CN110314521A - A kind of amino acid anionic functionalized ion liquid trapping nitric oxide and regenerated process - Google Patents
A kind of amino acid anionic functionalized ion liquid trapping nitric oxide and regenerated process Download PDFInfo
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- CN110314521A CN110314521A CN201910714327.8A CN201910714327A CN110314521A CN 110314521 A CN110314521 A CN 110314521A CN 201910714327 A CN201910714327 A CN 201910714327A CN 110314521 A CN110314521 A CN 110314521A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/24—Nitric oxide (NO)
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Abstract
The present invention provides a kind of amino acid anionic functionalized ion liquid trapping NO and regenerated processes.This method includes using amino acid anionic ion liquid as absorbent；The NO in flue gas is absorbed in the case where temperature is 20~60 DEG C, NO volumetric concentration is 0.05~2%；The NO in ionic liquid regeneration and recovered flue gas is realized at 80~120 DEG C of temperature, 1~100kPa using the method for flash distillation.This method can realize the NO absorbed in flue gas rapidly and efficiently, and realize the regeneration of absorbent and the recycling of NO, while functionalized ion liquid used in this method has the characteristics that nontoxic, environmental-friendly, can effectively reduce absorbent pollution on the environment.
Description
Technical field
The invention belongs to denitrating flue gas fields, are related to a kind of amino acid anionic functionalized ion liquid trapping flue gas
Middle nitric oxide (NO) and regenerated process.This method include using amino acid anionic ion liquid as absorbent,
The NO in flue gas is absorbed under the conditions of the volumetric concentration of 20~60 DEG C, NO are 0.05%~2%, then again using the method for flash distillation
The NO that raw ionic liquid and recycling are absorbed.
Technical background
Coal occupies absolute superiority in China's energy, is mainly used for coal fired power generation.In China's energy source,
Coal electricity accounts for 60% or more.The burning of annual coal generates a large amount of nitric oxide (NO).NO is cause atmosphere pollution main
One of pollution sources.If the NO that coal burning is generated is discharged, the environmental problems such as acid rain and photochemical pollution are not only resulted in, and
And damage can be generated to the existence of people and plant.In addition, NO is a kind of chemical industry product, it can be used for producing important industrial chemicals nitre
Acid (HNO3) and drug of the production containing NO.Therefore, carrying out trapping and resource utilization to the NO in flue gas after coal burning has
Important ecology, social and economic benefits.
Currently, be the denitration method for flue gas being most widely used using the selective catalytic reduction (SCR) that ammonia carries out,
But higher cost, and the disadvantages of there are NH_3 leakages, catalyst easy in inactivation.Other such as plasma removal method, active carbon adsorption
Its feasibility need further to study with economy.The advantages that bioanalysis is small, without secondary pollution due to its operating cost, by
Extensive concern, but current research all concentrates on direct oxidation or reduction, since NO is insoluble in water, directly makes the removal of bioanalysis
Efficiency is restricted.
Ionic liquid (ionic liquid, IL) is since it is with lower vapour pressure, wider liquid temperature range, pole
Feature that high stability and zwitterion structure is adjustable and the research for being widely used in flue gas desulfurization decarburization.But it is de- for flue gas
The relevant research of nitre is also less.(K.H.Chen, G.L.Shi, X.Y.Zhou, H.R.Li, C.M.Wang, the Highly such as Chen
efficient nitric oxide capture by azole-based ionic liquids through multiple-
Site absorption.Angew.Chem.Int.Ed.2016, (46), 14364-14368.) report a kind of azole ionic liquid
Body and the trapping for being used for NO；(Y.L.Sun, G.S.Wei, X.W.Tan, Z.H.Huang, L.H.Zhang, the Highly such as Sun
efficient nitric oxide absorption by environmentally friendly deep eutectic
Solvents based on 1,3-dimethylthiourea, Energy Fuels, 2017, (31), 12439-12445.) report
A kind of quaternary phosphonium class ionic liquid in road is also used for the trapping of NO.But these ionic liquid absorptions NO is mainly that physics is inhaled
It receives, has higher uptake to higher concentration NO, have lesser uptake to low concentration of NO, therefore pertain only to height in the two documents
The absorption of concentration NO.But the NO concentration in flue gas is very low, and generally below 2%, it needs the strong reduction that occurs of active force and learns work
Absorption.
