CN107096364B - For selective absorption of SO2Imidazole polymer absorbent and application thereof - Google Patents
For selective absorption of SO2Imidazole polymer absorbent and application thereof Download PDFInfo
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- CN107096364B CN107096364B CN201710297234.0A CN201710297234A CN107096364B CN 107096364 B CN107096364 B CN 107096364B CN 201710297234 A CN201710297234 A CN 201710297234A CN 107096364 B CN107096364 B CN 107096364B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
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Abstract
The invention discloses a method for selectively absorbing SO2Belonging to the field of environmental protection and gas purification. The absorbent comprises the following components: the imidazole polymer accounts for 10-50% by mass; 0.01-0.2% of antioxidant by mass percent; the activating additive accounts for 3.00-10.00% by mass; the balance being water. The invention provides the imidazole polymer aqueous solution absorbent by utilizing the proper alkalinity of the N atom on the 3-position in the imidazole functional group structure and considering the difficult volatility and the thermal stability of the polymer according to the principle of a PH buffer solution, and the preparation process is simple and the cost is low; to SO2Has high absorption selectivity and absorption efficiency, SO2Can be recycled.
Description
Technical Field
The invention belongs to the field of environmental protection and gas purification, and particularly relates to an imidazole polymer absorbent for selectively absorbing SO2 and application thereof.
Background
SO2Is one of the main atmospheric pollutants, SO2Is a main cause of environmental problems such as acid rain, haze and the like. The sulfur dioxide in the atmosphere mainly comes from burning of fossil fuels such as coal, and therefore the control and emission of the sulfur dioxide in flue gas are the main tasks of air pollution control. In 2011-2015, the total amount of sulfur dioxide discharged in China is about 2000 million tons and is the first in the world. With the increasing awareness of environmental protection and the increasingly strict requirements on the discharge of air pollutants, higher requirements are put forward on the flue gas desulfurization technology.
The flue gas desulfurization technology is various, and various countries in the world begin to research the desulfurization technology from the 20 th century 50 s, and the desulfurization technology reaches more than 200 so far. According to the dry-wet form of the desulfurization product, the flue gas desulfurization can be divided into wet method, semi-dry method and dry method. At present, the most mature flue gas desulfurization technology is wet process technology, which accounts for 85% of the total loading amount, wherein the limestone/gypsum wet process accounts for 36.7%, and in addition, ammonia-ammonium sulfate method, MgO method, activated carbon method, sodium-alkali method, electronic catalytic oxidation method, sodium-alkali cyclic absorption method and the like are also adopted. Although the wet desulfurization technology has the removal efficiency higher than 90 percent and high desulfurizer utilization rate, the equipment cost is about 10 percent of the total construction cost of a power plant, the operation cost is high, the management and maintenance are difficult, and secondary pollution is generated. Conventional non-resource SO2The removal technology consumes the absorbent and simultaneously generates a large amount of waste water, so that the waste water is not pollutedAccords with the concept of green chemical industry. Therefore, the resource SO with high efficiency, reasonable low energy consumption is developed2The removal technology has great significance.
Disclosure of Invention
The invention provides an imidazole polymer aqueous solution absorbent based on the proper alkalinity of N atoms on the 3-position in an imidazole functional group structure, according to the principle of a PH buffer solution and in consideration of the difficult volatility and the thermal stability of a polymer, and the preparation process is simple and the cost is low; to SO2Has high absorption selectivity and absorption efficiency, SO2Can be recycled.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
for selectively absorbing SO2The imidazole polymer absorbent of (a), the absorbent comprising the following components: water, imidazole polymer, antioxidant, activating additive; wherein the imidazole polymer has a general formula:
further, the corresponding monomer is 1-vinyl imidazole, and the connection form among the 1-vinyl imidazole monomer structural units is head-to-tail connection, tail-to-tail connection or head-to-head connection; wherein:
the head-tail connection refers to connection in the following form:
the tail-to-tail connection refers to connection in the following form:
the head-to-head connection means connection in the following form:
further, R in the general formula1And R2Are polymer end groups due to the free radical residue of the initiator during the polymerization process.
Further, the molecular weight of the imidazole polymer is within the range of 1000-100000; preferably, the molecular weight of the imidazole polymer is 1000 to 5000. The excessive molecular weight can cause the excessive viscosity of the absorbent, further influence the absorption performance of the absorbent, reduce the atom economy and reduce the SO of the absorbent per unit mass2The amount of absorption.
