CN105854529A - Non-aqueous solvent carbon dioxide capture liquid, method and system - Google Patents
Non-aqueous solvent carbon dioxide capture liquid, method and system Download PDFInfo
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- CN105854529A CN105854529A CN201610405254.0A CN201610405254A CN105854529A CN 105854529 A CN105854529 A CN 105854529A CN 201610405254 A CN201610405254 A CN 201610405254A CN 105854529 A CN105854529 A CN 105854529A
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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
- B01D53/18—Absorbing units; Liquid distributors therefor
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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
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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
- B01D2252/202—Alcohols or their derivatives
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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
- B01D2252/202—Alcohols or their derivatives
- B01D2252/2021—Methanol
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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
- B01D2252/202—Alcohols or their derivatives
- B01D2252/2023—Glycols, diols or their derivatives
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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
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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
- B01D2252/20421—Primary amines
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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
- B01D2252/20426—Secondary amines
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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
- B01D2252/20431—Tertiary amines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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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]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention provides a non-aqueous solvent carbon dioxide capture liquid, method and system and belongs to the field of carbon dioxide recovery. The non-aqueous solvent carbon dioxide capture liquid is prepared from, by weight, 60-80% of organic solvent and 20-40% of composite organic amine. The organic solvent comprises low alcohol and/or ethanediol. The composite organic amine comprises hindrance amine and active amine. The weight ratio of active amine to hindrance amine is (0.4-70):1. Hindrance amine contains primary amine or at least one piece of secondary amine, secondary amine is connected with secondary carbon atoms or tertiary carbon atoms, and primary amine is directly connected with the tertiary carbon atoms. Active amine comprises primary amine or secondary amine. The non-aqueous solvent carbon dioxide capture liquid has relatively low carbon dioxide desorption temperature and relatively low solvent specific heat capacity and latent heat of evaporation, therefore, energy consumption in the desorption process is effectively reduced, and the comprehensive capture cost of carbon dioxide is reduced.
Description
Technical field
The present invention relates to carbon dioxide recovery field, in particular to a kind of nonaqueous solvent titanium dioxide
Carbon trapping solution, method and system.
Background technology
In all of greenhouse gases, CO2Accounting for greenhouse gas emission total amount about 94%, greenhouse is imitated by it
The contribution answered has exceeded 60%, CO2A large amount of discharges cause global warming, extreme weather frequency
Send out the extensive attention waiting series of problems to cause international community.The most how to CO2Carry out efficiently
Trapping and utilize thus reducing discharge is the problem that whole world researcher is endeavoured to solve.
The CO that at present chemical absorption method is that technology is the most ripe, is most widely used2Capture method, and
Organic amine absorption process therein is because absorption rate is fast, absorptive capacity big, good absorbing effect, recovery product
Purity high has become widely used mainstream technology.
Chemical absorption method is mainly by absorbing carbon dioxide under the conditions of relative low temperature, passes through the most again
High temperature makes the mode of carbon dioxide desorbing to trap the carbon dioxide in various mixed gas.At present, make
More carbon-dioxide absorbent organic amine aqueous solution, by use various single or compound having
Machine amine aqueous solution, as absorbent, absorbs CO at relatively low temperature2, at high temperature carry out desorbing.But
It is, owing to organic amine aqueous solution containing substantial amounts of water, to cause the regeneration of absorption solution mistake at desorption under high temperature
Cheng Zhong, needs to be heated between 105～120 DEG C the organic amine aqueous solution absorbing carbon dioxide.Water
Sensible heat (specific heat capacity) and latent heat are big, and therefore, substantial amounts of water is heated and evaporates, and causes more than 20%
Reactivation heat the sensible heat of water and evaporation latent heat are provided, and the water of evaporation needs with a large amount of in regeneration overhead
Condensed water condense out thus keep regenerator in water balance.The heat absorption evaporation of water and low temperature cold
Coagulate and will consume substantial amounts of energy, cause regeneration energy consumption of a relatively high, and hot environment also causes inhaling
The series of problems such as the degraded of receipts agent and equipment corrosion.Along with the continued downturn of crude oil price, petrochemical industry is looked forward to
Industry is to CO2Trapping technique have higher requirement in terms of environmental protection and energy saving, the height of prior art is again
Raw energy consumption has become the bottleneck that restriction organic amine absorption process is the most persistently applied, reduces the most further again
Raw energy consumption is the emphasis of this area research.
Summary of the invention
It is an object of the invention to provide a kind of nonaqueous solvent collecting carbonic anhydride liquid, to realize titanium dioxide
Carbon carries out desorbing, and aqueous solution, the sensible heat of nonaqueous solvent and latent heat relatively at relatively low temperature
Low, thus can effectively reduce trapping cost and the trapping energy consumption of carbon dioxide.
