CN109201034A - A kind of hud typed denitrating catalyst and preparation method thereof - Google Patents

A kind of hud typed denitrating catalyst and preparation method thereof Download PDF

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CN109201034A
CN109201034A CN201710545809.6A CN201710545809A CN109201034A CN 109201034 A CN109201034 A CN 109201034A CN 201710545809 A CN201710545809 A CN 201710545809A CN 109201034 A CN109201034 A CN 109201034A
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rare earth
solution
earth oxide
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tio
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陈勇
胡建锋
吴晓东
吴新谦
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Longyan Cercis Innovation Research Institute
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Abstract

The present invention provides a kind of hud typed denitrating catalyst and preparation method thereof.The denitrating catalyst by the kernel as catalyst TiO2, the rare earth oxide as the first layer shell on kernel, the shell as catalyst Sb2O5Composition；The rare earth oxide is La2O3、CeO2、PrO2It is one or more.Denitrating catalyst active component rare earth oxide prepared by the present invention is evenly distributed on carrier TiO in the form of shell2On surface, the surface of carrier can be fully utilized；Meanwhile the surface of active component is forming a Sb2O5Protective layer, avoid active component and SO2Reaction occurs poisoning or is adsorbed by sulphur ammonium salt, and the catalyst of this core-shell structure can steadily protect its active component to avoid it that sulfur poisoning occurs.

Description

A kind of hud typed denitrating catalyst and preparation method thereof
Technical field
The present invention relates to field of denitration catalyst, in particular to a kind of hud typed denitrating catalyst and preparation method thereof.
Background technique
As China's atmosphere pollutants emission standards are increasingly stringenter, various pollutants Treatment process is also evolving, Wherein, NOxSCR denitration technology in removing sulfuldioxide, which has been commercially available, to be widely applied, corresponding SCR denitration It being widely used, V-W (Mo)/Ti is the most SCR denitration of current business application, but with people's environmental pollution Attention rate raising, prepare the toxic V compound in V-W (Mo)/Ti catalyst raw material and start to be limited use, because of this person Start exploitation substitution V-W (Mo)/Ti other SCR denitrations.
More for the research of substitution V based denitration catalyst at present has molecular sieve catalyst and rare-earth base catalyst, The primary raw material molecular sieve of middle molecular sieve catalyst is expensive, the higher cost of large-scale application, thus marketing degree It is limited.And rare earth based denitration catalyst then has the condition of large-scale application, because China is a rare earth resources big country, rare earth Resource is more sufficient, is especially to represent light rare earth elements with Ce, reserves are larger, so the research of Ce based denitration catalyst is more Extensively.
It is many study found that the characteristics of Ce based denitration catalyst is that activity is good, but is easy to happen sulfur poisoning.Cause Ce base , there is two o'clock in the reason of denitrating catalyst sulfur poisoning, first is that SO2And NH3Reaction generates ammonium hydrogen sulfate and is deposited on catalyst surface, hinders Reactant has been hindered to reach the chain carrier of catalyst surface；Second is that SO2It is easy and main active substances CeO2It is anti-that chemical combination occurs Ce should be generated2(SO4)3, so that the activity decline of catalyst, generally speaking SO2It is the main reason for causing catalyst poisoning.
There is researcher that W is introduced into Ce based denitration catalyst, to improve the sulfur poisoning-resistant of catalyst, but this changes Kind effect is limited, and catalyst is having SO2And H2Still poisoning can be gradually happened under conditions of O is existed simultaneously after long-play.
For this reason, it may be necessary to provide high activity and the preferable denitrating catalyst of anti-sulfur poisonous performance.
Summary of the invention
Other than adding W, Sb also has good activity as the sulfur resistive factor.Sb element is introduced to traditional V2O5/ TiO2In catalyst, the anti-SO of catalyst is found2Poisoning performance significantly improves, this illustrates that Sb has preferable resistance to SO_2.
The present invention is implemented as follows:
A kind of hud typed denitrating catalyst, the denitrating catalyst by the kernel as catalyst TiO2, as on kernel First layer shell rare earth oxide, as catalyst shell Sb2O5Composition；The rare earth oxide is La2O3、 CeO2、PrO2It is one or more.The effect of these three components is respectively as follows: TiO2The carrier of catalyst is served as, rare earth oxide is made For the main active component of catalyst, Sb2O5It is the protective layer of catalyst.
Preferentially, above-mentioned hud typed denitrating catalyst, rare earth oxide, Sb2O5、TiO2Total catalyst weight is accounted for respectively 1%~8%, 1%~8%, 84%~98%.
Preferentially, Sb2O5Presoma include antimony acetate, hydration antimonious acid, one of Antimony pentachloride or a variety of.
Preferentially, rare earth oxide La2O3Presoma include one of lanthanum nitrate, lanthanum acetate, lanthanum sulfate or a variety of.
Preferentially, rare earth oxide CeO2Presoma include one of cerous acetate, cerous nitrate, cerous sulfate or a variety of.
Preferentially, rare earth oxide PrO2Presoma include one of praseodymium acetate, praseodymium nitrate, praseodymium sulfate or a variety of.
A kind of preparation method preparing above-mentioned hud typed denitrating catalyst, includes the following steps:
1) preparation of mixed solution: dehydrated alcohol, ammonium hydroxide and ultrapure water are uniformly mixed and are prepared into mixed solution；
Specifically, taking mass ratio is (24~72): (1~3): dehydrated alcohol, ammonium hydroxide and the ultrapure water mixing of (6~18), 10 minutes~60 minutes acquisition mixed solutions of stirring at normal temperature, wherein ammonium hydroxide is the ammonia spirit of volume fraction 20%~30%, is surpassed The resistivity of pure water reaches 18M Ω cm or more.
