CN105617820A - Combined-type absorbent used for selectively absorbing SO2 and application of combined-type absorbent - Google Patents
Combined-type absorbent used for selectively absorbing SO2 and application of combined-type absorbent Download PDFInfo
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- CN105617820A CN105617820A CN201610176061.2A CN201610176061A CN105617820A CN 105617820 A CN105617820 A CN 105617820A CN 201610176061 A CN201610176061 A CN 201610176061A CN 105617820 A CN105617820 A CN 105617820A
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- acid
- absorption agent
- combined type
- selective absorbing
- type absorption
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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
- B01D53/14—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 by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
- B01D2252/103—Water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20415—Tri- or polyamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
- B01D2252/2053—Other nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/30—Ionic liquids and zwitter-ions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
A combined-type absorbent used for selectively absorbingSO2 comprises three ingredients: water, polyamino compound strong acid salt, and at least one of amide compounds and urea compounds, wherein the polyamino compound strong acid salt is obtained via reaction between a polyamino compound and organic strong acid/inorganic strong acid. As the alkalinities of different amido groups are different, the invention provides the combined-type absorbent according to a PH buffer solution principle, the preparation technology is simple, and the cost is low; the absorption selectivity of SO2 is high, the absorption efficiency is high, and SO2 can be recycled.
Description
Technical field
The invention belongs to functional ionic liquids field, especially relate to a kind of for selective absorbing SO2Combined type absorption agent and application.
Background technology
SO2Being one of main atmospheric polluting material, be the major cause forming acid rain and photo-chemical smog, 2,011 2015, China's sulfur dioxide emissions total amount all at about 2,000 ten thousand tons, occupied the first in the world. Raising along with environmental protection consciousness and the requirement increasingly stringent to air pollutant discharge, have higher requirement to flue gas desulfurization technique.
Flue gas desulfurization technique is varied, and desulfurization technology is studied in countries in the world from the fifties in 20th century, and desulfurization technology has reached kind more than 200 so far. By the dry wet form of desulfurization product, flue gas desulfurization can be divided into again wet method, semidrying and dry flue gas desulphurization. At present, the most ripe in flue gas desulfurization technique is Wet technique, accounts for the 85% of total installed capacity amount, wherein account for 36.7% with Wet Limestone/gypsum, in addition, also has ammonia ammonium sulphate process, MgO method, activated carbon method, sodium alkali, electronic catalytic oxidation style, sodium alkali absorption cycle etc. Although wet desulphurization technology removal efficiency is relatively up to more than 90%, sorbent utilization height, but its cost of equipment is about equivalent to the 10% of the whole construction cost in power station, and working cost is expensive, and management maintenance difficulty, produces secondary pollution. Traditional non-resource SO2Removing sulfuldioxide produces a large amount of waste water while consuming absorption agent, makes it not meet the theory of green chemical industry. Therefore, develop the resource utilization SO of efficient and rational less energy-consumption2Removing sulfuldioxide is significant.
Summary of the invention
The present invention based on multiple organic amine and amine salt to SO2Selective absorbing, utilize the alkalescence of different amido different, according to PH damping fluid principle, it is proposed to a kind of combined type SO2Absorption agent, preparation technology is simple, and cost is low; To SO2Absorption selectivity height, assimilated efficiency height, SO2Resourcebility.
For achieving the above object, the technical scheme of the present invention is achieved in that
A kind of for selective absorbing SO2Combined type absorption agent, it is characterised in that: comprise following three kinds of components: water, at least one in polyamine compounds strong acid salt, amides and carbamide compounds; Wherein, described polyamine compounds strong acid salt is obtained by polyamine compounds and organic acid or inorganic acid reaction.
Further, the general formula of described polyamine compounds is:
In formula, the number of atom N at least two, it is preferable that, the number of described atom N is 2-8; Described R1To RnIdentical or different; R1To RnIndependent is H, alkyl, cycloalkyl, alkoxyl group, haloalkyl, aryl, ether base separately, and as described R1To RnIt is not H when being positioned on non-end group position.
