CN114210694B - Device and method for mineralizing low-concentration carbon dioxide by using solid waste - Google Patents
Device and method for mineralizing low-concentration carbon dioxide by using solid waste Download PDFInfo
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- CN114210694B CN114210694B CN202111543451.6A CN202111543451A CN114210694B CN 114210694 B CN114210694 B CN 114210694B CN 202111543451 A CN202111543451 A CN 202111543451A CN 114210694 B CN114210694 B CN 114210694B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 76
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 76
- 239000002910 solid waste Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000001089 mineralizing effect Effects 0.000 title claims abstract description 33
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- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 238000003860 storage Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 86
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- 230000000052 comparative effect Effects 0.000 description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 239000003546 flue gas Substances 0.000 description 12
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- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 9
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- 239000013078 crystal Substances 0.000 description 8
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
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- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010882 bottom ash Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- LKIUTDSMFUMDHS-UHFFFAOYSA-N calcium oxygen(2-) silicon(4+) Chemical class [Si+4].[O-2].[Ca+2].[O-2].[O-2] LKIUTDSMFUMDHS-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Abstract
The invention relates to the field of waste treatment and carbon dioxide mineralization utilization, in particular to a method for quickly fixing carbon dioxide by utilizing bulk solid waste and application thereof. The device for mineralizing the low-concentration carbon dioxide by the solid wastes comprises a gas storage tank, a supercharger, a gas distribution bag and a plurality of groups of mineralizing reaction kettles with heating coils, wherein the outlet of the gas storage tank, the inlet of the supercharger, the outlet of the supercharger, the inlet of the gas distribution bag, the outlet of the gas distribution bag and the inlets of the plurality of groups of mineralizing reaction kettles are sequentially connected. The device and the method have low cost, realize high-efficiency resource utilization, realize the mineralization of low-concentration carbon dioxide gas and greatly reduce the internal defects of the mineralized product.
Description
Technical Field
The invention relates to the field of waste treatment and carbon dioxide mineralization utilization, in particular to a device and a method for mineralizing low-concentration carbon dioxide by using solid waste.
Background
Climate change is a significant global challenge facing our era. In order to solve the problem, china puts forward targets of 2030C peak reaching and 2060C neutralization. Carbon capture, utilization and sequestration (CCUS) is an important component of global climate solutions as an emission reduction scheme applicable to large carbon emission sources and the only technical means that has an opportunity to achieve negative emissions.
The carbon dioxide mineralization utilization technology is a more researched technology in the CCUS technical system at present, and the principle is that CO is introduced by utilizing calcium and magnesium oxides with certain activity under the condition of certain temperature and pressure 2 And the calcium and magnesium-containing alkaline earth metal ion minerals are converted into inorganic carbonate with higher thermal stability by participating in solidification. The industrial production of China is accompanied by a large amount of solid wastes, such as steel slag, fly ash and other bulk solid wastes, and the solid wastes contain a large amount of silicon-calcium oxides for mineralization, so that the bulk solid wastes are utilized to mineralize the steel slag, the fly ash and other bulk solid wastesCarbon oxidation technology in CO reduction 2 And the production of high-performance building materials and the resource utilization of solid wastes are realized while the emission is realized, and the method is a carbon emission reduction way with remarkable economic benefit.
The technology for mineralizing carbon dioxide by using bulk solid wastes is to utilize early-formed solid waste blanks and carbon dioxide to carry out mineralization reaction, and mineralized products are filled in crystal pores so as to enhance the strength of products. Patent CN108340480B discloses a method for curing concrete blocks by carbon dioxide step mineralization, which solves CO 2 The overall utilization rate of the gas is low, but the gas source is industrial grade CO 2 (99.5%) or carbon capture desorbed carbon dioxide gas, on one hand, the current industrial carbon dioxide has higher selling price and the carbon capture desorption cost is higher, so that the economic benefit of the mineralized building material is greatly reduced; on the other hand, the high-concentration carbon dioxide gas reacts violently with the solid waste in the initial stage of the reaction, and a large number of micro cracks are generated inside the block, which is not favorable for enhancing the strength of the building product. In addition, patent CN 113561303A discloses a CO 2 Device and method for mineralizing and curing concrete building blocks, and low-concentration CO is increased by using method 2 The mineralization efficiency is low, but the product intensity is low, continuous production cannot be realized, a series of problems of long and low-efficiency reaction silencing time and the like exist, and the large-scale production application is difficult to realize.
