Ternary mixed amine composition and application thereof, ternary mixed amine absorption liquid and preparation method and application thereof

Abstract

The invention belongs to the technical field of carbon dioxide absorption, and particularly relates to a ternary mixed amine composition and application thereof, a ternary mixed amine absorption liquid and a preparation method and application thereof. The invention provides a ternary mixed amine composition. The ternary mixed amine composition is prepared from ethanolamine, 2-amino-2-methyl-1-propanol and piperazine, the molar ratio of the ethanolamine to the 2-amino-2-methyl-1-propanol to the piperazine is 3 to (0.3 to 0.8) to (1.2 to 1.8). In order to improve the capture and desorption efficiency of carbon dioxide in ship tail gas, ethanolamine, 2-amino-2-methyl-1-propanol and piperazine triamine are compounded, and meanwhile, the mass ratio of the three amines is optimized, so that the steric effect of an absorption solution formed by the ternary mixed amine composition can be effectively improved, the absorption efficiency of carbon dioxide is improved, and the absorption efficiency of carbon dioxide is improved. And moreover, the desorption rate and efficiency are improved, the carbon dioxide is easy to regenerate, and meanwhile, the function of reducing the desorption energy consumption can be realized.

Description

Technical Field

[0001] The invention belongs to the technical field of carbon dioxide absorption, and specifically relates to a ternary mixed amine composition and application thereof, a ternary mixed amine absorption liquid and a preparation method and application thereof. Background Art

[0002] At present, the ship emission reduction route can be divided into energy efficiency technology optimization, clean fuel, power system optimization and carbon capture, utilization and storage technology (CCUS) of carbon dioxide in ship exhaust. Among them, CCUS technology is a strategic technology for realizing large-scale low-carbon utilization of fossil energy, which will have a profound impact on the low-carbon development of the shipping industry. In view of the problem of carbon dioxide emissions in ship exhaust, the characteristics of ship exhaust carbon dioxide absorption liquid are studied, and the absorption efficiency, desorption energy consumption and other performance research of carbon dioxide absorption liquid in ship exhaust are developed, which can provide a design basis for the development of ship carbon dioxide capture system.

[0003] In actual industrial applications, the absorption and desorption of carbon dioxide in ship exhaust gas can be achieved by chemical absorption. The essence of chemical absorption is to react a chemical solution (generally an aqueous solution of an alkaline absorbent) with carbon dioxide in flue gas produced after the combustion of fossil fuels to generate unstable salts, thereby achieving the purpose of absorbing carbon dioxide; then when external conditions change, such as temperature or pressure changes, the unstable salts can be reversely decomposed to release carbon dioxide, thereby achieving the capture and collection process of carbon dioxide in flue gas. In the process of ship exhaust treatment, due to the large exhaust gas flow rate, it is not conducive to the realization of exhaust gas circulation absorption, so the efficiency index of the absorption liquid absorbing carbon dioxide when it only converges with the exhaust gas once is particularly important. At the same time, for the desorption process, the industry often uses the form of high-temperature steam and absorption rich liquid confluence to realize the desorption of carbon dioxide in the rich liquid, so the efficiency and rate index of the absorption liquid desorbing carbon dioxide when it absorbs CO2 to saturation and then converges with the high-temperature steam only once is particularly important. In summary, it is necessary to study high-performance formulas that have good performance in both single absorption and single desorption.

[0004] However, the carbon dioxide absorption solution that is widely used at present has problems such as low absorption efficiency, slow single desorption rate and low efficiency during application. Summary of the invention

[0005] The purpose of the present invention is to provide a ternary mixed amine composition and its application, a ternary mixed amine absorption liquid and its preparation method and application. The ternary mixed amine absorption liquid provided by the present invention has excellent absorption efficiency, desorption rate and desorption effect when used for CO2 absorption.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The invention provides a ternary mixed amine composition, comprising ethanolamine, 2-amino-2-methyl-1-propanol and piperazine; the molar ratio of the ethanolamine, 2-amino-2-methyl-1-propanol and piperazine is 3: (0.3-0.8): (1.2-1.8).

[0008] Preferably, the molar ratio of ethanolamine, 2-amino-2-methyl-1-propanol and piperazine is 3:0.5:1.5.

[0009] The present invention provides the use of the ternary mixed amine composition described in the above technical solution in CO2 absorption.

[0010] The present invention provides a ternary mixed amine absorption liquid, comprising the ternary mixed amine composition described in the above technical solution and water; in the ternary mixed amine absorption liquid: the molar concentration of ethanolamine is 3 mol / L, the molar concentration of 2-amino-2-methyl-1-propanol is 0.3-0.8 mol / L, and the molar concentration of piperazine is 1.2-1.8 mol / L.

