A liquid-phase grinding carbon dioxide co-solvent and its preparation method and application

Abstract

The present invention relates to a preparation method of a liquid-phase grinding carbon dioxide co-solvent. The specific operation process includes the following steps: (1) Take carboxymethyl-β-cyclodextrin and thionyl chloride in a three-necked flask in a fume hood, heat under reflux in an oil bath with magnetic stirring, cool to room temperature and distill off thionyl chloride under reduced pressure to obtain product A; (2) Take product A, chitosan, N-methylformamide, and pyridine in a three-necked flask, heat under reflux in an oil bath with magnetic stirring, cool to room temperature, filter by suction, wash repeatedly with acetic acid and distilled water, and dry to obtain product B; (3) Take monoethanolamine, N-methyldiethanolamine, and distilled water in a three-necked flask, heat in a water bath with magnetic stirring, slowly dropwise add terpineol, and finally add product B, and stir evenly to obtain the carbon dioxide co-solvent. The present invention can promote the dissolution of carbon dioxide, accelerate the formation of calcium carbonate precipitation, and thus improve the reaction rate and reaction degree of mineral carbonization.

Description

Technical Field

[0001] The present invention relates to the technical field of additives, and particularly to a liquid-phase grinding carbon dioxide promoter, a preparation method thereof and an application thereof. Background Art

[0002] Carbon dioxide is the most important greenhouse gas in the atmosphere. Its average concentration reached a record high of 405.5 ppm in 2017. Carbon dioxide will bring many adverse effects, making the global climate abnormal. Climate change has had a destructive impact on the natural environment on which humans depend for survival, including the increase in extreme weather events, the rise in sea level, and the impact on crop growth. Therefore, controlling carbon emissions to slow down global warming has become an important global issue.

[0003] Wet carbon sequestration refers to the process in which carbon dioxide dissolves in water to form carbonic acid in a reaction solution medium, and ore gradually dissolves under the action of carbonic acid to form carbonate precipitates. The wet carbon sequestration process uses carbonizable industrial solid waste as raw material, which can not only realize the resource utilization of solid waste, but also sequester carbon dioxide. It is widely regarded as one of the carbon dioxide sequestration technologies with great application prospects at present. However, wet carbon sequestration has the problem of low solubility of carbon dioxide in water, which severely limits its industrial application.

[0004] Chinese Patent CN202111674577.7 discloses an additive for carbon mineralization products, a preparation method thereof and an application thereof. The additive includes porous materials such as hollow glass fibers, zeolites, mesoporous silica, and solid-liquid phase change materials such as paraffin, polyurethane, and dibasic fatty acids. The above patent uses the adsorption of porous materials to promote carbon mineralization. However, most adsorbents require high desorption energy to maintain continuous carbon dioxide capture, and the capture effect is not ideal.

[0005] Therefore, it is more valuable and has application prospects to prepare a liquid-phase grinding carbon dioxide promoter to promote carbon dioxide dissolution. Summary of the Invention

[0006] Aiming at the above technical problems, the present invention provides a liquid-phase grinding carbon dioxide promoter, a preparation method thereof and an application thereof. By adding the liquid-phase grinding carbon dioxide promoter prepared by the present invention, compared with the case without addition, the carbon sequestration amount is increased by 70%, and the carbon sequestration time is shortened by 40%.

[0007] Carboxymethyl-β-cyclodextrin has a porous surface structure and grafted functional groups such as CH2COO, and there are also a large number of hydroxyl groups in the skeleton. It has strong selective adsorption for carbon dioxide. The characteristics of its carbon dioxide adsorption can be attributed to the presence of molecular cavities, hydrogen bonds, OR groups and COOR groups. Alkalization and etherification destroy the hydrogen bonds by substituting the hydrogen of primary and secondary hydroxyl groups with sodium atoms and carboxymethyl groups, so that more internal hydrophobic cavities of β-cyclodextrin are exposed to carbon dioxide molecules, enabling more carbon dioxide molecules to be adsorbed into the molecular cavities. Compared with β-cyclodextrin, the carbon dioxide adsorption capacity of carboxymethyl-β-cyclodextrin is also significantly enhanced at low temperatures.

