CN102814175B - Preparation method of denitrifying catalyst - Google Patents
Preparation method of denitrifying catalyst Download PDFInfo
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- CN102814175B CN102814175B CN201210341828.4A CN201210341828A CN102814175B CN 102814175 B CN102814175 B CN 102814175B CN 201210341828 A CN201210341828 A CN 201210341828A CN 102814175 B CN102814175 B CN 102814175B
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Abstract
The invention discloses a preparation method of a catalyst, particularly a preparation method of a denitrifying catalyst applicable to selective catalytic reduction flue gas denitrification technique, which comprises the following steps: A. grinding titaniferous furnace slag, and carrying out magnetic separation to remove iron; B. adding the titaniferous furnace slag into hydrochloric acid, leaching, filtering, and washing the obtained filter residue with water; C. adding the filter residue into a sodium hydroxide solution to react, filtering, washing the obtained filter residue with water, carrying out immersion cleaning with hydrochloric acid, washing with water, drying, and grinding to obtain a titanium dioxide particle raw material; D. dissolving ammonium paratungstate in water, adding oxalic acid, immersing the titanium dioxide particle raw material in the solution, drying by distillation to remove water, and calcining to obtain a WO3-surface-supported TiO2 supporter; and E. dissolving ammonium metavanadate in water, adding oxalic acid, immersing the WO3-surface-supported TiO2 supporter in the solution, drying by distillation to remove water, and calcining to obtain the denitrifying catalyst. The invention can effectively enhance the activity of the denitrifying catalyst, thereby lowering the reaction temperature of oxynitride and ammonia gas.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, be specifically related to a kind of preparation method of the denitrating catalyst for selective catalytic reduction flue gas denitration technology.
Background technology
Denitrating catalyst is that to be applied in power plant be NH for ammonia SCR to a kind of general reference
3a kind of catalyst in-SCR denitration technology, it can reduce the reaction temperature of nitrogen oxide and ammonia, thereby makes the nitrogen oxide in flue gas be easy to be reduced into nitrogen by ammonia, thereby reduces the discharge of nitrogen oxide, reduce the pollution of nitrogen oxide to atmosphere, thereby reduce the harm of acid rain.
Theoretically, in the situation that not adding any catalyst, the reaction temperature of nitrogen oxide and ammonia is 900 ℃ of left and right, and in flue gas, contained nitrogen oxide main component is nitric oxide and nitrogen dioxide, and it is as follows with the reaction equation of ammonia respectively,
4NO+4NH
3+O
2＝4N
2+6H
2O
6NO
2+8NH
3=7N
2+12H
2O
From above formula, no matter be nitric oxide or nitrogen dioxide, after itself and ammonia gas react, all can generate the nitrogen G&W that contaminative is less.But above-mentioned reaction, because the condition of reaction own is harsher, needs the hot conditions of 900 ℃ just can carry out, therefore, existing NH
3in-SCR denitration technology, often can use a kind of denitrating catalyst, it can reduce the temperature that above-mentioned reaction needed is carried out, thereby reduces the difficulty of reaction condition.
Initial denitrating catalyst be with ceramic materials such as aluminium oxide as carrier, add the noble metals such as Pt or Pt-Rh as catalyst activity composition; This denitrating catalyst the earliest has higher activity, can make the reaction temperature of nitrogen oxide and ammonia lower, but because the cost of noble metal is higher, thereby limited the extensive use of this kind of denitrating catalyst.
The most frequently used denitrating catalyst is with titanium dioxide TiO at present
2for carrier, by V
2o
5(WO
3), Fe
2o
3, MgO, MoO
3deng metal oxide or a symphyogenetic mixture, mix with carrier, thereby obtain existing the most conventional denitrating catalyst.This denitrating catalyst cost is lower, its active denitrating catalyst not as precious metal, it can reduce, and the reaction temperature of nitrogen oxide and ammonia is minimum is only 320 ℃, although so its cost lower, but its activity is not ideal especially.
