CN102225332A - Nanometer linear structured TiO2 carrier with stainless steel substrate, denitration catalyst taking TiO2 carrier as carrier and preparation methods thereof - Google Patents
Nanometer linear structured TiO2 carrier with stainless steel substrate, denitration catalyst taking TiO2 carrier as carrier and preparation methods thereof Download PDFInfo
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- CN102225332A CN102225332A CN 201110115883 CN201110115883A CN102225332A CN 102225332 A CN102225332 A CN 102225332A CN 201110115883 CN201110115883 CN 201110115883 CN 201110115883 A CN201110115883 A CN 201110115883A CN 102225332 A CN102225332 A CN 102225332A
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Abstract
The invention provides a carrier which comprises a stainless steel substrate and a nanometer linear structured TiO2 attached to the surface of the stainless steel substrate. The invention further provides a denitration catalyst based on the carrier, wherein active components are loaded on the carrier for the denitration catalyst. The denitration catalyst provided by the invention has excellent economic benefit and can be widely applied to removing nitric oxide from various exhaust gases.
Description
Technical field
The present invention relates to the denitrating flue gas field, be specifically related to a kind of nano thread structure TiO
2Carrier, with it denitrating catalyst of carrier and preparation method thereof.
Background technology
Nitrogen oxide (NO
x) be the general name of the multiple compound of nitrogen and oxygen, specifically comprise N
2O, NO, NO
2, N
2O
4, N
2O
3And N
2O
5Deng.NO
xBe one of pollutant common in the atmosphere, NO
xAs primary pollution, itself can produce harm to health, and it can stimulate people's eye, nose, larynx and lung, makes the people suffer from respiratory disease easily.Even more serious is NO
xAlso can produce multiple secondary pollution, such as acid rain and photochemical pollution etc.
In order to reduce NO
xThe pollution problem that brings, people begin more and more to pay attention to NO
xThe research of control method.Control NO in the prior art
xThe method of discharging mainly contains two big classes, and the one, in fuel combustion process, control NO
xGeneration, promptly low NO
xCombustion technology; The 2nd, to the NO that generates
xCarry out purified treatment, i.e. gas denitrifying technology.In actual production, low NO
xCombustion technology take off NO
xEfficient is no more than 60% usually, can't satisfy the discharge standard of increasingly stringent.Therefore for strictness control NO
xDischarging, must use effective gas denitrifying technology.The selective catalytic reduction of denitration method for flue gas commonly used is sent out, non-selective catalytic reduction, absorption method and catalytic decomposition method etc., wherein selective catalytic reduction (Selective Catalytic Reduction, be called for short SCR) be the most ripe, use also method the most widely.The SCR ratio juris is under the condition that catalyst exists, to containing NO
xTail gas in spray into ammonia, urea or other nitrogen-containing compound make NO wherein
xBe reduced into N
2And water, the catalyst that uses in the SCR technology is normally with active component (V
2O
5, WO
3, MoO
3Deng) load on TiO
2, Al
2O
3, SiO
2, ZrO
2Deng what be prepared from the carrier, wherein again with vanadium titanium class use the most extensive.Early stage vanadium titanium class catalyst is to utilize TiO
2Powder is prepared from by infusion process active material on the area load of described carrier as carrier, and still the shortcoming of this dust carrier is, in the process of using the immersion process for preparing catalyst, and TiO
2Powder can be reunited in solution, thereby greatly reduces the specific area of described carrier, and then has reduced the catalytic activity of catalyst.
In order to overcome above-mentioned defective, Chinese patent literature CN101327427A discloses a kind of denitrating catalyst and preparation method thereof.Described denitrating catalyst comprises catalyst carrier and the active component that loads on the described carrier, and wherein said catalyst carrier is by metal titanium substrate and the TiO that covers the nano-porous structure on the described metal titanium substrate
2Membrane carrier constitutes.Described denitrating catalyst at first utilizes the chemical reaction between titanium and the hydrogen peroxide in the preparation, makes the TiO of one deck nano-porous structure on the metal titanium substrate surface
2Membrane carrier, a certain amount of V in the load in the above again
2O
5And WO
3, by appropriate heat treatment described catalyst is activated at last.Catalyst in this technology is owing to selected the TiO of the higher nano-porous structure of specific area for use
2Film replaces TiO
2Powder has effectively been avoided described TiO as carrier
2The agglomeration that powder occurs in preparation catalyst process, thus the specific area of described catalyst increased, improved the catalytic performance of described catalyst.
