CN107261767B - Flue gas decarbonizing agent and flue gas decarbonizing method - Google Patents
Flue gas decarbonizing agent and flue gas decarbonizing method Download PDFInfo
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- CN107261767B CN107261767B CN201710720297.2A CN201710720297A CN107261767B CN 107261767 B CN107261767 B CN 107261767B CN 201710720297 A CN201710720297 A CN 201710720297A CN 107261767 B CN107261767 B CN 107261767B
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- 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
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- 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
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- 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
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- 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
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
- B01D2252/2053—Other nitrogen compounds
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- 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
- B01D2252/50—Combinations of absorbents
- B01D2252/504—Mixtures of two or more absorbents
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention provides a smoke decarbonization composition, which comprises the following components: 5-50 parts by weight of a main absorbent; 0.1-20 parts by weight of an activator; 0.1-5 parts by weight of desorption auxiliary agent;0.05-2 parts of corrosion inhibitor; 25-95 parts by weight of water; the primary absorbent comprises diazabicyclooctane and diamine compounds containing hydroxyalkyl groups; the activating agent is selected from one or more of diethylenetriamine, tetraethylenepentamine, triethylene tetramine and triethylene diamine. The smoke decarbonization composition provided by the invention adopts diazabicyclooctane and diamine compound containing hydroxyalkyl as main absorbents, diethylenetriamine, tetraethylenepentamine, triethylene tetramine or triethylene diamine as activators, and components such as desorption auxiliaries and corrosion inhibitors are combined, and simultaneously, the smoke decarbonization composition has a good effect of removing carbon dioxide by combining a specific ratio, and CO is good2High absorption capacity, high absorption speed, high decarburization rate and low desorption energy consumption.
Description
Technical Field
The invention relates to the technical field of gas separation and purification, in particular to a flue gas decarburization composition and a flue gas decarburization method.
Background
In recent decades, due to CO2The excessive discharge causes the temperature on the earth surface to be continuously raised, great harm is brought to the environment, various natural disasters are more and more serious, and CO is generated in the utilization process of petroleum, coal, natural gas and the like2CO with different concentrations is also contained in various synthesizers, hydrogen energy source prepared gas, biorefinery purge gas, exhaust gas of metallurgy and power plants in the chemical, biological, energy, metallurgical and other industries2Removal of CO from the production line2Becomes an indispensable production process and reduces CO in the post-treatment link2The direct discharge of the waste water has great significance for protecting the environment on which the human lives. For discharged CO2The recycling, fixing, utilizing and recycling of the waste water become a very concerned problem in countries of the world, especially developed countries. CO22Emission reduction is a major global climate change problem and is a serious challenge for industrial economy, especially energy industry.
CO2The main technical flows of the removal process can be roughly classified into 3 categories: solvent absorption decarburization technology, membrane separation decarburization technology, solid adsorbent adsorption decarburization technology, wherein,the solvent absorption decarbonization technology is the most attractive separation technology which is applied most widely so far, and large-scale CO is currently adopted2The capture is mainly based on an organic amine method with good chemical selectivity under low partial pressure, and CO is captured by the amine method2In the process, the organic amine in the solution is easy to react with O2、CO2Carbide, etc. are chemically degraded and are also easily thermally degraded, especially with O in flue gas2The oxidative degradation of (a) is in the first place. The formation of organic amine degradation products promotes amine loss on one hand, and aggravates equipment corrosion and causes problems of solution foaming and the like on the other hand, so that production is unstable. The problem of amine degradation is always that the amine method is used for capturing CO in the flue gas2The technical problem which is difficult to solve exists in the process. In addition, the renewable cyclic absorption method is developed for more than ten years, the single-component high-energy-consumption absorbent is developed into the composite-component absorbent, and the problems of the components and the content of the absorbent are still the research hotspots of the scientific communities all over the world. In order to further improve the absorption capacity of the absorbent, improve the resistance of the absorbent against oxidative degradation, reduce corrosivity, reduce loss due to volatilization and energy consumption during regeneration, efforts have been made to develop efficient chemical solution absorbents.
