CN108404931A - Compound SCR denitration catalyst and preparation method thereof - Google Patents

Compound SCR denitration catalyst and preparation method thereof Download PDF

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Publication number
CN108404931A
CN108404931A CN201810468923.8A CN201810468923A CN108404931A CN 108404931 A CN108404931 A CN 108404931A CN 201810468923 A CN201810468923 A CN 201810468923A CN 108404931 A CN108404931 A CN 108404931A
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China
Prior art keywords
catalysis
scr denitration
temperature
denitration catalyst
catalyst
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CN201810468923.8A
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Chinese (zh)
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CN108404931B (en
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施雅琼
张现龙
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江苏浩日朗环保科技有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/84Catalysts 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
    • B01J23/889Manganese, technetium or rhenium
    • B01J23/8892Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8628Processes characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts

Abstract

This application discloses a kind of compound SCR denitration catalysts, include the first catalysis material with microcellular structure and is adsorbed in the second catalysis material of micropore inwall, wherein, the catalysis efficiency of the first catalysis material and the second catalysis material reaches highest at different temperature respectively.Disclosed herein as well is a kind of preparation methods of compound SCR denitration catalyst.The present invention can preferably solve the operating condition for making catalyst be adapted to larger temperature fluctuation, reduce additional equipment investment expense and software Meteorological;Simultaneously as ordinary temperature active constituent and low temperature active ingredient is made to realize prepared by layering, keep catalyst more selective to the improvement of nitrogen oxides in each temperature minizone.

Description

Compound SCR denitration catalyst and preparation method thereof

Technical field

This application involves removal of nitrogen oxide fields, more particularly to a kind of compound SCR denitration catalyst and its preparation side Method.

Background technology

SCR denitration is suitable for the removing of nitrogen oxides, and can be divided into ordinary temperature according to temperature in use requirement urges Agent and low temperature catalyst, the wherein temperature in use of ordinary temperature catalyst at 300~420 DEG C, low temperature catalyst 200 DEG C with It is interior.

Since the exhaust temperature of nitrogen oxides is broad, on specific a certain emission source, with the fluctuation of load, temperature Fluctuation is also bigger.

Current usual manner, one is load the progress denitration of ordinary temperature denitrating catalyst when the temperature is low to pass through The mode of heating flue gas improves flue-gas temperature and carries out denitration, and operation in this way improves the input of situ hardware and increases energy Consumption.

Another kind be load low-temperature denitration catalyst, when flue-gas temperature is excessively high by heat-exchanger rig reduce flue-gas temperature into Row denitration.But this solution increases the input of hardware device and the inputs of software overhead.

In conclusion current denitrating catalyst cannot be satisfied the larger applying working condition requirement of temperature fluctuation range, no matter Ordinary temperature catalyst or low temperature catalyst are all the higher performances of competence exertion within the scope of rational temperature space, right Temperature range can only be adjusted by additional auxiliary equipment in immalleable temperature range, increase the expense of additional engineering With.

Invention content

The purpose of the present invention is to provide a kind of compound SCR denitration catalysts and preparation method thereof, solve existing normal Rule catalyst, low temperature catalyst are unable to adaptive temperature and fluctuate larger use problem.

To achieve the above object, the present invention provides the following technical solutions:

The embodiment of the present application discloses a kind of compound SCR denitration catalyst, include the first catalysis material with microcellular structure, And it is adsorbed in the second catalysis material of micropore inwall, wherein

The catalysis efficiency of first catalysis material and the second catalysis material reaches highest at different temperature respectively.

Preferably, in above-mentioned compound SCR denitration catalyst, temperature of first catalysis material at 300~420 DEG C Degree window reaches 80% or more denitrification rate;

Second catalysis material reaches 80% or more denitrification rate in 120~200 DEG C of temperature window.

Preferably, in above-mentioned compound SCR denitration catalyst, first catalysis material is TiO2\V2O5\WO3

Preferably, in above-mentioned compound SCR denitration catalyst, second catalysis material is CeO2\MnO2\Fe2O3\ CuO。

Preferably, in above-mentioned compound SCR denitration catalyst, according to mass percent, CeO2: MnO2:Fe2O3:CuO =50~60:10~20:10~20:5~10.

Preferably, in above-mentioned compound SCR denitration catalyst, 60~100nm of pore diameter range of the first catalysis material.

Correspondingly, disclosed herein as well is a kind of preparation methods of compound SCR denitration catalyst, including:

(1), the first catalysis material with microcellular structure is prepared;

(2), the colloidal materials of the second catalysis material are prepared;

(3), the second catalysis material is coated in the micropore inwall of the first catalysis material using vacuum suction method;

(4), dry, roasting obtains compound SCR denitration catalyst.

Preferably, in the preparation method of above-mentioned compound SCR denitration catalyst, in step (1), by controlling roasting temperature Degree generates microcellular structure, 500~650 DEG C of calcination temperature, 20~35h of roasting time.

Preferably, in the preparation method of above-mentioned compound SCR denitration catalyst, in step (4), drying condition be 80~ 120 DEG C, drying time is 1~5h.