TiO except above-mentioned nano-porous structure
2, Chinese patent literature CN1807258A discloses a kind of preparation three-dimensional nanostructure TiO
2Method, the steps include: hydrofluoric acid, nitric acid are mixed with deionized water, join pickle; In hydrogen peroxide solution, add nitric acid and hexamethylenetetramine, obtain reactant liquor; With the pickle pickling of the surface of metallic titanium plate, be immersed in the reactant liquor, react more than 48 hours down at 60 ℃-80 ℃; Reacted titanium sheet washed with de-ionized water, drying 300-500 ℃ of insulation at least 10 minutes, promptly obtains the TiO of nanometer flower structure
2, the TiO of described nanometer flower structure
2After heat treatment keep the rule oriented pattern, crystal grain is tiny, has the big advantage of specific area.
In addition, Chinese patent literature CN101508463 also discloses a kind of preparation TiO
2The method of nano-wire array film, its step comprises: hydrofluoric acid, nitric acid are mixed with deionized water, join pickle; In hydrogen peroxide solution, add melamine and nitric acid, get reactant liquor; Pickling metal titanium plate pickle pickling is immersed in the reactant liquor, reacts 60-72 hour down at 60-90 ℃; Reacted titanium plate washed with de-ionized water, drying was 350-550 ℃ of insulation 1-2 hour.Prepared TiO
2Nano-wire array film is pure, and size is arranged regular, the crystallization ideal, and it is big to have specific area, with the firm advantage of matrix bond.
At above-mentioned existing nanoporous, nanometer flower and nano thread structure TiO
2In, the TiO of nano thread structure
2Caused people's attention because of having bigger specific area.In above-mentioned prior art, those skilled in the art is used to use Titanium as substrate, and this use titanium-base also generates nanostructured TiO by the oxidation of the hydrogen oxide aqueous solution on its surface
2Method, have simple advantage.But, because the price of described Titanium is very expensive, therefore use denitrating catalyst cost that Titanium prepares as substrate than higher, economic benefit is relatively poor.
Summary of the invention
Use denitrating catalyst cost that Titanium prepares as substrate than higher in order to solve in the prior art, the problem that economic benefit is relatively poor the invention provides a kind of nano thread structure TiO
2It is the denitrating catalyst of carrier that carrier reaches with it, and the present invention simultaneously also provides the preparation method of the two.
A kind of nano thread structure TiO described in the present invention
2Carrier, be that the technical scheme of the denitrating catalyst and preparation method thereof of carrier is with it:
A kind of carrier that is used for load denitration activity component, described carrier comprise stainless steel substrate and attached to the nano thread structure TiO on described stainless steel substrate surface
2
The preparation method of described carrier comprises:
(1) is consutrode with pure titanium silk, in air atmosphere, carries out electric arc spraying,, obtain the substrate that surface heat is coated with the TiN layer at the surface heat spraying TiN of described stainless steel substrate layer;
(2) stainless steel substrate that will be coated with the TiN layer through the surface heat after step (1) is handled immerses and contains 0.8-1.5wt%HNO
3, 0.01-0.02wt% hexamethylenetetramine and 20-25wt%H
2O
2Solution in, constant temperature was placed 10-15 hour under 60-90 ℃ condition, it was taken out dry, insulation is handled and is got final product under 400-500 ℃ of condition again.
The thickness of described thermal spraying TiN layer is 0.1-0.2mm.
In the preceding step of the surface of described stainless steel substrate being carried out blasting treatment that also comprises of described step (1).
It is 100-200 purpose emergy that granularity is adopted in described blasting treatment.
Between described step (1) and (2), also comprise step (1 ＇):
The stainless steel substrate that described surface heat is coated with the TiN layer immerses to place in 60-80 ℃ the mixed acid to be handled, and takes out water and washes, and carries out drying after rinsing well;
Described mixed acid is the mixed liquor of hydrofluoric acid, red fuming nitric acid (RFNA) and deionized water, and wherein said hydrofluoric acid accounts for the 18-25% that the 4-6% of described mixed acid gross mass, described red fuming nitric acid (RFNA) account for described mixed acid gross mass.
Baking temperature in described step (1 ＇) and the step (2) is 120-150 ℃.
The stainless steel substrate that in the described step (1 ＇) described surface heat is coated with the TiN layer immerses that to place the time of handling in 60-80 ℃ the mixed acid be 1-3 minute.
The time that insulation is handled in the described step (2) is 1-5h.
The load on the described carrier of claim 1 of described denitrating catalyst has active component.
Described active component is nanometer V
2O
5And WO
3
Described active component also comprises rare earth element.
The preparation method of described denitrating catalyst comprises:
(1) ammonium metavanadate, ammonium tungstate and oxalic acid are dissolved in the maceration extract that is configured to contain 0.015-0.02wt% ammonium metavanadate, 0.15-0.25wt% ammonium tungstate and 0.01-0.03wt% oxalic acid in the deionized water;
(2) described carrier is immersed in the described maceration extract, constant temperature is placed 24-72h under 60-90 ℃ of condition, and described carrier is taken out drying, then described carrier is incubated to handle under 450-550 ℃ of condition to get final product.
