparation method of supported composite oxide catalyst for catalytic combustion | |
| CN106881105A (en) | A kind of board-like low temperature catalyst with the self-assembly porous spherical titanium dioxide of crosslinking nano chain as carrier and its preparation method and application |
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 |