Disclosure of Invention
In view of the problems in the prior art, a first aspect of the present invention provides an apparatus for mineralizing low-concentration carbon dioxide with solid waste, comprising a gas storage tank, a pressure booster, a gas distribution bag, and a plurality of sets of mineralization reaction kettles with heating coils, which are connected in sequence, wherein an outlet of the gas storage tank, an inlet of the pressure booster, an outlet of the pressure booster, an inlet of the gas distribution bag, an outlet of the gas distribution bag, and inlets of the plurality of sets of mineralization reaction kettles are connected in sequence. Preferably, each group of the mineralization reaction kettles comprises 2 kettles A and B connected in parallel.
Preferably, a communicating valve is arranged between the kettle A and the kettle B.
In one embodiment, the device for mineralizing low-concentration carbon dioxide by using solid waste further comprises a gas-liquid heat exchanger and a heat conduction oil heater, wherein the gas-liquid heat exchanger is connected with the multiple groups of mineralization reaction kettles, and the heat conduction oil heater is respectively connected with the gas-liquid heat exchanger and the heating coil.
Preferably, the gas-liquid heat exchanger comprises a liquid inlet and a liquid outlet; a gas inlet and a gas outlet; the gas inlet of the gas-liquid heat exchanger is connected with the outlets of the multiple groups of mineralization reaction kettles, cold heat conduction oil enters the gas-liquid heat exchanger through the liquid inlet of the gas-liquid heat exchanger, after the waste heat of the reacted gas is recovered, the reacted gas is output from the liquid outlet of the gas-liquid heat exchanger and is conveyed to the heating coil through the heat conduction oil heater, and the temperature of the multiple groups of mineralization reaction kettles is guaranteed.
In a second aspect of the present invention, there is provided a method for mineralizing low-concentration carbon dioxide with solid waste, comprising: filling a formed blank body of solid waste into a plurality of groups of mineralization reaction kettles, introducing carbon dioxide-containing gas in a gas storage tank into the mineralization reaction kettles through a supercharger and a gas distribution bag, performing first-stage maintenance under the conditions of reaction pressure P, mineralization temperature T +/-5 ℃ and reaction time T, performing second-stage maintenance under the conditions of reaction pressure 4P, mineralization temperature 2T +/-5 ℃ and reaction time T, and performing third-stage maintenance under the conditions of reaction pressure 7P, mineralization temperature 3T +/-5 ℃ and reaction time T.
The applicant finds that the utilization rate of carbon dioxide can be increased under the action of low-concentration carbon dioxide through staged maintenance, the compactness of a mineralized product structure is guaranteed, and internal defects are reduced, and the applicant considers that the specific reason is that in the initial reaction stage, the rapid growth of the crystal phase of the mineralized product is prevented under the overhigh reaction pressure and temperature, so that microcracks are generated in the material, and the strength of the product is further influenced; and (3) increasing the contact probability and the reaction depth of the low-concentration carbon dioxide and the green body by gradually increasing the temperature and the pressure in the kettle as the reaction is carried out. In each stage of the reaction, the reaction pressure is further increased along with the gradient rise of the reaction temperature by additionally supplementing carbon dioxide gas, so that the concentration of the carbon dioxide in the mineralization environment is always maintained at a higher level, and the degree of the mineralization reaction under the condition of low concentration is further increased.