2) preparation of titaniferous mud paste sediment: butyl titanate and mixed solution obtained by step 1) are mixed and stirred for, Mixed solution is subjected to centrifugal treating after standing, the mixed liquor that centrifugal treating is crossed filters, and titaniferous mud is obtained after suction filtration Paste sediment；
Specifically, 6h~12h is stood after stirring 1h~6h, wherein the mass ratio of butyl titanate and mixed solution is (1 ~10): 100, after standing, mixed solution is subjected to centrifugal treating, time 12h, the mixed liquor that centrifugal treating is crossed into Row filters, and mud paste sediment is obtained after suction filtration.
3) preparation of solids containing titanium sample: titaniferous mud paste sediment obtained by step 2) is dried and is then carried out Solids containing titanium sample is made in calcining；
Specifically, it is dried in an oven, drying temperature is 80 DEG C~120 DEG C, and drying time is that 12h~for 24 hours will step Rapid 3) gained drying sample is placed in progress high-temperature calcination processing in calciner, and calcination temperature is 400 DEG C~600 DEG C, the time For 3h~5h.
4) preparation of dispersing liquid 1: being milled into powder for solids containing titanium sample, and powder is put into ultrapure water and carries out ultrasound Decentralized processing；
Specifically, calcining obtained solid sample is milled into powder, takes a certain amount of powder to be put into ultrapure water and is surpassed Sound decentralized processing, wherein the mass ratio of solid powder and ultrapure water is 1:(50~100).
5) preparation of rare earth oxide precursor solution: being made solution for the dissolution of rare earth oxide presoma ultrapure water, Hydrofluoric acid is added dropwise into rare earth oxide precursor solution according to the ratio that rare earth element/fluorine element molar ratio is 3:1, works as hydrogen After fluoric acid drips, the pH value of solution is adjusted to 8~9 with ammonium hydroxide；
Specifically, take a certain amount of rare earth oxide presoma ultrapure water dissolution that solution is made, according to rare earth element/F Molar ratio is that hydrofluoric acid is at the uniform velocity added dropwise into rare earth oxide precursor solution for the ratio of 3:1, is stirred continuously during dropwise addition Rare earth oxide precursor solution.After hydrofluoric acid drips, continue to be stirred solution, while gradually into mixed solution Ammonium hydroxide is added dropwise, adjusts the pH value of mixed solution to 8~9.
6)TiO2The preparation of@rare earth oxide mud paste sediment: to rare earth oxide precursor solution obtained by step 5) In dispersing liquid 1 obtained by step 4) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains and contains TiO2@rare earth oxide mud paste sediment；
Specifically, in adding procedure continue whipping step 6) gained mixed solution simultaneously it is heated, heating temperature 50 DEG C~80 DEG C, continue heating and stirring mixed solution 2h~4h after the completion of addition, mixed solution is stood into 6h~12h, stands knot Solution is filtered after beam, obtains mud paste sediment.
7)TiO2The preparation of@rare earth oxide core-shell structure sample: by TiO obtained by step 7)2@rare earth oxide mud paste Sediment is dried and calcination processing, obtains TiO2@rare earth oxide core-shell structure sample；
8) preparation of dispersing liquid 2: by TiO2@rare earth oxide core-shell structure sample is milled into powder, and powder is put into Ultrasonic disperse processing is carried out in ultrapure water；
Specifically, calcining obtained solid sample is milled into powder, takes a certain amount of powder to be put into ultrapure water and is surpassed Sound decentralized processing, wherein the mass ratio of solid powder and ultrapure water is 1:(50~100).
9)Sb2O5The preparation of precursor solution: by Sb2O5Solution is made in the dissolution of presoma ultrapure water, according to Sb/ fluorine member The molar ratio of element is the ratio of 3:1 to Sb2O5Hydrofluoric acid is added dropwise in precursor solution, after hydrofluoric acid drips, with ammonium hydroxide tune The pH value of solution is saved to 8~9；
Specifically, according to the ratio that Sb/ fluorine element molar ratio is 3:1 to Sb2O5Hydrogen fluorine is at the uniform velocity added dropwise in precursor solution Acid is stirred continuously Sb during dropwise addition2O5Precursor solution.After hydrofluoric acid drips, continue to be stirred solution, together When ammonium hydroxide is gradually added dropwise into mixed solution, adjust the pH value of mixed solution to 8~9.
10)TiO2@rare earth oxide/Sb2O5The preparation of mud paste sediment: to Sb obtained by step 9)2O5Precursor solution In dispersing liquid 2 obtained by step 8) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains TiO2@rare earth oxide/Sb2O5Mud paste sediment；
Specifically, in adding procedure continue whipping step 10) gained mixed solution simultaneously it is heated, heating temperature 50 DEG C~80 DEG C, continue heating and stirring mixed solution 2h~4h after the completion of addition, mixed solution is stood into 6h~12h, stands knot Solution is filtered after beam, obtains mud paste sediment.
11)TiO2@rare earth oxide/Sb2O5The preparation of hud typed denitrating catalyst: step 10) gained sediment is carried out Drying and calcination processing, i.e. acquisition TiO2@rare earth oxide/Sb2O5Hud typed denitrating catalyst.
Specifically, step 11) gained sediment is dried and calcination processing, the method and step 3) of drying and calcination Identical with the content of step 4), calcining is completed to obtain TiO2@rare earth oxide/Sb2O5Hud typed denitrating catalyst.
Preferably, the preparation method of above-mentioned hud typed denitrating catalyst, its resistance of ultrapure water used in the step Rate is more than 18M Ω cm or more.
Preferably, the preparation method of above-mentioned hud typed denitrating catalyst is related to drying steps in the step, dry Condition is equal are as follows: drying temperature is 80 DEG C~120 DEG C, and drying time is 12h~for 24 hours.
Preferably, the preparation method of above-mentioned hud typed denitrating catalyst is related to calcining step in the step, calcines Condition is equal are as follows: calcination temperature is 400 DEG C~600 DEG C, and calcination time is 3h~5h.
