A method for efficient integrated carbon sequestration by wet milling

Abstract

The application relates to the field of carbon dioxide storage technology, in particular to a high-efficiency integrated carbon fixation method using wet grinding, and discloses the high-efficiency integrated carbon fixation method using wet grinding, which comprises the following steps: placing 2000-3000 mass parts of calcium-based industrial solid waste, 5-10 mass parts of a grinding aid, 2000-3000 mass parts of deionized water, 1200-1500 mass parts of grinding balls and 5-10 mass parts of a surfactant into a wet grinder to perform wet grinding treatment. The high-efficiency integrated carbon fixation method using wet grinding increases the diffusion coefficient of CO2 in water by applying a high-temperature high-pressure supercritical grinding environment, eliminates the mass transfer resistance of CO2 in water, continuously creates new carbon mineralization reaction surfaces under the action of wet grinding, significantly promotes the rate of gas-solid form mineral carbonization reaction, completes the mineral carbonization reaction in a short time, and realizes that the carbon fixation raw material reaches the carbon fixation theoretical value in the mineral carbonization reaction.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of carbon dioxide sequestration, in particular to a high-efficiency integrated carbon sequestration method using wet grinding. BACKGROUND

[0002] At present, the global warming problem is still prominent, and the influence of greenhouse gases on the temperature of the earth is becoming more and more obvious. The melting of glaciers, the increase of ocean acidity, and the decrease of air quality have shown that the harm of greenhouse gases to the earth has reached a new height. Carbon capture and carbon sequestration (CCUS) technology has been widely pursued because carbon capture can directly reduce the concentration of greenhouse gas CO2 in the air, and carbon sequestration technology can permanently sequester CO2 and will not return to the atmosphere.

[0003] The existing CCUS technology is divided into dry carbon sequestration and wet carbon sequestration according to the carbon sequestration environment. The carbon sequestration efficiency of dry carbon sequestration is not high, and the carbon sequestration period is long. The carbon sequestration rate of wet carbon sequestration reaches the theoretical value due to the coexistence of gas-solid, gas-liquid-solid reactions, and high carbonation reaction efficiency. However, in the process of wet carbon sequestration, organic solutions, ammonia water, etc. are commonly used to increase the solubility of CO2, and the process is relatively complex. The rate of gas-solid form carbonation reaction is low, and the products generated by carbonation reaction will adhere to the surface of calcium-based particles, slowing down the overall process of carbonation and reducing the actual carbon sequestration conversion rate.

[0004] Chinese patent CN202110499389.9 proposes a carbon sequestration application system and method of concentrated seawater. The system includes a nanofiltration system, a carbon sequestration reactor, and a bipolar membrane electrodialysis device. The inlet of the nanofiltration system is connected to the concentrated seawater outlet of the seawater desalination system. The water production side of the nanofiltration is connected to the salt water inlet of the bipolar membrane electrodialysis device, and the concentrated water side of the nanofiltration is connected to the salt water inlet of the carbon sequestration reactor. The carbon sequestration reactor is in a tower cylinder structure, the lower part is a salt water pool, the bottom of the salt water pool has a sediment and liquid discharge port, the lower part of the salt water pool is arranged with a gas distributor, the gas distributor is immersed in the salt water, the inlet of the gas distributor is connected to the outlet of the carbon-rich flue gas, and the middle part of the carbon sequestration reactor is provided with a salt water spraying device. The outlet of the salt water pool and the fresh water outlet of the bipolar membrane electrodialysis device are both connected to the inlet of the seawater desalination system. This invention makes full use of high-valence salts and monovalent salts in concentrated seawater, and realizes the carbon sequestration application of flue gas. However, the process of this invention is relatively complicated, the reaction device is complex, the solubility of CO2 in seawater environment is not high, and the actual carbon sequestration rate is not high.