Another object of the present invention is to be supplied to a kind of side utilizing above-mentioned trapping solution trapping carbon dioxide
Method, uses above-mentioned trapping solution absorbing carbon dioxide, then makes carbon dioxide desorbing by heating, with reality
Existing technique is simpler, energy consumption smaller traps carbon dioxide.
Another object of the present invention is to be supplied to a kind of trapping system for implementing above-mentioned capture method
System, to realize reducing the desorption temperature of the carbon dioxide in nonaqueous solvent collecting carbonic anhydride liquid, reduces
Carbon dioxide comprehensively trap cost.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage:
Organic solvent 60～80%；Compound organic amine 20～40%；
Organic solvent includes lower alcohol and/or ethylene glycol；
Compound organic amine includes bulky amine and reactive amines；
The weight ratio of reactive amines and bulky amine is 0.4～70:1, bulky amine contain primary amino radical or at least one
Secondary amine, at least one secondary amine is connected with secondary carbon or tertiary carbon atom, and primary amino radical is directly and tertiary carbon
Atom connects；
Reactive amines includes primary amine or secondary amine.
Heretofore described lower alcohol is carbon number room temperature liquid alcohol below 6, such as, methanol,
Ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, hexanol etc..
A kind of utilize above-mentioned nonaqueous solvent collecting carbonic anhydride liquid trapping carbon dioxide method, including with
Lower step:
Make carbonated pending gas contact with above-mentioned nonaqueous solvent collecting carbonic anhydride liquid, catch
Liquid collecting absorbing carbon dioxide forms pregnant solution；Heating pregnant solution makes carbon dioxide desorbing from pregnant solution,
Form lean solution and stripping gas, collect stripping gas.
Present invention also offers the system of a kind of trapping for above-mentioned collecting carbonic anhydride method, including
Absorption plant and desorption apparatus.Absorption plant include absorption tower, for by top, absorption tower to absorption tower
Input the spray equipment of trapping solution and for by inputting carbonated bottom absorption tower to absorption tower
The air pump of pending gas.Air pump is connected with the bottom on absorption tower by pipeline.Spray equipment is arranged
In the tower top on absorption tower.Desorption apparatus includes desorber and the Multi-layer warming tower being arranged in desorber
Plate.Desorber is provided by the pipeline of rich solution pump and is connected with absorption tower.
Beneficial effects of the present invention:
The nonaqueous solvent collecting carbonic anhydride liquid that the present invention provides is the trapping solution of non-aqueous system, and it uses
Lower alcohol is that the compound organic amine of solvent dissolving is made.Nonaqueous solvent titanium dioxide compared to aqueous systems
Carbon trapping solution, the trapping solution that the present invention provides realizes the desorbing of carbon dioxide at relatively low temperature,
And relative aqueous solution, specific heat capacity and the evaporation latent heat of nonaqueous solvent are the most relatively low, thus effectively reduce
Energy consumption during collecting carbonic anhydride, and nonaqueous solvent collecting carbonic anhydride liquid is applicable not only to electricity
The low dividing potential drop carbon dioxide in flue gas such as factory's flue gas, regeneration fume from catalytic cracking, cement plant flue gas
Removing, it is possible to be applied to the removing of the elevated pressures carbon dioxide such as natural gas, hydrogen manufacturing synthesis gas.
The desorption temperature of the trapping solution that the present invention provides can reach 70～95 DEG C, the most existing ethanol
The desorption temperature 115 of amine aqueous solution～120 DEG C, also below in patent CN201210034134.6
100～105 DEG C.Owing to desorption temperature is relatively low, therefore, it is to avoid in hot environment, trapping solution is to setting
Standby corrosion, thus improve the service life of equipment, reduce trapping solution by high temperature action simultaneously
Decompose the loss caused.
Additionally, due to trapping solution is non-aqueous system, trapping carbon dioxide process will not produce sewage,
Thus it is made without recovery or the decontamination process of sewage, which simplifies the trapping work of carbon dioxide
Process flow, also correspondingly reduces recovery and the processing cost of sewage.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below will be to required in embodiment
Accompanying drawing to be used is briefly described, it will be appreciated that the following drawings illustrate only some of the present invention
Embodiment, is therefore not construed as the restriction to scope, for those of ordinary skill in the art,
On the premise of not paying creative work, it is also possible to obtain other relevant accompanying drawings according to these accompanying drawings.
The theory structure schematic diagram of the carbon dioxide capture system that Fig. 1 provides for the embodiment of the present invention 13.