Baking temperature in the described step (2) is 120-150 ℃.
In the described step (1), also comprise the step that in described maceration extract, adds rare earth element.
The insulation processing time is 1-5h described in the described step (2).
Described in the present invention is the nano thread structure TiO of substrate with the stainless steel
2Among the preparation method of carrier, step (1) is a consutrode with pure titanium silk, carries out electric arc spraying in air atmosphere, at the surface heat spraying TiN of described stainless steel substrate layer; Owing to contain a large amount of nitrogen in the air, therefore titanium silk and nitrogen react in the process of spraying, can form the TiN layer on the surface of described substrate.The thickness that the present invention also further defines described thermal spraying TiN layer is 0.1-0.2mm, crosses thin meeting and influence nano thread structure TiO if reason is described TiN layer
2The formation of layer blocked uply then can cause the combination of described TiN layer and stainless steel substrate firm inadequately, comes off easily.
The stainless steel substrate immersion that step (2) will be coated with the TiN layer through the surface heat after step (1) is handled contains 0.8-1.5wt%HNO
3, 0.01-0.02wt% hexamethylenetetramine and 20-25wt%H
2O
2Solution in, constant temperature was placed 10-15 hour under 60-90 ℃ condition, it was taken out dry, insulation is handled and is got final product under 400-500 ℃ of condition again.It is the nano thread structure TiO of substrate that method by this chemical conversion can obtain with the stainless steel
2, wherein the insulation purpose is to make described nano thread structure TiO under 400-500 ℃ of condition
2The crystalline form well-grown, in order to guarantee the growth result of described crystalline form, it is 1-5h that the present invention also further limits the time that described insulation handles; In addition, the present invention also further limits described baking temperature, is 120-150 ℃, and reason is, if the too high meeting of temperature is to described nano thread structure TiO
2Long-living influence causes its structure to change, and temperature is crossed and low can be caused dry needed overlong time, and the present invention has effectively avoided above-mentioned two kinds of situations by described temperature is limited.
In addition, in the preceding step of the surface of described substrate being carried out blasting treatment that also is provided with of step (1); The purpose of blasting treatment described here is the dirt removal on the described stainless steel substrate, and makes it reach certain roughness, thereby improves described stainless steel substrate and the described adhesion that is coated with interlayer, makes the two bonding better.The present invention also further limits and adopts granularity in the described blasting treatment process is 100-200 purpose emergy, reason can obtain different surface roughnesses after being to use different abrasive materials that described substrate is handled, by using 100-200 purpose emergy can obtain the most suitable roughness, make described stainless steel substrate and described TiN coating reach best adhesive effect.
The present invention also further is provided with step (1 ＇) between described step (1) and (2): the substrate that described surface heat is coated with the TiN layer immerses to place in 60-80 ℃ the mixed acid to be handled, and takes out water and washes, and carries out drying after rinsing well; Described mixed acid is the mixed liquor of hydrofluoric acid, red fuming nitric acid (RFNA) and deionized water, and wherein said hydrofluoric acid accounts for the 18-25% that the 4-6% of described mixed acid gross mass, described red fuming nitric acid (RFNA) account for described mixed acid gross mass; The purpose of soaking in mixed acid is to remove the impurity that contains in the described TiN layer, avoids described impurity to subsequent preparation nano thread structure TiO
2The harmful effect that produces.It is 1-3 minute that the present invention also further defines described standing time, and reason is that overlong time can cause the too much corrosion loss of TiN layer.
Of the present invention is the nano thread structure TiO of substrate with the corrosion resistant plate
2Carrier reaches and is with its denitrifying catalyst with selective catalytic reduction advantage as carrier:
(1) of the present invention is the nano thread structure TiO of substrate with the corrosion resistant plate
2Carrier prepares the TiO of nano thread structure again by the method for aqueous hydrogen peroxide solution oxidation by thermal spraying TiN layer on described corrosion resistant plate
2, have simple advantage, also overcome those skilled in the art simultaneously and be confined to use the technology prejudice of Titanium as substrate.
(2) of the present invention is the nano thread structure TiO of substrate with the corrosion resistant plate
2Carrier owing to adopted cheap stainless steel substrate, therefore effectively reduces the preparation cost of described carrier, and economy will be better than titanium-base of the prior art greatly; Simultaneously, described corrosion resistant plate is compared with other metallic plate, also has corrosion-resistant, resistant to elevated temperatures characteristic, also can satisfy the comparatively harsh environment for use of denitrating catalyst when reducing cost.
