Preparation method of carbon dioxide adsorption resin with core

Abstract

The invention discloses a preparation method of carbon dioxide adsorption resin with an inner core, and belongs to the technical field of adsorption resin. Comprising the following steps: carbonizing resin: selecting post-crosslinked resin, performing staged heating carbonization under the protection of nitrogen, and activating the resin by using high-temperature steam after carbonization; polymerizing a carbonized resin surface layer: uniformly mixing the carbonized resin with an oil phase, soaking for later use, adding the mixture into a water phase, raising the temperature at 78-95 DEG C, carrying out surface polymerization reaction, and synthesizing macroporous adsorption resin with a carbonized resin core; basic hydrolysis: adding the synthesized macroporous adsorption resin into a tetraethylenepentamine solution; a tetraethylenepentamine solution is used for hydrolysis under a strong alkaline condition to obtain amino-containing resin. The resin is macroporous adsorption resin with a resin carbon core, the strength of the resin can be improved, meanwhile, the specific surface area of the resin is greatly increased, and the highest CO2 air adsorption rate can reach 92.17%.

Description

Technical Field

[0001] The invention belongs to the technical field of adsorption resins, and in particular relates to a carbon dioxide adsorption resin with a carbonized resin core. Background Art

[0002] Carbon capture and storage (CCS, also translated as carbon capture and storage, carbon collection and storage, etc.) technology refers to the capture and separation of CO2 from emission sources such as energy utilization, industrial processes or the air, and transportation to suitable sites for utilization or storage via tank trucks, pipelines, ships, etc., ultimately achieving CO2 emission reduction. It is considered to be the most economical and feasible method to reduce greenhouse gas emissions on a large scale and slow global warming in the future.

[0003] Carbon capture and storage technology has the following important significance: reducing greenhouse gas emissions, supporting the sustainable use of fossil energy, and promoting industrial development. However, the technology currently faces some challenges and limitations: High cost: including equipment investment and operating costs in each link of capture, transportation and storage, resulting in high overall costs, which affects its widespread application. Energy consumption: A certain amount of energy is consumed in the carbon capture process, which may offset some of the emission reduction effects to a certain extent. Technology maturity: Some technical links (such as long-term and effective storage technology) still need further research and verification to ensure that carbon dioxide can be safely and stably stored.

[0004] Carbon dioxide capture technology can be divided into several categories, such as chemical absorption, physical adsorption, membrane separation, and cryogenic separation. When applied, the capture method and equipment should be selected according to the actual characteristics and parameters of the carbon dioxide emission source. Among the major carbon capture technologies, chemical absorption and physical absorption methods are relatively mature and have been widely used in the chemical industry. Summary of the invention

[0005] In order to solve the above problems, the present invention provides a method for preparing a carbon dioxide adsorption resin with a core. The prepared resin is a macroporous adsorption resin with a resin carbon core, which can increase the resin strength and greatly increase the specific surface area of ​​the resin. The adsorption of CO2 air can reach up to 92.17%.

[0006] The preparation method of the carbon dioxide adsorption resin having a core comprises the following steps:

[0007] Resin carbonization: Select post-crosslinking resin and perform carbonization at a temperature of 600-950°C under nitrogen protection. After carbonization, use high-temperature steam to activate the resin.

[0008] Carbonized resin surface polymerization: the carbonized resin and the oil phase are mixed evenly and then soaked for later use. The mixture of the carbonized resin and the oil phase is added to the water phase and heated at 78-95°C to perform surface polymerization reaction to synthesize a macroporous adsorption resin with a carbonized resin core;

[0009] In the oil phase, styrene is used as a monomer, triallyl isocyanurate and divinylbenzene are used as crosslinking agents, toluene and liquid paraffin are used as porogens, and BPO is used as an initiator.

[0010] The aqueous phase consists of water, polyvinyl alcohol, magnesium sulfate and sodium carbonate;

[0011] Alkaline hydrolysis: adding the macroporous adsorption resin synthesized in step (2) into a tetraethylenepentamine solution; using the tetraethylenepentamine solution to hydrolyze under strong alkaline conditions to obtain a resin containing amino groups.

[0012] In step (1), the post-crosslinking resin is a resin of type H103, H107 or AASI-1, with a specific surface area greater than 1000 m2 / g, a strength greater than 4N, and a particle size less than 0.5 mm.

