CN112191090A - Method and device for fixing carbon dioxide by cement-based material - Google Patents
Method and device for fixing carbon dioxide by cement-based material Download PDFInfo
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Abstract
The invention relates to a method and a device for fixing carbon dioxide by cement-based materials. The method can rapidly fix the carbon dioxide in a wider carbon dioxide concentration range by finely adjusting the temperature of the carbon dioxide within the range of 40-200 ℃ and utilizing the reaction of the cement-based material with the initial gap water content of 30-100% and the carbon dioxide within the temperature range, so as to convert the carbon dioxide into calcium carbonate or magnesium carbonate with stable performance.
Description
Technical Field
The invention relates to a method and a device for fixing carbon dioxide by using a cement-based material, which enable the cement-based material and the carbon dioxide to generate a rapid carbonization reaction by controlling the initial water-containing state of the cement-based material and the temperature of carbon dioxide gas, achieve the effects of rapidly fixing the carbon dioxide and improving the regeneration and compound utilization of the cement-based material, further effectively slow down the greenhouse effect, and belong to the field of cross comprehensive research of buildings, materials, chemistry and environment.
Background
Since the 80's of the 20 th century, the global carbon dioxide concentration has risen from 340ppm in 1980 to 410ppm in 2018, and this excessive emission of carbon dioxide caused by human activities has caused serious damage to the earth's environment, such as species extinction, seawater acidification, glacier melting, sea level rise, etc., and has been accelerated in recent years.
In order to relieve the greenhouse effect caused by excessive emission of carbon dioxide, on one hand, the combustion of fossil fuel needs to be reduced, green energy is developed, and the emission of carbon dioxide is reduced from the source; on the other hand, various carbon dioxide fixing techniques have been developed for absorbing carbon dioxide in the atmosphere and reducing or maintaining the carbon dioxide concentration in the atmosphere.
Therefore, research and development of carbon dioxide fixation technology is particularly important. Various carbon dioxide absorption techniques have been studied and developed, and as described in patent document 1, a direct fixation method is used to fix carbon dioxide to the ocean floor having a depth of 500 m or less, thereby fixing a large amount of carbon dioxide.
On the other hand, the demolition of cement-based materials structures such as common buildings is often accompanied by a large amount of solid waste, and the common treatment method is direct landfill or stacking treatment on site or used as roadbed materials, and the utilization efficiency is low. The cement-based material is mainly from hydrated cement slurry, contains rich active calcium elements, can generate carbonization reaction with carbon dioxide to generate calcium carbonate with stable performance, and is a potential ideal raw material for fixing carbon dioxide. Non-patent document 1 discloses that waste concrete of different sizes is used to perform a carbon dioxide absorption reaction at room temperature, but has a problem that the reaction rate is slow at room temperature and the humidity is strictly required. In order to improve the absorption efficiency of carbon dioxide, the reaction speed of the cement-based material and carbon dioxide needs to be increased.
The invention provides a method for directly contacting high-temperature carbon dioxide with waste cement-based materials to react by combining the characteristics of carbon dioxide generated in the combustion process of fossil fuels along with a large amount of waste heat. Under the control of reasonable parameters, the method can obviously improve the fixation efficiency of the carbon dioxide, simultaneously can improve the performance of the building solid waste, and can fully utilize the waste heat accompanying the discharge process of the carbon dioxide. The method has the characteristics of high carbonization speed and convenient implementation.
Documents of the prior art
Patent document
Patent document 1: US5397553A
Non-patent document
Non-patent document 1: kikuchi T, Kuroda Y. carbon dioxide uptake in removed and crushed Concrete [ J ]. Journal of Advanced Concrete Technology,2011,9(1): 115-.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to solve the problems of large investment and low fixing efficiency in the early stage of the traditional carbon dioxide fixing method, and simultaneously aims to explore a regeneration and utilization way of a cement-based material and fully absorb waste heat generated in the emission process of high-temperature carbon dioxide in industrial production. Thereby achieving the purpose of relieving the greenhouse effect.
Means for solving the problems
In order to achieve the purpose, the invention adopts the following technical scheme.
The scheme of the invention is a method for fixing carbon dioxide by using a cement-based material, which is characterized in that the cement-based material is contacted with a carbon dioxide-containing gas and reacts to absorb the carbon dioxide contained in the gas, wherein the temperature range of the carbon dioxide-containing gas is 40-200 ℃.