Therefore, NO technology is developed under a kind of absorbable low concentration for realizing that it is important that the recycling of gas cleaning and NO has
Meaning.This method absorbs the NO in flue gas using functionalization amino acid anionic ion liquid as absorbent, the absorbent
With NO weak chemical action can occur for the amido in amino acid anion, improve the absorption to low concentration of NO.With conventional method phase
Than there are absorbent of the invention many advantages can reuse, the NO desorbed if absorbent is nontoxic and environmental-friendly
It can be with resource utilization etc..Compared with the absorbent invented before, this method NO still with higher under lower NO partial pressure
Absorbability, therefore this method is more suitable for absorbing under low pressure, the case where closer to practical flue gas.
Summary of the invention
The object of the present invention is to provide one kind using amino acid anionic functionalized ion liquid as absorbent, efficient absorption
In flue gas NO and realize absorbent regeneration and NO recycling process.
The purpose of the present invention is adopt the following technical scheme that realize.
NO and regenerated process in a kind of amino acid anionic functionalized ion liquid trapping flue gas.This method packet
It includes using amino acid anionic ion liquid as absorbent, temperature is 20~60 DEG C, NO volumetric concentration is 0.05%~2%
Under the conditions of absorb NO in flue gas, then using the method regeneration of ionic liquid of flash distillation and the NO that is absorbed of recycling.
In the above method, the amino acid anionic functionalized ion liquid cation be selected from tetraethyl ammonium sun from
Son, tetrabutyl phosphorus cation, choline cation, 1- butyl -3- trimethylimadazolium cation, ethyl alcohol amine cation.
In the above method, the amino acid for synthesizing amino acid anionic functionalized ion liquid is selected from dried meat ammonia
Acid, sarcosine, glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine,
Tyrosine, cysteine, methionine, asparagine, glutamine, threonine, lysine, arginine, histidine.
In the above method, the regeneration flash temperature is 80 DEG C~120 DEG C.
In the above method, the regeneration flashing pressure is 1~100kPa.
The principle of the method for the present invention is: amido (including primary amine groups and secondary amine) in amino acid have stronger alkalinity and
Nucleophilicity, and NO can be considered a kind of lewis acid, after the amido in amino acid anionic functional ionic liquid is contacted with NO,
Reversible chemical reaction can occur with NO；In desorption, after temperature increases, the reaction force attenuation between amido and NO leads to its suction
It is closed flat weighing apparatus to be moved, therefore the NO absorbed under conditions of flash distillation can be desorbed out, while absorbent is regenerated.
Compared with prior art, the invention has the following advantages that (1) is compared with existing liquid-absorbant, (a) ammonia
Anion of the base acid as ionic liquid has environmental-friendly characteristic；(b) with the characteristic of functionalization, i.e., to low in flue gas
Concentration NO uptake with higher.(2) compared with traditional SCR method, (a) can be with the NO in recovered flue gas；(b) it does not consume
Ammonia.
Specific embodiment
The process provided by the invention with functionalization ionic liquid absorption NO is made into one below in conjunction with embodiment
Step detailed description, but it is not thereby limiting the invention.
Embodiment 1
1:1 weighs 25% tetraethyl ammonium hydroxide aqueous solution ([N in molar ratio2222] OH) 62.3120g and sarcosine
(Sar) 9.4215g is added in 250ml round-bottomed flask, at room temperature magnetic agitation 12h.Then it is evaporated off in temperature 70 C backspin
Extra moisture, and N is used at 100 DEG C2Purging obtains tetraethyl ammonium sarcosinate ionic liquid [N to constant weight2222][Sar]。
The amino acid functionalised ionic liquid 1.9555g is weighed, is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO body
Product content is 0.4%, N2Volume content is 99.6%) to be passed through in denitrification apparatus with the rate of 50ml/min, absorbs 30 DEG C of temperature.