[0013] In step (1), the temperature is raised in stages: the temperature is raised to 600°C and kept for 2 hours; the temperature is further raised to 800°C and kept for 2 hours; the temperature is further raised to 950°C and kept for 0.5 hours.

[0014] After the stage heating and insulation in step (1) is completed, the nitrogen is replaced with steam at 750-850°C, which is introduced into the carbonization furnace at a flow rate of 80-120 mL / min for continuous activation for 30 minutes; the diameter of the carbonized resin is less than 0.3 mm, the specific surface area is greater than 1000 m2 / g, and the average pore size is 3-15 nm.

[0015] In step (2), the mass ratio of styrene, triallyl isocyanurate, divinylbenzene, toluene, liquid paraffin and BPO is: 15-25: 5-15: 25-35: 25-35: 25-35: 25-35: 1.

[0016] In step (2), the mass ratio of water, polyvinyl alcohol, magnesium sulfate and sodium carbonate is 40-50:2.5-3:2-3:1.

[0017] In step (2), the mass ratio of the carbonized resin, the oil phase and the water phase is 1:2-3:6-7.5.

[0018] In step (2), the carbonized resin and the oil phase are mixed evenly and then soaked for 2 hours.

[0019] The preparation method of the tetraethylene pentamine solution in step (3) is as follows: 3 g of tetraethylene pentamine is added to 20 mL of 5% sodium hydroxide solution and stirred to mix evenly.

[0020] In step (3), 0.5-1.5 g of the macroporous adsorption resin with a carbonized resin core synthesized in step (2) is added to every 2 mL of sodium hydroxide solution.

[0021] Preferably, in step (2), the mass ratio of styrene, triallyl isocyanurate, divinylbenzene, toluene, liquid paraffin and BPO is 20:10:30:30:30:30:1.

[0022] Preferably, in step (2), the mass ratio of water, polyvinyl alcohol, magnesium sulfate and sodium carbonate is 300:20:15:7.

[0023] The invention also provides application of the resin in carbon dioxide adsorption.

[0024] Generally, resin adsorption is strongest on the surface layer, and the closer to the inside of the resin, the worse the adsorption performance. In order to improve the adsorption performance of carbon dioxide in the inner layer of the resin, the present invention selects resin carbon with large specific surface area and stable chemical properties as the inner core.

[0025] 1. Step-by-step: Multi-layer adsorption is a step-by-step process, and each layer of adsorption is based on the previous layer. This step-by-step feature makes the adsorption process more controllable and helps to improve the adsorption efficiency.

[0026] 2. Layer-by-layer penetration: As adsorption proceeds, the target substance will gradually penetrate from the outer layer of the adsorbent to the inner layer. This layer-by-layer penetration method helps to make full use of the internal space of the adsorbent and increase the adsorption capacity.

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] The present invention performs polymerization reaction on the surface of the carbonized resin to synthesize a macroporous adsorption resin with a resin carbon core. The resin structure is divided into a core resin carbon and an outer layer styrene polymer, which can increase the strength of the resin and greatly increase the specific surface area of ​​the resin. In addition, the adsorbed substance can be efficiently fixed. The amino group on the resin can adsorb carbon dioxide dissolved in water under water-containing conditions. The resin of the present invention can adsorb up to 92.17% of CO2 air. DETAILED DESCRIPTION

[0029] The present invention is further described below by means of specific examples. However, those skilled in the art should be aware that the specific examples of the present invention do not limit the present invention in any way, and any equivalent replacements made on the basis of the present invention fall within the protection scope of the present invention.

[0030] Example 1

[0031] 1. Resin carbonization

[0032] Process: Take 200ml of H103 resin with a particle size range of 0.1-0.5mm, load it into a quartz high-temperature carbonization furnace, and introduce nitrogen at a nitrogen flow rate of 200ml / min. Slowly heat it to 600℃ and keep it for 2h, then continue to heat it to 800℃ and keep it for 2h, then continue to heat it to 950℃ and keep it for 0.5 hour; after the insulation is completed, replace the nitrogen protective gas with high-temperature steam, introduce it into the carbonization furnace at a flow rate of 100ml / min, and continue to activate it at 800℃ for 30min. Turn off the steam and carbonization furnace, take out the resin and set it aside.