Further, described inorganic acid or organic acid be selected from hydrochloric acid, sulfuric acid, nitric acid, Hydrogen bromide, hydroiodic acid HI, phosphoric acid, boric acid, methylsulfonic acid, trifluoromethanesulfonic acid one or more, preferably, described organic acid or inorganic acid are at least one in phosphoric acid, sulfuric acid, nitric acid.
Further, in the mole number of the atom N of described polyamine compounds and described organic acid or inorganic acid, the ratio of the mole number of Hydrogen Proton is 2:1 to 5:1; When this value is less than 2:1, absorbs number of sites less, absorbed dose is reduced, when this value is greater than 5:1, the SO absorbed2Cannot fully desorb.
Further, described amides C atom number is 1-6, and in described carbamide compounds, carbon atom number is 1-6, it is preferable that, described amides or carbamide compounds are selected from methane amide, ethanamide, N, dinethylformamide, DMAC N,N' dimethyl acetamide, pyrrolidone, N-Methyl pyrrolidone, hexanolactam, urea, N-tert butyl urea, 1,1,3,3-tetramethyl-urea, 1,3-dimethyl urea, one or more in 1,3-dimethyl-imidazolinone.
Further, the mass percentage of described polyamine compounds strong acid salt is the Mole percent total content of 20-50%, amides and carbamide compounds is 10%-40%, and surplus is water. The strong acid salt of polyamine compounds is the main component playing sorption, amides and carbamide compounds can promote the dissolving of polyamine compounds strong acid salt, and play certain sorption, water is one of reactant of absorption process, therefore just can reach desirable assimilation effect according to said ratio.
Further, described R1To RnMiddle C atom number is less than or equal to 4, and too much C atom can reduce Atom economy, reduces the SO of unit mass absorption agent2Absorbed dose.
Further, in described polyamine compounds, the number of atom N is 2-8
Further, described one is used for selective absorbing SO2Combined type absorption agent be used for SO2Absorb.
The present invention absorbs SO2Principle be:
SO2First with the H in system2O reaction generates H2SO3, the polyamines class strong acid salt in system, all can there is protonation reaction in acid amides or sulfonylurea, the hydrogen ion in consumption system, promotes H2SO3Ionization, thus realize absorb SO2Object. The protonation reaction that amine substance occurs is the alkalescence based on amine substance, and wherein acid amides and sulfonylurea alkalescence are more weak, and many amine substances alkalescence is stronger; Therefore, many amine substances and strong acid reaction are made strong acid salt so that it is the stronger atom N of alkalescence is protonated in advance, and remaining atom N alkalescence is moderate, thus making polyamines class strong acid salt, acid amides or sulfonylurea all can occur deprotonation to react at relatively high temperatures, it is achieved SO2Desorb.
The combined type absorption agent of the present invention must be made up of water, many amine substances strong acid salt and acid amides or sulfonylurea three parts. Its reason is: the strong acid salt of many amine substances absorbs SO in the present invention2Essential substance, but it is water-soluble poor. Acid amides or sulfonylurea itself can absorb part SO2, but its another effect is the solubleness improving polyamines class strong acid salt in system, thus improve its content. Water forms H in system2SO3Reactant, therefore also essential.
Relative to prior art, the present invention has following advantage:
1. polycomponent is collaborative absorbs, SO2Absorbed dose is big, assimilated efficiency height.
2. absorption agent viscosity is little, and uptake rate is fast.
3. it is adjusted to suitable alkalescence by strong acid such that it is able to reversible absorption SO2, SO2Resourcebility.
4. couple SO2Absorption selectivity height, SO in stripping gas2Content height.
5. provide a kind of novel absorbed SO2Absorption agent, preparation technology is simple, and cost is low.