The beneficial effects of the present invention are:
Active component rare earth oxide is evenly distributed on carrier TiO in the form of shell2On surface, can fully it utilize The surface of carrier；Meanwhile the surface of active component is forming a Sb2O5Protective layer, avoid active component and SO2Reaction hair Raw poisoning is adsorbed by sulphur ammonium salt, and the catalyst of this core-shell structure can steadily protect its active component to avoid it that sulphur occurs Poisoning.
Detailed description of the invention
Fig. 1 is different rare earth oxide denitration efficiency figures.
Specific embodiment
In order to describe the technical content, the structural feature, the achieved object and the effect of this invention in detail, below in conjunction with embodiment And attached drawing is cooperated to be explained in detail.
Embodiment 1
A kind of hud typed denitrating catalyst, the denitrating catalyst by the kernel as catalyst TiO2, as on kernel First layer shell rare earth oxide, as catalyst shell Sb2O5Composition；Rare earth oxide, Sb2O5、TiO2It accounts for respectively 1%, 1%, the 98% of total catalyst weight；
The rare earth oxide is La2O3；Rare earth oxide La2O3Presoma include lanthanum nitrate；
The Sb2O5Presoma include antimony acetate.
The preparation method of above-mentioned hud typed denitrating catalyst, includes the following steps:
1) preparation of mixed solution: dehydrated alcohol, ammonium hydroxide and ultrapure water are uniformly mixed and are prepared into mixed solution；
2) preparation of titaniferous mud paste sediment: butyl titanate and mixed solution obtained by step 1) are mixed and stirred for, Mixed solution is subjected to centrifugal treating after standing, the mixed liquor that centrifugal treating is crossed filters, and titaniferous mud is obtained after suction filtration Paste sediment；
3) preparation of solids containing titanium sample: titaniferous mud paste sediment obtained by step 2) is dried and is then carried out Solids containing titanium sample is made in calcining；
4) preparation of dispersing liquid 1: being milled into powder for solids containing titanium sample, and powder is put into ultrapure water and carries out ultrasound Decentralized processing；
5) preparation of rare earth oxide precursor solution: solution is made in the dissolution of lanthanum nitrate ultrapure water, according to rare earth member The molar ratio of plain lanthanum/fluorine element is that hydrofluoric acid is added dropwise into solution for the ratio of 3:1, after hydrofluoric acid drips, with ammonium hydroxide tune The pH value of solution is saved to 8；
6)TiO2The preparation of@rare earth oxide mud paste sediment: to rare earth oxide precursor solution obtained by step 5) In dispersing liquid 1 obtained by step 4) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains and contains TiO2@rare earth oxide mud paste sediment；
7)TiO2The preparation of@rare earth oxide core-shell structure sample: by TiO obtained by step 7)2@rare earth oxide mud paste Sediment is dried and calcination processing, obtains TiO2@rare earth oxide core-shell structure sample；
8) preparation of dispersing liquid 2: by TiO2@rare earth oxide core-shell structure sample is milled into powder, and powder is put into Ultrasonic disperse processing is carried out in ultrapure water；
9)Sb2O5The preparation of precursor solution: solution is made in the dissolution of antimony acetate ultrapure water, according to rubbing for Sb/ fluorine element You are than being the ratio of 3:1 to Sb2O5Hydrofluoric acid is added dropwise in precursor solution, after hydrofluoric acid drips, adjusts solution with ammonium hydroxide PH value to 8；
10)TiO2@rare earth oxide/Sb2O5The preparation of mud paste sediment: to Sb obtained by step 9)2O5Precursor solution In dispersing liquid 2 obtained by step 8) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains TiO2@rare earth oxide/Sb2O5Mud paste sediment；
11)TiO2@rare earth oxide/Sb2O5The preparation of hud typed denitrating catalyst: step 10) gained sediment is carried out Drying and calcination processing, i.e. acquisition TiO2@rare earth oxide/Sb2O5Hud typed denitrating catalyst；
Its resistivity of ultrapure water used in the step is more than 18M Ω cm or more；
It is related to drying steps in the step, drying condition is equal are as follows: drying temperature is 80 DEG C, and drying time is for 24 hours；
It is related to calcining step in the step, calcination condition is equal are as follows: calcination temperature is 400 DEG C, calcination time 5h.
Embodiment 2
A kind of hud typed denitrating catalyst, the denitrating catalyst by the kernel as catalyst TiO2, as on kernel First layer shell rare earth oxide, as catalyst shell Sb2O5Composition；Rare earth oxide, Sb2O5、TiO2It accounts for respectively 4%, 4%, the 92% of total catalyst weight；
The rare earth oxide is CeO2；Rare earth oxide CeO2Presoma include cerous acetate, cerous sulfate；
The Sb2O5Presoma include hydration antimonious acid.
