(19)
(11)EP 4 070 883 A1

(12)EUROPEAN PATENT APPLICATION
published in accordance with Art. 153(4) EPC

(43)Date of publication:
12.10.2022 Bulletin 2022/41

(21)Application number: 20966699.9

(22)Date of filing:  29.12.2020
(51)International Patent Classification (IPC): 
B01J 23/28(2006.01)
B01J 23/34(2006.01)
B01J 23/888(2006.01)
B01D 53/86(2006.01)
B01J 23/30(2006.01)
B01J 23/887(2006.01)
B01J 23/889(2006.01)
B01D 53/56(2006.01)
(86)International application number:
PCT/CN2020/140493
(87)International publication number:
WO 2022/134137 (30.06.2022 Gazette  2022/26)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
KH MA MD TN

(30)Priority: 21.12.2020 CN 202011517634

(71)Applicant: Valiant Co., Ltd.
Yantai, Shandong 264006 (CN)

(72)Inventors:
  • LIU, Xiaoling
    Yantai, Shandong 264006 (CN)
  • YUAN, Hu
    Yantai, Shandong 264006 (CN)
  • XIE, Songwei
    Yantai, Shandong 264006 (CN)
  • MENG, Fanmin
    Yantai, Shandong 264006 (CN)

(74)Representative: Ipside 
7-9 Allées Haussmann
33300 Bordeaux Cedex
33300 Bordeaux Cedex (FR)

  


(54)METHOD FOR PREPARING HIGH-EFFICIENCY DENITRIFICATION ACTIVITY CATALYST


(57) A method for preparing an active catalyst for high-efficiency denitration is disclosed. The method comprises the following steps: a catalyst raw material is charged into a denitration reactor, NH3 and an inert gas are introduced and then heating is performed, and the temperature is held and then natural cooling is performed, thereby obtaining the catalyst. The beneficial effects of the invention are as follows. The active catalyst prepared by the method of the invention can greatly improve the denitration activity of the catalyst in low temperature range, and can not only improve the denitration efficiency of the catalyst under the condition without SO2 and H2O, but also can improve the denitration efficiency of the catalyst under the condition with both SO2 and H2O. The service life of the catalyst is prolonged under the premise of not changing the existing catalyst preparation process, and the economic benefit is significant. The denitration efficiency of a powder catalyst can be increased by 25%, and the denitration efficiency of a honeycombed catalyst or a corrugated catalyst can be increased by 20%.


Description

Technical Field



[0001] The invention relates to the field of catalysis, belongs to the air pollution control technology and the environmentally friendly catalyst material technology, and in particular relates to a method for preparing an active catalyst with high-efficiency denitration.

Background Art



[0002] The coal-dominated energy structure will lead to the increase of NOx emissions, which seriously pollutes the ecological environment. How to effectively eliminate NOx has become an important topic of concern currently in the field of environmental protection.

[0003] Among numerous NOx emission control technologies, the ammonia selective catalytic reduction (NH3-SCR) technology is one of the most widely used and mature flue gas denitration technologies currently in the world. It is widely used in denitration of flue gas from coal-fired power plants and industrial boilers and so on. This technology has the advantages of high denitration efficiency, good selectivity, reliable operation and convenient maintenance. A catalyst is a core part of a NH3-SCR system, and its performance directly affects the overall denitration efficiency and stability of the system, and is the key to the success or failure of a denitration project.

[0004] Calcination, as a key step in catalyst preparation, is an important factor affecting the catalyst activity. Excessive calcination temperature will cause catalyst sintering, resulting in catalyst deactivation. Different calcination atmospheres and different valence states of metal active components lead to different catalyst activities. A suitable calcination atmosphere can improve the catalyst activity. CN10808007 discloses a MnOx-CuSO4 composite oxide catalyst. The preparation process uses N2 as a calcination atmosphere. The catalyst has high low-temperature denitration activity and good resistance to SO2 poisoning. Compared with the current catalyst preparation process, the process is complicated, which is not conducive to mass production.