Embodiment
It should be noted that, when not conflicting, the embodiment in the present invention and the feature in embodiment can combine mutually.
Embodiment 1
Take diethylenetriamine 10.3g, add 1,1,3,3-tetramethyl-urea 11.0g successively, water 5g, purity be 98% vitriol oil 3.7g make absorption agent. Successively utilize pure SO2Gas and SO2The mixed gas that content is 8000ppm carries out absorption experiment at 30 DEG C.
This absorption agent is to pure SO2The absorbed dose 30g of gas, unit absorbed dose is 0.77g/g (SO2/ absorption agent). The desulfurization degree of this absorption agent mixed gas reaches 99.1%.
Comparative example 1
Take diethylenetriamine 10.3g, add water 16g successively, purity be 98% vitriol oil 3.7g make absorption agent. Successively utilize pure SO2Gas and SO2The mixed gas that content is 8000ppm carries out absorption experiment at 30 DEG C.
This absorption agent is to pure SO2The unit absorbed dose of gas is 0.43g/g (SO2/ absorption agent). The desulfurization degree of this absorption agent mixed gas reaches 75.2%.
Comparative example 1 is with the difference of embodiment 1, and not adding described acid amides or sulfonylurea in comparative example 1, but replaced as water, now, relative to embodiment 1, the unit absorbed dose of absorption agent declines greatly.
Comparative example 2
Take diethylenetriamine 10.3g, add 1,1,3,3-tetramethyl-urea 16g successively, purity be 98% vitriol oil 3.7g make absorption agent. Successively utilize pure SO2Gas and SO2The mixed gas that content is 8000ppm carries out absorption experiment at 30 DEG C.
This absorption agent is to pure SO2The unit absorbed dose of gas is 0.29g/g (SO2/ absorption agent). The desulfurization degree of this absorption agent mixed gas reaches 60.2%.
Comparative example 2 is with the difference of embodiment 1, and not adding described water in comparative example 2, but replaced as described acid amides or sulfonylurea, now, relative to embodiment 1, the unit absorbed dose of absorption agent declines greatly.
Comparative example 3
Take diethylenetriamine 8.2g, add 1,1,3,3-tetramethyl-urea 11g successively, water 5g, purity be 98% vitriol oil 5.8g make absorption agent. Successively utilize pure SO2Gas and SO2The mixed gas that content is 8000ppm carries out absorption experiment at 30 DEG C.
This absorption agent is to pure SO2The unit absorbed dose of gas is 0.46g/g (SO2/ absorption agent). The desulfurization degree of this absorption agent mixed gas reaches 73.2%.
Comparative example 3 is with the difference of embodiment 1, and the atom N in the diethylenetriamine of comparative example 3 is different from the ratio of H proton in the vitriol oil, and in comparative example 3, in atom N and the vitriol oil, the ratio of H proton is less than 2:1, and now, the assimilation effect of absorption agent is poor.
Embodiment 2
Take diethylenetriamine 10.3g, add N-Methyl pyrrolidone 11g successively, water 5g, purity be 98% vitriol oil 3.7g make absorption agent. Successively utilize pure SO2Gas and SO2The mixed gas that content is 8000ppm carries out absorption experiment at 30 DEG C.
Unit absorbed dose is 0.76g/g (SO2/ absorption agent). The desulfurization degree of this absorption agent mixed gas reaches 98.2%.
Embodiment 3
Take tetraethylethylenediamine 9.8g, add DMAC N,N' dimethyl acetamide 11g successively, water 5g, purity be 98% vitriol oil 4.2g make absorption agent. Successively utilize pure SO2Gas and SO2The mixed gas that content is 8000ppm carries out absorption experiment at 30 DEG C.
Unit absorbed dose is 0.69g/g (SO2/ absorption agent). The desulfurization degree of this absorption agent mixed gas reaches 97.2%.