[0008] Carbonic acid is an acid stronger than acetic acid and close to lactic acid. It is well known that acetic acid and lactic acid have the ability to dissolve chitosan. Therefore, carbon dioxide gas, that is, carbonic acid, also has this ability. Chitosan crosslinked with cyclodextrin is more easily soluble in aqueous solutions. At the same time, it has amino groups that can react with carbonic acid to form water-soluble chitosan cations and bicarbonate ions. Then, the calcium ions in the calcium-based solid waste react with the bicarbonate ions, and finally calcium carbonate precipitates are formed. Through this reaction, carbonic acid is consumed, which shows that chitosan can increase the solubility of carbon dioxide gas. When the reaction ends, chitosan can fill into the calcium-based solid waste in the form of fibers to achieve strengthening and toughening.

[0009] Terpineol, also known as terpinol, is industrially prepared from turpentine. It is a mixture mainly composed of a-terpineol. It is a colorless viscous liquid. It is inexpensive and is one of the varieties with a large output in synthetic fragrances. It is widely used in formulating daily and edible flavors. The polar hydroxyl groups in terpenol tend to interact with the aqueous phase, while other non-polar groups tend to be adsorbed on the surface of the bubbles. Terpenol often present at the gas-liquid interface can significantly reduce the surface tension of the bubbles, prevent bubble aggregation, improve the stability of small bubbles, and maintaining small carbon dioxide bubbles is beneficial to the mass transfer of carbon dioxide into the solution.

[0010] One of the technical solutions adopted by the present invention to achieve the purpose is: a preparation method of a liquid-phase grinding carbon dioxide promoter, and the specific operation process includes the following steps:

[0011] (1) Take 15 - 30 parts of carboxymethyl-β-cyclodextrin and 5 - 10 parts of thionyl chloride in a three-necked flask in a fume hood, heat under reflux in an oil bath and stir magnetically for 8 - 12 h, cool to room temperature and distill off thionyl chloride under reduced pressure to obtain product A;

[0012] (2) Take 15 - 30 parts of product A, 15 - 35 parts of chitosan, 5 - 10 parts of N-methylformamide, and 1 - 5 parts of pyridine in a three-necked flask, heat under reflux in an oil bath and stir magnetically for 10 - 16 h, cool to room temperature, filter by suction, wash repeatedly with acetic acid and distilled water, and dry to obtain product B;

[0013] (3) Take 5 - 15 parts of monoethanolamine, 5 - 15 parts of N - methyldiethanolamine, and 100 parts of distilled water in a three - necked flask, heat in a water bath and stir magnetically. Slowly add 5 - 10 parts of terpineol, and finally add 15 - 40 parts of product B. Stir evenly to obtain the liquid - phase grinding carbon dioxide promoter.

[0014] Furthermore, the pressure for vacuum distillation in step (1) is 1.33 - 3.33 kPa.

[0015] Furthermore, in step (2), the degree of deacetylation of chitosan is ≥85%, and the mass concentration of acetic acid is 5%.

[0016] Furthermore, the drying in step (2) is vacuum freeze - drying, and the freezing temperature is - 20 - 30 °C, and the drying time is 2 - 4 h.

[0017] Furthermore, the concentration of terpineol in step (3) is ≥1.5 mg / mL.

[0018] Furthermore, the heating temperatures in step (1), step (2), and step (3) are 60 - 80 °C, 80 - 100 °C, and 30 - 45 °C respectively.

[0019] Furthermore, the total mass of the liquid - phase grinding carbon dioxide promoter in step (3) is 1 - 5 wt% of the calcium - based solid waste.

[0020] The technical solution adopted by the present invention to achieve the second object is: prepared by using the above - mentioned preparation method of the liquid - phase grinding carbon dioxide promoter.

[0021] The technical solution adopted by the present invention to achieve the third object is: the specific operation process includes the following steps: add the above - mentioned liquid - phase grinding carbon dioxide promoter when the liquid - phase grinding equipment starts, first grind and disperse for 30 - 60 s, then start to introduce carbon dioxide gas, and control the liquid - phase grinding speed at 400 - 600 rps and the gas speed at 15 - 20 L / min.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] (1) The present invention solves the problem of slow carbon dioxide mass transfer rate during wet - process carbon sequestration by the synergistic effect of enhancing the carbon dioxide adsorption and reducing the surface tension of carbon dioxide bubbles.