CN102049173A A process for the deep removal of CO from gas mixtures2The method takes a composite amine aqueous solution as an absorbent, and the concentration of total amine in the absorbent is 20 to 50 percent by weight; the compound amine comprises: the main absorbent is MDEA, and the content of the MDEA accounts for 70-90% of the total amine concentration; the absorption aid is two of HEP, DMA2P and DMAE, and accounts for 10-30% of the total amine concentration. CA200710011508.1 method for recovering CO from waste gas2The composite decarbonization solution is used, and the components and the weight percentage of the composite solution are as follows: the composite amine aqueous solution comprises 20-60% of one or more kinds of amine with a low reaction rate and one or more kinds of amine with a low reaction rate, wherein the amine with a high reaction rate adopts monoethanolamine, diethanolamine or piperazine, the amine with a low reaction rate is MEDA, ANMP or TEA, the selective absorption component is polyol ether, the corrosion inhibitor is sodium vanadate, and the antioxidant component is sodium sulfate or copper acetate. CN200410066416.X improved N-methyldiethanolamine decarbonizing solutionThe composite activating agent mainly comprises N-methyldiethanolamine aqueous solution and an activating agent, wherein the activating agent comprises morpholine and piperazine, and the weight ratio of the activating agent to the N-methyldiethanolamine is 0.05-0.20. However, most of the existing flue gas decarburization absorbents have CO2Slow absorption speed, low desorption rate, high desorption energy consumption and the like.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a flue gas decarbonization composition, and the flue gas decarbonization composition provided by the present invention is CO2High absorption capacity, high absorption speed, high decarburization rate, low desorption energy consumption and low corrosion to equipment.
The invention provides a smoke decarbonization composition, which comprises the following components:
the primary absorbent comprises diazabicyclooctane and diamine compounds containing hydroxyalkyl groups;
the activating agent is selected from one or more of diethylenetriamine, tetraethylenepentamine, triethylene tetramine and triethylene diamine.
Preferably, in the main absorbent, the mass ratio of diazabicyclooctane to hydroxyalkyl-containing diamine compound is 1: 0.05 to 2;
the diamine compound containing hydroxyalkyl is selected from one or more of hydroxyethyl ethylenediamine, hydroxypropyl ethylenediamine, hydroxyethyl piperazine, ethyl piperazine, 1, 4-bis (2-hydroxyethyl) piperazine, 1, 4-bis (2-hydroxypropyl) piperazine, N-dimethyl piperazine, N-ethyl piperazine and N, N-diethyl piperazine.
Preferably, the desorption auxiliary agent is selected from one or more of citric acid, sodium lactate, sodium acetate, sodium citrate and lactic acid; the corrosion inhibitor consists of metal oxide and mono-oil imidazoline; the metal oxide is selected from one or more of vanadate, metavanadate, vanadium pentoxide, basic ketone carbonate and antimony potassium tartrate; the mass ratio of the metal oxide to the monooleimidazoline is 1: (0.05-2).
Preferably, the flue gas decarburization composition further comprises an antioxidant; the antioxidant is selected from one or more of 4-tert-butyl catechol, 2, 6-di-tert-butyl-p-cresol, acetone oxime, N, N-bis (2-hydroxyethyl) glycine, dodecyl hydroquinone, anthraquinone disulfonic acid and anthraquinone disulfonic acid sodium disulfonate; and 0.05-5 parts by weight of antioxidant.
Preferably, the flue gas decarbonization composition comprises:
preferably, the flue gas decarbonization composition comprises:
the invention provides a preparation method of a smoke decarburization composition, which comprises the following steps:
mixing the main absorbent, the activating agent, the desorption auxiliary agent, the corrosion inhibitor and water to obtain the smoke decarburization composition.
The invention provides a method for decarbonizing flue gas, which comprises the following steps:
contacting a mixed gas containing carbon dioxide with the decarburization composition as set forth in claim 1.
Preferably, the contacting conditions include: the temperature is 30-80 ℃, and the liquid-gas ratio is 0.05-3.0 kg/Nm3。
Preferably, the contacting is carried out in a countercurrent manner.
Compared with the prior art, the invention provides a smoke decarburization composition, which comprises the following components: 5-50 parts by weight of a main absorbent; 0.1-20 parts by weight of an activator; 0.1-5 parts by weight of desorption auxiliary agent; 0.05-2 parts of corrosion inhibitor; 25-95 parts by weight of water; the primary absorbent comprises diazabicyclooctane and diamine compounds containing hydroxyalkyl groups; the activating agent is selected from one or more of diethylenetriamine, tetraethylenepentamine, triethylene tetramine and triethylene diamine. The smoke decarbonization composition provided by the invention adoptsDiazabicyclooctane and diamine compound containing hydroxyalkyl are used as main absorbent, diethylenetriamine, tetraethylenepentamine, triethylene tetramine or triethylene diamine are used as activating agent, desorption auxiliary agent, corrosion inhibitor and other components are combined, and the effect of removing carbon dioxide is good and CO is good by combining specific proportion2High absorption capacity, high absorption speed, high decarburization rate and low desorption energy consumption.
