CN114345321A - Sulfur-resistant Ce-Mn-Zr catalyst and preparation method and application thereof - Google Patents
Sulfur-resistant Ce-Mn-Zr catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 59
- 239000011593 sulfur Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 48
- 239000011572 manganese Substances 0.000 claims description 31
- 239000012286 potassium permanganate Substances 0.000 claims description 28
- 229910052684 Cerium Inorganic materials 0.000 claims description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 20
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 32
- 238000012360 testing method Methods 0.000 description 12
- 229910016978 MnOx Inorganic materials 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 4
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses a sulfur-resistant Ce-Mn-Zr catalyst, and a preparation method and application thereof. The Ce-Mn-Zr catalyst contains ZrO as a transition metal2、MnO2And CeO2. The Ce-Mn-Zr catalyst is obtained by doping Zr, and the dispersity of active sites of the catalyst is improved by utilizing the stabilizing effect of Zr on the size of the catalyst and the cluster inhibiting effect of Zr, so that more active sites are exposed to delay the poisoning process of the catalyst. In addition, the Ce-Mn-Zr catalyst has higher sulfur resistance and can be used for treating SO2And in the existing condition, SCR denitration work is carried out for a long time.
Description
Technical Field
The invention belongs to the technical field of denitration catalytic materials, and particularly relates to a sulfur-resistant Ce-Mn-Zr catalyst, and a preparation method and application thereof.
Background
In non-electrical industries, e.g. steelworks, waste incinerators, combustion boilers, etc., SO2Is usually a catalyst in<The main cause of deactivation at 200 ℃. MnOxOften as NH3Low temperature catalyst for SCR reaction, CeO2Used as MnO due to its strong oxygen storage capacity and excellent redox propertiesXTo improve its denitration performance, but CeO2Is susceptible to SO2The application is limited due to the influence of the Ce-Mn catalyst, and the improvement of the sulfur resistance of the Ce-Mn catalyst is the current focus research direction.
The low-temperature denitration catalyst with high sulfur resistance is mainly used for improving the redox performance of the Ce-Mn catalyst in an element doping mode, and the surface of the catalyst is acidic or an element which can be preferentially sulfurized by sulfur dioxide is introduced to serve as a sacrificial agent to protect active sites on the surface of the catalyst. The catalyst prepared by the method has the advantages that the denitration performance can be obviously improved in a short time, and the exposed active sites of the catalyst are reduced in a large area and are deactivated due to long-time vulcanization. However, if the sulfur resistance of the catalyst needs to be further improved stably for a long period of time, it is necessary to expose more active sites, and this can be further achieved by controlling the dispersion state of the active sites.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a sulfur-resistant Ce-Mn-Zr catalyst and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a sulfur-resistant Ce-Mn-Zr catalyst containing ZrO2、MnO2And CeO2。
The invention obtains the Ce-Mn-Zr catalyst by doping Zr, and usesZr has a stabilizing effect on the size of the catalyst and a clustering inhibiting effect to increase the dispersity of the active sites of the catalyst, so that more active sites are exposed to delay the poisoning process of the catalyst. In addition, the Ce-Mn-Zr catalyst has higher sulfur resistance and can be used for treating SO2And in the existing condition, SCR denitration work is carried out for a long time.
The invention claims a preparation method of the sulfur-resistant Ce-Mn-Zr catalyst, which comprises the following steps:
(1) dissolving a cerium source and a manganese source in water, and uniformly mixing to obtain a mixed solution;
(2) adding a zirconium source into the mixed solution, uniformly stirring, and then carrying out hydrothermal reaction to obtain the sulfur-resistant Ce-Mn-Zr catalyst.
According to the invention, the catalyst is obtained by simple hydrothermal reaction of the cerium source, the manganese source and the zirconium source, and the preparation method is simple and is suitable for industrial large-scale production.
In a preferred embodiment of the present invention, in the step (1), the molar ratio of the cerium source to the manganese source is 1:1 to 10.
