Organic amine composition for capturing CO2 in flue gas, decarburization solvent containing same and decarburization method thereof

Abstract

The invention discloses an organic amine composition for capturing CO2 in flue gas, a decarburization solvent containing the composition and a decarburization method of the decarburization solvent, the organic amine composition comprises 2, 4, 6-trisubstituent-1, 3, 5-triazinane and tertiary alcohol amine, and substituent groups are selected from alcohol groups and / or hydroxyl groups. The composition and the decarburization solvent have excellent CO2 absorption performance and CO2 desorption performance when applied to decarburization, and indexes such as CO2 absorption capacity, absorption rate, desorption efficiency and desorption energy consumption can be considered at the same time.

Description

Technical Field

[0001] This invention belongs to the field of CCUS, specifically relating to an organic amine composition for capturing CO2 in flue gas, a decarbonization solvent containing the composition, and a decarbonization method thereof. Background Technology

[0002] Due to the large-scale use of fossil fuels, the total amount of CO2 emitted into the atmosphere globally each year has gradually increased, exceeding the carrying capacity of the global environment. In 2023, global energy-related CO2 emissions totaled 37.4 billion tons. China's CO2 emissions were approximately 12.665 billion tons, accounting for about 35% of global carbon emissions, with thermal power generation being the main CO2-emitting industry, accounting for about half of these emissions. Effectively reducing CO2 emissions into the atmosphere, protecting the human living environment, and promoting sustainable development are of great strategic significance and are a pressing issue of close concern to humanity today.

[0003] Coal-fired power plants are a long-term, stable, and concentrated source of CO2 emissions. Capturing CO2 from power plant flue gas will become one of the most direct and effective means of mitigating the greenhouse effect. Common CO2 decarbonization processes include solvent absorption, adsorption, membrane separation, and cryogenic separation, among which solvent absorption is currently the most mature technology. Solvent absorption utilizes a chemical solvent to undergo a reversible chemical reaction with CO2 to achieve the purpose of absorbing and desorbing CO2. Commonly used chemical solvents include ammonia, ionic liquids, potassium carbonate solution, and organic amine solution.

[0004] However, current decarbonization solvents or those with excellent CO2 absorption performance often have low desorption efficiency; conversely, those with high desorption efficiency may have high desorption energy consumption; and those with low desorption energy consumption may have poor absorption performance. It is difficult to simultaneously achieve optimal CO2 absorption capacity, absorption rate, desorption efficiency, and desorption energy consumption, thus hindering the large-scale application of CCUS technology. Therefore, there is an urgent need to develop novel, high-efficiency CO2 absorbents with low energy consumption for flue gas CO2 capture, while simultaneously possessing excellent CO2 absorption and desorption performance. Summary of the Invention

[0005] To overcome the problems existing in the prior art, the present invention provides an organic amine composition for capturing CO2 in flue gas, a decarbonization solvent containing the composition, and a decarbonization method thereof, wherein the composition and the decarbonization solvent have excellent CO2 absorption and CO2 desorption performance when applied to decarbonization, and can simultaneously take into account indicators such as CO2 absorption capacity, absorption rate, desorption efficiency and desorption energy consumption.

[0006] One object of the present invention is to provide an organic amine composition for capturing CO2 in flue gas, comprising 2,4,6-trisubstituted-1,3,5-triazine and tertiary alcoholamine, wherein the substituents are selected from alcohol groups and / or hydroxyl groups.

[0007] In a preferred embodiment, the 2,4,6-trisubstituted-1,3,5-triazine is selected from at least one of the compounds shown in formula (1):

[0008]

[0009] In formula (1), R1, R2, and R3 are each independently selected from hydroxyl, monohydric alcohol, or dihydric alcohol groups, wherein R1, R2, and R3 may be the same or different.

[0010] In a further preferred embodiment, in formula (1), R1, R2, and R3 are each independently selected from hydroxyl groups, C1-C10 monohydric alcohol groups, or C2-C10 dihydric alcohol groups, preferably from hydroxyl groups, C1-C5 monohydric alcohol groups, or C2-C5 dihydric alcohol groups.

[0011] In a further preferred embodiment, R1, R2, and R3 are each independently selected from hydroxyl, methanol, ethanol, propanol, propylene glycol, butanol, and butanediol.

[0012] In a preferred embodiment, the tertiary alcohol amine contains a tertiary amine group and at least one hydroxyl group, and preferably, the tertiary alcohol amine is selected from at least one of the compounds shown in formula (2) and formula (3):

[0013]

[0014] In formula (2), at least one of R4, R5, and R6 is selected from an alcohol group, and the other two are each independently selected from an alkyl group; in formula (3), R6, R7, R8, and R9 are each independently selected from an alkyl group.

[0015] In a further preferred embodiment, in formula (2), at least one of R4, R5, and R6 is selected from C1 to C10 alcohol groups (e.g., C1 to C5 alcohol groups), and the other two are each independently selected from C1 to C10 alkyl groups (e.g., C1 to C5 alkyl groups); in formula (3), R6, R7, R8, and R9 are each independently selected from C1 to C10 alkyl groups (e.g., C1 to C5 alkyl groups).

[0016] In a further preferred embodiment, the tertiary alcohol amine is selected from one or more of N-methyldiethanolamine, N,N-dimethylethanolamine, triethanolamine, triisopropanolamine, 1,3-di(dimethylamino)-2-propanol, 1,3-di(diethylamino)-2-propanol, and 1,3-di(ethylmethylamino)-2-propanol.

[0017] In a preferred embodiment, based on 100 wt% of the organic amine composition, the 2,4,6-trisubstituted-1,3,5-triazine accounts for 40-95 wt%, and the tertiary alcohol amine accounts for 5-60 wt%.

[0018] For example, based on 100 wt% of the organic amine composition, the 2,4,6-trisubstituted-1,3,5-triazine accounts for 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, or 90 wt%, and the tertiary alcohol amine accounts for 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, or 50 wt%.

