阅读说明：本技术 适用于低温scr脱硝催化剂的活性半焦载体制备方法 (Preparation method of active semicoke carrier suitable for low-temperature SCR denitration catalyst ) 是由 刘清才 吴泓利 彭靓 蒋历俊 杨鹏 高子涵 蔡泽龙 苏增辉 刘兰 杨臣 于 2019-09-04 设计创作，主要内容包括：本发明目的是针对现有技术存在的不足之处,提供适用于低温SCR脱硝催化剂的活性半焦载体制备方法。本发明充分利用半焦机械强度高、表面官能团丰富且易于活化、廉价易得等优点,采用本发明提供的方法对半焦进行活化处理,并进一步通过向活性半焦掺杂过渡金属锰和稀土元素铈的氧化物来提高其脱硝活性。(The invention aims to provide a preparation method of an active semicoke carrier suitable for a low-temperature SCR denitration catalyst aiming at the defects in the prior art. The method provided by the invention fully utilizes the advantages of high mechanical strength, abundant surface functional groups, easiness in activation, low price and easiness in obtaining and the like of the semicoke, carries out activation treatment on the semicoke by adopting the method provided by the invention, and further improves the denitration activity of the active semicoke by doping oxides of transition metal manganese and rare earth element cerium into the active semicoke.)

1. A preparation method of an active semicoke carrier suitable for a low-temperature SCR denitration catalyst is characterized by comprising the following steps:

1) taking the semi-coke raw material, grinding the semi-coke raw material, cleaning the semi-coke raw material by using the deionized water, and drying the semi-coke raw material;

2) multi-step activation treatment:

2-1) immersing the dried semi-coke particles obtained in the step 1) into hydrochloric acid for treatment;

2-2) filtering the semicoke particles treated in the step 2-1), and calcining under the inert gas protective atmosphere;

2-3) immersing the calcined semicoke particles into nitric acid for treatment;

3) filtering and washing the semicoke particles subjected to the multi-step activation treatment in the step 2) to be neutral, and drying to obtain an active semicoke carrier;

4) mixing inorganic salts of metal manganese and rare earth element cerium to be used as active components;

taking the active semicoke obtained in the step 3) as a carrier, and weighing the active component according to 5-10% of the mass of the carrier;

dissolving the weighed active components in water to obtain a precursor solution;

5) dipping the active semi-coke particles obtained in the step 3) into the precursor solution obtained in the step 4);

6) calcining the product obtained in the step 5) in an inert gas protective atmosphere, and cooling to obtain the active semicoke low-temperature SCR denitration catalyst.

2. A preparation method of an active semicoke carrier suitable for a low-temperature SCR denitration catalyst is characterized by comprising the following steps:

1) taking the semi-coke raw material, grinding the semi-coke raw material, cleaning the semi-coke raw material by using the deionized water, and drying the semi-coke raw material;

2) multi-step activation treatment:

2-1) calcining the dried semicoke particles obtained in the step 1) in an inert gas protective atmosphere;

2-2) immersing the calcined semicoke particles into nitric acid for treatment;

3) filtering and washing the semicoke particles subjected to the multi-step activation treatment in the step 2) to be neutral, and drying to obtain an active semicoke carrier;

4) mixing inorganic salts of metal manganese and rare earth element cerium to be used as active components;

taking the active semicoke obtained in the step 3) as a carrier, and weighing the active component according to 5-10% of the mass of the carrier;

dissolving the weighed active components in water to obtain a precursor solution;

5) dipping the active semi-coke particles obtained in the step 3) into the precursor solution obtained in the step 4);

6) calcining the product obtained in the step 5) in an inert gas protective atmosphere, and cooling to obtain the active semicoke low-temperature SCR denitration catalyst.

3. A preparation method of an active semicoke carrier suitable for a low-temperature SCR denitration catalyst is characterized by comprising the following steps:

1) taking the semi-coke raw material, grinding the semi-coke raw material, cleaning the semi-coke raw material by using the deionized water, and drying the semi-coke raw material;

2) multi-step activation treatment:

2-1) calcining the dried semicoke particles obtained in the step 1) in an inert gas protective atmosphere;

2-2) immersing the calcined semicoke particles into hydrochloric acid for treatment;

2-3) filtering the semicoke particles treated in the step 2-2), and then immersing in nitric acid for treatment;

3) filtering and washing the semicoke particles subjected to the multi-step activation treatment in the step 2) to be neutral, and drying to obtain an active semicoke carrier;

4) mixing inorganic salts of metal manganese and rare earth element cerium to be used as active components;

taking the active semicoke obtained in the step 3) as a carrier, and weighing the active component according to 5-10% of the mass of the carrier;

dissolving the weighed active components in water to obtain a precursor solution;

5) dipping the active semi-coke particles obtained in the step 3) into the precursor solution obtained in the step 4);

6) calcining the product obtained in the step 5) in an inert gas protective atmosphere, and cooling to obtain the active semicoke low-temperature SCR denitration catalyst.

