CN106732525A - A kind of denitrating catalyst and preparation method thereof and application method - Google Patents

A kind of denitrating catalyst and preparation method thereof and application method Download PDF

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Publication number
CN106732525A
CN106732525A CN201611121853.6A CN201611121853A CN106732525A CN 106732525 A CN106732525 A CN 106732525A CN 201611121853 A CN201611121853 A CN 201611121853A CN 106732525 A CN106732525 A CN 106732525A
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complex carrier
denitrating catalyst
catalyst
preparation
concave
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戴勇
宦斌
张海升
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Yangcheng Institute of Technology
Yancheng Institute of Technology
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Yangcheng Institute of Technology
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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
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to a kind of denitrating catalyst and preparation method thereof, the denitrating catalyst includes complex carrier and the active component being supported on the complex carrier, and the complex carrier is 10 by mass ratio:13 Concave-convex clay rod and activated carbon composition, the active component is vanadic anhydride；Concave-convex clay rod and activated carbon mix in aqueous acetic acid, be molded, drying, be calcined and obtain complex carrier, and complex carrier is in NH4VO3Impregnated in the aqueous solution, denitrating catalyst is obtained after drying, roasting.The Catalyst Production is simple, with low cost, being capable of NO_x Reduction by Effective.

Description

A kind of denitrating catalyst and preparation method thereof and application method
Technical field
The present invention relates to a kind of preparation method and applications of denitrating catalyst.
Background technology
Nitrogen oxides (NOx) it is main atmosphere pollution, acid rain, photochemical pollution, greenhouse effects and smelly can be caused The destruction of oxygen layer.NOxOne of main source be flue gas that fired coal combustion is discharged, containing substantial amounts of NO, NO2With a small amount of N2O； Next to that the tail gas of motor vehicle emission.With the development and the popularization of private savings automobile of China's power industry, NOxTotal emission volumn fast The growth of speed, control and improvement NOxPollution it is extremely urgent, the denitration of wherein coal-fired flue-gas is control NOxImportant measures it One.
Technology main selective catalytic-reduction denitrified (SCR), the SNCR of current coal-fired flue gas denitration Denitration (SNCR), liquid absorption method, plasma activation and absorption method etc..Wherein, with NH3For the SCR technology of reducing agent is Current denitrating flue gas most efficient method is also in the world using the method that most, technology is most ripe.SCR technology application of results Key be the suitable catalyst of selection, the species of catalyst, form, life-span and reaction temperature influence the effect of SCR method denitrations Rate.SCR catalyst at present using it is more be metal oxide, its reaction temperature is generally between 320-400 DEG C, from efficiently, warp Seen in the angle for helping and being easy to boiler matching, denitration is more superior in the range of 120-200 DEG C, therefore low-temperature SCR catalyst Research is increasingly taken seriously.
Concave-convex clay rod is a kind of cheap natural aluminium magensium silicate mineral, with unique fibrous crystalline structure and The physical and chemical performances such as superior colloid, absorption, catalysis and filling, in multiple fields such as environmental protection, chemical industry, light industry, agricultural, building materials Have and be extremely widely applied.Concave-convex clay rod has big specific surface area and preferable adsorption activity, the Mg in its structure2 +、Al3+It is easy to, by other metal ion exchangeds, form active sites, is a kind of good adsorbent and carrier.Attapulgite glues Soil is compared with the common desulphurization denitration adsorbent such as activated carbon, zeolite, and the specific surface area of Concave-convex clay rod is smaller, dispersiveness It is poor, it is therefore necessary to which that Concave-convex clay rod carrier is improved, corresponding catalyst is improved to denitrating flue gas effect.