Description of reference numerals:
Carbon dioxide capture system 100；Heat exchanger 101；Absorption tower 102；Spray equipment 103；Rich
Liquid pump 104；Desorber 105；Heating column plate 106；Condensing unit 107；Air pump 108；Waste gas recovery
Tank 109；Trapping solution flows to 111；Pending gas flow 112；Absorption tower 201；Desorber 202.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below will be to this
Technical scheme in bright embodiment is clearly and completely described.Unreceipted actual conditions in embodiment
Person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production of instrument
Manufacturer person, being can be by the commercially available conventional products bought and obtain.
Below nonaqueous solvent collecting carbonic anhydride liquid, the method and system of the embodiment of the present invention are had
Body explanation.
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage:
Organic solvent 60～80%；Compound organic amine 20～40%.Wherein, organic solvent includes lower alcohol
And/or ethylene glycol.Compound organic amine includes bulky amine and reactive amines, and the weight of reactive amines and bulky amine
Ratio is 0.4～70:1.Bulky amine contains primary amino radical or at least one secondary amine.At least one secondary amine is with secondary
Carbon atom or tertiary carbon atom connect.Primary amino radical is directly connected with tertiary carbon atom.Reactive amines include primary amine or
Secondary amine.It is preferred that the content of organic solvent is 64～75wt%, the content of compound organic amine is
25～36wt%.
Bulky amine is with multiple non-linear substituted radicals with sterically hindered structure on a kind of nitrogen-atoms
Alcamine compound.Due to the effect of space steric effect, resistance amine and the product of carbon dioxide
Stability relatively poor, such that it is able to fast desorption under the relatively gentle disturbed condition in the external world.
Due to the existence of space steric effect, compared to primary amine and the secondary amine of chain, bulky amine and carbon dioxide
Reactivity be under some influence, therefore, use reactive amines as activator, improve bulky amine with
The reactivity of carbon dioxide, improves reaction rate, reduces desorption temperature.By bulky amine and activity
The cooperation of amine so that the carbon-dioxide absorbent in trapping solution is simultaneously with high absorption rate and suction
Receipts amount, and also it is easier to desorbing.
Existing nonaqueous solvent collecting carbonic anhydride liquid is many with water as solvent, by water dissolution carbon dioxide
Absorbent forms, and water content therein has reached about 70wt%.Owing to water has of a relatively high
Latent heat and sensible heat, after water system trapping solution absorbing carbon dioxide, need to reach during heating desorption
The high desorption temperature of 100～120 DEG C.High desorption temperature causes the increase of energy consumption in desorption process, and
The easy explosive evaporation of the water capacity in desorption process, thus consume substantial amounts of energy.Additionally, due to need higher
Desorption temperature, is easily caused carbon-dioxide absorbent under high temperature action and degrades, and causes equipment rotten simultaneously
The problems such as erosion.Trapping solution in the present invention, with lower alcohol as solvent, is conducive to improving the problems referred to above.One
Aspect, has the relatively good compatibility between trapping solution and bulky amine and reactive amines, thus, it is more easy to
Mutually immiscible, and in the trapping solution formed, the dispersion of each composition is more uniform.On the other hand, lower alcohol
Latent heat and sensible heat are lower for water, so that the desorption temperature of carbon dioxide declines so that solve
The energy consumption being drawn through journey reduces.Owing to desorption temperature is low, desorption process is on bulky amine and the impact of reactive amines
Little, reduce bulky amine and the oxidation consumption problem of reactive amines and the etching problem of equipment.
The selection of bulky amine has multiple, preferably employs piperidines, piperazine, 2-amino-2-methyl-1-in the present invention
Propanol, 3-amino-3-methyl-1-butanol, 3-amino-3-methyl-2-butanol, 2-piperidine carbinols and 2-piperazine
One or more in pyridine ethanol.Reactive amines preferably employ serine, serine salt, monoethanolamine,
Appointing in 2-methylaminoethanol, piperazine, 2-Methylaminoethanol, 2-methylamino piperazine and diethanolamine
A kind of.
Lower alcohol preferably employs one or more of methanol, ethanol, propanol or butanol, the most excellent
Choosing uses ethanol, and it uses safety non-toxic, and price is lower.When selecting two kinds of alcohol as solvent,
The mass ratio of two kinds of alcohol is 1:10～10:1, such as, when ethanol and ethylene glycol are as solvent, and the matter of ethanol
Amount and the mass ratio of ethylene glycol be 1:10～10:1, methanol and ethanol as solvent time, the quality of methanol
It is 1:10～10:1 with the mass ratio of ethanol.When using containing the solvent of two or more compositions, in system
During standby trapping solution, preferably take to dissolve by several times compound organic amine with different solvents, the most again by difference
Secondary lysigenous solution mixes.