[0011] Preferably, in the ternary mixed amine absorption liquid, the molar concentration of 2-amino-2-methyl-1-propanol is 0.5 mol / L, and the molar concentration of piperazine is 1.5 mol / L.

[0012] The present invention provides a method for preparing the ternary mixed amine absorption liquid described in the above technical solution, comprising the following steps:

[0013] mixing ethanolamine and 2-amino-2-methyl-1-propanol to obtain a diamine mixture;

[0014] mixing the diamine mixture and a portion of water to obtain a diamine solution;

[0015] mixing the diamine solution and the piperazine to obtain a teramine solution;

[0016] The ternary amine solution and the remaining water are mixed to obtain the ternary mixed amine absorption liquid.

[0017] The present invention provides the use of the ternary mixed amine absorption liquid described in the above technical solution or the ternary mixed amine absorption liquid prepared by the preparation method described in the above technical solution in CO2 absorption.

[0018] Preferably, the application comprises the following steps:

[0019] The ternary mixed amine absorption liquid is contacted with the gas containing CO2 to absorb CO2.

[0020] Preferably, the application is carried out in an absorption tower; the ternary mixed amine absorption liquid and the gas containing CO2 are in countercurrent contact in the absorption tower;

[0021] The volume percentage of CO2 in the CO2-containing gas is 20-25%, and the flow rate of the CO2-containing gas is 5-6 m / s. 3 / h, the flow rate of the ternary mixed amine absorption liquid is 20-25L / h; the temperature of the CO2 absorption is room temperature.

[0022] Preferably, the CO2 absorption liquid is obtained after the CO2 absorption; and the method further comprises: desorbing the CO2 absorption liquid to obtain a recovered ternary mixed amine absorption liquid; the desorption is carried out in a desorption tower, the reagent used for the desorption is water vapor, and the CO2 absorption liquid and the water vapor are in countercurrent contact in the desorption tower;

[0023] The flow rate of the water vapor is 4.5 to 5 kg / h, and the flow rate of the CO2 absorption liquid is 40 to 45 L / h.

[0024] The present invention provides a ternary mixed amine composition, comprising ethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP) and piperazine (PZ); the molar ratio of the ethanolamine, 2-amino-2-methyl-1-propanol and piperazine is 3: (0.3-0.8): (1.2-1.8). In order to improve the capture and desorption efficiency of carbon dioxide from ship exhaust gas, the present invention adopts ethanolamine, 2-amino-2-methyl-1-propanol and piperazine ternary amine compounding, and optimizes the mass ratio of the three amines at the same time, which can effectively improve the steric effect of the absorption solution formed by the ternary mixed amine composition, improve the absorption efficiency of carbon dioxide, and improve the desorption rate and efficiency, so that carbon dioxide is conducive to regeneration, and at the same time can achieve the function of reducing desorption energy consumption.

[0025] The present invention provides a ternary mixed amine absorption liquid, comprising the ternary mixed amine composition described in the above technical solution and water; in the ternary mixed amine absorption liquid: the molar concentration of ethanolamine is 3 mol / L, the molar concentration of 2-amino-2-methyl-1-propanol is 0.3-0.8 mol / L, and the molar concentration of piperazine is 1.2-1.8 mol / L. From the results of the embodiment, it can be seen that the traditional 5 mol / LMEA solution has a single absorption efficiency of 36.87%, a single desorption rate of 0.953 L / min, and a single desorption efficiency of 4.219%. Compared with the traditional 5 mol / LMEA absorption liquid, the ternary mixed amine absorption liquid (with the components of 3 mol / LMEA+0.5 mol / LAMP+1.5 mol / LPZ) has a higher single absorption efficiency (51.40%), a faster desorption rate (2.124 L / min) and a higher desorption efficiency (8.231%). BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1A curve diagram of the outlet concentration of CO2 absorbed by a single time by the ternary mixed amine absorption solution (3 mol / L MEA+0.5 mol / LAMP+1.5 mol / LPZ solution) provided in Example 2 of the present invention;

[0027] Figure 2 A graph showing the instantaneous flow rate, cumulative flow rate and outlet temperature change of CO2 at a single desorption outlet of the ternary mixed amine absorption solution (3 mol / L MEA+0.5 mol / LAMP+1.5 mol / L PZ solution) provided in Example 2 of the present invention;

[0028] Figure 3 This is a curve diagram of the CO2 outlet concentration of a single absorption of a 5 mol / L MEA solution provided in Comparative Example 1 of the present invention;

[0029] Figure 4 The instantaneous flow rate, cumulative flow rate and outlet temperature change diagram of CO2 at a single desorption outlet of a 5 mol / L MEA solution provided in Comparative Example 1 of the present invention;