Embodiment 4
Take tetraethylethylenediamine 4.9g, add DMAC N,N' dimethyl acetamide 7g successively, water 16g, purity be 98% vitriol oil 2.1g make absorption agent. Successively utilize pure SO2Gas and SO2The mixed gas that content is 8000ppm carries out absorption experiment at 30 DEG C.
Unit absorbed dose is 0.61g/g (SO2/ absorption agent). The desulfurization degree of this absorption agent mixed gas reaches 93.2%.
Embodiment 5
Take triethylene tetramine 9.9g, add N-Methyl pyrrolidone 10g successively, water 6g, purity be 98% vitriol oil 4.1g make absorption agent. Successively utilize pure SO2Gas and SO2The mixed gas that content is 8000ppm carries out absorption experiment at 30 DEG C.
Unit absorbed dose is 0.73g/g (SO2/ absorption agent). The desulfurization degree of this absorption agent mixed gas reaches 97.5%.
Embodiment 6
Take pentamethyl-diethylenetriamine 11.6g, add N successively, dinethylformamide 8g, water 7g, purity be 98% vitriol oil 3.6g make absorption agent. Successively utilize pure SO2Gas and SO2The mixed gas that content is 8000ppm carries out absorption experiment at 30 DEG C.
Unit absorbed dose is 0.79g/g (SO2/ absorption agent). The desulfurization degree of this absorption agent mixed gas reaches 99.2%.
Embodiment 7
Take Tetramethyl Ethylene Diamine 11.3g, add DMAC N,N' dimethyl acetamide 8g successively, water 8g, purity be 85% phosphoric acid 2.7g make absorption agent. Successively utilize pure SO2Gas and SO2The mixed gas that content is 8000ppm carries out absorption experiment at 30 DEG C.
Unit absorbed dose is 0.73g/g (SO2/ absorption agent). The desulfurization degree of this absorption agent mixed gas reaches 98.6%.
The foregoing is only the better embodiment of the present invention, not in order to limit the invention, within the spirit and principles in the present invention all, any amendment of doing, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. one kind for selective absorbing SO2Combined type absorption agent, it is characterised in that: comprise following three kinds of components: at least one in water, polyamine compounds strong acid salt, amides and carbamide compounds; Wherein, described polyamine compounds strong acid salt is obtained by polyamine compounds and organic acid or inorganic acid reaction.
2. one according to claim 1 is used for selective absorbing SO2Combined type absorption agent, it is characterised in that: the general formula of described polyamine compounds is:
In formula, the number of atom N at least two, R1To RnIdentical or different; R1To RnIndependent is H, alkyl, cycloalkyl, alkoxyl group, haloalkyl, aryl and ether base separately, and as described R1To RnIt is not H when being positioned on non-end group position.
3. one according to claim 1 and 2 is used for selective absorbing SO2Combined type absorption agent, it is characterized in that: described inorganic acid or organic acid be selected from hydrochloric acid, sulfuric acid, nitric acid, Hydrogen bromide, hydroiodic acid HI, phosphoric acid, boric acid, methylsulfonic acid, trifluoromethanesulfonic acid one or more, preferably, described organic acid or inorganic acid are at least one in phosphoric acid, sulfuric acid, nitric acid.
4. one according to claim 1 is used for selective absorbing SO2Combined type absorption agent, it is characterised in that: in the mole number of the atom N of described polyamine compounds and described organic acid or inorganic acid, the ratio of the mole number of Hydrogen Proton is 2:1 to 5:1.
5. one according to claim 1 is used for selective absorbing SO2Combined type absorption agent, it is characterised in that: described amides C atom number is 1-6, and in described carbamide compounds, carbon atom number is 1-6, it is preferable that, described amides or carbamide compounds are selected from methane amide, ethanamide, N, dinethylformamide, DMAC N,N' dimethyl acetamide, pyrrolidone, N-Methyl pyrrolidone, hexanolactam, urea, N-tert butyl urea, 1,1,3,3-tetramethyl-urea, 1,3-dimethyl urea, one or more in 1,3-dimethyl-imidazolinone.