Detailed Description
The invention provides a smoke decarbonization composition, which comprises the following components:
the primary absorbent comprises diazabicyclooctane and diamine compounds containing hydroxyalkyl groups;
the activating agent is selected from one or more of diethylenetriamine, tetraethylenepentamine, triethylene tetramine and triethylene diamine.
The flue gas decarburization composition provided by the invention comprises 5-50 parts by weight of a main absorbent; preferably, the absorbent comprises 10-45 parts by weight of a main absorbent; more preferably, the absorbent composition comprises 13 to 40 parts by weight of a main absorbent.
The main absorbent is diazabicyclooctane and diamine compounds containing hydroxyalkyl. In the present invention, the sources of the diazabicyclooctane and the hydroxyalkyl group-containing diamine compound are not limited and may be commercially available.
Wherein, the alkyl in the diamine compound containing hydroxyalkyl is preferably C1-C5 alkyl; the diamine compound containing hydroxyalkyl is preferably one or more selected from hydroxyethyl ethylenediamine, hydroxypropyl ethylenediamine, hydroxyethyl piperazine, ethylpiperazine, 1, 4-bis (2-hydroxyethyl) piperazine, 1, 4-bis (2-hydroxypropyl) piperazine, N-dimethylpiperazine, N-ethylpiperazine and N, N-diethylpiperazine; more preferably one or more selected from hydroxyethylethylenediamine, hydroxypropylethylenediamine, hydroxyethylpiperazine, ethylpiperazine, 1, 4-bis (2-hydroxyethyl) piperazine, N-ethylpiperazine and N, N-diethylpiperazine.
According to the present invention, the mass ratio of the diazabicyclooctane to the hydroxyalkyl group-containing diamine compound is preferably 1: 0.05 to 2; more preferably 1: 0.5 to 1.5; most preferably 1: 0.7 to 1.4.
The invention creatively adopts the diazabicyclooctane and the diamine compound containing hydroxyalkyl as main absorption components, and can generate synergistic effect to have good absorption effect on carbon dioxide and high absorption capacity.
The flue gas decarburization composition provided by the invention comprises 0.1-20 parts by weight of an activating agent; preferably 1 to 15 parts by weight of an activator; more preferably 1.5 to 12 parts by weight of an activator; most preferably, the activator is included in an amount of 3 to 10 parts by weight.
The activating agent is selected from one or more of diethylenetriamine, tetraethylenepentamine, triethylene tetramine and triethylene diamine.
In the present invention, the source of the activator is not limited and may be commercially available.
The diazabicyclooctane and the diamine compound containing hydroxyalkyl are used as main absorption components, and are matched with an activating agent with specific type and proportion in a synergistic manner, so that the absorption effect of carbon dioxide is good, and CO is absorbed by2High absorption capacity, high absorption speed, high decarburization rate and low desorption energy consumption.
The flue gas decarburization composition provided by the invention comprises 0.1-5 parts by weight of desorption auxiliary agent; preferably, the desorption auxiliary agent comprises 0.5-4 parts by weight; more preferably, the desorption assistant comprises 1-3 parts by weight.
According to the invention, the desorption auxiliary agent is preferably selected from one or more of citric acid, sodium lactate, sodium acetate, sodium citrate and lactic acid; more preferably one or more of citric acid, sodium lactate, sodium citrate and lactic acid.
In the present invention, the source of the desorption assistant is not limited and may be commercially available.
The smoke decarburization composition provided by the invention comprises 0.05-2 parts by weight of corrosion inhibitor; preferably, the corrosion inhibitor comprises 0.5-1.5 parts by weight of corrosion inhibitor; more preferably 0.5 to 1.2 parts by weight of a corrosion inhibitor.
The corrosion inhibitor preferably consists of metal oxide and mono-oil imidazoline; the metal oxide is preferably selected from one or more of vanadate, metavanadate, vanadium pentoxide, basic ketone carbonate and antimony potassium tartrate; the metavanadate includes but is not limited to sodium metavanadate and potassium metavanadate; such vanadates include, but are not limited to, sodium vanadate and potassium vanadate.
