CN106215931A - A kind of low vanadium wide active temperature windows denitrating catalyst and preparation method thereof - Google Patents
A kind of low vanadium wide active temperature windows denitrating catalyst and preparation method thereof Download PDFInfo
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- CN106215931A CN106215931A CN201610559233.4A CN201610559233A CN106215931A CN 106215931 A CN106215931 A CN 106215931A CN 201610559233 A CN201610559233 A CN 201610559233A CN 106215931 A CN106215931 A CN 106215931A
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- catalyst
- ammonium
- weight portion
- vanadium
- denitrating 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
- 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
- B01D53/74—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
-
- 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 discloses a kind of low vanadium wide active temperature windows denitrating catalyst, and raw material is: ammonium metavanadate 0.05 0.2 weight portion, ammonium metatungstate 0.1 3 weight portion or ammonium metatungstate 0.1 3 weight portion and the mixing of ammonium molybdate 0.1 10 weight portion, TiO260 80 weight portions, additive 10 20 weight portion, deionized water 15 30 weight portion.The present invention controls the vanadium of low content in denitrating catalyst, thus is to a certain degree reducing the cost of catalyst, and the low content of vanadium in the range of this is difficult to cause secondary pollution.And the introducing that the present invention is by new auxiliary, promote vanadium dispersed level in the catalyst, make vanadium form avtive spot as much as possible at catalyst surface, increase the utilization rate of vanadium；Additionally, the introducing of new auxiliary, improve surface acidity and the redox ability of catalyst, improve the performance of catalyst.This catalyst shows at the pilot scale rank test system detection results of simulation industrial smoke and the industrial actual motion of demonstrative project, and this catalyst can preferably meet coal-burning power plant's varying load condition and use requirement.
Description
Technical field
The present invention relates to denitrating catalyst technical field, (denitrating catalyst is high to be specifically related to a kind of low vanadium wide active temperature
Active temperature windows extends to 250-420 DEG C) window denitrating catalyst and preparation method thereof.
Background technology
Domestic coal-burning power plant nitrogen oxides (NOx) reduces discharging and enters the key stage, and denitration technology is proposed new demand.Economical new
Under normality, domestic industry business electrical amount is remarkably decreased, and electric power outsourcing ratio etc. is improved in Energy restructuring, some areas in addition
Policy factor causes supply of electric power structural reform, " the 2016 annual whole nation power supply and demand situation analyses and prediction reports that middle Electricity Federation is issued
Accuse " in prediction annual thermal power generating equipment in 2016 utilize and hour will further decrease to about 4000 hours, it means that coal burning machine
Group underload, variable load operation operating mode will increase further.But Chinese Ministry of Environmental Protection on June 19th, 2015 to the environmental protection Room, Fujian Province
In " exceeding standard the writing a letter in reply of relevant issues about thermal power plant's SCR denitration system NOx emission under boiler at low load ruuning situation " clearly
Point out: " fossil-fuel power plant atmospheric pollutant emission standard " is state compulsion standard, and thermal power plant is when any operating load, it is necessary to reach
Mark discharge.Under low load condition, flue-gas temperature is relatively low, and traditional catalyst activity is the highest, and removal of nitrogen oxide effect is limited；And
And now SO in flue gas3、H2O、NH3Form liquid sulfuric acid hydrogen ammonium (ABS) Deng easily and stick to catalyst surface, cause catalyst
Adsorption is capped, and the problems referred to above all cause traditional catalyst to be difficult to the full load denitration of coal-burning power plant.For solving
This problem, domestic technique personnel propose the multiple systems modification scheme for the purpose of improving flue-gas temperature, by contrast, change
Kind traditional catalyst performance, carries out the research of the Novel SCR denitrating catalyst being applicable to coal-burning power plant's varying load condition and promotes
Application has higher comprehensive benefit.
