CN103127745A - Purification method for decarburization alcohol amine in CO2 recovery apparatus - Google Patents
Purification method for decarburization alcohol amine in CO2 recovery apparatus Download PDFInfo
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- CN103127745A CN103127745A CN2011103764901A CN201110376490A CN103127745A CN 103127745 A CN103127745 A CN 103127745A CN 2011103764901 A CN2011103764901 A CN 2011103764901A CN 201110376490 A CN201110376490 A CN 201110376490A CN 103127745 A CN103127745 A CN 103127745A
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- decarburization
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Abstract
The invention relates to a purification method for decarburization alcohol amine in a CO2 recovery apparatus, and belongs to the field of novel application of a process for purifying an alcohol amine solution by an anion exchange resin. The anion exchange resin is used for purifying a decarburization alcohol amine solution. The decarburization alcohol amine solution is added to a desalination resin tank (HSSX) from the top of the demineralization resin tank and desalted by exchanging with the resin; and a purified decarburization alcohol amine solution is obtained after the decarburization alcohol amine solution is discharged from the HSSX tank. The anion exchange resin is used for removing heat stable salts from the alcohol amine solution, so that an object for purifying the alcohol amine solution is realized. Besides, the anion exchange resin can be regenerated by using a small amount of a low concentration sodium hydroxide solution and service life of the resin is long, so that cost consumption of a purification system of the amine solution is reduced. Compared with a conventional purification treatment process for the decarburization alcohol amine solution in the CO2 recovery apparatus, the purification method for the decarburization alcohol amine in the CO2 recovery apparatus is simple in operations, has obvious effect, can realize full-automatic operations, has more obvious economic benefits, and is suitable for industrial popularization and application.
Description
Technical field
The present invention relates to carbon dioxide (CO
2) purification method of decarburization alkanolamine solution in retracting device, belong to a kind of new application that anion exchange resin purifies alkanolamine solution technique.
Background technology
Along with human society uses in a large number with coal and the oil fossil fuel as representative, cause greenhouse gases---the CO of global warming
2Discharge capacity sharply soaring, having a strong impact on the original balance in atmospheric thermodynamics and biosphere, and therefore causing greenhouse effects and caused problems a series of and that human habitat is closely related, seriously threatening the mankind's existence.
The CO that discharge because of combustion of fossil fuels global every year
2Reach 20,000,000,000 tons of left and right, the CO that the fossil energy burning produces
2Total amount accounts for 82% of greenhouse gases total amount.Along with the concern of countries in the world to the global greenhouse effect problem, CO
2Reduce discharging and day by day cause global attention.
Yet, on another aspect, CO
2Be but very useful, can produce the chemical industry new raw material and be permitted multiduty important source material.Along with people to shortage of resources, the attention of greenhouse effects of the earth problem, various fossil fuel go out CO as toxic emission after utilizing as: burnings such as coal, oil, natural gas
2, it reclaims, fixing, utilization and regenerated resources problem cause the concern of countries in the world.
The most frequently used method of present domestic recovery carbon dioxide is chemical absorption method, and it is take alkaline solution as absorbent, with CO
2Reaction generates certain compound.Absorbed CO
2Rich solution raise in temperature, during pressure decreased with CO
2Discharge.Most representative in these class methods is the hydramine method, and monoethanolamine (MEA) method, diethanol amine (DEA) method, diisopropanolamine (DIPA) (DIPA) method, N methyldiethanol amine (MDEA) method are arranged.The hydramine method reclaims CO
2Technical process be to make air-flow pass through the amine absorption tower, with poor amine liquid counter current contacting, with CO
2And a small amount of H
2The S sour gas is dissolved in amine liquid, and to form soluble pure amine salt (be protonated hydramine cation and HCO
3 -And HS
-In conjunction with).Then, water, unreacted hydramine and pure amine salt solution enter stripper, and this class hydramine salt decomposes regeneration and discharges CO
2And H
2S, the amine liquid after regeneration can enter the absorption tower again, stripper recycles.
