CN103933830A - CO2 trapping agent and preparation method thereof - Google Patents

CO2 trapping agent and preparation method thereof Download PDF

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Publication number
CN103933830A
CN103933830A CN201410048886.7A CN201410048886A CN103933830A CN 103933830 A CN103933830 A CN 103933830A CN 201410048886 A CN201410048886 A CN 201410048886A CN 103933830 A CN103933830 A CN 103933830A
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China
Prior art keywords
cyanoethyl
methyl ether
imidazoles
capturing agent
ethyl methyl
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CN201410048886.7A
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Chinese (zh)
Inventor
徐海涛
欧阳伟
徐玉韬
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Nanchang Hangkong University
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Nanchang Hangkong University
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Priority to CN201410048886.7A priority Critical patent/CN103933830A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)

Abstract

The present invention relates to a kind of CO2 capturing agent and preparation method thereof,Shown in the chemical formula such as formula (I) of the CO2 capturing agent,Preparation method are as follows: (1) intermediate product 1- cyanoethyl -3- ethyl methyl ether imidazoles villaumite is prepared by the electrophilic addition of 1- cyanoethyl imidazoles and 2- chloroethyl methyl ether; (2) anion exchange resin is used,1- cyanoethyl -3- ethyl methyl ether imidazoles villaumite is exchanged for hydroxide 1- cyanoethyl -3- ethyl methyl ether imidazoles; (3) pass through the neutralization reaction of hydroxide 1- cyanoethyl -3- ethyl methyl ether imidazoles and tricyano formic acid,CO2 capturing agent of the invention is made. The invention has the advantages that having the characteristics that capture capacity is high, acquisition speed is fast, it is low to absorb enthalpy, it can be used for capturing the CO2 in air. (I)