4. A preparation method of an active semicoke carrier suitable for a low-temperature SCR denitration catalyst is characterized by comprising the following steps:

1) taking the semi-coke raw material, grinding the semi-coke raw material, cleaning the semi-coke raw material by using the deionized water, and drying the semi-coke raw material;

2) multi-step activation treatment:

2-1) immersing the dried semi-coke particles obtained in the step 1) into hydrochloric acid for treatment;

2-2) filtering the semicoke particles treated in the step 2-1), and then immersing in nitric acid for treatment;

3) filtering and washing the semicoke particles subjected to the multi-step activation treatment in the step 2) to be neutral, and drying to obtain an active semicoke carrier;

4) mixing inorganic salts of metal manganese and rare earth element cerium to be used as active components;

taking the active semicoke obtained in the step 3) as a carrier, and weighing the active component according to 5-10% of the mass of the carrier;

dissolving the weighed active components in water to obtain a precursor solution;

5) dipping the active semi-coke particles obtained in the step 3) into the precursor solution obtained in the step 4);

6) calcining the product obtained in the step 5) in an inert gas protective atmosphere, and cooling to obtain the active semicoke low-temperature SCR denitration catalyst.

5. The preparation method of the active semicoke carrier applicable to the low-temperature SCR denitration catalyst according to any one of claims 1 to 4, characterized by comprising the following steps: in the step 1), grinding to 20-40 meshes, wherein the drying temperature is 90-110 ℃, and the drying time is 6-10 h.

6. The preparation method of the active semicoke carrier applicable to the low-temperature SCR denitration catalyst according to any one of claims 1 to 5, characterized by comprising the following steps:

the nitric acid treatment in the step 2) is carried out at the temperature of 60-80 ℃ for 2-3 h; the volume-mass ratio (mL: g) of the nitric acid solution to the semicoke particles is (3-5) to 1.

Controlling the calcination temperature in the step 2).

The temperature of the hydrochloric acid activation treatment in the step 2) is 60-80 ℃, and the treatment time is 1-2 h; the volume-to-mass ratio (mL: g) of the hydrochloric acid solution to the semicoke particles is (3-5) to 1.

7. The preparation method of the active semicoke carrier applicable to the low-temperature SCR denitration catalyst according to any one of claims 1 to 6, characterized by comprising the following steps: in the step 3), the temperature in the drying process is 90-110 ℃, and the drying time is 6-10 h.

8. The preparation method of the active semicoke carrier applicable to the low-temperature SCR denitration catalyst according to any one of claims 1 to 7, which is characterized by comprising the following steps: in the step 4), the molar ratio of the metal manganese to the rare earth element cerium is controlled.

9. The preparation method of the active semicoke carrier applicable to the low-temperature SCR denitration catalyst according to any one of claims 1 to 8, characterized by comprising the following steps: in the step 5), the mass ratio of the volume of the precursor liquid to the active semicoke particles is controlled.

In the step 5), after dipping the active carbocoal particles in the precursor solution, carrying out ultrasonic treatment and standing, then carrying out water bath evaporation to dryness, and finally carrying out drying treatment;

the ultrasonic frequency is 40KHz, and the ultrasonic time range is 30-60 min;

the water bath time is 1-3 h, and the water bath temperature is 40-60 ℃;

the drying temperature is 90-110 ℃, and the drying time is 6-10 h.

10. The preparation method of the active semicoke carrier applicable to the low-temperature SCR denitration catalyst according to any one of claims 1 to 9, characterized by comprising the following steps: in step 6), the product is in N₂Or calcining under the protective atmosphere of Ar inert gas:

and in the calcining treatment process, the heating rate and the cooling time are controlled.

Technical Field

The invention relates to the field of pollution control of atmospheric nitrogen oxides, in particular to a preparation method of an active semicoke carrier suitable for a low-temperature SCR denitration catalyst.