[0030] Figure 5 A curve of the outlet concentration of CO2 absorbed by a single time by the binary mixed amine absorption solution (4 mol / LMEA+1 mol / LAMP solution) provided in Comparative Example 2 of the present invention;

[0031] Figure 6 The instantaneous flow rate, cumulative flow rate and outlet temperature change diagram of CO2 at a single desorption outlet of the binary mixed amine absorption liquid (4 mol / LMEA+1 mol / LAMP solution) provided in Comparative Example 2 of the present invention;

[0032] Figure 7 A curve of the outlet concentration of CO2 absorbed by a single time by a binary mixed amine absorption solution (3 mol / LMEA+2 mol / LAMP solution) provided in Comparative Example 3 of the present invention;

[0033] Figure 8 The instantaneous flow rate, cumulative flow rate and outlet temperature change diagram of CO2 at a single desorption outlet of the binary mixed amine absorption liquid (3 mol / LMEA+2 mol / LAMP solution) provided in Comparative Example 3 of the present invention;

[0034] Fig. 9 A curve of the outlet concentration of CO2 absorbed by a single time by a ternary mixed amine absorption solution (3 mol / L MEA+1.5 mol / LAMP+0.5 mol / LPZ solution) provided in Comparative Example 4 of the present invention;

[0035] Fig.10 The instantaneous flow rate, cumulative flow rate and outlet temperature change diagram of CO2 at a single desorption outlet of the ternary mixed amine absorption solution (3 mol / L MEA+1.5 mol / LAMP+0.5 mol / L PZ solution) provided in Comparative Example 4 of the present invention;

[0036] Fig.11 A curve of the outlet concentration of CO2 absorbed by a single time by the ternary mixed amine absorption solution (3 mol / L MEA+1 mol / LAMP+1 mol / LPZ solution) provided in Comparative Example 5 of the present invention;

[0037] Fig.12 The instantaneous flow rate, cumulative flow rate and outlet temperature change diagram of CO2 at a single desorption outlet of the ternary mixed amine absorption solution (3 mol / L MEA+1 mol / LAMP+1 mol / LPZ solution) provided in Comparative Example 5 of the present invention;

[0038] Fig.13 It is a diagram of the device for absorption and desorption of ternary mixed amine absorption liquid in an embodiment of the present invention. DETAILED DESCRIPTION

[0039] The invention provides a ternary mixed amine composition, comprising ethanolamine, 2-amino-2-methyl-1-propanol and piperazine; the molar ratio of the ethanolamine, 2-amino-2-methyl-1-propanol and piperazine is 3: (0.3-0.8): (1.2-1.8).

[0040] In the present invention, unless otherwise specified, all preparation raw materials / components are commercially available products well known to those skilled in the art.

[0041] In the present invention, the ethanolamine (MEA) is in liquid state, and its chemical formula is C2H7NO, w≥99%. The 2-amino-2-methyl-1-propanol (AMP) is in liquid state, and its chemical formula is C4H 11 NO, w≥99%. The piperazine is preferably anhydrous piperazine, and the piperazine (PZ) is in a crystalline solid state with a chemical formula of C4H 10 N2, w≥99%; in the present invention, the molar ratio of ethanolamine, 2-amino-2-methyl-1-propanol and piperazine is preferably 3:0.5:1.5.

[0042] The present invention provides the use of the ternary mixed amine composition described in the above technical solution in CO2 absorption.

[0043] The present invention provides a ternary mixed amine absorption liquid, comprising the ternary mixed amine composition described in the above technical solution and water; in the ternary mixed amine absorption liquid: the molar concentration of ethanolamine is 3 mol / L, the molar concentration of 2-amino-2-methyl-1-propanol is 0.3-0.8 mol / L, and the molar concentration of piperazine is 1.2-1.8 mol / L.

[0044] In the present invention, the water is preferably deionized water. In the ternary mixed amine absorption liquid, the molar concentration of ethanolamine is 3 mol / L, the molar concentration of 2-amino-2-methyl-1-propanol is preferably 0.5 mol / L, and the molar concentration of piperazine is preferably 1.5 mol / L.

[0045] The present invention provides a method for preparing the ternary mixed amine absorption liquid described in the above technical solution, comprising the following steps:

[0046] mixing ethanolamine and 2-amino-2-methyl-1-propanol to obtain a diamine mixture;

[0047] mixing the diamine mixture and a portion of water to obtain a diamine solution;

[0048] mixing the diamine solution and the piperazine to obtain a teramine solution;

[0049] The ternary amine solution and the remaining water are mixed to obtain the ternary mixed amine absorption liquid.

