CN114259837B - Efficient capture method for carbon dioxide in flue gas - Google Patents
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Abstract
The invention discloses a method for efficiently trapping carbon dioxide in flue gas, and belongs to the technical field of gas adsorption and separation. Removing moisture and particle impurities from the flue gas by a flue gas treatment system, then introducing the flue gas into an adsorption tower to adsorb and capture carbon dioxide, and introducing hot steam into the adsorption tower to perform desorption and analysis after adsorption and capture are finished to finally obtain high-purity carbon dioxide; the adsorption tower is filled with a carbon dioxide adsorption material, and the filling volume of the carbon dioxide adsorption material is 60-85% of the volume of the adsorption tower; the adsorption pressure is 0.3-1.0 MPa, the adsorption temperature is 25-60 ℃, and the adsorption time is 0.1-5 h; the temperature of the hot steam is 120-180 ℃, and the desorption time is 2-5 h. According to the invention, the adsorption tower is adopted to capture the carbon dioxide in the flue gas, and then the hot steam is utilized to carry out desorption treatment, so that the carbon dioxide gas with high purity is finally obtained, and the whole process is green and environment-friendly, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of gas adsorption separation, and particularly relates to a method for efficiently capturing carbon dioxide in flue gas.
Background
The greenhouse effect is more and more obvious due to the increase of the emission amount of the carbon dioxide, and the recovery of the carbon dioxide becomes a research hotspot for inhibiting the further development of the greenhouse effect. The carbon dioxide obtained by separation and collection can be injected into petroleum and natural gas fields to improve the oil gas recovery ratio, and can also be widely used for synthesizing organic compounds, manufacturing carbonated beverages and the like to realize resource utilization.
Flue gas is a mixture of gas and smoke dust and is the main cause of atmospheric pollution in residential areas. The flue gas contains a considerable amount of carbon dioxide, so that the carbon dioxide in the flue gas is collected, recycled and reused while the emission of the flue gas is reduced, and the environmental protection is also exerted. The carbon dioxide adsorbent plays an important role in adsorbing and separating carbon dioxide in flue gas, and may be a material containing a high specific surface area such as silica, alumina, titania, zirconia, ceria, zeolite, a polymer material, or activated carbon, or a material containing an oxide or carbonate of an alkali metal or an alkaline earth metal. No matter which kind of composite material, it should satisfy that carbon dioxide adsorption efficiency is high to it is high just still to need to satisfy desorption analysis carbon dioxide efficiency.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for efficiently capturing carbon dioxide in flue gas, which is characterized in that an adsorption tower is adopted to capture carbon dioxide in flue gas, and then hot steam is utilized to perform desorption treatment, so that carbon dioxide gas with higher purity is obtained finally, the whole process is green and environment-friendly, and the method has good application prospect.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a high-efficiency capturing method of flue gas carbon dioxide is characterized in that the flue gas is subjected to moisture and particle impurities removal through a flue gas treatment system, then the flue gas enters an adsorption tower to be adsorbed and captured with carbon dioxide, and after adsorption and capture are finished, hot steam is introduced into the adsorption tower to be desorbed and resolved, so that high-purity carbon dioxide is finally obtained; the adsorption tower is filled with a carbon dioxide adsorption material, and the filling volume of the carbon dioxide adsorption material is 60-85% of the volume of the adsorption tower; the adsorption pressure is 0.3-1.0 MPa, the adsorption temperature is 25-60 ℃, and the adsorption time is 0.1-5 h; the temperature of the hot steam is 120-180 ℃, and the desorption time is 2-5 h.
According to the method for efficiently capturing the carbon dioxide in the flue gas, the filling volume of a carbon dioxide adsorption material is 75-80% of the volume of an adsorption tower; the adsorption pressure is 0.7-0.85 MPa, the adsorption temperature is 45-50 ℃, and the adsorption time is 2 h; the temperature of the hot steam is 150-160 ℃, and the desorption time is 2 h.
