CN107519735B - Composition for removing carbon dioxide from mixed gas and method for decarbonizing flue gas - Google Patents

Composition for removing carbon dioxide from mixed gas and method for decarbonizing flue gas Download PDF

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CN107519735B
CN107519735B CN201710719778.1A CN201710719778A CN107519735B CN 107519735 B CN107519735 B CN 107519735B CN 201710719778 A CN201710719778 A CN 201710719778A CN 107519735 B CN107519735 B CN 107519735B
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composition
flue gas
decarburization
desorption
weight
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CN107519735A (en
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邱正秋
黎建明
王建山
张小龙
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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
    • B01D53/1493Selection of liquid materials for use as absorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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
    • B01D53/1456Removing acid components
    • B01D53/1475Removing carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2252/00Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20Organic absorbents
    • B01D2252/205Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B01D2252/2053Other nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2

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; solution (II)0.1-5 parts by weight of an absorption aid; 25-95 parts by weight of water; the main absorbent is diazabicyclooctane; 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 as a main absorbent, diethylenetriamine, tetraethylenepentamine or triethylenediamine as an activating agent, and is combined with components such as a desorption auxiliary agent, and meanwhile, the composition has good effect of removing carbon dioxide by combining a specific proportion, and CO is good2High absorption capacity, high absorption speed, high decarburization rate and low desorption energy consumption.

