WO2025213795A1 - 一种二氧化碳捕集吸收剂及捕集吸收方法 - Google Patents

一种二氧化碳捕集吸收剂及捕集吸收方法

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Publication number
WO2025213795A1
WO2025213795A1 PCT/CN2024/136212 CN2024136212W WO2025213795A1 WO 2025213795 A1 WO2025213795 A1 WO 2025213795A1 CN 2024136212 W CN2024136212 W CN 2024136212W WO 2025213795 A1 WO2025213795 A1 WO 2025213795A1
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WIPO (PCT)
Prior art keywords
carbon dioxide
absorbent
dioxide capture
amine
capture absorbent
Prior art date
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Pending
Application number
PCT/CN2024/136212
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English (en)
French (fr)
Inventor
赵兴雷
叶舣
雍瑞生
郑家乐
李兴春
陈宏坤
吴百春
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China National Petroleum Corp
CNPC Research Institute of Safety and Environmental Technology Co Ltd
Original Assignee
China National Petroleum Corp
CNPC Research Institute of Safety and Environmental Technology Co Ltd
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Application filed by China National Petroleum Corp, CNPC Research Institute of Safety and Environmental Technology Co Ltd filed Critical China National Petroleum Corp
Publication of WO2025213795A1 publication Critical patent/WO2025213795A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1418—Recovery of products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20478—Alkanolamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives
    • B01D2252/602—Activators, promoting agents, catalytic agents or enzymes

Definitions

  • the present invention relates to a carbon dioxide capture absorbent, in particular to a carbon dioxide capture absorbent and a capture and absorption method, belonging to the field of carbon dioxide recovery.
  • CO2 capture, utilization and storage technology refers to the industrial process of separating carbon dioxide from the emission source and directly utilizing or storing it to achieve carbon dioxide emission reduction, including dry and wet methods, among which the wet method includes chemical absorption and physical absorption.
  • Chemical absorption is a process in which an emission source including carbon dioxide is brought into contact with an absorbent to undergo a chemical reaction, causing the carbon dioxide to be absorbed into a solution. The carbon dioxide is then desorbed by heating, and the absorbent is regenerated and recycled.
  • commonly used absorbents generally contain 60-70% water. This water will undergo a large amount of vaporization during the absorbent regeneration process, resulting in high regeneration energy consumption.
  • Existing research has shown that increasing the absorbent concentration can reduce the water content, thereby reducing the evaporation of water and the regeneration energy consumption.
  • this water-poor absorbent with a high absorbent concentration still has the following problems: (1) the regeneration effect of the absorbent becomes worse after increasing the absorbent concentration; (2) the water evaporation is still large, resulting in excessively high regeneration energy consumption.
  • the present invention provides a carbon dioxide capture absorbent having high carbon dioxide absorption and processing capacity, good regeneration effect and low regeneration energy consumption.
  • the present invention also provides a carbon dioxide capture and absorption method, which utilizes the above-mentioned carbon dioxide capture absorbent to capture and absorb carbon dioxide, has a large processing capacity, and the above-mentioned carbon dioxide capture absorbent has a good regeneration effect and low regeneration energy consumption, and has the advantages of being environmentally friendly and resource-saving.
  • a first aspect of the present invention provides a carbon dioxide capture absorbent, wherein the carbon dioxide capture absorbent comprises, by weight percentage, 40%-70% of a main absorbent, 1%-20% of a accelerator, 0.05%-1% of a corrosion inhibitor, and 0.1%-1% of an antioxidant; the balance being water;
  • the main absorbent comprises 0%-40% of aliphatic amine and 60%-100% of alcohol amine in terms of mass percentage, wherein the aliphatic amine comprises at least one of primary amine, secondary amine, tertiary amine and polyamine, and the alcohol amine comprises at least one of monohydroxy, dihydroxy and trihydroxy;
  • the salt includes at least one of a quaternary ammonium salt, an amino acid salt, and a citrate
  • the hindered amine includes at least one of 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and tert-butylaminoethoxyethanol
  • the sulfur-containing organic compound includes at least one of dimethyl sulfone, sulfolane, and dimethyl sulfoxide
  • the mass ratio of the salt, the hindered amine, and the sulfur-containing organic compound is (0-2):(0-4):(0-6);
  • the viscosity of the carbon dioxide capture absorbent is ⁇ 20cp.
  • the number of nitrogen atoms in the alcoholamine is ⁇ 3, and the number of carbon atoms is ⁇ 6.
  • the corrosion inhibitor comprises sodium metavanadate, and the mass percentage of the sodium metavanadate in the carbon dioxide capture absorbent is 0.05%-0.2%.
  • the antioxidant comprises potassium sodium tartrate, and the mass percentage of the potassium sodium tartrate in the carbon dioxide capture absorbent is 0.1%-0.3%.
  • a second aspect of the present invention provides a method for capturing and absorbing carbon dioxide, comprising the following steps:
  • the flow ratio of the carbon dioxide capture absorbent and the gas source including the carbon dioxide is 1.5-4:1;
  • the volume fraction of the carbon dioxide in the gas source comprising carbon dioxide is 5%-30%.
  • heating comprises preheating the carbon dioxide-enriched liquid using the hot solution obtained in step 2).
  • the carbon dioxide capture absorbent of the present invention has a high main absorbent content of 40% to 70% by mass, and includes a promoter, a corrosion inhibitor, and an antioxidant, so that the water content is lower than that of conventional carbon dioxide absorbents.
  • This is a water-poor absorbent with a high main absorbent concentration, which not only helps to increase the carbon dioxide absorption capacity of the carbon dioxide capture absorbent, but also helps to reduce the amount of water evaporation during the carbon dioxide desorption process, thereby helping to reduce regeneration energy consumption.
  • the present invention defines the formula of the main absorbent and promoter in the carbon dioxide capture absorbent and the viscosity of the carbon dioxide capture absorbent, which helps to improve the mass transfer performance of carbon dioxide in the aforementioned water-poor absorbent, thereby improving the ability of the carbon dioxide capture absorbent to capture and absorb carbon dioxide. More importantly, through the synergistic combination of the main absorbent, promoter, corrosion inhibitor, and antioxidant, the regeneration effect of the carbon dioxide capture absorbent is improved and the regeneration energy consumption is reduced, thereby helping to reduce the cost of carbon dioxide capture and absorption.
  • a first aspect of the present invention provides a carbon dioxide capture absorbent, which comprises, by weight percentage, 40%-70% of a main absorbent, 1%-20% of a accelerator, 0.05%-1% of a corrosion inhibitor, and 0.1%-1% of an antioxidant; the balance being water;
  • the main absorbent comprises 0%-40% of aliphatic amine and 60%-100% of alcohol amine in terms of mass percentage, wherein the aliphatic amine comprises at least one of primary amine, secondary amine, tertiary amine and polyamine, and the alcohol amine comprises at least one of monohydroxy, dihydroxy and trihydroxy;
  • the viscosity of the carbon dioxide capture absorbent is ⁇ 20cp.
  • the carbon dioxide capture absorbent of the present invention captures and absorbs carbon dioxide by chemically reacting with carbon dioxide, and then desorbs the carbon dioxide by heating.
  • the carbon dioxide capture absorbent can be regenerated and recycled.
  • the carbon dioxide capture absorbent's ability to absorb carbon dioxide, its regeneration effect, and its regeneration energy consumption are the three most critical properties that affect its application prospects.
