CN1259121C - Improved N-methyldiethanolamine decarbonizing solution - Google Patents
Improved N-methyldiethanolamine decarbonizing solution Download PDFInfo
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- CN1259121C CN1259121C CNB200410066416XA CN200410066416A CN1259121C CN 1259121 C CN1259121 C CN 1259121C CN B200410066416X A CNB200410066416X A CN B200410066416XA CN 200410066416 A CN200410066416 A CN 200410066416A CN 1259121 C CN1259121 C CN 1259121C
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- mdea
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- activator
- decarbonizing
- morpholine
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Abstract
The present invention relates to an N-methyldiethanolamine decarbonized solution which is composed of an N-methyldiethanolamine water solution and an activating agent, which is characterized in that the activating agent is composed of morpholine and piperazine or diethanolamine. The decarbonized solution of the present invention can be used for eliminating carbon dioxide in mixed gas of synthetic gas, city coal gas or natural gas, etc., and meanwhile, sulfide can be eliminated. The decarbonized solution has the advantages of large absorption capacity, high purification degree, low regeneration energy consumption, etc.
Description
Technical field
The present invention relates to a kind of decarbonizing solution that contains carbon dioxide in the carbon dioxide that removes, particularly a kind of N methyldiethanol amine (MDEA) decarbonizing solution.
Background technology
As everyone knows, from the gas that contains carbon dioxide, remove the technology that carbon dioxide is a kind of industrial extensive use.For example in natural gas, oil gas town gas and synthesis gas processing procedure, all need to remove carbon dioxide.On the other hand, carbon dioxide itself is a kind of essential industry raw material, can be used for making urea and organic synthesis raw material.
Since BASF AG after last century, the seventies was developed the piperazine Activated MDEA Decarbonizing Technology, because it has low regeneration energy consumption and high gas purification degree, solution are not degraded, to advantages such as carbon steel do not corrode, Activated MDEA Decarbonizing Technology worldwide is used widely.Become the low energy consumption chemical method decarburization technique of extensive use in the world so far.
So-called activation MDEA solution is actually a small amount of activator of adding in certain MDEA aqueous solution, improves the speed of MDEA solution absorption and desorption carbon dioxide, to keep lower regeneration energy consumption.About adding the research work of activator in the MDEA aqueous solution, be the focus that each researcher pays close attention to all the time.
Nineteen eighty-two, the patent of BASF AG (US.4,336,233) discloses a kind of method of removing carbon dioxide, hydrogen sulfide from admixture of gas, and its absorbent is to add piperazine in the MDEA aqueous solution as activator.The concentration of MDEA is 1.5～4.5mol/L, and the addition of piperazine is 0.05～0.8mol/L.
The C.N. of Combined Carbide Chemical And Plastic Technology Co.,Ltd relaxes piperazine amount that uncle's top grade people claims to add in its MDEA solution in patent in 2002 (US.P.6,337,059 and Chinese patent 00807037.7) greater than 1mol/L.They think that the amount of piperazine in solution is the key of this invention: greater than providing of the 1mol/L solution higher absorbability littler than piperazine addition.Its absorbent also comprises other chemical solvent or physical solvent in forming, as sulfolane or methoxyl group triethylene glycol etc.
People's such as research institute of southization group company Zhang Xuemo patent (ZL93110579.x) discloses a kind of polyamine process decarbonizing solution, it is based on the MDEA aqueous solution, that adds activator removes carbon dioxide (sulfide) solution, its activator is: A group: piperazine (1～5%)+diethanol amine (1～10%), this suitable sweet gas body: B group: N-methyl-monoethanolamine (0.1～10%)+diethanol amine (1～10%) and C group: N-methyl-monoethanolamine (0.1～10%)+piperazine (1～5%), the back is applicable to sulfurous gas for two groups.
The Liu Jian of China National Petroleum company Chinese patent in 2003 (ZL 00126925.9) is disclosed to be a kind of composite decarbonizing solution, and it consists of: MDEA (30～50%); Dimethyl hydramine (0.1～1.5%); Methylethanolamine (0.5～1.5%) and piperazine (1.0～2.0%), all the other are water.