And wherein, become study hotspot based on the middle low temperature SCR denitration catalyst of transition metal and rare earth element especially,
Such as Central South University Jiang Chongwen etc. obtain authorize the CN104492471A patent announced to provide with the one in ferrum, copper, manganese or
Several metal oxides are active component, the denitrating catalyst with SBA-15 silica mesoporous zeolite as carrier,
90-240 DEG C shows excellent denitration activity (80-99%)；Beijing University of Chemical Technology's Liu Zhimings etc. obtain and authorize the public affairs announced
Announcement number provides with copper, cerium as main active component for CN102962074B patent, the titanium denitrating catalyst as carrier, at 200-
400 DEG C show excellent denitration activity (91-99%)；The application such as Institute of High Energy Physcis, Academia Sinica's horse tinkling of pieces of jades
CN103769083A patent disclosure replaces vanadium, tungsten as active component with manganese, cerium, and titanium is the wide temperature window denitration catalyst of carrier
Agent, can keep the denitration activity of 90-97% at 200-400 DEG C.But, transition metal and rare earth element series catalysts are easily and sulfur
Oxide reacting generating salt, causes the permanent inactivation of catalyst.Meanwhile, catalyst redox hyperenergia, will cause
N2The problem that selectivity reduces.The problems referred to above all limit the industrialization promotion of transition metal and rare earth element series catalysts should
With.Visible, the popularization and application of non-vanadium system SCR denitration still have improves space further.
But, V2O5Leaching cause the disposal after catalysqt deactivation to there is challenge, if mishandling, easily draw
Play secondary pollution, so studying low V2O5The efficient SCR denitration of content is the most necessary.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, it is provided that a kind of low vanadium width being applicable to coal-burning power plant's varying load condition
Active temperature windows denitrating catalyst, this catalyst is successfully realized industry park plan, by pilot scale test system activity detect and
Industry actual motion shows, this catalyst not only can have preferable NOx removal effect under continuous underload worst cold case, with
Time show relatively low SO2Oxygenation efficiency, and stable, can preferably solve the traditional catalyst low temperature active that coal-burning power plant faces
The problems such as deficiency, transition metal and rare earth element series catalysts anti-sulfur poisonous performance difference, relatively low content of vanadium is also effectively reduced
Vanadium species leaches the secondary pollution to environment, it is achieved that the full load denitration of coal-fired plant flue gas, has the application of preferable market
It is worth.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: a kind of low vanadium wide active temperature windows takes off
Denox catalyst, prepares raw material and comprises active component presoma, auxiliary agent presoma, carrier, additive, and remaining is deionized water.
Active component presoma of the present invention is the ammonium salt containing object element, specially ammonium metavanadate, in catalysis
The ultimate constituent in agent is V2O5(active component), in order to reduce NOx.
Auxiliary agent presoma of the present invention be the ammonium salt containing object element, specially ammonium metatungstate or ammonium metatungstate and
The mixing of ammonium paramolybdate, corresponds to WO3、MoO3In one or both, in order to improve, catalyst surface is acid and oxidation-reduction quality
Active component dispersion, can be promoted, and prevent carrier from sintering.
Carrier of the present invention is titanium dioxide (TiO2), make active component, auxiliary agent be attached to its surface.
Additive of the present invention is glass fibre, CMC, ammonia etc., is used for improving catalyst pug performance and raising
Preformed catalyst intensity etc..
Described V2O5, its content in finished catalyst is not higher than 1.0%；
Described WO3, its mass percent in finished catalyst is not higher than 3%；
Described MoO3, its mass percent in finished catalyst is not higher than 10%；
Described TiO2, its mass percent in finished catalyst is not higher than 95%；
Remaining calcines afterproduct for additive.
Concrete, the catalyst of the present invention is prepared by each component following: ammonium metavanadate 0.05-0.2 weight portion, metatungstic acid
Ammonium 0.1-3 weight portion or ammonium metatungstate 0.1-3 weight portion and the mixing of ammonium molybdate 0.1-10 weight portion, TiO260-80 weight portion,
Additive 10-20 weight portion, deionized water 15-30 weight portion.
For achieving the above object, the preparation method that the present invention provides is: prepare ammonium metavanadate, metatungstic acid according to formula proportion
Ammonium or ammonium metatungstate and the mixed solution of ammonium paramolybdate, add in titanium dioxide with additive and mix, and obtains luming performance relatively
Good pug, pug is prepared as catalyst base substrate after old, and base substrate forms finished product after the heat treatments such as dry, calcining.
Described is old, and the time is 5-50 hour；
Described is dried, and temperature is 60-150 DEG C, and drying time is 1-15 hour；
Described calcining, temperature is 300-650 DEG C, and calcination time is 1-20 hour.