The method for efficiently capturing the carbon dioxide in the flue gas and the preparation method of the carbon dioxide adsorption material comprise the following steps:
(1) uniformly mixing a titanium tetrachloride solution, absolute ethyl alcohol and deionized water, adding ZSM-5 zeolite, adjusting the pH value of the solution to be alkaline, and heating for reaction;
(2) after the reaction is finished, adding rare earth metal oxide and 1-butyl-3-methylimidazole tetrafluoroborate into the reaction solution, mixing, and stirring for 2-3 hours under the action of ultrasound; and then filtering, washing a filter cake to be neutral, drying in an oven at 110-130 ℃, and grinding to obtain the carbon dioxide adsorbing material.
According to the efficient capture method of the flue gas carbon dioxide, the pH of a solution is adjusted to 8-10, and then the reaction is carried out for 1-3 h at 80-120 ℃; the concentration of the titanium tetrachloride solution is 0.05-1.5 mol/L, and the mass ratio of the titanium tetrachloride solution, absolute ethyl alcohol, deionized water and ZSM-5 type zeolite is 2-3: 1-5: 2-3: 1.
According to the efficient capture method of the flue gas carbon dioxide, the pH value of a solution is adjusted to 9, and then the reaction is carried out for 2-3 hours at the temperature of 90-100 ℃; the concentration of the titanium tetrachloride solution is 1.1mol/L, and the mass ratio of the titanium tetrachloride solution, absolute ethyl alcohol, deionized water and ZSM-5 type zeolite is 3:5:2: 1.
According to the method for efficiently capturing the carbon dioxide in the flue gas, the rare earth metal oxide is any one of lanthanum oxide, cerium oxide and erbium oxide; the mass ratio of the rare earth metal oxide to the 1-butyl-3-methylimidazole tetrafluoroborate to the ZSM-5 type zeolite is 0.03-0.5: 0.5-1.5: 1.
According to the method for efficiently capturing the carbon dioxide in the flue gas, the rare earth metal oxide is lanthanum oxide; the mass ratio of lanthanum oxide, 1-butyl-3-methylimidazole tetrafluoroborate and ZSM-5 type zeolite is 0.03:1.2: 1.
According to the efficient capture method of the carbon dioxide in the flue gas, the carbon dioxide adsorbing material is ground until the particle size is 4-10 mm.
The method for efficiently capturing the carbon dioxide in the flue gas comprises the following steps:
(1) uniformly mixing a titanium tetrachloride solution, absolute ethyl alcohol and deionized water, adding ZSM-5 zeolite, adjusting the pH value of the solution to be alkaline, and heating for reaction; adjusting the pH value of the solution to 9, and then reacting for 2-3 h at 90-100 ℃; the concentration of the titanium tetrachloride solution is 1.1mol/L, and the mass ratio of the titanium tetrachloride solution, absolute ethyl alcohol, deionized water and ZSM-5 type zeolite is 3:5:2: 1;
(2) after the reaction is finished, adding lanthanum oxide and 1-butyl-3-methylimidazole tetrafluoroborate into the reaction solution, mixing, and stirring for 2-3 hours under the ultrasonic action; then filtering, washing a filter cake to be neutral, drying in an oven at 110-130 ℃, and grinding to obtain a carbon dioxide adsorbing material; the mass ratio of lanthanum oxide, 1-butyl-3-methylimidazole tetrafluoroborate to ZSM-5 type zeolite is 0.03:1.2: 1;
(3) filling the carbon dioxide adsorbing material into an adsorption tower; the filling volume of the carbon dioxide adsorbing material is 75-80% of the volume of the adsorption tower;
(4) removing moisture and particle impurities from the flue gas by a flue gas treatment system, then introducing the flue gas into an adsorption tower to adsorb and capture carbon dioxide, and introducing hot steam into the adsorption tower to perform desorption and analysis after adsorption and capture are finished to finally obtain high-purity carbon dioxide; the adsorption pressure is 0.7-0.85 MPa, the adsorption temperature is 45-50 ℃, and the adsorption time is 2 h; the temperature of the hot steam is 150-160 ℃, and the desorption time is 2 h.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) according to the invention, the adsorption tower is adopted to capture the carbon dioxide in the flue gas, and then the hot steam is utilized to carry out desorption treatment, so that the carbon dioxide gas with high purity is finally obtained, and the whole process is green and environment-friendly, and has a good application prospect.