In sum, though existing MDEA decarbonizing solution has its advantage separately, its comprehensive decarburization capacity still leaves some room for improvement.
Summary of the invention
The object of the invention is, a kind of N methyldiethanol amine (MDEA) decarbonizing solution of improvement is provided, and overcomes the defective of the comprehensive decarburization capacity deficiency of existing MDEA decarbonizing solution existence.
The evaluation of design of the present invention and activator is such:
As everyone knows, absorption is the comprehensive linkage process that combines with the desorb carbon dioxide in the industrial production, in order to seek more good composite activating agent, the present invention is different from forefathers the investigation of decarbonizing solution mostly is limited to the situation that absorption and desorption are studied respectively, but under approaching industrial physical condition, set up a cover laboratory simulation decarbonization device, this device comprises the regenerator of pressurizing absorption tower and normal pressure, and all be under the adiabatic condition, combined operation on constant reboiler heating power basis reaches and considers different proportionings under the stable case, the decarburization effect of the different decarbonizing solutions of forming.This device and research method are more near industrial condition, and the result will be more true.
In addition, the present inventor thinks the decarbonizing solution evaluation criterion be should be: (1) decarbonization performance can be with the increment m of solution gas concentration lwevel in the absorption tower
2-m
1(unit is mol/m
3) judge that difference is big more, its absorbent properties are good more; (2) regenerability can lean solution in carbon dioxide content m
1Determine m
1More little, power of regeneration is strong more; (3) comprehensive decarburization capacity can be determined by the amount of solution absorption or desorb carbon dioxide: N=L (m
2-m
1).L is the internal circulating load of decarbonizing solution in the formula.When L is constant, m
2-m
1Increment can characterize the quality of decarbonizing solution performance relatively.
In the present invention, the selected of simulation decarbonization device condition also is according to industrial production reality: experiment absorption tower inlet temperature is chosen to be 60 ℃, and this temperature and industrial absorption tower inlet temperature are approaching; In the industry absorption tower, partial pressure of carbon dioxide is 0.5MPa at the bottom of the tower, and cat head is 0.003MPa, and its calculating mean value is 0.25MPa.Be the simplification process among the present invention, replace mist with pure carbon dioxide, the pressure on simulation absorption tower is got at the bottom of the industrial Tata and the mean value of cat head partial pressure of carbon dioxide, i.e. 0.2MPa and 0.3MPa.
The concentration of MDEA in the decarbonizing solution, drawing its optium concentration through the experiment of simulation decarbonization device is 3.0kmol/m
3, then as main body, the activator such as piperazine, diethanol amine, morpholine that adds different proportionings carries out the comparison of comprehensive decarbonization performance.
See Table 1 and table 2 in (keep under the constant situation of the molar concentration 3.0mol/L of total alkali, each activator is 0.1 with the MDEA weight ratio) different activator evaluation results under the identical experiment condition.The increment Delta N of absorbing carbon dioxide amount is with N ° of the MDEA solution that the do not add activator relative increment of benchmark as a comparison in the table, promptly Δ N%=N-N °/N ° * 100%.
The different activator evaluation results of table 1 (P=0.2MPa)
| Activator | N×10 -3(kmol/L) | ΔN(％) |
| -morpholine piperazine diethanol amine morpholine+piperazine morpholine+diethanol amine | 1.042 1.129 1.246 1.116 1.363 1.325 | - 8.35 19.58 7.10 30.81 27.16 |
The different activator evaluation results of table 2 (P=0.3MPa)
| Activator | N×10 -3(kmol/L) | ΔN(％) |
| -morpholine piperazine diethanol amine morpholine+piperazine morpholine+diethanol amine | 1.301 1.513 1.556 1.464 1.765 1.721 | - 16.30 19.60 12.53 35.66 32.28 |
By table 1 and table 2 as seen, the activity of experiment each activator of doing is an optimum with morpholine+piperazine and morpholine+diethanol amine, far above single activator.Simultaneously, though activity is relatively poor when diethanol amine adds separately, its advantage is that solution is difficult for bubbling; The piperazine activity is the highest, but its easy foaming; Morpholine is a kind of heterocyclic compound, and its activity is between piperazine and diethanol amine.
