CN101804292A - Special MDEA formula solution activated by functional ion liquid for CO2 gas absorption separation - Google Patents
Special MDEA formula solution activated by functional ion liquid for CO2 gas absorption separation Download PDFInfo
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Abstract
The invention relates to a special N-methyldiethanolamine formula solution activated by ion liquid for CO2 gas absorption separation, which consists of the following ingredients in mass percent: 35 to 50 percent of N-methyldiethanolamine, 5 to 20 percent of low-viscosity kalescent functional ion liquid, 15 to 30 percent of dimethyl ether of polyethlene glycol and/or sulfolane and 15 to 30 percent of water, wherein cations of the low-viscosity kalescent functional ion liquid are tetraalkylammonium ions, and anions of the low-viscosity kalescent functional ion liquid are amino acid radicals or organic carboxylate anions. The formula solution of the invention has the advantages that the high mass transfer performance of the absorption-desorption process is improved, the material consumption in the use process is low, the defect of high energy consumption because a large amount of water vapor is brought away during the absorbing agent regeneration, and the invention belongs to an energy-saving formula with high green degree. The regeneration temperature of the solution is lower than that of the traditional absorbing liquid, the grade of a heat source required to be provided in the regeneration process is reduced, energy sources can be saved, the stability of the absorbing agent solution in the operation is high, the consumption of each absorption-desorption circulation is low, and in addition, the cost is low.
Description
Technical field
The present invention relates to the reversible absorption of a kind of energy CO
2Formula solution, specifically, be a kind of formula solution of functionalized ion liquid.
Technical background
Along with the development of industrial society, atmosphere polluting problem gets more and more people's extensive concerning, wherein, and carbon dioxide (CO
2) as the topmost gas that causes greenhouse effects, in Kyoto Protocol, control the obligation that its discharge capacity has become the signtory power acquire full legal force.On the other hand, during chemical industry was produced, the decarburization of natural gas was a crucial link before it is used, and various synthesis gas, hydrogen energy source prepare in the mist such as gas and also contain various variable concentrations and the CO harmful to process
2, it is removed is one requisite production process.Generally speaking, CO
2Remove at aspects such as environmental protection, industrial production extremely important meaning arranged.
At present, the most frequently used decarbonization method is an organic amine aqueous solution absorption process, generally is with monoethanolamine (MEA), diethanol amine (DEA), diisopropanolamine (DIPA) (DIPA), and methyl diethanolamine (MDEA) is made into the mixed solution use with water.Though this method CO
2Assimilation effect is good, but has a lot of defectives.
(1) organic amine particularly these primary amine of MEA, DEA and secondary amine because activity is stronger, with CO
2Active force is strong, is difficult to resolve suction after the absorption, and relatively easy degraded is rotten, makes the absorbent stability decreases, and the cycle of recycling shortens.In addition, primary amine and secondary amine are because alkalescence is stronger, and therefore etching apparatus during regeneration makes to the requirement height of equipment material, has increased production cost.
(2) MDEA boiling point height (247 ℃), stability are high, little to equipment corrosion, can effectively remedy the defective of primary amine, secondary amine, are most widely used in smoke eliminator at present.Yet, because MDEA is a tertiary amine, there is not reactive hydrogen, it absorbs CO
2Speed very slow, generally need to add one or more compositions such as a spot of activator or promoter such as piperazine, MEA, DEA, DIPA, imidazoles, diethylenetriamine to constitute formula solution.But these activators or promoter itself have certain vapour pressure, at CO
2Meeting volatilization loss in the process that absorbs and resolve, both loss material and absorbability also caused environmental pollution.
(3) traditional absorbent often uses a large amount of water (mass content is about 40-50%) to dilute owing to have certain viscosity, and the steam of being taken out of in the absorption process is etching apparatus not only, thereby and need the extra step that dewaters to increase operating cost; Owing to evaporation of water is taken away a large amount of latent heat, cause the process energy consumption high in high temperature (100-150 ℃) desorption process.
All these or other shortcomings have determined that organic amine aqueous solution absorption process is not the green process of environmental friendliness, resource and an energy conservation, will be replaced by other more green green process or eliminate.