Absorption saturation to be achieved obtains the rich solution containing NO, uses the uptake of weight method measurement NO for 0.1397g, the absorption is calculated
The capacity that agent absorbs NO is 0.52mol NO/mol IL.Above-mentioned rich solution is heated to 80 DEG C, is flashed under 1kPa pressure,
Absorbed NO is desorbed, weight method measurement is used to desorb the quality of NO as 0.1090g, desorption efficiency is up to 78%.
Embodiment 2
1:1 weighs 25% tetrabutylammonium hydroxide phosphorus aqueous solution ([P in molar ratio4444] OH) 78.6436g and glycine
(Gly) it 5.3391 is added in 250ml round-bottomed flask, at room temperature magnetic agitation 12h.The extra moisture of 70 DEG C of revolving removings, and
N at 100 DEG C2Purging obtains 4-butyl-phosphonium glycinate ionic liquid [P to constant weight4444][Gly].It is amino acid functionalised to weigh this
Ionic liquid 1.9573g is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 0.4%, N2Volume
Content 99.6%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorb 20 DEG C of temperature.Absorption saturation to be achieved is obtained containing NO
Rich solution, use weight method measurement NO uptake for 0.1074g, be calculated the absorbent absorption NO capacity be
1.25mol NO/mol IL.It above-mentioned rich solution is heated to 120 DEG C, is flashed under 10kPa pressure, desorbed and absorbed
NO uses weight method measurement to desorb the quality of NO as 0.1020g, and desorption efficiency is up to 95%.
Embodiment 3
1:1 weighs 49% bursine aqueous solution (Ch) 24.2353g and proline (L-Pro) in molar ratio
13.1241g is added in 250ml round-bottomed flask, at room temperature magnetic agitation 12h.70 DEG C of revolvings remove extra moisture, and 100
N at DEG C2Purging obtains choline proline salt ionic liquid [Ch] [L-Pro] to constant weight.Weigh the amino acid functionalised ionic liquid
Body 1.7944g is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 0.09%, N2Volume content
99.91%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorbs 20 DEG C of temperature.Absorption saturation to be achieved is obtained containing NO's
Rich solution uses the uptake of weight method measurement NO for 0.1153g, and it is 0.43mol that the absorbent, which is calculated, to absorb the capacity of NO
NO/mol IL.Above-mentioned rich solution is heated to 90 DEG C, is flashed under 10kPa pressure, absorbed NO is desorbed, using title
Weight method measurement desorbs the quality of NO as 0.1014g, and desorption efficiency is up to 88%.
Embodiment 4
1:1 weighs chlorination 1- butyl -3- methylimidazole (BmimCl) 14.7611g and sodium hydroxide (NaOH) in molar ratio
3.3803g is dissolved separately in after ethyl alcohol and is added in 250ml round-bottomed flask, and magnetic agitation is for 24 hours at room temperature.After being filtered to remove insoluble matter
50 DEG C of revolvings remove etoh solvents, then 1:1 is weighed after aqueous solution is made in cysteine (Gys) 10.2391g circle is added in molar ratio
In the flask of bottom, magnetic agitation 6h at room temperature.70 DEG C of revolvings remove extra moisture, and the N at 100 DEG C2Purging is obtained to constant weight
1- butyl -3- methylimidazole cysteine ionic liquid [Bmim] [Gys].Weigh the amino acid functionalised ionic liquid
1.9009g is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 0.2%, N2Volume content
99.8%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorbs temperature 60 C.Absorption saturation to be achieved obtains the richness containing NO
Liquid uses the uptake of weight method measurement NO for 0.1069g, and it is 0.49mol that the absorbent, which is calculated, to absorb the capacity of NO
NO/mol IL.Above-mentioned rich solution is heated to 100 DEG C, is flashed under 10kPa pressure, absorbed NO is desorbed, using title
Weight method measurement desorbs the quality of NO as 0.0983g, and desorption efficiency is up to 92%.