[0005] The Chinese patent CN202011489290.2 proposes a method for carbon sequestration of high-alkalinity alumina red mud, characterized by the following steps: (1) drying the red mud and grinding it to a fine powder using a ball mill; (2) mixing the finely ground red mud, calcium oxide, and water from step (1) uniformly, adding ammonium dihydrogen phosphate, and stirring vigorously and allowing to stand, with 3-5 cycles; the mass ratio of finely ground red mud, calcium oxide, water, and ammonium dihydrogen phosphate is 50:(5-10):(15-25):(18-25); (3) collecting ammonia gas during the vigorous stirring and standing in step (2) through a one-way exhaust pipe, and then collecting the phosphorus-containing red mud residue; (4) introducing the collected ammonia gas in step (3) into a reaction kettle containing distilled water to produce saturated ammonia water, and passing excess carbon dioxide into the saturated ammonia water to produce ammonium bicarbonate. The carbon sequestration method described in the invention is simple in form, but the mineral carbonization product formed easily covers the red mud particles, easily terminates the mineral carbonization reaction, resulting in low carbon sequestration conversion rate and long carbon sequestration period. Therefore, a wet grinding high-efficiency integrated carbon sequestration method is proposed to solve the above problems. SUMMARY

[0006] (I) Technical problems solved

[0007] In view of the deficiencies of the prior art, the present invention provides a wet grinding high-efficiency integrated carbon sequestration method, which has the advantages of high-efficiency carbon sequestration, and solves the problems of low carbon sequestration conversion rate and long carbon sequestration period of existing carbon sequestration methods.

[0008] (II) Technical solutions

[0009] To achieve the above-mentioned purpose of high-efficiency carbon sequestration, the present invention provides the following technical solutions:

[0010] A wet grinding high-efficiency integrated carbon sequestration method, comprising the following steps:

[0011] 1) placing 2000-3000 parts by mass of calcium-based industrial solid waste, 5-10 parts by mass of grinding aid, 2000-3000 parts by mass of deionized water, 1200-1500 parts by mass of grinding balls, and 5-10 parts by mass of surfactant in a wet grinder for wet grinding treatment;

[0012] 2) introducing CO2 and maintaining a constant high temperature and high pressure in the grinding environment, and when the grinding environment pressure and gas velocity reach stability, the mineral carbonization reaction is terminated and the wet grinding is stopped to obtain a slurry;

[0013] 3) allowing the slurry to stand for 3-5 hours, then feeding it into a granulator, using a conveyor belt to convey it to a calcination furnace for calcination, and after calcination is completed, a carbon sequestration base material that can be used as an admixture is obtained.

[0014] Preferably, the grinding balls are zirconia balls with a diameter of 0.25-2.5 mm, the ball-to-material ratio is 1-1.5:1-1.5, and the water-to-material ratio is 1-1.5:1-1.5.

[0015] Preferably, the rotation speed of the wet grinder is 500-800 r / min, and the median particle size of the slurry is 0.8-1 μm.

[0016] Preferably, the concentration of CO2 is not less than 70%, and the feeding rate of CO2 is 18-20 mass parts / min.

[0017] Preferably, the high pressure maintained by the wet grinder is 23-24 MPa.

[0018] Preferably, the pre-treatment before the wet grinding process is to preheat the grinding environment to 300°C by oil bath heating, and the wet grinding process maintains the high temperature of the grinding slurry, the high temperature being 370-380°C and the maintaining mode being oil bath heating.

[0019] Preferably, the added calcium-containing industrial solid waste is a composite of two or more of fly ash, steel slag, magnesium slag, waste cement, and recycled concrete powder.

[0020] Preferably, the end condition of the mineral carbonation reaction is that the gas velocity at the inlet is equal to the gas velocity at the outlet, the gas velocity being 18-20 mass parts / min, the gas pressure is greater than 25.3-26.3 MPa, and the pH is 7-8.

[0021] Preferably, the added surfactant is a composite of one or more of quaternary ammonium salt, polycarboxylic acid-based water reducer, and triethanolamine water reducer.