In addition, the mode that existing direct use titanium dioxide raw material is prepared denitrating catalyst makes cost higher to a certain extent; And in existing many steel plant, in the process of metal smelting iron, can produce a kind of slag that contains substantial amount titanium resource, this slag is generally directly as waste product, to sell, and for the titanium resource being wherein rich in, is a kind of larger waste.
Summary of the invention
In view of this, the invention provides a kind of preparation method of denitrating catalyst, it not only can improve the activity of prepared denitrating catalyst effectively, thereby reduces better the reaction temperature of nitrogen oxide and ammonia; It can also utilize fully to the titanium resource in slag, thereby reduces the waste of titanium resource, and further the cost of denitrating catalyst is prepared in reduction.
For solving above technical problem, technical scheme of the present invention adopts a kind of preparation method of denitrating catalyst, and the preparation method of described denitrating catalyst comprises the steps:
A, Ti-containing slag is ground to 150-170 order, iron removal by magnetic separation;
B, by gained Ti-containing slag in A step, by solid-liquid mass ratio, be the hydrochloric acid that 1:1.5-2.5 adds 15%-25%, filter then gained filter residue washing leach 3.0-4.0 hour at 90-100 ℃ after;
C, by gained filter residue in B step, according to solid-liquid mass ratio, be the sodium hydrate aqueous solution that 1:1.0-1.5 adds 45%-55%, at 90-100 ℃, react after 2-3 hour and filter, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material;
D, ammonium paratungstate is soluble in water, then add oxalic acid to regulate its pH value for 3-4, the ratio that in C step, gained titanium dioxide granule raw material is 15-20:1 according to the mass ratio with ammonium paratungstate is immersed in solution, and evaporating water obtains area load WO at 500-600 ℃ after calcining
3tiO
2carrier;
E, ammonium metavanadate is soluble in water, then adds oxalic acid to regulate its pH value for 3-4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15-20:1 according to the mass ratio with ammonium metavanadate immerses in solution, and evaporating water obtains denitrating catalyst at 500-600 ℃ after calcining.
Preferably, described A step is that Ti-containing slag is ground to iron removal by magnetic separation after 160 orders.
Preferably, described B step is for being the hydrochloric acid solution that 1:2 adds 15%-20% by gained Ti-containing slag in A step by solid-liquid mass ratio, filters then gained filter residue washing at 95-100 ℃ after leaching 3.0-4.0 hour.
Preferably, described B step is for being that 1:2 adds 20% hydrochloric acid solution by gained Ti-containing slag in A step by solid-liquid mass ratio, filters then gained filter residue washing at 100 ℃ after leaching 3.0-4.0 hour.
Preferably, described C step is is the sodium hydrate aqueous solution that 1:1.0-1.5 adds 45%-50% by gained filter residue in B step by solid-liquid mass ratio, at 95-100 ℃, react after 2-3 hour and filter, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material.
Preferably, described C step is is that 1:1.3-1.5 adds 50% sodium hydrate aqueous solution by gained filter residue in B step by solid-liquid mass ratio, at 100 ℃, react after 2-3 hour and to filter, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain the granularity titanium dioxide granule raw material that is 0.1mm to 0.05mm.
Preferably, described D step is for to be dissolved in ammonium paratungstate in deionized water, then add oxalic acid to regulate its pH value for 3.5-4, the ratio that in C step, gained titanium dioxide granule raw material is 15-18:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 500-600 ℃ after calcining
3tiO
2carrier.
Preferably, described D step is for to be dissolved in ammonium paratungstate in deionized water, then adding oxalic acid to regulate its pH value is 3.5, the ratio that in C step, gained titanium dioxide granule raw material is 18:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 550 ℃ after calcining
3tiO
2carrier.