Up to the present with Concave-convex clay rod and activated carbon composite load reactive metal oxides vanadic anhydride in cigarette There is not been reported for application study state in gas simultaneous SO_2 and NO removal technology.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of denitrating catalyst, denitrating catalyst production Simply, it is with low cost, being capable of NO_x Reduction by Effective.
A kind of denitrating catalyst of the invention, including complex carrier and the activearm that is supported on the complex carrier Point, the complex carrier is 10 by mass ratio:Concave-convex clay rod and the activated carbon composition of 1-3, the active component is five oxygen Change two vanadium.
Further, complex carrier and the mass ratio of active component are 3-23 in the catalyst:1.
Further, cocatalyst is also loaded on the complex carrier, co-catalyst quality in the denitrating catalyst Percentage is 0.1-5%.
Further, the co-catalyst is one or two in nickel oxide or cobalt oxide.
A kind of preparation method of denitrating catalyst of the invention, comprises the following steps：
(1) by particle diameter for 45-60 μm Concave-convex clay rod powder and activated carbon add aqueous acetic acid in, be well mixed Add appropriate water to stir into pasty state afterwards, and be put into forming machine and be molded, through drying, roasting after, obtain Concave-convex clay rod and The complex carrier of activated carbon, wherein, activated carbon is 1-3 with the mass ratio of Concave-convex clay rod:10, preferably 1:10-5.
(2) complex carrier obtained in step (1) is put into the NH of 0.5-0.8mol/L4VO3In the aqueous solution, using etc. body Product dipping 2-7 hour, preferably 4-6 hours, then takes out and dries at 50-70 DEG C 2-3 hours respectively, drying at 90-110 DEG C 5-6 hours, it is calcined 2-3 hours at 200-400 DEG C after drying, preferably 200-300 DEG C, obtains denitrating catalyst.
Further, in step (1), 4-6h is dried at 90-110 DEG C.
Further, in step (1), under inert gas shielding, 1-5h, preferably 2-4 hours are calcined at 300-500 DEG C.
Further, in step (2), NH4VO3NH in the aqueous solution4VO3Concentration be 0.5-0.8mol/L.
A kind of application method of denitrating catalyst of the invention, denitrating catalyst is fitted into fixed bed reactors, Flue gas is passed through at 120-300 DEG C.
Further, the flue gas flow is 400-600mL/min, denitration rate 80-90%.
By such scheme, the present invention at least has advantages below：
1st, denitrating catalyst of the invention production is simple, with low cost, can NO_x Reduction by Effective, denitration rate reaches 80-90%；
2nd, the activated carbon that directly can be prepared using Concave-convex clay rod and agricultural wastes such as stalk is raw material preparation denitration Catalyst, preparation cost is low.
3rd, denitrating catalyst of the invention activity is high, stable performance, can Reusability, do not cause secondary pollution.
Described above is only the general introduction of technical solution of the present invention, in order to better understand technological means of the invention, And can be practiced according to the content of specification, described in detail as after with presently preferred embodiments of the present invention below.
Specific embodiment
With reference to embodiment, specific embodiment of the invention is described in further detail.Following examples are used for The present invention is illustrated, but is not limited to the scope of the present invention.
Embodiment 1
It is 700m that specific surface area is added in the Concave-convex clay rod powder that particle diameter is 60 μm2Activated carbon prepared by the rice husk of/g Powder, addition is the 12% of Concave-convex clay rod, by amount plus aqueous acetic acid simultaneously and uniform stirring is until into pasty state, extrusion Shaping, in an oven in 100 DEG C of dryings 3 hours, is calcined 2 hours at 300 DEG C under nitrogen protection, is made complex carrier；Will system Into complex carrier be put into the NH of 0.5mol/L4VO3In solution, using incipient impregnation 2 hours after, in 60 DEG C of dryings 3 hours, Then 3 hours prepared denitrating catalysts are calcined after 200 DEG C within 5 hours in 10 DEG C of dryings, are milled, the sieving of 40-60 mesh；Denitration is urged In 1.0 grams of loading fixed bed reactors of agent, 200 DEG C of ventilatory responses are warming up to, the composition of simulated flue gas is NH3500ppm, NO2 500ppm, Balance Air is N2O with 5%2, gas flow 500mL/min, denitration rate is 74%.