The preparation method of above-mentioned hud typed denitrating catalyst, includes the following steps:
1) preparation of mixed solution: dehydrated alcohol, ammonium hydroxide and ultrapure water are uniformly mixed and are prepared into mixed solution；
2) preparation of titaniferous mud paste sediment: butyl titanate and mixed solution obtained by step 1) are mixed and stirred for, Mixed solution is subjected to centrifugal treating after standing, the mixed liquor that centrifugal treating is crossed filters, and titaniferous mud is obtained after suction filtration Paste sediment；
3) preparation of solids containing titanium sample: titaniferous mud paste sediment obtained by step 2) is dried and is then carried out Solids containing titanium sample is made in calcining；
4) preparation of dispersing liquid 1: being milled into powder for solids containing titanium sample, and powder is put into ultrapure water and carries out ultrasound Decentralized processing；
5) preparation of rare earth oxide precursor solution: by cerous acetate, cerous sulfate, (molar ratio of cerous acetate and cerous sulfate is Solution 1:1) is made with ultrapure water dissolution, hydrogen fluorine is added dropwise into solution according to the ratio that Ce elements/fluorine element molar ratio is 3:1 Acid adjusts the pH value of solution to 9 with ammonium hydroxide after hydrofluoric acid drips；
6)TiO2The preparation of@rare earth oxide mud paste sediment: to rare earth oxide precursor solution obtained by step 5) In dispersing liquid 1 obtained by step 4) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains and contains TiO2@rare earth oxide mud paste sediment；
7)TiO2The preparation of@rare earth oxide core-shell structure sample: by TiO obtained by step 7)2@rare earth oxide mud paste Sediment is dried and calcination processing, obtains TiO2@rare earth oxide core-shell structure sample；
8) preparation of dispersing liquid 2: by TiO2@rare earth oxide core-shell structure sample is milled into powder, and powder is put into Ultrasonic disperse processing is carried out in ultrapure water；
9)Sb2O5The preparation of precursor solution: solution is made in hydration antimonious acid ultrapure water dissolution, according to Sb/ fluorine element Molar ratio is the ratio of 3:1 to Sb2O5Hydrofluoric acid is added dropwise in precursor solution, after hydrofluoric acid drips, is adjusted with ammonium hydroxide molten The pH value of liquid is to 9；
10)TiO2@rare earth oxide/Sb2O5The preparation of mud paste sediment: to Sb obtained by step 9)2O5Precursor solution In dispersing liquid 2 obtained by step 8) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains TiO2@rare earth oxide/Sb2O5Mud paste sediment；
11)TiO2@rare earth oxide/Sb2O5The preparation of hud typed denitrating catalyst: step 10) gained sediment is carried out Drying and calcination processing, i.e. acquisition TiO2@rare earth oxide/Sb2O5Hud typed denitrating catalyst；
Its resistivity of ultrapure water used in the step is more than 18M Ω cm or more；
It is related to drying steps in the step, drying condition is equal are as follows: drying temperature is 90 DEG C, drying time 20h；
It is related to calcining step in the step, calcination condition is equal are as follows: calcination temperature is 450 DEG C, calcination time 4.5h.
Embodiment 3
A kind of hud typed denitrating catalyst, the denitrating catalyst by the kernel as catalyst TiO2, as on kernel First layer shell rare earth oxide, as catalyst shell Sb2O5Composition；Rare earth oxide, Sb2O5、TiO2It accounts for respectively 6%, 6%, the 88% of total catalyst weight；
The rare earth oxide is PrO2；Rare earth oxide PrO2Presoma include praseodymium acetate, praseodymium nitrate, praseodymium sulfate；
The Sb2O5Presoma include Antimony pentachloride.
The preparation method of above-mentioned hud typed denitrating catalyst, includes the following steps:
1) preparation of mixed solution: dehydrated alcohol, ammonium hydroxide and ultrapure water are uniformly mixed and are prepared into mixed solution；
2) preparation of titaniferous mud paste sediment: butyl titanate and mixed solution obtained by step 1) are mixed and stirred for, Mixed solution is subjected to centrifugal treating after standing, the mixed liquor that centrifugal treating is crossed filters, and titaniferous mud is obtained after suction filtration Paste sediment；
3) preparation of solids containing titanium sample: titaniferous mud paste sediment obtained by step 2) is dried and is then carried out Solids containing titanium sample is made in calcining；
4) preparation of dispersing liquid 1: being milled into powder for solids containing titanium sample, and powder is put into ultrapure water and carries out ultrasound Decentralized processing；
5) preparation of rare earth oxide precursor solution: by praseodymium acetate, praseodymium nitrate, praseodymium sulfate (praseodymium acetate, praseodymium nitrate, sulphur The molar ratio of sour praseodymium is 1:1:1) solution is made with ultrapure water dissolution, the ratio for being 3:1 according to praseodymium element/fluorine element molar ratio Hydrofluoric acid is added dropwise into solution, after hydrofluoric acid drips, adjusts the pH value of solution to 8.5 with ammonium hydroxide；
6)TiO2The preparation of@rare earth oxide mud paste sediment: to rare earth oxide precursor solution obtained by step 5) In dispersing liquid 1 obtained by step 4) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains and contains TiO2@rare earth oxide mud paste sediment；
7)TiO2The preparation of@rare earth oxide core-shell structure sample: by TiO obtained by step 7)2@rare earth oxide mud paste Sediment is dried and calcination processing, obtains TiO2@rare earth oxide core-shell structure sample；
8) preparation of dispersing liquid 2: by TiO2@rare earth oxide core-shell structure sample is milled into powder, and powder is put into Ultrasonic disperse processing is carried out in ultrapure water；
9)Sb2O5The preparation of precursor solution: solution is made in the dissolution of Antimony pentachloride ultrapure water, according to Sb/ fluorine element Molar ratio is the ratio of 3:1 to Sb2O5Hydrofluoric acid is added dropwise in precursor solution, after hydrofluoric acid drips, is adjusted with ammonium hydroxide molten The pH value of liquid is to 8.5；
10)TiO2@rare earth oxide/Sb2O5The preparation of mud paste sediment: to Sb obtained by step 9)2O5Precursor solution In dispersing liquid 2 obtained by step 8) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains TiO2@rare earth oxide/Sb2O5Mud paste sediment；
11)TiO2@rare earth oxide/Sb2O5The preparation of hud typed denitrating catalyst: step 10) gained sediment is carried out Drying and calcination processing, i.e. acquisition TiO2@rare earth oxide/Sb2O5Hud typed denitrating catalyst；
Its resistivity of ultrapure water used in the step is more than 18M Ω cm or more；
It is related to drying steps in the step, drying condition is equal are as follows: drying temperature is 100 DEG C, drying time 18h；
It is related to calcining step in the step, calcination condition is equal are as follows: calcination temperature is 500 DEG C, calcination time 4h.
Embodiment 4
A kind of hud typed denitrating catalyst, the denitrating catalyst by the kernel as catalyst TiO2, as on kernel First layer shell rare earth oxide, as catalyst shell Sb2O5Composition；Rare earth oxide, Sb2O5、TiO2It accounts for respectively 8%, 8%, the 84% of total catalyst weight；
The rare earth oxide is La2O3、CeO2；Rare earth oxide La2O3Presoma include lanthanum sulfate, rare-earth oxidation Object CeO2Presoma include cerous nitrate；
The Sb2O5Presoma include antimony acetate, hydration antimonious acid.