As a kind of novel green solvent, ionic liquid is meant under room temperature and adjacent temperature the organic liquid material of being made up of ion fully, and its maximum characteristics are almost not have vapour pressure, and volatility is low, Heat stability is good, and with respect to other gas (as N
2, O
2, CO, CH
4, H
2, C
2H
6, C
2H
4Deng), it is to CO
2Solubility big and separation selectivity is high.Therefore, adopt the ionic liquid decarburization can eliminate the volatilization loss of steam and organic amine effectively, both saved energy consumption and resource, also protected environment effectively.At present, more existing researchers have carried out certain exploration on the one hand at this, people such as E.D.Bates (J.Am.Chem.Soc., 2002,124 (6), 926-927) synthetic [1-butyl-3-(1-amido alkyl) imidazoles] fluoboric acid root, people such as K.Fukumoto (J.Am.Chem.Soc., 2005,127,2398-2399) and people (Chem.Eur.J.2006,12 such as Zhang Suojiang, 4021-4026) synthetic amino acid ion liquid is under the room temperature normal pressure, and the amount of its absorbing carbon dioxide can reach nearly 0.5mol CO
2/ mol ionic liquid, the absorbability of absorbability and traditional organic amine absorbent is suitable, and equipment is not had corrosivity, and the absorbent consistency does not have volatilization loss yet in the process of absorption-desorb carbon dioxide repeatedly.But this class ionic liquid generally has higher viscosity (the high hundreds of of viscosity than water arrives thousands of times usually), has greatly limited CO
2The carrying out of mass transport process during reversible absorb, and its production prices and cost of material thereof be also than the high dozens to one hundred times of existing organic amine directly used both unrealisticly as absorbent, also do not have an economy, therefore still do not have the report of commercial Application so far.
At present, it is that cation, amino acid group or organic acid are anionic low viscosity alkalescent functionalized ion liquid (Chem.Comm.2008 with cheap tetra-allkylammonium that this laboratory has successfully synthesized a series of, 505-507, New J.Chem.2009,2385-2390).The viscosity that such ion liquid viscosity can be low to moderate 29mPaS (25 ℃, down with) and traditional organic amine liquid is (viscosity as MEA is 21mPaS, and the viscosity of MDEA is 76mPaS) quite.Just absorb CO
2Ability, be anion ion liquid with amino acid, its absorbability and MEA are suitable, if anion is organic acid, its absorbability is equivalent to MEA at least and absorbs CO
21/4 to 1/2 of ability.And it absorbs CO
2Speed and MEA very approaching, heat endurance also good (heat decomposition temperature is more than 180 ℃), in sum, such alkalescent functionalized ion liquid has possessed practical application foreground.Yet, though such ion liquid synthesizing with cost of material declines to a great extent than the above-mentioned amino functional ionic liquid of mentioning, still exceed several times than organic amine, directly use in actual industrial process, to also have suitable difficulty as absorbent.
If can will be that cation, amino acid group or organic acid are the composition of anionic alkalescent functionalized ion liquid as activator or promoter, utilize its CO of such ionic liquid with the tetra-allkylammonium
2Absorption and desorption speed fast, absorptive capacity is big, and low, the no vapour pressure of viscosity, the advantage that volatility is low cooperates CO
2Absorptive capacity is big, the MDEA of good stability uses, and is expected on the basis that increases cost not significantly, overcomes the above-mentioned various technical problems of mentioning well, will be the high CO of a kind of green degree
2Reversible absorption formula solution, this also constitutes the new approaches and the technical essential of the art of this patent.
The present invention simulates industrial the most frequently used mixing organic amine carbon rejection processes at present, propose with low viscous alkalescent functionalized ion liquid replace boiling point low, volatile organic amine is arranged as activator, be equipped with volatility low with stability preferably MDEA as CO
2Main absorbent components, with the NHD of low viscosity and low volatility and (or) sulfolane is as the dilution component, is mixed and made into novel MDEA formulation absorption liquid system with an amount of water again.Formulation absorption liquid of the present invention significantly reduces low, a series of problems such as reuse is poor, energy consumption material consumption height, operating cost is big, environmental pollution is serious of absorbent solution stability that steam volatilizees, the organic amine volatilization is brought when keeping conventional hybrid organic amine absorbent absorbability and the high mass-transfer performance of absorption-desorption process.