According to above-mentioned design and activator evaluation result, the inventor proposes following technical scheme:
The said N methyldiethanol amine of the present invention (MDEA) decarbonizing solution is made up of the N methyldiethanol amine aqueous solution and activator, it is characterized in that: said activator is made up of morpholine and piperazine, and the weight ratio of activator and N methyldiethanol amine is 0.05～0.20; Or form by morpholine and diethanol amine, the weight ratio of activator and N methyldiethanol amine is 0.05～0.25.The weight ratio of preferred activator and N methyldiethanol amine is 0.08～0.14.
The said decarbonizing solution of the present invention can be used for removing of carbon dioxide in the mists such as synthesis gas, town gas or natural gas, also can remove sulfide simultaneously.This decarbonizing liquid has that absorptive capacity is big, degree of purification is high, the regeneration low power consumption and other advantages.
The specific embodiment:
The invention will be further described below by embodiment, its objective is to be better understanding content of the present invention:
Embodiment 1
Adopt previously described laboratory simulation device and condition respectively to carrying out overall merit by morpholine (MAL) and piperazine (PZ) or morpholine (MAL) and diethanol amine (DEA) for the MDEA decarbonizing liquid performance of activator, evaluation result sees Table 3 and table 4:
Table 3: with morpholine (MAL) and piperazine (PZ) is that (experimental condition is that the molar concentration of solution total alkali is 3.0mol/L, and PZ and MDEA weight ratio are 0.1 for the MDEA decarbonizing liquid performance synthesis evaluation result of activator; W in the table
MAL/ W
MDEA+PZMAL and weight fraction (MDEA+PZ) in the expression solution):
| P (MPa) | W MAL/ W MDEA+PZ | m 1 (kmol/m 3) | m 2 (kmol/m 3) | m 2-m 1 (kmol/m 3) | N×10 -3 (kmol/h) |
| 0.2 | 0.00 0.02 0.05 0.08 0.10 0.12 0.15 0.20 | 0.107 0.103 0.158 0.177 0.218 0.224 0.278 0.322 | 1.419 1.434 1.496 1.605 1.653 1.632 1.619 1.595 | 1.312 1.330 1.337 1.428 1.435 1.408 1.341 1.273 | 1.246 1.264 1.270 1.356 1.363 1.337 1.273 1.209 |
| 0.3 | 0.00 0.02 0.05 0.08 0.10 0.12 0.15 0.20 | 0.198 0.201 0.284 0.366 0.404 0.432 0.456 0.474 | 1.836 1.846 2.052 2.185 2.262 2.191 2.045 1.870 | 1.638 1.645 1.768 1.819 1.858 1.759 1.589 1.396 | 1.556 1.562 1.679 1.728 1.765 1.671 1.509 1.326 |
By table 3 as seen, in the MDEA solution of PZ activation, add MAL and can obviously improve the solution decarbonization performance.During for 0.2MPa: add MAL to W
MAL/ W
MDEA+PZBe 0.15 (to be W
MAL/ W
MDEA=0.165) all effective, its optimum content is W
MAL/ W
MDEA+PZBe 0.10 (to be W
MAL/ W
MDEA=0.11); During for 0.3MPa: add MAL to W
MAL/ W
MDEA+PZBe 0.12 (to be W
MAL/ W
MDEA=0.132) all effective, its optimum content is W
MAL/ W
MDEA+PZBe 0.10 (to be W
MAL/ W
MDEA=0.11).