The mass ratio of the metal oxide to the monooleimidazoline is preferably 1: (0.05-2); more preferably 1: (0.1 to 1.5); most preferably 1: (0.5 to 1.3).
The decarbonization adsorbent CO is prepared by the synergistic effect of the desorption auxiliary agent and the corrosion inhibitor matched with the main absorption component and the activating agent2High absorption capacity, high absorption speed, high decarburization rate, low desorption energy consumption and low corrosion to equipment.
The flue gas decarburization composition provided by the invention comprises 25-95 parts by weight of water; preferably, 30 to 90 parts by weight of water is included.
The smoke decarburization composition provided by the invention preferably further comprises 0.05-5 parts by weight of an antioxidant; preferably 0.5-4 parts by weight of antioxidant; more preferably 0.5 to 3 parts by weight of an antioxidant.
According to the invention, the antioxidant is preferably selected from one or more of 4-tert-butyl catechol, 2, 6-di-tert-butyl-p-cresol, acetoxime, N, N-bis (2-hydroxyethyl) glycine, dodecyl hydroquinone, anthraquinone disulfonic acid and anthraquinone disulfonic acid sodium.
In the present invention, the source of the antioxidant is not limited and may be commercially available.
The flue gas decarburization composition of one embodiment of the invention comprises:
the flue gas decarburization composition of one embodiment of the invention comprises:
the flue gas decarburization composition of one embodiment of the invention comprises:
the flue gas decarburization composition of one embodiment of the invention comprises:
the flue gas decarburization composition of one embodiment of the invention comprises:
the invention provides a smoke decarbonization composition, which comprises the following components: 5-50 parts by weight of a main absorbent; 0.1-20 parts by weight of an activator; 0.1-5 parts by weight of desorption auxiliary agent; 0.05-2 parts of corrosion inhibitor; 25-95 parts by weight of water; the primary absorbent comprises diazabicyclooctane and diamine compounds containing hydroxyalkyl groups; the activating agent is selected from one or more of diethylenetriamine, tetraethylenepentamine, triethylene tetramine and triethylene diamine. The smoke decarbonization composition provided by the invention adopts diazabicyclooctane and diamine compound containing hydroxyalkyl as main absorbents, diethylenetriamine, tetraethylenepentamine, triethylene tetramine or triethylene diamine as activators, and components such as desorption auxiliaries and corrosion inhibitors are combined, and simultaneously, the smoke decarbonization composition has a good effect of removing carbon dioxide by combining a specific ratio, and CO is good2High absorption capacity, high absorption speed, high decarburization rate and low desorption energy consumption.
The invention provides a preparation method of a smoke decarburization composition, which comprises the following steps:
mixing the main absorbent, the activating agent, the desorption auxiliary agent, the corrosion inhibitor and water to obtain the smoke decarburization composition.
The preparation method of the flue gas decarburization composition provided by the invention is characterized in that the main absorbent, the activating agent, the desorption auxiliary agent and the corrosion inhibitor are added into water to obtain the flue gas decarburization composition.
When the composite also comprises an antioxidant, the main absorbent, the activating agent, the desorption auxiliary agent, the corrosion inhibitor, the antioxidant and the water are mixed to obtain the smoke decarbonization composite. Namely, the main absorbent, the activating agent, the desorption auxiliary agent, the antioxidant and the corrosion inhibitor are added into water to obtain the smoke decarbonization composition.
The specific compositions and proportions of the composition are clearly described above, and are not repeated herein. The mixing method of the present invention is not limited, and those skilled in the art will be familiar with it. Wherein the temperature of mixing is preferably 20 ℃ to 50 ℃.
The decarbonizing agent provided by the invention can remove and recover carbon dioxide gas mixed with limestone roasting kiln flue gas, blast furnace gas, natural gas and the like, and remove and recover carbon dioxide in gas such as power plant boiler flue gas, carbonic acid industrial tail gas and the like, and the decarbonizing solution has the advantages of large absorption capacity, high purification degree, high absorption speed, high desorption rate, low regeneration energy consumption and the like.
The invention provides a method for decarbonizing flue gas, which comprises the following steps:
and (3) contacting the mixed gas containing the carbon dioxide with the decarburization composition.
The method for decarbonizing the flue gas provided by the invention is to contact the mixed gas containing the carbon dioxide with the decarbonization composition.