Owing to numerous hardwares can be related to during the trapping of carbon dioxide, therefore, trapping
Liquid may produce certain corrosion to equipment, causes the damage of equipment.In order to alleviate trapping solution to setting
Standby etching problem, it is also possible to add anticorrosive reagent in trapping solution, reduces the corrosivity of trapping solution.
Trapping solution can add corrosion inhibiter, such as, can use alkyl imidazoline quaternary ammonium salt, specifically can use
Octadecylimidazoline quaternary amine salt form corrosion inhibiter, lauryl imidazoline quaternary amine salt form corrosion inhibiter.For
Some pending gases containing oxidizing gases, it is also possible to add antioxidative composition in trapping solution,
To avoid the problem that in trapping solution, compound organic amine is oxidized.The antioxidant added in trapping solution is such as
Can be sodium sulfite, sodium pyrosulfite, sodium sulfite or sodium thiosulfate.
When being added with corrosion inhibiter and antioxidant in trapping solution, in trapping solution, the content of each component is excellent
Elect following percentage by weight as.Organic solvent 70～75%, compound organic amine 22～28%, corrosion inhibiter
0.05～5%, described antioxidant 0.05～5%.
The condition that recommends of the nonaqueous solvent collecting carbonic anhydride liquid that the present invention provides is: absorb temperature
40～55 DEG C, absorption pressure 0.1～0.5MPa, desorption temperature 70～95 DEG C, desorption pressures 0.1MPa.
At identical CO2In the case of capture rate, such as the CO of 95%2Capture rate, absorbing temperature be
50 DEG C, under conditions of the mass concentration of compound organic amine is 36% in trapping solution, compound organic amine-methanol
The desorption temperature of trapping solution is 74 DEG C, and the desorption temperature of compound organic amine-ethanol trapping solution is 83 DEG C, and
The desorption temperature of compound organic amine-water absorbent then needs 102 DEG C.
At CO2When capture rate is 95%, the compound organic amine that mass concentration is 25% of compound organic amine-
The desorption temperature of water trapping solution is 102 DEG C, and desorbing energy consumption is 3.5GJ/tCO2；And corresponding being compounded with
The desorption temperature of machine amine-methanol trapping solution is 74 DEG C, and desorbing energy consumption is 2.71GJ/tCO2, desorbing energy consumption
Reduce about 22%.The desorption temperature about 95 DEG C of compound organic amine-ethylene glycol trapping solution.Due to ethylene glycol
Boiling point higher (197.3 DEG C), without evaporation latent heat, and the specific heat capacity of ethylene glycol is far below water, desorbing energy consumption
For 2.55GJ/tCO2, desorbing energy consumption is lower.The desorbing temperature of compound organic amine-ethylene glycol-ethanol trapping solution
Degree is 85 DEG C, and desorbing energy consumption is 2.60GJ/tCO2, is below using the compound organic amine with water as solvent
The desorbing energy consumption of-water trapping solution.
Present invention also offers a kind of collecting carbonic anhydride method, comprise the following steps:
Make carbonated pending gas contact with above-mentioned nonaqueous solvent collecting carbonic anhydride liquid, catch
Liquid collecting absorbing carbon dioxide forms pregnant solution, and heating pregnant solution makes carbon dioxide desorbing from pregnant solution,
Form lean solution and stripping gas, collect stripping gas.
It is preferred that pending gas takes the mode inversely contacted with trapping solution, so that both contacts
Time is longer, and both can contact more fully, the biography more fully of the carbon dioxide in pending gas
Matter, thus improve the trapping solution absorption to carbon dioxide.
Have in bulky amine in trapping solution and the nitrogen-atoms of reactive amines active hydrogen atom can directly with
Carbon dioxide reacts and generates the intermediate product that stability is relatively low, and it is easy desorbing two after being heated
Carbonoxide.Therefore, carbon dioxide and bulky amine and the reaction heat of reactive amines are made by heating pregnant solution
Mechanical balance is broken, and separates so that carbon dioxide is desorbed.
During heating desorption, need to heat pregnant solution with desorbing carbon dioxide, lower alcohol
Solvent can be a small amount of evaporation, thus causing the desorption gas collected is the mixed of carbon dioxide and solvent gas
Closing gas, this results in follow-up needs and carries out separating, purifying, and increases operation sequence.Ask for above-mentioned
Topic, carries out condensation process to the gas collected after desorbing in the present invention, makes the organic solvent in gas cold
Coagulate for liquid, thus and carbon dioxide separation, and then obtain the carbon dioxide that purity is of a relatively high.
Additionally, and the condensing temperature of carbon dioxide is relatively low, therefore, conventional condensing mode is difficult to
It is carried out Operation for liquefaction, and this allows for carbon dioxide in condensation process and is difficult to the coldest with organic solvent
Solidifying and mix, so that it is guaranteed that the content of the carbon dioxide in condensed fluid is little, it is to avoid to reclaiming, utilizing
The impact of organic solvent.The temperature of the gas produced during heating desorption carbon dioxide is higher than room temperature,
It is therefore possible to use room temperature water carries out condensation operation as coolant.
