CN103084146B - Composite decarburization absorbent - Google Patents
Composite decarburization absorbent Download PDFInfo
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- CN103084146B CN103084146B CN201110332227.2A CN201110332227A CN103084146B CN 103084146 B CN103084146 B CN 103084146B CN 201110332227 A CN201110332227 A CN 201110332227A CN 103084146 B CN103084146 B CN 103084146B
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- absorbent
- compound
- formula
- piperazine
- decarburization absorbent
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Abstract
The invention relates to a composite decarburization absorbent, which comprises monoethanolamine, an activator and water, and contains or does not contain a compound represented by a formula 1, wherein the activator is a compound represented by a formula 2, and R1-R5 are H or C1-C5 linear alkyl or cyclic alkyl in the compound represented by the formula 1 and the compound represented by the formula 2. The composite decarburization absorbent has characteristics of rapid absorption, large capacity and low regeneration energy consumption.
Description
Technical field
The invention belongs to gas separation technique field, be specifically a kind of can be from the mists such as natural gas, synthesis gas, flue gas the compound decarburization absorbent of carbon dioxide removal.
Technical background
In recent years, along with the lasting rising of global temperature on average, greenhouse gases are CO especially
2recovery problem, caused showing great attention to of scientific circles and national governments.According to the inter-governmental climate change work group of the United Nations measuring and calculating, in atmosphere with CO
2be that master's greenhouse gas concentration is from 2.8 × 10 of the industrialization initial stage
-4(volume fraction) is increased to current 3.56 × 10
-4, and become to continue ascendant trend.Greenhouse effects can cause many harm, and one of them significant impact is to make that sea level rise, and according to conservative estimation, in following 100 years, sea level is by lifting 40-50cm, and the safety in many coastal cities is all on the hazard.In the weather summit of Copenhagen, the GDP CO of the year two thousand twenty unit has made in the Chinese government
2discharge makes the formal commitment than decline 40%-45%'s in 2005, and the reduction of discharging pressure of every profession and trade is huge at present.
CO
2recovery technology varied, according to technological principle difference, can be divided into physical method, chemical method etc.Physical method is based on CO under pressure condition
2be dissolved in the principle of water and solvent, solvent absorbs CO from mist
2after, regeneration relies on the gentle handling of simple vacuum flashing to go out CO
2.Chemical method refers to the CO in chemical solvent and flue gas in absorption tower
2there is chemical reaction and form rich solution; This rich solution decomposites CO by heat effect in desorber again
2, absorb with desorb and hocket, reclaim CO thereby reach
2object.
CN101537340A discloses a kind of flue gas CO
2absorbent.Adopting monoethanolamine (MEA) is main component, contains N methyldiethanol amine (MDEA), sterically hindered amines (AMP, TBE, TBEE or TBPE) or piperazine (PZ) and forms mixed solvent.
It is R that WO9422560 discloses a kind of structural formula
1r
2nCH
2cH (OH) CH
2nHR
3carbon-dioxide absorbent, wherein R
1, R
2, R
3for H or alkyl component.
CN1354036A discloses a kind of low dividing potential drop CO that reclaims or remove
2improvement solution, this solution is the varies solution that contains monoethanolamine and reactive amines.Described reactive amines be on nitrogen-atoms with one or more non-linear carbochain alcohol amine compounds with space steric effect, amine concentration is 1.5-7.5mol/L.Can be used for the CO of the process gas such as natural gas, synthetic ammonia, coal gas, flue gas, kiln gas, fermentation gas
2separate.
CN101053751A discloses a kind of recovery carbon dioxide in waste gas composite decarbonizing solution, composition and the percentage by weight of this kind of composite solution are as follows: varies aqueous solution 20-60%, wherein contains one or more fast response rate amines of low concentration and one or more long response time rate amines of higher concentration; Polyalcohol ether 5-10%; Antioxidant 1-5%; Corrosion inhibiter 1-5%; All the other are water.Wherein fast response rate amines is MEA or DEA or piperazine, and long response time rate amines can adopt AMP or MEDA or TEA, and three can be used alone, and also can mix use.
Above-mentioned composite absorber, although part has been improved absorbent properties, also exists that absorbent absorption rate is low, capacity is little, the high problem of regeneration energy consumption.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of infiltration rate is fast, capacity is large, the low compound decarburization absorbent of regeneration energy consumption.
A kind of compound decarburization absorbent, contains monoethanolamine, activator and water, contains or do not contain formula 1 compound, and described activator is formula 2 compounds, in formula 1 and formula 2 compounds, and R
1-R
5be straight chained alkyl or cyclic alkyl that H or C atomicity are 1-5.
