CN101734658A - Method for absorbing and separating carbon dioxide - Google Patents
Method for absorbing and separating carbon dioxide Download PDFInfo
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- CN101734658A CN101734658A CN200910244197A CN200910244197A CN101734658A CN 101734658 A CN101734658 A CN 101734658A CN 200910244197 A CN200910244197 A CN 200910244197A CN 200910244197 A CN200910244197 A CN 200910244197A CN 101734658 A CN101734658 A CN 101734658A
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- carbonic acid
- acid gas
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Abstract
The invention discloses a method for absorbing and separating carbon dioxide, which comprises absorption and desorption of the carbon dioxide at certain temperature and specifically comprises the following steps: mixing alcamines compounds and ethylene glycol compounds to form solution so as to obtain an absorbent; making the absorbent contact the gas to be absorbed in gas-liquid mass transfer equipment to obtain a liquid product; and desorbing and separating the liquid product to obtain the carbon dioxide so as to realize the regeneration of the carbon dioxide. The absorbent adopted by the method can efficiently absorb the carbon dioxide, has little corrosion to the equipment, and can realize the regeneration of the carbon dioxide and the cyclic utilization of the absorbent.
Description
Technical field
The present invention relates to the absorption process of gas, particularly relate to the method for absorbing and separating of carbonic acid gas.
Background technology
The global greenhouse effect problem that is caused by Carbon emission has caused the extensive concern of various countries, and its reduction of discharging also comes into one's own day by day.Simultaneously, carbonic acid gas can be applied to multiple fields such as food-processing and industrial production as a kind of important industrial resources, therefore, realizes the enrichment of carbonic acid gas efficiently, economically, has good more practical value.
In recent years, the absorption of carbonic acid gas development was very rapid, can be divided into several big classes such as chemical solvents method, physical solvent process, membrane separation process, low temperature processing.The Financial cost of physical solvent process, membrane separation process and low temperature processing is too high, is not suitable for industrial application.At present, that often uses in the chemical solvents method is the amine aqueous solution method, and using comparatively sophisticated is Monoethanolamine MEA BASF (MEA) solution method and diethanolamine (DEA) solution method.The characteristics of these two methods are: absorption rate is fast, but because its regeneration temperature is higher, easily causes equipment corrosion, and regeneration power consumption simultaneously is also bigger.Replace water so seek new solvent, development less energy-consumption, high-level efficiency is little to equipment corrosion simultaneously, and utilizes the organic amine absorption agent to realize that carbon dioxide enriched method has important practice significance.
In sum, need provide a kind of less energy-consumption, high-level efficiency little to equipment corrosion simultaneously absorption agent, to realize the needs of rapid absorption carbonic acid gas.
Summary of the invention
For solving above-mentioned at least one technical problem, the invention provides a kind of method for absorbing and separating of carbonic acid gas, the speed of this method absorbing carbon dioxide is fast, and little to equipment corrosion.
In order to realize the foregoing invention purpose, the invention provides a kind of method for absorbing and separating of carbonic acid gas, specifically may further comprise the steps: a. with alcamine compound as solute, carbon atom less than 10 glycols compound as solvent, the mixed preparing agent that is absorbed; B. absorption agent is contacted with gas phase to be absorbed, obtain liquid product; C. liquid product is carried out desorb, separate obtaining carbonic acid gas.
Method provided by the present invention, with alcamine compound as solute, and with the low saturated vapor pressure higher-boiling compound of this class of glycols as solvent, be mixed with solution.When temperature is relatively low, the amino that comprises in the alcamine compound structure is alkalescence, Chemical bond effect that can be stronger with carbon dioxide generating, thus promoted the absorption of carbonic acid gas from the gas phase to the liquid phase, promptly under relatively low temperature condition, realize the efficient absorption of carbonic acid gas; Then, after the rising of gained liquidus temperature, the Chemical bond effect of alcamine compound and carbonic acid gas weakens, and can realize the mass transfer of carbonic acid gas from the liquid phase to the gas phase, i.e. the fast desorption of carbonic acid gas.In this process, since the introducing of glycols solvent, the problem of easily vaporizing in the time of overcoming usual water as solvent.At this moment, when temperature is elevated to desorption temperature, do not reach the boiling point of glycols solvent as yet, can not cause a large amount of vaporizations of solvent, can realize effective enrichment of carbonic acid gas and recycling of absorption agent like this, and reduce corrosion equipment.