(3) denitrating catalyst of the present invention is based on above-mentioned nano thread structure TiO
2Preparing carriers forms, described nano thread structure TiO
2Compare with nano-porous structure, have bigger specific area, improved the catalytic efficiency of described denitrating catalyst greatly.In addition, because there is not intersection each other in described nano thread structure, so the sintering phenomenon of effectively having avoided described catalyst in high temperature (about 300 ℃) use, to exist.
Description of drawings
In order to make technical scheme described in the present invention be convenient to more understand, below in conjunction with the drawings and specific embodiments to being the nano thread structure TiO of substrate with the corrosion resistant plate described in the present invention
2And be described further as effect denitrifying catalyst with selective catalytic reduction of carrier and preparation method thereof with it;
Illustrated in figures 1 and 2 be of the present invention be the field emission scanning electron microscope photo of substrate heat spraying TiN layer with the corrosion resistant plate;
Shown in Figure 3 be of the present invention be the X ray diffracting spectrum of substrate heat spraying TiN layer with the corrosion resistant plate: 1-TiN, 2-TiN
0.3
Shown in Figure 4 be of the present invention be the TiO that substrate heat spraying TiN stratification processing converted in-situ obtains with the corrosion resistant plate
2The field emission scanning electron microscope photo of nano thread structure carrier;
Shown in Figure 5 be of the present invention be the TiO that substrate heat spraying TiN stratification processing converted in-situ obtains with the corrosion resistant plate
2The X ray diffracting spectrum of nano thread structure carrier: 1-TiN, 2-TiN
0.3, 3-TiO
2
Shown in Figure 6 is the field emission scanning electron microscope photo of denitrating catalyst of the present invention;
Shown in Figure 7 is the structure chart of denitrating catalyst of the present invention.
The specific embodiment
The preparation method of the carrier of the denitration activity of load described in present embodiment component is:
(1) be consutrode with pure titanium silk, in air atmosphere, carry out electric arc spraying, at the surface heat spraying TiN of described stainless steel substrate layer, the thickness of described TiN layer is 0.2mm, described in the present embodiment with the stainless steel be substrate heat spraying TiN layer the field emission scanning electron microscope photo as depicted in figs. 1 and 2, as can be seen from the figure, the rough surface of described TiN layer helps improving the specific area of the catalyst that finally makes; Of the present invention with the stainless steel be substrate heat spraying TiN layer X ray diffracting spectrum as shown in Figure 2, the main thing of as can be seen from Figure 2 described thermal spraying TiN layer be TiN(thing phase 1 mutually, corresponding XRD standard card number is 87-0629), and TiN
0.3(thing phase 2, corresponding standard card number is 41-1352) is for 44.5 ° of diffraction maximums of locating that show come from stainless steel substrate;
(2) stainless steel substrate that will be coated with the TiN layer through the surface heat after step (1) is handled immerses and contains 1wt%HNO
3, 0.015wt% hexamethylenetetramine and 20wt%H
2O
2Solution in, constant temperature was placed 10 hours under 600 ℃ condition, it was taken out dry, insulation 0.5h gets final product under 400 ℃ of conditions again.
Described in the present embodiment be the TiO that substrate heat spraying TiN stratification processing converted in-situ obtains with the stainless steel
2The field emission scanning electron microscope photo of nano thread structure carrier as shown in Figure 3; Described is that substrate heat spraying TiN stratification is handled the TiO that converted in-situ obtains with the stainless steel
2The X ray diffracting spectrum of nano thread structure carrier as shown in Figure 4, comparison diagram 2 as can be known, described nano thread structure TiO
2Be anatase titania (thing phase 1, corresponding XRD standard card is well 21-1272).
That prepare is the nano thread structure TiO of substrate with the stainless steel with above-mentioned in the present embodiment
2For the preparation method of the denitrating catalyst of carrier is:
(1) ammonium metavanadate, ammonium tungstate and oxalic acid are dissolved in the maceration extract that is configured to contain 0.018wt% ammonium metavanadate, 0.12wt% ammonium tungstate and 0.02wt% oxalic acid in the deionized water;
(2) carrier for preparing in the present embodiment is immersed in the described maceration extract, again described solution is placed in the heater, constant temperature is placed 72h under 80 ℃ of conditions, described carrier is taken out dry, then described carrier is incubated 0.5h under 500 ℃ of conditions, promptly obtaining described is the nano thread structure TiO of substrate with the stainless steel
2Denitrating catalyst for carrier.The field emission scanning electron microscope photo of the described denitrating catalyst of present embodiment can be seen the precipitation of some active components as shown in Figure 5 from figure.