  • the carbon dioxide capture absorbent's ability to absorb carbon dioxide is expressed by the carbon dioxide removal rate, which is calculated as follows: (the concentration of carbon dioxide in the gas source at the absorption tower inlet - the concentration of carbon dioxide in the gas source at the absorption tower outlet) / the concentration of carbon dioxide in the gas source at the absorption tower inlet);
  • the regeneration effect of the carbon dioxide capture absorbent is expressed by the regeneration rate, which is calculated as follows: the amount of carbon dioxide desorbed from the carbon dioxide-enriched liquid / the amount of carbon dioxide in the carbon dioxide-enriched liquid before desorption;
  • the regeneration energy consumption refers to the heat energy consumed by the carbon dioxide capture absorbent during the process of desorbing carbon dioxide after absorbing carbon dioxide, and is calculated using the enthalpy value of the steam consumed per unit carbon dioxide capture amount.
  • the primary absorbent plays the role of absorbing carbon dioxide. Its mass percentage is 40%-70%. This high content is beneficial for increasing the carbon dioxide absorption capacity and improving the carbon dioxide absorption capacity. It also reduces the water content in the capture absorbent, thereby reducing the amount of water evaporation during the carbon dioxide desorption process, which helps reduce regeneration energy consumption.
  • the following uses fatty amine as an example to illustrate the reaction between the primary absorbent and CO2 :
  • Formula 1 represents the reaction of primary amines and secondary amines with CO 2
  • Formula 2 represents the reaction of tertiary amines and hindered amines with CO 2.
  • the reaction of alcoholamines with CO 2 is similar to the above reaction.
  • the present invention also solves the problem of difficult carbon dioxide mass transfer in water-lean absorbents with high main absorbent concentrations by optimizing the formula of the main absorbent and the promoter and limiting the viscosity of the capture absorbent.
  • the absorbent viscosity is ⁇ 20cp, which is coordinated with a higher concentration of the main absorbent and a specifically formulated promoter, thereby ensuring that the above-mentioned carbon dioxide capture absorbent has a higher ability to absorb carbon dioxide.
  • the promoter of the present invention comprises salts, hindered amines and sulfur-containing organic matter, wherein the salts comprise at least one of quaternary ammonium salts, amino acid salts and citrates, the hindered amines comprise at least one of 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol and tert-butylaminoethoxyethanol, and the sulfur-containing organic matter comprises at least one of dimethyl sulfone, sulfolane and dimethyl sulfoxide, and the mass ratio of the salts, the hindered amines and the sulfur-containing organic matter is (0-2):(0-4):(0-6).
  • the promoter of the present invention can, more importantly, reduce the pH value and hydrogen bond strength of the solution on the basis of limiting the viscosity of the absorbent, thereby improving the regeneration effect of the carbon dioxide capture absorbent of the present invention, avoiding the problem of poor regeneration effect of a water-lean absorbent with a relatively high concentration of a main absorbent, facilitating the recycling of the carbon dioxide capture absorbent, further reducing the regeneration energy consumption during carbon dioxide desorption, and having the advantages of cost savings and environmental friendliness.
  • the role of the corrosion inhibitor is to slow down the rate of corrosion of the equipment by the carbon dioxide capture absorbent and extend the service life of the equipment.
  • the present invention does not specifically limit the type of the above-mentioned corrosion inhibitor, and the corrosion inhibitor commonly used in the field can be used, such as oxidizing corrosion inhibitors and/or surface adsorption corrosion inhibitors.
  • the above-mentioned oxidizing corrosion inhibitor forms an oxidizing protective film by oxidizing the equipment, thereby slowing down the corrosion rate of the equipment.
  • the oxidizing corrosion inhibitor may include at least one of sodium molybdate, sodium metavanadate, sodium thiosulfate, zinc acetate, copper carbonate, sodium tungstate, sodium tetraborate, sodium vanadate and manganate; the above-mentioned surface adsorption corrosion inhibitor forms a protective film by adsorbing to the surface of the equipment to achieve the purpose of protecting the equipment.
  • the surface adsorption corrosion inhibitor may include a straight-chain alkane containing an amino group and a carbon atom number of 1-20.
  • Antioxidants can slow the oxidative degradation of carbon dioxide capture absorbents.
  • the present invention combines a specific primary absorbent, a accelerator, and an antioxidant at specific concentrations, maximizing the carbon dioxide absorption and regeneration capabilities of the carbon dioxide capture absorbent while minimizing regeneration energy consumption.
  • the present invention also does not specifically limit the type of antioxidant; antioxidants commonly used in the art may be used, such as at least one of acetaldehyde oxime, acetone oxime, hydroxyethylidene diphosphonic acid, ethylenediaminetetraacetic acid, ascorbic acid, sodium sulfite, potassium sulfite, ammonium sulfite, ammonium nitrite, and potassium sodium tartrate.
  • the carbon dioxide capture absorbent of the present invention has high carbon dioxide absorption capacity, good regeneration effect, low regeneration energy consumption, the advantages of cost saving and good environment, and has broad application prospects.
  • the number of nitrogen atoms in the above-mentioned fatty amine is ⁇ 3, and the number of carbon atoms is ⁇ 6, which is beneficial to increasing the absorption capacity of the carbon dioxide capture absorbent for carbon dioxide, and is also beneficial to reducing the viscosity of the carbon dioxide capture absorbent, improving the mass transfer effect of carbon dioxide, and thereby increasing the absorption capacity of the carbon dioxide capture absorbent for carbon dioxide, and is also beneficial to improving the regeneration effect of the carbon dioxide capture absorbent and reducing the regeneration energy consumption.
  • the number of nitrogen atoms in the above-mentioned alcohol amine is ⁇ 3, and the number of carbon atoms is ⁇ 6, which is beneficial to improving the absorption capacity of the carbon dioxide capture absorbent for carbon dioxide, increasing the water solubility of the absorbent, reducing volatility, and also beneficial to reducing the viscosity of the carbon dioxide capture absorbent, improving the mass transfer effect of carbon dioxide, thereby improving the absorption capacity of the carbon dioxide capture absorbent for carbon dioxide and reducing regeneration energy consumption.
  • the quaternary ammonium salt in the above-mentioned accelerator includes triethylammonium benzoate or methylbenzyl quaternary ammonium benzoate
  • the amino acid salt includes at least one of ⁇ -aminoacetate, 2-aminopropionate, 3-aminopropionate, 2-amino-3-methylbutyrate, ⁇ -aminoisocaproate, ⁇ -amino- ⁇ -methylvalerate, 2-aminophenylpropionate, ⁇ -imino acid salt, ⁇ -indolylalanine, L-2-amino-3-hydroxypropionate, 2-amino-3-p-hydroxyphenylpropionate, L-2-amino-3-mercaptopropionate, glutamate, methylthiobutyrate, ⁇ -hydroxy- ⁇ -aminobutyrate, aspartate, ⁇ -aminoglutarate, 2,6-diaminohexanoate, 2-amino-5-
  • the salts include amino acid salts
  • the hindered amines include 2-amino-2-methyl-1-propanol
  • the sulfur-containing organic matter includes dimethyl sulfone
  • the mass ratio of the salts, hindered amines and sulfur-containing organic matter is 1:2:3
  • the promoter composed of the above salts, hindered amines and sulfur-containing organic matter can better enhance the regeneration effect of the carbon dioxide capture absorbent and greatly reduce the regeneration energy consumption.