Summary of the invention
The objective of the invention is to simulate the organic amine aqueous solution absorption of the mixing CO that MDEA adds MEA or DEA
2Method, propose with low viscosity, weakly alkaline functionalized ion liquid as quick reversible absorption CO
2Activating component, with the low and stable MDEA preferably of volatility as CO
2The key component that absorbs, with the NHD of low viscosity and low volatility and (or) sulfolane is as the dilution component that replaces part water, an amount of water absorbs and this prescription thinking of dilution component as auxiliary, providing a kind of is the new formulation absorption liquid system of principal character with alkalescent functionalized ion liquid activator, when keeping conventional hybrid organic amine absorbent absorbability and the high mass-transfer performance of absorption-desorption process, farthest overcome it and take a large amount of steam out of and the shortcoming that causes high energy consumption, and reduce a series of problems that the organic amine volatilization is brought greatly.This new formulation absorption liquid system comprises 4 constituents: N methyldiethanol amine (MDEA), low viscosity and weakly alkaline functionalized ion liquid, NHD (mean molecule quantity is between 180-300) and (or) sulfolane, and water.
Technical scheme of the present invention is as follows:
-kind be exclusively used in CO
2The MDEA formula solution by the functionalized ion liquid activation of gas absorption separation, it is made up of following mass component:
As the N methyldiethanol amine (MDEA) that absorbs the main body composition: 35-50%
Low viscosity alkalescent functionalized ion liquid as quick reversible absorption activator: 5-20%
As the dilution component NHD and (or) sulfolane: 15-30%
As the auxiliary water that absorbs and dilute component: 15-30%
Wherein said low viscosity alkalescent functionalized ion liquid, its cation is a tetraalkyl ammonium ion, anion is amino acid group or organic carboxyl acid root anion.
Above-mentioned formula solution has lower viscosity under the ionic liquid room temperature as the activator use, viscosity＜300mPa.s, and preferred viscosity＜150mPa.s, and be liquid, its general structure is:
Wherein: R
1, R
2Expression has 1～6 carbon atom (C
1～C
6) the straight or branched alkyl, R
1And R
2Both can be identical, also can be different, preferred R
1, R
2For the carbon atom number is not more than 4 straight or branched alkyl, as methyl, ethyl, n-pro-pyl, isopropyl, acrylic, normal-butyl, isobutyl group etc., and R
2With R
1The carbon number difference, Y is an anion, n is anionic charge number or ion valence mumber, its numerical value is 1 or 2.
Above-mentioned formula solution, in the described alkalescent functionalized ion liquid general structure, Y
N-What represent is amino acid radical anion, used amino acid group is not more than 5 amino acid radical anion for the carbon atom number, as glycine root, L-alanine root, Beta-alanine root, GABA root, valine, N-methyl aminoacetic acid root, N-methyl-L-alanine root etc.
Above-mentioned formula solution, in the described alkalescent functionalized ion liquid general structure, Y
N-Also can be expressed as organic carboxyl acid root anion, preferably the carbon atom number is not more than 5 monocarboxylic acid root and dicarboxylic acids root, as formate, acetate, propionate, butyric acid root, methacrylate, acrylic acid root, malonate, succinic, glutarate, maleate, malate etc.
Above-mentioned formula solution, described MDEA and ionic liquid all are CO
2The active ingredient that absorbs is to CO
2The main contribution source of absorptive capacity size, the ratio that both total amounts account for the absorption liquid gross mass must be controlled at 40-65wt%, so that the absorptive capacity of this patent absorption liquid and traditional absorption liquid is suitable, also keeps low viscosity characteristics simultaneously, is beneficial to CO
2The mass transfer characteristic of absorption process.