[0024] (2) The present invention synergistically promotes the dissolution of carbon dioxide from two aspects: the physical adsorption of carbon dioxide by cyclodextrin and the reactivity of chitosan gel and organic amine with carbonic acid, greatly improving the dissolution rate and dissolution amount of carbon dioxide. At the end of the reaction, chitosan can fill into the calcium - based solid waste in the form of fibers to achieve strengthening and toughening.

[0025] (3) The liquid-phase grinding carbon dioxide promoter prepared by the present invention has excellent effects when used in combination with a liquid-phase grinding device. The promoter can reduce the time of the liquid-phase grinding aeration reaction, and the grinding device solves the problem that it is difficult to disperse the organic promoter evenly. Detailed Embodiments

[0026] The following will describe in detail the implementation schemes of the present invention in conjunction with embodiments, but the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained without any creative labor fall within the scope of protection of the present invention.

[0027] Example 1

[0028] Take 15 parts of carboxymethyl-β-cyclodextrin and 10 parts of thionyl chloride in a three-necked flask in a fume hood, heat under reflux in an oil bath and stir magnetically for 8 h, cool to room temperature and distill off thionyl chloride under reduced pressure to obtain product A;

[0029] Take 30 parts of product A, 35 parts of chitosan, 10 parts of N-methylformamide, and 5 parts of pyridine in a three-necked flask, heat under reflux in an oil bath and stir magnetically for 10 h, cool to room temperature, filter by suction, wash repeatedly with acetic acid and distilled water, and dry to obtain product B;

[0030] Take 15 parts of monoethanolamine, 15 parts of N-methyldiethanolamine, and 100 parts of distilled water in a three-necked flask, heat in a water bath and stir magnetically, slowly add 10 parts of terpineol, and finally add 40 parts of product B and stir evenly to obtain a carbon dioxide promoter.

[0031] Add the promoter when the liquid-phase grinding device is started, first grind and disperse for 30 s, then start to introduce carbon dioxide gas, control the liquid-phase grinding speed at 600 rps and the gas speed at 20 L / min. When the pH ≤ 7, it is regarded as the end of the reaction, record the reaction time, and cure and mold the slurry, and measure the carbon fixation rate by TG.

[0032] Among them, the total mass of the promoter is 5 wt% of the calcium-based solid waste; the heating temperatures in step (1), step (2), and step (3) are 70 °C, 90 °C, and 40 °C respectively.

[0033] Example 2

[0034] Take 30 parts of carboxymethyl-β-cyclodextrin and 10 parts of thionyl chloride in a three-necked flask in a fume hood, heat under reflux in an oil bath and stir magnetically for 12 h, cool to room temperature and distill off thionyl chloride under reduced pressure to obtain product A;

[0035] Take 15 parts of product A, 15 parts of chitosan, 5 parts of N-methylformamide, and 1 part of pyridine in a three-necked flask, heat under reflux in an oil bath, stir magnetically for 16 h, cool to room temperature, filter by suction, wash repeatedly with acetic acid and distilled water, and dry to obtain product B;

[0036] Take 5 parts of monoethanolamine, 5 parts of N-methyldiethanolamine, and 100 parts of distilled water in a three-necked flask, heat in a water bath, stir magnetically, slowly add 5 parts of terpineol, and finally add 15 parts of product B, stir evenly to obtain a carbon dioxide promoter.

[0037] Add the promoter when the liquid-phase grinding equipment is started, grind and disperse for 30 s first, then start to introduce carbon dioxide gas, control the liquid-phase grinding speed at 500 rps and the gas velocity at 15 L / min. When pH ≤ 7, it is regarded as the end of the reaction, record the reaction time, and cure and mold the slurry, and measure the carbon fixation rate by TG.

[0038] Among them, the total mass of the promoter is 5 wt% of the calcium-based solid waste; in step (1), in step (2), and in step (3), the heating temperatures are 60 °C, 80 °C, and 30 °C respectively.

