CN106807346A - A kind of denitration catalyst carrier and preparation method thereof and denitrating catalyst - Google Patents
A kind of denitration catalyst carrier and preparation method thereof and denitrating catalyst Download PDFInfo
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- CN106807346A CN106807346A CN201611259146.3A CN201611259146A CN106807346A CN 106807346 A CN106807346 A CN 106807346A CN 201611259146 A CN201611259146 A CN 201611259146A CN 106807346 A CN106807346 A CN 106807346A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to low-temperature denitration catalyst field, a kind of denitration catalyst carrier is disclosed, it is characterised in that the denitration catalyst carrier includes γ Al2O3, and it is supported on the γ Al2O3On waterproof mixture MO and acid active sites adjusting control agent R2On；Wherein, the waterproof mixture MO is one or more in MgO, CaO, BaO, SrO, ZnO, MnO and CuO；The acid active sites adjusting control agent R2OnIt is ZrO2、Sb2O3And TiO2In one or more.Denitrating catalyst containing the denitration catalyst carrier has the performance of methanol and the acid active sites of regulation and control concurrently in low-temperature denitration.
Description
Technical field
The present invention relates to low temperature (100-300 DEG C) field of denitration catalyst, in particular it relates to a kind of denitration catalyst carrier
And preparation method thereof and denitrating catalyst.
Background technology
Current thermal power plant's denitration technology both domestic and external is that, with high temperature SCR denitration technology as main flow, the technology is with not the same
The ammonia source (ammonia) for driving body acquisition is reducing agent, the nitrogen oxides in the high-temperature flue gas produced to coal-fired power plant station boiler
(NOx) reduced, reduzate is the N of environmental sound2.The SCR of industrial industrialization and large-scale application is urged at present
Agent is by main active component V2O5, coagent and nano carrier TiO2Formed by kneading, extrusion molding, drying, calcining
Cellular, corrugated plate shape, the integer catalyzer such as flat.This kind of catalytic treatment process has adapted to current thermal power station's high temperature and has taken off
The entirety dirt arrangement environment-friendly treating process high of nitre-dedusting-desulfurization.Catalyst in high temperature denitrating technique both domestic and external is all based on
What such arrangement technology was researched and developed.This arrangement makes catalyst be exposed in the environment of dirt high, on the one hand meeting
Make catalyst blockage, increase system pressure drop, increase system operation cost；On the other hand, calcium, phosphorus, the arsenic for containing in coal ash
Deng and its mineral matter can make catalyst poisoning and lose activity so that the denitration efficiency of catalyst and life-span are subject to extreme influence
And inactivate.In view of factors above, many companies and scientific research department all take off in effort exploitation thermal power station dedusting-desulfurization-low temperature at present
The low dirt environment-friendly treating process of nitre.
In addition, done using coal, natural gas or other fossil fuels the cement kiln of fuel, ceramic kiln, glass furnace,
The flue gas that the fire coals such as coking furnace (or other fuel) are produced is low-temperature flue gas, and general flue-gas temperature is between 100-300 DEG C.Water steams
Gas is one of main component in coal-fired (or other fuel) flue gas；In the low dirt environmental protection of thermal power station's dedusting-desulfurization-low-temperature denitration
In handling process, SCR is arranged in after wet desulphurization, and water vapour content is also higher；In addition, with NH3Selective catalysis are also
During nitrogen oxides in former flue gas, the protium in ammonia is oxidized the substantial amounts of water of generation.In certain steam partial pressure
Under the conditions of, vapor can interact with vanadium system SCR catalyst, so that catalyst surface property is influenceed, to active sites
Formation have certain negative effect, on vanadium Titanium series catalyst surface, H2O can decompose to form Bronsted acid, and by H2O
The acidic site being decomposed to form could typically be formed in high temperature (more than 350 DEG C), because in the case of less than 350 DEG C, it is substantial amounts of
Water is present makes catalyst surface hydroxylating, causes Bronsted acid activities position to reduce, and could only be weighed in high temperature (more than 350 DEG C)
New dehydration activity recovery position, the acidic site plays an important role to the carrying out of denitration reaction.But the TiO in vanadium Titanium series catalyst2
Cost is higher, accounts for the 90% of whole catalyst cost.And because in low temperature, its active sites is relatively few, so, low temperature takes off
The conversion ratio of nitre reaction loses its commercial value for using at low temperature just than relatively low.The low-temperature denitration catalysis of exploitation at present
Agent is substantially with γ-AL2O3It is main carriers.On γ-AL2O3The catalyst system and catalyzing done used in carrier is a lot, is directed to
Thermal and hydric environment catalystic converter system has the reaction systems such as oxidation, dehydration, hydration, amination, oxychlorination, carbonylation, in thermal and hydric environment
Under, γ-AL2O3The rehydrated phase transformation of meeting obtains boehmite, so that γ-AL2O3Lose activity.
In NH3Selective catalysis reduction coal-fired flue-gas during, the vapor in flue gas, and ammonia be oxidized after generate
Water, especially under the working condition of boiler power station dedusting-low dirt technology arrangement of desulfurization-denitration, denitration reaction unit is arranged in
After wet desulphurization, the vapor in flue gas is more, so centering low-temperature denitration catalyst carrier prevents rehydrated more added with existing
Real meaning.