Embodiment 5
1:1 weighs ethanol amine (MEA) 8.5676g and valine (Val) 16.4324g and 250ml round bottom burning is added in molar ratio
In bottle, magnetic agitation 12h at room temperature.70 DEG C of revolvings remove extra moisture, and the N at 100 DEG C2Purging obtains second to constant weight
Hydramine valine ionic liquid [MEA] [Val].The amino acid functionalised ionic liquid 2.0382g is weighed, homemade drum is added
In bubble denitrification apparatus, by simulated flue gas (NO volume content 0.1%, N2Volume content 99.9%) it is logical with the rate of 50ml/min
Enter in denitrification apparatus, absorbs temperature 50 C.Absorption saturation to be achieved obtains the rich solution containing NO, using the absorption of weight method measurement NO
Amount is 0.1064g, and it is 0.31mol NO/mol IL that the absorbent, which is calculated, to absorb the capacity of NO.Above-mentioned rich solution is heated to
80 DEG C, NO is desorbed by flash method at 10kPa, uses weight method measurement to desorb the quality of NO as 0.0766g, desorption efficiency
Up to 72%.
Embodiment 6
1:1 weighs a certain amount of ethanol amine (MEA) 10.1685g and alanine (Ala) 14.7794g and is added in molar ratio
In 250ml round-bottomed flask, magnetic agitation 12h at room temperature.70 DEG C of revolvings remove extra moisture, and the N at 100 DEG C2Purging is extremely
Constant weight obtains ethanol amine alanine ionic liquid [MEA] [Ala].The amino acid functionalised ionic liquid 1.9910g is weighed,
It is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 1%, N2Volume content 99%) with 50ml/min
Rate be passed through in denitrification apparatus, absorb 20 DEG C of temperature.Absorption saturation to be achieved obtains the rich solution containing NO, is measured using weight method
The uptake of NO is 0.6284g, and it is 1.58mol NO/mol IL that the absorbent, which is calculated, to absorb the capacity of NO.By above-mentioned richness
Liquid is heated to 80 DEG C, is flashed under 1kPa pressure, and absorbed NO is desorbed, and the matter of NO is desorbed using weight method measurement
Amount is 0.5028g, and desorption efficiency is up to 80%.
Embodiment 7
1:1 weighs 1- butyl -3- methylimidazole villaumite (BmimCl) 14.2774g and sodium hydroxide (NaOH) in molar ratio
3.2690g is dissolved separately in after ethyl alcohol and is added in 250ml round-bottomed flask, and magnetic agitation is for 24 hours at room temperature.After being filtered to remove insoluble matter
50 DEG C of revolvings remove etoh solvents, then 1:1 is weighed after aqueous solution is made in leucine (Leu) 10.7207g round bottom is added in molar ratio
In flask, magnetic agitation 6h at room temperature.70 DEG C of revolvings remove extra moisture, and the N at 100 DEG C2Purging obtains 1- to constant weight
Butyl -3- methylimidazole leucine ionic liquid [Bmim] [Leu].The amino acid functionalised ionic liquid 1.9655g is weighed,
It is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 2%, N2Volume content 98%) with 50ml/min
Rate be passed through in denitrification apparatus, absorb 40 DEG C of temperature.Absorption saturation to be achieved obtains the rich solution containing NO, is measured using weight method
The uptake of NO is 0.3152g, and it is 1.44mol NO/mol IL that the absorbent, which is calculated, to absorb the capacity of NO.By above-mentioned richness
Liquid is heated to 80 DEG C, is flashed under 20kPa pressure, and absorbed NO is desorbed, and desorbs NO's using weight method measurement
Quality is 0.2405g, and desorption efficiency is up to 67%.