(2) The carbon dioxide adsorbing material is obtained by modifying and compounding ZSM-5 zeolite by adopting a mixed solution of rare earth metal and ionic liquid, has high adsorption capacity on carbon dioxide, is easy to desorb and analyze the carbon dioxide, and has high efficiency.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
The preparation method of the carbon dioxide adsorbing material comprises the following steps:
(1) uniformly mixing a titanium tetrachloride solution with the concentration of 0.08mol/L, absolute ethyl alcohol and deionized water, adding ZSM-5 type zeolite, adjusting the pH value of the solution to 8, and heating to 80 ℃ for reaction for 1 h; the volume ratio of the titanium tetrachloride solution to the absolute ethyl alcohol to the deionized water to the ZSM-5 type zeolite is 2:1:3: 1;
(2) after the reaction is finished, adding lanthanum oxide and 1-butyl-3-methylimidazole tetrafluoroborate into the reaction solution for mixing, wherein the mass ratio of the rare earth lanthanum oxide to the 1-butyl-3-methylimidazole tetrafluoroborate to the ZSM-5 zeolite is 0.03:0.5: 1; stirring for 2 hours under the action of ultrasonic waves; and then filtering, washing a filter cake to be neutral, and drying in a drying oven at 110 ℃ to obtain the carbon dioxide adsorbing material, and grinding the carbon dioxide adsorbing material until the particle size is 4mm for later use.
A flue gas carbon dioxide efficient trapping method comprises the steps that moisture and particle impurities in flue gas are removed through a flue gas treatment system, then the flue gas enters an adsorption tower to be adsorbed and trapped for carbon dioxide, and after adsorption and trapping are finished, hot steam is introduced into the adsorption tower to be desorbed and resolved, and finally high-purity carbon dioxide is obtained; the adsorption tower is filled with a carbon dioxide adsorption material, and the filling volume of the carbon dioxide adsorption material is 65% of the volume of the adsorption tower; the adsorption pressure is 0.3MPa, the adsorption temperature is below 35 ℃, and the adsorption time is 2 h; the temperature of the hot steam is 120 ℃, and the desorption time is 2 h.
The content of carbon dioxide in the flue gas at the inlet of the adsorption tower is 12%, the content of carbon dioxide in the flue gas at the outlet of the adsorption tower is 0.6%, the carbon dioxide absorption rate reaches 95%, and the content of carbon dioxide in the desorbed gas is 98.3%.
Example 2
The preparation method of the carbon dioxide adsorbing material comprises the following steps:
(1) uniformly mixing a titanium tetrachloride solution with the concentration of 1.0mol/L, absolute ethyl alcohol and deionized water, adding ZSM-5 zeolite, adjusting the pH value of the solution to 10, and heating to 100 ℃ to react for 1 hour; the volume ratio of the titanium tetrachloride solution to the absolute ethyl alcohol to the deionized water to the ZSM-5 type zeolite is 2:3:3: 1;
(2) after the reaction is finished, adding lanthanum oxide and 1-butyl-3-methylimidazole tetrafluoroborate into the reaction solution for mixing, wherein the mass ratio of the rare earth lanthanum oxide to the 1-butyl-3-methylimidazole tetrafluoroborate to the ZSM-5 zeolite is 0.2:0.5: 1; stirring for 2 hours under the action of ultrasonic waves; and then filtering, washing a filter cake to be neutral, and drying in a drying oven at 110 ℃ to obtain the carbon dioxide adsorbing material, and grinding the carbon dioxide adsorbing material until the particle size is 4mm for later use.
A flue gas carbon dioxide efficient trapping method comprises the steps that moisture and particle impurities in flue gas are removed through a flue gas treatment system, then the flue gas enters an adsorption tower to be adsorbed and trapped for carbon dioxide, and after adsorption and trapping are finished, hot steam is introduced into the adsorption tower to be desorbed and resolved, and finally high-purity carbon dioxide is obtained; the adsorption tower is filled with a carbon dioxide adsorption material, and the filling volume of the carbon dioxide adsorption material is 75% of the volume of the adsorption tower; the adsorption pressure is 0.6MPa, the adsorption temperature is below 35 ℃, and the adsorption time is 2 h; the temperature of the hot steam is 120 ℃, and the desorption time is 2 h.
