CN112573554A - Carbide slag mineralization fixation of CO2Device and method for preparing fine calcium carbonate - Google Patents
Carbide slag mineralization fixation of CO2Device and method for preparing fine calcium carbonate Download PDFInfo
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Abstract
The invention discloses a method for mineralizing and fixing CO by carbide slag2And a device and a method for preparing fine calcium carbonate. The device is a novel circulation-separation integrated slag dissolving reactor for leaching calcium components in carbide slag, and consists of an airlift circulation reactor, a solid-liquid separator and other accessories. The invention also provides a novel method for mineralizing and fixing CO by using the carbide slag2A process for preparing calcium carbonate comprising the following cyclic process: a) carbide slag and NH4Placing the Cl solution in a circulation-separation integrated slag dissolving reactor, introducing air to form circulation to obtain CaCl2Solution and containing NH3Air; b) above NH-containing3Absorbing air with water to obtain ammonia water; NH removal3The back air is recycled; c) above CaCl2The solution and ammonia water are introduced into a mineralizing tower to react with CO in the waste gas2Reacting and separating to obtain calcium carbonate and NH4A Cl solution; d) will be provided withNH4The Cl solution is recycled after evaporation and concentration, and the evaporated water is used for absorbing ammonia gas to complete the circulation; the equipment is easy to enlarge and is beneficial to realizing large-scale industrial application.
Description
Technical Field
The invention relates to CO2The field of trapping and utilization, in particular to carbide slag mineralized and fixed CO2And a device and a method for preparing fine calcium carbonate.
Background
With the consumption of a large amount of fossil energy, CO in the atmosphere2The concentration increases year by year and the resulting greenhouse effect is more severe, and during the period 1906 to 2005, the temperature of the atmosphere around the world, which is on average near the ground, rises by 0.74 ℃, and global temperature increases bring about changes including elevation of sea level and rainfall, which cause extreme climatic events such as floods, drought, heat waves and hurricanes to become more frequent, which further leads to reduced crop production, glaciers, diminished species and excessive sickness. CO 22Is CO2The main ways of emission reduction mainly comprise geological storage, ocean storage and mineral carbonation fixation. CO 22The mineral carbonation fixation of (A) mimics CO in nature2Mineral absorption process of (i.e. CO)2A series of processes for reacting with ores containing alkaline or alkaline earth metal oxides to form permanent, more stable carbonates.
The carbide slag is solid waste generated in the production of PVC by a carbide method, the main component of the carbide slag is calcium hydroxide, and the carbide slag also contains trace organic and inorganic impurities (such as aluminum oxide, iron oxide, silicon dioxide, sulfide and the like). The carbide slag has high yield and strong alkalinity. At present, there are many reports on the comprehensive utilization of carbide slag, mainly utilizing the characteristic that carbide slag can chemically react with acidic oxides. Such as sulfur-fixing agent for coal, acidic waste water treatment, etc. Calcium hydroxide contained in carbide slag is good for mineralizing and fixing CO2The raw materials of (1). CO production using carbide slag2The carbonation fixation of the calcium carbonate can simultaneously prepare the calcium carbonate, thereby not only reducing the greenhouse gas CO2The discharge of the calcium carbide slag also solves the problem of environmental pollution of the calcium carbide slag, and the production of the calcium carbonate product with higher added value has important practical significance. At present, a lot of reports are available on the production of calcium carbonate by using carbide slag, and in summary, the calcium carbonate can be mainly divided into a calcination method and a leaching method. The calcining method is characterized in that calcium carbide slag is calcined at high temperature to obtain quicklime, and then the quicklime and CO are added2Or other carbonizing agent (carbonate, bicarbonate, etc.) to obtain calcium carbonate, such as CN102527225B,CN100457632C, CN109467322A and the like, and the obvious defects of the process are that impurities in the carbide slag, such as oxides of elements such as Si, Fe, Al and the like, cannot be removed, the impurities have great influence on the whiteness and the quality of the calcium carbonate product, and a large amount of energy consumption is consumed in the high-temperature calcination process. The leaching process for the production of calcium carbonate generally comprises two stages: a leaching stage and a carbonization stage. The leaching stage mainly comprises the step of leaching calcium ions in the carbide