Preferably, described E step, for ammonium metavanadate is dissolved in deionized water, then adds oxalic acid to regulate its pH value for 3.5-4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15-18:1 according to the mass ratio with ammonium metavanadate immerses in solution, and evaporating water obtains denitrating catalyst at 500-600 ℃ after calcining.
Preferably, described E step is for to be dissolved in ammonium metavanadate in deionized water, and then adding oxalic acid to regulate its pH value is 3.5, by gained area load WO in D step
3tiO
2the ratio that carrier is 15:1 according to the mass ratio with ammonium metavanadate immerses in solution, and evaporating water obtains denitrating catalyst at 600 ℃ after calcining.
Compared with prior art, the preparation method's of denitrating catalyst of the present invention principle is as follows:
The preparation method of described denitrating catalyst comprises the steps:
A, Ti-containing slag is ground to 150-170 order, iron removal by magnetic separation;
B, by gained Ti-containing slag in A step, by solid-liquid mass ratio, be the hydrochloric acid that 1:1.5-2.5 adds 15%-25%, filter then gained filter residue washing leach 3.0-4.0 hour at 90-100 ℃ after;
C, by gained filter residue in B step, according to solid-liquid mass ratio, be the sodium hydrate aqueous solution that 1:1.0-1.5 adds 45%-55%, at 90-100 ℃, react after 2-3 hour and filter, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material;
D, ammonium paratungstate is soluble in water, then add oxalic acid to regulate its pH value for 3-4, the ratio that in C step, gained titanium dioxide granule raw material is 15-20:1 according to the mass ratio with ammonium paratungstate is immersed in solution, and evaporating water obtains area load WO at 500-600 ℃ after calcining
3tiO
2carrier;
E, ammonium metavanadate is soluble in water, then adds oxalic acid to regulate its pH value for 3-4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15-20:1 according to the mass ratio with ammonium metavanadate immerses in solution, and evaporating water obtains denitrating catalyst at 500-600 ℃ after calcining.
In the preparation method of denitrating catalyst of the present invention, adopt the raw material using Ti-containing slag as initial extraction titanium dioxide, in existing Ti-containing slag owing to containing metal or the nonmetallic inclusions such as a certain amount of iron, magnesium, aluminium, silicon, it can produce certain toxicity to the denitrating catalyst preparing, therefore, in the preparation method of denitrating catalyst of the present invention, first need to remove most of metal or the nonmetallic inclusion in Ti-containing slag, adopt A of the present invention, B and C step.
Utilize the more existing common titanium dioxide granule raw material of titanium dioxide granule raw material that in the preparation method who prepares denitrating catalyst of the present invention, A, B, C step obtain to there is porousness better, spatial joint clearance between described titania molecule is larger, so the material that its surface can be adhered to just can have larger molecular structure.
In preparation method due to denitrating catalyst of the present invention, adopted that Ti-containing slag is this to be easy to get and raw material that price is comparatively cheap extracts the mode of titanium dioxide granule raw material, it has not only avoided the waste of titanium resource in Ti-containing slag, but also greatly reduces the existing production cost of preparing denitrating catalyst.
In the preparation method of denitrating catalyst of the present invention in D step and E step respectively by the first load WO in ammonium paratungstate and oxalic acid solution of gained titanium dioxide granule raw material
3, and then in ammonium metavanadate and oxalic acid solution supported V
2o
5after denitrating catalyst of the present invention; The present invention utilizes above-mentioned at titanium dioxide surface layering load WO
3and V
2o
5mode can be so that gained denitrating catalyst activity degree of the present invention be higher, thereby reduce better the reaction temperature of nitrogen oxides in effluent and ammonia, making its active temperature interval can be 200-420 ℃.
In the preparation method who prepares denitrating catalyst of the present invention, adopt gained titanium dioxide granule raw material in C step is successively carried out to load WO
3and V
2o
5mode, WO in gained denitrating catalyst
3and V
2o
5layering loads on titanium dioxide, will make like this it under the flue gas environment of the existence such as oxysulfide, water vapour, have good stability, reduces the poisoning situation of denitrating catalyst of the present invention.