6. one according to claim 1 is used for selective absorbing SO2Combined type absorption agent, it is characterised in that: the mass percentage of described polyamine compounds strong acid salt is the Mole percent total content of 20-50%, amides and carbamide compounds is 10%-40%, and surplus is water.
7. one according to claim 1 is used for selective absorbing SO2Combined type absorption agent, it is characterised in that: described R1To RnMiddle C atom number is less than or equal to 4.
8. one according to claim 1 is used for selective absorbing SO2Combined type absorption agent, it is characterised in that: in described polyamine compounds, the number of atom N is 2-8.
9. selective absorbing SO according to claim 12Combined type absorption agent be used for SO2Absorb.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610176061.2A CN105617820A (en) | 2016-03-24 | 2016-03-24 | Combined-type absorbent used for selectively absorbing SO2 and application of combined-type absorbent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610176061.2A CN105617820A (en) | 2016-03-24 | 2016-03-24 | Combined-type absorbent used for selectively absorbing SO2 and application of combined-type absorbent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107096364A (en) * | 2017-04-28 | 2017-08-29 | 天津大学 | For selective absorbing SO2Imidazoles polymer absorbing agent and its application |
| CN112957896A (en) * | 2021-02-08 | 2021-06-15 | 大连理工大学 | Novel aliphatic polyamine solution for capturing carbon dioxide in mixed gas and application thereof |
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| CN101537300A (en) * | 2009-04-17 | 2009-09-23 | 合肥工业大学 | Recyclable sulfur dioxide gas absorbent and preparation method thereof |
| US20100326276A1 (en) * | 2009-06-30 | 2010-12-30 | Blair Alan M | Acid gas scrubbing composition |
| CN102470340A (en) * | 2009-06-30 | 2012-05-23 | 纳尔科公司 | Acid gas scrubbing composition |
| CN103349886A (en) * | 2013-08-07 | 2013-10-16 | 北京国电龙源环保工程有限公司 | Reproducible polytertiaryamine sulfur dioxide absorbent and preparation method thereof |
| CN105289209A (en) * | 2015-10-19 | 2016-02-03 | 昆明理工大学 | Mixed organic solution for trapping CO2 and SO2 acid gas through phase transformation |
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2016
- 2016-03-24 CN CN201610176061.2A patent/CN105617820A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101537300A (en) * | 2009-04-17 | 2009-09-23 | 合肥工业大学 | Recyclable sulfur dioxide gas absorbent and preparation method thereof |
| US20100326276A1 (en) * | 2009-06-30 | 2010-12-30 | Blair Alan M | Acid gas scrubbing composition |
| CN102470340A (en) * | 2009-06-30 | 2012-05-23 | 纳尔科公司 | Acid gas scrubbing composition |
| CN103349886A (en) * | 2013-08-07 | 2013-10-16 | 北京国电龙源环保工程有限公司 | Reproducible polytertiaryamine sulfur dioxide absorbent and preparation method thereof |
| CN105289209A (en) * | 2015-10-19 | 2016-02-03 | 昆明理工大学 | Mixed organic solution for trapping CO2 and SO2 acid gas through phase transformation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107096364A (en) * | 2017-04-28 | 2017-08-29 | 天津大学 | For selective absorbing SO2Imidazoles polymer absorbing agent and its application |
| CN107096364B (en) * | 2017-04-28 | 2020-05-15 | 天津大学 | For selective absorption of SO2Imidazole polymer absorbent and application thereof |
| CN112957896A (en) * | 2021-02-08 | 2021-06-15 | 大连理工大学 | Novel aliphatic polyamine solution for capturing carbon dioxide in mixed gas and application thereof |
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Application publication date: 20160601 |