NHD in the above-mentioned prescription (mean molecule quantity is between 180-300) and sulfolane (＜50 ℃) at low temperatures itself are exactly CO preferably
2Physical absorbent, but because its absorptive capacity is littler than these chemical absorbents such as organic amine or alkalescent functionalized ion liquids, (the former is about 3.0mPa.s in this low viscosity of mainly utilizing them, the latter is 10.3mPa.s) and low volatility (boiling point be respectively 〉=285 and 285 ℃), use as diluent, be used to replace part water, thereby reduce the volatilization of water, reduce the regeneration energy consumption of absorption liquid greatly.NHD and sulfolane both can use separately, also can mix use in certain proportion, and overall control is at 15-30wt%.
Water in the above-mentioned prescription is the necessary material of MDEA formulation absorption liquid, because it participates in MDEA and CO
2Chemical reaction process, be the assistant of absorption-desorption process.Simultaneously, in the reaction later stage, along with the generation of product, it is big that the viscosity of absorption liquid becomes, and water still guarantees the product dissolving and becomes the retarder thinner of low viscosity solution, otherwise the absorption rate of solution can descend the dynamic process that influence absorbs greatly.In fact, be that 40wt% calculates with the content of MDEA, participate in CO
2The water content of the required consumption of chemical absorbing only need about 5wt%, remaining all plays the retarder thinner effect.The content of water has greatly influenced CO generally up to more than the 40wt% in traditional absorption liquid prescription
2Desorption process energy-conservation.This patent is by introducing low viscous alkalescent functionalized ion liquid as activator, and with low viscous NHD and (or) sulfolane is as diluent, the retarder thinner function that partly replaces water, thereby the content of water in prescription can be descended greatly, and control its content below 30wt%, reach the target that both reduces water content, simultaneously formulation absorption liquid is maintained than low viscosity in whole absorption process, be beneficial to CO
2The carrying out of mass transport process.This breadboard studies show that, MDEA and CO
2Product and alkalescent functionalized ion liquid and CO
2The product of reaction can both be dissolved in well NHD and (or) in the aqueous solution of sulfolane, and the increase of viscosity is limited, this attempts laying a good foundation in the innovation that reduces aspect the water content for this patent.In addition, because alkalescent functionalized ion liquid energy and CO
2Play fast reaction, its absorption rate at least with the absorption CO of MEA
2Speed is suitable, in the present invention's prescription the concentration higher than the activator in the conventional formulation absorption liquid is arranged by keeping the alkalescent functionalized ion liquid, and it absorbs CO
2Speed can be faster, this lays a good foundation to the requirement of formula solution viscosity of the present invention for reducing, and helps reducing greatly water content.
The principle of absorption of formulation absorption liquid of the present invention was both similar with the absorption mechanism that mixes the organic amine absorbing carbon dioxide, and difference is also arranged.Something in common is, with amino acid be anionic alkalescent functionalized ion liquid activator also can with CO
2Reaction generates aminoquinoxaline intermediate-ion (is example with the glycine ionic liquid):
The CO of formula (1) expression 1 molecule
2With the glycine tetraalkyl ammonium ion liquid reactions of 2 molecules, generate 1 aminoquinoxaline ionic compound intermediate (its molecular structure is suc as formula shown in the right of (1)).Then, quick proton-exchange reaction takes place with MDEA in ionic compound intermediate again in the presence of water, generates bicarbonate ion
With protonated
And restore primary amine groups in the amino acid ion liquid:
Owing to generally contain primary amine or secondary amine (when also having another substituting group on the amido) group in the amino acid ion liquid, itself and CO
2Reaction rate constant be far longer than MDEA and CO
2Reaction rate constant, therefore, the amino acid ion liquid of adding has changed MDEA and CO
2The reaction mechanism mechanism of reaction, reaction rate increases greatly and reacts (2) for fast response.Because amino acid ion liquid and CO
2Physical efficiency is promptly carried out proton exchange with MDEA in the middle of the aminoquinoxaline ionic compound that reaction back generates, and the amino acid ion liquid that dissociates again, makes that unreacted amino acid ion liquid concentration is constant substantially in the solution.So, amino acid ion liquid absorbs CO at MDEA
2Played the effect of homogeneous catalysis and activation in the process.