Background

Nitrogen Oxides (NO)_x) Second only to inhalable particles and SO₂The emission of one of the main atmospheric pollutants poses a great threat to human health and living environment. With the continuous and high-speed development of industry and urbanization in China, the emission of nitrogen oxides is continuously increased, and the nitrogen oxides become the air pollutants which are mainly controlled.

Nitrogen oxides have many different forms of compounds, among which the nitrogen oxides produced in industry are mainly NO and NO₂Collectively called NO_xNO accounts for over 90%, so the removal of nitrogen oxides is mainly directed to NO.

The SCR selective catalytic reduction technology is the most main flue gas NO at present_xThe principle of the removal is NH₃Is a reducing agent, selectively catalyzes and reduces nitrogen oxides in the flue gas under the action of a catalyst to finally generate nontoxic and harmless N₂And H₂And O. The most widely used SCR catalyst in industry is now expensive TiO₂As a carrier, loading an active component V₂O₅The prepared vanadium-titanium catalyst. The catalyst has higher denitration activity at the temperature of 300-400 ℃, but has lower denitration activity and narrow active temperature window under the low-temperature condition, thereby greatly limiting the application of the catalyst in the low-temperature flue gas denitration process. Therefore, the development of a low-temperature SCR denitration catalyst which is cheap and easy to obtain and has excellent performance still faces a great challenge.

Disclosure of Invention

The invention aims to provide a preparation method of an active semicoke carrier suitable for a low-temperature SCR denitration catalyst.

The first scheme is as follows:

a preparation method of an active semicoke carrier suitable for a low-temperature SCR denitration catalyst is characterized by comprising the following steps:

1) taking the semi-coke raw material, grinding the semi-coke raw material, cleaning the semi-coke raw material by using the deionized water, and drying the semi-coke raw material;

2) multi-step activation treatment:

2-1) immersing the dried semi-coke particles obtained in the step 1) into hydrochloric acid for treatment;

2-2) filtering the semicoke particles treated in the step 2-1), and calcining under the inert gas protective atmosphere;

2-3) immersing the calcined semicoke particles into nitric acid for treatment;

3) filtering and washing the semicoke particles subjected to the multi-step activation treatment in the step 2) to be neutral, and drying to obtain an active semicoke carrier;

4) mixing inorganic salts of metal manganese and rare earth element cerium to be used as active components;

taking the active semicoke obtained in the step 3) as a carrier, and weighing the active component according to 5-10% of the mass of the carrier;

dissolving the weighed active components in water to obtain a precursor solution;

5) dipping the active semi-coke particles obtained in the step 3) into the precursor solution obtained in the step 4);

6) calcining the product obtained in the step 5) in an inert gas protective atmosphere, and cooling to obtain the active semicoke low-temperature SCR denitration catalyst.

Scheme II:

a preparation method of an active semicoke carrier suitable for a low-temperature SCR denitration catalyst is characterized by comprising the following steps:

1) taking the semi-coke raw material, grinding the semi-coke raw material, cleaning the semi-coke raw material by using the deionized water, and drying the semi-coke raw material;

2) multi-step activation treatment:

2-1) calcining the dried semicoke particles obtained in the step 1) in an inert gas protective atmosphere;

2-2) immersing the calcined semicoke particles into nitric acid for treatment;

3) filtering and washing the semicoke particles subjected to the multi-step activation treatment in the step 2) to be neutral, and drying to obtain an active semicoke carrier;

4) mixing inorganic salts of metal manganese and rare earth element cerium to be used as active components;

taking the active semicoke obtained in the step 3) as a carrier, and weighing the active component according to 5-10% of the mass of the carrier;

dissolving the weighed active components in water to obtain a precursor solution;

5) dipping the active semi-coke particles obtained in the step 3) into the precursor solution obtained in the step 4);

6) calcining the product obtained in the step 5) in an inert gas protective atmosphere, and cooling to obtain the active semicoke low-temperature SCR denitration catalyst.

