CN103127815A - Method of improving trapping performance of sulfur dioxide through halide sulfur function - Google Patents
Method of improving trapping performance of sulfur dioxide through halide sulfur function Download PDFInfo
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- CN103127815A CN103127815A CN2013100535384A CN201310053538A CN103127815A CN 103127815 A CN103127815 A CN 103127815A CN 2013100535384 A CN2013100535384 A CN 2013100535384A CN 201310053538 A CN201310053538 A CN 201310053538A CN 103127815 A CN103127815 A CN 103127815A
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Abstract
The invention relates to a method of improving the trapping performance of sulfur dioxide through a halide sulfur function. According to the method of improving the trapping performance of the sulfur dioxide through the halide sulfur function, halogens are led to negative ions of functional ionic liquid, by means of the halide sulfur function and an electron-withdrawing function of the halogens, the absorptive capacity of the sulfur dioxide is improved, the desorption performance of the ionic liquid is improved, and therefore the efficient and reversible trapping of gaseous sulfur dioxide is achieved. Particularly, the method includes that negative ion functional ionic liquid containing the halogens serves as absorbent to absorb the gaseous sulfur dioxide, the absorption pressure is 0.001-0.1 MPa, the absorption temperature is below 20-100 DEG C, the absorption time is 0.1-0.3 hour, the desorption temperature is 60-130 DEG C, and the desorption time is between 0.1 hour and 3 hours. The method of improving the trapping performance of the sulfur dioxide through the halide sulfur function has the advantages of being good in ionic liquid stability, high in absorptive capacity, and easy in detachment, thereby having industrial utilization potentiality.
Description
Technical field
The present invention relates to a kind of method of utilizing the effect of halogen sulphur to improve sulfur dioxide capture performance, namely introduce halogen on the anion of functionalized ion liquid, utilize the effect of halogen sulphur and the electron attraction of halogen, not only improve the absorptive capacity of sulfur dioxide, and improve the desorption performance of ionic liquid, thereby realize the capture of efficient, reversible, the low energy consumption of sulfur dioxide gas, provide a kind of new potential method for industry captures sulfur dioxide.
Background technology
Along with the fast development of economic society and the raising of people's living standard, coal fire discharged sulfur dioxide worsens atmospheric environment, acid rain harm increases the weight of, and has had a strong impact on the mankind's existence and ecological environment, sulfur dioxide in flue gas remove the extensive concern that has caused domestic and international researcher.Desulfurization Technology how to develop efficient, economy, environmental protection is the common hot issue of paying close attention in the whole world.
At present, the method that traditional industry captures sulfur dioxide is lime, amine aqueous solution absorption process etc., has the advantages such as cost is low, absorption is fast, capacity is large, but also has some limitation: as volatile in solvent, generate the problems such as a large amount of by-products, the difficult regeneration of absorbent.In the last few years, ionic liquid is the advantages such as good stability, volatility are low, the gas dissolution ability strong, designability owing to having, and provided good alternative for the industry of sulfur dioxide captures.Many researchers adopt experiment and theoretical method to study the dissolubility of sulfur dioxide in different ionic liquid, show that ionic liquid absorbs approximately sulfur dioxide more than 1 mole as the imidazole type ion liquid every Molar Energy under normal pressure that contains the tetrafluoro boric acid anion, but under low pressure very little.Another kind method is to adopt the ionic liquid of anionic functional to carry out the chemistry capture of sulfur dioxide, the guanidine class ionic liquid that contains lactate as employings first such as Han comes sulfur dioxide absorption, every mole of ionic liquid can absorb the sulfur dioxide of 1.7 moles under normal pressure, after serve the researcher and also developed other and contain the ionic liquid of acetate, sulfuric ester, azole anion etc., be applied in the chemical absorbing of sulfur dioxide.Carrying out more research although capture at functionalized ion liquid at present both at home and abroad aspect sulfur dioxide, but still the ubiquity absorptive capacity high not enough, be difficult for the problems such as desorption, cycle performance be poor, affected its actual commercial Application.Therefore, the structural design by the anionic functional ionic liquid how, both improved the absorptive capacity of ionic liquid, improve again the desorption performance of ionic liquid, thereby realizing the absorption of sulfur dioxide gas high power capacity, low energy consumption, is that at present both at home and abroad the research ionic liquid captures one of the focus of sulfur dioxide and direction.