In the invention, the initial void water content of the cement-based material can be 30-100%.
In the present invention, the temperature range of the carbon dioxide-containing gas may be further 60 to 140 ℃.
In the present invention, the cement-based material may be any one selected from among engineering materials having cement as a cementitious material, such as hardened cement paste, concrete, waste concrete, and residual cast-in-place concrete.
In the present invention, the cement-based material may be a granular material having an equivalent circular diameter of 30mm or less.
In the present invention, the carbon dioxide-containing gas may be industrial waste gas from a cement plant or industrial waste gas from a coal-fired power plant, or a high-purity gas separated and recovered from the waste gas.
The scheme of the invention is a device for fixing carbon dioxide by cement-based materials, which is characterized by comprising the following components:
a gas introduction unit for introducing a carbon dioxide-containing gas;
a filler unit for introducing a cement-based material;
the reaction unit is used for enabling the cement-based material to be in contact with the gas containing carbon dioxide in the reaction unit and reacting to absorb the carbon dioxide contained in the gas;
a temperature adjusting unit, which is located between the gas introducing unit and the reaction unit, and is used for adjusting the temperature range of the carbon dioxide-containing gas to 40-200 ℃; and
a temperature measuring unit for measuring a temperature of the carbon dioxide-containing gas in the reaction unit.
In the present invention, the apparatus may further include:
a waste recovery unit, which is a recovery and reuse unit after the cement-based material absorbs carbon dioxide; and
and the waste gas recovery unit is used for recovering residual gas after the reaction.
In the present invention, the apparatus may further include a carbon dioxide concentration detecting unit which detects a concentration of carbon dioxide in the exhaust gas after the reaction, and when the concentration is lower than a threshold value, the exhaust gas is recovered by the exhaust gas recovering unit, and when the concentration is higher than the threshold value, the exhaust gas is mixed with the initial carbon dioxide-containing gas again, temperature-adjusted, and then reacted with the cement-based material.
In the present invention, in the reaction unit, the carbon dioxide-containing gas may be blown from below to above while the cement-based material is filled from above the reaction unit, and the carbon dioxide-containing gas and the cement-based material may be convectively reacted with each other to absorb the carbon dioxide contained in the gas.
In the present invention, a partition may be provided in the reaction unit with a stirring device to react the carbon dioxide-containing gas and the cement-based material while stirring them.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the scheme of the invention, by controlling reasonable reaction temperature conditions and the water-containing state of the cement-based material, the rapid fixation of industrially discharged high-temperature carbon dioxide and the full utilization of waste heat can be realized, and meanwhile, the performance of the cement-based material can be effectively improved. Thereby realizing the effect of alleviating greenhouse effect.
Drawings
Fig. 1 is a schematic view of an apparatus for fixing carbon dioxide with a cement-based material according to the present invention.
Fig. 2 is a schematic explanatory view of an apparatus used in an embodiment of the present invention.
Description of the symbols:
1-waste recovery unit, 2-gas leading-in unit, 3-temperature adjusting unit, 4-reaction unit, 5-packing unit, 6-carbon dioxide concentration detecting unit, 7-waste gas recovery unit, 8-temperature measuring unit;
1 '-nitrogen source, 2' -carbon dioxide source, 3 '-nitrogen gas flow meter, 4' -carbon dioxide flow meter, 5 '-carbon dioxide concentration meter, 6' -electric furnace, 7 '-heating zone, 8' -sample.
Detailed Description
The invention is further elucidated with reference to the drawings, and modifications of equivalent forms to the present invention will occur to those skilled in the art upon reading the present specification and fall within the scope of the appended claims.
The invention provides a method for fixing carbon dioxide by using a cement-based material, which is characterized in that the cement-based material is contacted with a carbon dioxide-containing gas and reacts to absorb the carbon dioxide contained in the gas, wherein the temperature of the carbon dioxide-containing gas is in the range of 40-200 ℃.
The above-mentioned carbon dioxide-containing gases are generally derived from industrially discharged or recycled gases, such as: industrial waste gas from cement plants (carbon dioxide concentration range is generally 20% to 30%), industrial waste gas from coal-fired power plants (carbon dioxide concentration range is generally 10% to 15%), and the like. The gas from industrial discharge or recovery is usually in the temperature range of 80-180 ℃, and the gas containing carbon dioxide can be directly used in the method of the invention, and the required external input energy is very little, and the method has the advantages of small energy consumption, simple equipment, high efficiency and the like.