[0033] Resin treatment: Take the above resin, add 2% hydrochloric acid to soak for 6 hours, wash with purified water until neutral. Then soak with 1% sodium hydroxide for 6 hours, and wash with purified water until neutral.

[0034] Resin indicators are shown in Table 1 below:

[0035] Table 1

[0036]

[0037] m: The percentage of resin mass within the particle size range to the total resin mass.

[0038] 2. Carbonized resin surface polymerization

[0039] Process: 20g styrene, 10g TAIC, 30g divinylbenzene, 30g liquid wax, 30g toluene and 1g BPO were mixed as the oil phase. 50g of the above carbonized resin was added to the oil phase and soaked for 2 hours for later use.

[0040] Take 300g water, 20g polyvinyl alcohol, 15g magnesium sulfate and 7g sodium carbonate and mix them as the water phase. Add the water phase into a three-necked flask, start stirring and heat to 55°C, and stop stirring until the mixture is completely dissolved and mixed evenly.

[0041] Add the mixture of oil phase and carbonized resin into the water phase, start stirring, slowly heat up to 78°C, keep warm for 4 hours, continue to heat up to 85°C and keep warm for 2 hours, continue to heat up to 95°C to recover toluene, keep warm for 6 hours to complete resin polymerization and obtain a macroporous adsorption resin with a carbonized resin core.

[0042] Resin treatment: Take out the polymerized resin and use a Soxhlet extractor with acetone as the medium to extract the porogen liquid wax. After the porogen is completely extracted, use anhydrous ethanol to elute the resin through the column until the absorbance of the eluent is less than 0.1, and then use water to wash away the ethanol to complete the resin cleaning.

[0043] Resin indicators are shown in Table 2 below:

[0044] Table 2

[0045]

[0046] m: The percentage of resin mass within the particle size range to the total resin mass.

[0047] 3. Alkaline hydrolysis

[0048] Process: Add 200 ml of 5% sodium hydroxide and 30 g of tetraethylenepentamine into a three-necked flask, take 100 g of the above-synthesized macroporous adsorption resin and add it into the three-necked flask, start stirring and heat to 85°C, keep warm for 6 hours to obtain a resin containing a large amount of amino groups.

[0049] Resin treatment: Take out the resin, wash it with purified water until it is neutral, add 5% sodium hydroxide and soak it for 2 hours to ensure that the functional groups of the resin are in the form of hydroxide. Then rinse it with deionized water until it is neutral.

[0050] Resin indicators are shown in Table 3 below:

[0051] Table 3

[0052] Moisture% Specific surface area㎡ / g Amino content mmol / g Strength N 55.9 798.6 8.61 14.2

[0053] 4. Adsorption performance test

[0054] Adsorption performance testing method: The resin structure is divided into an inner core resin carbon and an outer layer styrene polymer, which can increase the strength of the resin and greatly increase the specific surface area of ​​the resin. In addition, it can efficiently fix the adsorbed substance. Under water conditions, the amino group on the resin can adsorb carbon dioxide dissolved in water.

[0055] Adsorption experiment: Use the above resin to treat CO2-containing air: weigh 100 ml of resin and load it into four adsorption columns A, B, C, and D. Connect the 5 mg / L carbon dioxide gas line to the lower port of the A and C adsorption columns, and the 20 mg / L carbon dioxide gas line to the lower port of the B and D adsorption columns. Perform column penetration adsorption of different volumes at the same gas flow rate. 100L of gas passes through the A and C adsorption columns, and 200L of gas passes through the B and D adsorption columns, respectively, and is collected in sealed plastic bags. The carbon dioxide concentration is detected by gas chromatography. The resin adsorption efficiency is calculated by calculating the gas volume and concentration in the plastic bag (see Table 4).

[0056] Resin adsorption rate Cr = (1-V2C2 / V1C1) × 100%, where V1 is the intake volume (L), C1 is the intake concentration (mg / L), V2 is the gas volume after passing through the adsorption column (L), and C2 is the gas concentration after passing through the adsorption column (mg / L).