Summary of the invention
The halogen key is widely used in many fields such as biology, molecular recognition, crystal engineering, the autonomous dresses of supermolecule, but seldom is applied in the capture of gas.Purpose of the present invention just is to provide a kind of halogen sulphur that utilizes and is used for improving the method that functionalized ion liquid captures the sulfur dioxide performance, namely introduce halogen on the anion of functionalized ion liquid, utilize halogen with the effect of sulfur dioxide, improve the absorptive capacity of sulfur dioxide, and utilize the electrophilic performance of halogen, improve the desorption performance of ionic liquid, thereby realize efficient, the reversible capture of sulfur dioxide gas.Its concrete technical scheme is as follows:
The present invention is a kind of method that adopts halogen-containing anionic functional ionic liquid to capture sulfur dioxide, take halogen-containing anionic functional ionic liquid as absorbent, in order to sulfur dioxide absorption gas, absorption pressure is 0.001～0.1MPa, absorbing temperature is under 20 ℃～100 ℃, and soak time is 0.1～3 hour; The very easy desorption of sulfur dioxide that absorbs, desorption temperature is between 60～120 ℃, and desorption time is between 0.1～3 hour.
halogen-containing anionic functional ionic liquid of the present invention is myristyl three hexyl phosphorus Chlorobenzoic Acids, myristyl three hexyl phosphorus fluorinated acids, myristyl three hexyl phosphorus bromobenzoic acids, myristyl three hexyl phosphorus iodobenzoic acids, myristyl three hexyl phosphorus fluorophenols, myristyl three hexyl phosphorus chlorophenols, myristyl three hexyl phosphorus bromophenols, myristyl three hexyl phosphorus bromobenzene acetic acid, myristyl three hexyl phosphorus chlorophenyl acetic acids, myristyl three hexyl phosphorus monobromo-acetic acids, myristyl three hexyl phosphorus chloracetic acids, myristyl three hexyl phosphorus chloro imidazoles, myristyl three hexyl phosphorus chloro triazoles, myristyl three hexyl phosphorus bromo imidazoles, myristyl three hexyl phosphorus bromo triazoles, propyl group three hexyl phosphorus Chlorobenzoic Acids, propyl group three hexyl phosphorus chlorophenols, propyl group three hexyl phosphorus Chlorobenzoic Acids, butyl three hexyl phosphorus Chlorobenzoic Acids, butyl three hexyl phosphorus chlorophenols, ethyl tributyl phosphorus Chlorobenzoic Acid, ethyl tributyl phosphorus chlorophenol, ethyl-methyl imidazoles Chlorobenzoic Acid, ethyl-methyl imidazoles bromobenzoic acid, ethyl-methyl imidazoles chlorophenol, butyl methyl imidazoles bromobenzoic acid, butyl methyl imidazoles bromophenol, a kind of in tributyl ethyl ammonium Chlorobenzoic Acid or tributyl ethyl ammonium bromophenol.
Halogen-containing anionic functional ionic liquid of the present invention is myristyl three hexyl phosphorus bromobenzoic acids.
Absorption temperature of the present invention is between 20 ℃～60 ℃, and soak time is between 0.3～1 hour, and desorption temperature is between 80 ℃～100 ℃, and desorption time is between 0.5～1 hour.
Ionic liquid of the present invention can be take Chlorobenzoic Acid, bromobenzoic acid, chlorophenyl acetic acid, bromophenol etc. with myristyl three hexyl phosphorus hydroxide etc. as raw material, obtain by the reaction of acid-base neutralization method, the latter can synthesize by the strong-base anion-exchange resin method, the stability of these ionic liquids is very high, and decomposition temperature is generally greater than 300 ℃.
The present invention compares with conventional method, and is very novel, has following characteristic: 1) owing to having introduced halogen on anion, utilize the halogen sulphur effect of halogen and sulfur dioxide, its absorptive capacity is obviously improved; 2) due to the electron attraction of halogen, disperseed the electric charge on the anion, reduced the absorption energy of sulfur dioxide, make the easy desorption of sulfur dioxide of absorption; 3) adopting the non-amine type functionalized ion liquid of high stable is absorbent, has avoided the formation of hydrogen bond network after the system sulfur dioxide absorption, has reduced the viscosity after the system sulfur dioxide absorption, has obviously accelerated the speed of reaction.
The specific embodiment
Below by specific embodiment, technical solution of the present invention is done to describe more comprehensively.