[0039] Example 3

[0040] Take 30 parts of carboxymethyl-β-cyclodextrin and 10 parts of thionyl chloride in a three-necked flask in a fume hood, heat under reflux in an oil bath, stir magnetically for 12 h, cool to room temperature and distill off thionyl chloride under reduced pressure to obtain product A;

[0041] Take 15 parts of product A, 15 parts of chitosan, 5 parts of N-methylformamide, and 1 part of pyridine in a three-necked flask, heat under reflux in an oil bath, stir magnetically for 16 h, cool to room temperature, filter by suction, wash repeatedly with acetic acid and distilled water, and dry to obtain product B;

[0042] Take 5 parts of monoethanolamine, 5 parts of N-methyldiethanolamine, and 100 parts of distilled water in a three-necked flask, heat in a water bath, stir magnetically, slowly add 5 parts of terpineol, and finally add 15 parts of product B, stir evenly to obtain a carbon dioxide promoter.

[0043] Add the promoter when the liquid-phase grinding equipment is started, grind and disperse for 30 s first, then start to introduce carbon dioxide gas, control the liquid-phase grinding speed at 400 rps and the gas velocity at 15 L / min. When pH ≤ 7, it is regarded as the end of the reaction, record the reaction time, and cure and mold the slurry, and measure the carbon fixation rate by TG.

[0044] Among them, the total mass of the promoter is 3 wt% of the calcium-based solid waste; in step (1), in step (2), and in step (3), the heating temperatures are 70 °C, 90 °C, and 45 °C respectively.

[0045] Example 4

[0046] Take 15 parts of carboxymethyl-β-cyclodextrin and 5 parts of thionyl chloride in a three-necked flask, heat under reflux in an oil bath and stir magnetically for 10 h, cool to room temperature and distill off thionyl chloride under reduced pressure to obtain product A;

[0047] Take 30 parts of product A, 35 parts of chitosan, 10 parts of N-methylformamide and 5 parts of pyridine in a three-necked flask, heat under reflux in an oil bath and stir magnetically for 14 h, cool to room temperature, filter by suction, wash repeatedly with acetic acid and distilled water, and dry to obtain product B;

[0048] Take 15 parts of monoethanolamine, 15 parts of N-methyldiethanolamine and 100 parts of distilled water in a three-necked flask, heat in a water bath and stir magnetically, slowly add 10 parts of terpineol dropwise, and finally add 40 parts of product B and stir evenly to obtain a carbon dioxide promoter.

[0049] Add the promoter when the liquid-phase grinding equipment is started, first grind and disperse for 60 s, then start to introduce carbon dioxide gas, control the liquid-phase grinding speed at 600 rps and the gas speed at 20 L / min. When pH ≤ 7, the reaction is considered to be over, record the reaction time, and cure and mold the slurry, and measure the carbon fixation rate by TG.

[0050] Among them, the total mass of the promoter is 1 wt% of the calcium-based solid waste; in step (1), in step (2), and in step (3), the heating temperatures are 70 °C, 90 °C, and 40 °C respectively.

[0051] Example 5

[0052] Take 20 parts of carboxymethyl-β-cyclodextrin and 10 parts of thionyl chloride in a three-necked flask, heat under reflux in an oil bath and stir magnetically for 12 h, cool to room temperature and distill off thionyl chloride under reduced pressure to obtain product A;

[0053] Take 25 parts of product A, 30 parts of chitosan, 5 parts of N-methylformamide and 5 parts of pyridine in a three-necked flask, heat under reflux in an oil bath and stir magnetically for 16 h, cool to room temperature, filter by suction, wash repeatedly with acetic acid and distilled water, and dry to obtain product B;

[0054] Take 5 parts of monoethanolamine, 5 parts of N-methyldiethanolamine and 100 parts of distilled water in a three-necked flask, heat in a water bath and stir magnetically, slowly add 5 parts of terpineol dropwise, and finally add 30 parts of product B and stir evenly to obtain a carbon dioxide promoter.

[0055] Add the promoter when the liquid-phase grinding equipment is started, first grind and disperse for 60 s, then start to introduce carbon dioxide gas, control the liquid-phase grinding speed at 400 rps and the gas speed at 15 L / min. When pH ≤ 7, the reaction is considered to be over, record the reaction time, and cure and mold the slurry, and measure the carbon fixation rate by TG.

[0056] Among them, the total mass of the solubilizer is 5 wt% of the calcium-based solid waste; the heating temperatures in step (1), step (2), and step (3) are 80 °C, 100 °C, and 45 °C respectively.