γ-AL on hydrothermal stability2O3Preparation have different document reports for different catalyst system and catalyzings, such as：
CN1958456A Beijing University of Chemical Technology prevents the duct of aluminum oxide from sintering by introducing phosphate anion or phosphoric acid hydrogen radical ion
And high-temperature phase-change.
At least one of cobalt, zirconium, boron etc. are incorporated into γ-AL by US2004/0127586A12O3In, improve active oxidation
The basic activated center of alumina supporter.This modified active aluminum oxide carrier is particularly suitable for the basic activated center of F-T synthesis
Requirement.
Silica and some metal oxides are added to γ-AL by CN101786024B using infusion process2O3On, change
γ-AL2O3High-temperature hydrothermal stability, this method of modifying increased the quantity of the Lewis acid of carrier surface.
Above-mentioned prior art is substantially activated alumina is modified around high-temperature phase-change, or to γ-AL2O3High temperature
The containment of phase transformation is hydrated, or to γ-AL2O3High-temperature phase-change is to α-AL2O3It is modified, such as add lanthanide series rare-earth elements, Ke Yixian
Write and improve γ-AL2O3Mutually change to α-AL2O3Phase transition temperature.From practical application and the AL for having studied2O3—H2O systems phasor can
Know between 100 DEG C to 350 DEG C, still can there is part γ-AL2O3The phenomenon of low temperature hydration.Up to the present, do not see also
Reporting for work for hydration is prevented to the low temperature crossed for low-temperature denitration catalyst active aluminum oxide carrier.
In addition, for denitration catalyst system, particularly with V2O5/γ-AL2O3It is the low-temperature denitration of main catalyst system
Catalysis, because the result of hydro-combination process is to form the basic center with hydroxyl as principal character in catalyst surface, therefore must
The formation at the Bronsted acid activities center that can so influence to play primary attachment catalytic action in catalyst, so as to influence its active sites
Quantity, the quantity of active sites is a kind of amount that can quantify closely related with catalyst life.
Based on the new problem that above technical background and low-temperature denitration catalyst are faced, activated alumina low temperature is prevented to be hydrated
And re-forming for the acid active sites of control is the catalytic efficiency and the necessary antecedent in life-span for ensureing catalyst, and this some it is new
Problem was not all reported in conventional patent and document.
The content of the invention
The purpose of the present invention is to overcome during denitrating catalyst of the prior art can not have low temperature (100-300 DEG C) denitration concurrently
A kind of defect of methanol and the acid active sites of regulation and control, there is provided denitration catalyst carrier and preparation method thereof, and contain this
The denitrating catalyst of denitration catalyst carrier.
To achieve these goals, the invention provides a kind of denitration catalyst carrier, wherein, the denitrating catalyst is carried
Body includes γ-Al2O3, and it is supported on the γ-Al2O3On waterproof mixture MO and acid active sites adjusting control agent R2On；
Wherein, the waterproof mixture MO is one or more in MgO, CaO, BaO, SrO, ZnO, MnO and CuO, described
Acid active sites adjusting control agent R2OnIt is ZrO2、Sb2O3And TiO2In one or more.
Present invention also offers a kind of method for preparing denitration catalyst carrier, wherein, the method is comprised the following steps：
(1) by γ-Al2O3Impregnated in and contain ion M2+Solution in, then by being loaded with of being obtained after the dipping from
Sub- M2+γ-Al2O3It is dried, calcines；
(2) ion R will be containedn+Colloidal sol be coated on the material that step (1) is obtained, then the material after coating is done
Dry, calcining；
Wherein, ion M2+It is Mg2+、Ca2+、Ba2+、Sr2+、Zn2+、Mn2+And Cu2+In one or more, preferably Mg2+
And/or Sr2+；Ion Rn+It is Zr4+、Sb3+And Ti4+In one or more.
Present invention also offers the denitration catalyst carrier prepared by the method for the invention.
Present invention also offers a kind of denitrating catalyst, including active component and catalyst carrier, wherein, the catalyst
Carrier is denitration catalyst carrier of the present invention.
The present invention is by the γ-Al in denitration catalyst carrier2O3Upper load waterproof mixture and acid active sites regulation and control
Agent, makes the denitrating catalyst containing the denitration catalyst carrier have methanol and regulation and control concurrently in low temperature (100-300 DEG C) denitration
The performance of acid active sites.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
One or more can be obtained with combination with one another between the endpoint value of individual scope and single point value, and individually between point value
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of denitration catalyst carrier, wherein, the denitration catalyst carrier includes γ-Al2O3, and
It is supported on the γ-Al2O3On waterproof mixture MO and acid active sites adjusting control agent R2On；
Wherein, the waterproof mixture MO is one or more in MgO, CaO, BaO, SrO, ZnO, MnO and CuO, preferably
It is MgO and/or MnO, more preferably MgO；The acid active sites adjusting control agent R2OnIt is ZrO2、Sb2O3And TiO2In one
Plant or several, preferably TiO2。
In the present invention, M represents the metallic element in the waterproof mixture, and R represents the metal in acid active sites adjusting control agent
Element, n represents the chemical valence of metallic element R.