In one embodiment, a method of mineralizing low concentrations of carbon dioxide with solid waste, comprising: filling a formed green body of solid waste into a kettle A, filling the formed green body into a kettle B while sequentially performing first-stage maintenance and second-stage maintenance on the kettle A, after the second-stage maintenance and the filling of the kettle B in the kettle A are completed, taking the kettle A as a gas transmission kettle, taking the kettle B as a gas receiving kettle, opening a communicating valve to communicate the kettle A with the kettle B, and fully preheating the kettle B while performing gas partial pressure so as to reduce energy consumption; after the partial pressure is balanced, closing the communicating valve, ventilating and heating to ensure that the kettle A carries out the maintenance of the third stage and the kettle B carries out the maintenance of the first stage; then communicating the A kettle and the B kettle again for gas partial pressure, ventilating and heating the B kettle to ensure that the B kettle is in second-stage maintenance, exhausting and decompressing the A kettle, taking out a mineralized product, then filling a newly-formed blank again, converting the B kettle into a gas transmission kettle, converting the A kettle into a gas receiving kettle, and repeating the operation according to the gas transmission kettle and the gas receiving kettle.
After the second partial pressure, the carbon dioxide gas remaining in the input kettle is rapidly consumed because the gas receiving kettle is in the initial stage of the reaction.
Preferably, after the third-stage curing is finished, residual gas in the mineralization reaction kettle is conveyed to the gas-liquid heat exchanger, and after heat exchange is finished, the residual gas is directly discharged.
Preferably, when the pressure in the reaction kettle is lower than the set pressure value, the gas is supplied to the reaction kettle to the set pressure value.
The solid waste can be selected conventionally by those skilled in the art in this application, such as steel slag (blast furnace slag, converter slag, refining slag, desulfurizing slag, electric arc furnace oxidizing slag, reducing slag, etc.), furnace dust (fly ash, bottom ash, dust collecting ash, etc.), iron slag, fly ash, bottom ash, red mud, construction waste, waste cement, tailings, ore material, etc.
Preferably, the total content of calcium oxide, calcium hydroxide, calcium silicate, amorphous silica gel, magnesium oxide and magnesium hydroxide in the solid waste is more than 40 wt%.
The skilled person will be able to make routine selections for the carbon dioxide containing gas in the present application, such as coal fired power plant flue gas, lime kiln flue gas, steel plant flue gas, chemical plant flue gas, cement plant flue gas, etc.
The formed blank body of the solid waste is a mixture of the solid waste and water, and is obtained by pressure forming under the action of a press, and the specific operation can be selected by a person skilled in the art conventionally.
Preferably, the volume fraction of carbon dioxide in the carbon dioxide containing gas is between 5 and 80%.
Preferably, T is between 15 and 50 ℃, more preferably 30 ℃.
Preferably, P is from 0.1 to 0.8MPa, more preferably 0.3MPa.
Preferably, t is 20-300min, more preferably 60min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a device and a method for mineralizing low-concentration carbon dioxide by solid wastes, which do not need to collect the carbon dioxide in flue gas, can utilize the low-concentration carbon dioxide gas and directly mineralize and utilize the low-concentration carbon dioxide gas, thereby saving the high cost and corresponding energy consumption for carbon collection; according to the invention, through the design of the device, the synergistic and efficient resource utilization of the large amount of solid waste and low-concentration carbon dioxide is realized, the product quality is ensured, meanwhile, the use problem of a large amount of Portland cement in the traditional solid waste treatment means is also solved, and a new thought is provided for the low-carbon development of the building material industry in China; the invention realizes large-scale continuous production and provides a practical and feasible method for stable operation in a large-scale production scene.
2. The method adopts a three-stage mineralization method, the first-stage blank body reacts in a low-temperature and low-pressure environment, and the second-stage blank body reacts in a high-temperature and high-pressure environment, so that the design prevents the mineralization reaction in the initial stage of the reaction from rapidly proceeding to cause the excessive increase of the mineralization product; in addition, the disturbance of carbon dioxide gas in the environment is increased, the contact probability of carbon dioxide and a mineralized surface is increased, the reaction degree of mineralization is further enhanced, the maintenance effect of the central position of the blank is also enhanced, the mineralized product is filled in crystal pores in the product, and the product strength is further enhanced.
