Patent Application
20130230442
1. Field of the Invention
The invention relates to an emission reduction and resource utilization technology of carbon dioxide from flue gas of a power plant boiler, and more particularly to a method and an apparatus for collecting carbon dioxide from flue gas by using active sodium carbonate.
2. Description of the Related Art
Several methods for capturing CO2 have been developed. A chemical absorption method is widely applied in industries, and principle of the chemical absorption method is as follows: CO2 in the flue gas is prone to react with and be absorbed by a chemical solvent. A rich solution of the chemical solvent is acquired after absorbing CO2 to an equilibrium state; then the rich solution is introduced into a regeneration tower, heated and decomposed for releasing CO2 gas and being transformed into a barren solution. After that, the barren solution is recycled to absorb CO2 from the flue gas. Thus, by circulating an absorbent solution between an absorption tower and the regeneration tower, CO2 in the flue gas is captured, separated, and purified. Currently, the chemical absorption method using an amino alcohol solution to absorb CO2 is the most widely applied method, which specifically includes: an MEA method, an MDEA, and a mixed organic amines method. In productive practice, it has been proved that, although the chemical absorption method using the amino alcohol solution which has been applied for about twenty years in chemical field has the characteristics of fast absorption speed, strong absorption ability, it still has a common defect when it is utilized in treating flue gas from power plant that the oxidative degradation of the amino alcohol affects a long term and stable operation of the apparatus, thereby resulting a serious corrosion on the apparatus, and high energy consumption in regeneration. This is mainly because the flue gas of coal-fired power plant has the following characteristics, compared with that of the common chemical gas resource: 1) a large amount of the flue gas having a relatively low concentration of carbon oxide (10-15%); 2) the flue gas contains a relative high content of oxygen (5-10%), and dust including metal ion Fe and others, which accelerates the oxidative degradation of the organic amines, and results in a large consumption of the expensive amino alcohol absorbent. All these reasons account for the high cost of the method for collecting carbon dioxide by using amino alcohol.
Sodium carbonate is first used in industrialized manufacture of CO2 absorbents, which absorbs CO2 and produce NaHCO3. A temperature for complete decomposition of NaHCO3 into Na2CO3 and CO2 is 20-30° C. lower than a temperature of the regeneration of amino alcohol. Thus, for energy consumption of regeneration, the method by using sodium carbonate as the absorbent has an obvious advantage that it has 20-30% energy consumption lower than the method using amino alcohol as the absorbent. However, the alkalinity of sodium carbonate is weaker than that of amino alcohol, and has a low absorption speed, poor effect of absorption when sodium carbonate is used alone. Furthermore, a comprehensive energy consumption and cost of the method using sodium carbonate is not superior to the method using the organic amines, and the method using sodium carbonate has almost been abandoned.
In view of the above-described problems, it is one objective of the invention to provide a method and an apparatus for collecting carbon dioxide from flue gas by using active sodium carbonate that have a simple processing, simple structure of apparatus, low investment, and low production cost. The method and the apparatus are in accordance with the characteristics of the flue gas of the power plant boiler, solve problems of oxidative degradation of the organic amines, serious corrosion on the apparatus, and high energy consumption.