[0019] In a further preferred embodiment, based on 100 wt% of the organic amine composition, the 2,4,6-trisubstituted-1,3,5-triazine accounts for 50-90 wt%, and the tertiary alcohol amine accounts for 10-50 wt%.

[0020] A second objective of this invention is to provide the application of the organic amine composition described in one objective of this invention in decarbonization solvents, particularly in decarbonization solvents for capturing CO2 in flue gas.

[0021] A third objective of this invention is to provide a decarbonization solvent, comprising a CO2 absorbent and a solvent, wherein the CO2 absorbent is selected from the organic amine composition described in one objective of this invention.

[0022] In a preferred embodiment, the CO2 absorbent content is 5-75 wt% and the solvent content is 25-95 wt%, based on 100 wt% of CO2 absorbent and solvent.

[0023] For example, in the decarbonization solvent, the content of the CO2 absorbent is 6 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, or 75 wt%, and the content of the solvent is 25 wt%, 300 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, or 90 wt%.

[0024] In a further preferred embodiment, the CO2 absorbent content in the decarbonization solvent is 10-60 wt%, and the solvent content is 40-90 wt%.

[0025] In a preferred embodiment, the solvent is water.

[0026] In a preferred embodiment, the decarbonization solvent optionally contains an additive, the additive being present in an amount of 200–2000 mg / L, preferably 600–1300 mg / L, for example 200 mg / L, 500 mg / L, 800 mg / L, 1000 mg / L, 1200 mg / L, 1500 mg / L, 1800 mg / L, or 2000 mg / L.

[0027] In a further preferred embodiment, the additive includes at least one of an antifoaming agent, a corrosion inhibitor, and an antioxidant.

[0028] In a further preferred embodiment, the defoamer is selected from at least one of polydimethylsiloxane, polyethylene glycol, and polyether sulfate, and / or the corrosion inhibitor is selected from at least one of sodium hydroxyethylidene diphosphate, undecylhydroxyethyl imidazoline, and hexadecyl dimethyl tertiary amine, and / or the antioxidant is selected from at least one of 2,6-di-tert-butylphenol, hydroquinone, or diethylhydroxylamine.

[0029] In a preferred embodiment, the defoamer in the decarbonization solvent has a content of 50 mg / L to 800 mg / L, and / or the corrosion inhibitor has a content of 5 mg / L to 80 mg / L, and / or the antioxidant has a content of 200 mg / L to 1000 mg / L.

[0030] For example, in the decarbonization solvent, the content of the defoamer is 50 mg / L, 100 mg / L, 150 mg / L, 200 mg / L, 250 mg / L, 300 mg / L, 350 mg / L, 400 mg / L, 450 mg / L, 500 mg / L, 550 mg / L, 600 mg / L, 650 mg / L, 700 mg / L, 750 mg / L, or 800 mg / L, and / or, the The corrosion inhibitor has a content of 5 mg / L, 10 mg / L, 20 mg / L, 30 mg / L, 40 mg / L, 50 mg / L, 60 mg / L, 70 mg / L or 80 mg / L, and / or the antioxidant has a content of 200 mg / L, 300 mg / L, 400 mg / L, 500 mg / L, 600 mg / L, 700 mg / L, 800 mg / L, 900 mg / L or 1000 mg / L.

[0031] In a further preferred embodiment, the content of the defoamer in the decarbonization solvent is 100 mg / L to 500 mg / L, and / or the content of the corrosion inhibitor is 10 mg / L to 50 mg / L, and / or the content of the antioxidant is 500 mg / L to 800 mg / L.

[0032] The fourth objective of this invention is to provide a decarbonization method for capturing CO2 in flue gas, comprising: contacting the flue gas with the decarbonization solvent described in the third objective of this invention to absorb the CO2 therein.

[0033] In a preferred embodiment, the absorption is performed at 15°C to 60°C, preferably 20°C to 50°C, for example, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, or 60°C; and / or, the absorption is performed at 0 to 100 kPa (gauge pressure), for example, 0 kPa, 10 kPa, 20 kPa, 30 kPa, 40 kPa, 50 kPa, 60 kPa, 70 kPa, 80 kPa, 90 kPa, or 100 kPa.

[0034] In a further preferred embodiment, during the contact process: the residence time of the decarbonizing solvent is 1 min to 30 min, preferably 3 min to 20 min; and / or, the residence time of the flue gas phase is 5 s to 70 s, preferably 10 s to 50 s; and / or, the liquid-to-gas ratio is 1 L to 10 L of decarbonizing solvent / Nm³. 3 Smoke.

[0035] For example, during the contact process: the residence time of the decarbonizing solvent is 1 min, 5 min, 10 min, 15 min, 20 min, 25 min, or 30 min; and / or, the residence time of the flue gas phase is 5 s, 10 s, 20 s, 30 s, 40 s, 50 s, 60 s, or 70 s; and / or, the liquid-to-gas ratio is 1 L, 2 L, 4 L, 6 L, 8 L, or 10 L of decarbonizing solvent / Nm³. 3 Smoke.

[0036] In a further preferred embodiment, the decarbonization solvent flow rate is 0.2–10 ml / min, preferably 0.5–8 ml / min; and / or, the flue gas flow rate is 100–1300 ml / min, preferably 200–1000 ml / min.

[0037] Among them, the liquid-to-gas ratio (L / Nm 3 = (1000 / flue gas flow rate) * decarbonization solvent flow rate.

[0038] In a preferred embodiment, the flue gas is contacted counter-currently with the decarbonization solvent for absorption.

[0039] In a further preferred embodiment, the flue gas and the decarbonization solvent are in countercurrent contact within the absorption tower. Preferably, the flue gas is in countercurrent contact with the decarbonization solvent, which is in countercurrent contact from bottom to top.

[0040] In a preferred embodiment, the decarbonization solvent is regenerated after the contact. Preferably, the regeneration temperature is 80–130°C, more preferably 90–110°C, for example 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, or 130°C.