Preferably, in the preparation method of above-mentioned compound SCR denitration catalyst, in step (4), roasting condition 400 ~500 DEG C, roasting time is 3~8h.

Compared with the prior art, the advantages of the present invention are as follows:The present invention can preferably solve that catalyst is made to be adapted to The operating condition of larger temperature fluctuation reduces additional equipment investment expense and software Meteorological;Simultaneously as making conventional temperature It spends active constituent and low temperature active ingredient realizes prepared by layering, catalyst is made to be controlled nitrogen oxides in each temperature minizone Reason is more selective.

Description of the drawings

In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or will show below There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments described in application, for those of ordinary skill in the art, without creative efforts, Other drawings may also be obtained based on these drawings.

Fig. 1 show the preparation flow schematic diagram of compound SCR denitration catalyst in the specific embodiment of the invention.

Specific implementation mode

The embodiment of the present application discloses a kind of compound SCR denitration catalyst, includes the first catalysis material with microcellular structure Material and the second catalysis material for being adsorbed in micropore inwall, wherein

The catalysis efficiency of first catalysis material and the second catalysis material reaches highest at different temperature respectively.

In one embodiment, first catalysis material reaches 80% or more denitration in 300~420 DEG C of temperature window Rate;Second catalysis material reaches 80% or more denitrification rate in 120~200 DEG C of temperature window.In other embodiments, The best denitration temperature of one catalysis material can be the temperature window at 120~200 DEG C, the best denitration temperature of the second catalysis material Degree is at 300~420 DEG C.

It will be readily apparent, the best denitration temperature of the first catalysis material and the second catalysis material can be according to material Difference is changed, and this case does not limit.

First catalysis material main component is TiO2, V2O5, WO3、SiO2, CaO mixture, mass percent is respectively matter It is respectively 75~85%, 0.5~1.5%, 4~8%, 5~10%, 0.5~5% to measure percentage.

Typical proportion:

TiO285%, V2O50.8%, WO34.5% SiO28% CaO 1.7%

TiO285%, V2O50.6%, WO34.5% SiO28% CaO 1.9%

TiO285%, V2O51.0%, WO34.5% SiO28% CaO 1.5%

In one embodiment, the second catalysis material is CeO2\MnO2\Fe2O3\CuO。

In preferred volume embodiment, according to mass percent, CeO2:MnO2:Fe2O3:CuO=50~60:10~20: 10~20:5~10.

In other embodiments, the second catalysis material can also be CeO2、ZrO2、Fe2O3, CuO mixture.

Further, 60~100nm of pore diameter range of the first catalysis material.

In conjunction with shown in Fig. 1, the embodiment of the present application also discloses a kind of preparation method of compound SCR denitration catalyst, including:

(1), the first catalysis material with microcellular structure is prepared;Wherein 500~650 DEG C of calcination temperature, the time 20~ 35h,

(2), the colloidal materials of the second catalysis material are prepared;

(3), the second catalysis material is coated in the micropore inwall of the first catalysis material using vacuum suction method;

(4), dry, roasting obtains compound SCR denitration catalyst.

In a preferred embodiment, in step (4), drying condition is 80~120 DEG C, and drying time is 1~5h.

In a preferred embodiment, in step (4), roasting condition is 400~500 DEG C, and roasting time is 3~8h.

It is prepared due to realizing ordinary temperature catalyst and the combined type of low temperature coating colloidal materials, catalyst is allow to fit Answer the operating condition of larger temperature fluctuation;Simultaneously as ordinary temperature active constituent and low temperature active ingredient is made to realize layering system It is standby, keep catalyst more selective to the improvement of nitrogen oxides in each temperature minizone

The present invention is described further by the following example:According to following embodiments, the present invention may be better understood. However, as it will be easily appreciated by one skilled in the art that specific material ratio, process conditions and its result described in embodiment are only used In illustrating the present invention, without the present invention described in detail in claims should will not be limited.

Embodiment 1

It is prepared by (1) first catalysis material (ordinary temperature catalyst, 300~420 DEG C of best denitration temperature)

The preparation of ordinary temperature catalyst is realized by way of batch mixing, extrusion molding, drying, roasting.

Wherein, raw material includes:

60 parts of titanium dioxide;

0.5 part of ammonium metavanadate;

3 parts of ammonium metatungstate;

6 parts of glass fibre;

2 parts of wood pulp

1.5 parts of binder;

3 parts of silica;

2 parts of wollastonite;

20 parts of deionization;

8 parts of ammonium hydroxide.

When preparing ordinary temperature catalyst, product microstructure is especially adjusted, the control of temperature when passing through roasting, temperature The high sintering for causing material itself is spent, micropore is caused to collapse, on the contrary aperture increases are then aperture is constant, and hole diameter enlargement causes rationally 60~100nm of range, in order to a kind of microcellular structure is provided.

(2), prepared by the second catalysis material

Prepare low-temperature catalytic activity coating colloid material C eO2\MnO2\Fe2O3CuO, contain low temperature in this colloidal materials Catalytic active component, mass percent 55:15:20:10.