Embodiment 8
1:1 weighs choline (Ch) 11.0659g and isoleucine (Ile) 13.9341g and 250ml round bottom burning is added in molar ratio
In bottle, magnetic agitation 12h at room temperature.70 DEG C of revolvings remove extra moisture, and the N at 100 DEG C2Purging obtains gallbladder to constant weight
Alkali isoleucine ionic liquid [Ch] [Ile].The amino acid functionalised ionic liquid 1.9533g is weighed, homemade drum is added
In bubble denitrification apparatus, by simulated flue gas (NO volume content 0.4%, N2Volume content 99.6%) it is logical with the rate of 50ml/min
Enter in denitrification apparatus, absorbs 20 DEG C of temperature.Absorption saturation to be achieved obtains the rich solution containing NO, using the absorption of weight method measurement NO
Amount is 0.1650g, and it is 0.61mol NO/mol IL that the absorbent, which is calculated, to absorb the capacity of NO.Above-mentioned rich solution is heated to
120 DEG C, flashed under 1kPa pressure, desorb absorbed NO, use weight method measurement desorb the quality of NO for
0.1601g, desorption efficiency is up to 97%.
Embodiment 9
1:1 weighs 25% tetraethyl ammonium hydroxide aqueous solution ([N in molar ratio2222] OH) 47.1375g and phenylalanine
(Phe) 13.2156g is added in 250ml round-bottomed flask, at room temperature magnetic agitation 12h.70 DEG C of revolvings remove extra moisture, and
The N at 100 DEG C2Purging obtains tetraethyl ammonium phenylalanine ionic liquid [N to constant weight2222][Phe].Weigh the amino acid function
Ionic liquid 1.7974g can be changed, be added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 2%, N2Body
Product content 98%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorb 30 DEG C of temperature.Absorption saturation to be achieved is obtained containing NO
Rich solution, with weight method measurement NO uptake be 0.3644g, be calculated the absorbent absorb NO capacity be 1.99mol
NO/mol IL.Above-mentioned rich solution is heated to 90 DEG C, is flashed under 15kPa pressure, absorbed NO is desorbed, using title
Weight method measurement desorbs the quality of NO as 0.3024g, and desorption efficiency is up to 83%.
Embodiment 10
1:1 weighs 25% tetrabutylammonium hydroxide phosphorus aqueous solution ([P in molar ratio4444] OH) 57.5114g and tryptophan
(Trp) 10.6222g is added in 250ml round-bottomed flask, at room temperature magnetic agitation 12h.70 DEG C of revolvings remove extra moisture, and
The N at 100 DEG C2Purging obtains tetrabutyl phosphorus tryptophan ionic liquid [P to constant weight4444][Trp].This is claimed to take aminoacid functional
Change ionic liquid 1.9010g, is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 0.2%, N2Body
Product content 99.8%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorb 30 DEG C of temperature.Absorption saturation to be achieved is contained
The rich solution of NO uses the uptake of weight method measurement NO for 0.0636g, and the capacity that absorbent absorption NO is calculated is
0.52mol NO/mol IL.Above-mentioned rich solution is heated to 80 DEG C, is flashed under 1kPa pressure, absorbed NO is desorbed,
Weight method measurement is used to desorb the quality of NO as 0.0502g, desorption efficiency is up to 79%.
Embodiment 11
1:1 weighs a certain amount of ethanol amine (MEA) 9.1894g and serine (Ser) 15.8106g and is added in molar ratio
In 250ml round-bottomed flask, magnetic agitation 12h at room temperature.70 DEG C of revolvings remove extra moisture, and the N at 100 DEG C2Purging is extremely
Constant weight obtains ethanol amine serine ionic liquid [MEA] [Ser].The amino acid functionalised ionic liquid 1.9900g is weighed,
It is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 1%, N2Volume content 99%) with 50ml/min
Rate be passed through in denitrification apparatus, absorb 30 DEG C of temperature.Absorption saturation to be achieved obtains the rich solution containing NO, is measured using weight method
The uptake of NO is 0.5461g, and it is 1.52mol NO/mol IL that the absorbent, which is calculated, to absorb the capacity of NO.By above-mentioned richness
Liquid is heated to 80 DEG C, desorbs NO by flash method at 10kPa, and weight method measurement is used to desorb the quality of NO as 0.3986g,
Its desorption efficiency is up to 73%.