[0041] When the CO2 content in the flue gas after contact absorption is basically stable, it indicates that the contact absorption has reached equilibrium and the decarbonization solvent after contact absorption needs to be regenerated.

[0042] In a further preferred embodiment, the regenerated decarbonization solvent is recycled and used to absorb CO2 from the flue gas.

[0043] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values; these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In the following, various technical solutions can, in principle, be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] (1) The decarbonization solvent in this invention has a strong absorption capacity for CO2 in flue gas, wherein the CO2 loading of the decarbonization solvent can be as high as 3.76 mol / L and the CO2 removal efficiency can be as high as 99%.

[0046] (2) The decarbonization solvent in this invention has a strong desorption capacity for CO2 in flue gas. The regeneration temperature of the decarbonization solvent can be as low as 110℃, and the corresponding regeneration energy consumption is 1.82GJ / tCO2.

[0047] (3) The decarbonization solvent in this invention has stable chemical properties, low corrosivity to equipment, is non-toxic and not easily degraded, and can be used for low-pressure carbon capture of flue gas CO2, thereby reducing the cost of flue gas carbon capture. Attached Figure Description

[0048] Figure 1 A schematic diagram of the system structure for CO2 absorption and decarbonization solvent regeneration is shown.

[0049] 1—CO2 absorption tower; 2—decarbonization solvent rich liquid regeneration tower; 3—CO2 storage tank; 4—1# gas-liquid separator; 5—purified flue gas; 6—CO2 gas source control valve; 7—1# CO2 online gas detector; 8—gas flow meter; 9—rich liquid sampling port; 10—lean liquid pump; 11—1# condenser; 12—lean-rich liquid heat exchanger; 13—rich liquid heater; 14—regeneration tower heater; 15—reflux pump; 16—2# condenser; 17—desorption gas outlet; 18—lean liquid sampling port; 19—2# CO2 online gas detector; 20—2# gas-liquid separator; 21—3# CO2 online gas detector; 22—rich liquid pump.

[0050] Figure 2 The apparatus for measuring the CO2 loading of decarbonization solvent is shown.

[0051] Figure 2 In the middle, 23 is a three-necked flask containing the decarbonization solvent to be tested; 24 is an iron stand; 25 is a separatory funnel containing H2SO4 (1:1) solution; 26 is an inverted conical flask containing anhydrous ethanol; and 27 is a graduated cylinder.

[0052] Figure 3 Showing 3 # The CO2 loading of the decarbonization solvent varies with the absorption pressure.

[0053] Figure 4 Showing 3 # The CO2 loading of the decarbonization solvent varies with operating time. Detailed Implementation

[0054] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0055] It should also be noted that the various specific technical features described in the following embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations will not be described separately in this invention.

[0056] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0057] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0058] The specific evaluation method for the decarbonization solvent in this invention is as follows: According to Figure 1 The prepared decarbonization solvent is injected into the flue gas CO2 absorption system; the lean liquid pump 10 and the rich liquid pump 22 are turned on to circulate the decarbonization solvent within the system, and the circulation flow rate is adjusted; the rich liquid heater 13 and the regeneration tower heater 14 are turned on to control the temperature of the rich liquid entering the decarbonization solvent rich liquid regeneration tower 2, and to control the bottom temperature of the decarbonization solvent rich liquid regeneration tower 2. The heaters can accurately display the output power; turn on 1 # Condenser 11, 2 # Condenser 16 controls the temperature of the lean liquid entering CO2 absorption tower 1 and the outlet temperature of the reflux pump. The CO2 gas source control valve 6 of CO2 storage tank 3 is opened, and the gas flow meter 8 is adjusted to control the gas flow rate. In CO2 absorption tower 1, CO2 enters the decarbonization solvent liquid phase from the gas phase, and the purified gas enters the CO2 absorption tower 1 from the top. # The gas-liquid separator 4 discharges from the system; the decarbonization solvent absorbs CO2, becoming the decarbonization solvent rich liquid, which exits from the bottom of the CO2 absorption tower 1, passes through the lean-rich liquid heat exchanger 12, the rich liquid pump 22, and the rich liquid heater 13, and enters the decarbonization solvent rich liquid regeneration tower 2. CO2 and water vapor are desorbed in the tower, and both exit from the top of the decarbonization solvent rich liquid regeneration tower 2, passing through 2... # Condenser 16, inlet 2 # Gas-liquid separator 20, CO2 gas from 2 # The liquid water discharged from the top of the gas-liquid separator 20 is returned to the rich decarbonized solvent regeneration tower 2 via the reflux pump 15; the regenerated lean liquid is discharged from the bottom of the rich decarbonized solvent regeneration tower 2 and passes through the lean-rich liquid heat exchangers 12 and 13. # The condenser 11 is pumped into the top of the CO2 absorption tower 1 by the lean liquid pump 10 to complete the absorption-desorption cycle.

[0059] Among them 1 # CO2 online gas detector 7, 2 # CO2 online gas detectors 19, 3 # The online CO2 gas detector 21 analyzes the CO2 content in the raw gas, the purified gas, and the desorbed gas in real time. When 2 #When the CO2 online gas detector 19 shows that the CO2 volume fraction in the gas phase no longer fluctuates, it indicates that the system has reached equilibrium and the decarbonization solvent can be sampled and analyzed. The CO2 loading in the decarbonization solvent is sampled and analyzed from the rich liquid sampling port 9 and the lean liquid sampling port 18 every 20 minutes. The CO2 absorption tower 1 has temperature and pressure settings for monitoring the CO2 absorption process. The decarbonization solvent rich liquid regeneration tower 2 has temperature and pressure settings for monitoring the CO2 desorption process.