Amine aqueous solution is inevitably degraded in the process of long-term low temperature absorption and desorption under high temperature as a kind of recycling solvent.Alkanolamine solution is absorbing CO
2Process in, easily and the O in air-flow
2, chemical degradation occurs in sulfide etc., and thermal degradation also easily occurs, especially with cracking tail gas in O
2Oxidative degradation occupy the first.Hydramine and O
2Catabolite mainly contain amino-formaldehyde, amion acetic acid, glycolic acid, glyoxalic acid, oxalic acid etc., these organic acids are combined the salt that generates and can not be passed through the stripper disintegrating and regeneration with the hydramine cation.
These can not be referred to as by the pure amine salt of thermal regeneration heat stable salt (Heat Stable Salts is called for short HSS), and it brings following harm to device:
● the ability of amine absorption acid gas descends
● amine liquid bubbles, and carries secretly seriously, affects the downstream and produces
● the loss of amine liquid is large
● equipment corrosion is serious
● affect the effect of decarburization
Reclaim CO for pure amine absorption process
2The problem that device exists, the domestic processing method preferably that there is no at present is mainly to emit part amine liquid to replenish fresh amine liquid.If but the alkanolamine solution that pollutes is entered sewage disposal system, and sewage disposal system is caused very large pressure, also can consist of harm to environment and human body.Another kind method is that the alkanolamine solution that needs purify is introduced coking plant, carry out pyrolytic and process, but this technique easily causes the problems such as the corrosion of heating furnace water main and the obstruction of coking fractional distillation column tower tray.
Also has a kind of method that purifies amine liquid by distillation, this method that purifies amine liquid by distillation can be applied to monoethanolamine (MEA), but can not use in the higher boiling hydramine such as diethanol amine (DEA) method, diisopropanolamine (DIPA) (DIPA) method, N methyldiethanol amine (MDEA) system, because oxidation and degraded easily occur alkanolamine solution under hot conditions.And a large amount of steam of the method needs, energy consumption is high, and complicated operation, controls difficulty.Because the solvent in cleaning equipment is in high saline state always, there are very large problem in the corrosion of cleaning equipment and the stable operation of cleaning equipment in addition.
Summary of the invention
The purpose of this invention is to provide a kind of CO of being applied to
2The technique that in retracting device, the decarburization alkanolamine solution purifies, this technique can remove the heat stable salt in alkanolamine solution efficiently, and whole process energy consumption is low, without the environmental protection problem.
For achieving the above object, the present invention takes following technical scheme:
A kind of CO
2The purification method of decarburization alkanolamine solution in retracting device is characterized in that: adopt strong-base anion-exchange resin to purify the decarburization alkanolamine solution.
When purifying alkanolamine solution with anion exchange resin, the heat stable salt of sending out in degraded amine solution is easy to pollute resin, and when heat stable salt is dense, needs these resins of frequent regeneration, therefore purifies alkanolamine solution to anion exchange resin and has brought problem.So use anion exchange resin to purify alkanolamine solution, crucial is to select suitable resinous type.Preferably, can adopt the strong-base anion-exchange resin of polystyrene-divinylbenzene skeleton, this resinoid and other resin-phase ratio remove thiocyanate radical (SCN
-), ability of amino acid is strong; Resin regeneration technique is simple, uses the NaOH aqueous solution just can realize the regeneration of resin.
CO of the present invention
2In retracting device, the purification process technique of decarburization alkanolamine solution comprises the following steps: decarburization amine liquid is joined the desalination resin container from the top, with the resins exchange desalination, discharge the alkanolamine solution that is purified through the desalination resin container, described resin is the strong-basicity styrene series resin, preferably the strong-base anion-exchange resin of the strong-base anion-exchange resin of I type polystyrene-divinylbenzene skeleton, II type polystyrene-divinylbenzene skeleton.