Further, preferably to adopt described A step be that Ti-containing slag is ground to iron removal by magnetic separation after 160 orders to the preparation method of denitrating catalyst of the present invention.A step described in the preparation method of denitrating catalyst of the present invention is for to be ground to 150-170 order by Ti-containing slag, the mode of iron removal by magnetic separation; When Ti-containing slag being ground to higher than 170 order, meticulous degree of grinding can not increase the purity after its removal of impurities significantly; When Ti-containing slag being ground to lower than 150 order, excessively thick degree of grinding can make its follow-up impurity-eliminating effect not ideal enough.Given this, in A step of the present invention, Ti-containing slag is ground to iron removal by magnetic separation after 150-170 order; Further, the present invention preferably adopts described A step for Ti-containing slag being ground to iron removal by magnetic separation after 160 orders.
: 1.5-2.5 adds the hydrochloric acid of 15%-25% to B step described in the preparation method of denitrating catalyst of the present invention in order being 1 by gained Ti-containing slag in A step by solid-liquid mass ratio, filters then gained filter residue washing at 90-100 ℃ after leaching 3.0-4.0 hour.First the preparation method of denitrating catalyst of the present invention carries out the Ti-containing slag after grinding the mode of pickling after washing, and this mode can be removed in Ti-containing slag the metal impurities such as most iron, magnesium and aluminium preferably;
In addition, the filtrate that the present invention obtains Ti-containing slag pickling by filtration can be utilized the separated metal hydroxides such as iron hydroxide, magnesium hydroxide and aluminium hydroxide that obtain under the effect of hydrogen peroxide and ammonium chloride.
The present invention adopts the hydrochloric acid that the ratio that in A step, gained Ti-containing slag is 1:1.5-2.5 in solid-liquid mass ratio is added to 15%-25%, filters the mode of gained filter residue washing at 90-100 ℃ after leaching 3.0-4.0 hour; Further, the present invention can be preferably and adopt is the hydrochloric acid solution that 1:2 adds 15%-20% by gained Ti-containing slag in A step by solid-liquid mass ratio, filters after leaching 3.0-4.0 hour, then the embodiment of gained filter residue washing at 95-100 ℃; Preferred, it is that 1:2 adds 20% hydrochloric acid solution by solid-liquid mass ratio that described B step is preferably adopted as gained Ti-containing slag in A step, filters then gained filter residue washing at 100 ℃ after leaching 3.0-4.0 hour.
C step described in the preparation method of denitrating catalyst of the present invention is is the sodium hydrate aqueous solution that 1:1.0-1.5 adds 45%-55% by gained filter residue in B step according to solid-liquid mass ratio, at 90-100 ℃, react after 2-3 hour and filter, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material; The present invention adopts above-mentioned embodiment can remove most of nonmetallic inclusion contained in Ti-containing slag as silicon etc., the existence of this nonmetallic inclusion can affect the activity of the final gained denitrating catalyst of the present invention, so C step of the present invention has adopted alkali cleaning, washing, hydrochloric acid to embathe, wash the mode of post-drying grinding.
Preferred, it is the sodium hydrate aqueous solution that 1:1.0-1.5 adds 45%-50% by solid-liquid mass ratio that C step of the present invention is preferably adopted as gained filter residue in B step, at 95-100 ℃, react after 2-3 hour and filter, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material.
Preferred, it is that 1:1.3-1.5 adds 50% sodium hydrate aqueous solution by solid-liquid mass ratio that C step of the present invention is preferably adopted as gained filter residue in B step, at 100 ℃, react after 2-3 hour and to filter, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain the granularity titanium dioxide granule raw material that is 0.1mm to 0.05mm.