Embodiment 2
The preparation method of the carrier of the denitration activity of load described in present embodiment component is:
(1) be consutrode with pure titanium silk, carry out electric arc spraying in air atmosphere, at the surface heat spraying TiN of described iron substrate layer, the thickness of described TiN layer is 0.1mm;
The substrate that (1 ＇) is coated with the TiN layer with described surface heat immerses in 60 ℃ the mixed acid to be placed 4 minutes, took out water and washed, and carried out drying after rinsing well;
Described mixed acid is the mixed liquor of hydrofluoric acid, red fuming nitric acid (RFNA) and deionized water, wherein said hydrofluoric acid account for described mixed acid gross mass 4%, described red fuming nitric acid (RFNA) accounts for 18% of described mixed acid gross mass;
(2) substrate that will be coated with the TiN layer through the surface heat after step (1) is handled immerses and contains 0.8wt%HNO
3, 0.01wt% hexamethylenetetramine and 20wt%H
2O
2Solution in, constant temperature was placed 10 hours under 60 ℃ condition, it was taken out dry, insulation 1h gets final product under 400 ℃ of conditions again.
In the present embodiment be based on the above-mentioned preparation method who prepares the denitrating catalyst of carrier:
(1) ammonium metavanadate, ammonium tungstate and oxalic acid are dissolved in the maceration extract that is configured to contain 0.018wt% ammonium metavanadate, 0.12wt% ammonium tungstate and 0.02wt% oxalic acid in the deionized water;
(2) carrier for preparing in the present embodiment is immersed in the described maceration extract, again described solution is placed in the heater, constant temperature is placed 24h under 60 ℃ of conditions, and described carrier is taken out drying, then described carrier is incubated 2h under 450 ℃ of conditions and gets final product.
Embodiment 3
The preparation method of the carrier of the denitration activity of load described in present embodiment component is:
(1) be consutrode with pure titanium silk, carry out electric arc spraying in air atmosphere, at the surface heat spraying TiN of described stainless steel substrate layer, the thickness of described TiN layer is 0.2mm;
The stainless steel substrate that (1 ＇) is coated with the TiN layer with described surface heat immerses in 80 ℃ the mixed acid to be placed 3 minutes, took out water and washed, and carried out drying after rinsing well;
Described mixed acid is the mixed liquor of hydrofluoric acid, red fuming nitric acid (RFNA) and deionized water, wherein said hydrofluoric acid account for described mixed acid gross mass 4%, described red fuming nitric acid (RFNA) accounts for 18% of described mixed acid gross mass;
(2) stainless steel substrate that will be coated with the TiN layer through the surface heat after step (1) is handled immerses and contains 1.5wt%HNO
3, 0.02wt% hexamethylenetetramine and 25wt%H
2O
2Solution in, constant temperature was placed 15 hours under 90 ℃ condition, it was taken out dry, insulation 3h gets final product under 500 ℃ of conditions again.
Preparation method in the present embodiment is in the preceding step of the surface of described stainless steel substrate being carried out blasting treatment that also comprises of described step (1).
In the present embodiment be based on the above-mentioned preparation method who prepares the denitrating catalyst of carrier:
(1) ammonium metavanadate, ammonium tungstate and oxalic acid are dissolved in the maceration extract that is configured to contain 0.02wt% ammonium metavanadate, 0.25wt% ammonium tungstate and 0.03wt% oxalic acid in the deionized water;
(2) carrier for preparing in the present embodiment is immersed in the described maceration extract, again described solution is placed in the heater, constant temperature is placed 24h under 90 ℃ of conditions, and described carrier is taken out drying, then described carrier is incubated 3h under 550 ℃ of conditions and gets final product.
Embodiment 4
The preparation method of the carrier of the denitration activity of load described in present embodiment component is:
(1) be consutrode with pure titanium silk, carry out electric arc spraying in air atmosphere, at the surface heat spraying TiN of described stainless steel substrate layer, the thickness of described TiN layer is 0.2mm;
The stainless steel substrate that (1 ＇) is coated with the TiN layer with described surface heat immerses in 60 ℃ the mixed acid to be placed 1 minute, took out water and washed, and carried out drying after rinsing well;
Described mixed acid is the mixed liquor of hydrofluoric acid, red fuming nitric acid (RFNA) and deionized water, wherein said hydrofluoric acid account for described mixed acid gross mass 6%, described red fuming nitric acid (RFNA) accounts for 25% of described mixed acid gross mass;
(2) stainless steel substrate that will be coated with the TiN layer through the surface heat after step (1) is handled immerses and contains 0.8wt%HNO
3, 0.01wt% hexamethylenetetramine and 20wt%H
2O
2Solution in, constant temperature was placed 15 hours under 60 ℃ condition, it was taken out dry, insulation 3h gets final product under 400 ℃ of conditions again.