In the present invention, in the denitration catalyst carrier, content and the mol ratio of the content of Al elements of M element are
0.5-6：18, the content of R element is 0.05-0.6 with the mol ratio of the content of Al elements：1.M element and R element are in above range
It is interior, the methanol and acid active sites performance of control of the denitration catalyst carrier can be promoted.
Present invention also offers a kind of method for preparing denitration catalyst carrier, wherein, the method is comprised the following steps：
(1) by γ-Al2O3Impregnated in and contain ion M2+Solution in, then by being loaded with of being obtained after the dipping from
Sub- M2+γ-Al2O3It is dried, calcines；
(2) ion R will be containedn+Colloidal sol be coated on the material that step (1) is obtained, then the material after coating is done
Dry, calcining；
Wherein, ion M2+It is Mg2+、Ca2+、Ba2+、Sr2+、Zn2+、Mn2+And Cu2+In one or more, preferably Mg2+
And/or Mn2+, more preferably Mg2+；Ion Rn+It is Zr4+、Sb3+And Ti4+In one or more, preferably Ti4+。
In the present invention, by the drying in step (1), after calcining, obtain be loaded the γ of waterproof mixture MO-
Al2O3, by the drying in step (2), after calcining, what is obtained is to have loaded waterproof mixture MO and acid active sites adjusting control agent
R2Onγ-Al2O3.Waterproof mixture meets the ion M that water is formed2+Ionic product of the ionic product than aluminium ion and OH- with OH- is big, institute
With ion M2+Easily reacted with OH-ion, γ-Al are changed so as to avoid OH- from being reacted with aluminium ion2O3Crystal formation,
Namely the formation of γ-AlOOH phases is prevented so as to reach the life-span for preventing being hydrated and extend denitrating catalyst；It is described certain
The acid active sites adjusting control agent R of amount2OnIn γ-AL2O3On electric charge centered on Al form negative surplus, such negative surplus can
To form Bronsted acid, so as to provide necessary for ammonia and nitrogen oxides are smoothed out reaction in low-temperature denitration catalyst
Advantage.Wherein, M represents the metallic element in the waterproof mixture, and R represents the metal unit in acid active sites adjusting control agent
Element, n represents the chemical valence of metallic element R.
In the present invention, in step (1), what the dipping made to obtain described is loaded with ion M2+γ-Al2O3In, M element
The mol ratio of content of content and Al elements be 0.5-6：18.There is no particular limitation for number of times of the present invention to the dipping,
Can be for example one or many, as long as the purpose of above-mentioned dipping can be reached.
For the species of different flue gases, the content of suitable M element can be selected from above range.For example, in coal-fired electricity
In the denitrating technique of the low dirt arrangement of boiler of standing, because water vapour content is high, to add the waterproof mixture of formation more, and glass
Vapor in kiln, ceramic kiln flue gas can lack, and the water that main consideration ammonia is produced when being reduced is to hydration reaction
Influence is just.Therefore, the selection of the content of M element can be as shown in table 1.
Table 1
| Low dirt arranges flue gas | Glass furnace fume | Cement kiln flue gas | Ceramic kiln flue gas | Coking flue gas | |
| M:Al (mol ratio) | 3-5：18 | 2-3：18 | 1-2：18 | 0.5-1：18 | 4-6：18 |
In the present invention, the temperature control of the process of the drying and calcination in the step (1) is preferably the mistake of temperature programming
Journey, it is further preferred that in step (1), the dry process can include：It is warmed up to the programming rate of 4-6 DEG C/min
After 100-110 DEG C, constant temperature 12-18h；The process of the calcining includes：120-150 is warmed up to the programming rate of 3-4 DEG C/min
DEG C, constant temperature 30-40min, then 340-370 DEG C is warmed up to the programming rate of 3-4 DEG C/min, constant temperature 120-140min, then with
The programming rate of 5-6 DEG C/min is warmed up to 450-550 DEG C, constant temperature 4-6h.Under conditions of above-mentioned drying and calcination, further promote
Enter the methanol performance of denitration catalyst carrier.
In the present invention, under preferable case, in step (1), the material powder obtained after before being calcined first by drying
It is broken into the particulate matter of 180-220 mesh.
The present invention contains M to described2+Solution species do not have it is special must limit, can be the conventional selection in this area.
It is described to contain M in step (1) under preferable case2+Solution be to contain the ion M2+Nitrate solution, sulfate liquor
With one or more in chloride solution.
The present invention contains ion M to described2+Solution in ion M2+Content there is no particular limitation, can for this
The conventional selection in field.It is for example described to contain ion M2+Solution in ion M2+Content be 0.002-0.01mol/mL.