After A of the present invention, B, C tri-steps, in gained titanium dioxide granule raw material, the amount of contained titanium dioxide is more than 90%, and it can be used as the base stock of preparing denitrating catalyst completely.
D step of the present invention is that ammonium paratungstate is soluble in water, then add oxalic acid to regulate its pH value for 3-4, the ratio that in C step, gained titanium dioxide granule raw material is 15-20:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 500-600 ℃ after calcining
3tiO
2carrier; The present invention adopts the aforesaid way can be so that titanium dioxide granule raw material during as carrier, and its surface can be adhered to more WO as much as possible
3thereby, improve the activity of gained denitrating catalyst of the present invention.
Preferred, the present invention preferably adopts described D step for ammonium paratungstate is dissolved in deionized water, then add oxalic acid to regulate its pH value for 3.5-4, the ratio that in C step, gained titanium dioxide granule raw material is 15-18:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 500-600 ℃ after calcining
3tiO
2carrier.
Preferred, the present invention preferably adopts described D step for ammonium paratungstate is dissolved in deionized water, then adding oxalic acid to regulate its pH value is 3.5, the ratio that in C step, gained titanium dioxide granule raw material is 18:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 550 ℃ after calcining
3tiO
2carrier.
E step of the present invention is that ammonium metavanadate is soluble in water, then adds oxalic acid to regulate its pH value for 3-4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15-20:1 according to the mass ratio with ammonium metavanadate immerses in solution, and evaporating water obtains denitrating catalyst at 500-600 ℃ after calcining.The present invention adopts the aforesaid way can be so that load WO
3tiO
2the surface of carrier can be adhered to more V as much as possible
2o
5thereby, improve the activity of gained denitrating catalyst of the present invention.
Preferred, the present invention preferably adopts described E step for ammonium metavanadate is dissolved in deionized water, then adds oxalic acid to regulate its pH value for 3.5-4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15-18:1 according to the mass ratio with ammonium metavanadate immerses in solution, and evaporating water obtains denitrating catalyst at 500-600 ℃ after calcining.
Preferred, the present invention preferably adopts described E step for ammonium metavanadate is dissolved in deionized water, and then adding oxalic acid to regulate its pH value is 3.5, by gained area load WO in D step
3tiO
2the ratio that carrier is 15:1 according to the mass ratio with ammonium metavanadate immerses in solution, and evaporating water obtains denitrating catalyst at 600 ℃ after calcining.
The specific embodiment
In order to make those skilled in the art understand better technical scheme of the present invention, below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
A, Ti-containing slag is ground to 170 orders, iron removal by magnetic separation;
B, by gained Ti-containing slag in A step, by solid-liquid mass ratio, be that 1:1.5 adds 25% hydrochloric acid, filter then gained filter residue washing leach 4.0 hours at 90 ℃ after;
C, by gained filter residue in B step, according to solid-liquid mass ratio, be to add 45% sodium hydroxide solution at 1: 1.0, react after 2 hours and filter at 90 ℃, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material;
D, ammonium paratungstate is soluble in water, then adding oxalic acid to regulate its pH value is 3, and the ratio that in C step, gained titanium dioxide granule raw material is 20:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 500 ℃ after calcining
3tiO
2carrier;
E, ammonium metavanadate is soluble in water, then adding oxalic acid to regulate its pH value is 3, by gained area load WO in D step
3tiO
2the ratio that carrier is 20:1 according to the mass ratio with ammonium metavanadate immerses in solution, evaporating water, and at 500 ℃, after calcining, obtaining denitrating catalyst is embodiment 1.