(3), prepared by composite material

Load of the low temperature coating colloidal materials in ordinary temperature catalyst duct, load percentage be product weight 15~ 25%, by vacuum absorption device, coating colloidal materials are uniformly coated in catalyst cell walls, later by drying, The mode of roasting completes the sintering of low temperature coating material.

Wherein, drying condition is 100 DEG C, drying time 2h, and calcination condition is 450 DEG C, drying time 5h.

The sample of preparation is tested, the simulation coal steam-electric plant smoke ingredient for measurement is shown in Table 1, is gone to nitrogen oxides Except rate is shown in Table 2 and table 3.

The coal steam-electric plant smoke ingredient of 1 simulated determination of table

Gas NO NH3 SO2 H2O O2 N2 Volume fraction % 0~0.10 0~0.10 0.02~0.05 16 5.00 95

The removal rate of 2 nitrogen oxides of table

Test condition:Air speed 10000h-1, NH3/ NOx=1,1000ppmNO, 5vol%O2

The removal rate (being passed through steam and sulfur dioxide) of 3 nitrogen oxides of table

Test condition:Air speed 10000h-1, NH3/ NOx=1,1000ppmNO, 5vol%O2, 1000ppmSO2, 16vol% H2O

Here, it should also be noted that, in order to avoid having obscured the present invention because of unnecessary details, in the accompanying drawings only It shows the structure and/or processing step closely related with scheme according to the present invention, and is omitted little with relationship of the present invention Other details.

Finally, it is to be noted that, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive Property include so that including a series of elements process, method, article or equipment not only include those elements, but also Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic Element.

Claims (10)

1. a kind of compound SCR denitration catalyst, which is characterized in that include the first catalysis material with microcellular structure and suction Invest the second catalysis material of micropore inwall, wherein
The catalysis efficiency of first catalysis material and the second catalysis material reaches highest at different temperature respectively.
2. compound SCR denitration catalyst according to claim 1, which is characterized in that
First catalysis material reaches 80% or more denitrification rate in 300 ~ 420 DEG C of temperature window;
Second catalysis material reaches 80% or more denitrification rate in 120 ~ 200 DEG C of temperature window.
3. compound SCR denitration catalyst according to claim 1, which is characterized in that first catalysis material is TiO2\ V2O5\WO3\SiO2\CaO。
4. compound SCR denitration catalyst according to claim 1, which is characterized in that second catalysis material is CeO2\ MnO2\Fe2O3\CuO。
5. compound SCR denitration catalyst according to claim 3, which is characterized in that according to mass percent, CeO2: MnO2:Fe2O3:CuO=50~60:10~20:10~20:5~10.
6. compound SCR denitration catalyst according to claim 1, which is characterized in that the pore diameter range of the first catalysis material 60~100nm。
7. the preparation method of any compound SCR denitration catalyst of claim 1 to 6, which is characterized in that including:
(1), prepare with microcellular structure the first catalysis material;
(2), prepare the second catalysis material colloidal materials;
(3), using vacuum suction method by the second catalysis material be coated in the first catalysis material micropore inwall;
(4), dry, roasting obtain compound SCR denitration catalyst.
8. the preparation method of compound SCR denitration catalyst according to claim 7, which is characterized in that step(1)In, lead to It crosses control calcination temperature and generates microcellular structure, 500 ~ 650 DEG C of calcination temperature, 20 ~ 35h of roasting time.
9. the preparation method of compound SCR denitration catalyst according to claim 7, which is characterized in that step(4)In, it does Dry condition is 80 ~ 120 DEG C, and drying time is 1 ~ 5h.
10. the preparation method of compound SCR denitration catalyst according to claim 7, which is characterized in that step(4)In, roasting Burning condition is 400 ~ 500 DEG C, and roasting time is 3 ~ 8h.
CN201810468923.8A 2018-05-16 2018-05-16 Composite SCR denitration catalyst and preparation method thereof CN108404931B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105289648A (en) * 2015-12-01 2016-02-03 北京贞吉环保科技有限公司 Globular low temperature flue gas denitration catalyst as well as preparation method and application thereof
CN105833900A (en) * 2016-04-06 2016-08-10 山东成泰化工有限公司 Isomerization catalyst and preparation method thereof
CN107321149A (en) * 2017-08-23 2017-11-07 萍乡市华星化工设备填料有限公司 Low-temp desulfurization denitrating system in coking of coal
CN107398155A (en) * 2017-08-23 2017-11-28 萍乡市华星化工设备填料有限公司 Low-temp desulfurization denitrating system in a kind of coking of coal

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105289648A (en) * 2015-12-01 2016-02-03 北京贞吉环保科技有限公司 Globular low temperature flue gas denitration catalyst as well as preparation method and application thereof
CN105833900A (en) * 2016-04-06 2016-08-10 山东成泰化工有限公司 Isomerization catalyst and preparation method thereof
CN107321149A (en) * 2017-08-23 2017-11-07 萍乡市华星化工设备填料有限公司 Low-temp desulfurization denitrating system in coking of coal
CN107398155A (en) * 2017-08-23 2017-11-28 萍乡市华星化工设备填料有限公司 Low-temp desulfurization denitrating system in a kind of coking of coal

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