Embodiment 12
1:1 weighs 1- butyl -3- methylimidazole villaumite (BmimCl) 13.6734g and sodium hydroxide (NaOH) in molar ratio
3.1313g is dissolved separately in after ethyl alcohol and is added in 250ml round-bottomed flask, and magnetic agitation is for 24 hours at room temperature.After being filtered to remove insoluble matter
50 DEG C of revolvings remove etoh solvents, then 1:1 is weighed after aqueous solution is made in a certain amount of tyrosine (Tyr) 14.1838g in molar ratio
It is added in round-bottomed flask, at room temperature magnetic agitation 6h.70 DEG C of revolvings remove extra moisture, and the N at 100 DEG C2It purges to perseverance
Weight, obtains 1- butyl -3- methylimidazole tyrosine ionic liquid [Bmim] [Tyr].Weigh the amino acid functionalised ionic liquid
Body 1.2368g is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 0.9%, N2Volume content
99.1%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorbs 30 DEG C of temperature.Absorption saturation to be achieved obtains the richness containing NO
Liquid uses the uptake of weight method measurement NO for 0.1696g, and it is 1.46mol that the absorbent, which is calculated, to absorb the capacity of NO
NO/mol IL.Above-mentioned rich solution is heated to 80 DEG C, NO is desorbed by flash method at 100kPa, is measured and is desorbed using weight method
The quality of NO is 0.0763g out, and desorption efficiency is up to 45%.
Embodiment 13
1:1 weighs ethanol amine (MEA) 7.2614g and methionine (Met) 17.7386g and 250ml round bottom burning is added in molar ratio
In bottle, magnetic agitation 12h at room temperature.70 DEG C of revolvings remove extra moisture, and the N at 100 DEG C2Purging obtains second to constant weight
Hydramine methionine salt ionic liquid [MEA] [Met].The amino acid functionalised ionic liquid 1.8972g is weighed, homemade drum is added
In bubble denitrification apparatus, by simulated flue gas (NO volume content 2%, N2Volume content 98%) be passed through with the rate of 50ml/min it is de-
In nitre device, 40 DEG C of temperature are absorbed.Absorption to be achieved saturation obtains the rich solution containing NO, use the uptake of weight method measurement NO for
0.3979g, it is 1.47mol NO/mol IL that the absorbent, which is calculated, to absorb the capacity of NO.Above-mentioned rich solution is heated to 80 DEG C,
NO is desorbed by flash method at 10kPa, uses weight method measurement to desorb the quality of NO as 0.2785g, desorption efficiency reaches
70%.
Embodiment 14
1:1 weighs ethanol amine (MEA) 7.9037g and asparagine (Asn) 17.0963g and 250ml round bottom is added in molar ratio
In flask, magnetic agitation 12h at room temperature.70 DEG C of revolvings remove extra moisture, and the N at 100 DEG C2Purging is obtained to constant weight
Ethanol amine asparagine ionic liquid [MEA] [Asn].The amino acid functionalised ionic liquid 1.9352g is weighed, self-control is added
Bubble type denitrification apparatus in, by simulated flue gas (NO volume content 1%, N2Volume content 99%) it is logical with the rate of 50ml/min
Enter in denitrification apparatus, absorbs temperature 60 C.Absorption saturation to be achieved obtains the rich solution containing NO, using the absorption of weight method measurement NO
Amount is 0.2085g, and it is 0.69mol NO/mol IL that the absorbent, which is calculated, to absorb the capacity of NO.Above-mentioned rich solution is heated to
120 DEG C, NO is desorbed by flash method at 10kPa, uses weight method measurement to desorb the quality of NO as 0.1939g, desorbs
Rate is up to 93%.