The preparation method of above-mentioned hud typed denitrating catalyst, includes the following steps:
1) preparation of mixed solution: dehydrated alcohol, ammonium hydroxide and ultrapure water are uniformly mixed and are prepared into mixed solution；
2) preparation of titaniferous mud paste sediment: butyl titanate and mixed solution obtained by step 1) are mixed and stirred for, Mixed solution is subjected to centrifugal treating after standing, the mixed liquor that centrifugal treating is crossed filters, and titaniferous mud is obtained after suction filtration Paste sediment；
3) preparation of solids containing titanium sample: titaniferous mud paste sediment obtained by step 2) is dried and is then carried out Solids containing titanium sample is made in calcining；
4) preparation of dispersing liquid 1: being milled into powder for solids containing titanium sample, and powder is put into ultrapure water and carries out ultrasound Decentralized processing；
5) preparation of rare earth oxide precursor solution: by lanthanum sulfate, cerous nitrate (lanthanum sulfate, cerous nitrate molar ratio be Solution 1:2) is made with ultrapure water dissolution, hydrogen is added dropwise into solution according to the ratio that rare earth element/fluorine element molar ratio is 3:1 Fluoric acid adjusts the pH value of solution to 9 with ammonium hydroxide after hydrofluoric acid drips；
6)TiO2The preparation of@rare earth oxide mud paste sediment: to rare earth oxide precursor solution obtained by step 5) In dispersing liquid 1 obtained by step 4) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains and contains TiO2@rare earth oxide mud paste sediment；
7)TiO2The preparation of@rare earth oxide core-shell structure sample: by TiO obtained by step 7)2@rare earth oxide mud paste Sediment is dried and calcination processing, obtains TiO2@rare earth oxide core-shell structure sample；
8) preparation of dispersing liquid 2: by TiO2@rare earth oxide core-shell structure sample is milled into powder, and powder is put into Ultrasonic disperse processing is carried out in ultrapure water；
9)Sb2O5The preparation of precursor solution: by antimony acetate, hydration antimonious acid (antimony acetate, the molar ratio for being hydrated antimonious acid Solution is made for the dissolution of 1:1) ultrapure water, the molar ratio according to Sb/ fluorine element is the ratio of 3:1 to Sb2O5It is dripped in precursor solution Add hydrofluoric acid, after hydrofluoric acid drips, adjusts the pH value of solution to 8 with ammonium hydroxide；
10)TiO2@rare earth oxide/Sb2O5The preparation of mud paste sediment: to Sb obtained by step 9)2O5Precursor solution In dispersing liquid 2 obtained by step 8) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains TiO2@rare earth oxide/Sb2O5Mud paste sediment；
11)TiO2@rare earth oxide/Sb2O5The preparation of hud typed denitrating catalyst: step 10) gained sediment is carried out Drying and calcination processing, i.e. acquisition TiO2@rare earth oxide/Sb2O5Hud typed denitrating catalyst；
Its resistivity of ultrapure water used in the step is more than 18M Ω cm or more；
It is related to drying steps in the step, drying condition is equal are as follows: drying temperature is 110 DEG C, drying time 14h；
It is related to calcining step in the step, calcination condition is equal are as follows: calcination temperature is 550 DEG C, calcination time 3.5h.
Embodiment 5
A kind of hud typed denitrating catalyst, the denitrating catalyst by the kernel as catalyst TiO2, as on kernel First layer shell rare earth oxide, as catalyst shell Sb2O5Composition；Rare earth oxide, Sb2O5、TiO2It accounts for respectively 4%, 6%, the 90% of total catalyst weight；
The rare earth oxide is La2O3、CeO2、PrO2；Rare earth oxide La2O3Presoma include lanthanum nitrate, it is dilute Native oxide CeO2Presoma include cerous acetate, rare earth oxide PrO2Presoma include praseodymium sulfate；
The Sb2O5Presoma include antimony acetate, hydration antimonious acid, Antimony pentachloride.
The preparation method of above-mentioned hud typed denitrating catalyst, includes the following steps:
1) preparation of mixed solution: dehydrated alcohol, ammonium hydroxide and ultrapure water are uniformly mixed and are prepared into mixed solution；
2) preparation of titaniferous mud paste sediment: butyl titanate and mixed solution obtained by step 1) are mixed and stirred for, Mixed solution is subjected to centrifugal treating after standing, the mixed liquor that centrifugal treating is crossed filters, and titaniferous mud is obtained after suction filtration Paste sediment；
3) preparation of solids containing titanium sample: titaniferous mud paste sediment obtained by step 2) is dried and is then carried out Solids containing titanium sample is made in calcining；
4) preparation of dispersing liquid 1: being milled into powder for solids containing titanium sample, and powder is put into ultrapure water and carries out ultrasound Decentralized processing；
5) preparation of rare earth oxide precursor solution: by lanthanum nitrate, cerous acetate, praseodymium sulfate (lanthanum nitrate, cerous acetate, sulphur The molar ratio of sour praseodymium is 3:2:1) solution is made with ultrapure water dissolution, the ratio for being 3:1 according to rare earth element/fluorine element molar ratio Hydrofluoric acid is added dropwise into solution for example, after hydrofluoric acid drips, adjusts the pH value of solution to 8 with ammonium hydroxide；
6)TiO2The preparation of@rare earth oxide mud paste sediment: to rare earth oxide precursor solution obtained by step 5) In dispersing liquid 1 obtained by step 4) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains and contains TiO2@rare earth oxide mud paste sediment；
7)TiO2The preparation of@rare earth oxide core-shell structure sample: by TiO obtained by step 7)2@rare earth oxide mud paste Sediment is dried and calcination processing, obtains TiO2@rare earth oxide core-shell structure sample；
8) preparation of dispersing liquid 2: by TiO2@rare earth oxide core-shell structure sample is milled into powder, and powder is put into Ultrasonic disperse processing is carried out in ultrapure water；
9)Sb2O5The preparation of precursor solution: by antimony acetate, hydration antimonious acid, Antimony pentachloride (antimony acetate, hydration stibnous Sour, Antimony pentachloride molar ratio is 1:2:3) solution is made in ultrapure water dissolution, and it is the ratio of 3:1 according to the molar ratio of Sb/ fluorine element Example is to Sb2O5Hydrofluoric acid is added dropwise in precursor solution, after hydrofluoric acid drips, adjusts the pH value of solution to 9 with ammonium hydroxide；
10)TiO2@rare earth oxide/Sb2O5The preparation of mud paste sediment: to Sb obtained by step 9)2O5Precursor solution In dispersing liquid 2 obtained by step 8) is added dropwise, stirring dissolves it sufficiently, then stands solution, by the solution after standing into Row filters, and obtains TiO2@rare earth oxide/Sb2O5Mud paste sediment；
11)TiO2@rare earth oxide/Sb2O5The preparation of hud typed denitrating catalyst: step 10) gained sediment is carried out Drying and calcination processing, i.e. acquisition TiO2@rare earth oxide/Sb2O5Hud typed denitrating catalyst；
Its resistivity of ultrapure water used in the step is more than 18M Ω cm or more；
It is related to drying steps in the step, drying condition is equal are as follows: drying temperature is 120 DEG C, drying time 12h；
It is related to calcining step in the step, calcination condition is equal are as follows: calcination temperature is 600 DEG C, calcination time 3h.