The temperature range of the carbon dioxide-containing gas can be 40-200 ℃, and when the temperature is lower than 40 ℃, the reaction efficiency is low; above 200 ℃, excessive evaporation of water contained in the cement-based material leads to rapid decrease in the void water content, thereby resulting in decrease in the reaction rate and significant decrease in the absorption rate of carbon dioxide. From the viewpoint of further improving the degree of carbonization, that is, the carbon dioxide absorption rate and improving the energy efficiency, the temperature range of the carbon dioxide-containing gas is more preferably 60 to 140 ℃, and still more preferably 80 to 120 ℃.
The cement-based material can be engineering materials taking cement as a cementing material, such as hardened cement paste, concrete, waste concrete, residual cast-in-place concrete and the like. Such materials are widely used in industrial production, and generally, such cement-based wastes are considered as wastes, and have problems such as being not easily degraded and being difficult to handle, and recycling thereof has been a problem. The inventor creatively utilizes the cement-based material to react with high-temperature waste gas discharged in industrial production, thereby realizing the regeneration of the cement-based material while purifying and absorbing the waste gas and achieving the effect of one stone and two birds.
Such a cement-based material usually contains substances such as calcium oxide, silicon oxide, and magnesium oxide as components, and the regeneration of the cement-based material is realized by reacting the cement-based material with carbon dioxide gas under the specific conditions in the present invention to efficiently obtain calcium carbonate, magnesium carbonate, and the like. The initial void water content of the cement-based material is usually 30% -100%, and the inventor finds that the regeneration of the cement-based material can be realized by directly reacting the cement-based material with the carbon dioxide-containing gas in a specific temperature range, so that the stability of a system is ensured, the early-stage investment cost is greatly reduced, and the cement-based material has practicability and economy. From the viewpoint of further improving the reaction efficiency and reducing the energy consumption, the void water content of the cement-based material is more preferably 60% to 100%, and still more preferably 80% to 100%.
In the present invention, the void water content is defined as follows:
the void water content (water content in the cement-based material/water content in the cement-based material in a surface dry state) is multiplied by 100%
The cement-based material of the present invention includes a slurry, a colloidal substance, a liquid, and the like, which are obtained by directly using the above-described various cement-based wastes, and which have such a substance as a main component. From the viewpoint of easy availability and high reaction efficiency, it is preferable to use a granular material, which may be obtained by directly using various industrial cement-based raw materials or wastes or by dissolving a cement-based powder in water to prepare a slurry, solidifying the slurry, and crushing the solidified material. The particle equivalent circle diameter of the granular material is usually 30mm or less, preferably 0.05mm to 30mm, and when less than 0.05mm, the packing between particles is too dense to prevent the flow and reaction of the carbon dioxide-containing gas, and when more than 30mm, the specific surface area of the particles is too small to reduce the reaction efficiency, and the particle equivalent circle diameter is more preferably 0.1mm to 20mm, and still more preferably 0.5mm to 10 mm.
The method for fixing carbon dioxide by using the cement-based material is suitable for multiple purposes, can be used for quickly absorbing high-temperature carbon dioxide discharged by a cement plant, and can also be used for fixing carbon dioxide in waste gas discharged by a thermal power plant. Meanwhile, the construction solid waste contains a large amount of waste micro powder, and the method can be used for improving the property of the micro powder and improving the composite utilization efficiency of the construction solid waste. More widely, the method can be popularized to the mineral carbon fixation containing calcium or magnesium elements, and the calcium carbonate with stable performance can be generated by the reaction of the mineral carbon fixation containing calcium or magnesium elements and carbon dioxide.
Fig. 1 illustrates an apparatus for fixing carbon dioxide with a cement-based material according to the present invention, which mainly includes a waste recovery unit 1, a gas introduction unit 2, a temperature adjustment unit 3, a reaction unit 4, a packing unit 5, a carbon dioxide concentration detection unit 6, an exhaust gas recovery unit 7, and a temperature measurement unit 8. The device shown in fig. 1 is an example only, and the present invention is not limited in any way by this example.