slag by selecting a proper leaching agent. In the carbonization stage, the calcium ions are mixed with CO2Or reacting with a carbonizing agent to obtain a calcium carbonate product. The leaching agent is usually acid or acid salt, including hydrochloric acid, amino acid, fatty acid, ammonium chloride, etc., such as CN101264920B, CN101580257A, etc., by using hydrochloric acid as leaching agent, calcium chloride solution is obtained by reacting carbide slag with hydrochloric acid, and then the calcium chloride solution is mixed with carbonizing agent (sodium carbonate) or with CO under alkaline condition2The method has simple process, but continuously consumes acid and alkali in the process, generates chloride waste liquid, and has no prospect of large-scale production from the aspects of resource utilization and environment. CN101293663B, CN102992373A and the like use amino acid and fatty acid as leaching agents to prepare calcium carbonate, the prepared calcium carbonate has the characteristics of small particle size, good dispersibility and the like, but the cost is high when the amino acid is used as the leaching agent, and the acidity is higher than that of carbonic acid when the fatty acid is used as the leaching agent, so CO cannot be used2As the carbonizing agent, the carbonizing agent (carbonate, bicarbonate, etc.) is consumed continuously, and large-scale industrial application cannot be realized. The preparation of calcium carbonate by leaching carbide slag with ammonium chloride as a leaching agent is a relatively common process, and many reports are reported, such as CN102602973B (a method for synthesizing ultrafine calcium carbonate by using carbide slag), CN104229852B (a method for modifying the surface of fine calcium carbonate prepared from carbide slag), CN1854069A (a method for preparing ultrafine calcium carbonate from carbide slag), CN101020579A (a method for preparing high-purity light calcium carbonate micropowder from carbide slag), CN103738997A (a method for preparing nano calcium carbonate from carbide slag) and the like. The above methods all use ammonium chloride as leaching agent, and the difference is that the dispersing agent and the activating agent are different. These patents are feasible from the chemical principle, but the general problem is that the whole process is not aware of the ammonia gasThe separation and overflow problem, and the research only stays in the laboratory research and theoretical research stage, and the large-scale industrial application can not be realized.
In summary, the methods for preparing calcium carbonate by using carbide slag disclosed at present mostly focus on process design, lack related equipment design, and cannot realize large-scale industrial application. Meanwhile, the related patent taking ammonium chloride as a leaching agent does not consider the treatment and overflow risks of ammonia gas.
Disclosure of Invention
The invention aims to provide a method for mineralizing and fixing CO by carbide slag2And a device and a method for preparing fine calcium carbonate.
The invention is based on NH4Cl is used as a leaching agent in the process of leaching the carbide slag, and provides novel reaction equipment (circulation-separation integrated slag-dissolving reactor) and a method thereof, in particular, the carbide slag and NH4Placing the Cl solution in a circulation-separation integrated slag dissolving reactor, introducing air to generate circulation, and reacting to generate NH through the air3Gas is separated out and is carried out of the reaction system, so that the leaching reaction is promoted to be carried out continuously, unreacted residues are separated in a solid-liquid separator, and the obtained clear liquid is CaCl2Solution of NH-containing3The air is absorbed by water to prepare ammonia water, and the gas is recycled. Further, ammonia and CaCl2The solution enters a mineralization tower and CO in the waste gas2Reacting, and obtaining calcium carbonate and NH through solid-liquid separation4A Cl solution; reacting NH4And after the Cl solution is evaporated and concentrated, circulating the Cl solution to a circulation-separation integrated slag dissolving reactor for use, and absorbing ammonia gas by using evaporated water to complete circulation.
The invention firstly provides a circulation-separation integrated slag dissolving reactor for leaching calcium components in carbide slag, which comprises an airlift circulation reactor and a solid-liquid separator;
the solid-liquid separator is located at the bottom of the gas-lift loop reactor, and the two are coaxially arranged
A guide shell arranged along the height of the airlift loop reactor is arranged in the airlift loop reactor;
the airlift loop reactor is provided with at least one solid/liquid material inlet and a gas outlet;
the bottom of the airlift loop reactor is provided with a gas distributor;
the solid-liquid separator is provided with at least one baffling baffle;
the solid-liquid separator is provided with at least one clear liquid outlet and one solid outlet.