Further, the antioxidant is at least one selected from hydroquinone and derivatives thereof, catechol and derivatives thereof, anthraquinone and derivatives thereof.
Further, the activating additive is selected from alcamines, diamines, imidazoles and the like; preferably, the solvent is one or more selected from N-methyldiethanolamine and derivatives thereof, piperazine and derivatives thereof, ethylenediamine and derivatives thereof, and imidazole and derivatives thereof.
Further, the mass percent of the imidazole polymer is 10-50%, the mass percent of the antioxidant is 0.01-0.2%, the mass percent of the activating additive is 3.00-10.00%, and the balance is water. The imidazole polymer is a main component with absorption effect, the antioxidant has antioxidation effect, the activating additive can promote the dissolution of the imidazole polymer, reduce the viscosity of the system and play a certain absorption effect, and water is one of reactants in the absorption process, so that the ideal absorption effect can be achieved according to the proportion.
Further, the absorbent is used for SO2And (4) absorbing.
The invention absorbs SO2The principle of (1) is as follows:
SO2first with H in the system2Reaction of O to H2SO3The imidazole polymer and the activating additive in the system can generate protonation reaction, consume hydrogen ions in the system and promote H2SO3Thereby achieving SO absorption2The purpose of (1). Imidazoles as polymersThe protonation reaction that occurs between the compound and the activating additive is based on its appropriate basicity; the imidazole polymer and the activating additive can perform deprotonation reaction at higher temperature to realize SO2Desorption of (3).
The absorbent of the invention consists of water, imidazole polymer, antioxidant and activating additive, and is characterized in that: the imidazole-based polymers are SO absorbing polymers of the present invention2The activating additive itself can absorb a part of SO2It also serves to increase the solubility of the polymer in the system and to reduce the viscosity of the system to facilitate the absorption process. Water is formed in the system2SO3And therefore also indispensable.
Compared with the prior art, the invention has the following advantages:
1. multicomponent synergistic absorption of SO2The absorption capacity is large and the absorption efficiency is high.
2. The imidazole oligomer has higher thermal stability and difficult volatility, and is beneficial to long-term use of the absorbent.
3. With absorbents of suitable basicity, SO as to be able to reversibly absorb SO2，SO2Can be recycled.
4. Provides a novel absorbable SO2The absorbent has simple preparation process and low cost.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
Weighing 15.30g of poly 1-vinyl imidazole with average molecular weight of 2000, 0.20g of hydroquinone, 3.50g of piperazine and 30.60g of water to prepare an absorbent, and respectively utilizing pure SO2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption capacity of the gas was 15.84g, and the unit absorption capacity was 0.32g/g (SO)2Absorbent). The absorbent is used under the condition that the flow rate of the mixed gas is 400ml/minThe desulfurization rate of the catalyst reaches 98.8 percent.
Comparative example 1
Weighing 15.30g of poly 1-vinyl imidazole with average molecular weight of 2000, 0.20g of hydroquinone and 34.10g of water to prepare an absorbent, and respectively utilizing pure SO2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption capacity of the gas was 14.32g, and the unit absorption capacity was 0.29g/g (SO)2Absorbent). The desulfurization rate of the absorbent reaches 92.8 percent under the condition that the flow rate of the mixed gas is 400 ml/min.
Comparative example 1 differs from example 1 in that in comparative example 1, no activating additive is added, but instead water is used, at which point the unit absorption of the absorbent is greatly reduced relative to example 1.
Comparative example 2
Weighing 15.30g of poly 1-vinyl imidazole with the average molecular weight of 50000, 0.20g of hydroquinone, 3.50g of piperazine and 30.60g of water to prepare an absorbent, and respectively utilizing pure SO2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption capacity of the gas was 15.73g, and the unit absorption capacity was 0.32g/g (SO)2Absorbent). The desulfurization rate of the absorbent reaches 83.8 percent under the condition that the flow rate of the mixed gas is 400 ml/min.
Comparative example 2 differs from example 1 in that the use of a polyvinylimidazole having a higher molecular weight in comparative example 2 results in a higher viscosity of the absorbent system, at which the desulfurization efficiency of the absorbent is greatly reduced relative to example 1.