Compared with prior art, present invention is characterized in that
1. the present invention controls the vanadium of low content in denitrating catalyst, and the low content of vanadium in the range of this is difficult to cause secondary dirty
Dye.And the introducing that the present invention is by new auxiliary (additive, auxiliary agent etc.), promote vanadium dispersed level in the catalyst,
Make vanadium form avtive spot as much as possible at catalyst surface, increase the utilization rate of vanadium；Additionally, the introducing of new auxiliary, improve
The surface acidity of catalyst and redox ability, improve the performance of catalyst.
2. the denitrating catalyst high activity temperature window of the present invention extends to 250-420 DEG C；Existing traditional catalyst uses
Temperature is at 300-420 DEG C, and during coal-burning power plant's underrun, flue-gas temperature is less than 300 DEG C, and traditional catalyst cannot be in this work
Long-play under condition, the catalyst of the present invention has been widened low temperature active window, has been made catalyst the most also show preferably
Denitration performance so that this catalyst is suitable for coal unit variable load operation operating mode, can effectively help coal-burning power plant to realize
The minimum discharge of nitrogen oxides under full load；Compared with system reform scheme, after using the catalyst of the present invention, to unit thermal effect
Rate, properly functioning nothing impact, it is ensured that the performance driving economy of system and safety；Catalyst acquisition expenses changes less than system simultaneously
Make investment；Having only to carry out catalyst change, the duration is far below the system reform.
3. the catalyst of the present invention, owing to reducing the addition of active component, so that denitrating catalyst cost is bright
Aobvious reduction.
4. the catalyst of the present invention is in pilot test system simulates actual smoke test, shows preferably at 250-420 DEG C
Reactivity, denitrating catalyst SO under high temperature2Oxygenation efficiency is less than 1% (two-layer catalyst), absolutely proves the catalyst of the present invention
There is the denitration performance significantly better than traditional catalyst；And stable, can preferably solve the conventional catalyst that coal-burning power plant faces
The problems such as agent low temperature active deficiency, transition metal and rare earth element series catalysts anti-sulfur poisonous performance difference, it is achieved that coal-burning power plant
The full load denitration of flue gas, has preferable market using value.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail, but the present invention is not limited solely to following enforcement
Example.Embodiment:
Table 1 denitration performance test data
Note: SO2Oxygenation efficiency is the test value of 400 DEG C；V0 5W2M8Ti-1 is through 300 DEG C of calcination processing samples；V0.5W2M8Ti-2
Through 650 DEG C of calcination processing samples；If making cellular catalyst, its wall thickness is 1.1mm.
Wherein,
(1) catalyst prepared is V2O5-WO3-MoO3/TiO2, in experiment, a series of catalyst of preparation are designated as
VxWyMzTi, wherein x, y, z represents V in catalyst respectively2O5、WO3、MoO3Weight/mass percentage composition.
(2) method for preparing catalyst impact on catalyst performance
Catalyst V1W3M0Ti、V1W0M10Ti、V1W2M5Ti、V1W2M8Ti、V0.5W2M8The preparation method of Ti is the old time
32 hours；Baking temperature is 120 DEG C, and drying time is 10 hours；Calcining heat is 550 DEG C, and calcination time is 8 hours.
For investigating the preparation technology impact on catalyst performance, to V0.5W2M8The Ti catalyst modulation respectively old time is
10 hours, finding that catalyst blank forming effect is poor, yield rate is relatively low；Modulation baking temperature is 100 DEG C, then be dried to
Time lengthening during 2% water content to 14 hours；When modulation baking temperature is 150 DEG C, it is reduced to drying time 8.5 hours, but
Catalyst easily ftractures, and causes yield rate to be dropped to 80% by 95%；Modulation calcining heat is 300 DEG C, 650 DEG C time, catalyst
Performance (such as table 1) reduces, and is probably catalyst carrier sintering after 650 DEG C of process, causes specific surface area to decline caused, and 300 DEG C can
Can be that in catalyst, active substance oxidation is the most caused.
(3) active testing condition
The unification of smoke test condition is:
Table 2 active testing condition
Wherein test temperature spot is 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C.
The present invention will be described rather than limits the invention for above-described embodiment, in spirit and the power of the present invention
In the protection domain of profit claim, any modifications and changes to the present invention, fall within protection scope of the present invention.
Claims (10)
1. one kind low vanadium wide active temperature windows denitrating catalyst, it is characterised in that: prepare raw material comprise active component presoma,
Auxiliary agent presoma, carrier, additive, remaining is deionized water.
Low vanadium wide active temperature windows denitrating catalyst the most according to claim 1, it is characterised in that: described active group
Dividing presoma is the ammonium salt containing object element.