[0057] Table 4 Results of amino acid grafted resin treatment of CO2-containing air

[0058] serial number A B C D Resin state Dry Dry Wet Wet Intake volume / L 100 200 100 200 Intake air concentration / (mg / L) 5 20 5 20 Gas volume after passing through adsorption column / L 98.15 193.38 97.79 191.49 Gas concentration after passing through adsorption column / (mg / L) 1.17 6.42 0.40 2.36 Total resin adsorption efficiency / % 76.98 68.97 92.17 88.69

[0059] It can be seen from the above table that the wet resin has a better adsorption efficiency. A relatively low initial concentration can improve the adsorption efficiency of the resin. The resin of this embodiment can adsorb up to 92.17% of CO2 air.

Claims

1. A method for preparing a carbon dioxide adsorbent resin having a core, characterized in that: The following steps are involved: (1) Resin carbonization: Select post-crosslinking resin and perform carbonization at a temperature of 600-950°C under nitrogen protection. After carbonization, use high-temperature steam to activate the resin. (2) Carbonized resin surface polymerization: The carbonized resin and the oil phase are mixed evenly and then soaked for later use. The mixture of the carbonized resin and the oil phase is added to the water phase and heated in stages from 78 to 95°C for surface polymerization to synthesize a macroporous adsorption resin with a carbonized resin core; In the oil phase, styrene is used as a monomer, triallyl isocyanurate and divinylbenzene are used as crosslinking agents, toluene and liquid paraffin are used as porogens, and BPO is used as an initiator. The aqueous phase consists of water, polyvinyl alcohol, magnesium sulfate and sodium carbonate; (3) Alkaline hydrolysis: adding the macroporous adsorption resin synthesized in step (2) into a tetraethylenepentamine solution; hydrolyzing the macroporous adsorption resin under strong alkaline conditions using the tetraethylenepentamine solution to obtain a resin containing amino groups.

2. The method for preparing a carbon dioxide adsorbent resin having a core according to claim 1, characterized in that: The post-crosslinking resin in step (1) is a resin of type H103, H107 or AASI-1, with a specific surface area greater than 1000 m2 / g, a strength greater than 4N, and a particle size less than 0.5 mm.

3. The method for preparing a carbon dioxide adsorbent resin having a core according to claim 1, characterized in that: In step (1), the temperature is raised to 600°C and kept for 2 hours; the temperature is further raised to 800°C and kept for 2 hours; the temperature is further raised to 950°C and kept for 0.5 hours.

4. The method for preparing a carbon dioxide adsorbent resin having a core according to claim 1, characterized in that: After the heating and insulation in step (1) is completed, the nitrogen is replaced with steam at 750-850°C and introduced into the carbonization furnace at a flow rate of 80-120 mL / min for continuous activation for 30 minutes; the diameter of the carbonized resin is less than 0.3 mm and the specific surface area is greater than 1000 m 2 / g, and the average pore size is 3-15nm.

5. The method for preparing a carbon dioxide adsorbent resin having a core according to claim 1, characterized in that: In step (2), the mass ratio of styrene, triallyl isocyanurate, divinylbenzene, toluene, liquid paraffin and BPO is: 15-25: 5-15: 25-35: 25-35: 25-35: 25-35:

1.

6. The method for preparing a carbon dioxide adsorbent resin having a core according to claim 1, characterized in that: In step (2), the mass ratio of water, polyvinyl alcohol, magnesium sulfate and sodium carbonate is 40-50:2.5-3:2-3:

1.

7. The method for preparing a carbon dioxide adsorbent resin having a core according to claim 1, characterized in that: In step (2), the mass ratio of the carbonized resin, the oil phase and the water phase is 1:2-3:6-7.

5.

8. The method for preparing a carbon dioxide adsorbent resin having a core according to claim 1, characterized in that: In step (2), the carbonized resin and the oil phase are mixed evenly and then soaked for 2 hours.

9. The method for preparing a carbon dioxide adsorbent resin having a core according to claim 1, characterized in that: The preparation method of the tetraethylene pentamine solution in step (3) is to add 3 g of tetraethylene pentamine to 20 mL of 5% sodium hydroxide solution and stir to mix evenly.

10. The method for preparing a carbon dioxide adsorbent resin having a core according to claim 9, characterized in that: In step (3), 0.5-1.5 g of the macroporous adsorption resin having a carbonized resin core synthesized in step (2) is added to every 2 mL of sodium hydroxide solution.

Images