According to the present invention, the contact conditions are not particularly limited as long as the decarburization composition can be brought into sufficient contact with the mixed gas.
The present invention is not limited to mixed gases, including but not limited to CO2、O2、H2O、N2CO, trace carbides and nitrogen oxides.
The conditions of the contacting preferably include: the temperature is 30-80 ℃, and the liquid-gas ratio is 0.05-3.0 kg/Nm3(ii) a More preferably, the temperature is 40 to 60 ℃, and the liquid-gas ratio is 0.08 to 2.0kg/Nm3(ii) a Most preferably 40-60 ℃, and the liquid-gas ratio is 0.08-1.5 kg/Nm3。
The contact mode is preferably countercurrent contact, namely the flue gas decarburization composition is in countercurrent contact with the flue gas, so that the contact effect is greatly improved.
The invention adopts the temperature, the liquid-gas ratio and the countercurrent contact mode to remove the carbon dioxide, and has high efficiency and good effect.
When the decarbonizing agent absorbs carbon dioxide to enable the acidity of the absorbed rich solution to reach a certain acidity range, wherein the pH of the rich solution is 7.5-9.5, preferably the pH of the rich solution is 7.5-8.0, the decarbonizing agent can be desorbed, and the absorbed carbon dioxide can be separated from the decarbonizing agent, so that the decarbonizing agent can be regenerated. The desorption can be realized by heating the used decarbonizer, wherein the heating temperature can be 85-130 ℃, and preferably 90-115 ℃. The heating time may be 15 to 180 minutes, preferably 30 to 60 minutes.
In industrial production, the processes of decarbonization and desorption of flue gas can be respectively carried out in an absorption tower and a desorption tower, the types and the use methods of the absorption tower and the desorption tower are well known to those skilled in the art, and the details are not repeated.
In the following, preferred industrial application modes of the flue gas decarboniser of the invention are given:
and (3) decarbonizing flue gas: preheating the flue gas decarbonizer to 40-60 ℃ through a heat exchanger, spraying from the top end of an absorption tower, introducing flue gas from the bottom end of the absorption tower, and controlling the liquid-gas ratio to be 0.08-1.5 kg/m3The gas decarbonizing agent is reversely contacted with the gas containing carbon dioxide, and the purified gas is discharged into the atmosphere through the top of the tower to absorb CO2The decarbonizing agent is called rich liquid and enters a rich liquid tank from the bottom of the tower.
Desorbing: preheating the rich liquid obtained from a rich liquid tank of an absorption tower to 70-90 ℃ through a heat exchanger, spraying from the top end of a desorption tower, arranging a heat exchange device heated by steam at the bottom of the desorption tower, partially desorbing the rich liquid absorbing carbon dioxide in the desorption tower, heating the rich liquid to 95-120 ℃ in the heat exchange device for desorption again, and enabling the desorbed liquid to flow into the bottom of the desorption deviceHigh-temperature desorption gas and water vapor are discharged from the top end of the desorption tower and then enter a condenser and a vapor-liquid separator, condensed water which is cooled and separated from the desorption gas returns to the desorption tower, and the obtained relatively pure high-temperature CO2And (5) delivering the gas to the next process. The high-temperature desorption gas transfers heat to the rich liquid sprayed from the top end, and the rich liquid at 70-90 ℃ can be heated to be easily desorbed. The rich solution is called lean solution after desorption, is discharged from the bottom of the desorption tower, enters a lean solution tank and is used as a flue gas decarbonizer for recycling.
Flue gas decarbonizer oxidation resistance experiment: 200ml of flue gas decarbonizer solution, a high-pressure reaction kettle with oxygen partial pressure of 0.6MPa, the reaction temperature of 130 ℃, the reaction time of 4 hours, GC-MS and ICP instruments are adopted to measure the mass concentration of the flue gas decarbonizer solution before and after the reaction, and the degradation rate of the flue gas decarbonizer is calculated, and the experimental results are shown in Table 1.
Flue gas decarbonizer corrosion inhibition test: 400ml of flue gas decarbonizer solution, the temperature of the solution is 80 ℃, a full immersion test is carried out by adopting an A3 carbon steel standard test piece, the reaction time is 336h (14d), the weight of the A3 test piece before and after the reaction is measured, the corrosion rate of different flue gas decarbonizer solutions is calculated, and the experimental results are shown in Table 1.