The beneficial effect of compound decarburization adsorbent provided by the invention is:
Activator in compound decarburization absorbent provided by the invention is different from the mechanism of the reaction mechanism of carbon dioxide and monoethanolamine and carbon dioxide reaction, compared with conventional monoethanolamine absorbent, the absorbability of compound decarburization absorbent provided by the invention has obtained large increase, suppressed monoethanolamine degraded in absorption process simultaneously, reduce the probability that generates the accessory substances such as amino-formaldehyde, oxalic acid, solved monoethanolamine loss problem in absorption process.Under the prerequisite that compound decarburization absorbent provided by the invention is substantially suitable with single use guanidine compound assimilation effect in addition, cost significantly reduces.
Detailed description of the invention
Below illustrate the specific embodiment of the present invention:
A kind of compound decarburization absorbent, is characterized in that, contains monoethanolamine, activator and water, contains or do not contain formula 1 compound, and described activator is formula 2 compounds, in formula 1 and formula 2 compounds, and R
1-R
5be straight chained alkyl or cyclic alkyl that H or C atomicity are 1-5.
In absorbent provided by the invention, taking the gross weight of absorbent as benchmark, by weight percentage, in described compound decarburization adsorbent, the content of monoethanolamine is 12-40wt%, and the content of formula 1 compound is 0-5wt%, the content of formula 2 compounds is 0.1-30wt%, and all the other are water.Preferably, in described compound decarburization absorbent, the content of monoethanolamine is 15-26wt%, and the content of described formula 1 compound is 2-4wt%, and the content of formula 2 compounds is 2-16wt%, and all the other are water.
In absorbent provided by the invention, preferably, described formula 1 compound is selected from one or more in piperazine, N methyl piperazine, NEP, N-propyl group piperazine, N-isopropyl piperazine, N-butyl piperazine and N-isobutyl piperazine, more preferably piperazine.
Described piperazine, in formula 1 compound, R
1for H; Described N methyl piperazine, in formula 1 compound, R
1for methyl.Described NEP, in formula 1 compound, R
1for ethyl.Described N-propyl group piperazine, in formula 1 compound, R
1for propyl group.Described N-isopropyl piperazine, in formula 1 compound, R
1for isopropyl.Described N-butyl piperazine, in formula 1 compound, R
1for butyl.Described N-isobutyl piperazine, in formula 1 compound, R
1for isobutyl group.
In described formula 2 compounds, R
2, R
3, R
4, R
5be straight chained alkyl or cyclic alkyl that H or C atomicity are 1-5, wherein R
2, R
3, R
4, R
5can be identical or different.
Preferably, described formula 2 compounds are guanidine and/or 1,1,3,3-TMG, more preferably 1,1,3, and 3-TMG.
Described guanidine, in formula 2 compounds, R
2, R
3, R
4, R
5be all H.
Described 1,1,3,3-TMG, in formula 2 compounds, R
2, R
3, R
4, R
5it is all methyl.Be called for short TMG.
The process of compound decarburization absorbent absorbing and removing carbon dioxide in gas mixture provided by the invention, under temperature is the condition of 0-55 DEG C, mist is passed in described compound decarburization absorbent, described compound decarburization absorbent can divide the carbon dioxide that is pressed in 0.01-0.025MPa in absorbing and removing mist, absorbent after saturated, under an atmospheric pressure, is that under the condition of 50-110 DEG C, carbon dioxide is removed in desorb in temperature.Described mist is the gas that contains carbon dioxide, can be selected from natural gas, synthesis gas, flue gas etc.
In compound decarburization absorbent solution, monoethanolamine (MEA) and CO
2reaction equation as follows:
In compound decarburization absorbent solution, the compound of formula 1 is with piperazine compounds RR ' NH
2for example, itself and CO
2reaction equation as follows:
In compound decarburization absorbent solution, formula 2 compounds represent with B, the CO of its absorption
2react as follows.
Because the activator in compound decarburization absorbent of the present invention is different with carbon dioxide reaction mechanism from course of reaction and the monoethanolamine of carbon dioxide, therefore, compared with the monoethanolamine absorbent using with routine, the absorptive capacity of compound decarburization absorbent of the present invention is higher, suppressed monoethanolamine degraded simultaneously, reduce the probability that generates the accessory substances such as amino-formaldehyde, oxalic acid, solved monoethanolamine loss problem in absorption process.