The content of carbon dioxide in the flue gas at the inlet of the adsorption tower is 12%, the content of carbon dioxide in the flue gas at the outlet of the adsorption tower is 0.8%, the carbon dioxide absorption rate reaches 95%, and the content of carbon dioxide in the desorbed gas is 98.9%.
Example 3
The preparation method of the carbon dioxide adsorbing material comprises the following steps:
(1) uniformly mixing a titanium tetrachloride solution with the concentration of 0.08mol/L, absolute ethyl alcohol and deionized water, adding ZSM-5 type zeolite, adjusting the pH value of the solution to 8, and heating to 80 ℃ for reaction for 1 h; the volume ratio of the titanium tetrachloride solution to the absolute ethyl alcohol to the deionized water to the ZSM-5 type zeolite is 2:1:3: 1;
(2) after the reaction is finished, adding lanthanum oxide and 1-butyl-3-methylimidazole tetrafluoroborate into the reaction solution for mixing, wherein the mass ratio of the rare earth lanthanum oxide to the 1-butyl-3-methylimidazole tetrafluoroborate to the ZSM-5 zeolite is 0.03:0.5: 1; stirring for 2 hours under the action of ultrasonic waves; and then filtering, washing a filter cake to be neutral, and drying in a drying oven at 110 ℃ to obtain the carbon dioxide adsorbing material, and grinding the carbon dioxide adsorbing material until the particle size is 4mm for later use.
A flue gas carbon dioxide efficient trapping method comprises the steps that moisture and particle impurities in flue gas are removed through a flue gas treatment system, then the flue gas enters an adsorption tower to be adsorbed and trapped for carbon dioxide, and after adsorption and trapping are finished, hot steam is introduced into the adsorption tower to be desorbed and resolved, and finally high-purity carbon dioxide is obtained; the adsorption tower is filled with a carbon dioxide adsorption material, and the filling volume of the carbon dioxide adsorption material is 80% of the volume of the adsorption tower; the adsorption pressure is 0.8MPa, the adsorption temperature is 45 ℃, and the adsorption time is 2 h; the temperature of the hot steam is 120 ℃, and the desorption time is 2 h.
The content of carbon dioxide in the flue gas at the inlet of the adsorption tower is 15%, the content of carbon dioxide in the flue gas at the outlet of the adsorption tower is 1.0%, the carbon dioxide absorption rate reaches 93%, and the content of carbon dioxide in the desorbed gas is 99.5%.
Example 4
The preparation method of the carbon dioxide adsorbing material comprises the following steps:
(1) uniformly mixing a titanium tetrachloride solution with the concentration of 1.2mol/L, absolute ethyl alcohol and deionized water, adding ZSM-5 type zeolite, adjusting the pH value of the solution to 8, and heating to 120 ℃ to react for 1 h; the volume ratio of the titanium tetrachloride solution to the absolute ethyl alcohol to the deionized water to the ZSM-5 type zeolite is 2:5:2: 1;
(2) after the reaction is finished, adding lanthanum oxide and 1-butyl-3-methylimidazole tetrafluoroborate into the reaction solution for mixing, wherein the mass ratio of the rare earth lanthanum oxide to the 1-butyl-3-methylimidazole tetrafluoroborate to the ZSM-5 zeolite is 0.03:1.2: 1; stirring for 2 hours under the action of ultrasonic waves; and then filtering, washing a filter cake to be neutral, and drying in a drying oven at 110 ℃ to obtain the carbon dioxide adsorbing material, and grinding the carbon dioxide adsorbing material until the particle size is 6mm for later use.