Preparation method in the present embodiment is in the preceding step of the surface of described stainless steel substrate being carried out blasting treatment that also comprises of described step (1).
In the present embodiment be based on the above-mentioned preparation method who prepares the denitrating catalyst of carrier:
(1) ammonium metavanadate, ammonium tungstate and oxalic acid are dissolved in the maceration extract that is configured to contain 0.015wt% ammonium metavanadate, 0.15wt% ammonium tungstate and 0.01wt% oxalic acid in the deionized water;
(2) carrier for preparing in the present embodiment is immersed in the described maceration extract, again described solution is placed in the heater, constant temperature is placed 72h under 60 ℃ of conditions, and described carrier is taken out drying, then described carrier is incubated 2h under 450 ℃ of conditions and gets final product.
Embodiment 5
The preparation method of the carrier of the denitration activity of load described in present embodiment component is:
(1) be consutrode with pure titanium silk, carry out electric arc spraying in air atmosphere, at the surface heat spraying TiN of described stainless steel substrate layer, the thickness of described TiN layer is 0.1mm;
The stainless steel substrate that (1 ＇) is coated with the TiN layer with described surface heat immerses in 80 ℃ the mixed acid to be placed 3 minutes, took out water and washed, and carried out drying after rinsing well;
Described mixed acid is the mixed liquor of hydrofluoric acid, red fuming nitric acid (RFNA) and deionized water, wherein said hydrofluoric acid account for described mixed acid gross mass 4%, described red fuming nitric acid (RFNA) accounts for 18% of described mixed acid gross mass;
(2) stainless steel substrate that will be coated with the TiN layer through the surface heat after step (1) is handled immerses and contains 1.5wt%HNO
3, 0.02wt% hexamethylenetetramine and 25wt%H
2O
2Solution in, constant temperature was placed 10 hours under 90 ℃ condition, it was taken out dry, insulation 1h gets final product under 500 ℃ of conditions again.
Preparation method in the present embodiment is in the preceding step of the surface of described stainless steel substrate being carried out blasting treatment that also comprises of described step (1).
In the present embodiment be based on the above-mentioned preparation method who prepares the denitrating catalyst of carrier:
(1) ammonium metavanadate, ammonium tungstate and oxalic acid are dissolved in the maceration extract that is configured to contain 0.02wt% ammonium metavanadate, 0.25wt% ammonium tungstate and 0.03wt% oxalic acid in the deionized water;
(2) carrier for preparing in the present embodiment is immersed in the described maceration extract, again described solution is placed in the heater, constant temperature is placed 72h under 90 ℃ of conditions, and described carrier is taken out drying, then described carrier is incubated 2h under 550 ℃ of conditions and gets final product.
Embodiment 6
The preparation method of the carrier of the denitration activity of load described in present embodiment component is:
(1) be consutrode with pure titanium silk, carry out electric arc spraying in air atmosphere, at the surface heat spraying TiN of described stainless steel substrate layer, the thickness of described TiN layer is 0.2mm;
The stainless steel substrate that (1 ＇) is coated with the TiN layer with described surface heat immerses in 80 ℃ the mixed acid to be placed 3 minutes, took out water and washed, and carried out drying after rinsing well;
Described mixed acid is the mixed liquor of hydrofluoric acid, red fuming nitric acid (RFNA) and deionized water, wherein said hydrofluoric acid account for described mixed acid gross mass 5%, described red fuming nitric acid (RFNA) accounts for 20% of described mixed acid gross mass;
(2) stainless steel substrate that will be coated with the TiN layer through the surface heat after step (1) is handled immerses and contains 1.5wt%HNO
3, 0.02wt% hexamethylenetetramine and 25wt%H
2O
2Solution in, constant temperature was placed 12 hours under 80 ℃ condition, it was taken out dry, insulation 5h gets final product under 500 ℃ of conditions again.
Preparation method in the present embodiment is in the preceding step of the surface of described stainless steel substrate being carried out blasting treatment that also comprises of described step (1).
In the present embodiment be based on the above-mentioned preparation method who prepares the denitrating catalyst of carrier:
That prepare is the nano thread structure TiO of substrate with the stainless steel with above-mentioned in the present embodiment
2For the preparation method of the denitrating catalyst of carrier is:
(1) ammonium metavanadate, ammonium tungstate and oxalic acid are dissolved in the maceration extract that is configured to contain 0.02wt% ammonium metavanadate, 0.25wt% ammonium tungstate and 0.03wt% oxalic acid in the deionized water;
(2) carrier for preparing in the present embodiment is immersed in the described maceration extract, again described solution is placed in the heater, constant temperature is placed 72h under 80 ℃ of conditions, and described carrier is taken out drying, then described carrier is incubated 2h under 500 ℃ of conditions and gets final product.