Embodiment 15
1:1 weighs 25% tetraethyl ammonium hydroxide aqueous solution ([N in molar ratio2222] OH) 53.4761g and glutamine
(Gln) 13.2647g is added in 250ml round-bottomed flask, at room temperature magnetic agitation 12h.70 DEG C of revolvings remove extra moisture, and
The N at 100 DEG C2Purging obtains tetraethyl ammonium glutamine ionic liquid [N to constant weight2222][Gln].Weigh the amino acid function
Ionic liquid 1.3684g can be changed, be added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 0.6%, N2
Volume content 99.4%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorb 40 DEG C of temperature.Absorption saturation to be achieved obtains
Rich solution containing NO, the uptake with weight method measurement NO is 0.0785g, and the capacity that absorbent absorption NO is calculated is
0.53mol NO/mol IL.Above-mentioned rich solution is heated to 80 DEG C, NO is desorbed by flash method at 100kPa, using weight method
The quality that measurement desorbs NO is 0.0330g, and desorption efficiency is up to 42%.
Embodiment 16
1:1 weighs 25% tetraethyl ammonium hydroxide aqueous solution ([N in molar ratio2222] OH) 59.2947g and threonine
(Thr) 11.9878g is added in 250ml round-bottomed flask, at room temperature magnetic agitation 12h.70 DEG C of revolvings remove extra moisture, and
The N at 100 DEG C2Purging obtains tetraethyl ammonium threonine ionic liquid [N to constant weight2222][Thr].Weigh the aminoacid functional
Change ionic liquid 1.8972g, is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 2%, N2Volume
Content 98%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorb 20 DEG C of temperature.Absorption saturation to be achieved is obtained containing NO's
Rich solution uses the uptake of weight method measurement NO for 0.4651g, and it is 2.03mol that the absorbent, which is calculated, to absorb the capacity of NO
NO/mol IL.Above-mentioned rich solution is heated to 80 DEG C, NO is desorbed by flash method at 20kPa, is desorbed using weight method measurement
The quality of NO is 0.2725g, and desorption efficiency is up to 65%.
Embodiment 17
1:1 weighs 25% tetraethyl ammonium hydroxide aqueous solution ([N in molar ratio2222] OH) 47.2191g and lysine
(Lys) 14.6378g is added in 250ml round-bottomed flask, at room temperature magnetic agitation 12h.70 DEG C of revolvings remove extra moisture, and
The N at 100 DEG C2Purging obtains tetraethyl ammonium lysine salt ionic liquid [N to constant weight2222][Lys].Weigh the aminoacid functional
Change ionic liquid 1.8972g, is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 0.5%, N2Body
Product content 99.5%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorb temperature 60 C.Absorption saturation to be achieved is contained
The rich solution of NO uses the uptake of weight method measurement NO for 0.1076g, and the capacity that absorbent absorption NO is calculated is
0.59mol NO/mol IL.Above-mentioned rich solution is heated to 100 DEG C, NO is desorbed by flash method at 50kPa, using weight method
The quality that measurement desorbs NO is 0.0797g, and desorption efficiency is up to 74%.
Embodiment 18
1:1 weighs 25% tetrabutylammonium hydroxide phosphorus aqueous solution ([P in molar ratio4444] OH) 63.8961g and arginine
(Arg) 10.0661g is added in 250ml round-bottomed flask, at room temperature magnetic agitation 12h.70 DEG C of revolvings remove extra moisture, and
The N at 100 DEG C2Purging obtains tetrabutyl phosphorus arginine salt ionic liquid [P to constant weight4444][Arg].Weigh the aminoacid functional
Change ionic liquid 1.5779g, is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 0.7%, N2Body
Product content 99.3%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorb temperature 50 C.Absorption saturation to be achieved is contained
The rich solution of NO, the uptake with weight method measurement NO is 0.0700g, and the capacity that absorbent absorption NO is calculated is
3.17mol NO/mol IL.Above-mentioned rich solution is heated to 120 DEG C, NO is desorbed by flash method at 100kPa, using weight method
The quality that measurement desorbs NO is 0.0469g, and desorption efficiency is up to 67%.