In the present invention, it is preferable that in step (2), the coating makes in the material after the coating for obtaining, the R element
Content is 0.05-0.6 with the mol ratio of the content of Al elements：1.It is further preferred that the condition of the coating includes：Control institute
State and contain ion Rn+Colloidal sol pH be 5-10.Regulation institute shape can be reached by controlling the pH of colloidal sol and the content of R element
Into Bronsted acid acid intensity.For different R elements, can select within the above range suitable mol ratio and
PH, for example, the content of R element is as shown in table 2 with the selection of the mol ratio and pH of the content of Al elements.
Table 2
| R is Zr | R is Sb | R is Ti | |
| pH | 8-10 | 5-9 | 8-10 |
| R：Al (mol ratio) | 0.05-0.2：1 | 0.02-0.1：1 | 0.2-0.6：1 |
In the present invention, the temperature control of the process of the drying and calcination in the step (2) is preferably the mistake of temperature programming
Journey, it is further preferred that in step (2), the dry process can include：It is warmed up to the programming rate of 9-11 DEG C/min
After 100 DEG C -110, constant temperature 12-18h；The process of the calcining can include：The programming rate of 3-4 DEG C/min is warmed up to 120-
140 DEG C, constant temperature 30-40min, then 450-550 DEG C, constant temperature 4-6h are raised to 3-4 DEG C/min.In the condition of above-mentioned drying and calcination
Under, further promote the control ability of the acid active sites of denitration catalyst carrier.
It is described to contain ion R in the present inventionn+The preparation method of colloidal sol can be the conventional method in this area, such as institute
State and contain ion Rn+The preparation method of colloidal sol can include：Ion R will be containedn+Chloride be added to the water, in pH=5-10
Under conditions of be hydrolyzed reaction；
The present invention contains ion R to describedn+Colloidal sol in ion Rn+Content be not particularly limited, preferable case
Under, it is described to contain ion Rn+Colloidal sol in ion Rn+Content be 0.0013-0.002mol/mL.
Present invention also offers the denitration catalyst carrier prepared by method of the present invention.The denitrating catalyst
Supported on carriers has waterproof mixture of the present invention and acid active sites adjusting control agent so that the denitration catalyst carrier has concurrently anti-
Hydration and acid active sites performance of control, and suitable for low temperature (100-300 DEG C) denitration.
Present invention also offers a kind of denitrating catalyst, including active component and catalyst carrier, wherein, the catalyst
Carrier is denitration catalyst carrier of the present invention.
The present invention is not limited particularly the active component and the content of denitration catalyst carrier in the denitrating catalyst
It is fixed, can be the conventional selection in this area.Under preferable case, counted by 100 weight portions of the gross weight of the denitrating catalyst, institute
The content of active component is stated for 1-5 weight portions, the content of the denitration catalyst carrier is 95-99 weight portions.
There is no particular limitation for selection of the present invention to the active component, can be the conventional selection of ability, such as institute
Active component is stated for V2O5、CuO、MnO2、WO3And CeO2In one or more.
There is no particular limitation for preparation method of the present invention to the denitrating catalyst, can be the conventional side in this area
Method.For example, the preparation method of the denitrating catalyst can be：Denitration catalyst carrier is impregnated into the presoma of active component
In solution, the material after dipping is then dried into 720-1080min at 105-120 DEG C, then by dried material in 450-
240-360min is calcined at 600 DEG C.
Below will the present invention will be described in detail by embodiment.In following examples, preparation example and comparative example,
The content of the composition in denitration catalyst carrier is determined by the X-ray analyzer of model EDX-LEX；
The acid site type and acidity of denitrating catalyst are determined by the following method；
Instrument is gas chromatographic column
1st, catalyst sample pretreatment
(1) 80 mesh of screening or so catalyst sample precise 0.1g to be measured；
Load sample cell after (2) 300 DEG C of roasting 2h；
1h is swept in (3) 350 DEG C of He air-blowings；
(4) 120 DEG C, constant temperature 30 minutes are cooled to.
2nd, adsorption-desorption
(1) injection adsorbate NH3；
(2) with the intensification of 17 DEG C/min speed, control carrier gas speed 45ml/min is desorbed to terminating, and is desorbed
Spectrum；
(3) gradually change adsorbate sample size from low to high, repeat the above steps and obtain multigroup TPD spectrograms.
3rd, analyze data
Desorption peak position according to TPD spectrograms, and standard diagram contrast, judge the type in acid site, according to adsorbate NH3
Consumption calculate corresponding acidity size；
The denitration efficiency of denitrating catalyst is calculated by determining the change in concentration of the front and rear NO of reaction, equation below institute
Show：
Wherein, [NO]in,[NO]outRespectively represent NO reaction before and reacted concentration.
AL in denitrating catalyst2O3Crystal formation determined by the X-ray analyzer of model EDX-LE；
γ-AL2O3For the Luoyang Zhong Chao new materials limited company trade mark is the commercially available product of AL-1.
Embodiment 1
(1) by 5molMg (NO3)2It is added in 500ml deionized waters, 80 DEG C of heating stirrings are made into magnesium nitrate solution, so
18mol γ-Al are added afterwards2O3.Fully after absorption, Mg will be loaded with2+γ-Al2O3It is placed in vacuum drying chamber, with 5 DEG C/min
Programming rate be warmed up to 105 DEG C after, freeze-day with constant temperature 12h；The particle for being ground into 200 mesh is then taken out, is put into Muffle furnace with 3
DEG C/min is warmed up to 120 DEG C, constant temperature 30min, then 350 DEG C, constant temperature 120min, then with 5 DEG C/min liters are warmed up to 3 DEG C/min
Temperature is to 450 DEG C, constant temperature 4h.Material is taken out after Temperature fall.