To achieve the above objective, in accordance with one embodiment of the invention, there is provided a method for collecting carbon dioxide from flue gas by using active sodium carbonate. The method is a reprocessing of the flue gas of power plant boilers after common dust removal and desulfurization treatment, and comprises the following steps:
1) mixing an aqueous solution of sodium carbonate with an amino alcohol activator to yield a CO2 absorbent; evenly spraying the CO2 absorbent into the flue gas after the common dust removal and desulfurization treatment for fully contacting the flue gas flowing upwardly with the downwardly sprayed CO2 absorbent and for allowing CO2 in the flue gas to react with the amino alcohol activator and the aqueous solution of sodium carbonate: the amino alcohol activator first contacting with CO2 to form a zwitterionic intermediate and being free again in a subsequent hydration reaction of the zwitterionic intermediate, H+ produced from the hydration reaction being neutralized by alkali ion CO32− in the aqueous solution of sodium carbonate, and HCO3− produced from the hydration reaction contacting with metal ion Na+ in the aqueous solution of sodium carbonate and precipitating to produce a sodium bicarbonate slurry. Hereinbelow a reaction principle between the amino alcohol activator which is represented by capital letter A and the aqueous solution of sodium carbonate (Na2CO3) is explained:
First, the amino alcohol activator A contacts with CO2 to form the zwitterionic intermediate A.CO2, which is summarized by the following chemical equation:
CO2+A→A.CO2 (1-1)
Second, the hydration reaction of the zwitterionic intermediate A.CO2, the amino alcohol activator A is free again; HCO3− and CO32− are also produced, which is summarized by the following chemical equation:
A.CO2+H2O→HCO3−+H++A (1-2)
Third, H+ produced from the hydration reaction is neutralized by alkali ion CO32− in the aqueous solution of sodium carbonate, which is summarized by the following chemical equation:
CO32−+H+→HCO3− (1-3)
Fourth, HCO3− contacts with metal ion Na+ in the aqueous solution of sodium carbonate to precipitate gradually, which is summarized by the following chemical equation:
Na++HCO3−→NaHCO3↓ (1-4)
Because the amino alcohol activator A is prone to combine with CO2, the zwitterionic intermediate A.CO2 is immediately produced in a reaction zone of the reaction (1-1). As the hydration reaction of the zwitterionic intermediate A.CO2 is much faster than that of CO2, the production speed of HCO3− and H+ is very fast. Therefore, the amino alcohol activator A is recycled in the reaction zone between a combined state and a free state, which assures the neutralization reaction (1-3) continuously occurs, and a whole CO2 absorption speed of the method is much faster than the CO2 absorption speed by using Na2CO3 alone. Furthermore, because NaHCO3 has a relative small solubility in the CO2 absorbent solution, NaHCO3 crystallizes and precipitates with the increase of a production thereof, which decreases HCO3− in the absorbent solution, and further propels the whole reaction to a direction of CO2 absorption. Thus, the whole CO2 absorption effect of the method is relatively equal to a whole CO2 absorption effect by using the amino alcohol alone, but the production cost of the method is largely decreased.
2) thermally decomposing the sodium bicarbonate slurry obtained in step 1) to produce a highly concentrated CO2 gas and an aqueous solution of sodium carbonate, which is summarized by the following chemical equation:
2NaHCO3→Na2CO3+CO2↑+H2O
3) returning the aqueous solution of sodium carbonate obtained in step 2) to step 1) to form the CO2 absorbent for recycling;
4) cooling the highly concentrated CO2 gas separated from step 2) for condensing hot water vapor therein;
5) carrying out gas-liquid separation on the highly concentrated CO2 gas after cooling treatment of step 4), removing condensed water to yield highly purified CO2 gas having a purity exceeding 99%; and
6) drying, compressing, and condensing the highly purified CO2 gas to transform the highly purified CO2 gas into a liquid state, and obtaining a highly concentrated liquid CO2.
In a class of this embodiment, a concentration of the aqueous solution of sodium carbonate is 10-30 wt. %. The amino alcohol activator is monoethanolamine (MEA) or diethanolamine (DEA). A weight of monoethanolamine or diethanolamine being added is 0.5-6% of a weight of sodium carbonate being added. A circulating liquid-gas ratio between the CO2 absorbent and the flue gas is 5-25 L/m3. Thus, appropriate proportion of the amino alcohol activator and concentration of the aqueous water solution assure a fast reaction with CO2, decrease a dosage of the expensive absorbent to the utmost, prevent the corrosion of the apparatus caused by oxidative degradation of the amino alcohol, and largely decrease the investment on the apparatus and the operation cost.
In a class of this embodiment, a temperature of the reaction between CO2 in the flue gas and the CO2 absorbent in step 1) is controlled at 40-55° C.; and a pressure of the reaction is controlled at 3-300 kPa. Thus, the absorbent solution is capable of completely reacting with CO2 in the flue gas at a suitable temperature and pressure.