In addition, the price of activator guanidine compound is very expensive, and with 1,1,3,3-TMG, for example, price is about 60,000 yuan one ton, and allocates in compound decarburization absorbent as activator, has reduced absorbent cost.
Below in conjunction with embodiment, the present invention is described in detail, but the present invention is not therefore subject to any restriction.
In embodiment and comparative example, the CO using
2absorption test device flow chart as shown in Figure 1.Contain CO
2mist introduce through pipeline 1, after triple valve 7, introduce in absorption bottle 2 through pipeline 4, absorption bottle 2 is placed in water-bath 3 and controls temperature.Tail gas after absorption is drawn absorption bottle through pipeline 8, and through CO
2infrared analyzer 5 is measured the CO in tail gas
2volume content, then tail gas is introduced in tail gas absorption bottle and is processed through pipeline 11.The compound decarburization absorbent solution configuring is joined in absorption bottle, and water-bath reaches after design temperature, and mist, through passing into absorption bottle, is adopted as the CO in tail gas
2cO in content and mist
2when content initial value is identical, is considered as reaction and stops.
The CO using
2test device for desorption flow chart as shown in Figure 2.Compound decarburization absorbent after saturated is put into heating jacket 3, set desorption temperature, adopt CO
2infrared analyzer 5 is measured the CO in tail gas
2volume content, works as CO
2volume content is 0 o'clock, is considered as reaction and stops.
Monoethanolamine (MEA) used in embodiment and comparative example is produced by Xi Long chemical plant, Shantou, and 1,1,3,3-TMG and piperazine compounds are produced by lark prestige Science and Technology Ltd..
Adopt following methods to calculate the amine degradation rate of compound decarburization absorbent:
(1) phenolphthalein reagent is mixed with the absorption liquid after desorb
(2) HCl that splashes into 1mol/L, to neutral, passes into the nitrogen of 100ml/min in process, utilize CO
2cO in infrared spectrum analyser observation process
2amount.
Amine degradation rate=3[n (HCl)-n (CO
2)/2]/n (theoretical HCl) × 100%
Embodiment 1
Embodiment 1 illustrates that compound decarburization absorbent provided by the invention absorbs CO in gas
2effect.
The MEA that compound decarburization absorbent contains 17wt%, the piperazine of 1wt%, the TMG of 2wt% and the water of 80wt%.100mL compound decarburization absorbent is packed in absorption bottle under temperature is the condition of 30 DEG C and reacted.Measure carbon dioxide saturated absorption amount and the needed time of the uptake that reaches capacity of absorbent.100mL compound decarburization absorbent after carbon dioxide is saturated is put into desorption bottle, and temperature is controlled at 100 DEG C, measures regeneration rate.Operating condition and the results are shown in Table 1.
Comparative example 1
Comparative example 1 illustrates that compound decarburization absorbent of the prior art absorbs CO in gas
2effect.
The method of comparative example 1 and operating condition are with embodiment 1, and difference is the piperazine of MEA, 3wt% and the water of 80wt% that compound decarburization absorbent contains 17wt%.Operating condition and the results are shown in Table 1.
Embodiment 2
Embodiment 2 illustrates that compound decarburization absorbent provided by the invention absorbs CO in gas
2effect.
The MEA that compound decarburization absorbent contains 27wt%, the piperazine of 2wt%, the TMG of 6wt% and the water of 65wt%.100mL compound decarburization absorbent is packed in absorption bottle under temperature is the condition of 35 DEG C and reacted.Measure carbon dioxide saturated absorption amount and the needed time of the uptake that reaches capacity of absorbent.100mL compound decarburization absorbent after carbon dioxide is saturated is put into desorption bottle, and temperature is controlled at 100 DEG C, measures regeneration rate.Operating condition and the results are shown in Table 2.
Comparative example 2
Comparative example 2 illustrates that compound decarburization absorbent of the prior art absorbs CO in gas
2effect.
The method of comparative example 2 and operating condition be with embodiment 2, and difference is the compound decarburization absorbent MEA that contains 26wt% and the water of 74wt%.Operating condition and the results are shown in Table 2.
Embodiment 3
Embodiment 3 illustrates that compound decarburization absorbent provided by the invention absorbs CO in gas
2effect.
The MEA that compound decarburization absorbent contains 35wt%, the piperazine of 5wt%, the TMG of 10wt% and the water of 50wt%.100mL compound decarburization absorbent is packed in absorption bottle under temperature is the condition of 45 DEG C and reacted.Measure carbon dioxide saturated absorption amount and the needed time of the uptake that reaches capacity of absorbent.100mL compound decarburization absorbent after carbon dioxide is saturated is put into desorption bottle, and temperature is controlled at 60 DEG C, measures regeneration rate.Operating condition and the results are shown in Table 3.