The principle of absorption of the formulation absorption liquid of the present invention place different with traditional absorbent is that having the anionic alkalescent functionalized ion liquid of organic monoacid hydrate can also absorb CO with another kind of activate mechanism
2(is example with acetate ion liquid):
In the formula, n represents the number of water in the alkalescent functionalized ion liquid hydrate molecule, and its value is 2 to 12.Quick proton exchange takes place with MDEA in the acetate hydrate that generates (structure such as following formula the right second) again:
Regenerate ionic liquid hydrate after acetic acid anion that restores and tetraalkylammonium cation and water are compound, make the basic maintenance in system of its concentration constant, reach the effect of fast activating.
The process conditions of formula solution absorbing carbon dioxide of the present invention are: operating temperature is 0～60 ℃, and operating pressure is 1～30 atmospheric pressure.
Formulation absorption liquid of the present invention is absorbing CO
2After saturated, can be by heating up and decompression regeneration.Because the bicarbonate ion that absorption process generates, aminoquinoxaline compound intermediate etc. are all unstable, when temperature surpasses 80 ℃, pressure 0 to 0.1MPa the time, course of reaction should be main with formula (1) to the converse of formula (4), is decomposed into CO again
2And MDEA, ionic liquid plays fast desorption CO therein
2Activation and catalytic action.Finish CO
2The absorbent of desorb can be recycled, and promptly is recycled and reused for the carbon dioxide absorption process.
Reversible absorption CO of the present invention
2The advantage of formula solution be:
(1) both kept and the suitable absorbability of conventional hybrid organic amine absorbent, can also improve the high mass-transfer performance of absorption-desorption process to a certain extent;
(2) in the absorbent except that low amounts of water (mass content is not more than 30%), other material or non-volatile (as ionic liquid), perhaps volatility is very low (as MDEA, NHD, sulfolane etc.), material loss is few in the use, because of taking the high energy consumption shortcoming that a large amount of steam cause out of, be a kind of energy-conservation, Recipe that green intensity is high in the time of farthest overcoming absorbent regeneration again.
(3) non-volatile because of functionalized ion liquid, greatly reduce a series of problems that organic amine volatilization is brought, as environmental pollution, activator loss, absorption capacity of absorbent with absorption rate weakens, the repeated use cycle is short etc.;
(4) because of low viscosity, weakly alkaline functionalized ion liquid be absorption also be the activator of desorption process, the regeneration temperature of solution is lower than traditional absorption liquid, has both reduced the thermal source grade that regenerative process need provide, and also is expected to energy savings;
(5) the absorbent solution stability that is in operation is high, and the loss of each absorption-desorption cycle is little, and with low cost.
The specific embodiment
Embodiment 1
35 gram N methyldiethanol amines, 20 gram triethyl group butyl ammonium L-alanine radical ion liquid, 30 gram NHDs and 15 gram deionized waters are mixed, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 2
40 gram N methyldiethanol amines, 15 gram triethyl group butyl ammonium glycine radical ion liquid, 25 gram NHDs and 20 gram deionized waters are mixed, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 3
45 gram N methyldiethanol amines, 20 gram trimethyl butyl ammonium acetate ion liquid, 20 gram sulfolane and 15 gram deionized waters are mixed, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 4
50 gram N methyldiethanol amines, 15 gram two (triethyl group butyl ammonium) malonate ionic liquids, 20 gram NHDs and 15 gram deionized waters are mixed, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 5
40 gram N methyldiethanol amines, 20 gram trimethyl ethyl ammonium acetate ion liquid, 25 gram NHDs and 15 gram deionized waters are mixed, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 6
With 45 gram N methyldiethanol amines, 5 gram trimethyl butyl ammonium glycine ionic liquids, 5 gram trimethyl butyl ammonium L-alanine radical ion liquid mix with 10 gram NHDs, 10 gram sulfolane and 25 gram deionized waters, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 7
With 50 gram N methyldiethanol amines, 10 gram tributyl-methyl phosphonium ammonium glycine ionic liquids, 5 gram two (triethyl group butyl money) maleate ionic liquids mix with 15 gram NHDs and 20 gram deionized waters, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 8
With 45 gram N methyldiethanol amines, 10 gram trimethyl propyl ammonium L-alanine radical ion liquid, 5 gram two (triethyl group butyl ammonium) malonate ionic liquids, 15 gram sulfolane and 25 gram deionized waters mix, and fully stir, and make MDEA formulation absorption liquid of the present invention.