(2) by 0.5molTiCl4It is added in 300ml water, pH=10, is fully hydrolyzed and is made Ti (OH)4Colloidal sol, this is molten
Glue is coated on the material that above-mentioned steps (1) are obtained.Then it is placed in vacuum drying chamber, is raised to the programming rate of 10 DEG C/min
After 105 DEG C, freeze-day with constant temperature 15h；Then dried material is put into Muffle furnace, 120 DEG C, constant temperature is warmed up to 3 DEG C/min
30min, then 550 DEG C, constant temperature 4h are warmed up to 3 DEG C/min.
Denitration catalyst carrier A1 is obtained, in the denitration catalyst carrier A1, content and the Al elements of Mg elements
The mol ratio of content is 5：The content of 18, Ti elements is 0.5 with the mol ratio of the content of Al elements：1.
Denitration catalyst carrier Al is applied to the denitrating catalyst catalyst carrier that low dirt arranges flue gas.
Embodiment 2
(1) by 3molCu (NO3)2It is added in 500ml deionized waters, 80 DEG C of heating stirrings are made into copper nitrate solution, so
18mol γ-Al are added afterwards2O3.Fully after absorption, Cu will be loaded with2+γ-Al2O3It is placed in vacuum drying chamber, with 4 DEG C/min
Programming rate be raised to 100 DEG C after, freeze-day with constant temperature 15h；The particle for being ground into 200 mesh is then taken out, is put into Muffle furnace with 4
DEG C/programming rate of min is warmed up to 150 DEG C, constant temperature 40min, then 370 DEG C, constant temperature are warmed up to the programming rate of 4 DEG C/min
140min, is then warmed up to 550 DEG C, constant temperature 6h with the programming rate of 6 DEG C/min.Taken out after Temperature fall standby.
(2) by 0.5molTiCl4It is added in 300ml water, pH=8.5, is fully hydrolyzed and is made Ti (OH)4Colloidal sol, this is molten
Glue is coated on the material that above-mentioned steps (1) are obtained.Then it is placed in vacuum drying chamber, is raised to the programming rate of 10 DEG C/min
After 110 DEG C, freeze-day with constant temperature 18h；Be put into after having dried in Muffle furnace and be raised to 140 DEG C with 4 DEG C/min, constant temperature 40min, then with 4 DEG C/
Min is raised to 550 DEG C, constant temperature 6h.
Denitration catalyst carrier A2 is obtained, in the denitration catalyst carrier A2, content and the Al elements of Cu elements
The mol ratio of content is 3：The content of 18, Ti elements is 0.4 with the mol ratio of the content of Al elements：1.
Denitration catalyst carrier A2 is applied to the denitrating catalyst catalyst carrier of glass furnace fume.
Embodiment 3
(1) by 2molZn (NO3)2It is added in 500ml deionized waters, 80 DEG C of heating stirrings are made into magnesium nitrate solution, so
18mol γ-Al are added afterwards2O3.Fully after absorption, Zn will be loaded with2+γ-Al2O3It is placed in vacuum drying chamber, with 6 DEG C/min
Programming rate be raised to 100 DEG C after, freeze-day with constant temperature 12h；The particle for being ground into 200 mesh is then taken out, with the intensification speed of 4 DEG C/min
Degree is warmed up to 150 DEG C, constant temperature 40min, then is warmed up to 370 DEG C, constant temperature 130min, then with 5 with the programming rate of 3 DEG C/min
DEG C/programming rate of min is warmed up to 550 DEG C, constant temperature 5h.Taken out after Temperature fall standby.
(2) by 0.6molTiCl4It is added in 300ml water, pH=8, is fully hydrolyzed and is made Ti (OH)4Colloidal sol, by the colloidal sol
It is coated on the material that above-mentioned steps (1) are obtained.Then it is placed in vacuum drying chamber, is raised to the programming rate of 11 DEG C/min
After 110 DEG C, freeze-day with constant temperature 12h；Drying is put into Muffle furnace after terminating and is raised to 120 DEG C with 3 DEG C/min, constant temperature 30min, then with 4
DEG C/min is raised to 550 DEG C, constant temperature 5h.
Denitration catalyst carrier A3 is obtained, in the denitration catalyst carrier A3, content and the Al elements of Zn elements
The mol ratio of content is 2：The content of 18, Ti elements is 0.3 with the mol ratio of the content of Al elements：1.
Denitration catalyst carrier A3 is applied to the denitrating catalyst catalyst carrier of cement kiln flue gas.