Comparative example 3
28.30g of poly 1-vinyl imidazole with average molecular weight of 2000, 0.20g of hydroquinone, 3.50g of piperazine and 20.60g of water are weighed to prepare an absorbent, and pure SO is respectively utilized2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption capacity of the gas was 22.09g, and the unit absorption capacity was 0.42g/g (SO)2Absorbent). The desulfurization rate of the absorbent reaches 89.8 percent under the condition that the flow rate of the mixed gas is 400 ml/min.
Comparative example 3 differs from example 1 in that comparative example 3 uses an absorbent with a polyvinylimidazole content of 53.8%, and exceeding the preferred content of this component results in a higher viscosity of the absorbent system, at which the desulfurization efficiency of the absorbent is somewhat reduced relative to example 1. Meanwhile, although the unit absorption amount of the absorbent is greatly improved, the economic benefit of the main absorbent polyvinyl imidazole is reduced, and the industrial cost is improved.
Comparative example 4
Weighing 15.30g of poly 1-vinyl imidazole with average molecular weight of 2000, 0.20g of hydroquinone, 0.95g of piperazine and 32.60g of water to prepare an absorbent, and respectively utilizing pure SO2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption capacity of the gas was 14.71g, and the unit absorption capacity was 0.30g/g (SO)2Absorbent). The desulfurization rate of the absorbent reaches 94.6 percent under the condition that the flow rate of the mixed gas is 400 ml/min.
Comparative example 4 differs from example 1 in that the activator content of the absorbent used in comparative example 4 is 1.9%, in which case the unit absorption of the absorbent is significantly reduced relative to example 1.
Comparative example 5
Weighing 15.30g of poly 1-vinyl imidazole with average molecular weight of 2000, 0.20g of hydroquinone, 5.95g of piperazine and 30.60g of water to prepare an absorbent, and respectively utilizing pure SO2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption amount of the gas was 17.18g, and the unit absorption amount was 0.33g/g (SO)2Absorbent). The desulfurization rate of the absorbent reaches 98.9 percent under the condition that the flow rate of the mixed gas is 400 ml/min.
Comparative example 5 differs from example 1 in that the absorbent used in comparative example 5 has an activator content of 11.3%, and at this time, the increase in the unit absorption amount of the absorbent is extremely small as compared with example 1, and the effect of continuing to increase the content of the activator after exceeding the preferred content on the increase in the absorption amount is not significant any more, and the economical efficiency is lowered.
Example 2
Weighing 14.90g of poly-1-vinylimidazole with average molecular weight of 2000, 0.25g of anthraquinone, 4.70g of 1-methylimidazole and 30.20g of water to prepare absorbent, and respectively using pure SO2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption capacity of the gas was 16.54g, and the unit absorption capacity was 0.33g/g (SO)2Absorbent). The desulfurization rate of the absorbent reaches 99.1 percent under the condition that the flow rate of the mixed gas is 400 ml/min.
Example 3
14.10g of poly-1-vinylimidazole with an average molecular weight of 2000, 0.15g of catechol, 4.90g of N-methyldiethanolamine and 30.80g of water are weighed to prepare an absorbent, and pure SO is respectively utilized2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption capacity of the gas was 14.94g, and the unit absorption capacity was 0.30g/g (SO)2Absorbent). The desulfurization rate of the absorbent reaches 98.3 percent under the condition that the flow rate of the mixed gas is 400 ml/min.
Example 4
Weighing 15.30g of poly 1-vinyl imidazole with average molecular weight of 1000, 0.20g of hydroquinone, 3.50g of piperazine and 30.60g of water to prepare an absorbent, and respectively utilizing pure SO2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption amount of the gas was 16.37g, and the unit absorption amount was 0.33g/g (SO)2Absorbent). The desulfurization rate of the absorbent reaches 99.0 percent under the condition that the flow rate of the mixed gas is 400 ml/min.
Example 4
Weighing 15.30g of poly 1-vinyl imidazole with average molecular weight of 1000, 0.20g of hydroquinone, 3.50g of piperazine and 30.60g of water to prepare an absorbent, and respectively utilizing pure SO2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption amount of the gas was 16.37g, and the unit absorption amount was 0.33g/g (SO)2Absorbent). The desulfurization rate of the absorbent reaches 99.0 percent under the condition that the flow rate of the mixed gas is 400 ml/min.
