CN111603907A - Modified magnesium-based absorbent and preparation method thereof - Google Patents
Modified magnesium-based absorbent and preparation method thereof Download PDFInfo
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- CN111603907A CN111603907A CN202010424153.4A CN202010424153A CN111603907A CN 111603907 A CN111603907 A CN 111603907A CN 202010424153 A CN202010424153 A CN 202010424153A CN 111603907 A CN111603907 A CN 111603907A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
- C01B32/55—Solidifying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention belongs to the technical field of environmental pollution prevention and clean coal combustion, and particularly relates to a modified magnesium-based absorbent and a preparation method thereof, wherein the modified magnesium-based absorbent comprises the following steps: (1) dissolving magnesium-containing ore and organic matters in water, stirring to form sol, and drying the sol to form gel; (2) calcining the gel obtained in the step (1) at the temperature higher than 500 ℃ to obtain magnesium-based absorbent powder; (3) and (3) uniformly mixing the magnesium-based absorbent powder obtained in the step (2) with cement powder, adding a trace amount of water to enable the mixed powder to be in a mud shape, and extruding and crushing the mud into particles to obtain the modified magnesium-based absorbent. The modified magnesium-based absorbent prepared by the method can be applied to coal-fired flue gas absorption treatment, is mainly used for improving the carbonation conversion rate of the MgO-based adsorbent in long-term circulation and solving the problem that the carbon dioxide absorption capacity of the adsorbent is reduced after multiple cycles.
Description
Technical Field
The invention belongs to the technical field of environmental pollution prevention and clean coal combustion, and particularly relates to a modified magnesium-based absorbent and a preparation method thereof.
Background
Based on carbon dioxide (CO) caused by human activities2) The main reason why the emission of greenhouse gases is currently observed is known, and the international society has paid special attention to the reduction of greenhouse gases since the 90 th 20 th century, a series of international activitiesThe framework is built up step by step. In recent years, global greenhouse gas emission reduction activities have been more actively pursued. The distribution of carbon emission reduction obligations is also a hot issue for international politics, due to historical obligations and fair development. China has achieved remarkable effects in the aspects of ecological reconstruction, renewable energy development, energy conservation and emission reduction, and the like, and the development targets of autonomous emission reduction, biological carbon sequestration and non-fossil energy in 2020 are also established. At present, CO2Capture and sequestration of (CO)2Capture and Storage, CCS) technology is considered one of the most promising abatement technologies. This technology refers to the technology of separating, collecting and sequestering carbon dioxide from industrial and energy related sources to avoid its entry into the human atmosphere. The commercial use of this technology is well established, but the concept of long term sequestration of carbon dioxide is now only at the conceptual stage, and there is no facility for power plants to operate a complete carbon capture and sequestration facility. A power plant with a complete carbon collection and sequestration storage facility reduces carbon dioxide emissions by more than 80% over a power plant without such facility, but consumes 20% -90% of the additional energy. The trapping cost is high, and how to economically and efficiently trap CO on a large scale2Has become the focus of the scientific research field.
The mature carbon dioxide capture technology is roughly divided into two types; physical adsorption and chemical absorption. From the perspective of industrial flue gas characteristics and technology maturity in China, the chemical absorption method is very suitable for CO in industrial flue gas in China2And (4) trapping. The absorbent types used according to the chemical absorption method can be classified into two types of liquid absorbents and solid absorbents. A typical representative of liquid absorbents is the alcohol amine solution, which is well-established in the art and is used commercially on a large scale. However, due to the increasing economic and environmental requirements, alcohol amine solutions are increasingly not meeting the current industrial requirements. CO capture based on calcium and magnesium cycling2The technology is considered to be the most promising post-combustion CO capture today2One of the technical means of (1) can be directly used for the treatment of combustion flue gas in various factories. The magnesium ore content in China is rich, the distribution is wide, the cost is low, and a magnesium-based absorbent can be used for absorbing carbon dioxide and sulfur dioxide in tail gas of a coal-fired power station.
For the capture of carbon dioxide, the carbon dioxide in the coal-fired tail gas can be captured circularly by utilizing the carbonation/roasting reaction of the magnesium-based absorbent. The reaction formula is as follows:
MgO+CO2→MgCO3
MgCO3→MgO+CO2
however, in the case of cyclic absorption of carbon dioxide by using a general magnesium absorbent, after many carbonation cycles, the carbon dioxide absorption capacity of the magnesium-based absorbent in each carbonation reaction is greatly reduced. Thus, a new amount of magnesium-based absorbent needs to be added to the system. Therefore, the improvement of the carbon dioxide capture capacity of the magnesium-based absorbent in the multi-cycle carbonation reaction has great significance for reducing the carbon dioxide capture cost of the system. The batch preparation of high performance low cost adsorbents remains CO2The problem to be solved urgently in the trapping field.