Embodiment 4
(1) by 1molMn (NO3)2It is added in 500ml deionized waters, 80 DEG C of heating stirrings are made into magnesium nitrate solution, so
18mol γ-Al are added afterwards2O3.Fully after absorption, Mn will be loaded with2+γ-Al2O3It is placed in vacuum drying chamber, with 5 DEG C/min
Programming rate be raised to 105 DEG C after, freeze-day with constant temperature 12h；The particle for being ground into 200 mesh is then taken out, is put into Muffle furnace with 4
DEG C/programming rate of min is warmed up to 130 DEG C, constant temperature 35min, then 360 DEG C, constant temperature are warmed up to the programming rate of 4 DEG C/min
120min, is then warmed up to 450 DEG C, constant temperature 6h with the programming rate of 5 DEG C/min.Taken out after Temperature fall standby.
(2) by 0.5molTiCl4It is added in 300ml water, pH=8, is fully hydrolyzed and is made Ti (OH)4Colloidal sol, by the colloidal sol
It is coated on the material that above-mentioned steps (1) are obtained.Then it is placed in vacuum drying chamber, is raised to the programming rate of 10 DEG C/min
After 105 DEG C, freeze-day with constant temperature 15h；Be put into after having dried in Muffle furnace and be raised to 120 DEG C with 3 DEG C/min, constant temperature 30min, then with 3 DEG C/
Min is raised to 550 DEG C, constant temperature 4h.
Denitration catalyst carrier A4 is obtained, in the denitration catalyst carrier A4, content and the Al elements of Mn elements
The mol ratio of content is 0.7：The content of 18, Ti elements is 0.2 with the mol ratio of the content of Al elements：1.
Denitration catalyst carrier A4 is applied to the denitrating catalyst catalyst carrier of ceramic kiln flue gas.
Embodiment 5
Method according to embodiment 1 prepares denitration catalyst carrier, unlike, in step (1) and (2), it is dried
During with calcining, temperature programming is not carried out, be directly put into material in the drying box or Muffle furnace with target temperature.Specific step
It is rapid as follows：
(1) by 5molMg (NO3)2It is added in 500ml deionized waters, 80 DEG C of heating stirrings are made into magnesium nitrate solution, so
18mol γ-Al are added afterwards2O3.Fully after absorption, Mg will be loaded with2+γ-Al2O3It is placed in 105 DEG C of vacuum drying chamber, it is permanent
Temperature dries 12h；The particle for being ground into 200 mesh is then taken out, constant temperature 4h in 450 DEG C of Muffle furnace is put into.By thing after Temperature fall
Material takes out.
(2) by 0.5molTiCl4It is added in 300ml water, pH=10, is fully hydrolyzed and is made Ti (OH)4Colloidal sol, this is molten
Glue is coated on the material that above-mentioned steps (1) are obtained.Then it is placed on freeze-day with constant temperature 15h in 105 DEG C of vacuum drying chamber；Then will
Dried material is put into Muffle furnace, 550 DEG C of constant temperature 4h.
Denitration catalyst carrier A4 is obtained, in the denitration catalyst carrier A4, content and the Al elements of Mg elements
The mol ratio of content is 3：The content of 18, Ti elements is 0.2 with the mol ratio of the content of Al elements：1.
Comparative example 1
Method according to embodiment 1 prepares denitration catalyst carrier, unlike, not including step (2).Specific steps are such as
Under：
By 5molMg (NO3)2It is added in 500ml deionized waters, 80 DEG C of heating stirrings are made into magnesium nitrate solution, Ran Houjia
Enter 18mol γ-Al2O3.Fully after absorption, Mg will be loaded with2+γ-Al2O3It is placed in vacuum drying chamber, with the liter of 5 DEG C/min
After warm speed is warmed up to 105 DEG C, freeze-day with constant temperature 12h；Then take out the particle for being ground into 200 mesh, be put into Muffle furnace with 3 DEG C/
Min is warmed up to 120 DEG C, constant temperature 30min, then is warmed up to 350 DEG C with 3 DEG C/min, and then constant temperature 120min is heated up with 5 DEG C/min
To 450 DEG C, constant temperature 4h.Material is taken out after Temperature fall.
Denitration catalyst carrier D1 is obtained, in the denitration catalyst carrier D1, content and the Al elements of Mg elements
The mol ratio of content is 5：18.
Comparative example 2
Method according to embodiment 1 prepares denitration catalyst carrier, unlike, step (1) is not carried out, directly walked
Suddenly (2).Comprise the following steps that：
By 0.5molTiCl4It is added in 300ml water, pH=10, is fully hydrolyzed and is made Ti (OH)4Colloidal sol, the colloidal sol is applied
It is layed onto γ-Al2O3On.Then it is placed in vacuum drying chamber, after being raised to 105 DEG C with the programming rate of 10 DEG C/min, freeze-day with constant temperature
15h；Then dried material is put into Muffle furnace, 120 DEG C is warmed up to 3 DEG C/min, constant temperature 30min, then with 3 DEG C/min
It is warmed up to 550 DEG C, constant temperature 4h.
Denitration catalyst carrier D2 is obtained, in the denitration catalyst carrier D2, content and the Al elements of Ti elements
The mol ratio of content is 0.5：1.