According to the invention, the denitration performance and the sulfur resistance of the sulfur-resistant Ce-Mn-Zr catalyst are optimized by regulating and controlling the ratio of the cerium source to the manganese source, and the ratio of the cerium source to the manganese source in the above ratio range is beneficial to the formation of an amorphous structure of the Ce-Mn-Zr catalyst, so that the specific surface area is increased, and the denitration performance and the sulfur resistance of the material are improved.
As a preferred embodiment of the present invention, in the step (1), the molar ratio of the cerium source and the manganese source is 1: 3-5; more preferably, the molar ratio of the cerium source to the manganese source is 1: 4.
a large number of experiments show that the molar ratio of the cerium source to the manganese source is 1: and 4, the denitration performance and the sulfur resistance of the sulfur-resistant Ce-Mn-Zr catalyst are optimal.
As a preferred embodiment of the present invention, the content of the zirconium source is 0.7 to 5% by mass based on the total mass of the cerium source and the manganese source.
The addition of the zirconium source can improve the dispersibility of the material and reduce the agglomeration of species on the surface of the catalyst, but when the mass percentage of the zirconium source is more than 5%, the denitration performance of the catalyst is reduced.
As a preferred embodiment of the invention, the mass percentage of the zirconium source is 1-5% of the total mass of the cerium source and the manganese source; more preferably, the zirconium source is present in an amount of 3% by mass, based on the total mass of the cerium source and the manganese source.
As a preferred embodiment of the present invention, in the step (2), the stirring time is 1 to 3 hours.
In a preferred embodiment of the present invention, in the step (2), the temperature of the hydrothermal reaction is 70 to 220 ℃, and the time of the hydrothermal reaction is 8 to 72 hours.
According to the invention, the amorphous state of the catalyst is regulated and controlled by regulating and controlling the hydrothermal temperature and time, so that the denitration performance and the sulfur resistance of the catalyst are optimized, and the amorphous state of the catalyst is not favorably formed due to overhigh or overlong hydrothermal temperature and time, so that the denitration performance and the sulfur resistance of the catalyst are not favorably improved.
As a preferred embodiment of the present invention, the cerium source is at least one of cerium nitrate, cerium chloride, cerium carbonate, and cerium sulfate; the manganese source is potassium permanganate; the zirconium source is at least one of zirconium nitrate, zirconium chloride, zirconium carbonate and zirconium sulfate.
The invention also claims the application of the sulfur-resistant Ce-Mn-Zr catalyst in low-temperature denitration of flue gas.
Compared with the prior art, the invention has the beneficial effects that: the Ce-Mn-Zr catalyst is obtained by doping Zr, and the dispersity of active sites of the catalyst is improved by utilizing the stabilizing effect of Zr on the size of the catalyst and the cluster inhibiting effect of Zr, so that more active sites are exposed to delay the poisoning process of the catalyst. In addition, the Ce-Mn-Zr catalyst has higher sulfur resistance and can be used for treating SO2And in the existing condition, SCR denitration work is carried out for a long time.
Drawings
FIG. 1 is an XRD pattern of catalysts prepared in example 1 of the present invention and comparative examples 1 to 2;
FIG. 2 is a graph showing denitration performance of catalysts prepared in example 1 and comparative examples 1 to 2 of the present invention;
fig. 3 is a graph showing denitration stability of catalysts prepared in example 1 and comparative examples 1 to 2 of the present invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The preparation method of the sulfur-resistant Ce-Mn-Zr catalyst comprises the following steps:
(1) dissolving cerium nitrate and potassium permanganate in water, and uniformly mixing to obtain a mixed solution; the molar ratio of the cerium nitrate to the potassium permanganate is 1: 4;
(2) adding zirconium nitrate accounting for 3% of the total mass of cerium nitrate and potassium permanganate into the mixed solution, stirring for 2 hours until the mixture is uniform, and then carrying out hydrothermal reaction for 20 hours at 120 ℃ to obtain the sulfur-resistant Ce-Mn-Zr catalyst.