[0050] The present invention mixes ethanolamine and 2-amino-2-methyl-1-propanol to obtain a diamine mixture. The present invention has no special requirements for the specific implementation of the mixing of ethanolamine and 2-amino-2-methyl-1-propanol. The mixing temperature of ethanolamine and 2-amino-2-methyl-1-propanol is preferably room temperature.

[0051] After obtaining the diamine mixture, the present invention mixes the diamine mixture with a portion of water to obtain a diamine solution. In the present invention, the diamine mixture and a portion of water are preferably mixed under stirring, and the present invention preferably adds the portion of water to the diamine mixture.

[0052] After obtaining the diamine solution, the present invention mixes the diamine solution and the piperazine to obtain a triamine solution. The present invention preferably adds the piperazine to the diamine solution, and the second mixing and the mixing of the piperazine are preferably performed under stirring.

[0053] After obtaining the ternary amine solution, the present invention mixes the ternary amine solution with the remaining water to obtain the ternary mixed amine absorption liquid. The present invention preferably adds the remaining water to the ternary amine solution, and the mixing of the ternary amine solution and the remaining water is preferably carried out under stirring.

[0054] After the ternary amine solution and the remaining water are mixed, a fourth mixed material is obtained. In the present invention, the fourth mixed material is preferably allowed to stand and cool to room temperature to obtain the ternary mixed amine absorption liquid.

[0055] The present invention provides the use of the ternary mixed amine absorption liquid described in the above technical solution or the ternary mixed amine absorption liquid prepared by the preparation method described in the above technical solution in CO2 absorption.

[0056] In the present invention, the application is preferably: applying the ternary mixed amine absorption liquid to absorb carbon dioxide in ship exhaust gas.

[0057] In the present invention, the application comprises the following steps:

[0058] The ternary mixed amine absorption liquid is contacted with the gas containing CO2 to absorb CO2.

[0059] In the present invention, the application is carried out in an absorption tower; the ternary mixed amine absorption liquid is countercurrently contacted with the gas containing CO2 in the absorption tower. The gas containing CO2 is introduced from the bottom of the absorption tower, and the ternary mixed amine absorption liquid is sprayed downward from the top of the absorption tower. The volume percentage of CO2 in the gas containing CO2 is preferably 20-25%. The gas containing CO2 is specifically a mixed gas of CO2 and N2. The flow rate of the gas containing CO2 is preferably 5-6m / s. 3 / h. The flow rate of the ternary mixed amine absorption liquid is preferably 20-25 L / h; the temperature of the CO2 absorption is preferably room temperature. The operating pressure of the CO2 absorption is preferably normal pressure.

[0060] In the present invention, CO2 absorption liquid is obtained after the CO2 absorption; the present invention preferably further comprises: desorbing the CO2 absorption liquid to obtain a recovered ternary mixed amine absorption liquid. In the present invention, the desorption is preferably carried out in a desorption tower. The reagent used for the desorption is preferably water vapor, and the CO2 absorption liquid and the water vapor are in countercurrent contact in the desorption tower. The water vapor is introduced from the bottom of the desorption tower, and the temperature of the water vapor is preferably 110±5°C. The flow rate of the water vapor is preferably 4.5-5kg / h. The CO2 absorption liquid is introduced from the top of the desorption tower. The flow rate of the CO2 absorption liquid is preferably 40-45L / h. The operating pressure of the desorption is preferably normal pressure.

[0061] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0062] Example 1

[0063] In this example, 1L of ternary mixed amine absorption liquid (3 mol / LMEA+0.5 mol / LAMP+1.5 mol / LPZ solution) was prepared. The specific preparation method is as follows:

[0064] Step 1: Weigh 3 mol MEA (183.06 g) and 0.5 mol AMP (44.57 g) and mix them thoroughly in a beaker.

[0065] Step 2: After the mixed diamines are allowed to stand, deionized water is slowly added and continuously stirred to dissolve until the volume of the diamine mixed solution reaches 900 mL.

[0066] Step 3: Weigh 1.5 mol PZ (129.21 g) solid and add it into 900 mL of binary mixed amine solution and stir thoroughly.

[0067] Step 4: Slowly add deionized water and continue stirring to dissolve until the volume of the ternary mixed amine solution reaches 1 L. Continue stirring until all ingredients are dissolved.

[0068] Step 5: Cover the beaker with film and let it stand, waiting for the solution to return to room temperature. Thus, 1L of ternary mixed amine absorption solution is obtained.

[0069] The ternary mixed amine absorption liquid prepared in this example contains: 3 mol / LMEA, 0.5 mol / LAMP, and 1.5 mol / LPZ.

[0070] Example 2

[0071] In this example, 3L of ternary mixed amine absorption liquid (3mol / LMEA+0.5mol / LAMP+1.5mol / LPZ solution) was prepared. The specific preparation method is as follows:

[0072] Step 1: Weigh 9 mol MEA (549.18 g) and 1.5 mol AMP (133.71 g) and mix them thoroughly in a beaker.