In the reactor, the height-diameter ratio of the airlift loop reactor is 5-10;
the ratio of the inner diameter of the guide shell to the inner diameter of the airlift loop reactor is 0.5-0.8,
the height ratio of the guide shell to the airlift loop reactor is 0.6-1.
In the reactor, the volume ratio of the solid-liquid separator to the airlift loop reactor is 0.4-1; the ratio of the diameters of the solid-liquid separator and the gas lift loop reactor is 1.4:1 to 2: 1.
Further, the invention provides a method for leaching calcium components in carbide slag by using the reactor, which comprises the following steps:
1) adding carbide slag and NH from the solid/liquid material inlet4Cl solution, said carbide slag and NH4Reacting Cl in the airlift loop reactor;
2) introducing air from the gas distributor to form an airlift loop in the airlift loop reactor;
3) unreacted carbide slag separated by the solid-liquid separator is discharged from the solid outlet, and the separated CaCl-containing carbide slag is2Is discharged from the clear liquid outlet and contains NH3Is discharged from the gas outlet.
In the method, in the step 2), the apparent air velocity of the introduced air is 0.5-5 cm/s.
Based on the circulation-separation integrated slag dissolving reactor, the invention provides a method for leaching carbide slag and preparing calcium carbonate, which comprises the following circulation steps:
1) the method for leaching the calcium component in the carbide slag is adopted to leach the calcium component in the carbide slag to obtain the calcium component containing CaCl2And a solution containing NH3Air of (2);
2) said NH group3The air is absorbed by water in an ammonia absorption tower to obtain ammonia water; NH removal3The air after circulation is recycled to the circulation-separation integrated slag reactor for recycling;
3) the CaCl is added2The solution and the ammonia water are introduced into a mineralization tower and are introduced into the mineralization tower, wherein the solution contains CO2The suspension after the reaction is separated to obtain calcium carbonate and NH4A Cl solution;
4) adding the solution containing NH4The Cl solution is used as a raw material for recycling after evaporation and concentration, and the evaporated water is used as an absorption liquid for absorbing ammonia.
Specifically, the particle size of the carbide slag is 50-300 meshes.
In particular, the CO-containing2The gas includes, but is not limited to, waste gas containing CO such as waste gas of thermal power plant, waste gas of coal chemical industry, waste gas of cement plant, etc2An exhaust gas;
said CO-containing2CO in the gas of (2)2The content of (b) is 5 to 90% by volume, preferably 10 to 85% by volume.
Specifically, the weight ratio of the carbide slag (calculated by calcium hydroxide) to the ammonium chloride is 1: 2-8, preferably 1: 4-6.
Specifically, the mass concentration of the ammonium chloride solution is 5% to 40%, preferably 10% to 30%.
Compared with the prior art, the carbide slag mineralized and fixed CO provided by the invention2The device and the method for preparing the fine calcium carbonate have the following advantages:
1) provides a novel circulation-separation integrated slag dissolving reactor for leaching carbide slag;
2) provides a novel process flow for preparing calcium carbonate by using carbide slag;
3) easy to be enlarged and beneficial to realizing large-scale industrial application.
Drawings
FIG. 1 is a schematic structural diagram of a circulation-separation integrated slag melting reactor of the invention.
FIG. 2 is a flow chart of the process for leaching carbide slag and producing calcium carbonate according to the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The chemical reactions involved in the present invention are as follows:
1) leaching process
The leaching process takes place in a circulation-separation integrated reactor, carbide slag and NH4The Cl solution reacts as follows:
Ca(OH)2+2NH4Cl＝CaCl2+2H2O+2NH3
introducing air from a gas distributor at the bottom to generate a circular flow around the guide cylinder and continuously introducing NH generated by the reaction3The desorption is carried out in the air and is carried out of the reactor, thereby promoting the reaction to be continuously carried out rightwards, and being beneficial to complete leaching. Separating undissolved residue in a three-phase separator and discharging the residue out of the reaction system, wherein the clear liquid is CaCl2Solution, NH carried over by air3And (3) the ammonia enters an ammonia absorption tower, ammonia water is prepared after water absorption, and the air after deamination is introduced into the reactor for recycling.