[0005] The use of calcination to improve the catalyst activity has been used in hydrodesulfurization catalysts, but it is still blank in the field of flue gas denitration. For example, CN102407148 discloses a method for activating a hydrodesulfurization catalyst. In-situ calcination for carbonization and sulfurization of the catalyst can improve the hydrodesulfurization activity of the catalyst. CN106140323 discloses a hydrogenation catalyst activation method and use thereof. The catalyst is sulfurized in the presence of a mixed gas comprising hydrogen sulfide, an inert gas and hydrogen, and its desulfurization activity and stability are improved. On the premise of not changing the existing catalyst preparation process, the invention only adds one step of calcination, which can improve the denitration activity of the catalyst and prolong its service life, and has significant economic benefits.

Summary of the Invention



[0006] In view of the problem of low efficiency of the existing catalytic denitration, the invention provides a method for preparing an active catalyst for high-efficiency denitration: a catalyst raw material is charged into a denitration reactor, NH3 and an inert gas are introduced and then heating is performed, and the temperature is held and then natural cooling is performed, thereby obtaining the catalyst.

[0007] The active component of the catalyst raw material used in the invention is selected from one or more oxides of V, Mo, W, Ce, Fe, Co, Ni, Cu, Nb, Sn, Mn or La, the support is selected from one or more of titanium dioxide, titanium silicon powder, titanium tungsten powder, titanium tungsten silicon powder, silicon dioxide or aluminum oxide, and the finally formed active catalyst is a powder catalyst, a honeycombed catalyst or a corrugated catalyst.

[0008] The temperature of the denitration reactor is controlled at 300-550°C, the temperature holding time is 1-10h, NH3 and the inert gas are continuously introduced, and the inert gas is a common gas and may be one selected from nitrogen, helium or argon.

[0009] The beneficial effects of the invention are as follows. The active catalyst prepared by the method of the invention can greatly improve the denitration activity of the catalyst in a low temperature range, and can not only improve the denitration efficiency of the catalyst under the condition without SO2 and H2O, but also can improve the denitration efficiency of the catalyst under the condition with both SO2 and H2O. The service life of the catalyst is prolonged under the premise of not changing the existing catalyst preparation process, and the economic benefit is significant. The denitration efficiency of a powder catalyst can be increased by 25%, and the denitration efficiency of a honeycombed catalyst or a corrugated catalyst can be increased by 20%.

Detailed Description of Embodiments



[0010] The following describes the invention with reference to examples. Examples given are merely used for explaining the invention, and do not limit the scope of the invention.

Example 1



[0011] A method for preparing an active catalyst for high-efficiency denitration, comprising the following steps:
  1. (1) A CoMnCeTiO2 honeycombed extruded catalyst was charged into a denitration reactor to test the denitration performance of a fresh sample;
  2. (2) NH3 and N2 were introduced, and the heating was started;
  3. (3) the temperature was held at 300-350°C for 5-6h;
  4. (4) natural cooling was performed after the temperature holding was completed;
  5. (5) an activated sample was tested for denitration performance with the test conditions below:


Example 2



[0012] A method for preparing an active catalyst for high-efficiency denitration, comprising the following steps:
  1. (1) A VMoNiTiO2 honeycombed extruded catalyst was charged into a denitration reactor to test the denitration performance of a fresh sample;
  2. (2) NH3 and He were introduced, and heating was started;
  3. (3) the temperature was held at 350-400°C for 3-4h;
  4. (4) natural cooling was performed after the temperature holding was completed;
  5. (5) an activated sample was tested for denitration performance with the test conditions below:


Example 3



[0013] A method for preparing an active catalyst for high-efficiency denitration, comprising the following steps:
  1. (1) A VMoTiO2 powder catalyst was charged into a denitration reactor to test the denitration performance of a fresh sample;
  2. (2) NH3 and N2 were introduced, and the heating was started;
  3. (3) the temperature was held at 450-500°C for 1-2h;
  4. (4) natural cooling was performed after the temperature holding was completed;
  5. (5) an activated sample was tested for denitration performance with the test conditions below:


Example 4



[0014] A method for preparing an active catalyst for high-efficiency denitration, comprising the following steps:
  1. (1) A VWCeTiO2 powder catalyst was charged into a denitration reactor to test the denitration performance of a fresh sample;
  2. (2) NH3 and N2 were introduced, and the heating was started;
  3. (3) the temperature was held at 400-450°C for 7-8h;
  4. (4) natural cooling was performed after the temperature holding was completed;
  5. (5) an activated sample was tested for denitration performance with the test conditions below:


Example 5



[0015] A method for preparing an active catalyst for high-efficiency denitration, comprising the following steps:
  1. (1) A MnCeTiO2 powder catalyst was charged into a denitration reactor to test the denitration performance of a fresh sample;
  2. (2) NH3 and He were introduced, and heating was started;
  3. (3) the temperature was held at 300-350°C for 9-10h;
  4. (4) natural cooling was performed after the temperature holding was completed;
  5. (5) an activated sample was tested for denitration performance with the test conditions below:


Example 6



[0016] A method for preparing an active catalyst for high-efficiency denitration, comprising the following steps:
  1. (1) A VWTiO2 honeycombed coated catalyst was charged into a denitration reactor to test the denitration performance of a fresh sample;
  2. (2) NH3 and N2 were introduced, and the heating was started;
  3. (3) the temperature was held at 400-450°C for 2-3h;
  4. (4) natural cooling was performed after the temperature holding was completed;
  5. (5) an activated sample was tested for denitration performance with the test conditions below:


Example 7



[0017] A method for preparing an active catalyst for high-efficiency denitration, comprising the following steps:
  1. (1) A VMoWTiO2 honeycombed coated catalyst was charged into a denitration reactor to test the denitration performance of a fresh sample;
  2. (2) NH3 and Ar were introduced, and heating was started;
  3. (3) the temperature was held at 450-500°C for 8-9h;
  4. (4) natural cooling was performed after the temperature holding was completed;
  5. (5) an activated sample was tested for denitration performance with the test conditions below:


Example 8



[0018] A method for preparing an active catalyst for high-efficiency denitration, comprising the following steps:
  1. (1) A VMoCeTiO2 corrugated catalyst was charged into a denitration reactor to test the denitration performance of a fresh sample;
  2. (2) NH3 and He were introduced, and heating was started;
  3. (3) the temperature was held at 500-550°C for 4-6h;
  4. (4) natural cooling was performed after the temperature holding was completed;
  5. (5) an activated sample was tested for denitration performance with the test conditions below:


Example 9



[0019] A method for preparing an active catalyst for high-efficiency denitration, comprising the following steps:
  1. (1) A VWCoTiO2 corrugated catalyst was charged into a denitration reactor to test the denitration performance of a fresh sample;
  2. (2) NH3 and N2 were introduced, and the heating was started;
  3. (3) the temperature was held at 450-500°C for 1-2h;
  4. (4) natural cooling was performed after the temperature holding was completed;
  5. (5) an activated sample was tested for denitration performance with the test conditions below:


Comparative example 1



[0020] A method for preparing a denitration catalyst, comprising the following steps:
  1. (1) A TiO2 honeycombed coated catalyst was charged into a denitration reactor to test the denitration performance of a fresh sample;
  2. (2) NH3 and N2 were introduced, and the heating was started;
  3. (3) the temperature was held at 400-450°C for 2-3h;
  4. (4) natural cooling was performed after the temperature holding was completed;
  5. (5) an activated sample was tested for denitration performance with the test conditions below:



[0021] The catalysts obtained in Examples 1-9 and Comparative Example 1 were tested for catalytic denitration effects at different temperatures, and the denitration efficiencies are shown in Table 1.
Table 1. Denitration efficiency at different temperatures
Catalyst Denitration efficiency (%) Temperature (°C)180200250300350400Remark
Example 1 55.6 68.7 76.5 84.3 90.6 87.1 Fresh sample
77.5 86.0 92.1 96.6 98.9 93.2 Activated sample
Example 2 38.7 53.8 66.7 78.8 89.4 93.5 Fresh sample
63.7 74.0 84.4 92.5 97.1 99.0 Activated sample
Example 3 33.9 57.7 73.7 87.2 95.9 98.9 Fresh sample
56.8 79.8 91.3 97.5 99.2 99.8 Activated sample
Example 4 27.7 42.3 53.8 66.7 78.8 89.4 Fresh sample
55.4 68.6 79.4 88.8 94.9 98.1 Activated sample
Example 5 49.3 68.2 82.1 92.6 98.1 93.5 Fresh sample
71.3 89.0 95.2 98.2 99.6 94.3 Activated sample
Example 6 52.6 68.7 76.5 84.3 90.6 93.6 Fresh sample
69.8 85.9 93.8 95.6 96.8 97.0 Activated sample
Example 7 40.2 58.5 73.3 81.9 88.5 92.1 Fresh sample
64.5 80.8 92.7 94.5 95.1 97.1 Activated sample
Example 8 39.6 56.3 68.3 80.0 87.7 92.3 Fresh sample
58.6 73.9 85.6 91.5 94.7 95.6 Activated sample
Example 9 46.3 65.9 78.9 84.0 91.1 92.7 Fresh sample
65.6 79.9 88.3 92.7 96.3 97.2 Activated sample
Comparative example 1 3.0 3.5 3.9 3.9 4.1 4.3 Fresh sample
3.2 3.6 3.8 4.0 4.2 4.4 Activated sample


[0022] It can be seen from the test results in Table 1 that the denitration efficiencies of all the catalysts of Examples 1-9 are increased after calcination and activation, and that with the increase of the test temperature, the differences between the activated samples and the fresh samples are reduced, and when the test temperature is 180°C, the differences between the two are the largest (15-30%), indicating that the method provided by the invention can greatly improve the denitration activity of the catalyst in low temperature range.

[0023] Comparative Example 1 has no active component with TiO2 as the support, the fresh sample and the activated sample have similar denitration efficiencies, and the denitration efficiencies at 180-400°C are less than 5%, indicating that the method provided by the invention cannot improve the denitration activity of the support.

[0024] The above-mentioned descriptions are merely preferred embodiments of the invention but not intended to limit the invention, and any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the invention should be included within the scope of protection of the present solution.


Claims

1. A method for preparing an active catalyst for high-efficiency denitration, comprising the following steps: a catalyst raw material is charged into a denitration reactor, NH3 and an inert gas are introduced and then heating is performed, and the temperature is held and then natural cooling is performed, thereby obtaining the catalyst.
 
2. The method for preparing an active catalyst for high-efficiency denitration according to claim 1, wherein the active component of the catalyst raw material is selected from one or more oxides of V, Mo, W, Ce, Fe, Co, Ni, Cu, Nb, Sn, Mn or La, and the support is selected from one or more of titanium dioxide, titanium silicon powder, titanium tungsten powder, titanium tungsten silicon powder, silicon dioxide or aluminum oxide.
 
3. The method for preparing an active catalyst for high-efficiency denitration according to claim 1, wherein the inert gas is one of nitrogen, helium or argon.
 
4. The method for preparing an active catalyst for high-efficiency denitration according to claim 1, wherein the temperature is 300-550°C, and the temperature holding time is 1-10h.
 
5. The method for preparing an active catalyst for high-efficiency denitration according to claim 1, wherein the resulting active catalyst is a powder catalyst, a honeycombed catalyst or a corrugated catalyst.
 





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Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description