Owing to the reaction of trapping solution and carbon dioxide is influenced by temperature relatively big, in absorption process, as
Really the temperature of trapping solution or the temperature of pending gas are too high, can affect the normal trapping of carbon dioxide,
Reduce amount of collected and the efficiency of carbon dioxide.
Therefore, the temperature of trapping solution and carbonated pending gas is unsuitable too high, in the present invention
Being used in 40～55 DEG C of absorptions carrying out carbon dioxide, the preferable temperature of trapping solution and pending gas is
40～55 DEG C.Therefore, before making carbonated pending gas inversely contact with trapping solution, also
Pending gas can be carried out cooling process.By the temperature of pending gas is reduced so that it is right
The thermal agitation of trapping solution is less, prevents a large amount of evaporations and the oxidation of trapping solution, obtains of a relatively high simultaneously
Reaction rate.
For the capture method of above-mentioned carbon dioxide, present invention also offers corresponding collecting carbonic anhydride
System is in order to implement above-mentioned capture method.
Specifically, carbon dioxide capture system includes absorption plant and desorption apparatus.Wherein, dress is absorbed
Put and include absorption tower, for being inputted spray equipment and the use of trapping solution to absorption tower by top, absorption tower
In by the air pump inputting carbonated pending gas bottom absorption tower to absorption tower.
Air pump is connected with the bottom on absorption tower by pipeline.Spray equipment is arranged in the tower top on absorption tower.
Desorption apparatus includes desorber and the Multi-layer warming column plate being arranged in desorber, and desorber is by arranging
The pipeline having rich solution pump is connected with absorption tower.
Further, trapping system also includes condensing unit and heat exchanger, and condensing unit passes through pipeline
Being connected with the gas outlet of desorber, air pump is connected with absorption tower by heat exchanger.
In the present invention, during the trapping of carbon dioxide, the absorption temperature of the carbon dioxide absorbed is
Being preferably 40～55 DEG C, absorption pressure is preferably 0.1～0.5MPa.The carbon dioxide desorbing of desorber
Temperature is preferably 70～95 DEG C, and desorption pressures is preferably 0.1～0.3MPa.
Embodiment 1
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage: 2kg
2-amino-2-methyl-1-propanol, the diethanolamine of 5.5kg, the ethanol of 30kg.This nonaqueous solvent two
The manufacture method of carbonoxide trapping solution is as follows: 2-amino-2-methyl-1-propanol and diethanolamine are joined
In ethanol, being sufficiently stirred for preparing trapping solution, the desorption temperature of its carbon dioxide is 83 DEG C.
Embodiment 2
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage:
The 2-amino-2-methyl-1-propanol of 52.6kg, the diethanolamine of 0.8kg, the ethanol of 80kg.This is non-aqueous
The manufacture method of solvents carbon dioxide trapping solution is as follows: by 2-amino-2-methyl-1-propanol and diethanolamine
Joining in ethanol, be sufficiently stirred for preparing trapping solution, the desorption temperature of its carbon dioxide is 86 DEG C.
Embodiment 3
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage:
The 2-piperidine ethanol of 12.8kg, the piperazine of 1.3kg, the methanol of 33kg.This nonaqueous solvent carbon dioxide is caught
The manufacture method of liquid collecting is as follows: joins in methanol by 2-piperidine ethanol and diethanolamine, is sufficiently stirred for
Preparing trapping solution, the desorption temperature of carbon dioxide is 70 DEG C.
Embodiment 4
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage: 17kg
2-piperidine ethanol, the diethanolamine of 1kg, the methanol of 32kg.This nonaqueous solvent collecting carbonic anhydride
The manufacture method of liquid is as follows: join in methanol by 2-piperidine ethanol and diethanolamine, is sufficiently stirred for system
Obtaining trapping solution, the desorption temperature of its carbon dioxide is 72 DEG C.
Embodiment 5
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage: 4kg
2-amino-2-methyl-1-propanol, the 2-piperidine ethanol of 3.2kg, the diethanolamine of 0.1kg, 22kg
Ethylene glycol.The manufacture method of this nonaqueous solvent collecting carbonic anhydride liquid is as follows: by 2-amino-2-methyl-1-
Propanol, 2-piperidine ethanol and diethanolamine join in ethylene glycol, are sufficiently stirred for preparing trapping solution, its
The desorption temperature of carbon dioxide is 95 DEG C.