Example 2
The preparation method of the sulfur-resistant Ce-Mn-Zr catalyst comprises the following steps:
(1) dissolving cerium chloride and potassium permanganate in water, and uniformly mixing to obtain a mixed solution; the molar ratio of the cerium nitrate to the potassium permanganate is 1: 1;
(2) adding zirconium chloride accounting for 0.7 percent of the total mass of the cerium nitrate and the potassium permanganate into the mixed solution, stirring for 1 hour till uniformity, and then carrying out hydrothermal reaction for 8 hours at 160 ℃ to obtain the sulfur-resistant Ce-Mn-Zr catalyst.
Example 3
The preparation method of the sulfur-resistant Ce-Mn-Zr catalyst comprises the following steps:
(1) dissolving cerium sulfate and potassium permanganate in water, and uniformly mixing to obtain a mixed solution; the molar ratio of the cerium nitrate to the potassium permanganate is 1: 10;
(2) adding zirconium sulfate accounting for 5% of the total mass of the cerium nitrate and the potassium permanganate into the mixed solution, stirring for 3 hours until the mixture is uniform, and then carrying out hydrothermal reaction for 72 hours at 70 ℃ to obtain the sulfur-resistant Ce-Mn-Zr catalyst.
Example 4
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the embodiment and the embodiment 1 is that: in the step (1), the molar ratio of the cerium nitrate to the potassium permanganate is 1: 1.
Example 5
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the embodiment and the embodiment 1 is that: in the step (1), the molar ratio of the cerium nitrate to the potassium permanganate is 1: 3.
Example 6
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the embodiment and the embodiment 1 is that: in the step (1), the molar ratio of the cerium nitrate to the potassium permanganate is 1: 5.
Example 7
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the embodiment and the embodiment 1 is that: in the step (1), the molar ratio of the cerium nitrate to the potassium permanganate is 1: 10.
Example 8
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the embodiment and the embodiment 1 is that: in the step (2), the mass of the zirconium nitrate is 0.7% of the total mass of the cerium nitrate and the potassium permanganate.
Example 9
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the embodiment and the embodiment 1 is that: in the step (2), the mass of the zirconium nitrate is 1% of the total mass of the cerium nitrate and the potassium permanganate.
Example 10
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the embodiment and the embodiment 1 is that: in the step (2), the mass of the zirconium nitrate is 5% of the total mass of the cerium nitrate and the potassium permanganate.
Example 11
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the embodiment and the embodiment 1 is that: in the step (2), the temperature of the hydrothermal reaction is 70 ℃.
Example 12
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the embodiment and the embodiment 1 is that: in the step (2), the temperature of the hydrothermal reaction is 180 ℃.
Example 13
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the embodiment and the embodiment 1 is that: in the step (2), the temperature of the hydrothermal reaction is 220 ℃.
Comparative example 1
The preparation method of the Ce-Mn catalyst comprises the following steps:
(1) dissolving cerium nitrate and potassium permanganate in water, and uniformly mixing to obtain a mixed solution; the molar ratio of the cerium nitrate to the potassium permanganate is 1: 4;
(2) carrying out hydrothermal reaction on the mixed solution at 120 ℃ for 20h to obtain the Ce-Mn catalyst.
Comparative example 2
MnO of this comparative examplexThe preparation method of the catalyst comprises the following steps:
dissolving manganese nitrate and potassium permanganate in water, uniformly mixing, and carrying out hydrothermal reaction for 26 hours at 120 ℃ to obtain the MnOxA catalyst; the molar ratio of manganese nitrate to potassium permanganate is 3: 2.
Comparative example 3
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the comparative example and the example 1 is that: in the step (1), the molar ratio of the cerium nitrate to the potassium permanganate is 1: 0.5.
Comparative example 4
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the comparative example and the example 1 is that: in the step (1), the molar ratio of the cerium nitrate to the potassium permanganate is 1: 12.