In a class of this embodiment, a temperature of the thermal decomposition of the sodium bicarbonate slurry in step 2) is controlled at 80-130° C. Within such a temperature range, sodium bicarbonate is quickly decomposed for releasing a large amount of CO2 and acquiring the highly concentrated CO2 gas.
In a class of this embodiment, the highly concentrated CO2 gas is cooled to a temperature of 20-35° C. Thus, a large amount of water vapor is condensed, thereby improving the purity of the CO2 gas.
An apparatus for collecting carbon dioxide from flue gas by using active sodium carbonate to carry out the above method, comprises: an absorption tower, a regeneration tower, a slanting board sedimentation pool, a cooler, a gas-liquid separator, a desiccator, a compressor, and a condenser. The absorption tower comprises a flue gas inlet at a lower part, a flue gas outlet at a top, and a slurry outlet at a bottom. The regeneration tower comprises a feed inlet and a decomposed gas outlet at an upper part, and a feed outlet at a lower part. The slanting board sedimentation pool comprises a slurry inlet and an absorbent inlet at an upper part, a supernatant outlet, and an underflow outlet. A plurality of absorbent spray layers and at least one demister device are arranged one after another from bottom to top between the flue gas inlet and the flue gas outlet of the absorption tower. The slurry outlet of the absorption tower communicates with the slurry inlet of the slanting board sedimentation pool. The absorbent inlet of the slanting board sedimentation pool communicates with an absorbent container. The supernatant outlet of the slanting board sedimentation pool is connected to the absorbent spray layers of the absorption tower via a circulating pump. The underflow outlet of the slanting board sedimentation pool is connected to the feed inlet of the regeneration tower via a sodium bicarbonate pump. The feed outlet of the regeneration tower is connected to the absorbent inlet of the slanting board sedimentation pool via a sodium carbonate pump. The decomposed gas outlet of the regeneration tower is connected to an inlet of the gas-liquid separator via the cooler. A gas outlet of the gas-liquid separator is in series connected with the desiccator, the compressor, and the condenser. Thus, during the absorption of CO2, treatments of CO2 gas comprising regeneration, dehydration, desiccation, compression, and condensation are continuously carried out until a highly purified liquid carbon dioxide is acquired.
In a class of this embodiment, the underflow outlet of the slanting board sedimentation pool is connected to the feed inlet of the regeneration tower via the sodium bicarbonate pump and a heat exchanger. The feed outlet of the regeneration tower is connected to the absorbent inlet of the slanting board sedimentation pool via the sodium carbonate pump and the heat exchanger. Thus, an exhaust heat of a barren solution of sodium carbonate in the regeneration tower is fully utilized, that is, preheating a rich solution of sodium bicarbonate introduced into the regeneration tower, and meanwhile cooling down the barren solution of sodium carbonate; thereby realizing a benign recycling of the heat exchange and saving the heat energy resource.
In a class of this embodiment, a liquid outlet of the gas-liquid separator is connected to the absorbent inlet of the slanting board sedimentation pool. Therefore, the condensed water separated from the gas-liquid separator is returned to the slanting board sedimentation pool for water recycling, thereby reducing the water consumption in the whole process and lowering the production cost.
In a class of this embodiment, three absorbent spray layers are employed. A filler layer is arranged beneath an upmost absorbent spray layer. A uniform flow sieve plate is arranged beneath each of the other two absorbent spray layers. Furthermore, a ratio between an aperture area and a plate area of the uniform flow sieve plate is 30-40%. On one hand, through the uniform flow sieve plate, the upward gas flow becomes more uniform, which effectively eliminates a dead angle of the flue gas and is conducive to full contact between the flue gas and the absorbent; on the other hand, under the spraying action of absorbent through a plurality of absorbent spray layers, a spraying coverage of the absorbent on a cross section of the absorption tower is 300% above, thereby assuring a full contact between CO2 in the flue gas and the absorbent and a complete chemical reaction for absorbing CO2.