One of according to the embodiment of the present invention, the concentration of alcamine compound is 0.1～10mol/L in the described absorption agent of step a.Absorption process, uptake rate can be subjected to the molecular diffusivity and the solute concentration influence of solubility coefficient, liquid phase, and in above-mentioned concentration range, the efficient of absorption agent absorbing carbon dioxide is higher.
One of according to the embodiment of the present invention, alcamine compound described in the step a comprises Monoethanolamine MEA BASF or/and diethanolamine.
One of according to the embodiment of the present invention, the compound of glycols described in the step a comprises at least a in ethylene glycol, glycol ether, triglycol, the Tetraglycol 99.
One of according to the embodiment of the present invention, the working pressure among the step b is not less than 4kPa, and service temperature is 10～80 ℃.
According to the withstand voltage degree of service temperature and equipment, can suitably regulate pressure, so that absorbing carbon dioxide better.
One of according to the embodiment of the present invention, the working pressure among the step c is 0.2～200kPa, described service temperature is 50～110 ℃.
When operation, this pressure and temperature condition can make carbonic acid gas finish desorb fast, also can not make solvent vaporize in a large number simultaneously, thereby is beneficial to the desorption efficiency that improves carbonic acid gas.
The present invention carries out the absorption extraction of carbonic acid gas by aforesaid method, all makes progress in the following areas:
At first, method provided by the present invention, its carbon dioxide absorption system reaction conditions is lower, and is higher to the specific absorption of carbonic acid gas, and desorb is rapid, and makes its regeneration reach the enrichment purpose, and reaction cost is low and the reaction times short.
Secondly, introduce the glycols compound, when the carbonic acid gas desorb, heat up and when regulating pressure as solvent, can not cause a large amount of vaporizations of solvent, be beneficial to the purity that improves regenerating carbon dioxide, reduce the loss amount of absorption agent simultaneously, realize the efficient recovery and the recycle of absorption agent.
The 3rd, solvent is difficult for vaporization, can avoid the corrosion to equipment, increases the service life.
Embodiment
The method for absorbing and separating of a kind of carbonic acid gas provided by the invention is to absorb carbonic acid gas in the gas, and makes its regenerated method, comprises the absorption and desorption at a certain temperature of described carbonic acid gas.Wherein, specifically may further comprise the steps: at first, alcamine compound and carbon atom are mixed with solution less than 10 glycols compound, agent is absorbed.Wherein, alcamine compound comprises Monoethanolamine MEA BASF or/and diethanolamine; The glycols compound comprises at least a in ethylene glycol, glycol ether, triglycol, the Tetraglycol 99, adopts glycol ether usually or/and the triglycol effect is better.In addition, because absorption process, uptake rate can be subjected to the molecular diffusivity and the solute concentration influence of solubility coefficient, liquid phase, therefore during the absorption agent absorbing carbon dioxide, carbon dioxide absorption efficient was higher when the concentration of alcamine compound was 0.1mol/L～10mol/L.Then, in the gas separation equipment or gas-liquid mass transfer (contact) equipment of routine, make absorption agent and wait that absorbing gas phase fully contacts, working pressure is not less than 4kPa, and service temperature is 10～80 ℃, obtains liquid product.At last, be that 0.2～200kPa, temperature are to carry out desorb under 50～110 ℃ the condition with liquid product at pressure, thereby realize the regeneration of carbonic acid gas, reclaim absorption agent simultaneously, make its recycle.The specific absorption that gets carbonic acid gas is greater than 90% after testing, and promptly absorbed carbonic acid gas accounts for the ratio of total carbon dioxide volume in the mixed gas greater than 90%.
When temperature was relatively low, the amino that comprises in the alcamine compound structure was alkalescence, Chemical bond effect that can be stronger with carbon dioxide generating, thus promoted the absorption of carbonic acid gas from the gas phase to the liquid phase; After the rising of gained liquidus temperature, the Chemical bond effect of alcamine compound and carbonic acid gas weakens, and can realize the mass transfer of carbonic acid gas from the liquid phase to the gas phase.The present invention will hang down the high boiling glycols compound of saturated vapor pressure as solvent, in the carbonic acid gas desorption process, when temperature is elevated to desorption temperature, can not reach the boiling point of solvent, therefore can not cause a large amount of vaporizations of solvent, can realize effective enrichment of carbonic acid gas and recycling of absorption agent like this, and reduce corrosion equipment.In the whole process, the absorption agent reusable edible constitutes continuous absorption and regenerating carbon dioxide.