Embodiment 6
The ratio for being 24:1:6 according to mass ratio, takes dehydrated alcohol, ammonium hydroxide (volume fraction 20%) and ultrapure water (resistance Rate is 18M Ω cm) it mixes, mixed solution is obtained after stirring at normal temperature 10min.It is measured according to the 1/100 of the quality of mixed solution Butyl titanate is added in mixed solution, stands 6h again after stirring 1h, after standing, by solution centrifugal treating 12h, after centrifugation Acquired solution is filtered, and is filtered and is obtained mud paste sediment, mud paste sediment is put into baking oven, dry at 80 DEG C Dry gained sample is put into Muffle furnace, calcines 3h at 400 DEG C by 12h.Calcining gained sample is milled into powder, then This powder is put into ultrapure water progress ultrasonic disperse processing, this dispersion solution is labeled as A, wherein the quality of ultrapure water is 50 times of powder quality.According to TiO2And CeO2Mass ratio be 1:98, measure cerous acetate ultrapure water dissolution solution is made, press Hydrofluoric acid is at the uniform velocity added dropwise into cerous acetate solution according to the ratio that Ce/F molar ratio is 3:1, is stirred continuously acetic acid during dropwise addition Cerium solution.After hydrofluoric acid drips, continue to be stirred solution, while ammonium hydroxide being gradually added dropwise into mixed solution, adjust The pH value of mixed solution is labeled as B to 8, by this mixed solution.B solution is stirred and is heated, the temperature of B solution is made to reach 50 DEG C, Solution A is gradually added into B solution, continues to heat and be stirred solution 2h after the completion of solution A addition, then by mixed solution 6h is stood, filters solution after standing, filters and obtains mud paste sediment, mud paste sediment is put into baking oven In, dry gained sample is put into Muffle furnace, calcines 3h at 400 DEG C by the dry 12h at 80 DEG C, by calcining gained sample It is milled into powder, this powder is TiO2@CeO2Core-shell structure powder.By this TiO2@CeO2Core-shell structure powder is put into ultrapure water Middle progress ultrasonic disperse processing, the quality of ultrapure water are 50 times of powder quality, this dispersion solution is labeled as C.According to TiO2 And Sb2O5Mass ratio be 1:98, measure antimony acetate, with ultrapure water dissolution solution is made, according to Sb/F molar ratio be 3:1 ratio Hydrofluoric acid is at the uniform velocity added dropwise into antimony acetate solution for example, and antimony acetate solution is stirred continuously during dropwise addition.When hydrofluoric acid drips Later, continue to be stirred solution, while ammonium hydroxide being gradually added dropwise into mixed solution, adjust the pH value of mixed solution to 8, by this Solution is labeled as D.Solution D is stirred and heated, the temperature of solution D is made to reach 50 DEG C, C solution is gradually added into solution D, C is molten Continues to heat and be stirred solution 2h after the completion of liquid addition, mixed solution is then stood into 6h, after standing by solution into Row filters, and filters and obtains mud paste sediment, mud paste sediment is put into baking oven, the dry 12h at 80 DEG C, by dry institute It obtains sample to be put into Muffle furnace, calcines 3h at 400 DEG C, calcining gained sample is milled into powder, this powder is TiO2@ CeO2/Sb2O5Nucleocapsid catalyst.