Embodiment 7
The preparation method of the carrier of the denitration activity of load described in present embodiment component is:
(1) be consutrode with pure titanium silk, carry out electric arc spraying in air atmosphere, at the surface heat spraying TiN of described stainless steel substrate layer, the thickness of described TiN layer is 0.2mm;
The stainless steel substrate that (1 ＇) is coated with the TiN layer with described surface heat immerses in 80 ℃ the mixed acid to be placed 2 minutes, took out water and washed, and carried out drying after rinsing well;
Described mixed acid is the mixed liquor of hydrofluoric acid, red fuming nitric acid (RFNA) and deionized water, wherein said hydrofluoric acid account for described mixed acid gross mass 4%, described red fuming nitric acid (RFNA) accounts for 18% of described mixed acid gross mass;
(2) stainless steel substrate that will be coated with the TiN layer through the surface heat after step (1) is handled immerses and contains 0.8wt%HNO
3, 0.01wt% hexamethylenetetramine and 20wt%H
2O
2Solution in, constant temperature was placed 12 hours under 80 ℃ condition, it was taken out dry, insulation 1h gets final product under 450 ℃ of conditions again.
Preparation method in the present embodiment is in the preceding step of the surface of described stainless steel substrate being carried out blasting treatment that also comprises of described step (1).
In the present embodiment be based on the above-mentioned preparation method who prepares the denitrating catalyst of carrier:
(1) ammonium metavanadate, ammonium tungstate and oxalic acid are dissolved in the maceration extract that is configured to contain 0.015wt% ammonium metavanadate, 0.15wt% ammonium tungstate and 0.01wt% oxalic acid in the deionized water, at the rare earth element that in described maceration extract, adds 0.1 wt %, described rare earth element is an erbium, as selectable embodiment, also can be other any one rare earth elements; Addition to described rare earth element among the present invention does not have particular determination, but considers the cost factor of rare earth element, and the addition of rare earth element described in the present invention is preferably 0.1-0.4 wt %.
(2) carrier for preparing in the present embodiment is immersed in the described maceration extract, again described solution is placed in the heater, constant temperature is placed 72h under 80 ℃ of conditions, and described carrier is taken out drying, then described carrier is incubated 5h under 500 ℃ of conditions and gets final product.
As selectable embodiment, the described stainless steel substrate in the foregoing description can be an arbitrary shape, can be set to plane or corrugated surface as the surface of described stainless steel substrate preferred embodiment, as shown in Figure 6.Why being arranged to plane or corrugated surface, is to consider when practical application, and the form that described catalyst normally replaces mutually with tabular and corrugated layer is placed.This setup makes and leaves the space between described catalyst layer and the layer, helps the carrying out of denitrating flue gas reaction.
In the above-described embodiments, carry out in the step of blasting treatment on the surface that described step (1) is preceding described stainless steel substrate, described blasting treatment can be adopted the suitable abrasive material of any granularity, but in order to obtain best roughness, doing the preferred employing of invention granularity is 100-200 purpose emergy.
In the foregoing description, described is the nano thread structure TiO of substrate with the corrosion resistant plate
2The preparation method in, baking temperature in step (3) and the step (4) can be to be lower than 200 degrees centigrade arbitrary temp, as preferred embodiment, described baking temperature can be arranged to the arbitrary temp between 120-150 ℃, equally, among the preparation method of described denitrating catalyst, the preparation temperature in the step (2) also can be set to be lower than 200 degrees centigrade arbitrary temp, and further preferably is set to the arbitrary temp between 120-150 ℃.
The denitration effect experimental example of denitrating catalyst of the present invention
In order to further specify the denitration effect of denitrating catalyst of the present invention, the present invention has designed a denitration test macro and has simulated following flue gas condition:
Temperature: 250 ℃;
NO in the flue gas
xConcentration: 640ppm;
NH
3: NO
xConcentration ratio be 1:1
O
2Concentration: 5.5%
Carrier gas N
2Flow velocity is 2L/min;
A kind of denitrating catalyst for preparing among above-mentioned each embodiment is replaced the form of arranging with 11 tabulars and 12 corrugated form one group, in described denitration test macro, put into 3 groups, test the NO of every kind of denitrating catalyst
xRemoval efficiency obtains following result:
Comparative example
Comparative example is selected for use with nano-porous structure TiO
2For the denitrating catalyst of carrier carries out the denitration experiment, identical in the placement form of flue gas condition and described catalyst and the above-mentioned experimental example, the NO that finally obtains
xRemoval efficiency is 86%.