Embodiment 1
Be in the 5ml glass container of 1cm at an internal diameter, add ionic liquid myristyl three hexyl phosphorus bromobenzoic acid 1.3g (0.02mol), then slowly pass into sulfur dioxide gas, flow 60ml/min, pressure 0.1MPa, controlling the absorption temperature is 20 ℃, and controlling soak time is 0.5 hour, and the absorptive capacity that shows sulfur dioxide in this ionic liquid of weighing is 4.10 moles/mole ionic liquids.
Reference examples 1
Be in the 5ml glass container of 1cm at an internal diameter, add ionic liquid myristyl three hexyl phosphorus benzoic acid 1.2g (0.02mol), then slowly pass into sulfur dioxide gas, flow 60ml/min, pressure 0.1MPa, controlling the absorption temperature is 20 ℃, and controlling soak time is 0.5 hour, and the absorptive capacity that shows sulfur dioxide in this ionic liquid of weighing is 3.50 moles/mole ionic liquids.
Embodiment 2-10
Be similar to embodiment 1, controlling sulfur dioxide gas pressure is 0.1 MPa, and absorbing temperature is 20 ℃, changes the kind of ionic liquid, result such as following table (table 1) that sulfur dioxide absorbs:
The impact that table 1 different ionic liquid kind captures sulfur dioxide
Embodiment 11-21
Be similar to embodiment 1, adopting myristyl three hexyl phosphorus bromobenzoic acids is absorbent, and sulfur dioxide absorption gas changes conditions such as absorbing temperature, gas pressure and soak time, absorbs result such as following table (table 2):
The impact that the different acceptance conditions of table 2 absorb sulfur dioxide
Embodiment 22
Be in the 5ml glass container of 1cm at an internal diameter, add the ionic liquid myristyl three hexyl phosphorus bromobenzoic acid 1.3g (0.02mol) of sulfur dioxide absorption, then slowly pass into nitrogen, flow 60ml/min, pressure 0.1MPa, controlling desorption temperature is 120 ℃, and controlling desorption time is 0.5 hour, weighs to show the sulfur dioxide that absorbs in this ionic liquid desorption fully.
Reference examples 22
Be in the 5ml glass container of 1cm at an internal diameter, add the ionic liquid myristyl three hexyl phosphorus benzoic acid 1.3g (0.02mol) of sulfur dioxide absorption, then slowly pass into nitrogen, flow 60ml/min, pressure 0.1MPa, controlling desorption temperature is 120 ℃, and controlling desorption time is 0.5 hour, and weighing shows the sulfur dioxide residue 0.35mol/mol IL that absorbs in this ionic liquid.
Embodiment 23-30
Be similar to embodiment 22, controlling nitrogen pressure is 0.1 MPa, and flow 60ml/min changes the kind of ionic liquid and the temperature of desorption, the result of desorption such as following table (table 3):
The impact of table 3 different ionic liquid kind on the sulfur dioxide desorption
Claims (7)
1. method that adopts halogen-containing anionic functional ionic liquid to capture sulfur dioxide, it is characterized in that take halogen-containing anionic functional ionic liquid as absorbent, in order to sulfur dioxide absorption gas, the absorption pressure of described method is 0.001～0.1MPa, absorbing temperature is under 20 ℃～100 ℃, and soak time is 0.1～3 hour; The very easy desorption of sulfur dioxide that absorbs, desorption temperature is between 60～120 ℃, and desorption time is between 0.1～3 hour.
2. method according to claim 1, is characterized in that described halogen-containing anionic functional ionic liquid is myristyl three hexyl phosphorus Chlorobenzoic Acids, myristyl three hexyl phosphorus fluorinated acids, myristyl three hexyl phosphorus bromobenzoic acids, myristyl three hexyl phosphorus iodobenzoic acids, myristyl three hexyl phosphorus fluorophenols, myristyl three hexyl phosphorus chlorophenols, myristyl three hexyl phosphorus bromophenols, myristyl three hexyl phosphorus bromobenzene acetic acid, myristyl three hexyl phosphorus chlorophenyl acetic acids, myristyl three hexyl phosphorus monobromo-acetic acids, myristyl three hexyl phosphorus chloracetic acids, myristyl three hexyl phosphorus chloro imidazoles, myristyl three hexyl phosphorus chloro triazoles, myristyl three hexyl phosphorus bromo imidazoles, myristyl three hexyl phosphorus bromo triazoles, propyl group three hexyl phosphorus Chlorobenzoic Acids, propyl group three hexyl phosphorus chlorophenols, propyl group three hexyl phosphorus Chlorobenzoic Acids, butyl three hexyl phosphorus Chlorobenzoic Acids, butyl three hexyl phosphorus chlorophenols, ethyl tributyl phosphorus Chlorobenzoic Acid, ethyl tributyl phosphorus chlorophenol, ethyl-methyl imidazoles Chlorobenzoic Acid, ethyl-methyl imidazoles bromobenzoic acid, ethyl-methyl imidazoles chlorophenol, butyl methyl imidazoles bromobenzoic acid, butyl methyl imidazoles bromophenol, a kind of in tributyl ethyl ammonium Chlorobenzoic Acid or tributyl ethyl ammonium bromophenol.