2) Mineralization process
The calcium chloride solution and ammonia water are mixed with introduced CO in a mineralizing tower2The gas reacts as follows:
CaCl2+2NH3·H2O+CO2+＝CaCO3+2NH4Cl+H2O
produced CaCO3And NH4The suspension of Cl is subjected to solid-liquid separation to obtain CaCO3Solid and NH4Cl solution, NH4The Cl solution is concentrated by an evaporator and then used in the 1) leaching process, and the evaporated water is condensed and then used for the NH3Absorption of (2).
The structure schematic diagram of the circulation-separation integrated slag dissolving reactor provided by the invention is shown in figure 1, and comprises an airlift circulation reactor 1 and a solid-liquid separator 2, wherein a guide shell 3 arranged along the height of the airlift circulation reactor 1 is arranged in the airlift circulation reactor 1, a solid/liquid material inlet 8 and a gas outlet 9 are arranged at the upper part of the airlift circulation reactor 1, and a gas distributor 4 is arranged at the bottom of the airlift circulation reactor 1. The solid-liquid separator 2 is positioned at the bottom of the gas lift type loop reactor 1, and a baffling plate 5 is arranged at the lower part of the gas distributor 2 in the solid-liquid separator 2. The upper part of the baffle 5 is a circular flow area, and the lower part is a solid settling area; the upper part of the solid-liquid separator 2 is provided with a clear liquid outlet 6, and the lower part is provided with a solid outlet 7.
Specifically, the height-diameter ratio of the gas-lift loop reactor 1 may be 5 to 10, the ratio of the inner diameter of the guide cylinder 3 to the inner diameter of the gas-lift loop reactor 1 may be 0.5 to 0.8, the height ratio of the guide cylinder 3 to the gas-lift loop reactor 1 is 0.6 to 1, the volume ratio of the solid-liquid separator 2 to the gas-lift loop reactor 1 may be 0.4 to 1, and the diameter ratio of the solid-liquid separator to the gas-lift loop reactor is 1.4:1 to 2: 1.
The flow of the method for leaching the carbide slag and preparing the calcium carbonate by adopting the circulation-separation integrated slag dissolving reactor is shown in figure 2, and the method comprises the following specific steps:
in the slag dissolving reactor I, carbide slag 101 and NH are added4Introducing air 103 into Cl solution 102 to form circulation flow so as to lead carbide slag and NH4Cl reacts in the slag dissolving reactor I, and generated ammonia gas is desorbed from the solution by air 103 and is carried into an ammonia absorption tower II along with air 104; undissolved solid 106 is separated from the solid-liquid separator at the bottom of the reactor I and discharged from the reaction system, and CaCl is contained2The solution 105 is discharged into the mineralizing column III. In the ammonia absorption tower II, NH in the air 104 is absorbed by the water 2013To form ammonia 202, remove NH3And the air enters the slag melting reactor I for recycling. Ammonia 202 and containing CaCl2In the mineralisation column III with the CO-containing solution entering the column 2301, 301 of CO2Is absorbed and mineralized and then is discharged (302) from the top of the tower, and the generated product contains CaCO3And NH4Discharging the Cl suspension 303 into a solid-liquid separator IV, and separating to obtain CaCO3Solid 401 and containing NH4A solution 402 of Cl, the solution 402 passing through an evaporatorV concentration to obtain NH4The concentrated Cl 102 is used by condensing evaporated water (201) and absorbing ammonia.