Embodiment 9
45 gram N methyldiethanol amines, 5 gram triethyl group butyl ammonium Beta-alanine radical ion liquid, 5 gram trimethyl butyl ammonium propionate ion liquid are mixed with 15 gram sulfolane, 15 gram NHDs and 15 gram deionized waters, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 10
37 gram N methyldiethanol amines, 3 gram two (triethyl group butyl ammonium) malate ionic liquids, 10 gram triethyl group butyl ammonium acetate ion liquid are mixed with 30 gram NHDs and 20 gram deionized waters, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 11
45 gram N methyldiethanol amines, 10 gram tripropyl ammonium methyl N-methyl aminoacetic acid radical ion liquid are mixed with 15 gram NHDs and 30 gram deionized waters, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 12
With 40 gram N methyldiethanol amines, 15 gram triethyl group butyl ammonium valine radical ion liquid, 15 gram NHDs, 30 gram deionized waters mix, and fully stir, and make MDEA formulation absorption liquid of the present invention.
Embodiment 13
45 gram N methyldiethanol amines, 10 gram two (triethyl group butyl ammonium) glutarate ionic liquids, 20 gram sulfolane and 25 gram deionized waters are mixed, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 14
37 gram N methyldiethanol amines, 3 gram TBuA aminobutyric acid radical ion liquid, 10 gram two (triethyl group propyl ammonium) malonate ionic liquids are mixed with 25 gram sulfolane and 25 gram deionized waters, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 15
45 gram N methyldiethanol amines, 10 gram tributyl hexyl ammonium L-alanine radical ion liquid are mixed with 20 gram sulfolane and 25 gram deionized waters, fully stir, make MDEA decarburization formulation absorption liquid of the present invention.
Embodiment 16
30 gram N methyldiethanol amines, 20 gram trimethyl propyl ammonium N-methyl-L-alanine radical ion liquid are mixed with 30 gram NHDs and 20 gram deionized waters, fully stir, make MDEA formulation absorption liquid of the present invention.
Embodiment 17
With 45 gram N methyldiethanol amines, 15 gram trimethyl propyl ammonium acrylic acid radical ion liquid and 10 gram NHDs, 10 gram sulfolane and 20 gram deionized waters mix, and fully stir, and make MDEA formulation absorption liquid of the present invention.
Embodiment 18
Prepare 100 gram formulation absorption liquid respectively by embodiment 1-17, under 25 ℃, absorption liquid is placed absorption bottle respectively, pure carbon dioxide gas under 1 atmospheric pressure is pressed in the absorption liquid by the bubbling mode respectively absorbs, at set intervals absorption liquid is weighed, when absorption liquid weight no longer increases, stop to add CO
2Test result shows that the weight of the absorption liquid of embodiment 1-17 increases by 10.8,11.8,12.6,13.2 respectively, and 11.5,12.4,13.8,12.9,12.3,10.1,12.5,11.5,12.1,10.0,12.4,9.9,12.4 grams are converted to the CO under the standard conditions
2The gas solubility data are respectively 52.9,57.4,61.7,64.7,56.3,60.7,67.5,63.0,60.1,49.4,61.2,56.4,59.2,48.7,60.7,48.4,60.5Nm
3/ m
3, suitable with the absorptive capacity scope of traditional activation MDEA absorption liquid.
Embodiment 19
Repeat embodiment 18, test 40 ℃ under, embodiment 1-17 formulation absorption liquid 100 restrains CO
2The saturated absorption amount.Test result shows that the weight of the absorption liquid of embodiment 1-17 increases by 9.8,10.6,11.4,11.9,10.4 respectively, 11.1,12.4,11.6,11.1,9.1,11.3,10.4,10.9,9.0,11.2,8.9,11.2 grams, the CO2 gas solubility data that are converted under the standard conditions are respectively 47.6,51.7,55.5,58.2,50.7,54.6,60.8,56.7,54.1,44.5,55.0,50.7,53.3,43.9,54.6,43.6,54.5Nm
3/ m
3, suitable with the absorptive capacity scope of traditional activation MDEA absorption liquid.