[0060] Figure 1 The baseline operating conditions for the comprehensive evaluation device of decarbonization solvent shown are as follows: the decarbonization solvent feed flow rate at the top of the CO2 absorption tower (1) is 1 ml / min to 10 ml / min, and the gas feed flow rate at the bottom of the tower is 220 ml / min to 1000 ml / min. The decarbonization solvent feed flow rate at the top of the tower, the gas feed flow rate at the bottom of the tower, the CO2 concentration at the gas inlet, and the reaction temperature and pressure are adjusted respectively to study the absorption and desorption performance of carbon solvent for CO2 under different process conditions.

[0061] The analysis of CO2 loading in the decarbonization solvent in this invention is based on the utilization of Figure 2 The CO2 loading determination device for the decarbonization solvent shown is as follows: When the decarbonization solvent is lean, measure 1 ml of the decarbonization solvent and inject it into the three-necked flask 23. When the decarbonization solvent is rich, dilute it 10 times and measure 1 ml of it into the three-necked flask 23. Open the separatory funnel 25 and slowly add sulfuric acid solution. The sulfuric acid solution reacts with the decarbonization solvent, and carbonate, bicarbonate, carbamate, etc. decompose and release CO2 gas. When the bubbles stop, close the separatory funnel 25. Record the liquid level change in the graduated cylinder 27, and obtain the CO2 gas volume V1 accordingly.

[0062] Calculation of CO2 loading of the decarbonization solvent:

[0063]

[0064] Where: L CO2 V1 is the CO2 loading of the decarbonization solvent, in mol / L; V2 is the volume of CO2 released, in ml; T is the ambient temperature during the detection process, in °C; V0 is the volume of the decarbonization solvent (10 when the decarbonization solvent is lean). -3 L; when the decarbonization solvent is a rich solution, it is 10. -4 L).

[0065] Calculation of regeneration energy consumption for the decarbonized solvent-rich solution:

[0066]

[0067] Where: W1 is the power of the rich liquid heater, W; W2 is the power of the regeneration tower heater, W; L CO2CO2 loading of the decarbonization solvent-rich solution, in mol / L; L' CO2 CO2 loading of the decarbonization solvent-poor solution, in mol / L; v L The flow rate of the decarbonization solvent is ml / min.

[0068] The regeneration rate of the decarbonization solvent:

[0069]

[0070] in: The degree of regeneration of the decarbonization solvent, expressed as % (L). CO2 CO2 loading of the decarbonization solvent-rich solution, in mol / L; L' CO2 The CO2 loading of the decarbonized solvent-poor solution.

[0071] The CO2 removal efficiency is:

[0072]

[0073] Where: η is the CO2 removal rate, %; C in 1 # CO2 content displayed by online CO2 gas detector, %; C out 2 # The CO2 content displayed by the online CO2 gas detector is %.

[0074] 1,3-Di(dimethylamino)-2-propanol, 1,3-Di(diethylamino)-2-propanol, and 1,3-Di(diisopropylamino)-2-propanol were prepared using the method described in the example of US4304910A;

[0075] The CO2 absorption agent (CAS: 2455524-43-1) in Examples 1 and 5 can be commercially available or prepared using the method disclosed in Example WO2020249428A1 as shown in the following formula;

[0076]

[0077] The CO2 absorption agent (CAS: 2455524-49-7) in Example 2 can be commercially available or prepared using the method disclosed in Example WO2020249428A1. The difference lies in the raw materials used (4-hydroxybutyraldehyde is replaced with glycolaldehyde, and 4-hydroxybutyraldehyde is purchased from Shanghai Maclean Biochemical Technology Co., Ltd.). It is prepared according to the following formula.

[0078]

[0079] The CO2 absorption agent (CAS: 958816-68-7) in Example 3 can be commercially available (supplier: Ambeed) or prepared using methods disclosed in the prior art, as follows:

[0080]

[0081] The CO2 absorption agent in Example 4 can be commercially available (supplier: AOPHARM) or prepared using methods disclosed in the prior art.

[0082] The CO2 absorption agent in Example 6 can be commercially available or prepared using the method disclosed in Example WO2020249428A1. The difference lies in the raw materials used (3-hydroxypropanal replaces glycolaldehyde, and 4-hydroxybutanal is purchased from Shanghai Maclean Biochemical Technology Co., Ltd.), and it is prepared according to the following formula.

[0083]

[0084] The polydimethylsiloxane (CAS: 9006-65-9) used in the examples was purchased from Shanghai Yuanye Biotechnology Co., Ltd.

[0085] Example 1

[0086] Prepare the decarbonization solvent according to Table 1-1, and inject it into the flue gas CO2 absorption system to treat the CO2 in the flue gas (Table 1-2). Apply the CO2 absorption and desorption conditions according to Table 1-3. Figure 1 The decarbonization solvent comprehensive evaluation device shown is used for evaluation. When 2 # The online CO2 gas detector 19 showed that the CO2 volume fraction in the gas phase was stable at 1.24 v%, indicating that the system had reached equilibrium. # The online CO2 gas detector 21 showed that the CO2 content in the desorbed gas 17 was above 90%; samples were taken every 20 minutes from the rich liquid sampling port 9 and the lean liquid sampling port 18, using... Figure 2 The CO2 loading of the decarbonization solvent CO2 loading device was analyzed in Example 1. The CO2 loading in the rich decarbonization solvent solution and the poor decarbonization solvent solution were 2.46 mol CO2 / L and 0.14 mol CO2 / L, respectively. The power W1 of the rich solution heater was recorded as 0.51 W and the power W2 of the regeneration tower heater was recorded as 2.52 W.