[0022] The mechanism of the method is as follows:

[0023] Ca in the calcium-containing industrial solid waste 2+ A large amount of CO3 is dissolved under the wet grinding process, and CO3 is formed by the CO2 introduced into the solution 2- The gas-liquid solid form mineral carbonation reaction occurs, the activation energy of the calcium particles is increased under the grinding environment of high temperature and high pressure supercritical conditions, the diffusion coefficient and propagation rate of CO2 in water are increased, the mass transfer resistance of CO2 in water is eliminated, and new gas-solid reaction surfaces are continuously created under the action of the intense mechanical force of the wet grinding, which significantly promotes the progress of the gas-solid form mineral carbonation reaction, shortens the time of the mineral carbonation reaction by 80-90%, and finally precipitates rapidly in the form of stable calcite; when the reaction ends, the CO2 in the solution quickly reaches a supersaturated state, and the mineral carbonation reaction process is accurately judged by observing the gas velocity table, the gas pressure table, and the pH meter.

[0024] (Three) beneficial effects

[0025] Compared with the prior art, the present application provides a high-efficiency integrated carbon fixation method using wet grinding, which has the following beneficial effects:

[0026] 1. The high-efficiency integrated carbon fixation method using wet grinding increases the diffusion coefficient of CO2 in water and eliminates the mass transfer resistance of CO2 in water by applying a high-temperature and high-pressure supercritical grinding environment, significantly improves the gas-solid form mineral carbonation reaction, completes the mineral carbonation reaction in a short time, and realizes that the carbon fixation raw material reaches the carbon fixation theoretical value in the mineral carbonation reaction.

[0027] 2. The high-efficiency integrated carbon fixation method using wet grinding increases the specific surface area of calcium-based solid waste particles by superfine processing of calcium-based particles, and cooperates with the stirring process of grinding to make the calcium-based solid waste particles uniformly distributed in the solution. The violent collision of the grinding medium makes the calcium carbonate particles attached to the surface of the calcium-based particles continuously peel off, continuously creating new carbon mineralization reaction surfaces for the gas-solid form mineral carbonation reaction. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 A flowchart of the high-efficiency integrated carbon fixation method using wet grinding is provided for the present application.

[0029] Figure 2 A test result diagram of the high-efficiency integrated carbon fixation method using wet grinding is provided for the present application. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present application will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0031] Embodiment one:

[0032] 2000 parts by mass of calcium-based industrial solid waste, 5 parts by mass of grinding aid, 3000 parts by mass of deionized water, 1200 parts by mass of grinding ball, and 10 parts by mass of surfactant were placed in a wet grinding tank for wet grinding treatment. At the same time of starting wet grinding, high-purity CO2 was introduced at a gas velocity of 18 parts by mass / min, and the wet grinder rotated at a speed of 500 r / min. The grinding environment was kept constant at a high temperature of 370-380℃ and a high pressure of 23-24MPa. When the grinding environment pressure and gas velocity reached stability, the mineral carbonation reaction was completed and the wet grinding was stopped.

[0033] Embodiment two:

[0034] Put 3000 parts by mass of calcium-based industrial solid waste, 10 parts by mass of grinding aid, 2000 parts by mass of deionized water, 1200 parts by mass of grinding ball, 5 parts by mass of surfactant in the wet grinding tank for wet grinding treatment; at the same time of starting wet grinding, high-purity CO2 is introduced, the CO2 gas velocity is 20 parts by mass / min, the wet grinding machine speed is 1000 r / min, and the grinding environment is kept constant at high temperature of 370-380℃ and high pressure of 23-24MPa, when the grinding environment pressure and gas velocity reach stability, the mineral carbonation reaction end condition stops wet grinding.

