CN107640768B - Preparation method of nitrogen-rich modified desulfurization adsorption material - Google Patents
Preparation method of nitrogen-rich modified desulfurization adsorption material Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen-rich modified desulfurization porous adsorption material, which takes raw coal and semi coke particles as main raw materials and takes adhesive and deionized water as auxiliary forming agents, and the porous carbon material is obtained by mixing, forming, carbonizing and activating by steam in sequence; finally, the porous adsorption material with high desulfurization efficiency is formed by the heat treatment of the nitrogenous reagent. The method has the advantages of simple process and mild operation conditions, and the desulfurization rate of the obtained porous adsorption material is stabilized to be more than 92%.
Description
Technical Field
The invention belongs to the technical field of preparation of desulfurization materials, and particularly relates to a preparation method of a nitrogen-rich modified desulfurization porous adsorption material.
Background
In recent years, limestone is widely adopted in industryThe wet flue gas desulfurization technology represented by gypsum method is used for removing SO in flue gas2Absorbing and generating gypsum as a byproduct. However, the practical current situation shows that the technology has the problems of large amount of gypsum as a byproduct, low utilization value of the byproduct, serious corrosion of equipment and the like.
The porous carbon material has rich raw material sources, developed pore structures and various modification methods, and shows good desulfurization performance under appropriate reaction conditions, so that the porous carbon material shows good application prospects in the field of dry desulfurization. The desulfurization performance of the porous carbon material depends not only on the pore structure thereof but also is affected by the surface chemical properties (especially, surface oxygen-containing functional groups and nitrogen-containing functional groups). However, from the existing research results, the porous carbon materials reported at present generally have the defects of single surface structure, low adsorption capacity, small number of oxygen-containing and nitrogen-containing functional groups on the surface, unstable desulfurization efficiency and the like.
Therefore, it is necessary to develop a novel porous adsorbent having a rich nitrogen-containing functional group, a developed pore structure, and high desulfurization efficiency based on the existing research.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen-rich modified desulfurization porous adsorption material, which is prepared by adopting a method with cheap and easily-obtained raw materials, mild operation conditions, simple and controllable process, rich nitrogen-containing functional groups and high desulfurization efficiency.
The invention is realized by adopting the following technical scheme:
a preparation method of a nitrogen-rich modified desulfurization porous adsorption material comprises the following steps:
(1) grinding raw coal and semi-coke particles with the mass ratio of 3:2 into 220-mesh and 300-mesh coal powder; uniformly mixing the coal powder, the adhesive and the deionized water at a mass ratio of 60-80:20-30:15-25 at a stirring speed of 600-750r/min, and extruding the mixture into a cylinder by using a flat die rolling granulator under the pressure of 30-45MPa to obtain formed carbon;
(2) the molded carbon is heated to 650-750 ℃ from room temperature in a high-temperature tube furnace and carbonized for 1-3h, then the temperature is heated to 850-950 ℃, water vapor of 15-35mL/min is introduced for activation for 2-4h, and the temperature is naturally reduced to room temperature to obtain a porous material;
(3) and (3) raising the temperature of the porous material obtained in the step (2) to 600-800 ℃ from the room temperature in a high-temperature tube furnace, introducing 20-40mL/min of nitrogen-containing reagent, keeping the temperature for 1-3h, and naturally cooling to obtain the nitrogen-rich modified desulfurization porous adsorption material.
In the preparation method, in the step (1), the raw coal is one or a mixture of more of bituminous coal, anthracite and gas fat coal. The adhesive is starch or resol.
In the preparation method, in the step (3), the nitrogen-containing reagent is triethanolamine, tetraethylenepentamine or ammonia water.
The preparation method of the nitrogen-rich modified desulfurization porous adsorption material provided by the invention has the advantages that the raw materials are cheap and easy to obtain, the operation condition is mild, the process is simple and controllable, and the nitrogen-containing functional groups are rich, and specifically, raw coal and semi-coke particles are used as main raw materials, an adhesive and deionized water are used as auxiliary forming agents, and the porous carbon material is obtained through mixing, forming, carbonization and steam activation in sequence; finally, the porous adsorption material with high desulfurization efficiency is formed by the heat treatment of the nitrogenous reagent. And the desulfurization rate of the obtained porous adsorption material is stabilized to be more than 92 percent.