Compared with a conventional processing that employs an amino alcohol to remove carbon dioxide, advantages of the invention are summarized as follows:
The invention is described hereinbelow with reference to accompanying drawings, in which the sole FIGURE is a connection structure diagram of an apparatus for collecting carbon dioxide from flue gas by using active sodium carbonate.
For further illustrating the invention, experiments detailing an apparatus and a method for collecting carbon dioxide from flue gas by using active sodium carbonate are described below combined with the drawing.
As shown in the FIGURE, an apparatus for collecting carbon dioxide from flue gas by using active sodium carbonate comprises: an absorption tower 1, a regeneration tower 10, a cooler 17, a gas-liquid separator 16, a desiccator 15, a compressor 14, and a condenser 13. Three absorbent spray layers 20 and one demister device 21 are arranged one after another from bottom to top between a flue gas inlet 5 and a flue gas outlet 22 of the absorption tower 1. The flue gas inlet 5 is disposed at the lower part of the absorption tower 1 and the flue gas outlet 22 is disposed at the top of the absorption tower 1. A filler layer 3 is arranged beneath an upmost absorbent spray layer 20. A uniform flow sieve plate 4 is arranged beneath each of the other two absorbent spray layers 20. A ratio between an aperture area and a plate area of the uniform flow sieve plate 4 is 38%. Such a combination of spraying structure assures a spraying coverage of the absorbent on a cross section of the absorption tower is 350% above. The demister device 21 comprises: an upper demisting filer screen, a lower demisting filer screen, and a cleaning spray component arranged between the two demisting filer screens for removing absorbent droplets in the flue gas.
A slurry outlet at the bottom of the absorption tower 1 communicates with a slurry inlet 6a at the upper part of a slanting board sedimentation pool 6, and the sodium bicarbonate slurry is capable of flowing into the slanting board sedimentation pool 6 under the gravity thereof. An absorbent inlet 6b at the upper part of the slanting board sedimentation pool 6 communicates with an absorbent container 19 for replenishing sodium carbonate, amino alcohol activator, and a process water. Sodium carbonate is a predominate ingredient in a supernatant of the slanting board sedimentation pool 6, and a sodium bicarbonate slurry is the predominate ingredient in an underflow. A supernatant outlet 6c of the slanting board sedimentation pool 6 is connected to the three absorbent spray layers 20 of the absorption tower 1 via a circulating pump 8. An underflow outlet 6d of the slanting board sedimentation pool 6 is connected to a feed inlet at the upper part of the regeneration tower 10 via a sodium bicarbonate pump 7 and a heat exchanger 18. A feed outlet at the lower part of the regeneration tower 10 is connected to the absorbent inlet 6b of the slanting board sedimentation pool 6 via a sodium carbonate pump 9 and a heat exchanger 18. A supporting boiling unit 11 of the regeneration tower 10 is arranged outside a bottom of the regeneration tower 10.
A decomposed gas outlet at the upper part of the regeneration tower 10 is connected to an inlet of the gas-liquid separator 16 via the cooler 17. A liquid outlet of the gas-liquid separator 16 is connected to the absorbent inlet 6b of the slanting board sedimentation pool 6. A gas outlet of the gas-liquid separator 16 is in series connected with the desiccator 15, the compressor 14, and the condenser 13. An outlet of the condenser 13 is connected to a storage tank of liquid carbon dioxide 12. Each of the above devices are commonly used devices in the chemical industry, thus, structures thereof are not described herein.
In operation test of the above apparatus, parameter of mix proportion of the CO2 absorbent is selected from the following in accordance with different content of CO2 in the flue gas:
Specific process flow of the invention is as follows: flue gas discharged from a coal-fired power plant is input into the absorption tower 1 via the flue gas inlet 5 after common dust removal and desulfurization treatment. The flue gas passes through the uniform flow sieve plate 4 and the filler layer 3 and flows upwards. Meanwhile, the aqueous solution of sodium carbonate added with the amino alcohol activator is sprayed downwards via the absorbent spray layers 20. A circulating liquid-gas ratio between the CO2 absorbent and the flue gas is controlled within 5-25 L/m3, particularly within 12-22 L/m3. A temperature of a reaction between CO2 in the flue gas and the CO2 absorbent is controlled at 40-55° C.; a pressure of the reaction is controlled at 3-300 kPa, particularly at 5−200 kPa. Thus, the upwardly flowing flue gas fully contacts with the downwardly sprayed CO2 absorbent at the filler layer 3 and the uniform flow sieve plates 4 for allowing CO2 in the flue gas reacting with and being absorbed by the amino alcohol activator and the aqueous solution of sodium carbonate.