Disclosure of Invention
It is an object of the present invention to provide a modified magnesium-based absorbent having improved carbonation conversion of MgO-based sorbent over long-term cycling.
The second purpose of the invention is to provide a preparation method of the modified magnesium-based absorbent, which has simple and convenient preparation process and easy adjustment, is mainly used for improving the carbonation conversion rate of the MgO-based adsorbent in long-term circulation and solving the problem that the carbon dioxide absorption capacity of the adsorbent is reduced after multiple cycles.
The scheme adopted by the invention for realizing one of the purposes is as follows: a preparation method of a modified magnesium-based absorbent is used for preparing absorbent particles capable of efficiently absorbing carbon dioxide in smoke, and comprises the following steps:
(1) dissolving magnesium-containing ore and organic matters in water, stirring to form sol, and drying the sol to form gel;
(2) calcining the gel obtained in the step (1) at the temperature higher than 500 ℃ to obtain magnesium-based absorbent powder;
(3) and (3) uniformly mixing the magnesium-based absorbent powder obtained in the step (2) with cement powder, adding a trace amount of water to enable the mixed powder to be in a mud shape, and extruding and crushing the mud into particles to obtain the modified magnesium-based absorbent.
Preferably, in the step (1), the magnesium-containing ore is at least one of magnesite, brucite, dolomite and olivine.
Preferably, in the step (1), the organic substance is any one of citric acid, urea, glycine, glutamic acid, gluconic acid or ethylenediaminetetraacetic acid.
Preferably, in the step (1), the molar ratio of magnesium ions to organic matters is (0.1-4): 1. preferably, the molar ratio of magnesium ions to organic compounds is
More preferably
The specific gravities of magnesium and organic matters in different proportions in the invention have influence on the performance of the prepared magnesium-based absorbent for absorbing carbon dioxide after 10 cycles, when the proportion is less than 0.1:1, the performance of the obtained absorbent is poor, and when the proportion is more than 4:1, the performance improvement range of the obtained absorbent is not obvious.
Preferably, in the step (1), the stirring temperature is 50-90 ℃; the drying temperature is 100-200 ℃.
Preferably, in the step (2), the calcination temperature is 500-700 ℃. The calcination time is preferably 0.5 hour or more, and may be selected according to the actual requirements.
Preferably, in the step (3), the mass ratio of the magnesium-based absorbent powder to the cement powder is (1-4): 1.
The second scheme adopted by the invention for achieving the purpose is as follows: the modified magnesium-based absorbent is prepared by the preparation method.
The invention has the following advantages and beneficial effects:
in the preparation method, the magnesium-containing ore and the organic matter are uniformly mixed in water, the dried gel is calcined at the temperature of more than 500 ℃, and the rapid combustion of the organic matter generates fiercely-combusted flame to form rich pores on the surface of the magnesium-based substance, so that the rich pore structure is very favorable for the magnesium-based absorbent to have a rapid carbonation reaction rate. In addition, the cement can be used as an atomic skeleton substance between crystal grains of the magnesium-based absorbent, so that the anti-sintering capacity of the magnesium-based absorbent is improved, and finally the stability of the absorbent for collecting carbon dioxide in a multi-cycle manner is improved.
The modified magnesium-based absorbent prepared by the method can be applied to coal-fired flue gas absorption treatment, is mainly used for improving the carbonation conversion rate of the MgO-based adsorbent in long-term circulation and solving the problem that the carbon dioxide absorption capacity of the adsorbent is reduced after multiple cycles.
Drawings
Fig. 1 is a process flow diagram of a method for preparing a magnesium-based absorbent according to an embodiment of the present invention.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
This example provides a method for preparing modified magnesium-based absorbent particles, including the following steps:
at room temperature, 42g of magnesite (MgCO) are first introduced3Content greater than 80%) and 105g of citric acid monohydrate (C)6H807-H20) Put into a beaker, added with 50mL of water and stirred to dissolve.
The molar ratio of magnesium ions to water is preferably not less than 10:1, but this is not limited in the present invention and can be selected specifically according to actual needs.
Then, the mixture was stirred at a constant temperature of 70 ℃ for 1.5 hours to form a sol, and then dried in a drying oven at 100 ℃ for 2 hours to form a gel.
The gel was quickly placed in a 75CTC muffle furnace, air was introduced, and calcination was carried out at 600 c for 1 hour to obtain about 20g of white magnesium-based absorbent powder.
Finally, the resulting magnesium-based absorbent powder is dry blended with 8g of cement and a small amount of water is added to form a paste (cement has binding properties). And (3) extruding the paste in an extruder, and crushing and screening to obtain the modified magnesium-based carbon dioxide absorbent particles.
The adsorbent particles are preferably applied before use
Drying for more than 1 hr to evaporate water completely.