Drawings
FIG. 1 shows an SEM image (a in the figure) and a corresponding cross-sectional view (b in the figure) of a nitrogen-enriched modified desulphurized porous adsorbent material prepared in example 1.
FIG. 2 shows an SEM image (a in the figure) and a corresponding cross-sectional view (b in the figure) of the nitrogen-enriched modified desulphurized porous adsorbent material prepared in example 2.
FIG. 3 shows an SEM image (a in the figure) and a corresponding cross-sectional view (b in the figure) of the nitrogen-enriched modified desulphurized porous adsorbent material prepared in example 3.
FIG. 4 shows the desulfurization application at different temperatures of example 4 and the desulfurization profiles at different temperatures of comparative examples 1 and 2.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
The method comprises the steps of taking raw coal and semi-coke particles as main raw materials, taking an adhesive and deionized water as auxiliary forming agents, and sequentially carrying out mixing, forming, carbonization and steam activation to obtain a porous carbon material; finally, the porous adsorbing material with high desulfurization efficiency is formed by heat treatment of the nitrogenous reagent, and the instrument and equipment used in the test, the test condition, the measurement step and the treatment of the measurement result are determined. Provides a theoretical basis for the preparation research and design of the high-efficiency desulfurization activated carbon.
Example 1
1. 51g of bituminous coal and 34g of semi-coke particles are ground into 220-mesh coal powder; uniformly mixing 48g of coal powder, 16g of resol and 12g of deionized water at a stirring speed of 600r/min, and extruding into a cylinder shape by using a flat die rolling granulator under the pressure of 30MPa to obtain formed carbon;
2. carbonizing the formed carbon in a high-temperature tube furnace from room temperature to 650 ℃ for 1h, then heating to 850 ℃, introducing 35mL/min of water vapor for activation for 4h, and naturally cooling to room temperature to obtain a porous carbon material;
3. and (3) raising the temperature of 150g of the porous material from room temperature to 600 ℃ in a high-temperature tube furnace, introducing 40mL/min triethanolamine, keeping the temperature for 1h, and naturally cooling to obtain the nitrogen-enriched modified desulfurization porous adsorption material.
Figure 1 shows an SEM image of a nitrogen-enriched modified desulphurised porous adsorbent material prepared in example 1 and a corresponding cross-sectional view thereof.
Example 2
1. Grinding 60g of coking coal and 20g of semi coke particles into 260-mesh coal powder; uniformly mixing 70g of coal powder, 25g of starch and 20g of deionized water at a stirring speed of 700r/min, and extruding into a cylinder shape by using a flat die rolling granulator under the pressure of 40MPa to obtain formed carbon;
2. the molded carbon is heated from room temperature to 700 ℃ in a high-temperature tube furnace for carbonization for 2h, then the temperature is heated to 900 ℃, 15mL/min of water vapor is introduced for activation for 2h, and the temperature is naturally reduced to room temperature to obtain a porous carbon material;
3. and (3) heating 200g of the porous material in a high-temperature tube furnace from room temperature to 700 ℃, introducing 40mL/min ammonia water, keeping for 3h, and naturally cooling to obtain the nitrogen-enriched modified desulfurization porous adsorption material.
Figure 2 shows an SEM image of the nitrogen-rich modified desulphurised porous adsorbent material prepared in example 2 and a corresponding cross-sectional view.
Example 3
1. Grinding 66g of anthracite and 44g of semi-coke particles into 300-mesh coal powder; uniformly mixing 80g of coal powder, 30g of starch and 25g of deionized water at a stirring speed of 750r/min, and extruding into a cylinder shape by using a flat die rolling granulator under the pressure of 45MPa to obtain formed carbon;
2. the molded carbon is heated to 750 ℃ from the room temperature in a high-temperature tube furnace for carbonization for 3h, then the temperature is heated to 950 ℃, 25mL/min of water vapor is introduced for activation for 3h, and the temperature is naturally reduced to the room temperature to obtain a porous carbon material;
3. and (3) heating 300g of the porous material to 800 ℃ from room temperature in a high-temperature tube furnace, introducing 50mL/min of tetraethylenepentamine, keeping for 2h, and naturally cooling to obtain the nitrogen-enriched modified desulfurization porous adsorption material.