[0087] Table 1-1 1 # Decarbonization solvent composition

[0088]

[0089]

[0090] Table 1-2 Flue Gas Composition

[0091] project Content (mol%) <![CDATA[CO2]]> 15 <![CDATA[O2]]> 6 <![CDATA[N2]]> 79

[0092] Table 1-3 1 # CO2 absorption and desorption conditions of decarbonization solvent

[0093] project numerical values Decarbonization solvent flow rate (ml / min) 0.9 Decarbonization solvent residence time (min) 20 flue gas flow rate (ml / min) 336 Flue gas residence time s 35 <![CDATA[Liquid-gas ratio L / Nm 3 > 2.67 <![CDATA[CO2 absorption reaction temperature °C]]> 30 <![CDATA[CO2 absorption reaction pressure kPa]]> 10 Decarbonization solvent regeneration reaction temperature (°C) 110

[0094] According to the energy consumption calculation formula for decarbonization solvent regeneration, the degree of regeneration of decarbonization solvent, and the CO2 removal efficiency calculation formula of the present invention, the energy consumption for decarbonization solvent regeneration, and the CO2 removal efficiency in Example 1 are calculated respectively. # The regeneration energy consumption, regeneration degree, and CO2 removal efficiency of the decarbonization solvent are shown in Table 1-4.

[0095] Table 1-4 1 # Performance indicators of decarbonization solvents

[0096]

[0097]

[0098] Example 2

[0099] Prepare the decarbonization solvent according to Table 2-1, and inject it into the flue gas CO2 absorption system to treat the flue gas in Table 2-2. Apply the CO2 absorption and desorption conditions according to Table 2-3. Figure 1 The decarbonization solvent comprehensive evaluation device shown is used for evaluation. When 2 # The online CO2 gas detector 19 shows that the CO2 volume fraction in the gas phase is stable at 0.10 v%, indicating that the system has reached equilibrium. # The online CO2 gas detector 21 showed that the CO2 content in the desorbed gas 17 was above 96%; samples were taken every 20 minutes from the rich liquid sampling port 9 and the lean liquid sampling port 18, using... Figure 2 The CO2 loading of the decarbonization solvent CO2 loading device was analyzed in Example 1. The CO2 loading in the rich decarbonization solvent solution and the poor decarbonization solvent solution were 0.64 mol CO2 / L and 0.20 mol CO2 / L, respectively. The power W1 of the rich solution heater was recorded as 3.03 W and the power W2 of the regeneration tower heater was recorded as 1.04 W.

[0100] Table 2-1 2 # Decarbonization solvent composition

[0101]

[0102]

[0103] Table 2-2 Flue Gas Composition

[0104] project Content (mol%) <![CDATA[CO2]]> 10 <![CDATA[O2]]> 11 N2 79

[0105] Table 2-3 2 # CO2 absorption and desorption conditions of decarbonization solvent

[0106] project numerical values Decarbonization solvent flow rate (ml / min) 6.0 Decarbonization solvent residence time (min) 3 flue gas flow rate (ml / min) 596 Flue gas residence time s 20 <![CDATA[Liquid-gas ratio L / Nm 3 > 10 <![CDATA[CO2 absorption reaction temperature °C]]> 50 <![CDATA[CO2 absorption reaction pressure kPa]]> 0 Decarbonization solvent regeneration reaction temperature (°C) 90

[0107] The energy consumption calculation formula for decarbonization solvent regeneration, the regeneration degree calculation formula for decarbonization solvent, and the CO2 removal efficiency calculation formula of the present invention are used to calculate the CO2 removal efficiency in Example 2. # The energy consumption, regeneration rate, and CO2 removal efficiency of the decarbonization solvent are shown in Table 2-4.

[0108] Table 2-4 2 # Performance indicators of decarbonization solvents

[0109]

[0110]

[0111] Example 3

[0112] Prepare the decarbonization solvent according to Table 3-1, and inject it into the flue gas CO2 absorption system to treat the flue gas in Table 3-2. Apply the CO2 absorption and desorption conditions according to Table 3-3. Figure 1 The decarbonization solvent comprehensive evaluation device shown is used for evaluation. When 2 # The online CO2 gas detector 19 shows that the CO2 volume fraction in the gas phase is stable at 2.2 v%, indicating that the system has reached equilibrium. # The online CO2 gas detector 21 showed that the CO2 content in the desorbed gas 17 was above 90%; samples were taken every 20 minutes from the rich liquid sampling port 9 and the lean liquid sampling port 18, using... Figure 2 The CO2 loading of the decarbonization solvent CO2 loading device was used to analyze the CO2 loading in the rich and poor decarbonization solvent solutions in Example 1, which were 3.76 mol CO2 / L and 0.25 mol CO2 / L, respectively. The power W1 of the rich solution heater was recorded as 0.51 W, and the power W2 of the regeneration tower heater was recorded as 3.70 W.

[0113] Table 3-1 3 # Decarbonization solvent composition

[0114]

[0115] Table 3-2 Flue Gas Composition

[0116] project Content (mol%) <![CDATA[CO2]]> 10 <![CDATA[O2]]> 11 N2 79

[0117] Table 3-3 3 # CO2 absorption and desorption conditions of decarbonization solvent

[0118] project numerical values Decarbonization solvent flow rate (ml / min) 0.9 Decarbonization solvent residence time (min) 20 flue gas flow rate (ml / min) 894 Flue gas residence time s 10 <![CDATA[Liquid-gas ratio L / Nm 3 > 1 <![CDATA[CO2 absorption reaction temperature °C]]> 20 <![CDATA[CO2 absorption reaction pressure kPa]]> 10 Decarbonization solvent regeneration reaction temperature (°C) 110

[0119] The energy consumption calculation formula for decarbonization solvent regeneration, the regeneration degree calculation formula for decarbonization solvent, and the CO2 removal efficiency calculation formula of the present invention are used to calculate the 3 in Example 3 respectively. # The energy consumption, regeneration rate, and CO2 removal efficiency of the decarbonization solvent are shown in Table 3-4.