[0073] Step 2: After the mixed diamines are allowed to stand, deionized water is slowly added and continuously stirred to dissolve until the volume of the diamine mixed solution reaches 2700 mL.

[0074] Step 3: Weigh 4.5 mol PZ (387.63 g) solid and add it into 2700 mL of binary mixed amine solution and stir thoroughly.

[0075] Step 4: Slowly add deionized water and continue stirring to dissolve until the volume of the ternary mixed amine solution reaches 3 L. Continue stirring until all ingredients are dissolved.

[0076] Step 5: Cover the beaker with film and let it stand, waiting for the solution to return to room temperature. Thus, 3L of ternary mixed amine absorption liquid is obtained.

[0077] The ternary mixed amine absorption liquid prepared in this example contains: 3 mol / LMEA, 0.5 mol / LAMP, and 1.5 mol / LPZ.

[0078] Example 3

[0079] In order to simulate actual industrial conditions, this embodiment designs a device that can realize the gas-liquid interaction function in the spray tower. The process flow chart is as follows: Fig.13 The main body of the test device includes an absorption tower (T01), a desorption tower (T02), a 10L lean liquid tank, a 10L rich liquid tank, etc., equipped with CO2 concentration meter, flow meter, steam generator and condenser and other equipment. The absorption tower and the desorption tower are filled with ceramic fillers (accounting for about 80% of the total volume) to ensure complete gas-liquid reaction.

[0080] 3 L of ternary mixed amine absorption liquid (3 mol / L MEA+0.5 mol / LAMP+1.5 mol / LPZ) prepared in Example 2 was stored in a lean liquid tank and a single absorption experiment was carried out.

[0081] In order to evaluate the performance of the solution for single absorption, the absorption efficiency is used as the main criterion. The absorption efficiency is defined as the ratio of the amount of CO2 absorbed to the total amount of CO2 introduced, which can be calculated through the concentration change curve. Control the gas valve and flowmeter to introduce CO2 and N2, with the CO2 flow rate of 1m 3 / h, N2 flow rate is 4m 3 / h, and after mixing and stabilization, it is introduced into the bottom of the absorption tower. The ternary mixed amine absorption liquid prepared in Example 2 is pumped to the top of the absorption tower by the absorption liquid inlet pump (P02) and sprayed downward at a flow rate of 20L / h, and reacts with the mixed gas introduced to absorb CO2 in the mixed gas. There is a CO2 concentration meter at the outlet of the absorption tower to detect the change in the outlet CO2 concentration.

[0082] The single absorption CO2 outlet concentration curve is as follows Figure 1 According to the data, the absorption efficiency is calculated to be 51.40%.

[0083] Example 4

[0084] In this example, a desorption experiment is performed on the absorption liquid after absorbing CO2 in Example 3.

[0085] After the ternary mixed amine absorption liquid in Example 3 absorbed CO2 to saturation, according to the titration results, its loading amount was 0.521 mol CO2 / mol Amine, where "Amine" represents the sum of the moles of MEA, AMP and PZ in the ternary mixed amine absorption liquid. The total CO2 loading amount in the ternary mixed amine absorption liquid was 7.821 mol.

[0086] In order to evaluate the performance of single desorption of ternary mixed amine absorption liquid, desorption efficiency and desorption rate are used as the main criteria. The desorption efficiency is defined as the ratio of the single desorption CO2 amount to the total CO2 load of the solution before desorption. The single desorption amount can be obtained by data recording, and the total CO2 load can be obtained by titration; the desorption rate is defined as the ratio of the desorption amount to the desorption time.

[0087] Water vapor (temperature 110℃) is introduced into the bottom of the desorption tower, and the steam flow rate is 4.5kg / h. The absorbed saturated liquid is stored in the rich liquid tank under the absorption tower, and is pumped to the top of the desorption tower by the desorption liquid inlet pump (P01) for downward spraying at a flow rate of 40L / h, and reacts with the introduced steam to desorb the absorbed CO2. The remaining steam is completely condensed by the condenser. There are CO2 flowmeters and thermometers at the outlet of the absorption tower to detect the instantaneous flow rate, cumulative flow rate and outlet temperature change of CO2 desorption.

[0088] The instantaneous flow rate, cumulative flow rate and outlet temperature of CO2 at a single desorption outlet are as follows: Figure 2 The single desorption volume of the solution is 14.42L, and the average desorption rate is 2.124L / min. Combined with the total CO2 loading of the saturated solution, the single desorption efficiency is calculated to be 8.231%.