The invention will be further described below by specific embodiment, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
Embodiment 1
At first, as solute, triglycol is as solvent with Monoethanolamine MEA BASF, mixed preparing solution 1L, and the agent that is absorbed, wherein, the concentration of Monoethanolamine MEA BASF is 0.1mol/L.Then, in temperature is 50 ℃, and pressure is under the condition of 200kPa, makes absorption agent fully contact 7 minutes with carbonic acid gas with nitrogen mixture in gas-liquid mass transfer (contact) equipment, wherein carbonic acid gas and nitrogen mixture total amount are 0.5mol, and the carbon dioxide volume fraction is 5%.At last, the liquid product that obtains at 50 ℃, is carried out desorb under the pressure 0.2kPa, realize the regeneration of carbonic acid gas, reclaim absorption agent simultaneously, make its recycle.
Get the specific absorption of carbonic acid gas after testing greater than 90%.
Embodiment 2
At first, as solute, glycol ether is as solvent with diethanolamine, mixed preparing solution 1L, and the agent that is absorbed, wherein, the concentration of diethanolamine is 1.5mol/L.Then, in temperature is 25 ℃, and pressure is under the condition of 4kPa, makes absorption agent fully contact 3 minutes with carbonic acid gas with nitrogen mixture in gas separation equipment, wherein carbonic acid gas and nitrogen mixture total amount are 0.01mol, and the carbon dioxide volume fraction is 60%.At last, the liquid product that obtains at 80 ℃, is carried out desorb under the pressure 2kPa, realize the regeneration of carbonic acid gas, reclaim absorption agent simultaneously, make its recycle.
Get the specific absorption of carbonic acid gas after testing greater than 90%.
Embodiment 3
At first, as solute, triglycol is as solvent with diethanolamine, mixed preparing solution 1L, and the agent that is absorbed, wherein, the concentration of diethanolamine is 2mol/L.Then, in temperature is 35 ℃, and pressure is under the condition of 500kPa, makes absorption agent fully contact 5 minutes with carbonic acid gas with nitrogen mixture in gas separation equipment, wherein carbonic acid gas and nitrogen mixture total amount are 1mol, and the carbon dioxide volume fraction is 30%.At last, the liquid product that obtains at 110 ℃, is carried out desorb under the pressure 200kPa, realize the regeneration of carbonic acid gas, reclaim absorption agent simultaneously, make its recycle.
Get the specific absorption of carbonic acid gas after testing greater than 90%.
Embodiment 4
At first, as solute, triglycol is as solvent with Monoethanolamine MEA BASF, mixed preparing solution 2L, and the agent that is absorbed, wherein, the concentration of Monoethanolamine MEA BASF is 10mol/L.Then, in temperature is 80 ℃, and pressure is under the condition of 500kPa, makes absorption agent fully contact 6 minutes with carbonic acid gas with nitrogen mixture in gas-liquid mass transfer (contact) equipment, wherein carbonic acid gas and nitrogen mixture total amount are 10mol, and the carbon dioxide volume fraction is 60%.At last, the liquid product that obtains at 110 ℃, is carried out desorb under the pressure 20kPa, realize the regeneration of carbonic acid gas, reclaim absorption agent simultaneously, make its recycle.
Get the specific absorption of carbonic acid gas after testing greater than 90%.
Embodiment 5
At first, as solute, glycol ether is as solvent with Monoethanolamine MEA BASF and diethanolamine, mixed preparing solution 2L, and the agent that is absorbed, wherein, the concentration of solute Monoethanolamine MEA BASF is 1.5mol/L, the concentration of diethanolamine is 1.5mol/L.Then, in temperature is 40 ℃, and pressure is under the condition of 350kPa, makes absorption agent fully contact 3 minutes with carbonic acid gas with nitrogen mixture in gas-liquid mass transfer (contact) equipment, wherein carbonic acid gas and nitrogen mixture total amount are 6mol, and the carbon dioxide volume fraction is 40%.At last, the liquid product that obtains at 80 ℃, is carried out desorb under the pressure 40kPa, realize the regeneration of carbonic acid gas, reclaim absorption agent simultaneously, make its recycle.