Embodiment 19
1:1 weighs 25% tetrabutylammonium hydroxide phosphorus aqueous solution ([P in molar ratio4444] OH) 66.8634g and histidine
(His) 9.3726g is added in 250ml round-bottomed flask, at room temperature magnetic agitation 12h.The extra moisture of 70 DEG C of revolving removings, and
N at 100 DEG C2Purging obtains tetrabutyl phosphorus histidine ionic liquid [P to constant weight2222][His].It is amino acid functionalised to weigh this
Ionic liquid 1.7352g is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 0.05%, N2Volume
Content 99.95%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorb 10 DEG C of temperature.Absorption saturation to be achieved is contained
The rich solution of NO, the uptake with weight method measurement NO is 0.0604g, and the capacity that absorbent absorption NO is calculated is
0.48mol NO/mol IL.Above-mentioned rich solution is heated to 90 DEG C, NO is desorbed by flash method at 100kPa, using weight method
The quality that measurement desorbs NO is 0.0344g, and desorption efficiency is up to 57%.
Embodiment 20
Ionic liquid [Ch] [L-Pro] is produced using the method for embodiment 3.Weigh [Ch] [L-Pro] ionic liquid
1.2338g is added in homemade bubble type denitrification apparatus, by simulated flue gas (NO volume content 0.16%, N2Volume content
99.84%) it is passed through in denitrification apparatus with the rate of 50ml/min, absorbs 30 DEG C of temperature.Absorption saturation to be achieved is obtained containing NO's
Rich solution, the capacity which absorbs NO is 0.51mol NO/mol IL.Above-mentioned rich solution is heated to 80 DEG C, in 1kPa pressure
Under flashed, desorb absorbed NO, recycle NO and absorbent regeneration, the lean solution after desorption is used for reabsorption simulation cigarette
NO in gas.It being absorbed by 5 times, desorption cycle, 5 absorptive capacities of absorbent are respectively 0.51mol NO/mol IL,
0.52mol NO/mol IL, 0.53mol NO/mol IL, 0.51mol NO/mol IL, 0.52mol NO/mol IL；5 times
Desorption efficiency is respectively 81%, 82%, 81%, 82%, 82%.
Claims (6)
1. nitric oxide (NO) and regenerated process in a kind of amino acid anionic functionalized ion liquid trapping flue gas.
This method includes using amino acid anionic ion liquid as absorbent, temperature is 20~60 DEG C, NO volumetric concentration is
The NO in flue gas is absorbed under the conditions of 0.05~2%, the NO then absorbed using the method regeneration of ionic liquid and recycling of flash distillation.
2. the method according to claim 1, wherein the amino acid anionic functionalized ion liquid sun
Ion is selected from tetraethylammonium cation, tetrabutyl phosphorus cation, choline cation, 1- butyl -3- trimethylimadazolium cation, second
Alcohol amine cation.
3. the method according to claim 1, wherein it is described for synthesizing amino acid anionic functionalization from
The amino acid of sub- liquid is selected from proline, sarcosine, glycine, alanine, valine, leucine, isoleucine, phenylpropyl alcohol ammonia
Acid, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine, threonine, relies ammonia at proline
Acid, arginine, histidine.
4. the method according to claim 1, wherein the flash temperature of the regeneration of ionic liquid be 80 DEG C~
120℃。
5. the method according to claim 1, wherein the flashing pressure of the regeneration of ionic liquid be 1~
100kPa。
6. the method according to claim 1, wherein the flashing pressure of the regeneration of ionic liquid be 1~
10kPa。
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| CN114748986A (en) * | 2022-04-22 | 2022-07-15 | 昆明理工大学 | Synchronous defluorination and denitration method for composite absorbent |
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| CN107115761A (en) * | 2016-02-24 | 2017-09-01 | 北京化工大学 | A kind of utilization ionic liquid composite absorber absorbs the process of hydrogen sulfide |
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