[0089] In order to verify the superiority of the ternary mixed amine absorption liquid formula provided by the present invention, the following comparative examples are used to conduct experimental comparisons using 30% MEA solution commonly used in industry, binary mixed amine absorption liquid and ternary mixed amine absorption liquids of other proportions.

[0090] Comparative Example 1: 30% MEA solution

[0091] In this comparative example, MEA was weighed and placed in a beaker, deionized water was slowly added and continuously stirred to dissolve, and 3 L of MEA 5 mol / L solution was prepared.

[0092] Carry out absorption experiment according to Example 3:

[0093] According to the method of Example 3, an absorption experiment was carried out on 3L of 5mol / LMEA solution prepared in Comparative Example 1. The CO2 outlet concentration curve of 3L of 5mol / LMEA solution prepared in Comparative Example 1 for single absorption is as follows: Figure 3 According to the absorption efficiency formula in Example 3, the absorption efficiency is calculated to be 36.87%.

[0094] Carry out desorption experiment according to Example 4:

[0095] According to the absorption test, the 5 mol / L MEA solution prepared in Comparative Example 1 absorbed CO2 to saturation. According to the titration results, its loading capacity was 0.370 mol CO2 / molAmine, and the total CO2 loading capacity of the solution was 5.545 mol.

[0096] For 3L of 5mol / L MEA solution (absorbing CO2 to saturation), the instantaneous flow rate, cumulative flow rate and outlet temperature of CO2 at a single desorption outlet are as follows: Figure 4 The single desorption volume of the solution is 5.24L, and the average desorption rate is 0.953L / min. Combined with the total CO2 loading of the saturated solution, the single desorption efficiency is calculated to be 4.219%.

[0097] Comparative Example 2: Binary mixed amine absorption solution (4 mol / LMEA + 1 mol / LAMP solution)

[0098] This comparative example prepares 3L of binary mixed amine absorption liquid, and the specific preparation method is as follows:

[0099] Step 1: Weigh MEA and AMP and mix them thoroughly in a beaker.

[0100] Step 2: After the mixed diamines are allowed to stand, deionized water is slowly added and continuously stirred to dissolve until the volume of the diamine mixed solution reaches 3 L.

[0101] Step 3: Cover the beaker with film and let it stand, waiting for the solution to return to room temperature. Thus, 3L of binary mixed amine absorption liquid is obtained.

[0102] The binary mixed amine absorption liquid prepared in this comparative example contains: 4 mol / LMEA and 1 mol / LAMP.

[0103] Carry out absorption experiment according to Example 3:

[0104] According to the method of Example 3, 3L of 4mol / LMEA+1mol / LAMP solution prepared in Comparative Example 2, the single absorption CO2 outlet concentration curve is as follows: Figure 5 As shown in Figure 2, the absorption efficiency is calculated to be 42.72% according to the formula.

[0105] Carry out desorption experiment according to Example 4:

[0106] After the diamine mixed solution of Comparative Example 2 absorbed CO2 to saturation, according to the titration results, its loading amount was 0.402 mol CO2 / molAmine, and the total CO2 loading amount of the solution was 6.027 mol.

[0107] For 3L of 4mol / L MEA+1mol / LAMP solution (absorbing CO2 to saturation), the instantaneous flow rate, cumulative flow rate and outlet temperature of CO2 at a single desorption outlet are as follows: Figure 6 The single desorption volume of the solution is 6.29L, and the average desorption rate is 1.134L / min. Combined with the total CO2 loading of the saturated solution, the single desorption efficiency is calculated to be 4.659%.

[0108] Comparative Example 3: Binary mixed amine absorption solution (3 mol / LMEA + 2 mol / LAMP solution)

[0109] This comparative example prepares 3L of binary mixed amine absorption liquid, and the specific preparation method is as follows:

[0110] Step 1: Weigh MEA and AMP and mix them thoroughly in a beaker.

[0111] Step 2: After the mixed diamines are allowed to stand, deionized water is slowly added and continuously stirred to dissolve until the volume of the diamine mixed solution reaches 3 L.

[0112] Step 3: Cover the beaker with film and let it stand, waiting for the solution to return to room temperature. Thus, 3L of binary mixed amine absorption liquid is obtained.

[0113] Carry out absorption experiment according to Example 3:

[0114] For 3L of 3mol / L MEA+2mol / LAMP solution, the single absorption CO2 outlet concentration curve is as follows Figure 7 As shown in Figure 2, the absorption efficiency is calculated to be 43.49% according to the formula.

[0115] Carry out desorption experiment according to Example 4:

[0116] After the solution absorbed CO2 to saturation, according to the titration results, its loading capacity was 0.455 mol CO2 / mol Amine, and the total CO2 loading capacity of the solution was 6.830 mol.