From above-mentioned experimental result as can be seen, adopt with nano-porous structure TiO
2For the denitrating catalyst of carrier carries out denitration experiment, its NO
xRemoval efficiency is 86%, is lower than the denitration efficiency of the denitrating catalyst described in the experimental example.See the nano thread structure TiO described in the present invention thus
2For the denitrating catalyst of carrier than catalyst of the prior art, have higher denitration efficiency, so the technical scheme described in the present invention has tangible technique effect than prior art.
Though the present invention elaborates it by the specific embodiment; but; the any form that does not exceed the claim protection domain that those skilled in the art should be understood that on this basis to be made and the variation of details all belong to invention which is intended to be protected.
Claims (16)
1. carrier that is used for load denitration activity component, described carrier comprise stainless steel substrate and attached to the nano thread structure TiO on described stainless steel substrate surface
2
2. the preparation method of carrier according to claim 1 comprises:
(1) is consutrode with pure titanium silk, in air atmosphere, carries out electric arc spraying,, obtain the substrate that surface heat is coated with the TiN layer at the surface heat spraying TiN of described stainless steel substrate layer;
(2) stainless steel substrate that will be coated with the TiN layer through the surface heat after step (1) is handled immerses and contains 0.8-1.5wt%HNO
3, 0.01-0.02wt% hexamethylenetetramine and 20-25wt%H
2O
2Solution in, constant temperature was placed 10-15 hour under 60-90 ℃ condition, it was taken out dry, insulation is handled and is got final product under 400-500 ℃ of condition again.
3. preparation method according to claim 2 is characterized in that, the thickness of described thermal spraying TiN layer is 0.1-0.2mm.
4. the preparation method of carrier according to claim 2 is characterized in that, in the preceding step of the surface of described stainless steel substrate being carried out blasting treatment that also comprises of described step (1).
5. preparation method according to claim 4 is characterized in that, it is 100-200 purpose emergy that granularity is adopted in described blasting treatment.
6. according to the preparation method of claim 2 or 4 described carriers, it is characterized in that, between described step (1) and (2), also comprise step (1 ＇):
The stainless steel substrate that described surface heat is coated with the TiN layer immerses to place in 60-80 ℃ the mixed acid to be handled, and takes out water and washes, and carries out drying after rinsing well;
Described mixed acid is the mixed liquor of hydrofluoric acid, red fuming nitric acid (RFNA) and deionized water, and wherein said hydrofluoric acid accounts for the 18-25% that the 4-6% of described mixed acid gross mass, described red fuming nitric acid (RFNA) account for described mixed acid gross mass.
7. preparation method according to claim 6 is characterized in that, the baking temperature in described step (1 ＇) and the step (2) is 120-150 ℃.
8. according to claim 6 or 7 described preparation methods, it is characterized in that the stainless steel substrate that in the described step (1 ＇) described surface heat is coated with the TiN layer immerses that to place the time of handling in 60-80 ℃ the mixed acid be 1-3 minute.
9. preparation method according to claim 2 is characterized in that, the time that insulation is handled in the described step (2) is 1-5h.
10. a denitrating catalyst is characterized in that, the load on the described carrier of claim 1 of described denitrating catalyst has active component.
11. denitrating catalyst according to claim 10 is characterized in that, described active component is nanometer V
2O
5And WO
3
12. denitrating catalyst according to claim 11 is characterized in that, described active component also comprises rare earth element.
13. the preparation method of the denitrating catalyst described in claim 10 or 11 or 12 comprises:
(1) ammonium metavanadate, ammonium tungstate and oxalic acid are dissolved in the maceration extract that is configured to contain 0.015-0.02wt% ammonium metavanadate, 0.15-0.25wt% ammonium tungstate and 0.01-0.03wt% oxalic acid in the deionized water;
(2) described carrier is immersed in the described maceration extract, constant temperature is placed 24-72h under 60-90 ℃ of condition, and described carrier is taken out drying, then described carrier is incubated to handle under 450-550 ℃ of condition to get final product.
14. the preparation method according to the denitrating catalyst described in the claim 13 is characterized in that, the baking temperature in the described step (2) is 120-150 ℃.
15. the preparation method according to the denitrating catalyst described in the claim 13 is characterized in that, in the described step (1), also comprises the step that adds rare earth element in described maceration extract.
16. the preparation method according to the denitrating catalyst described in the claim 13 is characterized in that, the insulation processing time is 1-5h described in the described step (2).
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| CN107537465A (en) * | 2017-09-25 | 2018-01-05 | 长沙理工大学 | A kind of denitrating catalyst component and preparation method thereof |
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| CN115672299B (en) * | 2021-07-30 | 2024-04-30 | 国家能源投资集团有限责任公司 | Titanium dioxide nanowire and preparation method thereof, denitration catalyst and preparation method thereof, and flue gas denitration method |
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