The flue gas after being removed from a large amount of CO2 continues flowing upward, passes through the demister device 21 for further removing absorbent droplets from the flue gas, and finally a cleaning flue gas is discharged directly into the atmosphere. The sodium bicarbonate slurry produced by absorbing CO2 falls down to a bottom of the absorption tower 1, and is introduced into the slanting board sedimentation pool 6 for stratifying after passing through the slurry outlet of the absorption tower 1. Sodium carbonate is the predominate ingredient in the supernatant of the slanting board sedimentation pool 6, and the sodium bicarbonate slurry is the predominate ingredient in the underflow.
The sodium bicarbonate slurry is transported to an endothermic tube of the heat exchanger 18 via the sodium bicarbonate pump 7 and input into the regeneration tower 10 from the feed inlet after heat absorption. The sodium bicarbonate slurry is prayed into each sieve plate of the regeneration tower, heated and decomposed by an upward flowing water vapor; CO2 is released. Incompletely decomposed sodium bicarbonate slurry falls down to the bottom of the regeneration tower 10, and is heated by the supporting boiling unit 11 of the regeneration tower 10 to a temperature of 80-130° C. and further decomposed for releasing high concentrated CO2 gas while an aqueous solution of sodium carbonate is acquired.
The aqueous solution of sodium carbonate in the regeneration tower 10 is raised up by the sodium carbonate pump 9 and input into an exothermic tube of the heat exchanger 18 for heat release. Thereafter, the aqueous solution of sodium carbonate is input into the slanting board sedimentation pool 6 from the absorbent inlet 6b, and further transported into the absorbent spray layers 2 of the absorption tower 1 via the circulating pump 8 for recycling.
The highly concentrated CO2 gas released from the regeneration tower along with a large amount of water vapor flow out of the regeneration tower 10 through the decomposed gas outlet of the regeneration tower 10, and into the cooler 17 in which CO2 gas is cooled to a temperature of 25-35° C. and most of the water vapor is condensed.
A highly concentrated CO2 gas is acquired after being treated by the cooler 17, and transported into the gas liquid separator 16, in which the condensed water is completely separated from CO2 gas under a centrifugal force, and a highly purified CO2 gas having a purity exceeding 99% is obtained. The separated condensed water is transported through the water outlet of the gas liquid separator 16 and the absorbent inlet 6b of the slanting board sedimentation pool 6, and finally into the slanting board sedimentation pool 6 for recycling. The separated highly purified CO2 gas is transported to the desiccators 15 for drying treatment, and then into the compressor for compression. The compressed CO2 gas is transported into the condenser 13 for being condensed into the liquid state and obtaining a highly concentrated industrialized liquid CO2 product, which is finally input into the storage tank of liquid carbon dioxide 12 for storing.
While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201010510906.X | Oct 2010 | CN | national |
This application is a continuation-in-part of International Patent Application No. PCT/CN2011/078394 with an international filing date of Aug. 15, 2011, designating the United States, now pending, and further claims priority benefits to Chinese Patent Application No. 201010510906.X filed Oct. 18, 2010. The contents of all of the aforementioned applications, including any intervening amendments thereto, are incorporated herein by reference. Inquiries from the public to applicants or assignees concerning this document or the related applications should be directed to: Matthias Scholl P.C., Attn.: Dr. Matthias Scholl Esq., 14781 Memorial Drive, Suite 1319, Houston, Tex. 77079.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2011/078394 | Aug 2011 | US |
| Child | 13865219 | US |