Embodiment 2
A, Ti-containing slag is ground to 150 orders, iron removal by magnetic separation;
B, by gained Ti-containing slag in A step, by solid-liquid mass ratio, be that 1:2.5 adds 15% hydrochloric acid, filter then gained filter residue washing leach 3.0 hours at 100 ℃ after;
C, by gained filter residue in B step, according to solid-liquid mass ratio, be that 1:1.5 adds 55% sodium hydroxide solution, react after 3 hours and filter at 100 ℃, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material;
D, ammonium paratungstate is soluble in water, then adding oxalic acid to regulate its pH value is 4, and the ratio that in C step, gained titanium dioxide granule raw material is 15:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 600 ℃ after calcining
3tiO
2carrier;
E, ammonium metavanadate is soluble in water, then adding oxalic acid to regulate its pH value is 4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15:1 according to the mass ratio with ammonium metavanadate immerses in solution, evaporating water, and at 600 ℃, after calcining, obtaining denitrating catalyst is embodiment 2.
Embodiment 3
A, Ti-containing slag is ground to 160 orders, iron removal by magnetic separation;
B, by gained Ti-containing slag in A step, by solid-liquid mass ratio, be that 1:2 adds 25% hydrochloric acid, filter then gained filter residue washing leach 4.0 hours at 90 ℃ after;
C, by gained filter residue in B step, according to solid-liquid mass ratio, be to add 55% sodium hydroxide solution at 1: 1.5, react after 3 hours and filter at 100 ℃, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material;
D, ammonium paratungstate is soluble in water, then adding oxalic acid to regulate its pH value is 4, and the ratio that in C step, gained titanium dioxide granule raw material is 15:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 600 ℃ after calcining
3tiO
2carrier;
E, ammonium metavanadate is soluble in water, then adding oxalic acid to regulate its pH value is 4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15:1 according to the mass ratio with ammonium metavanadate immerses in solution, evaporating water, and at 600 ℃, after calcining, obtaining denitrating catalyst is embodiment 3.
Embodiment 4
A, Ti-containing slag is ground to 160 orders, iron removal by magnetic separation;
B, by gained Ti-containing slag in A step, by solid-liquid mass ratio, be that 1:2 adds 20% hydrochloric acid, filter then gained filter residue washing leach 4.0 hours at 100 ℃ after;
C, by gained filter residue in B step, according to solid-liquid mass ratio, be to add 55% sodium hydroxide solution at 1: 1.5, react after 3 hours and filter at 100 ℃, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material;
D, ammonium paratungstate is soluble in water, then adding oxalic acid to regulate its pH value is 4, and the ratio that in C step, gained titanium dioxide granule raw material is 15:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 600 ℃ after calcining
3tiO
2carrier;
E, ammonium metavanadate is soluble in water, then adding oxalic acid to regulate its pH value is 4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15:1 according to the mass ratio with ammonium metavanadate immerses in solution, evaporating water, and at 600 ℃, after calcining, obtaining denitrating catalyst is embodiment 4.
Embodiment 5
A, Ti-containing slag is ground to 160 orders, iron removal by magnetic separation;
B, by gained Ti-containing slag in A step, by solid-liquid mass ratio, be that 1:2 adds 20% hydrochloric acid, filter then gained filter residue washing leach 4.0 hours at 100 ℃ after;
C, by gained filter residue in B step, according to solid-liquid mass ratio, be to add 50% sodium hydroxide solution at 1: 1.3, react after 3 hours and filter at 100 ℃, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material;
D, ammonium paratungstate is soluble in water, then adding oxalic acid to regulate its pH value is 4, and the ratio that in C step, gained titanium dioxide granule raw material is 15:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 600 ℃ after calcining
3tiO
2carrier;
E, ammonium metavanadate is soluble in water, then adding oxalic acid to regulate its pH value is 4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15:1 according to the mass ratio with ammonium metavanadate immerses in solution, evaporating water, and at 600 ℃, after calcining, obtaining denitrating catalyst is embodiment 5.