3. The invention provides a system of mutually guiding gas by a group of two kettles, and is matched with a three-stage mineralization reaction method, so that the continuity of the whole mineralization reaction section is realized, the low-efficiency silent time is reduced, and the possibility is provided for industrial large-scale continuous production.
4. The invention realizes direct mineralization and utilization of low-concentration carbon dioxide, and reduces the high cost and corresponding energy consumption of carbon capture. The maintenance system of sectional heating and pressurizing improves the contact probability and the reaction depth of the low-concentration carbon dioxide and the mineralization interface in the mineralization reaction kettle; the mutual gas guiding of the two reaction kettles also ensures the maximum utilization of carbon dioxide gas; meanwhile, the concentration of carbon dioxide in the mineralization reaction kettle is always maintained at a higher level by continuously supplementing air, and the low-concentration carbon dioxide has higher reaction activity by combining the three technologies.
5. The invention realizes the maximum utilization of heat and further reduces the comprehensive carbon emission. The process of mutually guiding the gas of the two kettles realizes partial pressure and full energy exchange, and saves the heat required by preheating the reaction kettle; meanwhile, the invention also reasonably utilizes the reaction heat released in the mineralization reaction process, and reduces the energy required by the temperature rise of the reaction kettle; meanwhile, after the reaction in the third stage is finished, the residual heat of the residual gas passes through the heat exchange device and is used for maintaining partial heat required by the first two reaction stages, and the utilization rate of the heat is further improved.
Drawings
FIG. 1 is a schematic view of an apparatus for mineralizing low concentration carbon dioxide with solid waste according to the present application;
FIG. 2 is a schematic diagram of the process for mineralizing low concentration carbon dioxide from solid waste according to the present application;
FIG. 3 is a graph of the effect of carbon dioxide absorption rate and compressive strength;
FIG. 4 is an SEM image of the mineralized product.
Detailed Description
The present invention will be described below by way of specific embodiments, but is not limited to the specific examples given below.
Examples
Example 1
A device for mineralizing low-concentration carbon dioxide by solid waste comprises a gas storage tank, a supercharger, a gas distribution bag, a plurality of groups of mineralization reaction kettles with heating coils and a gas-liquid heat exchanger which are sequentially connected, as shown in figure 1. Each group of the mineralization reaction kettles comprises 2 kettles A and B which are connected in parallel and communicated, and a communicating valve is arranged between the communicated mineralization reaction kettles so as to communicate or close the communication of the smoke in the reaction kettles.
Wherein, the export of gas storage tank links to each other with the import of booster, and the booster export links to each other with minute gas bag import for carry out the tonifying qi at any time, and the export of minute gas bag links to each other with multiunit mineralize mineralization reation kettle's import, and gas-liquid heat exchanger's gas inlet links to each other with multiunit mineralize mineralization reation kettle's export. Cold heat conducting oil enters the gas-liquid heat exchanger through a liquid inlet of the gas-liquid heat exchanger, the temperature of the cold heat conducting oil is increased after waste heat of gas after reaction is recovered, and the cold heat conducting oil is conveyed to the heating coil pipe through a liquid outlet of the gas-liquid heat exchanger after a heat source is additionally supplemented through the heat conducting oil heater and is used for ensuring the temperature of the multiple groups of the mineralization reaction kettles.