Embodiment 7
The ratio for being 49:3:15 according to mass ratio takes dehydrated alcohol, ammonium hydroxide (volume fraction 25%) and ultrapure water (electricity Resistance rate is 18M Ω cm) it mixes, mixed solution is obtained after stirring at normal temperature 30min.It is measured according to the 1/20 of the quality of mixed solution Butyl titanate is added in mixed solution, stands 9h again after stirring 3h, after standing, by solution centrifugal treating 12h, after centrifugation Acquired solution is filtered, and is filtered and is obtained mud paste sediment, mud paste sediment is put into baking oven, dry at 100 DEG C Dry gained sample is put into Muffle furnace, calcines 4h at 500 DEG C by 18h.Calcining gained sample is milled into powder, then This powder is put into ultrapure water progress ultrasonic disperse processing, this dispersion solution is labeled as A, wherein the quality of ultrapure water is 70 times of powder quality.According to TiO2And La2O3Mass ratio be 1:23, measure lanthanum nitrate ultrapure water dissolution solution is made, press Hydrofluoric acid is at the uniform velocity added dropwise into lanthanum nitrate hexahydrate according to the ratio that La/F molar ratio is 3:1, is stirred continuously nitric acid during dropwise addition Lanthanum solution.After hydrofluoric acid drips, continue to be stirred solution, while ammonium hydroxide being gradually added dropwise into mixed solution, adjust The pH value of mixed solution is labeled as B to 9, by this mixed solution.B solution is stirred and is heated, the temperature of B solution is made to reach 65 DEG C, Solution A is gradually added into B solution, continues to heat and be stirred solution 3h after the completion of solution A addition, then by mixed solution 10h is stood, filters solution after standing, filters and obtains mud paste sediment, mud paste sediment is put into baking oven In, dry gained sample is put into Muffle furnace, calcines 4h at 450 DEG C by the dry 18h at 100 DEG C, by calcining gained sample It is milled into powder, this powder is TiO2@La2O3Core-shell structure powder.By this TiO2@La2O3Core-shell structure powder is put into ultrapure Ultrasonic disperse processing is carried out in water, the quality of ultrapure water is 75 times of powder quality, this dispersion solution is labeled as C.According to TiO2And Sb2O5Mass ratio be 1:23, measure Antimony pentachloride, with ultrapure water dissolution solution is made, according to Sb/F molar ratio be 3: Hydrofluoric acid is at the uniform velocity added dropwise into Antimony pentachloride solution for 1 ratio, and antimony acetate solution is stirred continuously during dropwise addition.Work as hydrofluoric acid After dripping, continue to be stirred solution, while ammonium hydroxide being gradually added dropwise into mixed solution, adjust the pH value of mixed solution to 9, this solution is labeled as D.Solution D is stirred and heated, the temperature of solution D is made to reach 70 DEG C, it is molten that C is gradually added into solution D Liquid continues to heat and be stirred solution 3h after the completion of C solution addition, and mixed solution is then stood 9h, will after standing Solution is filtered, and is filtered and is obtained mud paste sediment, mud paste sediment is put into baking oven, the dry 19h at 100 DEG C, Dry gained sample is put into Muffle furnace, calcines 4h at 450 DEG C, calcining gained sample is milled into powder, this powder is For TiO2@La2O3/Sb2O5Nucleocapsid catalyst.
Embodiment 8
The ratio for being 72:1:18 according to mass ratio takes dehydrated alcohol, ammonium hydroxide (volume fraction 30%) and ultrapure water (electricity Resistance rate is 18M Ω cm) it mixes, mixed solution is obtained after stirring at normal temperature 60min.It is measured according to the 1/10 of the quality of mixed solution Butyl titanate is added in mixed solution, stands 12h again after stirring 6h, after standing, by solution centrifugal treating 12h, centrifugation Acquired solution is filtered afterwards, is filtered and is obtained mud paste sediment, mud paste sediment is put into baking oven, is done at 120 DEG C It is dry for 24 hours, dry gained sample is put into Muffle furnace, calcines 5h at 600 DEG C.Calcining gained sample is milled into powder, so This powder is put into progress ultrasonic disperse processing in ultrapure water afterwards, this dispersion solution is labeled as A, wherein the quality of ultrapure water It is 100 times of powder quality.According to TiO2And PrO2Mass ratio be 2:21, measure praseodymium sulfate ultrapure water dissolution solution is made, Hydrofluoric acid is at the uniform velocity added dropwise into praseodymium sulfate solution according to the ratio that Pr/F molar ratio is 3:1, is stirred continuously sulphur during dropwise addition Sour praseodymium solution.After hydrofluoric acid drips, continue to be stirred solution, while ammonium hydroxide being gradually added dropwise into mixed solution, adjust The pH value of mixed solution is saved to 9, this mixed solution is labeled as B.B solution is stirred and heated, the temperature of B solution is made to reach 80 DEG C, solution A is gradually added into B solution, continues to heat and be stirred solution 4h after the completion of solution A addition, it then will mixing Solution left standstill 12h filters solution after standing, filters and obtains mud paste sediment, mud paste sediment is put into It is dry at 120 DEG C that dry gained sample is put into Muffle furnace, calcines 5h at 500 DEG C for 24 hours in baking oven, by calcining gained Sample is milled into powder, this powder is TiO2@PrO2Core-shell structure powder.By this TiO2@PrO2Core-shell structure powder is put into super Ultrasonic disperse processing is carried out in pure water, the quality of ultrapure water is 100 times of powder quality, this dispersion solution is labeled as C.According to TiO2And Sb2O5Mass ratio be 2:21, measure hydration antimonious acid, with ultrapure water dissolution solution is made, be according to Sb/F molar ratio Hydrofluoric acid is at the uniform velocity added dropwise into hydration stibnous acid solution in the ratio of 3:1, and hydration stibnous acid solution is stirred continuously during dropwise addition. After hydrofluoric acid drips, continue to be stirred solution, while ammonium hydroxide being gradually added dropwise into mixed solution, adjusts mixed solution PH value to 9, this solution is labeled as D.Solution D is stirred and heated, so that the temperature of solution D is reached 80 DEG C, gradually into solution D C solution is added, continues to heat and be stirred solution 4h after the completion of C solution addition, mixed solution is then stood into 12h, stand After solution is filtered, filter obtain mud paste sediment, mud paste sediment is put into baking oven, at 120 DEG C It is dry that dry gained sample is put into Muffle furnace, calcines 5h at 600 DEG C for 24 hours, calcining gained sample is milled into powder, This powder is TiO2@PrO2/Sb2O5Nucleocapsid catalyst.
Nucleocapsid denitrating catalyst performance test: according to the above scheme, nucleocapsid denitrating catalyst is placed on to the fixation continuously flowed In bed reaction device, reaction pressure is normal pressure, reaction velocity 5000h-1, the concentration of NO is 500~3000mg/ in mixed gas m3, reaction temperature is 300 DEG C~500 DEG C.