In order to further illustrate the present invention, the flue gas decarburization composition provided by the present invention is described in detail below with reference to examples.
Example 1
This example is used to illustrate the flue gas decarbonizer provided by the present invention.
(1) The composition of the simulated smoke is (volume): CO22：20.25％；O2：8.27％；H2O：10.12％；N2: 59.01, CO: 2.35 percent; trace amounts of sulfides and nitrogen oxides.
(2) Preparation of a flue gas decarboniser
70 g of diazabicyclooctane, 50 g of hydroxyethyl piperazine, 30 g of tetraethylenepentamine, 10 g of citric acid, 5 g of dodecyl hydroquinone, 3 g of antimony potassium tartrate and 2 g of monoolein imidazoline were added to 500 ml of water, stirred uniformly and quantified to 1000 g with distilled water, thereby obtaining the smoke decarbonizer.
(3) Decarbonization of flue gases
Heating 1000 g of the decarbonizer prepared in (2) to 50 ℃, feeding the decarbonizer into a packed tower provided with a glass net ring from the upper end of the packed tower by using a micro vacuum pump, feeding the simulated flue gas in (1) into a flue gas pipe from the bottom end of the packed tower, and leading the gas to be in reverse contact with liquid sprayed from the upper end, wherein the liquid-gas ratio is 0.25kg/Nm3The purified gas is discharged from the top of the absorption tower and absorbs SO2The rich liquid enters a rich liquid tank. The composition of the gas discharged from the top of the column was measured by an enhanced flue gas analyzer (model: Vario Plus, Germany), the amount of carbon dioxide in the rich solution (i.e., absorption capacity) was measured by a method of collecting CO2 gas, the absorption amount was calculated by the following formula,
absorption capacity is the amount of carbon dioxide after absorption-the amount of carbon dioxide before absorption
The results are shown in Table 1.
(4) Desorption of
After the decarbonization of the flue gas is finished, the decarbonized rich liquid obtained in the step 3 is put into a three-neck flask, a thermometer is inserted into one neck, a flue gas pipe is inserted into one neck and leads to the bottom of the decarbonized rich liquid, nitrogen is introduced into the flue gas pipe, and the introduction speed is 2 multiplied by 10-4Nm3Min, introducing for 80 min, heating to 100 deg.C, desorbing the absorbed carbon dioxide to obtain barren solution, and collecting CO2The amount of carbon dioxide remaining in the lean solution was measured by a gas method, the desorption amount and the desorption rate were calculated by the following formulas,
desorption capacity is the amount of carbon dioxide before desorption-the amount of carbon dioxide after desorption
The desorption rate was defined as desorption amount/amount of carbon dioxide before desorption × 100%
And (3) repeating the steps (3) and (4) with the obtained lean solution, measuring the composition of the gas after decarburization and the absorption capacity at the time of secondary decarburization using the decarburization agent, and calculating the secondary desorption amount and the secondary desorption rate, wherein the secondary desorption rate is equal to the secondary desorption amount divided by the secondary absorption amount, and so on. The results are shown in Table 1.
Example 2
This example is used to illustrate the flue gas decarbonizer provided by the present invention.
(1) The composition of the simulated smoke is (volume): CO22：20.25％；O2：8.27％；H2O：10.12％；N2: 59.01, CO: 2.35 percent; trace amounts of sulfides and nitrogen oxides.
(2) Preparation of a flue gas decarboniser
50 g of diazabicyclooctane, 70 g of hydroxyethyl ethylenediamine, 30 g of diethylenetriamine, 10 g of lactic acid, 5 g of anthraquinone disulfonic acid sodium, 3 g of vanadium pentoxide and 2 g of monoolein imidazoline are added into 500 ml of water, the mixture is uniformly stirred, and the distilled water is used for quantifying to 1000 g, so that the smoke decarbonizer is obtained.
Steps (3) and (4) were carried out for decarburization of flue gas, for desorption of a decarburization agent, and for measurement of absorption capacity, desorption amount and desorption rate in the same manner as in example 1, and the results are shown in Table 1.
Example 3
This example is used to illustrate the flue gas decarbonizer provided by the present invention.
(1) The composition of the simulated smoke is (volume): CO22：20.25％；O2：8.27％；H2O：10.12％；N2: 59.01, CO: 2.35 percent; trace amounts of sulfides and nitrogen oxides.