[0035] Example three:

[0036] Put 2000 parts by mass of calcium-based industrial solid waste, 6 parts by mass of grinding aid, 3000 parts by mass of deionized water, 1500 parts by mass of grinding ball, 9 parts by mass of surfactant in the wet grinding tank for wet grinding treatment; at the same time of starting wet grinding, high-purity CO2 is introduced, the CO2 gas velocity is 19 parts by mass / min, the wet grinding machine speed is 600 r / min, and the grinding environment is kept constant at high temperature of 370-380℃ and high pressure of 23-24MPa, when the grinding environment pressure and gas velocity reach stability, the mineral carbonation reaction end condition stops wet grinding.

[0037] Example four:

[0038] Put 3000 parts by mass of calcium-based industrial solid waste, 7 parts by mass of grinding aid, 3000 parts by mass of deionized water, 1500 parts by mass of grinding ball, 8 parts by mass of surfactant in the wet grinding tank for wet grinding treatment; at the same time of starting wet grinding, high-purity CO2 is introduced, the CO2 gas velocity is 18.5 parts by mass / min, the wet grinding machine speed is 1000 r / min, and the grinding environment is kept constant at high temperature of 370-380℃ and high pressure of 23-24MPa, when the grinding environment pressure and gas velocity reach stability, the mineral carbonation reaction end condition stops wet grinding.

[0039] Example five:

[0040] Put 2400 parts by mass of calcium-based industrial solid waste, 8 parts by mass of grinding aid, 2800 parts by mass of deionized water, 1300 parts by mass of grinding ball, 7 parts by mass of surfactant in the wet grinding tank for wet grinding treatment; at the same time of starting wet grinding, high-purity CO2 is introduced, the CO2 gas velocity is 19 parts by mass / min, the wet grinding machine speed is 800 r / min, and the grinding environment is kept constant at high temperature of 370-380℃ and high pressure of 23-24MPa, when the grinding environment pressure and gas velocity reach stability, the mineral carbonation reaction end condition stops wet grinding.

[0041] Example six:

[0042] Put 2600 parts by mass of calcium + based industrial solid waste, 9 parts by mass of grinding aid, 2500 parts by mass of deionized water, 1400 parts by mass of grinding ball, 6 parts by mass of surfactant in the wet grinding tank for wet grinding treatment; at the same time of starting wet grinding, high-purity CO2 is introduced, the CO2 gas velocity is 20 parts by mass / min, the wet grinding machine speed is 900 r / min, and the grinding environment is kept constant at high temperature of 370-380℃ and high pressure of 23-24MPa, when the grinding environment pressure and gas velocity reach stability, the mineral carbonization reaction end condition stops wet grinding.

[0043] Comparative Example 1: (only carbon humidification)

[0044] Step one: Put 2000 parts by mass of calcium-based industrial solid waste, 5 parts by mass of grinding aid, 3000 parts by mass of deionized water, 1200 parts by mass of grinding ball, 10 parts by mass of surfactant in the wet grinding tank for wet grinding treatment; at the same time of starting wet grinding, high-purity CO2 is introduced, the CO2 gas velocity is 18 parts by mass / min, the wet grinding machine speed is 1000 r / min, and the grinding environment is kept constant at temperature of 70℃ and pressure of normal pressure, when the grinding environment pressure and gas velocity reach stability, the mineral carbonization reaction end condition stops wet grinding.

[0045] Comparative Example 2: (only carbon, no grinding and stirring treatment)

[0046] Put 2000 parts by mass of calcium-based industrial solid waste, 5 parts by mass of grinding aid, 3000 parts by mass of deionized water, 0 parts by mass of grinding ball, 10 parts by mass of surfactant in the wet grinding tank for wet grinding treatment; at the same time of starting wet grinding, high-purity CO2 is introduced, the CO2 gas velocity is 18 parts by mass / min, the wet grinding machine speed is 0 r / min, and the grinding environment is kept constant at high temperature of 370-380℃ and high pressure of 23-24MPa, when the grinding environment pressure and gas velocity reach stability, the mineral carbonization reaction end condition stops wet grinding.