The acid site type and acidity of A1, A2, A3, A4, A5, D1 and D2 are determined, as a result as shown in table 3：
Table 3
| A1 | A2 | A3 | A4 | A5 | D1 | D2 | |
| Acid site type | Bronsted acid | Bronsted acid | Bronsted acid | Bronsted acid | Bronsted acid | Lewis acid | Bronsted acid |
| Acidity (mmol/g.cat) | 1.650 | 1.550 | 1.50 | 1.45 | 1.11 | 0.80 | 1.60 |
Preparation example 1
A1 denitration catalyst carriers are immersed in the manganese nitrate solution that concentration is 50 weight %, then by the thing after dipping
Material dries 720min at 105 DEG C, then dried material is calcined into 240min at 450 DEG C.Denitrating catalyst Z1 is obtained (to contain
There is the MnO of 3.9 weight %2)。
Preparation example 2-5
Method according to preparation example 1 prepares denitrating catalyst, unlike, A1 is replaced using A2, A3, A4 and A5.Obtain
Denitrating catalyst Z1 (the MnO containing 3.9 weight %2), the Z2 (MnO containing 3.9 weight %2), Z3 (contain 3.9 weight %'s
MnO2), the Z4 (MnO containing 3.9 weight %2), the Z5 (MnO containing 3.9 weight %2)。
The acid site type and acidity of Z1, Z2, Z3, Z4, Z5 are determined, as a result as shown in table 4.
Contrast preparation example 1-2
Method according to preparation example 1 prepares denitrating catalyst, unlike, A1 is replaced using D1, D2.Obtain denitration catalyst
Agent DZ1 (the MnO containing 3.9 weight %2), the DZ2 (MnO containing 3.9 weight %2)
The acid site type and acidity of DZ1, DZ2 are determined, as a result as shown in table 4.
Table 4
| Z1 | Z2 | Z3 | Z4 | Z5 | DZ1 | DZ2 | |
| Acid site type | Bronsted acid | Bronsted acid | Bronsted acid | Bronsted acid | Bronsted acid | Lewis acid | Bronsted acid |
| Acidity (mmol/g.cat) | 1.80 | 1.70 | 1.60 | 1.65 | 1.30 | 1.0 | 1.80 |
Test case
By Z1, Z2, Z3, Z4, Z5, DZ1, DZ2, (water vapour content is 20 volume %, temperature with low dirt arrangement flue gas respectively
Be 200 DEG C) and mixture (content of ammonia be 0.1 volume %) haptoreaction 48h of ammonia after, after determining haptoreaction
Z1 ', Z2 ', Z3 ', Z4 ', Z5 ', DZ1 ', the crystal formation of DZ2 ', acid site type, acidity and denitration efficiency, as a result such as the institute of table 5
Show.
Table 5
| Z1’ | Z2’ | Z3’ | Z4’ | Z5’ | DZ1’ | DZ2’ | |
| Acid site type | Bronsted acid | Bronsted acid | Bronsted acid | Bronsted acid | Bronsted acid | Lewis acid | Lewis alkali |
| Acidity (mmol/g.cat) | 1.75 | 1.6 | 1.55 | 1.6 | 1.2 | 0.5 | 0 |
| Crystal formation | γ-AlOOH | ||||||
| Denitration efficiency (%) | 99 | 97 | 95 | 97 | 85 | 0 | 0 |
Contrast table 3 and table 4, the denitrating catalyst acidity of corresponding preparation in table 4 are accordingly enhanced a bit, illustrate adding for manganese
Plus continue to enhance γ-Al2O3The negative surplus of electric charge, it is ensured that the formation in denitrating catalyst activated centre.By with upper table 4 and table 5
Comparative result can be seen that acid site type of the denitrating catalyst containing denitration catalyst carrier of the invention after denitration
Without change, and acidity, substantially without change, denitrating catalyst is still γ-Al2O3Crystal formation, from the alkali of the DZ2 ' of comparative example
γ-AlOOH the phases of formation and the formation of the heart, illustrate the necessity of methanol, illustrate denitration catalyst carrier of the invention
Serve the effect of preferable methanol and the acid active sites of regulation and control.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (11)
1. a kind of denitration catalyst carrier, it is characterised in that the denitration catalyst carrier includes γ-Al2O3, and be supported on
γ-the Al2O3On waterproof mixture MO and acid active sites adjusting control agent R2On；
Wherein, the waterproof mixture MO is one or more in MgO, CaO, BaO, SrO, ZnO, MnO and CuO, the acidity
Active sites adjusting control agent R2OnIt is ZrO2、Sb2O3And TiO2In one or more.
2. denitration catalyst carrier according to claim 1, wherein, in the denitration catalyst carrier, M element contains
Amount is 0.5-6 with the mol ratio of the content of Al elements：18, the content of R element is 0.05- with the mol ratio of the content of Al elements
0.6：1.
3. a kind of method for preparing denitration catalyst carrier, it is characterised in that the method is comprised the following steps：
(1) by γ-Al2O3Impregnated in and contain ion M2+Solution in, be then loaded with ion M by what is obtained after the dipping2+
γ-Al2O3It is dried, calcines；
(2) ion R will be containedn+Colloidal sol be coated on the material that step (1) is obtained, then the material after coating is dried,
Calcining；
Wherein, ion M2+It is Mg2+、Ca2+、Ba2+、Sr2+、Zn2+、Mn2+And Cu2+In one or more；Ion Rn+It is Zr4+、
Sb3+And Ti4+In one or more.