Description

Composition for removing carbon dioxide from mixed gas and method for decarbonizing flue gas
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 and solid adsorbent adsorption decarburization technology, wherein the solvent absorption decarburization technology is the most attractive and widely applied technology so farSeparation techniques, current large scale CO2The 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 solution mainly comprises N-methyldiethanolamine aqueous solution and activating agent, wherein the activating agent comprises morpholine andpiperazine, wherein 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 and low desorption energy consumption.
The invention provides a smoke decarbonization composition, which comprises the following components:
Figure GDA0001472186180000021
the main absorbent is diazabicyclooctane;
the activating agent is selected from one or more of diethylenetriamine, tetraethylenepentamine, triethylene tetramine and triethylene diamine.
Preferably, the desorption auxiliary agent is one or more selected from citric acid, sodium lactate, sodium acetate, sodium citrate and lactic acid.
Preferably, the flue gas decarbonization composition further comprises a corrosion inhibitor; the corrosion inhibitor is 0.05-2 parts by weight.
Preferably, 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 dodecyl hydroquinone, anthraquinone disulfonic acid and anthraquinone disulfonic acid sodium sulfonate; and 0.05-5 parts by weight of antioxidant.
Preferably, the flue gas decarbonization composition comprises:
Figure GDA0001472186180000031
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 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; 25-95 parts by weight of water; the main absorbent is diazabicyclooctane; 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 as a main absorbent, diethylenetriamine, tetraethylenepentamine or triethylenediamine as an activating agent, and is combined with components such as a desorption auxiliary agent, and meanwhile, the composition has good effect of removing carbon dioxide by combining a specific proportion, and CO is good2High 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:
Figure GDA0001472186180000041
the main absorbent is diazabicyclooctane;
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. The source of said diazabicyclooctane is not limited in the present invention, and it may be commercially available.
The invention creatively adopts the diazabicyclooctane as a main absorption component, has 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 is used as a main absorption component, and is cooperatively matched with an activating agent with specific type and proportion, so that the diazabicyclooctane has good absorption effect on carbon dioxide, and CO (carbon monoxide)2High 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 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 flue gas decarburization composition provided by the invention preferably further comprises 0.05-2 parts by weight of a 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 prepared by the synergistic effect of the desorption auxiliary agent and the corrosion inhibitor, the main absorption component and the activator has good corrosion resistance.
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 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:
Figure GDA0001472186180000051
the flue gas decarburization composition of one embodiment of the invention comprises:
Figure GDA0001472186180000052
Figure GDA0001472186180000061
the flue gas decarburization composition of one embodiment of the invention comprises:
Figure GDA0001472186180000062
the flue gas decarburization composition of one embodiment of the invention comprises:
Figure GDA0001472186180000063
the flue gas decarburization composition of one embodiment of the invention comprises:
Figure GDA0001472186180000064
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; 25-95 parts by weight of water; the main absorbent is diazabicyclooctane; 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 as a main absorbent, diethylenetriamine, tetraethylenepentamine or triethylenediamine as an activating agent, and is combined with components such as a desorption auxiliary agent, and meanwhile, the composition has good effect of removing carbon dioxide by combining a specific proportion, 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 and water to obtain the smoke decarburization composition.
According to the preparation method of the flue gas decarburization composition, the main absorbent, the activating agent and the desorption auxiliary agent are added into water, so that the flue gas decarburization composition can be obtained.
When the composite also comprises the corrosion inhibitor, the main absorbent, the activating agent, the desorption auxiliary agent, the corrosion inhibitor and the water are mixed to obtain the smoke decarburization composition. Namely, the main absorbent, the activating agent, the desorption auxiliary agent and the corrosion inhibitor are added into water to obtain the smoke decarbonization composition.
When the composite also comprises an antioxidant, the main absorbent, the activating agent, the desorption auxiliary agent, the antioxidant, the corrosion inhibitor 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 the rich liquid 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, and performing heat exchangeHeating the desorption device to 95-120 ℃ for desorption again, enabling the desorbed liquid to flow into the bottom of the desorption device, discharging high-temperature desorption gas and water vapor from the top end of the desorption tower, then enabling the high-temperature desorption gas and the water vapor to enter a condenser and a vapor-liquid separator, returning condensed water which is cooled and separated from the desorption gas to the desorption tower, and obtaining 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
120 g of diazabicyclooctane, 30 g of tetraethylenepentamine, 10 g of citric acid, 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.
(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 flue gas decarburization is finished, putting the decarburization rich solution obtained in the step 3 into a three-neck flask, inserting a thermometer into one neck, introducing a smoke pipe into the bottom of the decarburization rich solution, introducing nitrogen into the smoke pipe at the speed of 2 × 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
Desorption rate-amount of carbon dioxide desorbed/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
Adding 120 g of diazabicyclooctane, 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 into 500 ml of water, uniformly stirring, and quantifying to 1000 g by using distilled water, thereby obtaining the smoke 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.
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, 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
220 g of diazabicyclooctane, 15 g of diethylenetriamine, 15 g of tetraethylenepentamine, 10 g of sodium acetate, 5 g of dodecyl hydroquinone, 3 g of antimony potassium tartrate and 2 g of monoolein imidazoline are added into 500 ml of water, stirred uniformly and 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.
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
220 g of diazabicyclooctane, 15 g of diethylenetriamine, 15 g of tetraethylenepentamine and 10 g of sodium acetate are added into 500 ml of water, stirred uniformly and quantified to 1000 g by using distilled water, thereby obtaining the smoke 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.
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
Figure GDA0001472186180000131
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 (6)

1. The flue gas decarburization composition is characterized by comprising the following components:
Figure FDA0002425196750000011
the main absorbent is diazabicyclooctane;
the activating agent is selected from one or more of diethylenetriamine, tetraethylenepentamine, triethylene tetramine and triethylene diamine;
the flue gas decarbonization composition also comprises a corrosion inhibitor; 0.05-2 parts by weight of corrosion inhibitor; 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);
the desorption auxiliary agent is selected from one or more of citric acid, sodium lactate, sodium acetate, sodium citrate and lactic acid;
the antioxidant is selected from one or more of dodecyl hydroquinone, anthraquinone disulfonic acid and anthraquinone disulfonic acid sodium sulfonate.
2. The composition of claim 1, wherein the flue gas decarbonization composition comprises:
Figure FDA0002425196750000012
3. 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 antioxidant, the corrosion inhibitor and water to obtain the smoke decarburization composition.
4. A method of decarbonizing flue gases, comprising:
contacting a mixed gas containing carbon dioxide with the decarburization composition as set forth in claim 1.
5. The decarburization method according to claim 4, wherein the conditions of the contact include: the temperature is 30-80 ℃, and the liquid-gas ratio is 0.05-3.0 kg/Nm3
6. The decarburization method according to claim 4, wherein the contact is carried out in a countercurrent manner.
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