Example 2
A method for mineralizing low-concentration carbon dioxide by solid waste, as shown in fig. 2, specifically comprises the following steps:
(1) Placing the pressed and formed blank body in a mineralization reaction kettle A, then sealing the reaction kettle, and filling flue gas into the kettle A (namely a gas transmission kettle), wherein the flue gas comprises 12.71mol% of carbon dioxide, 75.88mol% of nitrogen, 6.23mol% of water vapor and 5.18mol% of oxygen;
(2) Curing in the first stage: maintaining the reaction temperature at 30 ℃ and the reaction pressure at 0.3MPa, and maintaining for 1h; filling the blank into a B kettle (namely a gas receiving kettle) while the A kettle reacts;
(3) And (3) two-stage maintenance: continuously introducing flue gas into the kettle A, raising the temperature, maintaining the reaction temperature at 60 ℃ and the reaction pressure at 1.2MPa, and maintaining for 1h;
(4) After the kettle B (gas receiving kettle) is filled, a valve of the kettle B is closed, then the kettle B is communicated with the kettle A (gas transmission kettle) for partial pressure and heat conduction, and after the partial pressure is balanced, the communicating valve is closed; respectively introducing flue gas into the kettle A and the kettle B, heating, maintaining the reaction condition of the kettle A at 90 ℃ and 2.1MPa, and maintaining for 1h (third-stage maintenance), and maintaining the reaction condition of the kettle B at 30 ℃ and 0.3MPa for 1h (first-stage maintenance);
(5) After the third-stage maintenance of the A kettle and the first-stage maintenance of the B kettle are finished, the A kettle (namely, the gas transmission kettle) and the B kettle (namely, the gas receiving kettle) are communicated again, the pressure division and the heat conduction are carried out again, and after the pressure division is balanced, the communication valve is closed; introducing flue gas into the B kettle, heating, maintaining the reaction condition of the B kettle at 60 ℃ and 1.2MPa, and maintaining for 1h (second-stage maintenance); meanwhile, the residual gas in the kettle A is conveyed to a gas-liquid heat exchanger by an air pump, the residual gas is directly discharged after the gas-liquid heat exchange is finished, and the mineralized product is taken out from the kettle A and is simultaneously filled with the unreacted green body again.
(5) And (5) converting the B kettle into a gas transmission kettle after the second-stage maintenance is finished, simultaneously just filling the A kettle to form a gas receiving kettle, and repeating the steps (4) to (5) according to the operation of the gas transmission kettle and the gas receiving kettle to realize continuous production.
When the first and second stages of curing are carried out in the A kettle for the first time, heat is provided by the heat conducting oil heater. And (5) in and after the first stage of maintenance and the second stage of maintenance, the required temperature is provided by the heat output by the gas-liquid heat exchanger, and the heat source required by the third stage of maintenance is obtained by heating a heat-conducting oil heater.
Comparative example 1
A method for mineralizing low-concentration carbon dioxide by solid waste specifically comprises the following steps:
and (3) placing the pressed and formed blank body into a mineralization reaction kettle, then closing the reaction kettle, filling smoke with the same components as those in the embodiment 2, curing for 3 hours at the temperature of 30 ℃ and under the pressure of 0.3MPa, then closing a ventilation valve, discharging gas, and taking out the mineralization product.
Comparative example 2
A method for mineralizing low-concentration carbon dioxide by solid waste specifically comprises the following steps:
and (3) placing the pressed and formed blank body into a mineralization reaction kettle, then closing the reaction kettle, filling flue gas with the same components as those in the example 2, curing for 3 hours at the temperature of 60 ℃ and under the pressure of 1.2MPa, then closing a ventilation valve, discharging gas, and taking out the mineralized product.
Comparative example 3
A method for mineralizing low-concentration carbon dioxide by solid wastes comprises the following specific steps:
and (3) placing the pressed and formed blank body into a mineralization reaction kettle, then closing the reaction kettle, filling smoke with the same components as those in the embodiment 2, curing for 3 hours at 90 ℃ and 2.1MPa, then closing a ventilation valve, discharging gas, and taking out the mineralized product.
Comparative example 4
A method for mineralizing low-concentration carbon dioxide by solid wastes comprises the following specific steps:
placing the pressed and formed blank body into a mineralization reaction kettle, then sealing the reaction kettle, filling smoke with the same components as in example 2, curing for 1 hour at 30 ℃ and 0.3MPa, then curing for 1 hour at 30 ℃ and 1.2MPa, finally curing for 1 hour at 30 ℃ and 2.1MPa, closing a ventilation valve after curing, discharging gas, and taking out the mineralization product.