Examples 1,
The carbide slag raw material A is selected as an experimental raw material, the main element composition is shown in table 1,
TABLE 1 composition of main elements of carbide slag raw material A
The carbide slag raw material A is dried for 2 hours, volatile components such as sulfide, organic matters and the like in the carbide slag raw material A are removed, the carbide slag raw material A is ground to 100 meshes, the ground carbide slag is added into a circulation-separation integrated slag reactor 1 (the height-diameter ratio is 9.5, the inner diameter ratio of a guide cylinder to the inner diameter ratio of the reactor is 0.75, the height-ratio of the guide cylinder to the reactor is 0.84, the volume ratio of a solid-liquid separator to the reactor is 0.3, the diameter ratio of the solid-liquid separator to the reactor is 1:7:1) at the speed of 0.5kg/h, meanwhile, ammonium chloride solution with the mass fraction of 10% is added into the circulation-separation integrated slag reactor from the solid/liquid material inlet 8 at the speed of 12.77kg/h, air is introduced into a gas distributor 4, the flow rate of the air is 200L/h (the apparent gas velocity is 0.7cm/s), an ammonia absorption tower (the diameter is 6cm, height of 1m) is absorbed by countercurrent contact, water flow is 1.66kg/h, ammonia water with mass fraction of 10% is prepared, and air after deamination returns to the slag dissolving reactor 1 for recycling. Continuously discharging undissolved carbide slag residues from a solid-liquid separator at a slag discharge rate of 0.294kg/h and a calcium chloride-containing solution discharge rate of 12.79kg/h, pumping the calcium chloride-containing solution and ammonia water into a carbonization tower (a bubble tower with a diameter of 14cm and a height of 95cm), introducing simulated thermal power plant waste gas with a carbon dioxide content of 12% and an empty tower gas velocity of 1cm/s, and generating a slag containing CaCO3And NH4The Cl suspension was discharged at 14.88kg/h into a solid-liquid separator and separated to give CaCO3Solid (0.51kg/h) and NH-containing4Cl solution (14.37kg/h) containing NH4The Cl solution is evaporated by an evaporator, the evaporation rate is 1.63kg water/h, 0.06kg ammonium chloride is added to ensure that the concentration is kept at 10 percent and the solution returns to the slag melting reactor I, and the solution is evaporatedAfter the generated water is condensed, 0.03kg/h of water is supplemented for the ammonia absorption tower to absorb ammonia gas. The calcium carbonate precipitate obtained in the experiment is dried at 105 ℃ and then is analyzed by XRD to obtain vaterite type calcium carbonate with the particle size of 5 mu m, the whiteness of 98.5 and the purity of 99.2 percent. The extraction rate of calcium ions in the carbide slag is 91 percent, and CO is2The mineralization absorption rate of (a) is 90%.
Examples 2,
The carbide slag A in the embodiment 1 is selected as an experimental raw material, the experimental process is basically the same, the difference is that the carbide slag is premixed to prepare suspension and then added into a reactor, different solution concentration parameters, reactor parameters and the like are selected, and the concrete operation is as follows: drying the carbide slag raw material A for 2h, removing volatile components such as sulfide, organic matters and the like in the carbide slag raw material A, grinding the carbide slag raw material A to 200 meshes, mixing the ground carbide slag with 6.39kg/h ammonium chloride solution (the mass fraction is 20%) at the speed of 0.5kg/h to prepare suspension, adding the suspension into a circulation-separation integrated slag dissolving reactor I (the height-diameter ratio is 8, the inner diameter ratio of a guide cylinder to the inner diameter ratio of the reactor is 0.6, the height-ratio of the guide cylinder to the reactor is 0.7, the volume ratio of a solid-liquid separator to the reactor is 0.5, the diameter ratio of the solid-liquid separator to the reactor is 2:1) through a solid/liquid material inlet 8, introducing air through a gas distributor 4, enabling the flow rate of the air to be 200L/h (the apparent gas velocity is 0.5cm/s), enabling an ammonia absorption tower (the diameter is 5cm and the height is 1.5m) to be in countercurrent contact absorption, spraying water from the top of the tower at the spraying speed, ammonia water with the mass fraction of 15% is obtained through preparation, and air after deamination returns to the slag dissolving reactor I for recycling. Continuously discharging undissolved carbide slag residues from the solid-liquid separator; the discharge rate of the solution containing calcium chloride is 6.5kg/h, the solution containing calcium chloride and ammonia water are pumped into a carbonization tower (a bubble tower, the diameter is 10cm, the height is 1m), simulated coal chemical waste gas is introduced, the content of carbon dioxide is 75 percent, the air speed of an empty tower is 0.35cm/s, and the generated solution containing CaCO3And NH4The Cl suspension was discharged into a solid-liquid separator at 8.05kg/h and separated to give CaCO3Solid (0.49kg/h) and NH-containing4The solution of Cl (7.56 kg/h) contained NH4The Cl solution is evaporated by an evaporator, the evaporation rate is 1.04kg water/h, 0.09kg ammonium chloride is added to maintain the concentration at 20 percent and then returns to the slag melting reactor I, the evaporated water is condensed and 0.03kg water is added for useAbsorbing ammonia gas in an ammonia absorption tower. The calcium carbonate precipitate obtained in the experiment is dried at 105 ℃ and then is analyzed by XRD to obtain vaterite type calcium carbonate with the particle size of 2 mu m, the whiteness of 97.5 and the purity of 98.1 percent. The extraction rate of calcium ions in the carbide slag is 93 percent, and CO is added2The mineralization absorption of (a) was 85%.