Attached drawing 1 is nucleocapsid catalyst prepared by embodiment 6 to embodiment 8 in catalytic denitration efficiency situation.It can from table To find out, under experimental conditions, the TiO in the present invention2@rare earth oxide/Sb2O5Nucleocapsid catalyst can be effectively catalyzed also Former NOx。
The above description is only an embodiment of the present invention, is not intended to limit scope of patent protection of the invention, all utilizations Equivalent structure or equivalent flow shift made by description of the invention and accompanying drawing content is applied directly or indirectly in other correlations Technical field, be included within the scope of the present invention.

Claims (10)

1. a kind of hud typed denitrating catalyst, which is characterized in that the denitrating catalyst by the kernel as catalyst TiO2, make The Sb of rare earth oxide for the first layer shell on kernel, the shell as catalyst2O5Composition；The rare earth oxide is La2O3、CeO2、PrO2It is one or more.
2. hud typed denitrating catalyst as described in claim 1, which is characterized in that rare earth oxide, Sb2O5、TiO2It accounts for respectively 1%~8%, 1%~8%, the 84%~98% of total catalyst weight.
3. hud typed denitrating catalyst as claimed in claim 2, which is characterized in that Sb2O5Presoma include antimony acetate, water Close one of antimonious acid, Antimony pentachloride or a variety of.
4. hud typed denitrating catalyst as claimed in claim 2, which is characterized in that rare earth oxide La2O3Presoma include One of lanthanum nitrate, lanthanum acetate, lanthanum sulfate are a variety of.
5. hud typed denitrating catalyst as claimed in claim 2, which is characterized in that rare earth oxide CeO2Presoma include One of cerous acetate, cerous nitrate, cerous sulfate are a variety of.
6. hud typed denitrating catalyst as claimed in claim 2, which is characterized in that rare earth oxide PrO2Presoma include One of praseodymium acetate, praseodymium nitrate, praseodymium sulfate are a variety of.
7. a kind of preparation method of the hud typed denitrating catalyst as described in claim 1 to 6 is any, includes the following steps:
1) preparation of mixed solution: dehydrated alcohol, ammonium hydroxide and ultrapure water are uniformly mixed and are prepared into mixed solution；
2) preparation of titaniferous mud paste sediment: butyl titanate and mixed solution obtained by step 1) are mixed and stirred for, and are stood Mixed solution is subjected to centrifugal treating later, the mixed liquor that centrifugal treating is crossed filters, and titaniferous mud paste is obtained after suction filtration Sediment；
3) preparation of solids containing titanium sample: titaniferous mud paste sediment obtained by step 2) is dried and is then forged It burns, solids containing titanium sample is made；
4) preparation of dispersing liquid 1: solids containing titanium sample is milled into powder, powder is put into ultrapure water and carries out ultrasonic disperse Processing；
5) preparation of rare earth oxide precursor solution: being made solution for the dissolution of rare earth oxide presoma ultrapure water, according to Rare earth element/fluorine element molar ratio is that hydrofluoric acid is added dropwise into rare earth oxide precursor solution in the ratio of 3:1, works as hydrofluoric acid After dripping, the pH value of solution is adjusted to 8~9 with ammonium hydroxide；
6)TiO2The preparation of@rare earth oxide mud paste sediment: dropwise into rare earth oxide precursor solution obtained by step 5) Dispersing liquid 1 obtained by step 4) is added, stirring dissolves it sufficiently, then stands solution, the solution after standing is filtered, It obtains and contains TiO2@rare earth oxide mud paste sediment；
7)TiO2The preparation of@rare earth oxide core-shell structure sample: by TiO obtained by step 7)2@rare earth oxide mud paste precipitating Object is dried and calcination processing, obtains TiO2@rare earth oxide core-shell structure sample；
8) preparation of dispersing liquid 2: by TiO2@rare earth oxide core-shell structure sample is milled into powder, and powder is put into ultrapure water Middle progress ultrasonic disperse processing；
9)Sb2O5The preparation of precursor solution: by Sb2O5Solution is made in the dissolution of presoma ultrapure water, according to rubbing for Sb/ fluorine element You are than being the ratio of 3:1 to Sb2O5Hydrofluoric acid is added dropwise in precursor solution, after hydrofluoric acid drips, adjusts solution with ammonium hydroxide PH value to 8~9；
10)TiO2@rare earth oxide/Sb2O5The preparation of mud paste sediment: to Sb obtained by step 9)2O5In precursor solution by It is added dropwise to dispersing liquid 2 obtained by step 8), stirring dissolves it sufficiently, then stands solution, the solution after standing is taken out Filter obtains TiO2@rare earth oxide/Sb2O5Mud paste sediment；
11)TiO2@rare earth oxide/Sb2O5The preparation of hud typed denitrating catalyst: step 10) gained sediment is dried And calcination processing, i.e. acquisition TiO2@rare earth oxide/Sb2O5Hud typed denitrating catalyst.
8. the preparation method of hud typed denitrating catalyst as claimed in claim 7, which is characterized in that used in the step Its resistivity of ultrapure water is more than 18M Ω cm or more.
9. the preparation method of hud typed denitrating catalyst as claimed in claim 7, which is characterized in that be related in the step Drying steps, drying condition are equal are as follows: drying temperature is 80 DEG C~120 DEG C, and drying time is 12h~for 24 hours.
10. the preparation method of hud typed denitrating catalyst as claimed in claim 7, which is characterized in that involved in the step To calcining step, calcination condition is equal are as follows: calcination temperature is 400 DEG C~600 DEG C, and calcination time is 3h~5h.
CN201710545809.6A 2017-07-06 2017-07-06 A kind of hud typed denitrating catalyst and preparation method thereof Pending CN109201034A (en)

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CN116328757A (en) * 2021-12-16 2023-06-27 中国科学院大连化学物理研究所 Hollow metal oxide @ TiO 2 Core-shell structured catalyst and preparation method and application thereof

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