Low vanadium wide active temperature windows denitrating catalyst the most according to claim 2, it is characterised in that: described ammonium salt is
Ammonium metavanadate, it is V in finished catalyst2O5, content is not higher than 1.0%.
Low vanadium wide active temperature windows denitrating catalyst the most according to claim 1, it is characterised in that: before described auxiliary agent
Driving body is the ammonium salt containing object element, specially ammonium metatungstate or be the mixing of ammonium metatungstate and ammonium paramolybdate.
Low vanadium wide active temperature windows denitrating catalyst the most according to claim 4, it is characterised in that: described metatungstic acid
Ammonium, it is WO in finished catalyst3, mass percent is not higher than 3%；Described ammonium paramolybdate, it is in finished catalyst
For MoO3, mass percent is not higher than 10%.
Low vanadium wide active temperature windows denitrating catalyst the most according to claim 1, it is characterised in that: described carrier is
Titanium dioxide, its mass percent in finished catalyst is not higher than 95%.
Low vanadium wide active temperature windows denitrating catalyst the most according to claim 1, it is characterised in that: described additive
For one or more in glass fibre, CMC, ammonia.
8., according to the low vanadium wide active temperature windows denitrating catalyst described in claim 1-7 any claim, its feature exists
In: described catalyst is prepared by each component following: ammonium metavanadate 0.05-0.2 weight portion, ammonium metatungstate 0.1-3 weight portion
Or ammonium metatungstate 0.1-3 weight portion and the mixing of ammonium molybdate 0.1-10 weight portion, TiO260-80 weight portion, additive 10-20
Weight portion, deionized water 15-30 weight portion.
The preparation method of low vanadium wide active temperature windows denitrating catalyst the most according to claim 8, it is characterised in that: press
Prepare the mixed solution of ammonium metavanadate, ammonium metatungstate and ammonium paramolybdate according to formula proportion respectively, add in titanium dioxide with additive
Mixing, obtain the preferable pug of performance that lumps, pug is prepared as catalyst base substrate after old, and base substrate is through being dried, forging
Burning forms finished product after processing.
The preparation method of low vanadium wide active temperature windows denitrating catalyst the most according to claim 9, it is characterised in that:
Described is old, and the time is 5-50 hour；Described is dried, and temperature is 60-150 DEG C, and drying time is 1-15 hour；Described
Calcining, temperature is 300-650 DEG C, and calcination time is 1-20 hour.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107051203A (en) * | 2017-06-21 | 2017-08-18 | 重庆大学 | A kind of middle low temperature sulfur-containing smoke gas efficient denitrifying device and method based on Fast SCR reactions |
| CN107597198A (en) * | 2017-09-11 | 2018-01-19 | 北京方信立华科技有限公司 | A kind of SCR denitration hardening hydrosol and preparation method thereof and method for curing |
| CN110694612A (en) * | 2019-10-25 | 2020-01-17 | 内蒙古希捷环保科技有限责任公司 | Rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst and preparation method thereof |
| CN111167437A (en) * | 2020-01-09 | 2020-05-19 | 华侨大学 | Honeycomb low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition and preparation method thereof |
| CN112403486A (en) * | 2020-11-19 | 2021-02-26 | 高化学（江苏）化工新材料有限责任公司 | V/Cu/B/W-TiO2-ZrO2Composite low-temperature denitration catalyst and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107051203A (en) * | 2017-06-21 | 2017-08-18 | 重庆大学 | A kind of middle low temperature sulfur-containing smoke gas efficient denitrifying device and method based on Fast SCR reactions |
| CN107597198A (en) * | 2017-09-11 | 2018-01-19 | 北京方信立华科技有限公司 | A kind of SCR denitration hardening hydrosol and preparation method thereof and method for curing |
| CN110694612A (en) * | 2019-10-25 | 2020-01-17 | 内蒙古希捷环保科技有限责任公司 | Rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst and preparation method thereof |
| CN111167437A (en) * | 2020-01-09 | 2020-05-19 | 华侨大学 | Honeycomb low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition and preparation method thereof |
| CN112403486A (en) * | 2020-11-19 | 2021-02-26 | 高化学（江苏）化工新材料有限责任公司 | V/Cu/B/W-TiO2-ZrO2Composite low-temperature denitration catalyst and preparation method thereof |
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Application publication date: 20161214 |