The desalination resin container is referred to as the HSSX tank, namely except the heat stable salt tank.After HSSX tank operation certain hour, the amine liquid exchange capacity differential pressure that reaches setting when exchange capacity is during greater than setting value, and resin lost efficacy basically, need to its processings of regenerating, make it again possess the sub-ability of disengaging.The resin regeneration process comprises:
(1) row's amine is just washed: at first water is added the HSSX tank from the top, the purification amine in the HSSX tank is pressed into user's amine pipeline, circulation flushing after rinsing end, then enters water tank with demineralized water with washing pressure in tank, to reduce the loss of amine;
(2) regeneration: demineralized water (is namely referred to utilize various water treatment technologies, remove in the water such as suspension, colloid and inorganic cation, anion resulting finished product water after impurity) add the HSSX tank from the bottom, squeeze into alkali with measuring pump simultaneously, alkali can be NaOH solution, demineralized water and alkali are mixed into the NaOH solution that mass fraction is 3-4% in pipe-line mixer, carry out the reverse regeneration that contacts with resin, the regeneration that is conducive to resin is complete; Control the alkali flow, when alkali consumption reaches setting value, regeneration ending;
(3) clean: after regeneration ending, stop into alkali lye, continue adverse current and advance demineralized water, regulate flow of inlet water for setting value, carry out cleaning operation.Change immediately the desalination step after replacement completion over to, namely begin new circulation.
Use the inventive method to have following effect:
1, greatly reduce equipment corrosion, extend the service life of amine treating apparatus, reduce the maintenance and operation expense of equipment.
2, reduce the amine liquid loss of amine treating apparatus, reduced the operating cost of device.
3, improved CO
2The decarburization efficient of retracting device.
Advantage of the present invention is:
1, adopt strong-base anion-exchange resin to purify alkanolamine solution, can efficiently remove amino acid and other heat stable salt anion in deteriorated alkanolamine solution.
HSSX desalination process provided by the present invention uses strong-basicity styrene series anion exchange resin to be used for removing anion and the amino acid that the decarburization alkanolamine solution forms heat stable salt, to reach the purpose of removing heat stable salt.The amino acid molecular amount is large, polarity is little, and general resin is difficult to remove.The HSSX desalination process is that unique being proved can make the system salt content keep stablizing low-level (the HSS anion-content is less than 0.5%) and the life-span reaches the technology of 18 months.
Technique of the present invention can be used for purifying all alkanolamines such as monoethanolamine (MEA), diethanol amine (DEA), diisopropanolamine (DIPA) (DIPA), N methyldiethanol amine (MDEA), bulky amine.
2, the present invention adopts strong-base anion-exchange resin to purify alkanolamine solution, and simple to operate, energy consumption is low.
During regeneration, the concentration of alkali only needs 3-4%, and consumption is little, and the low concentration that regeneration produces contains alkali waste water and can directly enter sewage disposal system, can not affect its operation.Whole purification process low energy consumption, low material consumption, simple to operate, clean-up effect obviously, non-environmental-pollution.
The present invention will be further described below by the drawings and specific embodiments, but and do not mean that limiting the scope of the invention.
Description of drawings
Fig. 1 is alkanolamine solution purification flow chart in prior art.
Fig. 2 is decarburization chain triacontanol amine solution process for purifying flow chart in the present invention.
The specific embodiment
Comparative Examples
In prior art, as Bo Yuan associating chemical industry CO
2The purification method of monoethanolamine in retracting device (MEA), its technological process as shown in Figure 1,11 for reclaiming heater, 12 is condenser, 13 is return tank.Go solution to reclaim heater for contaminated MEA is shunted a part from systemic circulation liquid, adopt distillating method that MEA is wherein extracted, thereby reach the purpose that MEA purifies.Its treatment step is:
1) the preparation mass fraction is 40% Na
2CO
3The aqueous solution and contaminated amine liquid are mixed into recovery heater 11.
2) thus separate by the temperature, pressure amine liquid that its mid-boiling point is lower that adjusting is reclaimed in heater 11, reflux through condenser 12 amine liquid collected in return tank 13.
This method that purifies amine liquid by distillation can be applied to monoethanolamine (MEA), but can not use in the higher boiling hydramine such as diethanol amine (DEA) method, diisopropanolamine (DIPA) (DIPA) method, N methyldiethanol amine (MDEA) system, because oxidation and degraded easily occur alkanolamine solution under hot conditions.And a large amount of steam of the method needs, energy consumption is high, and complicated operation, controls difficulty.Because the solvent in cleaning equipment is in high saline state always, there are very large problem in the corrosion of cleaning equipment and the stable operation of cleaning equipment in addition.