The third scheme is as follows:

a preparation method of an active semicoke carrier suitable for a low-temperature SCR denitration catalyst is characterized by comprising the following steps:

1) taking the semi-coke raw material, grinding the semi-coke raw material, cleaning the semi-coke raw material by using the deionized water, and drying the semi-coke raw material;

2) multi-step activation treatment:

2-1) calcining the dried semicoke particles obtained in the step 1) in an inert gas protective atmosphere;

2-2) immersing the calcined semicoke particles into hydrochloric acid for treatment;

2-3) filtering the semicoke particles treated in the step 2-2), and then immersing in nitric acid for treatment;

3) filtering and washing the semicoke particles subjected to the multi-step activation treatment in the step 2) to be neutral, and drying to obtain an active semicoke carrier;

4) mixing inorganic salts of metal manganese and rare earth element cerium to be used as active components;

taking the active semicoke obtained in the step 3) as a carrier, and weighing the active component according to 5-10% of the mass of the carrier;

dissolving the weighed active components in water to obtain a precursor solution;

5) dipping the active semi-coke particles obtained in the step 3) into the precursor solution obtained in the step 4);

6) calcining the product obtained in the step 5) in an inert gas protective atmosphere, and cooling to obtain the active semicoke low-temperature SCR denitration catalyst.

And the scheme is as follows:

a preparation method of an active semicoke carrier suitable for a low-temperature SCR denitration catalyst is characterized by comprising the following steps:

1) taking the semi-coke raw material, grinding the semi-coke raw material, cleaning the semi-coke raw material by using the deionized water, and drying the semi-coke raw material;

2) multi-step activation treatment:

2-1) immersing the dried semi-coke particles obtained in the step 1) into hydrochloric acid for treatment;

2-2) filtering the semicoke particles treated in the step 2-1), and then immersing in nitric acid for treatment;

3) filtering and washing the semicoke particles subjected to the multi-step activation treatment in the step 2) to be neutral, and drying to obtain an active semicoke carrier;

4) mixing inorganic salts of metal manganese and rare earth element cerium to be used as active components;

taking the active semicoke obtained in the step 3) as a carrier, and weighing the active component according to 5-10% of the mass of the carrier;

dissolving the weighed active components in water to obtain a precursor solution;

5) dipping the active semi-coke particles obtained in the step 3) into the precursor solution obtained in the step 4);

6) calcining the product obtained in the step 5) in an inert gas protective atmosphere, and cooling to obtain the active semicoke low-temperature SCR denitration catalyst.

Further, in the step 1), grinding to 20-40 meshes, wherein the drying temperature is 90-110 ℃, and the drying time is 6-10 h;

further, the concentration of the nitric acid adopted in the step 2) is 40-60 wt.%; the temperature of the nitric acid treatment is 60-80 ℃, and the treatment time is 2-3 h; the volume-mass ratio (mL: g) of the nitric acid solution to the semicoke particles is (3-5) to 1.

In the step 2), the calcining temperature is 600-800 ℃, the calcining time is 2-4 h, and the heating rate is 5-10 ℃/min.

The concentration of hydrochloric acid adopted in the step 2) is 15-25 wt.%; the temperature of the hydrochloric acid activation treatment is 60-80 ℃, and the treatment time is 1-2 h; the volume-to-mass ratio (mL: g) of the hydrochloric acid solution to the semicoke particles is (3-5) to 1.

Further, in the step 3), the temperature in the drying process is 90-110 ℃, and the drying time is 6-10 h;

further, in the step 4), the molar ratio of the manganese metal to the rare earth element cerium is 0.1-0.5 Ce/(Mn + Ce)

Further, in the step 5), the mass ratio of the volume of the precursor liquid to the active semicoke particles is (5-20) to 1

In the step 5), after dipping the active carbocoal particles in the precursor solution, carrying out ultrasonic treatment and standing, then carrying out water bath evaporation to dryness, and finally carrying out drying treatment;

the ultrasonic frequency is 40KHz, and the ultrasonic time range is 30-60 min;

the water bath time is 1-3 h, and the water bath temperature is 40-60 ℃;

the drying temperature is 90-110 ℃, and the drying time is 6-10 h;

further, in step 6), the product is in N₂Or calcining under the protective atmosphere of Ar inert gas:

in the calcining treatment process, the temperature of the muffle furnace is increased to 300-500 ℃ from room temperature at the heating rate of 5-10 ℃/min, and the muffle furnace is naturally cooled to room temperature after being calcined for 2-4 h.

The method has the advantages of high mechanical strength, abundant surface functional groups, easiness in activation, low cost, easiness in obtaining and the like, and the activated semicoke is subjected to activation treatment by the method, and the denitration activity of the activated semicoke is improved by doping oxides of transition metal manganese and rare earth element cerium into the activated semicoke.

Drawings

FIG. 1 is a graph showing the variation curve of denitration activity of an active semicoke catalyst with temperature according to different preparation methods

Detailed Description

The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.