[0117] For 3L of 3mol / L MEA+2mol / LAMP solution (absorbing CO2 to saturation), the instantaneous flow rate, cumulative flow rate and outlet temperature of CO2 at a single desorption outlet are as follows: Figure 8 The single desorption volume of the solution is 7.64L, and the average desorption rate is 1.180L / min. Combined with the total CO2 loading of the saturated solution, the single desorption efficiency is calculated to be 4.993%.

[0118] Comparative Example 4: Ternary mixed amine absorption solution (3 mol / LMEA + 1.5 mol / LAMP + 0.5 mol / LPZ solution)

[0119] This comparative example prepares 3L of ternary mixed amine absorption liquid, and the specific preparation method is as follows:

[0120] Step 1: Weigh MEA and AMP and mix them thoroughly in a beaker.

[0121] Step 2: After the mixed diamine is allowed to stand, deionized water is slowly added and continuously stirred to dissolve.

[0122] Step 3: Weigh PZ solid and add it into the binary mixed amine solution and stir thoroughly.

[0123] Step 4: Slowly add deionized water and continue stirring to dissolve until the volume of the ternary mixed amine solution reaches 3 L. Continue stirring until all ingredients are dissolved.

[0124] Step 5: Cover the beaker with film and let it stand, waiting for the solution to return to room temperature. Thus, 3L of ternary mixed amine absorption liquid is obtained.

[0125] The ternary mixed amine absorption liquid prepared in this comparative example contains: 3 mol / LMEA, 1.5 mol / LAMP, and 0.5 mol / LPZ.

[0126] Carry out absorption experiment according to Example 3:

[0127] For 3L of 3mol / L MEA+1.5mol / LAMP+0.5mol / L PZ solution, the single absorption CO2 outlet concentration curve is as follows Fig. 9 As shown in Figure 2, the absorption efficiency is calculated to be 44.21% according to the formula.

[0128] Carry out desorption experiment according to Example 4:

[0129] After the solution absorbed CO2 to saturation, according to the titration results, its loading capacity was 0.492 mol CO2 / mol Amine, and the total CO2 loading capacity of the solution was 7.375 mol.

[0130] For 3L of 3mol / L MEA+1.5mol / LAMP+0.5mol / L PZ solution (absorbing CO2 to saturation), the instantaneous flow rate, cumulative flow rate and outlet temperature of CO2 at a single desorption outlet are as follows: Fig.10 The single desorption volume of the solution is 10.85 L, and the average desorption rate is 1.727 L / min. Combined with the total CO2 loading of the saturated solution, the single desorption efficiency is calculated to be 6.568%.

[0131] Comparative Example 5: Ternary mixed amine absorption solution (3mol / LMEA+1mol / LAMP+1mol / LPZ solution)

[0132] This comparative example prepares 3L of ternary mixed amine absorption liquid, and the specific preparation method is as follows:

[0133] Step 1: Weigh MEA and AMP and mix them thoroughly in a beaker.

[0134] Step 2: After the mixed diamine is allowed to stand, deionized water is slowly added and continuously stirred to dissolve.

[0135] Step 3: Weigh PZ solid and add it into the binary mixed amine solution and stir thoroughly.

[0136] Step 4: Slowly add deionized water and continue stirring to dissolve until the volume of the ternary mixed amine solution reaches 3 L. Continue stirring until all ingredients are dissolved.

[0137] Step 5: Cover the beaker with film and let it stand, waiting for the solution to return to room temperature. Thus, 3L of ternary mixed amine absorption liquid is obtained.

[0138] The ternary mixed amine absorption liquid prepared in this comparative example contains: 3 mol / L MEA, 1 mol / LAMP, and 1 mol / LPZ.

[0139] Carry out absorption experiment according to Example 3:

[0140] After the solution absorbed CO2 to saturation, according to the titration results, its loading capacity was 0.455 mol CO2 / mol Amine, and the total CO2 loading capacity of the solution was 6.830 mol.

[0141] For 3L of 3mol / L MEA+1mol / LAMP+1mol / LPZ solution, the single absorption CO2 outlet concentration curve is as follows Fig.11 As shown in Figure 2, the absorption efficiency is calculated to be 46.73% according to the formula.

[0142] Carry out desorption experiment according to Example 4:

[0143] After the solution absorbed CO2 to saturation, according to the titration results, its loading capacity was 0.542 mol CO2 / mol Amine, and the total CO2 loading capacity of the solution was 8.134 mol.

[0144] For 3L of 3mol / L MEA+1mol / LAMP+1mol / LPZ solution (absorbing CO2 to saturation), the instantaneous flow rate, cumulative flow rate and outlet temperature of CO2 at a single desorption outlet are as follows: Fig.12 The single desorption volume of the solution is 7.64L, and the average desorption rate is 1.415L / min. Combined with the total CO2 loading of the saturated solution, the single desorption efficiency is calculated to be 5.966%.