Comparative example 5
A method for mineralizing low-concentration carbon dioxide by solid wastes is similar to the method of the comparative example 4, and is characterized in that the temperature of the curing stage is 60 ℃.
Comparative example 6
A method for mineralizing low-concentration carbon dioxide by solid wastes is similar to the method in the comparative example 4, and is characterized in that the temperature in the curing stage is 90 ℃.
The green body press forming operations in examples and comparative examples were as follows:
will contain 70.82wt% of MgO, caO and SiO 2 Mixing certain steel mill steel slag with water to ensure that the weight ratio of liquid to solid is 0.1; the mixture was then press-molded under a pressure of 40MPa using a press machine to obtain a green body of 20 mm. Times.20 mm. Wherein the steel slag is detected by X-ray fluorescence (XRF) to obtain a specific component packageComprises the following steps: 43.15wt% CaO, 15.28wt% SiO 2 5.31wt% of Al 2 O 3 12.39wt% of MgO, 0.92wt% of P 2 O 5 6.95wt% Fe 2 O 3 11.6wt% FeO, 1.21wt% MnO.
Performance evaluation
The results are shown in table 1 and figure 1 after testing, wherein the absorption rate of carbon dioxide is the percentage of the mass of carbon dioxide absorbed by solid wastes to the mass of the mineralized product, the content of carbon dioxide absorbed by solid wastes is obtained by testing TG/DTG curve of the mineralized product, and the content of carbon dioxide absorbed by solid wastes is the weight reduction amount of 550-850 ℃; the mass of the mineralized product is the mass of the mineralized product at 105 ℃; the compressive strength was measured according to GBT4111-2013 "test methods for concrete blocks and bricks".
TABLE 1
It can be seen from the test results of comparative example 2 and comparative examples 1 to 3 that the increase of temperature and pressure alone has little influence on the reaction rate of carbon dioxide and the compressive strength of the mineralized product, and compared with the multi-stage pressure-supplemented gas guiding method in example 2, the absorption rate of carbon dioxide and the compressive strength of the mineralized product have a larger difference, because the total amount of carbon dioxide in the mineralization environment is lower and cannot be sufficiently mineralized with the body.
In addition, according to the test results in table 1, the method of comparative example 3 in which the temperature and pressure are high increases the absorption rate of carbon dioxide with respect to the method of comparative example 2, but the strength thereof is reduced, and it can be seen that the high temperature and high pressure alone are disadvantageous to the strength of the product, on the contrary. The excessive temperature and pressure can lead the mineralized product in the green body to excessively grow in a short time, thus leading the interior to be easy to generate microcracks and reducing the strength of the final product. As can be seen from the SEM images of the mineralized product in fig. 4 (wherein the left image a is the SEM image of the mineralized product obtained by the method of comparative example 1, and the right image b is the SEM image of the mineralized product obtained by the method of example 2), the mineralized product obtained by the method of example 2 has a compact structure, because more calcium carbonate crystals are generated and filled in the gaps of the crystals, which is the same as the above results of the compressive strength and the carbon dioxide absorption rate.
Therefore, the multiple pressure supplementing and gas guiding method provided by the invention can ensure that the carbon dioxide can meet the amount required by a mineralized product, and simultaneously increases the disturbance of the carbon dioxide, so that the mineralization reaction is easier to occur. In addition, the staged mineralization mode also enables the crystals of the mineralization products at the early stage of mineralization to grow smoothly, reduces the microcracks in the products and ensures the strength of the final products.
The performance test results of comparative examples 4-6 show that partial pressure maintenance can indeed increase the mineralization reaction degree, but the reaction temperature is low, so that the disturbance of carbon dioxide in the environment is low, carbon dioxide cannot be in full contact with a mineralized surface, and particularly in the later reaction period, the lower temperature is not enough to enable the carbon dioxide to react fully; in addition, as in comparative example 3, the crystal growth at high temperature was excessive, the internal structure of the product was damaged, and the strength of the product was lowered. The three-stage heating and pressure boosting maintenance provided by the invention can ensure that crystals grow slowly in the initial reaction stage, and can provide proper reaction conditions for mineralization reaction in the later reaction stage.