Embodiment 6
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage: 2kg
2-amino-2-methyl-1-propanol, the piperazine of 1.8kg, the 2-methylaminoethanol of 7.5kg, the second of 20kg
Glycol, the ethanol of 10kg.The manufacture method of this nonaqueous solvent collecting carbonic anhydride liquid is as follows: by 2-ammonia
Base-2-methyl isophthalic acid-propanol, piperazine and 2-methylaminoethanol join in the mixed liquor of ethylene glycol and ethanol,
Being sufficiently stirred for preparing trapping solution, the desorption temperature of its carbon dioxide is 85 DEG C.
Embodiment 7
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage: 1kg
Piperidines, the piperazine of 0.8kg, the 2-methylaminoethanol of 4.2kg, the ethylene glycol of 21kg.This non-aqueous
The manufacture method of agent collecting carbonic anhydride liquid is as follows: piperidines, piperazine and 2-methylaminoethanol are added
In ethylene glycol, being sufficiently stirred for preparing trapping solution, the desorption temperature of its carbon dioxide is 94 DEG C.
Embodiment 8
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage: 6kg
Piperidines, the piperazine of 4.9kg, the monoethanolamine of 1.8kg, the methanol of 27kg.This nonaqueous solvent dioxy
The manufacture method changing carbon trapping solution is as follows: join in methanol by piperidines, piperazine and monoethanolamine,
Being sufficiently stirred for preparing trapping solution, the desorption temperature of its carbon dioxide is 74 DEG C.
Embodiment 9
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage: 12kg
Piperidines, the monoethanolamine of 14kg, the methanol of 70kg, the octadecylimidazoline quaternary amine of 1.6kg,
The sodium pyrosulfite of 0.4kg.The manufacture method of this nonaqueous solvent collecting carbonic anhydride liquid is as follows: by piperidines,
Monoethanolamine, octadecylimidazoline quaternary amine and sodium pyrosulfite join in methanol, fully stir
Mixing obtains trapping solution, and the desorption temperature of its carbon dioxide is 73 DEG C.
Embodiment 10
A kind of nonaqueous solvent collecting carbonic anhydride liquid, the following components including by weight percentage: 22kg
Piperidines, the monoethanolamine of 2kg, the methanol of 75kg, the octadecylimidazoline quaternary amine of 0.5kg,
The sodium sulfite of 0.5kg.The manufacture method of this nonaqueous solvent collecting carbonic anhydride liquid is as follows: by piperidines,
Monoethanolamine, octadecylimidazoline quaternary amine and sodium pyrosulfite join in methanol, fully stir
Mixing obtains trapping solution, and the desorption temperature of its carbon dioxide is 72 DEG C.
Comparative example 1
The monoethanolamine formation of the piperidines of 6kg, the piperazine of 2kg, 1kg is dissolved with 27kg water for solvent
Water system trapping solution, its desorption temperature is 102 DEG C.
Embodiment 11
A kind of collecting carbonic anhydride method, comprises the following steps: first, makes the carbonated of 40 DEG C
Volume content be 20% the nonaqueous solvent collecting carbonic anhydride liquid that provides of flue gas and embodiment 3 in pressure
Strong is contact under conditions of 0.1MPa, and trapping solution absorbing carbon dioxide forms pregnant solution.Secondly, exist
Under the conditions of 0.1MPa, heating pregnant solution is to 70 DEG C, makes carbon dioxide desorbing from pregnant solution, forms lean solution
And stripping gas, collect stripping gas, complete the trapping to carbon dioxide.
Embodiment 12
A kind of collecting carbonic anhydride method, comprises the following steps: first, by the carbon dioxide body of 100 DEG C
Long-pending content be 11% flue gas be cooled to 50 DEG C, the most again with embodiment 5 provide nonaqueous solvent two
Carbonoxide trapping solution contacts under conditions of 0.2MPa, and trapping solution absorbing carbon dioxide forms pregnant solution.
Secondly, heating pregnant solution under the conditions of 0.06MPa is 95 DEG C to temperature, makes carbon dioxide from pregnant solution
Middle desorbing, forms lean solution and stripping gas, collects stripping gas.Again, the stripping gas that collection obtains is entered
Row reflux cooling to 20 DEG C, regather gas, complete the trapping to carbon dioxide.
Controlled trial 1
Subjects: temperature is 40 DEG C, the flue gas of the volume content 10% of carbon dioxide.
Test method: the carbon dioxide in flue gas is trapped according to the method for embodiment 11, respectively
The nonaqueous solvent collecting carbonic anhydride liquid and first using embodiment 1 to embodiment 8 to be provided compares
Trapping solution, the second comparison trapping solution carry out collecting carbonic anhydride to flue gas.