Table 4: with morpholine (MAL) and diethanol amine (DEA) is the MDEA decarbonizing liquid performance synthesis evaluation result (experimental condition is that the molar concentration of solution total alkali is 3.0mol/L, and DEA and MDEA weight ratio are 0.1) of activator:
| P (MPa) | W MAL/ W MDEA+DEA | m 1 (kmol/m 3) | m 2 (kmol/m 3) | m 2-m 1 (kmol/m 3) | N×10 -3 (kmol/h) |
| 0.2 | 0.00 0.02 0.05 0.08 0.10 0.12 0.15 0.20 | 0.104 0.117 0.154 0.181 0.216 0.242 0.276 0.322 | 1.278 1.311 1.502 1.569 1.611 1.577 1.558 1.527 | 1.174 1.194 1.348 1.388 1.395 1.335 1.282 1.205 | 1.115 1.134 1.281 1.318 1.325 1.268 1.218 1.145 |
| 0.3 | 0.00 0.02 0.05 0.08 0.10 0.12 0.15 0.20 | 0.187 0.193 0.254 0.338 0.398 0.418 0.422 0.441 | 1.728 1.826 2.004 2.105 2.210 2.165 2.111 1.998 | 1.541 1.633 1.750 1.767 1.812 1.747 1.689 1.557 | 1.464 1.551 1.665 1.678 1.721 1.659 1.605 1.479 |
By table 4 as seen, in the MDEA of DEA activation, add the decarbonization performance that MAL obviously improves solution, for when 0.2MPa and the 0.3MPa: add MAL to W
MAL/ W
MDEA+DEA=0.20 (is W
MAL/ W
MDEA=0.22) all effective, and its optimum content is W
MAL/ W
MDWA+DEA=0.10 (is W
MAL/ W
MDEA=0.11).
Embodiment 2
Certain is produced 40000 tons of synthetic ammonia decarbonization devices per year and selects the said MDEA decarbonizing solution of the present invention for use (MDEA concentration is 36 weight %; Activator is morpholine and diethanol amine; The weight ratio of morpholine and MDEA is 0.06; The weight ratio of diethanol amine and MDEA is 0.2) carry out decarburization.The back production system of going into operation is stable, and absorptive capacity is big, every cubic metre of solution absorbing carbon dioxide 20～22Nm
3Consume low: MDEA consumes 0.097 kilogram of/ton ammonia; Diethanol amine consumes 0.019 kilogram of/ton ammonia; Morpholine consumes 0.013 kilogram of/ton ammonia; Steam consumption is less than 1.2 tons of/ton ammonia.
Embodiment 3
Once adopted existing MDEA decarbonizing solution in certain formic acid subsidiary factory synthesis gas decarbonization process, 60% and the solution degradation thing that only can reach the design load after the driving are many.(MDEA concentration is 30 weight % to use the said MDEA decarbonizing solution of the present invention instead; Activator is morpholine and piperazine, the weight ratio of morpholine, piperazine and MDEA is 0.1: 0.1: 1) after, use the result to show: MDEA does not have obvious degradation, the activator stable content, carbon dioxide content is produced load and is reached designed capacity less than 0.1% behind the purified synthesis gas.
Claims (3)
1, a kind of N methyldiethanol amine decarbonizing solution, it is made up of the N methyldiethanol amine aqueous solution and activator, it is characterized in that, and said activator is made up of morpholine and piperazine, and the weight ratio of activator and N methyldiethanol amine is 0.05～0.20.
2, a kind of N methyldiethanol amine decarbonizing solution, it is made up of the N methyldiethanol amine aqueous solution and activator, it is characterized in that, and said activator is made up of morpholine and diethanol amine, and the weight ratio of activator and N methyldiethanol amine is 0.05～0.25.
As claim 1 or 2 said decarbonizing solutions, it is characterized in that 3, wherein the weight ratio of activator and N methyldiethanol amine is 0.08～0.14.
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| CN101822932B (en) * | 2010-06-12 | 2013-01-02 | 中国石油集团工程设计有限责任公司 | Composite decarbonization solvent for eliminating carbon dioxide in natural gases |
| CN102423620B (en) * | 2011-10-26 | 2013-10-30 | 康达新能源设备股份有限公司 | Compound decarbonizing solvent for removing carbon dioxide from biogas |
| FR2990878B1 (en) * | 2012-05-25 | 2014-05-16 | Total Sa | PROCESS FOR THE PURIFICATION OF GASEOUS MIXTURES CONTAINING ACIDIC GASES |
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