Comparative example 5
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the comparative example and the example 1 is that: in the step (2), the mass of the zirconium nitrate is 0.3% of the total mass of the cerium nitrate and the potassium permanganate.
Comparative example 6
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the comparative example and the example 1 is that: in the step (2), the mass of the zirconium nitrate is 9% of the total mass of the cerium nitrate and the potassium permanganate.
Comparative example 7
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the comparative example and the example 1 is that: in the step (2), the temperature of the hydrothermal reaction is 50 ℃.
Comparative example 8
The only difference between the preparation method of the sulfur-resistant Ce-Mn-Zr catalyst in the comparative example and the example 1 is that: in the step (2), the temperature of the hydrothermal reaction is 280 ℃.
Test example 1
Fig. 1 is an XRD chart of the catalysts prepared in example 1 of the present invention and comparative examples 1-2. In FIG. 1 OMS-2 is a MnOx catalyst prepared in comparative example 2, Ce-Mn is a Ce-Mn catalyst prepared in comparative example 1, Ce-Mn-Zr is a Ce-Mn-Zr catalyst prepared in example 1, KMn5O16(JDPDS-29-1020) is a standard card of crystal structure of MnOx catalyst, CeO2(JDPDS-34-0394) is CeO2The standard card of (1). As can be seen from the figure, after Ce is doped, the MnOx catalyst is transformed into an amorphous structure; and the Ce-Mn-Zr catalyst has no impurity peak, which shows that the obtained Ce-Mn-Zr catalyst has higher purity.
Test example 2
The invention relates to a test example for testing denitration performance of a sulfur-resistant Ce-Mn-Zr catalyst, which is used for measuring denitration performance of the catalyst at different temperatures.
Test samples: catalysts prepared in examples and comparative examples.
And (3) testing conditions are as follows: the catalyst is placed in a denitration evaluation device, and the denitration catalytic performance of the catalyst is tested within the range of 50-280 ℃. Reaction gas: 60-70ppmNO, 60ppmNH3GHSV of 2000h-1. The test results are shown in table 1, and the reaction window temperature in table 1 is a temperature range in which the denitration efficiency is more than 80%.
TABLE 1
In FIG. 2 OMS-2 is the MnOx catalyst prepared in comparative example 2, Ce-Mn is the Ce-Mn catalyst prepared in comparative example 1, and Ce-Mn-Zr is the Ce-Mn-Zr catalyst prepared in example 1. As can be seen from the data in Table 1 and FIG. 2, the Ce-Mn-Zr catalysts prepared in the examples of the present invention have excellent denitration performance compared to the comparative examples 2-8, wherein the Ce-Mn-Zr catalyst described in example 1 has the best denitration performance, and the denitration efficiency at 50-220 ℃ is more than 80%. According to examples 1, 4-7 and comparative examples 3-4, it can be seen that when the molar ratio of cerium nitrate to potassium permanganate is 1:4, the denitration performance of the Ce-Mn-Zr catalyst is optimal, and the ratio of the cerium nitrate to the potassium permanganate is within the range defined by the invention, so that the prepared Ce-Mn-Zr catalyst has better denitration performance. As can be seen from the data of examples 1, 8-10 and comparative examples 5-6, the highest denitration efficiency of the Ce-Mn-Zr catalyst is as high as 100% within the limits of the present invention. According to the data of examples 1, 11-12 and comparative examples 7-8, it can be seen that the hydrothermal temperature is too high and too low, which is not good for improving the denitration performance of the Ce-Mn-Zr catalyst.
Test example 3
The invention relates to a test example for testing the sulfur resistance of a sulfur-resistant Ce-Mn-Zr catalyst.
Test samples: catalysts prepared in examples and comparative examples.