Figure 3 shows an SEM image of the nitrogen-rich modified desulphurised porous adsorbent material prepared in example 3 and a corresponding cross-sectional view.
As can be seen from FIGS. 1, 2 and 3, the nitrogen-rich modified desulfurization porous adsorption material prepared by the embodiments 1, 2 and 3 of the present invention is a cylindrical material, and the interior of the porous carbon material has rich pores.
Example 4
The nitrogen-rich modified desulfurization porous adsorption materials prepared in the embodiments 1, 2 and 3 of the invention are used for testing desulfurization performance under different reaction times respectively. The method is used for preparing the nitrogen-rich modified desulfurization porous adsorption material and testing the desulfurization performance of the adsorption material, and the quality of the adsorption material is evaluated according to the test result.
The specific experimental conditions were: the desulfurization reaction was carried out on a quartz tube reactor having an inner diameter of 30 mm. Experimental simulation smoke composition is 0.06% H2O、0.15% SO2、10% O2，N2Balance, operating temperature of 150 ℃, flue gas flow rate of 600mL/min, 15g of porous material and space velocity of 4000h-1. Outlet SO2The concentration was measured on-line in real time using a smoke analyzer (KM950, Kane, UK).
Comparative example 1
The porous carbon material obtained in example 1 by only steam activation (step 3) was used to test desulfurization performance at different reaction times, and the specific experimental conditions were the same as those in example 4.
Comparative example 2
The porous carbon material obtained by water vapor activation in example 2 (actual step 3) was used to test desulfurization performance at different temperatures, and the specific experimental conditions were the same as those in example 4.
The desulfurization performance of the samples 1, 2 and 3 and the comparative examples 1 and 2 at different reaction times were respectively detected on line in real time, specifically, as shown in fig. 4, the desulfurization rates of the porous carbon materials obtained by the examples 1 and 2 only through the activation of water vapor were low and unstable, while the desulfurization rates of the nitrogen-rich modified desulfurization porous adsorption materials prepared by the examples 1, 2 and 3 were stable at more than 92%.
The porous carbon material reported at present generally has the defects of single surface structure, low adsorption capacity, small quantity of oxygen-containing and nitrogen-containing functional groups on the surface, unstable desulfurization efficiency and the like. The method summarizes the preparation method of the nitrogen-rich modified desulfurization porous adsorption material through a large number of tests. By the test method, the desulfurization performance of the porous carbon material can be improved, the desulfurization rate of the obtained carbon porous material is stabilized to be more than 92%, and scientific basis is provided for the preparation of the high-efficiency desulfurization activated carbon.
It should be noted that modifications and applications may occur to those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (1)
1. A preparation method of a nitrogen-rich modified desulfurization adsorbing material is characterized by comprising the following steps: the method comprises the following steps:
(1) grinding raw coal and semi-coke particles with the mass ratio of 3:2 into 220-mesh and 300-mesh coal powder; uniformly mixing the coal powder, the adhesive and the deionized water at a mass ratio of 60-80:20-30:15-25 at a stirring speed of 600-750r/min, and extruding the mixture into a cylinder by using a flat die rolling granulator under the pressure of 30-45MPa to obtain formed carbon; the raw coal is one or a mixture of more of bituminous coal, anthracite and gas fat coal; the adhesive is starch or resol;
(2) the molded carbon is heated to 650-750 ℃ from room temperature in a high-temperature tube furnace and carbonized for 1-3h, then the temperature is heated to 850-950 ℃, water vapor of 15-35mL/min is introduced for activation for 2-4h, and the temperature is naturally reduced to room temperature to obtain a porous material;
(3) raising the temperature of the porous material obtained in the step (2) to 600-800 ℃ from room temperature in a high-temperature tube furnace, and then introducing 20-40mL/min of a nitrogen-containing reagent, wherein the nitrogen-containing reagent is triethanolamine, tetraethylenepentamine or ammonia water; and keeping for 1-3h, and then naturally cooling to obtain the nitrogen-rich modified desulfurization porous adsorption material.
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