[0047] Comparative Example 3: (only carbon, stirring, no grinding treatment)

[0048] Put 2000 parts by mass of calcium-based industrial solid waste, 5 parts by mass of grinding aid, 3000 parts by mass of deionized water, 0 parts by mass of grinding ball, 10 parts by mass of surfactant in the wet grinding tank for wet grinding treatment; at the same time of starting wet grinding, high-purity CO2 is introduced, the CO2 gas velocity is 18 parts by mass / min, the wet grinding machine speed is 1000 r / min, and the grinding environment is kept constant at high temperature of 370-380℃ and high pressure of 23-24MPa, when the grinding environment pressure and gas velocity reach stability, the mineral carbonization reaction end condition stops wet grinding.

[0049] The test results of the above examples and comparative examples are shown in Table 1 as follows: Figure 1 It can be seen from Table 1 that the carbonation rate of the calcium-based industrial solid waste is the highest in Example 1, and the carbonation rate of the calcium-based industrial solid waste is the lowest in Comparative Example 2.Figure 1 It can be known that, on the basis of wet grinding, increasing the supercritical condition of high temperature and high pressure helps to improve the actual carbon fixation rate, and the actual carbon fixation rate is the highest when the grinding medium and the grinding rotation speed are the maximum, compared with the three ways of only passing carbon and wet grinding, only passing carbon without grinding, not stirring, only passing carbon and stirring without grinding, the actual highest carbon fixation rate of wet grinding combined with the supercritical condition of high temperature and high pressure can reach 95%, which is much higher than the carbon fixation rate of the three comparative examples, and helps to make the carbon fixation rate of the carbon fixation reaction reach the theoretical value.

[0050] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, the scope of the present application being defined by the appended claims and their equivalents.

Claims

1. A method for efficient integrated carbon sequestration using wet milling, characterized by, The method comprises the following steps: 1) placing 2000-3000 parts by mass of calcium-based industrial solid waste, 5-10 parts by mass of grinding aid, 2000-3000 parts by mass of deionized water, 1200-1500 parts by mass of grinding balls, and 5-10 parts by mass of surfactant in a wet grinder for wet grinding treatment; 2) introducing CO2 and maintaining a constant high temperature and high pressure in the grinding environment; when the grinding environment pressure and gas velocity reach stability, the end condition of the mineral carbonation reaction is reached, and the wet grinding is stopped to obtain a slurry; 3) placing the slurry for 3-5 h and feeding it into a granulator, conveying it to a calcining furnace using a conveyor belt, and calcining it to obtain a carbon sequestration base material that can be used as an admixture; The concentration of CO2 is not less than 70%, and the introduction gas velocity of CO2 is 18-20 parts by mass / min; The high pressure maintained by the wet grinder is 23-24 MPa; The wet grinding treatment is preheated to 300 DEG C by oil bath heating before the pretreatment, and the high temperature of the grinding slurry is maintained during the wet grinding process, which is 370-380 DEG C and is maintained by oil bath heating.

2. The method for high-efficiency integrated carbon sequestration by wet grinding according to claim 1, characterized in that, The grinding balls are zirconia balls with a diameter of 0.25-2.5 mm, the ball-to-material ratio is 1-1.5:1-1.5, and the water-to-material ratio is 1-1.5:1-1.

5.

3. The method of claim 1, wherein the method is characterized by, The rotation speed of the wet grinder is 500-800 r / min, and the median particle size of the slurry is 0.8-1 mu m.

4. The method for high-efficiency integrated carbon sequestration by wet grinding according to claim 1, characterized in that, The added calcium-containing industrial solid waste is a composite of multiple types of fly ash, steel slag, magnesium slag, waste cement, and recycled concrete powder.

5. The method of claim 1, wherein the method is characterized by, The end condition of the mineral carbonation reaction is that the gas velocity at the inlet and outlet is 18-20 parts by mass / min, the gas pressure is greater than 25.3-26.3 MPa, and the pH is 7-8.

6. The method of claim 1, wherein the method is characterized by, The added surfactant is a composite of one or more of quaternary ammonium salt, polycarboxylic acid-based water reducer, and triethanolamine water reducer.

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