Comparative example 3
Comparative example 3 illustrates that compound decarburization absorbent of the prior art absorbs CO in gas
2effect.
The method of comparative example 3 and operating condition are with embodiment 3, and difference is the piperazine of MEA, 15wt% and the water of 50wt% that compound decarburization absorbent contains 35wt%.Operating condition and the results are shown in Table 3.
Embodiment 4
Embodiment 4 illustrates that compound decarburization absorbent provided by the invention absorbs CO in gas
2effect.
The water of the MEA that compound decarburization absorbent contains 35wt%, the TMG of 30wt% and 35wt%.100mL compound decarburization absorbent is packed in absorption bottle under temperature is the condition of 50 DEG C and reacted.Measure carbon dioxide saturated absorption amount and the needed time of the uptake that reaches capacity of absorbent.100mL compound decarburization absorbent after carbon dioxide is saturated is put into desorption bottle, and temperature is controlled at 60 DEG C, measures regeneration rate.Operating condition and the results are shown in Table 4.
Comparative example 4
Comparative example 4 illustrates that compound decarburization absorbent of the prior art absorbs CO in gas
2effect.
The method of comparative example 4 and operating condition are with embodiment 4, and difference is the piperazine of MEA, 30wt% and the water of 35wt% that compound decarburization absorbent contains 35wt%.Operating condition and the results are shown in Table 4.
Embodiment 5
Embodiment 5 illustrates that compound decarburization absorbent provided by the invention absorbs CO in gas
2effect.
1-ethyl piperazidine, the guanidine of 3wt% and the water of 83wt% of MEA, 2wt% that compound decarburization absorbent contains 12wt%.100mL compound decarburization absorbent is packed in absorption bottle under temperature is the condition of 30 DEG C and reacted.Measure carbon dioxide saturated absorption amount and the needed time of the uptake that reaches capacity of absorbent.100mL compound decarburization absorbent after carbon dioxide is saturated is put into desorption bottle, and temperature is controlled at 60 DEG C, measures regeneration rate.Operating condition and the results are shown in Table 5.
Comparative example 5
Comparative example 5 illustrates that compound decarburization absorbent of the prior art absorbs CO in gas
2effect.
The method of comparative example 5 and operating condition be with embodiment 5, and difference is the compound decarburization absorbent MEA that contains 17wt% and the water of 83wt%.Operating condition and the results are shown in Table 5.
Embodiment 6
Embodiment 6 illustrates that compound decarburization absorbent provided by the invention absorbs CO in gas
2effect.
1-methyl piperazine, the guanidine of 5wt% and the water of 74wt% of MEA, 1wt% that compound decarburization absorbent contains 20wt%.100mL compound decarburization absorbent is packed in absorption bottle under temperature is the condition of 30 DEG C and reacted.Measure carbon dioxide saturated absorption amount and the needed time of the uptake that reaches capacity of absorbent.100mL compound decarburization absorbent after carbon dioxide is saturated is put into desorption bottle, and temperature is controlled at 60 DEG C, measures regeneration rate.Operating condition and the results are shown in Table 6.
Comparative example 6
Comparative example 6 illustrates that compound decarburization absorbent of the prior art absorbs CO in gas
2effect.
The method of comparative example 6 and operating condition be with embodiment 6, and difference is the compound decarburization absorbent MEA that contains 26wt% and the water of 74wt%.Operating condition and the results are shown in Table 6.
Embodiment 7
Embodiment 7 illustrates that compound decarburization absorbent provided by the invention absorbs CO in gas
2effect.
The MEA that compound decarburization absorbent contains 20wt%, the piperazine of 1wt%, the TMG of 5wt% and the water of 74wt%.100mL compound decarburization absorbent is packed in absorption bottle under temperature is the condition of 30 DEG C and reacted.Measure carbon dioxide saturated absorption amount and the needed time of the uptake that reaches capacity of absorbent.100mL compound decarburization absorbent after carbon dioxide is saturated is put into desorption bottle, and temperature is controlled at 60 DEG C, measures regeneration rate.Operating condition and the results are shown in Table 7.
Comparative example 7
Comparative example 7 illustrates that compound decarburization absorbent of the prior art absorbs CO in gas
2effect.
The method of comparative example 7 and operating condition be with embodiment 7, difference be compound decarburization absorbent solution contain 26wt% 1,1,3, the water of 3-TMG and 74wt%.Operating condition and the results are shown in Table 7.