  • the present invention further limits the boiling point of the hindered amine in the above-mentioned promoter to be greater than 160°C. This is beneficial to preventing the hindered ammonium from volatilizing due to heat, improving the stability of the carbon dioxide capture absorbent during the desorption process, improving the regeneration effect of the carbon dioxide capture absorbent, and also helping to reduce regeneration energy consumption and save costs.
  • the inventors have found through extensive research that when the corrosion inhibitor includes sodium metavanadate, and the mass percentage of sodium metavanadate in the carbon dioxide capture absorbent is 0.05%-0.2%, preferably 0.1%, it helps to further reduce the corrosion rate of the equipment.
  • the antioxidant includes potassium sodium tartrate
  • the mass percentage of potassium sodium tartrate in the above-mentioned carbon dioxide capture absorbent is 0.1%-0.3%, preferably 0.2%
  • the oxidative degradation rate of the carbon dioxide capture absorbent can be more significantly reduced, and the antioxidant can cooperate with the main absorbent, promoter, etc. to achieve a better regeneration effect of the carbon dioxide capture absorbent.
  • the carbon dioxide capture absorbent has a carbon dioxide removal rate of 60%-90%, a regeneration rate of 50%-85%, and a regeneration energy consumption of 2.2-3.2 GJ/t. This indicates that the carbon dioxide capture absorbent of the present invention has a high carbon dioxide absorption capacity, good regeneration efficiency, and low regeneration energy consumption.
  • a second aspect of the present invention provides a method for capturing and absorbing carbon dioxide, comprising the following steps:
  • the flow ratio of the carbon dioxide capture absorbent and the gas source including carbon dioxide is (1.5-4):1;
  • the carbon dioxide-enriched liquid is subjected to a heating treatment to desorb carbon dioxide from the carbon dioxide-enriched liquid, thereby obtaining a hot solution and carbon dioxide.
  • the above-mentioned carbon dioxide capture and absorption method is a method for capturing and absorbing carbon dioxide using the carbon dioxide capture absorbent of the present invention.
  • the gas source including carbon dioxide is brought into contact with a carbon dioxide capture absorbent, so that the carbon dioxide undergoes mass transfer and diffusion in the carbon dioxide capture absorbent, undergoes a chemical reaction with the carbon dioxide capture absorbent, and is then captured and absorbed by the carbon dioxide capture absorbent, thereby obtaining a carbon dioxide-enriched liquid.
  • the above-mentioned gas source should be fully contacted with the carbon dioxide capture absorbent.
  • the present invention does not limit the specific contact method.
  • the gas source can be introduced into the bottom of the absorption tower, and the carbon dioxide capture absorbent can be introduced into the top of the absorption tower, so that the two can be in countercurrent contact in the absorption tower.
  • This countercurrent contact method has the advantages of large contact area and sufficient reaction, so that the carbon dioxide can be fully absorbed by the capture absorbent.
  • the present invention does not limit the flow rate of the above-mentioned gas source and carbon dioxide capture absorbent into the absorption tower, as long as the gas source and carbon dioxide capture absorbent are fully in contact. It can be adjusted based on the carbon dioxide absorption capacity of the carbon dioxide capture absorbent and the carbon dioxide content in the gas source.
  • the carbon dioxide capture absorbent when the flow rate ratio of the carbon dioxide capture absorbent and the gas source including carbon dioxide is (1.5-4):1 (L/h)/(Nm 3 /h), preferably (1.8-3.6):1 (L/h)/(Nm 3 /h), the carbon dioxide capture absorbent can completely capture and absorb the carbon dioxide, indicating that the carbon dioxide capture absorbent of the present invention has a high carbon dioxide absorption capacity.
  • step 2) after the carbon dioxide-enriched liquid is heated to a certain degree, carbon dioxide can be desorbed therefrom, thereby obtaining a hot solution and carbon dioxide, which can be directly utilized or sealed, thereby achieving the capture, absorption and utilization of carbon dioxide.
  • the above-mentioned carbon dioxide desorption process can be carried out in a regeneration tower, which is provided with a heating device and a gas collection device, which is conducive to the desorption and collection of carbon dioxide.
  • the above-mentioned method of heating the carbon dioxide-enriched liquid can be heating with saturated steam, which is conducive to rapid heating of the carbon dioxide-enriched liquid and saving energy.
  • saturated steam for example, in some embodiments, steam with a pressure of 0.4 MPa is used for heating.
  • the carbon dioxide capture and absorption method provided by the present invention utilizes the above-mentioned carbon dioxide capture absorbent to efficiently capture and absorb carbon dioxide, has a large processing capacity, high processing efficiency, and is simple to operate, and is suitable for industrial promotion.
  • the above-mentioned carbon dioxide capture and absorption method can be used to capture and absorb carbon dioxide in flue gas emitted by power plants.
  • the carbon dioxide in the gas source can be effectively captured and absorbed by the capture and absorption method of the present invention.
  • step 2) the carbon dioxide-enriched liquid is heated, and carbon dioxide is desorbed therefrom, resulting in a hot solution and carbon dioxide.
  • the hot solution has a relatively high heat content.
  • the heating process includes preheating the carbon dioxide-enriched liquid using the hot solution obtained in step 2), i.e., using the hot solution as a heat source for the next carbon dioxide desorption step. Part of the heat in the hot solution is transferred to the carbon dioxide-enriched liquid to be desorbed for carbon dioxide desorption. This fully utilizes the heat in the hot solution, avoids energy waste, and further reduces regeneration energy consumption.
  • the above-mentioned preheating process can be carried out in a heat exchanger.
  • the carbon dioxide-enriched liquid can be introduced from the bottom of the regeneration tower and heated with saturated water vapor to produce a mixed gas of water vapor and carbon dioxide.
  • This mixed gas flows from bottom to top and countercurrently contacts the preheated carbon dioxide-enriched liquid introduced from the top of the regeneration tower, achieving mass and heat transfer.
  • desorbed carbon dioxide is obtained from the top of the regeneration tower, and a hot solution is obtained from the bottom of the regeneration tower.
  • This embodiment provides a carbon dioxide capture absorbent, which comprises, by weight percentage, 40% of a main absorbent, 10% of a promoter, 1% of sodium molybdate, and 0.5% of sodium sulfite; the balance being water;
  • the main absorbent includes 12.5% ethylenediamine and 87.5% diethanolamine according to mass percentage;
  • the accelerator includes salts, hindered amines and sulfur-containing organic matter, wherein the salt is sodium citrate, the hindered amine is 2-amino-2-methyl-1,3-propanediol (AMP), and the sulfur-containing organic matter is dimethyl sulfoxide, and the mass ratio of the above salts to the hindered amine is 1:2:3;
  • the viscosity of the carbon dioxide capture absorbent is ⁇ 20 cp.
  • This embodiment also provides a method for capturing and absorbing carbon dioxide, comprising the following steps:
  • Flue gas containing carbon dioxide is introduced into the bottom of an absorption tower at a rate of 830 Nm 3 /h, and countercurrently contacts the carbon dioxide capture absorbent introduced into the top of the absorption tower at a rate of 1500 L/h, so that the carbon dioxide is captured and absorbed by the carbon dioxide capture absorbent to obtain a carbon dioxide-enriched liquid;
  • the volume fraction of carbon dioxide in the flue gas is 12%, and the flow ratio of the carbon dioxide capture absorbent to the flue gas containing carbon dioxide is 1.8:1 (L/h/(Nm 3 /h));
  • the carbon dioxide-enriched liquid is introduced into the bottom of a regeneration tower at a rate of 1550 L/h and heated with saturated steam at a rate of 180 kg/h and a pressure of 0.4 MPa to produce a mixed gas of water vapor and carbon dioxide; carbon dioxide-enriched liquid preheated to 85-95° C. is introduced into the top of the regeneration tower at a rate of 150 L/h and countercurrently contacts the mixed gas. After sufficient reaction, a hot solution is obtained from the bottom of the regeneration tower, and carbon dioxide gas is obtained from the top of the regeneration tower;
  • the carbon dioxide enriched liquid is preheated by using the hot solution in the heat exchanger.