[0120] Table 3-4 3 # Performance indicators of decarbonization solvents

[0121]

[0122]

[0123] Example 4

[0124] Prepare the decarbonization solvent according to Table 4-1, and inject it into the flue gas CO2 absorption system to treat the flue gas in Table 4-2. Apply the CO2 absorption and desorption conditions according to Table 4-3. Figure 1 The decarbonization solvent comprehensive evaluation device shown is used for evaluation. When 2 # The online CO2 gas detector 19 shows that the CO2 volume fraction in the gas phase is stable at 3.4 v%, indicating that the system has reached equilibrium. # The online CO2 gas detector 21 showed that the CO2 content in the desorbed gas 17 was above 90%; samples were taken every 20 minutes from the rich liquid sampling port 9 and the lean liquid sampling port 18, using... Figure 2 The CO2 loading of the decarbonization solvent CO2 loading device was analyzed in Example 1. The CO2 loading in the rich decarbonization solvent solution and the poor decarbonization solvent solution were 1.64 mol CO2 / L and 0.12 mol CO2 / L, respectively. The power W1 of the rich solution heater was recorded as 2.02 W and the power W2 of the regeneration tower heater was recorded as 6.91 W.

[0125] Table 4-1 4 # Decarbonization solvent composition

[0126]

[0127] Table 4-2 Flue Gas Composition

[0128] project Content (mol%) <![CDATA[CO2]]> 20 <![CDATA[O2]]> 1 <![CDATA[N2]]> 79

[0129] Table 4-3 4 # CO2 absorption and desorption conditions of decarbonization solvent

[0130] project numerical values Decarbonization solvent flow rate (ml / min) 3.6 Decarbonization solvent residence time (min) 5 flue gas flow rate (ml / min) 715 Flue gas residence time s 16 <![CDATA[Liquid-gas ratio L / Nm 3 > 5 <![CDATA[CO2 absorption reaction temperature °C]]> 30 <![CDATA[CO2 absorption reaction pressure kPa]]> 30 Decarbonization solvent regeneration reaction temperature (°C) 110

[0131] The energy consumption calculation formula for decarbonization solvent regeneration, the regeneration degree calculation formula for decarbonization solvent, and the CO2 removal efficiency calculation formula of the present invention are used to calculate the 4 in Example 4 respectively.# The energy consumption, regeneration rate, and CO2 removal efficiency of the decarbonization solvent are shown in Table 4-4.

[0132] Table 4-4 4 # Performance indicators of decarbonization solvents

[0133]

[0134]

[0135] Example 5

[0136] Prepare the decarbonization solvent according to Table 5-1, and inject it into the flue gas CO2 absorption system to treat the flue gas in Table 5-2. Apply the CO2 absorption and desorption conditions according to Table 5-3. Figure 1 The decarbonization solvent comprehensive evaluation device shown is used for evaluation. When 2 # The online CO2 gas detector 19 showed that the CO2 volume fraction in the gas phase was stable at 1.41 v%, indicating that the system had reached equilibrium. # The online CO2 gas detector 21 showed that the CO2 content in the desorbed gas 17 was above 95%; samples were taken every 20 minutes from the rich liquid sampling port 9 and the lean liquid sampling port 18, using... Figure 2 The CO2 loading of the decarbonization solvent CO2 loading device was analyzed in Example 1. The CO2 loading in the rich decarbonization solvent solution and the poor decarbonization solvent solution were 2.37 mol CO2 / L and 0.07 mol CO2 / L, respectively. The power W1 of the rich solution heater was recorded as 0.52 W and the power W2 of the regeneration tower heater was recorded as 2.35 W.

[0137] Table 5-1 5 # Decarbonization solvent composition

[0138]

[0139]

[0140] Table 5-2 Flue Gas Composition

[0141] project Content (mol%) <![CDATA[CO2]]> 15 <![CDATA[O2]]> 6 <![CDATA[N2]]> 79

[0142] Table 5-3 5 # CO2 absorption and desorption conditions of decarbonization solvent

[0143] project numerical values Decarbonization solvent flow rate (ml / min) 0.9 Decarbonization solvent residence time (min) 20 flue gas flow rate (ml / min) 373 Flue gas residence time s 35 <![CDATA[Liquid-gas ratio L / Nm 3 > 3 <![CDATA[CO2 absorption reaction temperature °C]]> 50 <![CDATA[CO2 absorption reaction pressure kPa]]> 0 Decarbonization solvent regeneration reaction temperature (°C) 100

[0144] According to the energy consumption calculation formula for decarbonization solvent regeneration, the degree of regeneration calculation formula for decarbonization solvent, and the CO2 removal efficiency calculation formula of the present invention, the 5 in Example 5 are calculated respectively. # The regeneration energy consumption, regeneration degree, and CO2 removal efficiency of the decarbonization solvent are shown in Table 5-4.

[0145] Table 5-4 5 # Performance indicators of decarbonization solvents

[0146]

[0147] Example 6

[0148] Prepare the decarbonization solvent according to Table 6-1, and inject it into the flue gas CO2 absorption system to treat the flue gas in Table 6-2. Apply the CO2 absorption and desorption conditions according to Table 6-3. Figure 1 The decarbonization solvent comprehensive evaluation device shown is used for evaluation. When 2 # The online CO2 gas detector 19 showed that the CO2 volume fraction in the gas phase was stable at 1.84 v%, indicating that the system had reached equilibrium. # The online CO2 gas detector 21 showed that the CO2 content in the desorbed gas 17 was above 95%; samples were taken every 20 minutes from the rich liquid sampling port 9 and the lean liquid sampling port 18, using... Figure 2 The CO2 loading of the decarbonization solvent CO2 loading device was analyzed in Example 1. The CO2 loading in the rich decarbonization solvent solution and the poor decarbonization solvent solution were 0.93 mol CO2 / L and 0.03 mol CO2 / L, respectively. The power W1 of the rich solution heater was recorded as 0.56 W and the power W2 of the regeneration tower heater was recorded as 0.95 W.