[0145] From the absorption and desorption experimental results of the above embodiments and comparative examples, it can be seen that the ternary mixed amine absorption liquid with the composition of 3 mol / LMEA+0.5 mol / LAMP+1.5 mol / L PZ in Examples 1-2 has higher single absorption efficiency, faster desorption rate and higher desorption efficiency compared with the commonly used single amine absorption liquid (Comparative Example 1), binary mixed amine absorption liquid (Comparative Example 2 and Comparative Example 3) and ternary mixed amine absorption liquid with other proportions (Comparative Example 4 and Comparative Example 5).

[0146] As can be seen from the above embodiments, the present invention provides a ternary mixed amine absorption liquid, comprising the ternary mixed amine composition described in the above technical solution and water; in the ternary mixed amine absorption liquid: the molar concentration of ethanolamine is 3 mol / L, the molar concentration of 2-amino-2-methyl-1-propanol is 0.3-0.8 mol / L, and the molar concentration of piperazine is 1.2-1.8 mol / L. In order to improve the capture and desorption efficiency of carbon dioxide from ship exhaust gas, the present invention adopts ethanolamine, 2-amino-2-methyl-1-propanol and piperazine ternary amine compound, and optimizes the mass ratio of the three amines, which can effectively improve the steric effect of the absorption solution formed by the ternary mixed amine composition, improve the absorption efficiency of carbon dioxide, and improve the desorption rate and efficiency, so that carbon dioxide is conducive to regeneration, and at the same time can achieve the function of reducing desorption energy consumption.

[0147] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A ternary mixed amine composition, characterized in that: The invention comprises ethanolamine, 2-amino-2-methyl-1-propanol and piperazine; the molar ratio of the ethanolamine, 2-amino-2-methyl-1-propanol and piperazine is 3: (0.3-0.8): (1.2-1.8).

2. The ternary mixed amine composition according to claim 1, characterized in that: The molar ratio of the ethanolamine, 2-amino-2-methyl-1-propanol and piperazine is 3:0.5:1.

5.

3. Use of the ternary mixed amine composition according to claim 1 or 2 in CO2 absorption.

4. A ternary mixed amine absorption liquid, characterized in that: It comprises the ternary mixed amine composition according to claim 1 or 2 and water; in the ternary mixed amine absorption liquid: the molar concentration of ethanolamine is 3 mol / L, the molar concentration of 2-amino-2-methyl-1-propanol is 0.3-0.8 mol / L, and the molar concentration of piperazine is 1.2-1.8 mol / L.

5. The ternary mixed amine absorption liquid according to claim 4, characterized in that: In the ternary mixed amine absorption liquid, the molar concentration of 2-amino-2-methyl-1-propanol is 0.5 mol / L, and the molar concentration of piperazine is 1.5 mol / L.

6. The method for preparing the ternary mixed amine absorption liquid according to claim 4 or 5, characterized in that: The following steps are involved: mixing ethanolamine and 2-amino-2-methyl-1-propanol to obtain a diamine mixture; mixing the diamine mixture and a portion of water to obtain a diamine solution; mixing the diamine solution and the piperazine to obtain a teramine solution; The ternary amine solution and the remaining water are mixed to obtain the ternary mixed amine absorption liquid.

7. Use of the ternary mixed amine absorption liquid according to claim 4 or 5 or the ternary mixed amine absorption liquid prepared by the preparation method according to claim 6 in CO2 absorption.

8. The use according to claim 7, characterized in that: The application comprises the following steps: The ternary mixed amine absorption liquid is contacted with the gas containing CO2 to absorb CO2.

9. The use according to claim 8, characterized in that: The application is carried out in an absorption tower; the ternary mixed amine absorption liquid is in countercurrent contact with the gas containing CO2 in the absorption tower; The volume percentage of CO2 in the CO2-containing gas is 20-25%, and the flow rate of the CO2-containing gas is 5-6 m / s. 3 / h, the flow rate of the ternary mixed amine absorption liquid is 20-25L / h; the temperature of the CO2 absorption is room temperature.

10. The use according to claim 8, characterized in that: After the CO2 absorption, a CO2 absorption liquid is obtained; and the method further comprises: desorbing the CO2 absorption liquid to obtain a recovered ternary mixed amine absorption liquid; the desorption is carried out in a desorption tower, the reagent used for the desorption is water vapor, and the CO2 absorption liquid and the water vapor are in countercurrent contact in the desorption tower; The flow rate of the water vapor is 4.5 to 5 kg / h, and the flow rate of the CO2 absorption liquid is 40 to 45 L / h.

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