  • This embodiment is basically the same as embodiment 1, except that:
  • the mass percentage of the main absorbent in the carbon dioxide capture absorbent is 50%, and other conditions remain unchanged.
  • This embodiment is basically the same as embodiment 1, except that:
  • the mass percentage of the main absorbent in the carbon dioxide capture absorbent is 60%, and other conditions remain unchanged.
  • This embodiment is basically the same as embodiment 1, except that:
  • the mass percentage of the main absorbent in the carbon dioxide capture absorbent is 70%, and other conditions remain unchanged.
  • This embodiment is basically the same as embodiment 1, except that:
  • the mass percentage of the accelerator in the carbon dioxide capture absorbent is 20%, and the mass percentage of the sodium sulfite is 1%; other conditions remain unchanged.
  • This embodiment is basically the same as embodiment 1, except that:
  • the main absorbent comprises 12.5% of ethylenediamine and 87.5% of monoethanolamine in terms of mass percentage.
  • This embodiment is basically the same as embodiment 1, except that:
  • the main absorbent comprises 12.5% of diethylenetriamine and 87.5% of diethanolamine in terms of mass percentage.
  • This embodiment is basically the same as embodiment 1, except that:
  • the accelerators include salts, hindered amines and sulfur-containing organic matter, the salts are ⁇ -aminoacetate and 2-aminopropionate, the hindered amine is 2-amino-2-methyl-1-propanol, and the sulfur-containing organic matter is dimethyl sulfone.
  • the mass ratio of the above salts, hindered amines and sulfur-containing organic matter is 1:2:3; other conditions remain unchanged.
  • This embodiment is basically the same as embodiment 1, except that:
  • the hindered ammonium was replaced by 2-amino-2-methyl-1-propanol (AMPD) instead of 2-amino-2-methyl-1,3-propanediol (AMP); other conditions remained unchanged.
  • AMPD 2-amino-2-methyl-1-propanol
  • AMP 2-amino-2-methyl-1,3-propanediol
  • This embodiment is basically the same as embodiment 1, except that:
  • the accelerator includes salts, hindered amines and sulfur-containing organic matter, the salt is sodium 2-aminopropionate, the hindered amine is 2-amino-2-methyl-1-propanol, and the sulfur-containing organic matter is dimethyl sulfone.
  • the mass ratio of the above salts, hindered amines and sulfur-containing organic matter is 1:2:3; other conditions remain unchanged.
  • This embodiment is basically the same as embodiment 1, except that:
  • This embodiment is basically the same as embodiment 1, except that:
  • This embodiment is basically the same as embodiment 1, except that:
  • the volume fraction of carbon dioxide in the flue gas is 20%.
  • This embodiment is basically the same as embodiment 1, except that:
  • the main absorbent includes 12.5% aminooctane and 87.5% diethanolamine in terms of mass percentage; other conditions remain unchanged.
  • This embodiment is basically the same as embodiment 1, except that:
  • the main absorbent includes 12.5% ethylenediamine and 87.5% N-methylcyclohexylamine in terms of mass percentage; other conditions remain unchanged.