Embodiment 2：
It is 700m that specific surface area is added in the Concave-convex clay rod powder that particle diameter is 45 μm2Activated carbon prepared by the rice husk of/g Powder, addition is the 20% of Concave-convex clay rod, by amount plus aqueous acetic acid simultaneously and uniform stirring is until into pasty state, extrusion Shaping, in an oven in 100 DEG C of dryings 5 hours, is calcined 2 hours at 350 DEG C under nitrogen protection, is made complex carrier；Will system Into complex carrier be put into the NH of 0.5mol/L4VO3In solution, using incipient impregnation 2 hours after, in 60 DEG C of dryings 3 hours, Then 3 hours prepared denitrating catalysts are calcined after 300 DEG C within 5 hours in 10 DEG C of dryings, are milled, the sieving of 40-60 mesh；Denitration is urged In 1.0 grams of loading fixed bed reactors of agent, 200 DEG C of ventilatory responses are warming up to, the composition of simulated flue gas is NH3500ppm, NO2 500ppm, Balance Air is N2O with 5%2, gas flow 500mL/min, denitration rate is 85%.
Embodiment 3：
It is 700m that specific surface area is added in the Concave-convex clay rod powder that particle diameter is 60 μm2Activated carbon prepared by the rice husk of/g Powder, addition is the 30% of Concave-convex clay rod, by amount plus aqueous acetic acid simultaneously and uniform stirring is until into pasty state, extrusion Shaping, in an oven in 100 DEG C of dryings 4 hours, is calcined 2 hours at 350 DEG C under nitrogen protection, is made complex carrier；Will system Into complex carrier be put into the NH of 0.5mol/L4VO3In solution, using incipient impregnation 2 hours after, in 60 DEG C of dryings 3 hours, Then 3 hours prepared denitrating catalysts are calcined after 300 DEG C within 5 hours in 10 DEG C of dryings, are milled, the sieving of 40-60 mesh；Denitration is urged In 1.0 grams of loading fixed bed reactors of agent, 250 DEG C of ventilatory responses are warming up to, the composition of simulated flue gas is NH3500ppm, NO2 500ppm, Balance Air is N2O with 5%2, gas flow 500mL/min, denitration rate is 70%.
Embodiment 4：
It is 700m that specific surface area is added in the Concave-convex clay rod powder that particle diameter is 60 μm2Activated carbon prepared by the rice husk of/g Powder, addition is the 20% of Concave-convex clay rod, by amount plus aqueous acetic acid simultaneously and uniform stirring is until into pasty state, extrusion Shaping, in an oven in 100 DEG C of dryings 5 hours, is calcined 2 hours at 300 DEG C under nitrogen protection, is made complex carrier；Will system Into complex carrier be put into the NH of 0.5mol/L4VO3In solution, using incipient impregnation 2 hours after, in 60 DEG C of dryings 3 hours, Then 3 hours prepared denitrating catalysts are calcined after 300 DEG C within 5 hours in 10 DEG C of dryings, are milled, the sieving of 40-60 mesh；Denitration is urged In 1.0 grams of loading fixed bed reactors of agent agent, 200 DEG C of ventilatory responses are warming up to, the composition of simulated flue gas is NH3600ppm, NO2500ppm, Balance Air is N2O with 5%2, gas flow 500mL/min, denitration rate is 90%.
Embodiment 5：
It is 700m that specific surface area is added in the Concave-convex clay rod powder that particle diameter is 60 μm2Activated carbon prepared by the rice husk of/g Powder, addition is the 20% of Concave-convex clay rod, by amount plus aqueous acetic acid simultaneously and uniform stirring is until into pasty state, extrusion Shaping, in an oven in 100 DEG C of dryings 3 hours, is calcined 2 hours at 350 DEG C under nitrogen protection, is made complex carrier；Will system Into complex carrier be put into the NH of 0.5mol/L4VO3In solution, using incipient impregnation 2 hours after, in 60 DEG C of dryings 3 hours, Then it is calcined prepared denitrating catalyst agent in 3 hours after 300 DEG C within 5 hours in 10 DEG C of dryings, mills, the sieving of 40-60 mesh；By denitration In 1.0 grams of loading fixed bed reactors of catalyst, 200 DEG C of ventilatory responses are warming up to, the composition of simulated flue gas is NH3 1000ppm, NO2800ppm, Balance Air is N2O with 5%2, gas flow 500mL/min, denitration rate is 81%.
The above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill For the those of ordinary skill in art field, on the premise of the technology of the present invention principle is not departed from, can also make it is some improvement and Modification, these are improved and modification also should be regarded as protection scope of the present invention.