From table 1-7, what compound decarburization absorbent provided by the invention used with routine contains compared with monoethanolamine absorbent, in the situation that absorbent mass concentration is identical, has absorptive capacity high, the feature that absorption rate is fast.After compound decarburization absorbent absorption provided by the invention is saturated, reclaim in the process of carbon dioxide in desorb, under identical desorption temperature, regeneration rate is higher, and regeneration energy consumption is low.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Claims (7)
1. a compound decarburization absorbent, is characterized in that, is made up of, or is made up of monoethanolamine, activator, formula 1 compound and water monoethanolamine, activator and water, and described activator is formula 2 compounds, in formula 1 compound and formula 2 compounds, and R
1-R
5be straight chained alkyl or cyclic alkyl that H or C atomicity are 1-5;
2. according to the absorbent of claim 1, it is characterized in that, taking the gross weight of absorbent as benchmark, by weight percentage, the content of described monoethanolamine is the heavy % of 12-40, and the content of described formula 1 compound is 0-5%, the content of formula 2 compounds is 0.1-30%, and all the other are water.
3. according to the absorbent of claim 2, it is characterized in that, taking the gross weight of absorbent as benchmark, by weight percentage, the content of described monoethanolamine is the heavy % of 15-26, and the content of described formula 1 compound is 2-4%, the content of formula 2 compounds is 2-16%, and all the other are water.
4. according to claim 1,2 or 3 absorbent, it is characterized in that, described formula 1 compound is selected from one or more in piperazine, N methyl piperazine, NEP, N-propyl group piperazine, N-isopropyl piperazine, N-butyl piperazine and N-isobutyl piperazine.
5. according to the absorbent of claim 4, it is characterized in that, described formula 1 compound is piperazine.
6. according to claim 1,2 or 3 absorbent, it is characterized in that, described formula 2 compounds are guanidine and/or 1,1,3,3-TMG.
7. according to the absorbent of claim 4, it is characterized in that, described formula 2 compounds are 1,1,3,3-TMG.
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|---|---|---|---|
| CN201110332227.2A CN103084146B (en) | 2011-10-28 | 2011-10-28 | Composite decarburization absorbent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110332227.2A CN103084146B (en) | 2011-10-28 | 2011-10-28 | Composite decarburization absorbent |
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| CN103084146B true CN103084146B (en) | 2014-08-20 |
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Families Citing this family (2)
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| CN114015486A (en) * | 2021-08-10 | 2022-02-08 | 陕西省石油化工研究设计院 | Activation synergist based on MDEA method natural gas decarbonization |
| CN114768477B (en) * | 2022-03-18 | 2023-11-17 | 中国科学技术大学 | Carbon dioxide trapping method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4100257A (en) * | 1977-02-14 | 1978-07-11 | Exxon Research & Engineering Co. | Process and amine-solvent absorbent for removing acidic gases from gaseous mixtures |
| EP0558019B1 (en) * | 1992-02-27 | 1996-12-27 | The Kansai Electric Power Co., Inc. | Method for removing carbon dioxide from combustion exhaust gas |
| CN1277150A (en) * | 1999-06-10 | 2000-12-20 | 普拉塞尔技术有限公司 | Recovery of carbon dioxide with compound amine blend |
| CN101396636A (en) * | 2007-09-27 | 2009-04-01 | 韩国电力公社 | High effective absorbent for separating acid gas |
| CN101537340A (en) * | 2009-04-30 | 2009-09-23 | 西安热工研究院有限公司 | Smoke CO*absorbent |
-
2011
- 2011-10-28 CN CN201110332227.2A patent/CN103084146B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4100257A (en) * | 1977-02-14 | 1978-07-11 | Exxon Research & Engineering Co. | Process and amine-solvent absorbent for removing acidic gases from gaseous mixtures |
| EP0558019B1 (en) * | 1992-02-27 | 1996-12-27 | The Kansai Electric Power Co., Inc. | Method for removing carbon dioxide from combustion exhaust gas |
| CN1277150A (en) * | 1999-06-10 | 2000-12-20 | 普拉塞尔技术有限公司 | Recovery of carbon dioxide with compound amine blend |
| CN101396636A (en) * | 2007-09-27 | 2009-04-01 | 韩国电力公社 | High effective absorbent for separating acid gas |
| CN101537340A (en) * | 2009-04-30 | 2009-09-23 | 西安热工研究院有限公司 | Smoke CO*absorbent |
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