Embodiment
CO of the present invention
2The purification method of decarburization alkanolamine solution in retracting device adopts strong-base anion-exchange resin to purify the decarburization alkanolamine solution.Decarburization amine liquid is joined the HSSX tank from the top, with the resins exchange desalination, discharge the decarburization alkanolamine solution that is purified through the HSSX tank, described resin is strong-basicity styrene series anion exchange resin, for example the strong-base anion-exchange resin of the strong-base anion-exchange resin of I type polystyrene-divinylbenzene skeleton or II type polystyrene-divinylbenzene skeleton.
CO of the present invention
2The purification process technique of decarburization alkanolamine solution in retracting device, its technological process as shown in Figure 2, wherein 21 is the HSSX tank, 22 for the circulation flow container, 23 is pump.Comprise the following steps:
● desalination
The poor amine liquid that does not purify from the user enters HSSX tank 21 from the top, with the resins exchange desalination, Flow-rate adjustment to setting value, is got back to user's amine pipeline after HSSX tank 21 purifies.
After HSSX tank 21 operation certain hours, the amine liquid exchange capacity differential pressure that reaches setting when exchange capacity is during greater than setting value, and resin lost efficacy basically, need to its processings of regenerating, make it again possess the sub-ability of disengaging.
● row's amine is just washed
Replacing water (the hydramine mass concentration is 3% demineralized water approximately) forward enters HSSX tank 21 from the top, the purification amine in HSSX tank 21 is pressed into user's amine pipeline.Regulate flow of inlet water and be setting value, when the water inlet volume reached setting value, the purification amine in HSSX tank 21 all was pressed into user's amine pipeline.Also need to continue circulation flushing this moment, rinse and finish with demineralized water, flushing water in tank to be pressed into the replacing water case, to reduce the loss of amine.
● regeneration
The demineralized water adverse current enters HSSX tank 21 from the bottom, squeeze into alkali with measuring pump simultaneously, is mixed at pipe-line mixer the NaOH solution that mass fraction is 3-4%, carries out the reverse regeneration that contacts with resin.Resin in tank is carried out from bottom to top backwash, so that resin can become flexible and again arrange, regenerated liquid is evenly distributed, improve regeneration effect.Control the alkali flow, when alkali consumption reaches setting value, regeneration ending.
● clean
After regeneration ending, stop into alkali lye, continue adverse current and advance demineralized water, regulate flow of inlet water for setting value, carry out cleaning operation.Can discharge remaining in the middle alkali lye of resin by cleaning, in the salkali waste of discharge, the pressure of utilization itself send sewage disposal system (acid water pot).When going out the water power dodar after setting value, clean and finish.
● just wash
The replacing water forward enters HSSX tank 21, then is back to the displacement water tank.Adjust flux after moving to setting value, is just being washed end for setting value.
● advance the amine setting-out
Amine liquid forward enters HSSX tank 21, and adjust flux is pressed into the displacement water tank for setting value with the replacing water in HSSX tank 21, when advancing the amine volume when setting value, stops setting-out.Stop changing immediately the desalination step over to after setting-out, namely begin new circulation.
The size of HSSX tank 21 can be set as required, and for example the diameter of HSSX tank 21 can be 800mm in the present embodiment, and the height of its straight section part is 1700mm, and flow set is 5～8m
2/ h.This technique can purify all alkanolamines such as monoethanolamine (MEA), diethanol amine (DEA), diisopropanolamine (DIPA) (DIPA), N methyldiethanol amine (MDEA).
Reclaim at present 1000 side CO according to Bo Yuan
2/ hour calculating (a year operation was calculated by 8000 hours) has been done following contrast, result such as table 1 with the strong alkalinity anion exchange process amine purification system energy consumption of the present embodiment.
Table 1 amine purifies the energy consumption table
Remarks: amine by 10000 yuan/tons, steam by 40 yuan/tons, Na
2CO
3Technical grade by 2000 yuan/tons, NaOH chemical grade by 4000 yuan/tons, 230/ liter of calculating of Medium Replacement.