The waste recovery unit 1 is a recovery and reuse unit after the cement-based material absorbs carbon dioxide. The carbon dioxide-containing gas may be derived from carbon dioxide in a cement plant, a coal-fired power plant, or the like, an industrial manufacturing plant that provides energy by burning fossil fuels, or a carbon dioxide source recovered by a recovery device. Taking a cement plant as an example, the temperature of the exhaust gas containing carbon dioxide discharged by the cement plant is about 100 ℃. The temperature regulating unit 3 is used for finely regulating the temperature of the carbon dioxide waste gas so that the carbon dioxide waste gas is introduced into the reaction unit 4 at a constant temperature. The lower part of the reaction unit 4 is provided with a carbon dioxide gas inlet, and the upper part is provided with an outlet. High-temperature gas containing carbon dioxide diffuses from bottom to top, a subarea is arranged in the reaction unit 4, and a stirring device is introduced, so that the contact area of the carbon dioxide and the cement-based material is increased to the maximum extent, the reaction speed is increased, and the reaction unit 4 has a heat preservation function to ensure that reactants react at a specific temperature. The cement-based material may enter the reaction unit 4 through the filler unit 5 at a specific speed, opposite to the direction of movement of the carbon dioxide-containing gas. The carbon dioxide concentration detection unit 6 can detect the concentration of carbon dioxide in the exhaust gas after reaction, when the concentration is lower than a threshold value, the carbon dioxide is recovered through the exhaust gas recovery unit 7, and when the concentration is higher than the threshold value, the part of gas is mixed with the initial high-temperature carbon dioxide-containing gas again, the temperature is adjusted, and then the mixture reacts with the cement-based material.
Examples
In this example, a test of carbon dioxide absorption by a cement-based material was carried out using the apparatus shown in fig. 2. The apparatus shown in FIG. 2 comprises a nitrogen source 1 ', a carbon dioxide source 2', a nitrogen flow meter 3 ', a carbon dioxide flow meter 4', a carbon dioxide concentration meter 5 ', an electric furnace 6', a heating zone 7 'and a sample 8'. Characterized in that a nitrogen source 1 'and a carbon dioxide source 2' are supplied with nitrogen and carbon dioxide respectively through a nitrogen flow meter 3 'and a carbon dioxide flow meter 4'. After the two gases are mixed, the concentration of carbon dioxide in the mixed gas is corrected by a carbon dioxide concentration meter 5 ', the temperature of the carbon dioxide is controlled by a heating zone 7 ' in an electric furnace 6 ', and a sample 8 ' is arranged in the middle of the heating zone 7 ' in the process of absorbing the carbon dioxide.
On-site investigation revealed that the concentration of carbon dioxide discharged from cement plants was 20% to 25%, and the accompanying temperature was 100 ℃. Setting the carbon dioxide concentration to be 25% as a basic working condition, and adjusting the carbon dioxide concentration by combining a carbon dioxide flowmeter and a nitrogen flowmeter with a carbon dioxide concentration meter.
Sample 8' was high strength cement (JIS R5210) produced by the Japan Pacific Cement company, and its chemical composition is shown in Table 1. By adding water and mixing, the water cement ratio is controlled to be 70%, after 1 day of hardening and demoulding, the mixture is maintained in saturated lime water for more than 90 days at normal temperature, and hardened cement paste is formed. The method comprises the following steps of crushing the raw materials in a vacuum environment to form small particles with the particle size range of 0.8-1 mm, setting the initial water content state of the particles to be a saturated water content state, setting the heating temperature range of air of an electric furnace in a heating area 7' to be 20-200 ℃, checking the temperature by a thermometer, setting the carbonization reaction time to be 10 minutes, and calculating the carbonization degree as the ratio of the amount of calcium elements for actually fixing carbon dioxide to the amount of calcium elements theoretically available for fixing carbon dioxide.
Table 1: ingredient table measured by cement sample XRF (X-ray fluorescence spectrometer)
The amount of calcium that actually fixes carbon dioxide is determined as follows:
the theoretical maximum carbon dioxide absorption can be calculated by preparing a cement ingredient table of the sample, and the calculation process is shown in table 2 below, and the result shows that 51.3% of carbon dioxide can be absorbed by cement per unit mass.
Table 2: theoretical absorption value calculation table of carbon dioxide
Therefore, after cement hydration and carbonization, thermogravimetric analysis is carried out by a thermogravimetric analyzer according to the element conservation law capable of being combined with carbon dioxide, and then the content of calcium carbonate in a unit weight sample after burning loss can be calculated. Thereby, the amount of carbon dioxide absorbed can be quantified. The calculation formula of the carbonization degree is as formula (1)
Wherein: c represents the amount of carbon dioxide absorbed in the sample, C0Representing the amount of carbon dioxide absorbed in the non-carbonized sample, Cmax being the maximum amount of carbon dioxide absorbed calculated theoretically.