Wherein, first comparison trapping solution be made by following methods: by the 2-piperidine ethanol of 20kg,
The piperazine of 20kg, the lauryl imidazoline quaternary amine salt form corrosion inhibiter of 0.2kg, the thiosulfuric acid of 0.2kg
Sodium joins in the deionized water of 49.6kg, is heated to 30 DEG C, is sufficiently stirred for, to obtain final product.Second comparison
Trapping solution is made by following methods: take the 2-amino-2-methyl-1-propanol of 30kg, 20kg successively
2-piperidine ethanol, the diethanolamine of 5kg, the octadecylimidazoline quaternary amine salt form corrosion inhibiter of 0.5kg,
The sodium sulfite of 0.5kg, joins in 44.0kg deionized water, is heated to 60 DEG C, is sufficiently stirred for
45min, to obtain final product.
Different trapping solutions are as shown in table 1 to the trapping effect of carbon dioxide in flue gas.
Table 1 trapping solution trapping effect to carbon dioxide
As seen from the above table, the nonaqueous solvent compared to water system of the collecting carbonic anhydride agent that the present invention provides
Collecting carbonic anhydride liquid, has the lowest desorption temperature, and equilibrium solution pipette is the highest.
Embodiment 13
Refering to Fig. 1, present embodiments provide a kind of carbon dioxide capture system 100, including waste gas recovery
Tank 109, absorption plant 201 and desorption apparatus 202.
Wherein, absorption plant 201 include absorption tower 102, for by top, absorption tower 102 to absorption tower
The spray equipments 103 of 102 input trapping solutions and for by defeated to absorption tower 102 bottom absorption tower 102
Enter the air pump 108 of carbonated pending gas.
Air pump 108 is connected with the bottom on absorption tower 102 by pipeline.Spray equipment 103 is arranged at suction
Receiving in the tower top of tower 102, spray equipment 103 includes interconnective tube for transfusion and shower, transfusion
Pipe connects formation infusion channel with shower, and connects with the tube chamber of extraneous trapping solution feeding pipeline.Useless
Gas recycling can 109 is connected with the waste gas delivery outlet on absorption tower 102.Desorption apparatus 202 includes desorber
105 and the Multi-layer warming column plate 106 that is arranged in desorber 105, desorber 105 is provided by richness
The pipeline of liquid pump 104 is connected with absorption tower 102.
Above-mentioned carbon dioxide capture system 100 can take the trapping that following method carries out carbon dioxide, its
In, trapping solution flow to 111 and pending gas flow 112 refer to Fig. 1.
Nonaqueous solvent collecting carbonic anhydride liquid is entered by the tower top on absorption tower 102 by spray equipment 103
Row spray, passes through air pump 108 by absorption tower 102 by the pending gas containing carbon dioxide simultaneously
Tower rising pouring enters.Trapping solution is moved at the bottom of tower by the tower top on absorption tower 102, correspondingly, and pending gas
Moved to tower top by the bottom of the tower on absorption tower 102.
Trapping solution and pending gas make move toward one another on absorption tower 102, by contacting with each other, and then
Mass transfer and reaction, trapping solution absorbs the carbon dioxide in pending gas and forms pregnant solution, and passes through
Export at the bottom of the tower on absorption tower 102.Through deviating from the pending gas of carbon dioxide via absorption tower 102
Tower top export and enter storage in waste gas recovery tank 109.
In pregnant solution is input to desorber 105 by pipeline under the effect of rich solution pump 104 and heating tower
Plate 106 contacts, and heating column plate 106 produces heat effect to pregnant solution, so that in pregnant solution
The intermediate product decomposes that carbon dioxide and amine are formed, carbon dioxide desorbing forms lean solution and stripping gas
Body, desorption gas is exported by the tower top of desorber 105, and lean solution resides in desorber 105, or
Carry out storing or secondary utilization by discharging at the bottom of tower.
Due to the difference of the character of carbonated pending gas, its temperature has different difference,
When its temperature too high or too low time, the trapping solution absorbance to carbon dioxide can be reduced.Therefore, right
The temperature of pending gas is controlled, and is conducive to improving the trapping solution absorption to carbon dioxide.In order to
Lowering the temperature pending gas, carbon dioxide capture system 100 also includes heat exchanger 101, air pump
108 are connected with absorption tower 102 by heat exchanger 101.When carbon dioxide is trapped, first will
Pending gas, through heat exchanger 101 regulating and controlling temperature, when temperature reaches requirement, is re-introduced into absorption
In tower 102.