  • This comparative example is basically the same as Example 1, except that:
  • the main absorbent includes 100% di-n-butylamine according to mass percentage; other conditions remain unchanged.
  • This comparative example is basically the same as Example 1, except that:
  • the accelerator is a sulfur-containing organic compound, and the sulfur-containing organic compound is dimercaprol.
  • This comparative example is basically the same as Example 1, except that:
  • the main absorbent is 12.5% diethylenetriamine and 87.5% triisopropanolamine.
  • the viscosity of the carbon dioxide capture absorbent of this comparative example is 35 cp.
  • Regeneration rate amount of carbon dioxide desorbed from the carbon dioxide-enriched liquid / amount of carbon dioxide in the carbon dioxide-enriched liquid before desorption, wherein the amount of carbon dioxide desorbed from the carbon dioxide-enriched liquid is measured by a wet gas flow meter, and the amount of carbon dioxide in the carbon dioxide-enriched liquid before desorption is measured by acid-base titration. Specific results of the regeneration rate are shown in Table 1;
  • Example 5 increases the concentration of the promoter, thereby improving the carbon dioxide removal rate and reducing the regeneration energy consumption of the carbon dioxide capture absorbent;
  • Examples 6 and 7 adjusted the formulation of the main absorbent, thereby improving the performance of the carbon dioxide capture absorbent;
  • Examples 8 and 10 optimize the formulation of the promoter, and based on Example 1, further improve the performance of the carbon dioxide capture absorbent.

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Abstract

一种二氧化碳捕集吸收剂及捕集吸收方法。该吸收剂按照质量百分含量包括主吸收剂40％-70％，促进剂1％-20％，缓蚀剂0.05％-1％，抗氧化剂0.1％-1％；余量为水。其中，主吸收剂按照质量百分含量包括脂肪胺0-40％、醇胺60-100％；促进剂包括盐类、位阻胺与包括S＝O的含硫有机物中的至少一种，盐类、位阻胺和含硫有机物的质量比为(0-2)：(0-4)：(0-6)；吸收剂的粘度≤20cp。上述配方提高了吸收剂的二氧化碳捕集吸收能力和再生效果，并能降低再生能耗。

Description

一种二氧化碳捕集吸收剂及捕集吸收方法
本申请要求于2024年04月08日提交中国专利局、申请号为202410418036.5、申请名称为“一种二氧化碳捕集吸收剂及捕集吸收方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种二氧化碳捕集吸收剂，尤其涉及一种二氧化碳捕集吸收剂及捕集吸收方法，属于二氧化碳回收领域。
背景技术
CO2捕集利用与封存技术(CCUS)是指将二氧化碳从排放源中分离出来或直接利用或封存，以达到二氧化碳减排的工业过程，包括干法和湿法，其中，湿法包括化学吸收法和物理吸收法。
化学吸收法是将包括二氧化碳的排放源与吸收剂接触进行化学反应，使二氧化碳被吸收到溶液中，然后通过加热将二氧化碳解吸出来，吸收剂得以再生并循环利用的工艺过程。目前常用的吸收剂中一般含有60-70％的水，这部分水在吸收剂再生过程中会发生大量汽化，造成再生能耗居高不下。现有研究中通过提高吸收剂浓度可以降低含水量，进而降低水的蒸发量、再生能耗，但是这种具有较高吸收剂浓度的贫水吸收剂仍存在以下问题：(1)增加吸收剂浓度后吸收剂的再生效果变差；(2)水蒸发量仍较大导致再生能耗依然过高。
一种二氧化碳吸收能力高、再生效果好和再生能耗低的二氧化碳吸收剂是较为缺乏的。
发明内容
本发明提供一种二氧化碳捕集吸收剂，该二氧化碳捕集吸收剂具有较高的二氧化碳吸收处理能力，且再生效果好、再生能耗低。
本发明还提供一种二氧化碳捕集吸收方法，该方法利用上述二氧化碳捕集吸收剂捕集吸收二氧化碳，处理量大，且上述二氧化碳捕集吸收剂的再生效果较好，再生能耗较低，具有环境友好、资源节约的优势。
本发明第一方面提供一种二氧化碳捕集吸收剂，其中，所述二氧化碳捕集吸收剂按照质量百分含量包括主吸收剂40％-70％，促进剂1％-20％，缓蚀剂0.05％-1％，抗氧化剂0.1％-1％；余量为水；
其中，所述主吸收剂按照质量百分含量包括脂肪胺0％-40％、醇胺60％-100％，所述脂肪胺包括伯胺、仲胺、叔胺、多元胺中的至少一种，所述醇胺包括单羟基、双羟基、三羟基中的至少一种；
所述促进剂包括盐类、位阻胺与包括S＝O的含硫有机物中的至少一种，所述盐类包括季胺盐、氨基酸盐、柠檬酸盐中的至少一种，所述位阻胺包括2-氨基-2-甲基-1,3-丙二醇、2-氨基-2-甲基-1-丙醇、叔丁胺基乙氧基乙醇中的至少一种，所述含硫有机物包括二甲基砜、环丁砜、二甲基亚砜的至少一种，所述盐类、位阻胺和含硫有机物的质量比为(0-2)：(0-4)：(0-6)；
所述二氧化碳捕集吸收剂的粘度≤20cp。
如上所述的二氧化碳捕集吸收剂，其中，所述脂肪胺中氮原子数量≤3，碳原子数量≤6；
和/或，所述醇胺中氮原子数量≤3，碳原子数量≤6。