Example 5
Weighing 15.30g of poly-1-vinylimidazole with average molecular weight of 5000, 0.20g of hydroquinone, 3.50g of piperazine and 30.60g of water to prepare an absorbent, and respectively utilizing pure SO2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption amount of the gas was 15.37g, and the unit absorption amount was 0.31g/g (SO)2Absorbent). The desulfurization rate of the absorbent reaches 97.5 percent when the flow rate of the mixed gas is 400 ml/min.
Example 6
Weighing 15.30g of poly-1-vinylimidazole with average molecular weight of 10000, 0.20g of hydroquinone, 3.50g of piperazine and 30.60g of water to prepare an absorbent, and respectively using pure SO2Gas and SO2The absorption test was carried out at 30 ℃ for a mixed gas containing 1.2 Vol% (volume percentage, the same applies hereinafter).
The absorbent has good absorption effect on pure SO2The absorption capacity of the gas was 14.88g, and the unit absorption capacity was 0.30g/g (SO)2Absorbent). The desulfurization rate of the absorbent reaches 94.1 percent under the condition that the flow rate of the mixed gas is 400 ml/min.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. One kind is usedIn selective absorption of SO2The imidazole polymer absorbent of (1), characterized in that: the absorbent comprises the following components: water, imidazole polymer, antioxidant, activating additive; wherein the imidazole polymer has a general formula:
2. selective SO absorption according to claim 12The imidazole polymer absorbent of (1), characterized in that: the corresponding monomer is 1-vinyl imidazole, and the connection form among the 1-vinyl imidazole monomer structural units is head-to-tail connection, tail-to-tail connection or head-to-head connection; wherein:
the head-tail connection refers to connection in the following form:
the tail-to-tail connection refers to connection in the following form:
the head-to-head connection means connection in the following form:
3. selective SO absorption according to claim 1 or 22The imidazole polymer absorbent of (1), characterized in that: in the general formula R1And R2Are polymer end groups due to the free radical residue of the initiator during the polymerization process.
4. Selective SO absorption according to claim 12Of imidazole polymerAn agent characterized by: the molecular weight of the imidazole polymer is within the range of 1000-100000.
5. Selective SO absorption according to claim 12The imidazole polymer absorbent of (1), characterized in that: the antioxidant is at least one of hydroquinone and derivatives thereof, catechol and derivatives thereof, anthraquinone and derivatives thereof.
6. Selective SO absorption according to claim 12The imidazole polymer absorbent of (1), characterized in that: the activating additive is at least one of alcohol amine substance, diamine substance and imidazole substance.
7. Selective SO absorption according to claim 12The imidazole polymer absorbent of (1), characterized in that: the mass percentage of the imidazole polymer is 10-50%, the mass percentage of the antioxidant is 0.01-0.2%, the mass percentage of the activating additive is 3.00-10.00%, and the balance is water.
8. Use of the absorbent according to claim 1 for SO2And (4) absorbing.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003022892A2 (en) * | 2001-09-01 | 2003-03-20 | Universität Stuttgart Institut Für Chemische Verfahrenstechnik | Oligomers and polymers containing sulfonite groups and method for the production thereof |
| CN101537304A (en) * | 2009-04-17 | 2009-09-23 | 合肥工业大学 | Cyclic amine sulfur dioxide gas absorbent and preparation method thereof |
| CN103657342A (en) * | 2013-12-10 | 2014-03-26 | 陕西省石油化工研究设计院 | High-efficiency regenerative SO2 absorbent |
| CN105617820A (en) * | 2016-03-24 | 2016-06-01 | 天津大学 | Combined-type absorbent used for selectively absorbing SO2 and application of combined-type absorbent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003022892A2 (en) * | 2001-09-01 | 2003-03-20 | Universität Stuttgart Institut Für Chemische Verfahrenstechnik | Oligomers and polymers containing sulfonite groups and method for the production thereof |
| CN101537304A (en) * | 2009-04-17 | 2009-09-23 | 合肥工业大学 | Cyclic amine sulfur dioxide gas absorbent and preparation method thereof |
| CN103657342A (en) * | 2013-12-10 | 2014-03-26 | 陕西省石油化工研究设计院 | High-efficiency regenerative SO2 absorbent |
| CN105617820A (en) * | 2016-03-24 | 2016-06-01 | 天津大学 | Combined-type absorbent used for selectively absorbing SO2 and application of combined-type absorbent |
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