(2) Preparation of a flue gas decarboniser
120 g of diazabicyclooctane, 100 g of hydroxyethyl piperazine, 15 g of triethylene diamine, 15 g of tetraethylenepentamine, 10 g of lactic acid, 5 g of hydroquinone, 3 g of antimony potassium tartrate and 2 g of monoolein imidazoline are added into 500 ml of water, the mixture is uniformly stirred, and the distilled water is used for quantifying to 1000 g, so that the smoke decarbonizer is obtained.
Steps (3) and (4) were carried out for decarburization of flue gas, for desorption of a decarburization agent, and for measurement of absorption capacity, desorption amount and desorption rate in the same manner as in example 1, and the results are shown in Table 1.
Example 4
This example is used to illustrate the flue gas decarbonizer provided by the present invention.
(1) The composition of the simulated smoke is (volume): CO22：20.25％；O2：8.27％；H2O：10.12％；N2: 59.01, CO: 2.35 percent; trace amount of sulfide and oxynitride.
(2) Preparation of a flue gas decarboniser
100 g of diazabicyclooctane, 120 g of hydroxyethyl piperazine, 20 g of diethylenetriamine, 10 g of tetraethylenepentamine, 10 g of sodium lactate, 5 g of dodecyl hydroquinone, 2 g of antimony potassium tartrate and 3 g of monoolein imidazoline are added into 500 ml of water and stirred uniformly, and the amount of distilled water is quantified to 1000 g, so that the smoke decarbonizer is obtained.
Steps (3) and (4) were carried out for decarburization of flue gas, for desorption of a decarburization agent, and for measurement of absorption capacity, desorption amount and desorption rate in the same manner as in example 1, and the results are shown in Table 1.
Example 5
This example is used to illustrate the flue gas decarbonizer provided by the present invention.
(1) The composition of the simulated smoke is (volume): CO22：20.25％；O2：8.27％；H2O：10.12％；N2: 59.01, CO: 2.35 percent; trace amounts of sulfides and nitrogen oxides.
(2) Preparation of a flue gas decarboniser
100 g of diazabicyclooctane, 120 g of hydroxyethyl piperazine, 20 g of diethylenetriamine, 10 g of tetraethylenepentamine, 10 g of sodium lactate, 2 g of antimony potassium tartrate and 3 g of monoolein imidazoline are added into 500 ml of water, the mixture is uniformly stirred, and the amount of the mixture is quantified to 1000 g by using distilled water, so that the smoke decarbonizer is obtained.
Steps (3) and (4) were carried out for decarburization of flue gas, for desorption of a decarburization agent, and for measurement of absorption capacity, desorption amount and desorption rate in the same manner as in example 1, and the results are shown in Table 1.
Comparative example 1
This example is used to illustrate the flue gas decarbonizer provided by the present invention.
(1) The composition of the simulated smoke is (volume): CO22：20.25％；O2：8.27％；H2O：10.12％；N2: 59.01, CO: 2.35 percent; trace amounts of sulfides and nitrogen oxides.
(2) Preparation of a flue gas decarboniser
250 g of diazabicyclooctane, 5 g of dodecyl hydroquinone, 3 g of antimony potassium tartrate and 2 g of monooleline imidazoline are added into 500 ml of water, the mixture is uniformly stirred, and the distilled water is used for quantifying to 1000 g, so that the smoke decarbonizer is obtained.
Steps (3) and (4) were carried out for decarburization of flue gas, for desorption of a decarburization agent, and for measurement of absorption capacity, desorption amount and desorption rate in the same manner as in example 1, and the results are shown in Table 1.
Comparative example 2
This example is used to illustrate the flue gas decarbonizer provided by the present invention.
(1) The composition of the simulated smoke is (volume): CO22：20.25％；O2：8.27％；H2O：10.12％；N2: 59.01, CO: 2.35 percent; trace amounts of sulfides and nitrogen oxides.
(2) Preparation of a flue gas decarboniser
300 g of N-methyldiethanolamine, 1 g of dimethylethanolamine, 5 g of methylethanolamine and 10 g of dioxane are added into 500 ml of water and stirred uniformly, and the amount of the solution is quantified to 1000 g by using distilled water, so that the smoke decarbonizer is obtained.
Steps (3) and (4) were carried out for decarburization of flue gas, for desorption of a decarburization agent, and for measurement of absorption capacity, desorption amount and desorption rate in the same manner as in example 1, and the results are shown in Table 1.