如上所述的二氧化碳捕集吸收剂，其中，所述盐类包括氨基酸盐，位阻胺包括2-氨基-2-甲基-1-丙醇，所述含硫有机物包括二甲基砜，所述盐类、位阻胺与含硫有机物的质量比为1：2：3。
如上所述的二氧化碳捕集吸收剂，其中，所述位阻胺的沸点＞160℃。
如上所述的二氧化碳捕集吸收剂，其中，所述缓蚀剂包括偏钒酸钠，且所述偏钒酸钠在所述二氧化碳捕集吸收剂中的质量百分含量为0.05％-0.2％。
如上所述的二氧化碳捕集吸收剂，其中，所述抗氧化剂包括酒石酸钾钠，且所述酒石酸钾钠在所述二氧化碳捕集吸收剂中的质量百分含量为0.1％-0.3％。
如上所述的二氧化碳捕集吸收剂，其中，所述二氧化碳捕集吸收剂的二氧化碳脱除率为60-90％，所述二氧化碳捕集吸收剂的再生率为50％-85％，所述二氧化碳捕集吸收剂的再生能耗为2.2-3.2GJ/t。
本发明第二方面提供一种二氧化碳捕集吸收方法，其中，包括以下步骤：
1)将包括所述二氧化碳的气源与权利要求1-7任一项所述的二氧化碳捕集吸收剂接触，使所述二氧化碳被所述二氧化碳捕集吸收剂捕集吸收，得到二氧化碳富集液；
其中，所述二氧化碳捕集吸收剂和包括所述二氧化碳的气源的流量比例为1.5-4:1；
2)对所述二氧化碳富集液进行加热处理，使二氧化碳从所述二氧化碳富集液中解吸，得到热溶液和所述二氧化碳。
如上所述的方法，其中，所述二氧化碳在所述包括二氧化碳的气源中的体积分数为5％-30％。
如上所述的方法，其中，所述加热包括利用步骤2)得到的所述热溶液对所述二氧化碳富集液进行预热。
本发明的二氧化碳捕集吸收剂中主吸收剂的质量百分含量较高，达到40％-70％，且包括促进剂、缓蚀剂、抗氧化剂，使得水的质量百分含量低于常规的二氧化碳吸收剂，属于具有较高主吸收剂浓度的贫水吸收剂，不仅有利于提高二氧化碳捕集吸收剂对二氧化碳的吸收容量，还有利于降低二氧化碳解析过程中水分蒸发量，进而有利于降低再生能耗。本发明对二氧化碳捕集吸收剂中的主吸收剂和促进剂的配方以及该二氧化碳捕集吸收剂的粘度均进行了限定，有利于提升二氧化碳在前述贫水吸收剂中的传质性能，进而提高了该二氧化碳捕集吸收剂捕集吸收二氧化碳的能力，更重要的是，通过主吸收剂、促进剂、缓蚀剂和抗氧化剂的协同配合，提高了该二氧化碳捕集吸收剂的再生效果并降低了再生能耗，进而有利于降低二氧化碳捕集吸收成本。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明第一方面提供一种二氧化碳捕集吸收剂，该二氧化碳捕集吸收剂按照质量百分含量包括主吸收剂40％-70％，促进剂1％-20％，缓蚀剂0.05％-1％，抗氧化剂0.1％-1％；余量为水；
其中，上述主吸收剂按照质量百分含量包括脂肪胺0％-40％、醇胺60％-100％，上述脂肪胺包括伯胺、仲胺、叔胺、多元胺中的至少一种，上述醇胺包括单羟基、双羟基、三羟基中的至少一种；
上述促进剂包括盐类、位阻胺与包括S＝O的含硫有机物中的至少一种，上述盐类包括季胺盐、氨基酸盐、柠檬酸盐中的至少一种，上述位阻胺包括2-氨基-2-甲基-1,3-丙二醇、2-氨基-2-甲基-1-丙醇、叔丁胺基乙氧基乙醇中的至少一种，上述含硫有机物包括二甲基砜、环丁砜、二甲基亚砜的至少一种，上述盐类、位阻胺和含硫有机物的质量比为(0-2)：(0-4)：(0-6)；
上述二氧化碳捕集吸收剂的粘度≤20cp。
本发明的二氧化碳捕集吸收剂通过与二氧化碳发生化学反应对二氧化碳进行捕集吸收，然后再通过加热将二氧化碳解吸出来，上述二氧化碳捕集吸收剂得以再生并循环利用。
该二氧化碳捕集吸收剂吸收二氧化碳的能力、再生效果以及再生能耗是影响其应用前景最为关键的三个性能。在本发明中，该二氧化碳捕集吸收剂吸收二氧化碳的能力用二氧化碳脱除率表示，二氧化碳脱除率＝(吸收塔入口气源中二氧化碳的浓度-吸收塔出口气源中二氧化碳的浓度)/吸收塔入口气源中二氧化碳的浓度；二氧化碳捕集吸收剂的再生效果用再生率表示，再生率＝从二氧化碳富集液中解吸出的二氧化碳的量/解吸前二氧化碳富集液中二氧化碳的量表示；再生能耗指该二氧化碳捕集吸收剂吸收二氧化碳后受热解吸二氧化碳过程中消耗的热能，用单位二氧化碳捕集量消耗蒸汽量的焓值进行计算。
本发明二氧化碳捕集吸收剂中，主吸收剂起着吸收二氧化碳的作用，其质量百分含量为40％-70％，含量较高，有利于增加二氧化碳的吸收容量，提高二氧化碳的吸收能力，还降低了捕集吸收剂中水的含量，使二氧化碳解吸过程中水分蒸发量得以减少，有利于降低再生能耗。下面以脂肪胺为例说明主吸收剂与CO2发生的反应：

式1表示伯胺、仲胺与CO2发生的反应，式2表示叔胺、位阻胺与CO2发生的反应。醇胺与CO2发生的反应类似上述反应。
同时本发明还通过对主吸收剂和促进剂进行配方优化并限定捕集吸收剂的粘度，吸收剂粘度≤20cp与较高浓度的主吸收剂、特定配方的促进剂等协同配合，解决了具有较高浓度主吸收剂的贫水吸收剂存在的二氧化碳传质难的问题，从而确保了上述二氧化碳捕集吸收剂具有较高的吸收二氧化碳的能力。
本发明的促进剂包括盐类、位阻胺与含硫有机物，盐类包括季胺盐、氨基酸盐、柠檬酸盐中的至少一种，位阻胺包括2-氨基-2-甲基-1,3-丙二醇、2-氨基-2-甲基-1-丙醇、叔丁胺基乙氧基乙醇中的至少一种，含硫有机物包括二甲基砜、环丁砜、二甲基亚砜的至少一种，盐类、位阻胺和含硫有机物的质量比为(0-2)：(0-4)：(0-6)；上述促进剂除了具有辅助二氧化碳吸收、提高二氧化碳吸收能力的作用外，更重要的是，在限定吸收剂的粘度的基础上，上述配方的促进剂可以降低溶液的pH值及溶液的氢键强度，从而提高了本发明二氧化碳捕集吸收剂的再生效果，避免了具有较高浓度主吸收剂的贫水吸收剂存在的再生效果差的问题，有利于二氧化碳捕集吸收剂的循环利用，进一步降低了二氧化碳解吸过程中的再生能耗，具有成本节约、环境友好的优点。
缓蚀剂的作用是减缓二氧化碳捕集吸收剂对设备的腐蚀速度，延长设备的使用年限。本发明对上述缓蚀剂的种类不做特别限定，使用本领域常用的缓蚀剂即可，例如使用氧化型缓蚀剂和/或表面吸附型缓蚀剂。上述氧化型缓蚀剂通过氧化设备形成一层氧化保护膜，进而减缓对设备的腐蚀速度，氧化型缓蚀剂可包括钼酸钠、偏钒酸钠、硫代硫酸钠、乙酸锌、碳酸铜、钨酸钠、四硼酸钠、钒酸钠和锰酸盐中的至少一种；上述表面吸附型缓蚀剂通过吸附到设备的表面，形成一层保护膜，来实现保护设备的目的，表面吸附型缓蚀剂可包括含一个氨基且碳原子数在1-20的直链烷烃。
抗氧化剂可减缓二氧化碳捕集吸收剂的氧化降解速度。本发明通过将特定的主吸收剂、促进剂和抗氧化剂在特定浓度下搭配使用，三者互相配合，使二氧化碳捕集吸收剂的吸收二氧化碳能力、再生能力最大化同时使再生能耗最小化。本发明同样对上述抗氧化剂的种类不做特别限定，使用本领域常用的抗氧化剂即可，例如乙醛肟、丙酮肟、羟基乙叉二膦酸、乙二胺四乙酸、抗坏血酸、亚硫酸钠、亚硫酸钾、亚硫酸铵、亚硝酸铵、酒石酸钾钠中的至少一种。
本发明的二氧化碳捕集吸收剂具有较高的二氧化碳吸收能力，再生效果好，再生能耗低，具有成本节约、环境优好的优点，应用前景广阔。
在一些实施例中，上述脂肪胺中氮原子数量≤3，碳原子数量≤6，有利于提高二氧化碳捕集吸收剂对二氧化碳的吸收容量，还有利于降低二氧化碳捕集吸收剂的粘度，改善二氧化碳的传质效果，进而提高二氧化碳捕集吸收剂对二氧化碳的吸收能力，且有利于提高二氧化碳捕集吸收剂的再生效果并降低再生能耗。
在一些实施例中，上述醇胺中氮原子数量≤3，碳原子数量≤6，有利于提高二氧化碳捕集吸收剂对二氧化碳的吸收容量，增加吸收剂的水溶性，降低挥发性，还有利于降低二氧化碳捕集吸收剂的粘度，改善二氧化碳的传质效果，进而提高二氧化碳捕集吸收剂对二氧化碳的吸收能力，降低再生能耗。