Embodiment 6
A, Ti-containing slag is ground to 160 orders, iron removal by magnetic separation;
B, by gained Ti-containing slag in A step, by solid-liquid mass ratio, be that 1:2 adds 20% hydrochloric acid, filter then gained filter residue washing leach 4.0 hours at 100 ℃ after;
C, by gained filter residue in B step, according to solid-liquid mass ratio, be that 1:1.3 adds 50% sodium hydroxide solution, react after 3 hours and filter at 100 ℃, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material;
D, ammonium paratungstate is soluble in water, then adding oxalic acid to regulate its pH value is 3.5, the ratio that in C step, gained titanium dioxide granule raw material is 18:1 according to the mass ratio with ammonium paratungstate is immersed in solution, and evaporating water obtains area load WO at 550 ℃ after calcining
3tiO
2carrier;
E, ammonium metavanadate is soluble in water, then adding oxalic acid to regulate its pH value is 4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15:1 according to the mass ratio with ammonium metavanadate immerses in solution, evaporating water, and at 600 ℃, after calcining, obtaining denitrating catalyst is embodiment 6.
Embodiment 7
A, Ti-containing slag is ground to 160 orders, iron removal by magnetic separation;
B, by gained Ti-containing slag in A step, by solid-liquid mass ratio, be that 1:2 adds 20% hydrochloric acid, filter then gained filter residue washing leach 4.0 hours at 100 ℃ after;
C, by gained filter residue in B step, according to solid-liquid mass ratio, be to add 50% sodium hydroxide solution at 1: 1.3, react after 3 hours and filter at 100 ℃, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material;
D, ammonium paratungstate is soluble in water, then adding oxalic acid to regulate its pH value is 3.5, the ratio that in C step, gained titanium dioxide granule raw material is 18:1 according to the mass ratio with ammonium paratungstate is immersed in solution, and evaporating water obtains area load WO at 550 ℃ after calcining
3tiO
2carrier;
E, ammonium metavanadate is soluble in water, then adding oxalic acid to regulate its pH value is 3.5, by gained area load WO in D step
3tiO
2the ratio that carrier is 15:1 according to the mass ratio with ammonium metavanadate immerses in solution, evaporating water, and at 600 ℃, after calcining, obtaining denitrating catalyst is embodiment 7.
Above-mentioned gained embodiment 1-7 is carried out to the NH of flue gas respectively at 200 ℃, 250 ℃, 300 ℃ and 420 ℃ of leukemia
3-SCR denitration reaction, detects respectively the percentage that the content of its nitrogen oxide after denitrating flue gas accounts for nitrogen oxides in effluent content before denitration, and acquired results is listed in table one.
By above-mentioned gained embodiment 1-7 respectively at containing and do not contain in the flue gas of oxysulfide and/or moisture and carry out denitration at 200 ℃, in detecting after each embodiment after denitrating flue gas, the content of nitrogen oxide accounts for the percentage of nitrogen oxides in effluent content before denitration, and acquired results is listed in table two.
Table one
Table two
Below be only the preferred embodiment of the present invention, it should be pointed out that above-mentioned preferred embodiment should not be considered as limitation of the present invention, protection scope of the present invention should be as the criterion with claim limited range.For those skilled in the art, without departing from the spirit and scope of the present invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. a preparation method for denitrating catalyst, is characterized in that: the preparation method of described denitrating catalyst comprises the steps:
A, Ti-containing slag is ground to 150-170 order, iron removal by magnetic separation;
B, by gained Ti-containing slag in A step, by solid-liquid mass ratio, be the hydrochloric acid solution that 1:2 adds 15%-20%, filter then gained filter residue washing leach 3.0-4.0 hour at 95-100 ℃ after;
C, by gained filter residue in B step, according to solid-liquid mass ratio, be the sodium hydrate aqueous solution that 1:1.0-1.5 adds 45%-55%, at 90-100 ℃, react after 2-3 hour and filter, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material;
D, ammonium paratungstate is soluble in water, then add oxalic acid to regulate its pH value for 3-4, the ratio that in C step, gained titanium dioxide granule raw material is 15-20:1 according to the mass ratio with ammonium paratungstate is immersed in solution, and evaporating water obtains area load WO at 500-600 ℃ after calcining
3tiO
2carrier;
E, ammonium metavanadate is soluble in water, then adds oxalic acid to regulate its pH value for 3-4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15-20:1 according to the mass ratio with ammonium metavanadate immerses in solution, and evaporating water obtains denitrating catalyst at 500-600 ℃ after calcining.