Get the specific absorption of carbonic acid gas after testing greater than 90%.
Embodiment 6
At first, as solute, triglycol is as solvent with Monoethanolamine MEA BASF and diethanolamine, mixed preparing solution 2L, and the agent that is absorbed, wherein, the concentration of solute Monoethanolamine MEA BASF is 0.5mol/L, the concentration of diethanolamine is 1.5mol/L.Then, in temperature is 10 ℃, and pressure is under the condition of 300kPa, makes absorption agent fully contact 5 minutes with carbonic acid gas with nitrogen mixture in gas-liquid mass transfer (contact) equipment, wherein carbonic acid gas and nitrogen mixture total amount are 5mol, and the carbon dioxide volume fraction is 50%.At last, the liquid product that obtains at 100 ℃, is carried out desorb under the pressure 30kPa, realize the regeneration of carbonic acid gas, reclaim absorption agent simultaneously, make its recycle.
Get the specific absorption of carbonic acid gas after testing greater than 90%.
Embodiment 7
At first, with Monoethanolamine MEA BASF and diethanolamine as solute, the mixture of glycol ether and triglycol is as solvent, mixed preparing solution 2L, the agent that is absorbed, wherein, the mass ratio of solvent glycol ether and triglycol is 1: 1, the concentration of solute Monoethanolamine MEA BASF is 2mol/L, and the concentration of diethanolamine is 2mol/L.Then, in temperature is 55 ℃, and pressure is under the condition of 400kPa, makes absorption agent fully contact 6 minutes with carbonic acid gas with nitrogen mixture in gas-liquid mass transfer (contact) equipment, wherein carbonic acid gas and nitrogen mixture total amount are 5mol, and the carbon dioxide volume fraction is 80%.At last, the liquid product that obtains at 90 ℃, is carried out desorb under the pressure 50kPa, realize the regeneration of carbonic acid gas, reclaim absorption agent simultaneously, make its recycle.
Get the specific absorption of carbonic acid gas after testing greater than 90%.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (8)
1. the method for absorbing and separating of a carbonic acid gas may further comprise the steps:
(a) with alcamine compound as solute, carbon atom less than 10 glycols compound as solvent, the mixed preparing agent that is absorbed;
(b) absorption agent is contacted with gas phase to be absorbed, obtain liquid product;
(c) liquid product is carried out desorb, separate obtaining carbonic acid gas.
The method of claim 1, wherein in the described absorption agent of step (a) concentration of alcamine compound be 0.1～10mol/L.
3. the method for claim 1, wherein alcamine compound described in the step (a) comprises Monoethanolamine MEA BASF or/and diethanolamine.
4. the method for claim 1, wherein glycols compound described in the step (a) comprises at least a in ethylene glycol, glycol ether, triglycol, the Tetraglycol 99.
5. the working pressure of the method for claim 1, wherein described step (b) is not less than 4kPa.
6. the service temperature of the method for claim 1, wherein described step (b) is 10～80 ℃.
7. the working pressure of the method for claim 1, wherein described step (c) is 0.2～200kPa.
8. the temperature of the method for claim 1, wherein described step (c) operation is 50～110 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910244197A CN101734658A (en) | 2009-12-30 | 2009-12-30 | Method for absorbing and separating carbon dioxide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910244197A CN101734658A (en) | 2009-12-30 | 2009-12-30 | Method for absorbing and separating carbon dioxide |
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| CN101734658A true CN101734658A (en) | 2010-06-16 |
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| CN200910244197A Pending CN101734658A (en) | 2009-12-30 | 2009-12-30 | Method for absorbing and separating carbon dioxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084041A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Composite decarburization absorbent |
| CN103084040A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Method for absorption removing of carbon dioxide |
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2009
- 2009-12-30 CN CN200910244197A patent/CN101734658A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084041A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Composite decarburization absorbent |
| CN103084040A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Method for absorption removing of carbon dioxide |
| CN103084040B (en) * | 2011-10-28 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of method of absorbing and removing carbon dioxide |
| CN103084041B (en) * | 2011-10-28 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of Composite decarburization absorbent |
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Open date: 20100616 |