进一步地，上述促进剂中的季铵盐包括苯甲酸三乙基铵盐或苯甲酸甲基苄基季铵盐，氨基酸盐包括α-氨基乙酸盐、2-氨基丙酸盐、3-氨基丙酸盐、2-氨基-3-甲基丁酸盐、α-氨基异己酸盐、α-氨基-β-甲基戊酸盐、2-氨基苯丙酸盐、α-亚氨基酸盐、β-吲哚基丙氨酸盐、L-2-氨基-3-羟基丙酸盐、2-氨基-3-对羟苯基丙酸盐、L-2-氨基-3-巯基丙酸盐、谷氨酸盐、甲硫基丁氨酸盐、β-羟基-α-氨基丁酸盐、天门冬氨酸盐、α-氨基戊二酸盐、2,6-二氨基己酸盐、2-氨基-5-胍基戊酸盐、α-氨基β-咪唑基丙酸盐、苯甲酸三乙基铵盐中的至少一种，有利于增强二氧化碳捕集吸收剂的再生效果，并使再生能耗大大降低。
更进一步地，当盐类包括氨基酸盐，位阻胺包括2-氨基-2-甲基-1-丙醇，含硫有机物包括二甲基砜，且盐类、位阻胺与含硫有机物的质量比为1：2：3时，由上述盐类、位阻胺与含硫有机物组成的促进剂能够更好地增强二氧化碳捕集吸收剂的再生效果，并使再生能耗大大降低。
由于二氧化碳解吸过程为吸热过程，所以为了避免二氧化碳捕集吸收剂中的成分受热降解或挥发，本发明进一步限定上述促进剂中位阻胺的沸点需＞160℃，有利于避免位阻铵受热挥发，提高二氧化碳捕集吸收剂在解吸过程中的稳定性，提高二氧化碳捕集吸收剂的再生效果，也有利于降低再生能耗、节约成本。
发明人通过大量研究发现，当缓蚀剂包括偏钒酸钠，且偏钒酸钠在上述二氧化碳捕集吸收剂中的质量百分含量为0.05％-0.2％，优选0.1％时，有助于进一步减小设备的腐蚀速度。
当抗氧化剂包括酒石酸钾钠，且酒石酸钾钠在上述二氧化碳捕集吸收剂中的质量百分含量为0.1％-0.3％，优选0.2％时，可以更明显地降低二氧化碳捕集吸收剂的氧化降解速度，与主吸收剂、促进剂等相互配合，使二氧化碳捕集吸收剂的再生效果更好。
在一些实施例中，上述二氧化碳捕集吸收剂的二氧化碳脱除率为60％-90％，二氧化碳捕集吸收剂的再生率为50％-85％，二氧化碳捕集吸收剂的再生能耗为2.2-3.2GJ/t。可以看出，本发明的二氧化碳捕集吸收剂具有较高的二氧化碳吸收能力，且再生效果好、再生能耗低。
本发明第二方面提供一种二氧化碳捕集吸收方法，包括以下步骤：
1)将包括二氧化碳的气源与本发明第一方面的二氧化碳捕集吸收剂接触，使二氧化碳被二氧化碳捕集吸收剂捕集吸收，得到二氧化碳富集液；
其中，上述二氧化碳捕集吸收剂和包括二氧化碳的气源的流量比例为(1.5-4):1；
2)对该二氧化碳富集液进行加热处理，使二氧化碳从二氧化碳富集液中解吸，得到热溶液和二氧化碳。
上述二氧化碳捕集吸收方法为使用本发明的二氧化碳捕集吸收剂进行二氧化碳捕集吸收的方法。
上述步骤1)中将包括二氧化碳的气源与二氧化碳捕集吸收剂接触，使二氧化碳在二氧化碳捕集吸收剂中进行传质扩散，与二氧化碳捕集吸收剂发生化学反应，进而被二氧化碳捕集吸收剂捕集吸收，从而得到二氧化碳富集液。
在上述过程中，为了提高二氧化碳的处理效率，应将上述气源与二氧化碳捕集吸收剂进行充分接触，本发明不限定具体接触方式，例如可将气源通入吸收塔底部，将二氧化碳捕集吸收剂通入吸收塔顶部，使两者在吸收塔内逆流接触，这种逆流接触的方式具有接触面积大、反应充分的优点，可使二氧化碳充分被捕集吸收剂吸收。
本发明不限定上述气源和二氧化碳捕集吸收剂通入吸收塔的流速，只要使气源和二氧化碳捕集吸收剂充分接触即可，可结合二氧化碳捕集吸收剂的吸收二氧化碳的能力以及气源中二氧化碳的含量进行调整。
在一些实施例中，上述二氧化碳捕集吸收剂和包括二氧化碳的气源的流量比例为(1.5-4)：1(L/h)/(Nm3/h)，优选(1.8-3.6):1(L/h)/(Nm3/h)时，二氧化碳捕集吸收剂可将上述二氧化碳完全捕集吸收，说明本发明二氧化碳捕集吸收剂具有较高的二氧化碳吸收能力。
上述步骤2)中二氧化碳富集液受热至一定程度后二氧化碳可从中解吸，从而得到热溶液和二氧化碳，将该二氧化碳或直接利用或封存，从而实现了二氧化碳的捕集吸收利用。
上述二氧化碳解吸过程可在再生塔中进行，再生塔中设置有加热装置和气体收集装置，有利于进行二氧化碳解吸和收集。
一般地，上述对二氧化碳富集液进行加热处理的方式可采用饱和水蒸气加热，有利于对二氧化碳富集液快速加热且有利于节约能耗。例如在一些实施例中，采用压力为0.4MPa的水蒸气进行加热。
本发明提供的二氧化碳捕集吸收方法，利用上述二氧化碳捕集吸收剂对二氧化碳进行高效捕集吸收，处理量大，处理效率高，且操作简单，适于工业化推广。
上述二氧化碳捕集吸收方法可用于捕集吸收电厂排放烟气中二氧化碳。
二氧化碳在上述包括二氧化碳的气源中的体积分数为5％-30％时，通过本发明的捕集吸收方法可有效地将上述气源中的二氧化碳进行捕集吸收。
步骤2)中二氧化碳富集液受热后二氧化碳从中解吸，得到热溶液和二氧化碳，该热溶液具有较高热量。为了避免该热溶液中热量的浪费，因此上述加热包括利用步骤2)得到的热溶液对二氧化碳富集液进行预热，即将热溶液用作下一次二氧化碳解吸的热源，将热溶液中的部分热量转移到待解吸的二氧化碳富集液中用于二氧化碳的解吸，从而充分利用热溶液中的热量，避免能耗浪费，进一步降低了再生能耗。
上述预热过程可在换热器中进行。
在一些实施例中，为了以最低能耗使二氧化碳从二氧化碳解吸液中解吸出来，上述步骤2)中可将二氧化碳富集液从再生塔底部通入并经饱和水蒸气进行加热进而产生水蒸气和二氧化碳的混合气体，该混合气体自下而上流动，与从再生塔顶部通入的预热后的二氧化碳富集液逆流接触，实现传质和传热，反应结束后从再生塔顶部得到解吸的二氧化碳，从再生塔底部得到热溶液。上述过程充分利用热交换、逆流接触等方式使再生能耗实现最小化。
以下，通过具体实施例和对比例对本发明的二氧化碳捕集吸收剂以及二氧化碳捕集吸收方法进行更为详细的介绍。
实施例1
本实施例提供一种二氧化碳捕集吸收剂，按照质量百分含量包括主吸收剂40％，促进剂10％，钼酸钠1％，亚硫酸钠0.5％；余量为水；
其中，主吸收剂按照质量百分含量包括12.5％乙二胺、87.5％二乙醇胺；
促进剂包括盐类、位阻胺与含硫有机物，盐类为柠檬酸钠，位阻胺为2-氨基-2-甲基-1,3-丙二醇(AMP)，含硫有机物为二甲基亚砜，上述盐类和位阻胺的质量比为1：2：3；
该二氧化碳捕集吸收剂的粘度≤20cp。
本实施例还提供一种二氧化碳捕集吸收方法，包括以下步骤：
1)将包括二氧化碳的烟气以830Nm3/h通入吸收塔底部，与吸收塔顶部以1500L/h通入的上述二氧化碳捕集吸收剂逆流接触，使二氧化碳被上述二氧化碳捕集吸收剂捕集吸收，得到二氧化碳富集液；
其中，烟气中二氧化碳的体积分数为12％，二氧化碳捕集吸收剂和包括二氧化碳的烟气的流量比例为1.8:1(L/h/(Nm3/h))；
2)将上述二氧化碳富集液以1550L/h通入再生塔底部，用流量为180kg/h、压力为0.4MPa的饱和水蒸气对其进行加热处理得到水蒸气和二氧化碳混合气体；从再生塔顶部以150L/h通入预热至85-95℃的二氧化碳富集液，与上述混合气体逆流接触，充分反应后从再生塔底部得到热溶液，从再生塔顶部得到二氧化碳气体；
其中，在换热器内利用上述热溶液对二氧化碳富集液进行预热处理。
实施例2
本实施例与实施例1基本一致，区别在于：
二氧化碳捕集吸收剂中主吸收剂的质量百分含量为50％，其他条件保持不变。
实施例3
本实施例与实施例1基本一致，区别在于：
二氧化碳捕集吸收剂中主吸收剂的质量百分含量为60％，其他条件保持不变。