A high-efficiency capturing method of flue gas carbon dioxide is characterized in that the flue gas is subjected to moisture and particle impurities removal through a flue gas treatment system, then the flue gas enters an adsorption tower to be adsorbed and captured with carbon dioxide, and after adsorption and capture are finished, hot steam is introduced into the adsorption tower to be desorbed and resolved, so that high-purity carbon dioxide is finally obtained; the adsorption tower is filled with a carbon dioxide adsorption material, and the filling volume of the carbon dioxide adsorption material is 85% of the volume of the adsorption tower; the adsorption pressure is 0.3MPa, the adsorption temperature is 35 ℃, and the adsorption time is 2 h; the temperature of the hot steam is 150 ℃, and the desorption time is 3 h.
The content of carbon dioxide in the flue gas at the inlet of the adsorption tower is 20%, the content of carbon dioxide in the flue gas at the outlet of the adsorption tower is 1.2%, the carbon dioxide absorption rate reaches 94%, and the content of carbon dioxide in the desorbed gas is 97.6%.
Example 5
The preparation method of the carbon dioxide adsorbing material comprises the following steps:
(1) uniformly mixing a titanium tetrachloride solution with the concentration of 0.08mol/L, absolute ethyl alcohol and deionized water, adding ZSM-5 type zeolite, adjusting the pH value of the solution to 9, and heating to 95 ℃ for reaction for 2.5 hours; the volume ratio of the titanium tetrachloride solution to the absolute ethyl alcohol to the deionized water to the ZSM-5 type zeolite is 3:5:2: 1;
(2) after the reaction is finished, adding lanthanum oxide and 1-butyl-3-methylimidazole tetrafluoroborate into the reaction solution for mixing, wherein the mass ratio of the rare earth lanthanum oxide to the 1-butyl-3-methylimidazole tetrafluoroborate to the ZSM-5 zeolite is 0.03:1.2: 1; stirring for 2 hours under the ultrasonic action; and then filtering, washing a filter cake to be neutral, and drying in a drying oven at 110 ℃ to obtain the carbon dioxide adsorbing material, and grinding the carbon dioxide adsorbing material until the particle size is 4mm for later use.
A high-efficiency capturing method of flue gas carbon dioxide is characterized in that the flue gas is subjected to moisture and particle impurities removal through a flue gas treatment system, then the flue gas enters an adsorption tower to be adsorbed and captured with carbon dioxide, and after adsorption and capture are finished, hot steam is introduced into the adsorption tower to be desorbed and resolved, so that high-purity carbon dioxide is finally obtained; the adsorption tower is filled with a carbon dioxide adsorption material, and the filling volume of the carbon dioxide adsorption material is 78% of the volume of the adsorption tower; the adsorption pressure is 0.7MPa, the adsorption temperature is below 50 ℃, and the adsorption time is 2 h; the temperature of the hot steam is 160 ℃, and the desorption time is 2 h.
The content of carbon dioxide in the flue gas at the inlet of the adsorption tower is 20%, the content of carbon dioxide in the flue gas at the outlet of the adsorption tower is 0.8%, the carbon dioxide absorption rate reaches 96%, and the content of carbon dioxide in the desorbed gas is 98.1%.
Claims (8)
1. A high-efficiency capturing method of flue gas carbon dioxide is characterized in that the flue gas is subjected to moisture and particle impurities removal through a flue gas treatment system, then enters an adsorption tower to be adsorbed and captured with the carbon dioxide, and after adsorption and capture are finished, hot steam is introduced into the adsorption tower to be desorbed and resolved, so that high-purity carbon dioxide is finally obtained; the adsorption tower is filled with a carbon dioxide adsorption material, and the filling volume of the carbon dioxide adsorption material is 60-85% of the volume of the adsorption tower; the adsorption pressure is 0.3-1.0 MPa, the adsorption temperature is 25-60 ℃, and the adsorption time is 0.1-5 h; the temperature of the hot steam is 120-180 ℃, and the desorption time is 2-5 h;
the preparation method of the carbon dioxide adsorbing material comprises the following steps:
(1) uniformly mixing a titanium tetrachloride solution, absolute ethyl alcohol and deionized water, adding ZSM-5 zeolite, adjusting the pH value of the solution to be alkaline, and heating for reaction;
(2) after the reaction is finished, adding rare earth metal oxide and 1-butyl-3-methylimidazole tetrafluoroborate into the reaction solution, mixing, and stirring for 2-3 hours under the action of ultrasound; and then filtering, washing a filter cake to be neutral, drying in an oven at 110-130 ℃, and grinding to obtain the carbon dioxide adsorbing material.