Further, owing to the desorption process of carbon dioxide relates to heating operation, therefore, rich solution warp
After crossing carbon dioxide desorbing formed gas in can mix the organic solvent in trapping solution, organic solvent with
The carbon dioxide desorbed is discharged, thus causes the loss of trapping solution.In order to trapping solution is carried out back
Receive and utilize, utilize simultaneously and reclaim the higher carbon dioxide of purity.Preferably to the gas produced in desorption process
Body carries out condensation operation.Such as, desorber 105 gas exported is cooled down by condenser,
The organic solvent condensate in gas is made to be that liquid separates with gaseous carbon dioxide by cooling.The present embodiment
In, carbon dioxide capture system 100 is provided with condensing unit 107, and condensing unit 107 is by pipe
Road is connected with the gas outlet of desorber 105.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for
For those skilled in the art, the present invention can have various modifications and variations.All essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement etc. made, should be included in the present invention
Protection domain within.
Claims (10)
1. a nonaqueous solvent collecting carbonic anhydride liquid, it is characterised in that include by weight percentage
The following components of meter:
Organic solvent 60～80%；Compound organic amine 20～40%；
Described organic solvent includes lower alcohol and/or ethylene glycol；
Described compound organic amine includes the weight of bulky amine and reactive amines, described reactive amines and described bulky amine
Amount ratio is 0.4～70:1；
Described bulky amine contains primary amino radical or at least one secondary amine, and at least one secondary amine described is with secondary
Carbon atom or tertiary carbon atom connect, and described primary amino radical is directly connected with tertiary carbon atom；
Described reactive amines includes primary amine or secondary amine.
Nonaqueous solvent collecting carbonic anhydride liquid the most according to claim 1, it is characterised in that institute
State bulky amine include piperidines, piperazine, 2-amino-2-methyl-1-propanol, 3-amino-3-methyl-1-butanol,
One or more in 3-amino-3-methyl-2-butanol, 2-piperidine carbinols and 2-piperidine ethanol.
Nonaqueous solvent collecting carbonic anhydride liquid the most according to claim 1 or claim 2, it is characterised in that
Described reactive amines includes serine, piperazine, serine salt, monoethanolamine, 2-methylaminoethanol, N-
Any one or more in methyl-ethanolamine, 2-methylamino piperazine and diethanolamine.
Nonaqueous solvent collecting carbonic anhydride liquid the most according to claim 1, it is characterised in that institute
State nonaqueous solvent collecting carbonic anhydride liquid and also include that corrosion inhibiter and antioxidant, described antioxidant include
Sodium sulfite, sodium pyrosulfite, sodium sulfite or sodium thiosulfate, described corrosion inhibiter includes alkyl
Imidazoline quaternary ammonium salt, the weight percent content of each component is as follows:
Described organic solvent 70～75%, described compound organic amine 22～28%, described corrosion inhibiter
0.05～5%, described antioxidant 0.05～5%.
Nonaqueous solvent collecting carbonic anhydride liquid the most according to claim 1, it is characterised in that institute
State lower alcohol selected from methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol,
One or more in hexanol, when described organic solvent is made up of two kinds of solvents, the matter of two kinds of solvents
Amount ratio is 1/10～10/1.
6. a collecting carbonic anhydride method, it is characterised in that comprise the following steps:
Make the nonaqueous solvent two that carbonated pending gas is described with one of claim 1 to 5
Carbonoxide trapping solution contacts, and described trapping solution absorbing carbon dioxide forms pregnant solution；
Heat described pregnant solution and make carbon dioxide desorbing from described pregnant solution, form lean solution and desorbing
Gas, collects described stripping gas.
Collecting carbonic anhydride method the most according to claim 6, it is characterised in that described receipts
After collecting described stripping gas, also include: described stripping gas is condensed；
Before making carbonated pending gas inversely contact with described trapping solution, also include: right
Described pending gas carries out cooling process.
Collecting carbonic anhydride method the most according to claim 7, it is characterised in that described in add
The described pregnant solution of heat makes carbon dioxide during desorbing from described pregnant solution, and the temperature of described pregnant solution is
70～95 DEG C, pressure is at below 0.1MPa.
9. for implementing a trapping system for the collecting carbonic anhydride method described in claim 6,
It is characterized in that, including absorption plant and desorption apparatus, described absorption plant include absorption tower, for
To the spray equipment of described absorption tower input trapping solution and contain dioxy for the input to described absorption tower
Changing the air pump of the pending gas of carbon, described air pump is connected with described absorption tower by pipeline, described spray
Shower device is arranged in described absorption tower, and described desorption apparatus includes desorber and is arranged at described desorbing
Multi-layer warming column plate device in tower, described desorber is provided by the pipeline of rich solution pump and described absorption
Tower connects.
Trapping system the most according to claim 9, it is characterised in that described trapping system is also
Including condensing unit and heat exchanger, described condensing unit is connected by the gas outlet of pipeline with desorber
Connecing, described air pump is connected with described absorption tower by described heat exchanger.
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