实施例4
本实施例与实施例1基本一致，区别在于：
二氧化碳捕集吸收剂中主吸收剂的质量百分含量为70％，其他条件保持不变。
实施例5
本实施例与实施例1基本一致，区别在于：
二氧化碳捕集吸收剂中促进剂的质量百分含量为20％，亚硫酸钠的质量百分含量为1％；其他条件保持不变。
实施例6
本实施例与实施例1基本一致，区别在于：
主吸收剂按照质量百分含量包括12.5％乙二胺、87.5％的单乙醇胺。
实施例7
本实施例与实施例1基本一致，区别在于：
主吸收剂按照质量百分含量包括12.5％二乙烯三胺、87.5％的二乙醇胺。
实施例8
本实施例与实施例1基本一致，区别在于：
促进剂包括盐类、位阻胺与含硫有机物，盐类为α氨基乙酸盐和2氨基丙酸盐，位阻胺为2-氨基-2-甲基-1-丙醇，含硫有机物为二甲基砜，上述盐类、位阻胺与含硫有机物的质量比为1：2：3；其他条件保持不变。
实施例9
本实施例与实施例1基本一致，区别在于：
位阻铵用2-氨基-2-甲基-1-丙醇(AMPD)替换2-氨基-2-甲基-1,3-丙二醇(AMP)；其他条件保持不变。
实施例10
本实施例与实施例1基本一致，区别在于：
促进剂包括盐类、位阻胺与含硫有机物，盐类为2-氨基丙酸钠，位阻胺为2-氨基-2-甲基-1-丙醇，含硫有机物为二甲基砜，上述盐类、位阻胺与含硫有机物的质量比为1：2：3；其他条件保持不变。
实施例11
本实施例与实施例1基本一致，区别在于：
用偏钒酸钠0.2％替换钼酸钠1％。
实施例12
本实施例与实施例1基本一致，区别在于：
用酒石酸钾钠0.3％替换亚硫酸钠0.5％。
实施例13
本实施例与实施例1基本一致，区别在于：
烟气中二氧化碳的体积分数为20％。
实施例14
本实施例与实施例1基本一致，区别在于：
主吸收剂按照质量百分含量包括12.5％氨基辛烷、87.5％的二乙醇胺；其他条件保持不变。
实施例15
本实施例与实施例1基本一致，区别在于：
主吸收剂按照质量百分含量包括12.5％乙二胺、87.5％的N-甲基环己胺；其他条件保持不变。
对比例1
本对比例与实施例1基本一致，区别在于：
主吸收剂按照质量百分含量包括100％二正丁胺；其他条件保持不变。
对比例2
本对比例与实施例1基本一致，区别在于：
促进剂为含硫有机物，含硫有机物为二巯基丙醇。
对比例3
本对比例与实施例1基本一致，区别在于：
主吸收剂为12.5％二乙烯三胺、87.5％的三异丙醇胺，
本对比例二氧化碳捕集吸收剂的粘度为35cp。
试验例
1、对上述实施例和对比例以下参数进行检测：
1)二氧化碳脱除率：气源中二氧化碳的浓度通过红外光谱方法进行检测，二氧化碳脱除率＝(吸收塔入口气源中二氧化碳的浓度-吸收塔出口气源中二氧化碳的浓度)/吸收塔入口气源中二氧化碳的浓度，具体结果见表1；
2)吸收剂的再生率：再生率＝从二氧化碳富集液中解吸出的二氧化碳的量/解吸前二氧化碳富集液中二氧化碳的量表示，其中，从二氧化碳富集液中解吸出的二氧化碳的量通过湿式气体流量计检测，解吸前二氧化碳富集液中二氧化碳的量通过酸碱滴定检测，再生率的具体结果见表1；
3)再生能耗：用单位二氧化碳捕集量消耗蒸汽量的焓值进行计算，计算公式：再生能耗＝蒸汽耗量×(再沸器入口蒸汽焓值-再沸器出口蒸汽焓值)/解吸出的二氧化碳的量，具体结果见表1；
4)挂片腐蚀速率：采用HGT2159-91规定的方法检测，具体结果见表1。
2、检测结果
表1二氧化碳捕集吸收剂的相关参数

表1的结果表明：
1)实施例1-4的二氧化碳脱除率数据说明主吸收剂浓度提高有助于提高二氧化碳脱除率；
2)实施例5调高了促进剂的浓度，提高了二氧化碳脱除率并降低了二氧化碳捕集吸收剂的再生能耗；
3)与实施例1、14和15相比，实施例6和7调整了主吸收剂的配方，使二氧化碳捕集吸收剂的性能有所改善；
4)实施例8和10对促进剂的配方进行优化，在实施例1的基础上，进一步改善了二氧化碳捕集吸收剂的性能。
5)对比例1-3的二氧化碳捕集吸收剂配方与实施例1不同，导致其出现了二氧化碳脱除率低、再生率低或再生能耗高等问题。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

  1. 一种二氧化碳捕集吸收剂，其特征在于，所述二氧化碳捕集吸收剂按照质量百分含量包括主吸收剂40％-70％，促进剂1％-20％，缓蚀剂0.05％-1％，抗氧化剂0.1％-1％；余量为水；
    其中，所述主吸收剂按照质量百分含量包括脂肪胺0-40％、醇胺60-100％，所述脂肪胺包括伯胺、仲胺、叔胺、多元胺中的至少一种，所述醇胺包括单羟基、双羟基、三羟基中的至少一种；
    所述促进剂包括盐类、位阻胺与包括S＝O的含硫有机物中的至少一种，所述盐类包括季胺盐、氨基酸盐、柠檬酸盐中的至少一种，所述位阻胺包括2-氨基-2-甲基-1,3-丙二醇、2-氨基-2-甲基-1-丙醇、叔丁胺基乙氧基乙醇中的至少一种，所述含硫有机物包括二甲基砜、环丁砜、二甲基亚砜的至少一种，所述盐类、位阻胺和含硫有机物的质量比为(0-2)：(0-4)：(0-6)；
    所述二氧化碳捕集吸收剂的粘度≤20cp。
  2. 根据权利要求1所述的二氧化碳捕集吸收剂，其特征在于，所述脂肪胺中氮原子数量≤3，碳原子数量≤6；
    和/或，所述醇胺中氮原子数量≤3，碳原子数量≤6。
  3. 根据权利要求1或2所述的二氧化碳捕集吸收剂，其特征在于，所述盐类包括氨基酸盐，位阻胺包括2-氨基-2-甲基-1-丙醇，所述含硫有机物包括二甲基砜，所述盐类、位阻胺与含硫有机物的质量比为1：2：3。
  4. 根据权利要求1-3任一项所述的二氧化碳捕集吸收剂，其特征在于，所述位阻胺的沸点＞160℃。
  5. 根据权利要求1-4任一项所述的二氧化碳捕集吸收剂，其特征在于，所述缓蚀剂包括偏钒酸钠，且所述偏钒酸钠在所述二氧化碳捕集吸收剂中的质量百分含量为0.05％-0.2％。
  6. 根据权利要求1-5任一项所述的二氧化碳捕集吸收剂，其特征在于，所述抗氧化剂包括酒石酸钾钠，且所述酒石酸钾钠在所述二氧化碳捕集吸收剂中的质量百分含量为0.1％-0.3％。
  7. 根据权利要求1-6任一项所述的二氧化碳捕集吸收剂，其特征在于，所述二氧化碳捕集吸收剂的二氧化碳脱除率为60％-90％，所述二氧化碳捕集吸收剂的再生率为50％-85％，所述二氧化碳捕集吸收剂的再生能耗为2.2-3.2GJ/t。
  8. 一种二氧化碳捕集吸收方法，其特征在于，包括以下步骤：
    1)将包括所述二氧化碳的气源与权利要求1-7任一项所述的二氧化碳捕集吸收剂接触，使所述二氧化碳被所述二氧化碳捕集吸收剂捕集吸收，得到二氧化碳富集液；
    其中，所述二氧化碳捕集吸收剂和包括所述二氧化碳的气源的流量比例为(1.5-4):1；
    2)对所述二氧化碳富集液进行加热处理，使二氧化碳从所述二氧化碳富集液中解吸，得到热溶液和所述二氧化碳。
  9. 根据权利要求8所述的方法，其特征在于，所述二氧化碳在所述包括二氧化碳的气源中的体积分数为5％-30％。
  10. 根据权利要求8或9所述的方法，其特征在于，所述加热包括利用步骤2)得到的所述热溶液对所述二氧化碳富集液进行预热。
PCT/CN2024/136212 2024-04-08 2024-12-02 一种二氧化碳捕集吸收剂及捕集吸收方法 Pending WO2025213795A1 (zh)

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