Embodiment 20
Repeat embodiment 18, test 60 ℃ under, embodiment 1-17 formulation absorption liquid 100 restrains CO
2The saturated absorption amount.Test result shows that test result shows that the weight of the absorption liquid of embodiment 1-15 increases by 8.0,8.6,9.2,9.6 respectively, 8.4,9.0,10.0,9.4,8.9,7.3,9.1,8.4,8.8,7.2,9.0,7.3,9.0 gram, the CO2 gas solubility data that are converted under the standard conditions are respectively 38.9,42.0,44.9,46.7,41.1,44.0,49.0,45.9,43.6,35.8,44.4,41.1,42.8,35.3,44.1,35.8,43.9Nm
3/ m
3, suitable with the absorptive capacity scope of traditional activation MDEA absorption liquid.
Embodiment 21
The process of 100.0 gram formulation absorption liquid of embodiment 1 preparation press embodiment 18 repeats, the test result discovery absorbent uptake (52.9Nm that can reach capacity in 25 minutes
3/ m
3).Stop ventilation, add air set pipe (condensate temperature is 0 ℃) above absorption bottle, and absorbent is heated rapidly to 100 ℃, the temperature of keeping 100 ℃ was intermittently bled each 30 seconds 3 times with vavuum pump after 20 minutes again in 5 minutes.Stop to weigh after the desorb operation, find that absorbent weight is constant substantially, illustrate that absorbent does not have loss and CO substantially
2Desorb is more complete.So repeat absorption-desorb operation 5 times, find that the saturated absorption amount of follow-up each time is respectively 51.0,50.9,50.8,50.9Nm except that the first time (fresh absorption liquid)
3/ m
3, than primary 52.9Nm
3/ m
3Slightly descend, but do not change substantially, illustrate that each desorption process can reach equal desorb degree under same condition with the cycle-index of absorption-desorb, and the CO of absorption again of the absorbent behind the desorption and regeneration
2Ability and speed can remain unchanged.
Embodiment 22
With 100.0 gram formulation absorption liquid of embodiment 4 preparations, repeat the CO of embodiment 19
2Absorption process, test result are found the absorbent uptake (58.2Nm that can reach capacity in 25 minutes
3/ m
3).Absorb-desorb according to embodiment 21, test finds that the saturated absorption amount of follow-up each time is respectively 56.9,56.9,56.8,56.8Nm again
3/ m
3, do not change substantially with the cycle-index of absorption-desorb, it is good to illustrate that this composite absorber repeats assimilation effect.
Embodiment 23
With 100.0 gram formulation absorption liquid of embodiment 7 preparations, repeat the CO of embodiment 20
2Absorption process, test result are found the absorbent uptake (49.0Nm that can reach capacity in 25 minutes
3/ m
3).Stop ventilation, with CO
2Air inlet pipe changes air set pipe (condensate temperature is-5 ℃) into, and absorbent is heated rapidly to 120 ℃, and the temperature of keeping 120 ℃ was reduced to room temperature after 60 minutes, weighed, and finds that formulation absorption liquid weight is 100.1g, illustrates that the absorption liquid elementary solution sucks entirely.So repeat absorption-desorb operation 5 times, find that the saturated absorption amount of follow-up each time is respectively 48.2,48.1,48.1,48.1Nm except that the first time (fresh absorption liquid)
3/ m
3, than primary 49.0Nm
3/ m
3Slightly descend, but do not change substantially, illustrate that each desorption process can reach equal desorb degree under same condition with the cycle-index of absorption-desorb, and the CO of absorption again of the absorbent behind the desorption and regeneration
2Ability and speed can remain unchanged.