[0149] Table 6-1 6 # Decarbonization solvent composition

[0150]

[0151]

[0152] Table 6-2 Flue Gas Composition

[0153] project Content (mol%) <![CDATA[CO2]]> 10 <![CDATA[O2]]> 11 N2 79

[0154] Table 6-3 6 # CO2 absorption and desorption conditions of decarbonization solvent

[0155] project numerical values Decarbonization solvent flow rate (ml / min) 1.0 Decarbonization solvent residence time (min) 18 flue gas flow rate (ml / min) 242 Flue gas residence time s 49 <![CDATA[Liquid-gas ratio L / Nm 3 > 4.1 <![CDATA[CO2 absorption reaction temperature °C]]> 30 <![CDATA[CO2 absorption reaction pressure kPa]]> 10 Decarbonization solvent regeneration reaction temperature (°C) 100

[0156] The energy consumption calculation formula for decarbonization solvent regeneration, the regeneration degree calculation formula for decarbonization solvent, and the CO2 removal efficiency calculation formula of the present invention are used to calculate the 6 in Example 6 respectively. # The regeneration energy consumption, regeneration degree, and CO2 removal efficiency of the decarbonization solvent are shown in Table 6-4.

[0157] Table 6-4 6 # Performance indicators of decarbonization solvents

[0158] project numerical values <![CDATA[Energy consumption for decarbonized solvent regeneration, GJ / tCO2]]> 2.29 Regeneration rate % of decarbonization solvent 96.7 <![CDATA[CO2 removal efficiency %]]> 83.1 Decarbonization solvent regeneration temperature (°C) 100 <![CDATA[CO2 loading of decarbonization solvent, mol CO2 / L]]> 0.93

[0159] As can be seen from the above evaluation results, the 1 provided by the present invention # ~6 # The decarbonization solvent has advantages such as large CO2 absorption capacity and low regeneration energy consumption. The regeneration energy consumption index of the decarbonization solvent can be as low as 1.82 GJ / tCO2, which is 48.3% more energy-efficient than traditional decarbonization solvents. The decarbonization solvent has a strong desorption capacity for CO2 in flue gas.

[0160] Example 7

[0161] With 3 # Taking decarbonization solvent as an example, the CO2 loading of the decarbonization solvent under different absorption pressure conditions was investigated. The CO2 absorption and desorption conditions in Table 3-3 were applied... Figure 1 The decarbonization solvent comprehensive evaluation device shown treats the flue gas in Table 3-2. Adjust the CO2 gas source control valve (6) and gas flow meter (8) to control the pressure of the CO2 absorption tower (1) sequentially to 0 kPa, 10 kPa, 20 kPa, 50 kPa, 60 kPa, 80 kPa, and 100 kPa. After the system reaches equilibrium, utilize... Figure 2 The CO2 loading of the decarbonization solvent-rich solution was analyzed using a decarbonization solvent CO2 loading measuring device, and the results were 3.48 mol CO2 / L, 3.76 mol CO2 / L, 3.95 mol CO2 / L, 4.07 mol CO2 / L, 4.14 mol CO2 / L, 4.20 mol CO2 / L, and 4.25 mol CO2 / L, respectively. # The curve showing the change in CO2 loading of the decarbonization solvent with absorption pressure is shown below. Figure 3 .

[0162] according to Figure 3 The decarbonization solvent in this invention maintains a high CO2 loading in the CO2 absorption reaction pressure range of 10 kPa to 100 kPa (gauge pressure).

[0163] Example 8

[0164] With 3 # Taking decarbonization solvents as an example, we examine 3 # The CO2 loading of the decarbonization solvent varies with operating time. The CO2 absorption and desorption conditions are as shown in Table 3-3. Figure 1 The decarbonization solvent comprehensive evaluation device shown treats the flue gas in Table 3-2. After the system reaches equilibrium, it utilizes... Figure 2 The CO2 loading of the decarbonization solvent CO2 loading assay device was used to analyze the CO2 loading of the decarbonization solvent-rich solution. (See...) Figure 4 .

[0165] according to Figure 4The decarbonization solvent in this invention maintains a high CO2 loading even after long-term operation.

[0166] Comparative Example 1

[0167] Comparative Example 1 replicates the process of Example 1, except that in the decarbonization solvent, 30.0 wt% of the CO2 absorbent was replaced with 30.0 wt% of N-methyldiethanolamine CO2 absorbent (i.e., N-methyldiethanolamine CO2 absorbent was 35 wt%, and the CO2 absorbent was 0 wt%). All other conditions remained unchanged. Figure 2 The CO2 loading of the decarbonization solvent was analyzed using a CO2 loading measuring device in Comparative Example 1. The CO2 loading in the rich and poor decarbonization solvent solutions was 1.18 mol CO2 / L and 0.09 mol CO2 / L, respectively. The power W1 of the rich solution heater was recorded as 0.51 W, and the power W2 of the regeneration tower heater was recorded as 1.34 W.

[0168] Table 1d-1 Performance indicators of decarbonization solvent in Comparative Example 1

[0169] project numerical values <![CDATA[Energy consumption for decarbonized solvent regeneration, GJ / tCO2]]> 2.57 Regeneration rate of decarbonization solvent (%) 92.5 <![CDATA[CO2 removal efficiency %]]> 43.7 Decarbonization solvent regeneration temperature (°C) 110 <![CDATA[CO2 loading of decarbonization solvent, mol CO2 / L]]> 1.18

[0170] It can be seen that the energy consumption for decarbonization solvent regeneration in Example 1 is significantly lower than that in Comparative Example 1, and the CO2 removal efficiency and CO2 loading of the decarbonization solvent in Example 1 are significantly higher than those in Comparative Example 1.

[0171] Comparative Example 2

[0172] Comparative Example 1 replicates the process of Example 2, except that in the decarbonization solvent, 10.0 wt% of the triethanol CO2 absorption aid is replaced with the CO2 absorption main agent from Example 2 (i.e., 0 wt% triethanol CO2 absorption aid and 20 wt% CO2 absorption main agent), while other conditions remain unchanged. Figure 2 The CO2 loading of the decarbonization solvent was analyzed using a CO2 loading measuring device in Comparative Example 1. The CO2 loading in the rich and poor decarbonization solvent solutions was 0.53 mol CO2 / L and 0.09 mol CO2 / L, respectively. The power W1 of the rich solution heater was recorded as 3.03 W, and the power W2 of the regeneration tower heater was recorded as 0.82 W.