Can very clearly see from the result that table 1 is shown, remove the technique of HSSX by ion exchange resin, processing that the operation of same amine liquid consumes is original 21% (59.8 ten thousand with respect to 282.56 ten thousand), and this technological operation is simple, there is no environmental issue.
Anion exchange resin provided by the present invention purifies the technique of amine liquid, removes heat stable salt in alkanolamine solution with strong-basicity styrene series anion exchange resin, thereby realizes the purpose that alkanolamine solution purifies.The technique of removing heat stable salt in the present invention can be so that be issued to the purpose of purification alkanolamine solution in the situation of low energy consumption, and the anion exchange resin that uses in the present invention can be regenerated with the sodium hydroxide solution of a small amount of low concentration, the resin long service life, thus the cost consumption of amine purification system reduced.With existing CO
2In retracting device, the purification process technique of decarburization alkanolamine solution is compared, advantage of the present invention is: this technological operation is simple, successful, can realize full automatic working, few and the environmental sound of resin regeneration material consumption, the resin long service life, thereby can obtain more obvious economic benefit, be suitable for industry to be applied.
Claims (6)
1. CO
2The purification method of decarburization alkanolamine solution in retracting device is characterized in that: adopt strong-base anion-exchange resin to purify the decarburization alkanolamine solution.
2. CO according to claim 1
2The purification method of decarburization alkanolamine solution in retracting device is characterized in that: concrete steps comprise decarburization amine liquid are joined the desalination resin container from the top, with the resins exchange desalination, discharge the decarburization alkanolamine solution that is purified through the desalination resin container.
3. CO according to claim 1
2The purification method of decarburization alkanolamine solution in retracting device is characterized in that: described anion exchange resin is the strong-base anion-exchange resin of I type polystyrene-divinylbenzene skeleton or the strong-base anion-exchange resin of II type polystyrene-divinylbenzene skeleton.
4. according to CO claimed in claim 1
2The purification method of decarburization alkanolamine solution in retracting device is characterized in that: also comprise the resin regeneration operation, concrete steps are:
(1) row's amine is just washed: at first water is added the desalination resin container from the top, the purification amine in the desalination resin container is pressed into the amine pipeline, circulation flushing after rinsing end, then enters water tank with demineralized water with washing pressure in tank;
(2) regeneration: demineralized water is added the desalination resin container from the bottom, squeeze into alkali with measuring pump simultaneously, carry out the reverse regeneration that contacts with resin; Control the alkali flow, when alkali consumption reaches setting value, regeneration ending;
(3) clean: after regeneration ending, stop into alkali lye, continue adverse current and advance demineralized water, carry out cleaning operation.
5. according to CO claimed in claim 4
2The purification method of decarburization alkanolamine solution in retracting device is characterized in that: described alkali is NaOH.
6. the described CO of any one in 5 according to claim 1
2The purification method of decarburization alkanolamine solution in retracting device is characterized in that: described decarburization alkanolamine solution comprises monoethanolamine, diethanol amine, diisopropanolamine (DIPA), N methyldiethanol amine and bulky amine.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979716A (en) * | 2014-05-22 | 2014-08-13 | 西安热工研究院有限公司 | System and method for purifying and recycling amine liquid of smoke CO2 trapping system for coal-fired power plant |
| CN106268176A (en) * | 2015-05-22 | 2017-01-04 | 西安长庆科技工程有限责任公司 | A kind of raw natural gas depth decarburization technique |
| CN107921430A (en) * | 2015-08-20 | 2018-04-17 | Eco-Tec有限公司 | A kind of method that carbamate is stripped from ion exchange resin |
| WO2024012042A1 (en) * | 2022-07-12 | 2024-01-18 | 中国石油天然气股份有限公司 | Method for regenerating alkanolamine solution |
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| CN103979716A (en) * | 2014-05-22 | 2014-08-13 | 西安热工研究院有限公司 | System and method for purifying and recycling amine liquid of smoke CO2 trapping system for coal-fired power plant |
| CN106268176A (en) * | 2015-05-22 | 2017-01-04 | 西安长庆科技工程有限责任公司 | A kind of raw natural gas depth decarburization technique |
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Application publication date: 20130605 |