Claims (10)

1. a kind of denitrating catalyst, it is characterised in that：Including complex carrier and the activearm being supported on the complex carrier Point, the complex carrier is 10 by mass ratio:Concave-convex clay rod and the activated carbon composition of 1-3, the active component is five oxygen Change two vanadium.
2. denitrating catalyst according to claim 1, it is characterised in that：Complex carrier and active component in the catalyst Mass ratio be 3-23:1.
3. denitrating catalyst according to claim 2, it is characterised in that：Co-catalysis have been also loaded on the complex carrier Agent, co-catalyst mass percent is 0.1-5% in the denitrating catalyst.
4. denitrating catalyst according to claim 3, it is characterised in that：The co-catalyst is in nickel oxide or cobalt oxide One or two.
5. a kind of preparation method of denitrating catalyst as claimed in claim 1, it is characterised in that comprise the following steps：
(1) Concave-convex clay rod and activated carbon is added and mix in aqueous acetic acid and in the pasty state, after shaping, drying, being calcined, Obtain complex carrier；
(2) complex carrier obtained in step (1) be impregnated in into NH4VO3In the aqueous solution, then take out, after drying, being calcined, obtain To denitrating catalyst.
6. preparation method according to claim 5, it is characterised in that：In step (1), 4-6h is dried at 90-110 DEG C.
7. preparation method according to claim 5, it is characterised in that：In step (1), under inert gas shielding, 300- 1-5h is calcined at 500 DEG C.
8. preparation method according to claim 5, it is characterised in that：In step (2), NH4VO3NH in the aqueous solution4VO3It is dense It is 0.5-0.8mol/L to spend.
9. the application method of a kind of denitrating catalyst as any one of claim 1-4, it is characterised in that：Denitration is urged Agent is fitted into fixed bed reactors, and flue gas is passed through at 120-300 DEG C.
10. application method according to claim 9, it is characterised in that：The flue gas flow is 400-600mL/min.
CN201611121853.6A 2016-12-08 2016-12-08 A kind of denitrating catalyst and preparation method thereof and application method Pending CN106732525A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109847580A (en) * 2019-03-21 2019-06-07 青岛大学 Denitration filtrate and preparation method thereof based on plasma pre-treatment and infusion process
CN110665460A (en) * 2019-10-10 2020-01-10 邓晖 Irradiation modified attapulgite/activated carbon composite carbon rod and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103182243A (en) * 2013-03-25 2013-07-03 江苏中材环境工程有限公司 Preparation and application method of smoke denitrifying agent

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103182243A (en) * 2013-03-25 2013-07-03 江苏中材环境工程有限公司 Preparation and application method of smoke denitrifying agent

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109847580A (en) * 2019-03-21 2019-06-07 青岛大学 Denitration filtrate and preparation method thereof based on plasma pre-treatment and infusion process
CN109847580B (en) * 2019-03-21 2022-04-08 青岛大学 Denitration filter material based on plasma pretreatment and impregnation method and preparation method thereof
CN110665460A (en) * 2019-10-10 2020-01-10 邓晖 Irradiation modified attapulgite/activated carbon composite carbon rod and preparation method thereof

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