Comparative example 3
This example is used to illustrate the flue gas decarbonizer provided by the present invention.
(1) The composition of the simulated smoke is (volume): CO22：20.25％；O2：8.27％；H2O：10.12％；N2: 59.01, CO: 2.35 percent; trace amounts of sulfides and nitrogen oxides.
(2) Preparation of a flue gas decarboniser
250 g of hydroxyethyl ethylenediamine, 100 g of 2-amino-2-methyl-1-propanol, 50 g of dimethylethanolamine, 50 g of ethanolamine, and 50 g of piperazine were added to 500 ml of water, stirred uniformly, and quantified to 1000 g with distilled water, thereby obtaining a flue gas decarbonizer.
Steps (3) and (4) were carried out for decarburization of flue gas, for desorption of a decarburization agent, and for measurement of absorption capacity, desorption amount and desorption rate in the same manner as in example 1, and the results are shown in Table 1.
TABLE 1
The results in table 1 show that the decarbonizer provided by the invention can be used for removing and recovering carbon dioxide in flue gas, and the desulfurization solution has the advantages of high purification degree, large absorption capacity, high absorption speed, high desorption rate, low regeneration energy consumption and the like.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The flue gas decarburization composition is characterized by comprising the following components:
the primary absorbent comprises diazabicyclooctane and diamine compounds containing hydroxyalkyl groups; in the main absorbent, the mass ratio of diazabicyclooctane to diamine compound containing hydroxyalkyl is 1: 0.05 to 2;
the diamine compound containing hydroxyalkyl is selected from one or more of hydroxyethyl ethylenediamine, hydroxypropyl ethylenediamine, hydroxyethyl piperazine, ethyl piperazine, 1, 4-bis (2-hydroxyethyl) piperazine, 1, 4-bis (2-hydroxypropyl) piperazine, N-dimethyl piperazine, N-ethyl piperazine and N, N-diethyl piperazine;
the activating agent is selected from one or more of diethylenetriamine, tetraethylenepentamine, triethylene tetramine and triethylene diamine; the corrosion inhibitor consists of metal oxide and mono-oil imidazoline;
the desorption auxiliary agent is selected from one or more of citric acid, sodium lactate, sodium acetate, sodium citrate and lactic acid; the metal oxide is selected from one or more of vanadate, metavanadate, vanadium pentoxide, basic ketone carbonate and antimony potassium tartrate; the mass ratio of the metal oxide to the monooleimidazoline is 1: (0.05-2);
the antioxidant is selected from one or more of 4-tert-butyl catechol, 2, 6-di-tert-butyl-p-cresol, acetone oxime, N, N-bis (2-hydroxyethyl) glycine, dodecyl hydroquinone, anthraquinone disulfonic acid and anthraquinone disulfonic acid sodium disulfonate.
2. The composition of claim 1, wherein the flue gas decarbonization composition comprises:
3. the composition of claim 1, wherein the flue gas decarbonization composition comprises:
4. a method of making a flue gas decarbonization composition in accordance with claim 1 comprising:
mixing the main absorbent, the activating agent, the desorption auxiliary agent, the corrosion inhibitor and water to obtain the smoke decarburization composition.
5. A method of decarbonizing flue gases, comprising:
contacting a mixed gas containing carbon dioxide with the decarburization composition as set forth in claim 1.
6. The decarburization method according to claim 5, wherein the conditions of the contact include: the temperature is 30-80 ℃, and the liquid-gas ratio is 0.05-3.0 kg/Nm3。
7. The decarburization method according to claim 5, wherein the contact is carried out in a countercurrent manner.
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| CN109173727B (en) * | 2018-10-31 | 2021-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for regenerating ineffective complexing denitration agent |
| CN109529543A (en) * | 2018-11-30 | 2019-03-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Fume desulfurizing agent and preparation method thereof and sulfur method |
| CN112143536A (en) * | 2019-06-27 | 2020-12-29 | 中石化南京化工研究院有限公司 | Absorption liquid for corrosion prevention of decarburization system in natural gas |
| EP4098348A4 (en) * | 2020-01-28 | 2024-02-28 | Tosoh Corporation | Composition for carbon dioxide separation and method for separating carbon dioxide |
| CN114699899B (en) * | 2022-04-07 | 2023-04-07 | 合肥工业大学 | Hydroxyalkyl piperazinyl compound organic amine carbon trapping agent |
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