Embodiment 24
Press embodiment 1 preparation 5L formulation absorption liquid, join the packed tower that tower diameter is 30mm, height 1500mm from the flow velocity of cat head with 2.0mL/s, the efficient Θ ring of filling Ф 3x3mm in the packed tower, feed 40 ℃, the simulated flue gas of 0.103MPa with the speed of 1.0m/s at the bottom of the tower, forming (percentage by volume) is CO
2: N 15%,
2: O 76%,
2: SO 3%,
2: 50ppm, H
2O:6%.Gas and liquid phase counter current contacting reached to steady state operation after 10 minutes, analyzed the gas phase that is absorbed back gas and formed CO
2Concentration＜100ppm, SO
2Concentration＜1ppm.
Embodiment 25
Press embodiment 9 preparation 5L formulation absorption liquid, join the packed tower that tower diameter is 30mm, height 2000mm from the flow velocity of cat head with 2.0mL/s, the efficient Θ ring of filling Ф 3x3mm in the packed tower, feed 65 ℃, the simulated flue gas of 0.103MPa with the speed of 1.5m/s at the bottom of the tower, forming (percentage by volume) is CO
2: N 20%,
2: O 71%,
2: H2O:3.9% 5%.Gas and liquid phase counter current contacting reached to steady state operation after 15 minutes, analyzed the gas phase that is absorbed back gas and formed CO
2Concentration＜300ppm.
Claims (10)
1. one kind is exclusively used in CO
2The N methyldiethanol amine formula solution by low viscosity, the activation of alkalescent functionalized ion liquid of gas absorption separation, it is characterized in that: it is made up of following mass component:
As the N methyldiethanol amine that absorbs the main body composition: 35-50%
Low viscosity alkalescent functionalized ion liquid as quick reversible absorption activator: 5-20%
As the dilution component NHD and (or) sulfolane: 15-30%
As the auxiliary water that absorbs and dilute component: 15-30%
The cation of wherein said low viscosity alkalescent functionalized ion liquid is a tetraalkyl ammonium ion, and anion is amino acid group or organic carboxyl acid root anion.
According to claim 1 above-mentioned formula solution, it is characterized in that: have lower viscosity under the ionic liquid room temperature of using as activator, viscosity＜300mPa.s, its general structure is:
Wherein: R
1, R
2Expression has 1～6 carbon atom (C
1～C
6) the straight or branched alkyl, R
1And R
2Identical or inequality, Y is an anion, and n is anionic charge number or ion valence mumber, and its numerical value is 1 or 2.
3. formula solution according to claim 2 is characterized in that: in the described general structure, and R
1, R
2Be not more than 6 straight or branched alkyl for the carbon atom number.
4. formula solution according to claim 1 is characterized in that: in the described alkalescent functionalized ion liquid general structure, and Y
N-What represent is amino acid radical anion, and used amino acid group is not more than 5 amino acid radical anion for the carbon atom number.
5. formula solution according to claim 1 is characterized in that: in the described alkalescent functionalized ion liquid general structure, and Y
N-Being expressed as organic carboxyl acid root anion, is that the carbon atom number is not more than 5 monocarboxylic acid root and dicarboxylic acids root.
6. formula solution according to claim 1, it is characterized in that: described alkalescent functionalized ion liquid is one or more amino acid radical ion liquid, or one or more organic acid ionic liquid, also can be that amino acid radical ion liquid and organic acid ionic liquid mix use.
7. according to the described formula solution of claim 1, it is characterized in that: described N methyldiethanol amine and ionic liquid all are CO
2The ratio that the active ingredient that absorbs, both total amounts account for prescription liquid gross mass must be controlled at 40-65wt%.
8. according to the described formula solution of claim 1, it is characterized in that: described dilution component is a sulfolane, or mean molecule quantity is the NHD between the 180-300, and the two can use separately, also can mix use, the overall control of dilution component is at 15-30wt%.
9. formula solution according to claim 1 is characterized in that: the process conditions of described formula solution absorbing carbon dioxide are: operating temperature is 0～60 ℃, and operating pressure is 1～30 atmospheric pressure.
10. formulation absorption liquid according to claim 1 is characterized in that: the desorption technique condition of the prescription liquid after described carbon dioxide absorption is saturated is: operating temperature is 80～120 ℃, and operating pressure is 0～1 atmospheric pressure.
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