3. method according to claim 2, is characterized in that described halogen-containing anionic functional ionic liquid is myristyl three hexyl phosphorus bromobenzoic acids.
4. according to claim 1 and 2 or 3 described methods, is characterized in that described absorption temperature is between 20 ℃～60 ℃.
5. according to claim 1 and 2 or 3 described methods, is characterized in that described soak time is between 0.3～1 hour.
6. according to claim 1 and 2 or 3 described methods, is characterized in that described desorption temperature is between 80 ℃～100 ℃.
7. according to claim 1 and 2 or 3 described methods, is characterized in that described desorption time is between 0.5～1 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923036A (en) * | 2015-06-09 | 2015-09-23 | 河南师范大学 | Method for catching sulfur dioxide by adopting halogenated carboxylic acid ion liquid |
| CN105944509A (en) * | 2016-06-27 | 2016-09-21 | 河南师范大学 | Method for capturing sulfur dioxide by using aldehyde-group-containing anion functionalized ionic liquid |
| CN106422674A (en) * | 2016-11-08 | 2017-02-22 | 河南师范大学 | Method for solidifying and storing sulfur dioxide through positive ion functional ionic liquid |
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| WO2001049672A1 (en) * | 1999-12-30 | 2001-07-12 | H. Lundbeck A/S | Method for the preparation of citalopram |
| JP2003093835A (en) * | 2001-09-27 | 2003-04-02 | Hitachi Ltd | Regeneration method for gas absorbing liquid and regeneration system for gas absorbing liquid |
| US20110296992A1 (en) * | 2010-06-03 | 2011-12-08 | E. I. Du Pont De Nemours And Company | Sulfur compounds for carbon dioxide and sulfur dioxide removal |
| CN102274674A (en) * | 2011-06-20 | 2011-12-14 | 浙江大学 | Method for capturing carbon dioxide (CO2) by high-stability substituted phenol ionic liquid |
| CN102430319A (en) * | 2011-11-09 | 2012-05-02 | 浙江大学 | Method for catching carbon dioxide by adopting alcohol amine type ion liquid |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001049672A1 (en) * | 1999-12-30 | 2001-07-12 | H. Lundbeck A/S | Method for the preparation of citalopram |
| JP2003093835A (en) * | 2001-09-27 | 2003-04-02 | Hitachi Ltd | Regeneration method for gas absorbing liquid and regeneration system for gas absorbing liquid |
| US20110296992A1 (en) * | 2010-06-03 | 2011-12-08 | E. I. Du Pont De Nemours And Company | Sulfur compounds for carbon dioxide and sulfur dioxide removal |
| CN102274674A (en) * | 2011-06-20 | 2011-12-14 | 浙江大学 | Method for capturing carbon dioxide (CO2) by high-stability substituted phenol ionic liquid |
| CN102430319A (en) * | 2011-11-09 | 2012-05-02 | 浙江大学 | Method for catching carbon dioxide by adopting alcohol amine type ion liquid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923036A (en) * | 2015-06-09 | 2015-09-23 | 河南师范大学 | Method for catching sulfur dioxide by adopting halogenated carboxylic acid ion liquid |
| CN105944509A (en) * | 2016-06-27 | 2016-09-21 | 河南师范大学 | Method for capturing sulfur dioxide by using aldehyde-group-containing anion functionalized ionic liquid |
| CN106422674A (en) * | 2016-11-08 | 2017-02-22 | 河南师范大学 | Method for solidifying and storing sulfur dioxide through positive ion functional ionic liquid |
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