2. The method for efficiently capturing carbon dioxide in flue gas according to claim 1, wherein the filling volume of the carbon dioxide adsorbing material is 75-80% of the volume of the adsorption tower; the adsorption pressure is 0.7-0.85 MPa, the adsorption temperature is 45-50 ℃, and the adsorption time is 2 h; the temperature of the hot steam is 150-160 ℃, and the desorption time is 2 h.
3. The method for efficiently capturing carbon dioxide in flue gas according to claim 1, wherein the pH of the solution is adjusted to 8-10, and then the reaction is carried out at 80-120 ℃ for 1-3 h; the concentration of the titanium tetrachloride solution is 0.05-1.5 mol/L, and the mass ratio of the titanium tetrachloride solution, absolute ethyl alcohol, deionized water and ZSM-5 type zeolite is 2-3: 1-5: 2-3: 1.
4. The method for efficiently capturing carbon dioxide in flue gas according to claim 1, wherein the pH of the solution is adjusted to 9, and then the reaction is carried out at 90-100 ℃ for 2-3 h; the concentration of the titanium tetrachloride solution is 1.1mol/L, and the mass ratio of the titanium tetrachloride solution, absolute ethyl alcohol, deionized water and ZSM-5 type zeolite is 3:5:2: 1.
5. The flue gas carbon dioxide high efficiency capture method of claim 1, wherein the rare earth metal oxide is any one of lanthanum oxide, cerium oxide and erbium oxide; the mass ratio of the rare earth metal oxide to the 1-butyl-3-methylimidazole tetrafluoroborate to the ZSM-5 type zeolite is 0.03-0.5: 0.5-1.5: 1.
6. The flue gas carbon dioxide high efficiency capture method of claim 1, wherein the rare earth metal oxide is lanthanum oxide; the mass ratio of lanthanum oxide, 1-butyl-3-methylimidazole tetrafluoroborate to ZSM-5 zeolite is 0.03:1.2: 1.
7. The method for efficiently capturing carbon dioxide in flue gas according to claim 1, wherein the carbon dioxide adsorbing material is ground to have a particle size of 4 to 10 mm.
8. The flue gas carbon dioxide high-efficiency capturing method according to claim 1, characterized by comprising the following steps:
(1) uniformly mixing a titanium tetrachloride solution, absolute ethyl alcohol and deionized water, adding ZSM-5 zeolite, adjusting the pH value of the solution to 9, and then reacting for 2-3 hours at 90-100 ℃; the concentration of the titanium tetrachloride solution is 1.1mol/L, and the mass ratio of the titanium tetrachloride solution, absolute ethyl alcohol, deionized water and ZSM-5 type zeolite is 3:5:2: 1;
(2) after the reaction is finished, adding lanthanum oxide and 1-butyl-3-methylimidazole tetrafluoroborate into the reaction solution, mixing, and stirring for 2-3 hours under the ultrasonic action; then filtering, washing a filter cake to be neutral, drying in an oven at 110-130 ℃, and grinding to obtain a carbon dioxide adsorbing material; the mass ratio of lanthanum oxide, 1-butyl-3-methylimidazole tetrafluoroborate to ZSM-5 type zeolite is 0.03:1.2: 1;
(3) filling the carbon dioxide adsorbing material into an adsorption tower; the filling volume of the carbon dioxide adsorbing material is 75-80% of the volume of the adsorption tower;
(4) removing moisture and particle impurities from the flue gas by a flue gas treatment system, then introducing the flue gas into an adsorption tower to adsorb and capture carbon dioxide, and introducing hot steam into the adsorption tower to perform desorption and analysis after adsorption and capture are finished to finally obtain high-purity carbon dioxide; the adsorption pressure is 0.7-0.85 MPa, the adsorption temperature is 45-50 ℃, and the adsorption time is 2 h; the temperature of the hot steam is 150-160 ℃, and the desorption time is 2 h.
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