While embodiments in accordance with the invention have been described above, these embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments described. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated.
Claims (10)
1. A circulation-separation integrated slag dissolving reactor for leaching calcium components in carbide slag comprises a gas-lift circulation reactor and a solid-liquid separator;
the solid-liquid separator is located at the bottom of the gas-lift loop reactor, and the two are coaxially arranged
A guide shell arranged along the height of the airlift loop reactor is arranged in the airlift loop reactor;
the airlift loop reactor is provided with at least one solid/liquid material inlet and a gas outlet;
the bottom of the airlift loop reactor is provided with a gas distributor;
the solid-liquid separator is provided with at least one baffling baffle;
the solid-liquid separator is provided with at least one clear liquid outlet and one solid outlet.
2. The reactor of claim 1, wherein: the height-diameter ratio of the airlift loop reactor is 5-10;
the ratio of the inner diameter of the guide shell to the inner diameter of the airlift loop reactor is 0.5-0.8,
the height ratio of the guide shell to the airlift loop reactor is 0.6-1.
3. The reactor according to claim 1 or 2, characterized in that: the volume ratio of the solid-liquid separator to the airlift loop reactor is 0.4-1; the diameter ratio of the solid-liquid separator to the airlift loop reactor is 1.4: 1-2: 1
4. A method for leaching the calcium component of carbide slag using a reactor according to any one of claims 1-3, comprising the steps of:
1) adding carbide slag and NH from the solid/liquid material inlet4Cl solution, said carbide slag and NH4Reacting Cl in the airlift loop reactor;
2) introducing air from the gas distributor to form an airlift loop in the airlift loop reactor;
3) unreacted carbide slag separated by the solid-liquid separator is discharged from the solid outlet, and the separated CaCl-containing carbide slag is2Is discharged from the clear liquid outlet and contains NH under the action of the air-lift circulation3Is discharged from the gas outlet.
5. The method of claim 4, wherein: in the step 2), the apparent air velocity of the introduced air is 0.5-5 cm/s.
6. A method for leaching carbide slag and producing calcium carbonate using a reactor according to any one of claims 1-3, comprising the following cyclic steps:
1) leaching the calcium component of the carbide slag by the method of claim 4 or 5 to obtain a CaCl-containing solution2And a solution containing NH3Air of (2);
2) said NH group3The air is absorbed by water in an ammonia absorption tower to obtain ammonia water; NH removal3The air after circulation is recycled to the circulation-separation integrated slag reactor for recycling;
3) the CaCl is added2The solution and the ammonia water are introduced into a mineralization tower and are introduced into the mineralization tower, wherein the solution contains CO2After the reaction of the gasSeparating the suspension to obtain calcium carbonate and NH4A Cl solution;
4) adding the solution containing NH4The Cl solution is used as a raw material for recycling after evaporation and concentration, and the evaporated water is used as an absorption liquid for absorbing ammonia.
7. The method of claim 6, wherein: the particle size of the carbide slag is 50-300 meshes.
8. The method according to claim 6 or 7, characterized in that: said CO-containing2CO in the gas of (2)2The volume content of (A) is 5-90%.
9. The method according to any one of claims 6-8, wherein: the mass ratio of the carbide slag (calculated by calcium hydroxide) to the ammonium chloride is 1: 2-8.
10. The method according to any one of claims 6-8, wherein: the mass concentration of the ammonium chloride solution is 5-40%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115487659A (en) * | 2022-10-27 | 2022-12-20 | 原初科技（北京）有限公司 | CO fixation with calcium silicate-containing substances 2 And method for preparing calcium carbonate |
| CN115779844A (en) * | 2023-02-09 | 2023-03-14 | 原初科技（北京）有限公司 | Slag reactor and slag method |
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| CN115487659A (en) * | 2022-10-27 | 2022-12-20 | 原初科技（北京）有限公司 | CO fixation with calcium silicate-containing substances 2 And method for preparing calcium carbonate |
| CN115779844A (en) * | 2023-02-09 | 2023-03-14 | 原初科技（北京）有限公司 | Slag reactor and slag method |
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