4. method according to claim 3, wherein, in step (1), what the dipping made to obtain described is loaded with ion M2+
γ-Al2O3In, the content of M element is 0.5-6 with the mol ratio of the content of Al elements：18.
5. the method according to claim 3 or 4, wherein, in step (1), the dry process includes：With 4-6 DEG C/
After the programming rate of min is warmed up to 100-110 DEG C, constant temperature 12-18h；The process of the calcining includes：With the liter of 3-4 DEG C/min
Warm speed is warmed up to 120-150 DEG C, constant temperature 30-40min, then is warmed up to 340-370 DEG C with the programming rate of 3-4 DEG C/min, permanent
Warm 120-140min, is then warmed up to 450-550 DEG C, constant temperature 4-6h with the programming rate of 5-6 DEG C/min.
6. the method according to claim 3 or 4, wherein, it is described to contain M in step (1)2+Solution be containing it is described from
Sub- M2+Nitrate solution, sulfate liquor and chloride solution in one or more；
Preferably, it is described to contain ion M2+Solution in ion M2+Content be 0.002-0.01mol/mL.
7. method according to claim 3, wherein, in step (2), the coating makes in the material after the coating for obtaining,
The content of the R element is 0.05-0.6 with the mol ratio of the content of Al elements：1；Preferably, the condition of the coating includes：
Control is described to contain ion Rn+Colloidal sol pH be 5-10.
8. the method according to claim 3 or 7, wherein, in step (2), the dry process includes：With 9-11 DEG C/
After the programming rate of min is warmed up to 100 DEG C -110, constant temperature 12-18h；The process of the calcining includes：The intensification of 3-4 DEG C/min
Speed is warmed up to 120-140 DEG C, constant temperature 30-40min, then is raised to 450-550 DEG C, constant temperature 4-6h with 3-4 DEG C/min.
9. the method according to claim 3 or 7, wherein, it is described to contain ion Rn+The preparation method of colloidal sol include：To contain
There is ion Rn+Chloride be added to the water, be hydrolyzed reaction under conditions of pH=5-10；
Preferably, it is described to contain ion Rn+Colloidal sol in ion Rn+Content be 0.0013-0.002mol/mL.
10. the denitration catalyst carrier that the method as described in claim 3-9 is prepared.
A kind of 11. denitrating catalysts, including active component and catalyst carrier, it is characterised in that the catalyst carrier is power
Profit requires the denitration catalyst carrier described in 1,2 and 10；
Preferably, counted by 100 weight portions of the gross weight of the denitrating catalyst, the content of the active component is 1-5 weight
Part, the content of the denitration catalyst carrier is 95-99 weight portions；
It is further preferred that the active component is V2O5、CuO、MnO2、WO3And CeO2In one or more.
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| CN108187753A (en) * | 2017-12-26 | 2018-06-22 | 宁波市河清源技术转移服务有限公司 | A kind of preparation method of tail gas catalytic purification agent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101554584A (en) * | 2008-08-19 | 2009-10-14 | 北京银飞思达科技有限公司 | Catalyst used for ammonia selective catalytic reduction of nitrogen oxides to nitrogen gas and preparation method thereof |
| CN102049257A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Catalyst for simultaneously reducing SO2 and NO with CO as well as preparation and application of catalyst |
| CN102631921A (en) * | 2012-03-23 | 2012-08-15 | 华烁科技股份有限公司 | Nitric acid exhaust gas denitration catalyst and preparation method thereof |
| CN104959035A (en) * | 2006-05-29 | 2015-10-07 | 株式会社卡特勒 | NOx reduction catalyst system and NOx reduction method |
| CN105126816A (en) * | 2015-08-28 | 2015-12-09 | 山东天璨环保科技有限公司 | Smoke denitration catalyst and preparing method thereof |
-
2016
- 2016-12-30 CN CN201611259146.3A patent/CN106807346A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104959035A (en) * | 2006-05-29 | 2015-10-07 | 株式会社卡特勒 | NOx reduction catalyst system and NOx reduction method |
| CN101554584A (en) * | 2008-08-19 | 2009-10-14 | 北京银飞思达科技有限公司 | Catalyst used for ammonia selective catalytic reduction of nitrogen oxides to nitrogen gas and preparation method thereof |
| CN102049257A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Catalyst for simultaneously reducing SO2 and NO with CO as well as preparation and application of catalyst |
| CN102631921A (en) * | 2012-03-23 | 2012-08-15 | 华烁科技股份有限公司 | Nitric acid exhaust gas denitration catalyst and preparation method thereof |
| CN105126816A (en) * | 2015-08-28 | 2015-12-09 | 山东天璨环保科技有限公司 | Smoke denitration catalyst and preparing method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187753A (en) * | 2017-12-26 | 2018-06-22 | 宁波市河清源技术转移服务有限公司 | A kind of preparation method of tail gas catalytic purification agent |
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