Claims (5)
1. The device for mineralizing low-concentration carbon dioxide by using solid wastes is characterized by comprising a gas storage tank, a supercharger, a gas distribution bag and a plurality of groups of mineralizing reaction kettles with heating coils, wherein the outlet of the gas storage tank, the inlet of the supercharger, the outlet of the supercharger, the inlet of the gas distribution bag, the outlet of the gas distribution bag and the inlets of the plurality of groups of mineralizing reaction kettles are sequentially connected; each group of mineralization reaction kettles comprises 2 kettles A and 2 kettles B which are connected in parallel, a communicating valve is arranged between the kettles A and B, the device for mineralizing the low-concentration carbon dioxide by the solid wastes further comprises a gas-liquid heat exchanger and a heat-conducting oil heater, the gas-liquid heat exchanger is connected with the mineralization reaction kettles, the heat-conducting oil heater is respectively connected with the gas-liquid heat exchanger and a heating coil, and the gas-liquid heat exchanger comprises a liquid inlet, a liquid outlet, a gas inlet and a gas outlet; the gas inlet of the gas-liquid heat exchanger is connected with the outlets of the multiple groups of mineralization reaction kettles, cold heat conduction oil enters the gas-liquid heat exchanger through the liquid inlet of the gas-liquid heat exchanger, and after the waste heat of the reacted gas is recovered, the cold heat conduction oil is conveyed to the heating coil pipe through the heat conduction oil heater at the liquid outlet of the gas-liquid heat exchanger;
the method for mineralizing the low-concentration carbon dioxide by the solid waste by using the device comprises the following steps: filling a formed blank body of solid waste into a plurality of groups of mineralization reaction kettles, introducing carbon dioxide-containing gas in a gas storage tank into the mineralization reaction kettles through a supercharger and a gas distribution bag, performing first-stage maintenance under the conditions of reaction pressure P, mineralization temperature T +/-5 ℃ and reaction time T, performing second-stage maintenance under the conditions of reaction pressure 4P, mineralization temperature 2T +/-5 ℃ and reaction time T, and performing third-stage maintenance under the conditions of reaction pressure 7P, mineralization temperature 3T +/-5 ℃ and reaction time T.
2. The apparatus for mineralizing low concentration carbon dioxide with solid waste as set forth in claim 1, wherein the method for mineralizing low concentration carbon dioxide with solid waste using the apparatus comprises: filling a formed green body of solid waste into a kettle A, filling the formed green body into a kettle B while sequentially performing first-stage maintenance and second-stage maintenance on the kettle A, wherein after the second-stage maintenance and the filling of the kettle B in the kettle A are completed, the kettle A is used as a gas transmission kettle, the kettle B is used as a gas receiving kettle, a communicating valve is opened, the kettle A and the kettle B are communicated, and gas partial pressure is performed; after the partial pressure is balanced, closing the communicating valve, ventilating and heating to ensure that the kettle A carries out the maintenance of the third stage and the kettle B carries out the maintenance of the first stage; then communicating the A kettle and the B kettle again for gas partial pressure, ventilating and heating the B kettle to ensure that the B kettle is in second-stage maintenance, exhausting and decompressing the A kettle, taking out a mineralized product, then filling a newly-formed blank again, converting the B kettle into a gas transmission kettle, converting the A kettle into a gas receiving kettle, and repeating the operation according to the gas transmission kettle and the gas receiving kettle.
3. The apparatus for mineralizing low concentration carbon dioxide with solid waste as set forth in claim 2, wherein T is 15 to 50 ℃.
4. The apparatus for mineralizing low concentration carbon dioxide with solid waste as claimed in claim 3, wherein P is 0.1-0.8MPa.
5. The apparatus for mineralizing low concentration carbon dioxide in solid waste according to any one of claims 1 to 4, wherein t is 20 to 300min.
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