In order to verify the circulating carbon dioxide absorption capacity of the modified magnesium-based absorbent prepared in this example, the properties of the modified magnesium-based absorbent particles may be compared with those of the general magnesium oxide particles.
Specifically, firstly, after the modified magnesium-based absorbent prepared in this embodiment and the ordinary magnesium oxide particles are ground, the particles of 250-400um are screened out and put into a thermogravimetric analyzer for testing the absorption capacity of carbon dioxide.
The focus of carbon dioxide absorption capacity is on the mass of carbon dioxide that can be absorbed per gram of absorbent in a number of cycles. The reaction conditions are as follows: carbonation was carried out in an atmosphere of carbon dioxide with a volume fraction of 15% at 300 ℃ for 15 minutes, in an atmosphere of pure nitrogen at 600 ℃ for 10 minutes, and repeated cycles of the test. The temperature rise and cooling process of the thermogravimetric analyzer is carried out under the condition of pure nitrogen. The experimental result shows that although the modified magnesium-based absorbent prepared by the invention absorbs less carbon dioxide in the first cycle than the common magnesium oxide absorbent, the magnesium-based absorbent prepared by the invention has higher conversion rate than the common magnesium-based absorbent per gram after 20 cycles of reaction. The carbon dioxide absorption capacity of the prepared modified magnesium-based absorbent is 1.5 times that of the common magnesium oxide, and the modified magnesium-based absorbent particles prepared by the invention have good circulating carbon dioxide absorption capacity.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (8)
1. A preparation method of a modified magnesium-based absorbent is used for preparing absorbent particles capable of efficiently absorbing carbon dioxide in smoke, and is characterized by comprising the following steps:
(1) dissolving magnesium-containing ore and organic matters in water, stirring to form sol, and drying the sol to form gel;
(2) calcining the gel obtained in the step (1) at the temperature higher than 500 ℃ to obtain magnesium-based absorbent powder;
(3) and (3) uniformly mixing the magnesium-based absorbent powder obtained in the step (2) with cement powder, adding a trace amount of water to enable the mixed powder to be in a mud shape, and extruding and crushing the mud into particles to obtain the modified magnesium-based absorbent.
2. The method for preparing a modified magnesium-based absorbent according to claim 1, characterized in that: in the step (1), the magnesium-containing ore is at least one of magnesite, brucite, dolomite and olivine.
3. The method for preparing a modified magnesium-based absorbent according to claim 1, characterized in that: in the step (1), the organic matter is any one of citric acid, urea, glycine, glutamic acid, gluconic acid or ethylenediamine tetraacetic acid.
4. The method for preparing a modified magnesium-based absorbent according to claim 1, characterized in that: in the step (1), the stirring temperature is 50-90 ℃; the drying temperature is 100-200 ℃.
5. The method for preparing a modified magnesium-based absorbent according to claim 1, characterized in that: in the step (1), the molar ratio of magnesium ions to organic matters is (0.1-4): 1.
6. the method for preparing a modified magnesium-based absorbent according to claim 1, characterized in that: in the step (2), the calcination temperature is 500-700 ℃.
7. The method for preparing a modified magnesium-based absorbent according to claim 1, characterized in that: in the step (3), the mass ratio of the magnesium-based absorbent powder to the cement powder is (1-4): 1.
8. A modified magnesium-based absorbent characterized by: prepared by the preparation method of any one of claims 1 to 7.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2760272C1 (en) * | 2021-02-25 | 2021-11-23 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Новосибирский государственный аграрный университет" | Method for obtaining modified activated carbon |
| CN114213049A (en) * | 2021-12-09 | 2022-03-22 | 中海石油(中国)有限公司 | Carbon dioxide corrosion resistant material for oil well cement and preparation method and application thereof |
| CN114468040A (en) * | 2022-02-16 | 2022-05-13 | 北京鉴真保鲜科技有限公司 | Method for inhibiting self-ripening of fruits and vegetables |
| CN114560716A (en) * | 2022-03-28 | 2022-05-31 | 武汉理碳环保科技有限公司 | Forsterite honeycomb body, preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2760272C1 (en) * | 2021-02-25 | 2021-11-23 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Новосибирский государственный аграрный университет" | Method for obtaining modified activated carbon |
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| CN114213049B (en) * | 2021-12-09 | 2022-08-02 | 中海石油(中国)有限公司 | Carbon dioxide corrosion resistant material for oil well cement and preparation method and application thereof |
| CN114468040A (en) * | 2022-02-16 | 2022-05-13 | 北京鉴真保鲜科技有限公司 | Method for inhibiting self-ripening of fruits and vegetables |
| CN114560716A (en) * | 2022-03-28 | 2022-05-31 | 武汉理碳环保科技有限公司 | Forsterite honeycomb body, preparation method and application thereof |
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