Description

A kind of CO 2capturing agent and preparation method thereof
Technical field
The present invention relates to a kind of gas entrapment agent and preparation method thereof, be specifically related to a kind of CO 2capturing agent and preparation method thereof, belongs to new type chemical material and preparing technical field thereof.
Background technology
The global warming that " greenhouse effects " cause is considered to one of the most urgent now environmental problem.It has been generally acknowledged that, the greenhouse gases that the main cause of " greenhouse effects " is are to the discharge in atmosphere.Wherein, carbon dioxide (CO 2) be topmost greenhouse gases, it is mainly derived from fossil fuel as the burning of coal and oil.
Cut down CO 2a kind of mode of discharge is from air, effectively to catch CO 2.CO 2can be isolated in geology series of rocks once be hunted down, also can be used as the synthetic organic-fuel of raw material and chemical products.
At present, there is multiple CO 2catching method.In commercial scale, most popular method is Chemical Trapping method, and the capturing agent of use is mainly the alkanolamine aqueous solution, as MEA, N methyldiethanol amine, diethanol amine and triethanolamine etc.The alkanolamine aqueous solution and CO 2there is chemical bond and catch, when apply heat to it, capturing agent and CO 2between chemical bond key destroyed, make CO 2be desorbed, capturing agent regeneration, and be reused for and catch CO 2.
But there are some shortcomings in the agent of alkanolamine aqueous solution capture, as being used for destroying capturing agent and CO in capturing agent regenerative process 2between the high temperature of chemical bond key can cause alkanolamine that irreversible decomposition occurs, alkanolamine itself or catabolite have certain corrosivity to device, a large amount of decentralized medium water causes regenerative process energy consumption very high.Therefore, be necessary development of new CO 2capturing agent.
In recent years, ion liquid type CO 2capturing agent receives people's concern.Ionic liquid is a kind of low temperature molten salt, under lower than 100 DEG C of conditions, and the liquid being formed by anion and cation completely.The ion liquid type CO of different structure is all disclosed in U.S. Patent Publication No. 6849774,6623659 and Chinese Patent Application No. CN 101935311 A 2capturing agent.But these capturing agents are compared with alkanolamine, and capture ability is lower, and speed is slower.
For CO 2the problem that capturing agent exists, develops and a kind ofly catches that capacity is high, acquisition speed is fast, the low novel ion liquid type CO of regeneration energy consumption 2capturing agent is very necessary.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of CO 2capturing agent, this capturing agent has that the capacity of catching is high, acquisition speed is fast, absorb the features such as the low and then regeneration energy consumption of enthalpy is low, is particularly suitable for catching airborne CO 2, the present invention provides the preparation method of this class capturing agent simultaneously for this reason.
The present invention is achieved like this, and it is characterized in that chemical formula structure is as follows:
（Ⅰ）
CO of the present invention 2the preparation method of capturing agent, its characterization step is as follows:
(1) in reactor, add 1.2 molar part 1-cyanoethyl imidazoles and 1.0 molar part 2-chloroethyl methyl ethers and equal-volume toluene, room temperature electric stirring 30 minutes, raw material is fully mixed, be warming up to 60 DEG C with the speed of 10 DEG C/min, 60 DEG C of stirring reaction 8-10 hour of constant temperature, be down to room temperature, extract and remove excessive 1-cyanoethyl imidazoles and unreacted 2-chloroethyl methyl ether with equal-volume cyclohexane, 60 DEG C of vacuum drying are removed toluene in 24 hours, obtain intermediate product 1-cyanoethyl-3-ethyl methyl ether imidazoles villaumite;
(2) use absolute ethyl alcohol as solvent, 1-cyanoethyl-3-ethyl methyl ether imidazoles villaumite is dissolved, and by 717 type strong basicity I type anion exchange resin, 1-cyanoethyl-3-ethyl methyl ether imidazoles villaumite is exchanged for to hydroxide 1-cyanoethyl-3-ethyl methyl ether imidazoles;
(3) by hydroxide 1-cyanoethyl-3-ethyl methyl ether imidazoles with etc. molar part tricyano formic acid add in reactor, 25 DEG C of stirring reactions 24 hours, 70 DEG C of vacuum drying dewater for 24 hours, obtain CO of the present invention 2capturing agent.
CO provided by the invention 2capturing agent can be caught airborne CO under temperature 20-50 DEG C, the condition of 1atm 2, under 25 DEG C, 1atm condition, quantity of the catch is the highest can reach 1.06 mol CO 2/ mol capturing agent.Described capturing agent is caught CO 2after exist with the form of a phase, i.e. CO 2be captured into the separation that does not produce solids of sedimentation or second liquid phase in described capturing agent.Described capturing agent maintains lower viscosity in whole acquisition procedure, and under 20 DEG C, 1atm condition, described capturing agent is saturated while catching, and the peak of viscosity is 56 mPaS.In addition, described capturing agent is caught CO 2speed, under 25 DEG C, 1atm condition, saturated capture time is 7 minutes, its speed is suitable with the alkanolamine aqueous solution.
CO provided by the invention 2capturing agent can be after saturated catching mode by heating to the CO catching 2carry out desorb, make capturing agent regeneration.The temperature of desorption and regeneration is between 60-70 DEG C, and desorption efficiency is higher than 95%, and the capturing agent after desorb can be reused for catches CO 2, circulate after 5 times catch capacity, acquisition speed does not reduce.
Advantage of the present invention is: (1) the present invention is to provide the novel CO of a class 2capturing agent, has developed CO 2the new varieties of capturing agent; (2) CO provided by the invention 2capturing agent volatility is very low, and repeatedly circulation after catch capacity, acquisition speed does not reduce, and has high stability; (3) CO provided by the invention 2capturing agent has the lower viscosity of maintenance in the high capacity of catching, faster acquisition speed and acquisition procedure; (4) CO provided by the invention 2capturing agent is low owing to absorbing enthalpy, low by the regeneration energy consumption of heating desorption; (5) CO provided by the invention 2capturing agent preparation method is easy, and equipment needed thereby is simple, suitable for mass production application.
Brief description of the drawings
Fig. 1 is that the present invention measures CO 2the structural representation of the equipment of catch/desorption ability.