2. the preparation method of denitrating catalyst according to claim 1, is characterized in that: described A step is that Ti-containing slag is ground to iron removal by magnetic separation after 160 orders.
3. the preparation method of denitrating catalyst according to claim 2, it is characterized in that: described B step is is that 1:2 adds 20% hydrochloric acid solution by gained Ti-containing slag in A step by solid-liquid mass ratio, leach 3.0-4.0 hour at 100 ℃ after, filter then gained filter residue washing.
4. the preparation method of denitrating catalyst according to claim 3, it is characterized in that: described C step is is the sodium hydrate aqueous solution that 1:1.0-1.5 adds 45%-50% by gained filter residue in B step by solid-liquid mass ratio, at 95-100 ℃, react after 2-3 hour and filter, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain titanium dioxide granule raw material.
5. the preparation method of denitrating catalyst according to claim 4, it is characterized in that: described C step is is that 1:1.3-1.5 adds 50% sodium hydrate aqueous solution by gained filter residue in B step by solid-liquid mass ratio, at 100 ℃, react after 2-3 hour and to filter, the washing of gained filter residue, hydrochloric acid embathe, wash post-drying and grinds to obtain the granularity titanium dioxide granule raw material that is 0.1mm to 0.05mm.
6. the preparation method of denitrating catalyst according to claim 5, it is characterized in that: described D step is for to be dissolved in ammonium paratungstate in deionized water, then add oxalic acid to regulate its pH value for 3.5-4, the ratio that in C step, gained titanium dioxide granule raw material is 15-18:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 500-600 ℃ after calcining
3tiO
2carrier.
7. the preparation method of denitrating catalyst according to claim 6, it is characterized in that: described D step is for to be dissolved in ammonium paratungstate in deionized water, then adding oxalic acid to regulate its pH value is 3.5, the ratio that in C step, gained titanium dioxide granule raw material is 18:1 according to the mass ratio with ammonium paratungstate is immersed in solution, evaporating water obtains area load WO at 550 ℃ after calcining
3tiO
2carrier.
8. the preparation method of denitrating catalyst according to claim 7, is characterized in that: described E step, for ammonium metavanadate is dissolved in deionized water, then adds oxalic acid to regulate its pH value for 3.5-4, by gained area load WO in D step
3tiO
2the ratio that carrier is 15-18:1 according to the mass ratio with ammonium metavanadate immerses in solution, and evaporating water obtains denitrating catalyst at 500-600 ℃ after calcining.
9. the preparation method of denitrating catalyst according to claim 8, is characterized in that: described E step is for to be dissolved in ammonium metavanadate in deionized water, and then adding oxalic acid to regulate its pH value is 3.5, by gained area load WO in D step
3tiO
2the ratio that carrier is 15:1 according to the mass ratio with ammonium metavanadate immerses in solution, and evaporating water obtains denitrating catalyst at 600 ℃ after calcining.
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| CN106732545A (en) * | 2016-12-28 | 2017-05-31 | 河北省沙河玻璃技术研究院 | A kind of SCR denitration suitable for flue gas of glass melting furnace and preparation method thereof |
| CN106944040B (en) * | 2017-03-14 | 2019-07-23 | 上海大学 | Using containing Titanium slag and the method for preparing catalyst for purification of nitrogen oxides containing manganese mud |
| CN113546689B (en) * | 2021-07-22 | 2023-10-31 | 安徽元琛环保科技股份有限公司 | Method for reducing iron content by regenerating and recovering waste SCR denitration catalyst |
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