[0173] Table 2d-1 Performance indicators of decarbonization solvents in Comparative Example 2

[0174] project numerical values <![CDATA[Energy consumption of decarbonized solvent regeneration, GJ / tCO2]]> 2.66 Regeneration rate of decarbonization solvent (%) 62.2 <![CDATA[CO2 removal efficiency %]]> 74.2 Decarbonization solvent regeneration temperature (°C) 90 <![CDATA[CO2 loading of the decarbonization solvent, mol CO2 / L]]> 0.53

[0175] It can be seen that the energy consumption for decarbonization solvent regeneration in Example 2 is significantly lower than that in Comparative Example 2, and the regeneration degree, CO2 removal efficiency, and CO2 loading of the decarbonization solvent in Example 2 are all significantly higher than those in Comparative Example 2.

[0176] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

Claims

1. An organic amine composition for capturing CO2 from flue gas, comprising 2,4,6-trisubstituted-1,3,5-triazine and tertiary alcoholamine, wherein the substituents are selected from alcohol groups and / or hydroxyl groups.

2. The organic amine composition according to claim 1, characterized in that, The 2,4,6-trisubstituted-1,3,5-triazine is selected from at least one of the compounds shown in formula (1): In formula (1), R1, R2, and R3 are each independently selected from hydroxyl, monohydric alcohol, or dihydric alcohol groups, wherein R1, R2, and R3 may be the same or different. Preferably, in formula (1), R1, R2, and R3 are each independently selected from hydroxyl groups, C1-C10 monohydric alcohol groups, or C2-C10 dihydric alcohol groups, and more preferably from hydroxyl groups, C1-C5 monohydric alcohol groups, or C2-C5 dihydric alcohol groups.

3. The organic amine composition according to claim 1, characterized in that, The tertiary alcohol amine contains a tertiary amine group and at least one hydroxyl group, and preferably, the tertiary alcohol amine is selected from at least one of the compounds shown in formula (2) and formula (3): In formula (2), at least one of R4, R5, and R6 is selected from an alcohol group, and the other two are each independently selected from an alkyl group; in formula (3), R6, R7, R8, and R9 are each independently selected from an alkyl group. Preferably, in formula (2), at least one of R4, R5, and R6 is selected from C1 to C10 alcohol groups, and the other two are each independently selected from C1 to C10 alkyl groups; in formula (3), R6, R7, R8, and R9 are each independently selected from C1 to C10 alkyl groups. More preferably, the tertiary alcohol amine is selected from one or more of N-methyldiethanolamine, N,N-dimethylethanolamine, triethanolamine, triisopropanolamine, 1,3-di(dimethylamino)-2-propanol, 1,3-di(diethylamino)-2-propanol, and 1,3-di(ethylmethylamino)-2-propanol.

4. The organic amine composition according to any one of claims 1 to 3, characterized in that, Based on 100 wt% of the organic amine composition, the 2,4,6-trisubstituted-1,3,5-triazine accounts for 40-95 wt%, preferably 50-90 wt%, and the tertiary alcohol amine accounts for 5-60 wt%, preferably 10-50 wt%.

5. The use of the organic amine composition according to any one of claims 1 to 4 in decarbonization solvents, particularly in decarbonization solvents for capturing CO2 in flue gas.

6. A decarbonization solvent comprising a CO2 absorbent and a solvent, wherein the CO2 absorbent is selected from the organic amine compositions according to any one of claims 1 to 4; preferably, the solvent is water.

7. The decarbonization solvent according to claim 6, characterized in that, Based on 100wt% of CO2 absorbent and solvent, the content of CO2 absorbent is 5-75wt%, and the content of solvent is 25-95wt%; preferably, the content of CO2 absorbent is 10-60wt%, and the content of solvent is 40-90wt%.

8. The decarbonization solvent according to claim 6, characterized in that, The decarbonization solvent optionally contains an additive, the content of which is 200-2000 mg / L, preferably 600-1300 mg / L; Preferably, the additive includes at least one of an antifoaming agent, a corrosion inhibitor, and an antioxidant; preferably, the antifoaming agent is selected from at least one of polydimethylsiloxane, polyethylene glycol, and polyether sulfate, and / or, the corrosion inhibitor is selected from at least one of sodium hydroxyethylidene diphosphate, undecylhydroxyethyl imidazoline, and hexadecyl dimethyl tertiary amine, and / or, the antioxidant is selected from at least one of 2,6-di-tert-butylphenol, hydroquinone, or diethylhydroxylamine; More preferably, in the decarbonization solvent, the content of the defoamer is 50 mg / L to 800 mg / L, and / or the content of the corrosion inhibitor is 5 mg / L to 80 mg / L, and / or the content of the antioxidant is 200 mg / L to 1000 mg / L.

9. A decarbonization method for capturing CO2 in flue gas, comprising: The flue gas contacts the decarbonization solvent according to any one of claims 6 to 8 to absorb the CO2 therein.

10. The decarbonization method according to claim 9, characterized in that, The absorption is carried out at 15°C to 60°C, preferably 20°C to 50°C; and / or, The absorption is carried out at 0–100 kPa (gauge pressure); and / or, The residence time of the decarbonization solvent is 1 min to 30 min, preferably 3 min to 20 min; and / or, The residence time of the flue gas in the gas phase is 5s to 70s, preferably 10s to 50s; and / or, The liquid-to-gas ratio is 1L to 10L of decarbonization solvent / Nm³ 3 Smoke; and / or, The absorption is performed by the flue gas coming into counter-current contact with the decarbonization solvent. Preferably, the flue gas and the decarbonization solvent come into counter-current contact within the absorption tower. More preferably, the flue gas comes into counter-current contact with the decarbonization solvent, which flows from bottom to top; and / or, After the contact, the decarbonization solvent is regenerated. Preferably, the regeneration temperature is 80-130°C, more preferably 90-110°C, and even more preferably, the regenerated decarbonization solvent is recycled.

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