Mass flow controller in the drawings, 1, high-pressure carbon dioxide air accumulator, 2, high pressure nitrogen air accumulator, 3,, 4, mixed gas tank, 5, Pressure gauge, 6, triple valve, 7, catch-desorb reactor, 8, balance, 9, thermometer, 10, holding furnace, 11, infrared flue gas analyzer.
Detailed description of the invention
The present invention illustrates by following examples, but the present invention is not limited to following embodiment, and before and after not departing from, under the scope of described aim, change is included in technical scope of the present invention.
Embodiment 1
(1) to add in reactor 1.2 moles of 1-cyanoethyl imidazoles and 1.0 molar part 2-chloroethyl methyl ethers and etc. 66 milliliters of toluene, room temperature electric stirring 30 minutes, be warming up to 60 DEG C with the speed of 10 DEG C/min, 60 DEG C of stirring reactions of constant temperature 8 hours, be down to room temperature, divide extractive reaction liquid four times with 200 milliliters of cyclohexanes, remove excessive 1-cyanoethyl imidazoles and unreacted 2-chloroethyl methyl ether, 60 DEG C of vacuum drying are removed residual toluene in 24 hours, obtain intermediate product 1-cyanoethyl-3-ethyl methyl ether imidazoles villaumite.
(2) 1-cyanoethyl-3-ethyl methyl ether imidazoles villaumite is mixed with to the ethanol solution of 1N, solution is passed through to 717 type strong basicity I type anion exchange resin, obtain the ethanolic solution of hydroxide 1-cyanoethyl-3-ethyl methyl ether imidazoles, remove ethanol by Rotary Evaporators, obtain hydroxide 1-cyanoethyl-3-ethyl methyl ether imidazoles;
(3) 1.0 moles of hydrogen oxidation 1-cyanoethyl-3-ethyl methyl ether imidazoles and 1.0 moles of tricyano formic acid are added in reactor, 25 DEG C of electric stirring reactions 24 hours, reactant liquor is dewatered 70 DEG C of vacuum drying for 24 hours, obtain the CO of weak yellow liquid of the present invention 2capturing agent, productive rate 85%.
Embodiment 2
(1) to add in reactor 1.2 moles of 1-cyanoethyl imidazoles and 1.0 moles of 2-chloroethyl methyl ethers and etc. 66 milliliters of toluene, room temperature electric stirring 30 minutes, be warming up to 60 DEG C with the speed of 10 DEG C/min, 60 DEG C of stirring reactions of constant temperature 10 hours, be down to room temperature, divide extractive reaction liquid four times with 200 milliliters of cyclohexanes, remove excessive 1-cyanoethyl imidazoles and unreacted 2-chloroethyl methyl ether, 60 DEG C of vacuum drying are removed residual toluene in 24 hours, obtain intermediate product 1-cyanoethyl-3-ethyl methyl ether imidazoles villaumite;
(2) 1-cyanoethyl-3-ethyl methyl ether imidazoles villaumite is mixed with to the ethanol solution of 1N, solution is passed through to 717 type strong basicity I type anion exchange resin, obtain the ethanolic solution of hydroxide 1-cyanoethyl-3-ethyl methyl ether imidazoles, remove ethanol by Rotary Evaporators, obtain hydroxide 1-cyanoethyl-3-ethyl methyl ether imidazoles;
(3) 1.0 moles of hydrogen oxidation 1-cyanoethyl-3-ethyl methyl ether imidazoles and 1.0 moles of tricyano formic acid are added in reactor, 25 DEG C of electric stirring reactions 24 hours, reactant liquor is dewatered 70 DEG C of vacuum drying for 24 hours, obtain the CO of weak yellow liquid of the present invention 2capturing agent, productive rate 89%.
Test implementation example 1
As shown in Figure 1, carry out in the following way CO 2the test of catch/desorption ability:
First, utilize nitrogen (nitrogen gas purity is higher than 99.99%) to purge successively main road and bypath system, residual air in system is removed clean;
Rotate triple valve 6, keep bypass opening state, in catch-desorb reactor 7, (with 100 milliliters of stainless steel reaction tanks of thermometer) inject the CO of the embodiment 1 to embodiment 2 weighing 2capturing agent;
Catch-desorb reactor 7 is installed in (OF-22 of Jeiotech company type, heat-preserving range 20-180 DEG C, precision ± 0.1 DEG C) in holding furnace 10, to keep certain temperature;
Holding temperature is set, reaches after design temperature constant temperature 2 hours;
Require mass flow controller 3(Kofloc company 8500 types, control range 2%-100%, precision ± 1.5%FS according to simulated air concentration and volume flow rate) arrange, make nitrogen and CO 2in the interior abundant mixing of mixed gas tank 4, preparation simulated air, treats (Photon of Madur company type, measurement category 0-50%, resolution ratio 0.01%) CO in infrared flue gas analyzer 11 2after concentration stabilize, triple valve 6 is turned to main road opening state;
Carry out CO 2capture ability test, monitoring catch-desorb reactor 7 changes in weight (BAS124S-CW of Sartorius company type electronic balance, range of weighing 0-500 g, precision ± 0.01g);
After constant weight, capture ability test finishes;
Triple valve 6 is turned to bypass opening state;
Close high-pressure carbon dioxide air accumulator 1(CO 2purity is higher than 99.99%), only open nitrogen, purge whole bypath system, treat that infrared flue gas analyzer 11 shows CO in exit gas 2concentration is 0 o'clock, and nitrogen is switched to main road system, as desorb source of the gas;
Desorption temperature is set, reaches after design temperature constant temperature 2 hours;
Carry out desorption ability test, catch-desorb of monitoring reactor 7 changes in weight;
After constant weight, desorption ability test finishes;
Repeat the above catch-desorption cycle that operated repeatedly.
Test implementation example 2
The CO that utilizes the embodiment of testing of equipment shown in Fig. 11 to embodiment 2 to provide 2the CO of capturing agent 2catch/desorption ability.
Capture ability test condition: 50 milliliters of capturing agent consumptions, absorption pressure 1atm, catches 20 DEG C of temperature, 25 DEG C, 30 and 50 DEG C, CO in simulated air 2volumetric concentration 0.05%, simulated air volume flow rate 500 ml/min.
Desorption ability test condition: desorption pressures 1atm, 70 DEG C of desorption temperatures, stripping gas volume source flow rate 500 ml/min.
In above-mentioned test, capture time is defined as from starting to pass into simulated air to the catch-desorb reactor constant weight time used to catch-desorb reactor; Desorption time is defined as from starting to pass into desorb source of the gas to the catch-desorb reactor constant weight time used to saturated catch-desorb reactor of catching; Desorption efficiency is defined as total CO that capturing agent is caught 2residual CO after amount and desorb 2total CO that the difference of amount and capturing agent are caught 2the ratio of amount; Capture time and desorption time use the SEIKO Seiko S143 of company type stopwatch record, precision ± 0.01 second; Viscosity is used the NDJ-7 of Fei Kete company type rotary viscosity design determining, 75 revs/min of rotating speeds, measurement category 1-10 6mPaS, precision ± 2%, absorbs enthalpy and calculates according to B3LYP/6-31++G (d, p).Test result is recorded in table 1.
Table 1