[0057] Comparative Example 1

[0058] When starting the liquid-phase grinding equipment, no solubilizer is added. First, grind and disperse for 60 s, then start to introduce carbon dioxide gas. Control the liquid-phase grinding speed at 600 rps and the gas velocity at 20 L / min. When pH ≤ 7, it is regarded as the end of the reaction. Record the reaction time, and cure and mold the slurry, and measure the carbon sequestration rate by TG.

[0059] Table 1 Test Results

[0060] Name Carbon sequestration rate (%) Carbon sequestration time (min) Example 1 54％ 7.3 Example 2 57％ 6.9 Example 3 43％ 8.1 Example 4 35％ 9.5 Example 5 49％ 7.8 Comparative Example 1 27％ 14.6

[0061] It can be seen from Table 1 that by adding the carbon dioxide solubilizer prepared by the present invention, the carbon sequestration rate can be significantly improved, and the carbon sequestration time will also be shortened. This shows that the present invention can accelerate the rate and degree of the carbon sequestration reaction and solve the problem of low solubility of carbon dioxide in the carbon sequestration reaction.

[0062] As mentioned above, it is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modification and equivalent replacement made within the technical scope disclosed by the present invention shall be included in the protection scope of the invention.

Claims

1. A method for preparing a liquid phase grinding carbon dioxide solubilizing agent, characterized in that: The specific operation process includes the following steps: (1) Take 15 - 30 parts of carboxymethyl-β-cyclodextrin and 5 - 10 parts of thionyl chloride in a three-necked flask in the fume hood, heat under reflux in an oil bath and stir magnetically for 8 - 12 h, cool to room temperature and distill off thionyl chloride under reduced pressure to obtain product A; (2) Take 15 - 30 parts of product A, 15 - 35 parts of chitosan, 5 - 10 parts of N-methylformamide, and 1 - 5 parts of pyridine in a three-necked flask, heat under reflux in an oil bath and stir magnetically for 10 - 16 h, cool to room temperature, filter by suction, wash repeatedly with acetic acid and distilled water, and dry to obtain product B; (3) Take 5 - 15 parts of monoethanolamine, 5 - 15 parts of N-methyldiethanolamine, and 100 parts of distilled water in a three-necked flask, heat in a water bath and stir magnetically, slowly dropwise add 5 - 10 parts of terpineol, and finally add 15 - 40 parts of product B, and stir evenly to obtain the liquid-phase grinding carbon dioxide promoter.

2. The method for preparing a liquid-phase grinding carbon dioxide solubilizing agent according to claim 1, characterized in that: In step (1), the pressure for distilling off under reduced pressure is 1.33 - 3.33 kPa.

3. The method for preparing a liquid-phase grinding carbon dioxide solubilizing agent according to claim 1, characterized in that: In step (2), the deacetylation degree of the chitosan is ≥85%, and the mass concentration of the acetic acid is 5%.

4. The preparation method of a liquid-phase grinding carbon dioxide co-solvent according to claim 1, characterized in that: In step (2), the drying is vacuum freeze-drying, and the freezing temperature is -20 - 30 °C, and the drying time is 2 - 4 h.

5. The preparation method of a liquid-phase grinding carbon dioxide co-solvent according to claim 1, characterized in that: In step (3), the concentration of the terpineol is ≥1.5 mg / mL.

6. The preparation method of a liquid-phase grinding carbon dioxide promoter according to claim 1, wherein: The heating temperatures in step (1), step (2), and step (3) are 60 - 80 °C, 80 - 100 °C, and 30 - 45 °C respectively.

7. The preparation method of a liquid-phase grinding carbon dioxide co-solvent according to claim 1, characterized in that: In step (3), the total mass of the liquid-phase grinding carbon dioxide promoter is 1 - 5 wt% of the calcium-based solid waste.

8. A liquid-phase grinding carbon dioxide promoter, characterized in that: It is prepared by the preparation method of the liquid-phase grinding carbon dioxide promoter described in any one of claims 1 - 7.

9. Application of a liquid-phase grinding carbon dioxide co-solvent, characterized in that: The specific operation process includes the following steps: Add the liquid-phase grinding carbon dioxide promoter of claim 8 when the liquid-phase grinding equipment is started, first grind and disperse for 30 - 60 s, then start to introduce carbon dioxide gas, and control the liquid-phase grinding speed at 400 - 600 rps and the gas speed at 15 - 20 L / min.