And (3) testing conditions are as follows: the catalyst is placed in a denitration evaluation device, the denitration catalytic performance stability of the catalyst at 150 ℃ is tested, and the denitration catalytic performance of the catalyst is tested when the catalyst is just stabilized at 150 ℃ at 0h, namely at 38 h. Reaction gas: 60-70ppmNO, 60ppmNH3，60mg/m3SO2GHSV of 2000h-1。
TABLE 2
In FIG. 3 OMS-2 is the MnOx catalyst prepared in comparative example 2, Ce-Mn is the Ce-Mn catalyst prepared in comparative example 1, and Ce-Mn-Zr is the Ce-Mn-Zr catalyst prepared in example 1. As can be seen from the data of Table 2 and FIG. 3, the Ce-Mn-Zr catalysts prepared in the examples of the present invention have better sulfur resistance than the comparative examples.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A sulfur-resistant Ce-Mn-Zr catalyst, characterized in that the Ce-Mn-Zr catalyst comprises a transition metal which is ZrO2、MnO2And CeO2。
2. The method of preparing the sulfur-resistant Ce-Mn-Zr catalyst according to claim 1, characterized by comprising the steps of:
(1) dissolving a cerium source and a manganese source in water, and uniformly mixing to obtain a mixed solution;
(2) adding a zirconium source into the mixed solution, uniformly stirring, and then carrying out hydrothermal reaction to obtain the sulfur-resistant Ce-Mn-Zr catalyst.
3. The method for preparing the sulfur-resistant Ce-Mn-Zr catalyst according to claim 2, wherein in the step (1), the molar ratio of the cerium source to the manganese source is 1:1 to 10.
4. The method for preparing a sulfur-resistant Ce-Mn-Zr catalyst according to claim 3, wherein in the step (1), the molar ratio of the cerium source to the manganese source is 1: 3-5; more preferably, the molar ratio of the cerium source to the manganese source is 1: 4.
5. the method for preparing the sulfur-resistant Ce-Mn-Zr catalyst according to claim 2, wherein the mass percentage of the zirconium source is 0.7-5% based on the total mass of the cerium source and the manganese source.
6. The method for preparing the sulfur-resistant Ce-Mn-Zr catalyst according to claim 5, wherein the mass percentage of the zirconium source is 1 to 5% based on the total mass of the cerium source and the manganese source.
7. The method for producing a sulfur-resistant Ce-Mn-Zr catalyst according to claim 5, wherein the mass percentage of the zirconium source is 3% based on the total mass of the cerium source and the manganese source.
8. The preparation method of the sulfur-resistant Ce-Mn-Zr catalyst according to claim 2, wherein in the step (2), the temperature of the hydrothermal reaction is 70-220 ℃, and the time of the hydrothermal reaction is 8-72 h.
9. The method for preparing the sulfur-resistant Ce-Mn-Zr catalyst according to claim 2, wherein said cerium source is at least one of cerium nitrate, cerium chloride, cerium carbonate, and cerium sulfate; the manganese source is potassium permanganate; the zirconium source is at least one of zirconium nitrate, zirconium chloride, zirconium carbonate and zirconium sulfate.
10. The use of the sulfur-resistant Ce-Mn-Zr catalyst of claim 1 in low temperature denitration of flue gas.
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| US20120036834A1 (en) * | 2010-08-10 | 2012-02-16 | GM Global Technology Operations LLC | Mn, Ce and Zr MIXED OXIDES OXIDATION CATALYST |
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| CN106423148A (en) * | 2016-11-07 | 2017-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Zirconium-doped cerium-manganese oxide catalyst as well as preparation and application |
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| US20120036834A1 (en) * | 2010-08-10 | 2012-02-16 | GM Global Technology Operations LLC | Mn, Ce and Zr MIXED OXIDES OXIDATION CATALYST |
| WO2012071971A1 (en) * | 2010-12-01 | 2012-06-07 | 中国科学院生态环境研究中心 | Ce-based composite oxide catalyst, preparation method and application thereof |
| CN106423148A (en) * | 2016-11-07 | 2017-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Zirconium-doped cerium-manganese oxide catalyst as well as preparation and application |
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