Claims (2)

1. a CO 2capturing agent, is characterized in that chemical formula structure is as follows:
?。
2. a CO according to claim 1 2the preparation method of capturing agent, is characterized in that method step is as follows:
(1) in reactor, add 1.2 molar part 1-cyanoethyl imidazoles and 1.0 molar part 2-chloroethyl methyl ethers and equal-volume toluene, stirring at room temperature 30 minutes, be warming up to 60 DEG C with the speed of 10 DEG C/min, 60 DEG C of stirring reaction 8-10 hour of constant temperature, be down to room temperature, remove excessive 1-cyanoethyl imidazoles and unreacted 2-chloroethyl methyl ether with cyclohexane extraction, 60 DEG C of vacuum drying remove toluene in 24 hours, obtain intermediate product 1-cyanoethyl-3-ethyl methyl ether imidazoles villaumite;
(2) use absolute ethyl alcohol as solvent, 1-cyanoethyl-3-ethyl methyl ether imidazoles villaumite, by 717 type strong basicity I type anion exchange resin, is exchanged for to hydroxide 1-cyanoethyl-3-ethyl methyl ether imidazoles;
(3) by hydroxide 1-cyanoethyl-3-ethyl methyl ether imidazoles with etc. molar part tricyano formic acid add in reactor, 25 DEG C of stirring reactions 24 hours, 70 DEG C of vacuum drying dewater for 24 hours, obtain CO of the present invention 2capturing agent.
CN201410048886.7A 2014-02-12 2014-02-12 CO2 trapping agent and preparation method thereof Pending CN103933830A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101489994A (en) * 2006-07-27 2009-07-22 尼吉康株式会社 Ionic compound
WO2012076367A1 (en) * 2010-12-08 2012-06-14 Lonza Ltd 3-cyanopyridinium tricyanomethanides
CN102895844A (en) * 2012-10-10 2013-01-30 南昌航空大学 Liquid carbon dioxide absorbent and preparation method thereof
CN103214608A (en) * 2013-05-02 2013-07-24 南昌航空大学 Polymer-type carbon dioxide absorbent and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101489994A (en) * 2006-07-27 2009-07-22 尼吉康株式会社 Ionic compound
WO2012076367A1 (en) * 2010-12-08 2012-06-14 Lonza Ltd 3-cyanopyridinium tricyanomethanides
CN102895844A (en) * 2012-10-10 2013-01-30 南昌航空大学 Liquid carbon dioxide absorbent and preparation method thereof
CN103214608A (en) * 2013-05-02 2013-07-24 南昌航空大学 Polymer-type carbon dioxide absorbent and preparation method thereof

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