Meanwhile, in order to investigate the carbon dioxide absorption efficiency in the higher concentration range, 100% carbon dioxide concentration environments were set at 20 ℃ and 100 ℃. The results of the sample carbonization degree are shown in Table 3.
Table 3: degree of carbonization at different temperatures
As shown in Table 3, the absorption efficiency of carbon dioxide can be greatly improved within a specific temperature range (40 ℃ to 200 ℃), the maximum improvement efficiency occurs at 100 ℃, and the improvement efficiency is 126%. Under higher carbon dioxide concentration, such as 100 percent, the absorption efficiency of the carbon dioxide at 100 ℃ can reach 145.5 percent. Therefore, the cement-based material in the high-temperature environment can greatly improve the fixation efficiency of carbon dioxide.
It should be noted that the above-mentioned embodiments are merely illustrative of the present invention, and the present invention may be embodied in other specific forms or other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.
Claims (11)
1. A method for fixing carbon dioxide by cement-based materials, characterized in that carbon dioxide contained in the gas is absorbed by bringing the cement-based materials into contact with and reacting with a carbon dioxide-containing gas, the temperature of which is in the range of 40 ℃ to 200 ℃.
2. The method for sequestration of carbon dioxide with a cement-based material according to claim 1, characterized in that: the initial gap water content of the cement-based material is 30-100%.
3. Method for fixing carbon dioxide with cement-based materials according to claim 1 or 2, characterized in that the temperature of the carbon dioxide containing gas ranges from 60 ℃ to 140 ℃.
4. The method for fixing carbon dioxide with a cement-based material according to claim 1 or 2, wherein the cement-based material is any one of engineering materials selected from hardened cement paste, concrete, waste concrete and residual cast-in-place concrete, having cement as a cementitious material.
5. A method for fixing carbon dioxide with a cement-based material according to claim 1 or 2, characterized in that the cement-based material is a granular material with an equivalent circular diameter smaller than or equal to 30 mm.
6. The method for fixing carbon dioxide with a cement-based material according to claim 1 or 2, wherein the carbon dioxide-containing gas is derived from an industrial waste gas of a cement plant or an industrial waste gas of a coal-fired power plant, or a high-purity gas obtained by separating and recovering the waste gas.
7. An apparatus for fixing carbon dioxide with a cement-based material, comprising:
a gas introduction unit for introducing a carbon dioxide-containing gas;
a filler unit for introducing a cement-based material;
the reaction unit is used for enabling the cement-based material to be in contact with the gas containing carbon dioxide in the reaction unit and reacting to absorb the carbon dioxide contained in the gas;
a temperature adjusting unit, which is located between the gas introducing unit and the reaction unit, and is used for adjusting the temperature range of the carbon dioxide-containing gas to 40-200 ℃; and
a temperature measuring unit for measuring a temperature of the carbon dioxide-containing gas in the reaction unit.
8. The apparatus for sequestration of carbon dioxide with a cement-based material as claimed in claim 7, further comprising:
a waste recovery unit, which is a recovery and reuse unit after the cement-based material absorbs carbon dioxide; and
and the waste gas recovery unit is used for recovering residual gas after the reaction.
9. The apparatus for sequestration of carbon dioxide with a cement-based material according to claim 8, characterized in that it further comprises a carbon dioxide concentration detection unit which detects the concentration of carbon dioxide in the exhaust gas after the reaction, and when the concentration is lower than a threshold value, it is recovered by said exhaust gas recovery unit, and when the concentration is higher than the threshold value, it is re-mixed with the initial carbon dioxide-containing gas, temperature-adjusted, and then reacted with the cement-based material.
10. An apparatus for fixing carbon dioxide with a cement-based material according to claim 7, wherein in the reaction unit, a carbon dioxide-containing gas is blown in from below to above while filling the cement-based material from above the reaction unit, and the carbon dioxide-containing gas and the cement-based material are convectively reacted with each other to absorb carbon dioxide contained in the gas.
11. An apparatus for sequestration of carbon dioxide with a cement-based material according to claim 7, characterised in that a partition is provided in said reaction unit with stirring means to react the carbon dioxide containing gas and the cement-based material while stirring them.
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| JP7074943B1 (en) | 2021-02-22 | 2022-05-24 | 日本コンクリート工業株式会社 | Powder manufacturing method |
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