CN103463950B - A kind of capture method of temperate condition carbon dioxide - Google Patents
A kind of capture method of temperate condition carbon dioxide Download PDFInfo
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- CN103463950B CN103463950B CN201310360933.7A CN201310360933A CN103463950B CN 103463950 B CN103463950 B CN 103463950B CN 201310360933 A CN201310360933 A CN 201310360933A CN 103463950 B CN103463950 B CN 103463950B
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- Prior art keywords
- carbon dioxide
- absorbent
- glycidol
- reaction
- carbonic acid
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 58
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000010521 absorption reaction Methods 0.000 claims abstract description 27
- 230000002745 absorbent Effects 0.000 claims abstract description 21
- 239000002250 absorbent Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 230000008439 repair process Effects 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229940072033 potash Drugs 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229960004424 carbon dioxide Drugs 0.000 description 37
- 238000003756 stirring Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 9
- 238000004949 mass spectrometry Methods 0.000 description 8
- 238000012797 qualification Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 carbonate ester Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Gas Separation By Absorption (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of capture method of temperate condition carbon dioxide, comprise the regenerative process of the absorption process of carbon dioxide, the release of carbon dioxide and absorbent, the absorption process of carbon dioxide utilizes glycidol for absorbent and reaction raw materials, direct reaction under catalyst-free condition prepares carbonic acid glyceride by glycidol and carbon dioxide, and the release of carbon dioxide and the regenerative process of absorbent are decomposed by the carbonic acid glyceride generated to generate glycidol and carbon dioxide.Adopt technique provided by the invention, simple to operate, absorption efficiency is high, and the operating cost of whole piece technique is very low.The catalyst that technical scheme raw material of the present invention is inexpensive, trapping process does not need costliness, zero-emission, process green, the utilization rate of easy operation control simultaneously, absorbent/reaction raw materials is higher, for suitability for industrialized production provides new thinking.
Description
Technical field
The present invention relates to a kind of chemical method, specifically, is a kind of capture method of temperate condition carbon dioxide.
Background technology
In recent years, a large amount of discharges of greenhouse gases particularly carbon dioxide cause the environmental problems such as greenhouse effects, therefore control and the discharge that reduces carbon dioxide has also become the focal issue that international community pays special attention to.In China, energy loss industry such as coal electricity, iron and steel, chemical industry and petrochemical industry etc. occupy critical role in the industry, also be the important industry of CO2 emission, the method capturing carbon dioxide therefore finding a kind of high-efficient simple is all significant for global living environment or for China's industrial development simultaneously.
The collecting carbonic anhydride technology greatly developed at present has chemical absorption method, absorption method and membrane separation process.Wherein chemical absorption method because of its economically viable feature be more used for research, common absorbent has ammoniacal liquor, NaOH, hydramine etc., and developed recently gets up utilizes the epoxide technique preparing five-membered ring carbonate ester that is coupled with carbon dioxide to have development prospect especially.For this reason, a lot of scholar did effort in this reaction, and a lot of people once used different catalyst systems to carry out to impel this reaction.Some homogeneous catalysts, such as quaternary ammonium salt (as Et4NBr), alkali halide (as KI) are all common in the cycloaddition reaction (Coordination Chemistry Reviews1996,153, the 155-174 that report catalysis epoxidation thing and carbon dioxide; Catal Sci Technol2012; The Journal of Organic Chemistry1993,58,6198-6202); Also document is had to adopt more complicated homogeneous catalyst, such as transient metal complex (Chemical Communications2003,2042-2043), Schiff (Journal of the American Chemical Society1983,105,1304-1309) even ionic liquid (Chemical Communications2003,896-897) etc.Simultaneously, some comparatively environmentally friendly heterogeneous catalysts are as SmOCl (J.Catal2002,209,547-550), Mg-Al composite oxides (Journal of the American Chemical Society1999,121,4526-4527), Polymer-supported type catalyst (Journal of the American Chemical Society2005,127,4182-4183) also have silica-based loaded catalyst (Chemical Communications2006,1664-1666) to be also all used to this reaction of catalysis to carry out.
Summary of the invention
The present invention is problems of the prior art, provides the circulation use technology of efficient, the trapping that realizes to environmental protection carbon dioxide, enrichment and absorbent/reaction raw materials; Specifically utilize glycidol for absorbent and reaction raw materials, direct reaction under catalyst-free condition prepares the object that carbonic acid glyceride reaches chemisorbed carbon dioxide by glycidol and carbon dioxide, simultaneously, present invention provides a kind of technology carbonic acid glyceride generated can being decomposed generation glycidol and carbon dioxide, thus achieve the high concentration enrichment with carbon dioxide that recycles of absorbent/reaction raw materials (glycidol).Concrete technical scheme of the present invention is as follows:
The invention discloses a kind of capture method of temperate condition carbon dioxide, comprise the regenerative process of the absorption process of carbon dioxide, the release of carbon dioxide and absorbent, the absorption process of carbon dioxide utilizes glycidol for absorbent and reaction raw materials, direct reaction under catalyst-free condition prepares carbonic acid glyceride by glycidol and carbon dioxide, and the release of carbon dioxide and the regenerative process of absorbent are decomposed by the carbonic acid glyceride generated to generate glycidol and carbon dioxide.
As further improvement, the concrete steps of the absorption process of carbon dioxide of the present invention are as follows:
(1), in the reactor, adopt DMF (DMF) to make solvent, add glycidol, control its concentration in 6.5-7.0 mol/L;
(2), in reactor, CO is filled with
2;
(3), by the above-mentioned reactant liquor mixed under agitation, be warming up to 90 ~ 140 degree, isothermal reaction 2 ~ 8 hours, after reaction, the fluid ester solution that purity is higher can be obtained, achieve the MODEL OF CHEMICAL ABSORPTION PROCESS of carbon dioxide;
The concrete steps of the release of described carbon dioxide and the regenerative process of absorbent are as follows:
(1), get a certain amount of carbon dioxide absorption after the product carbonic acid glyceride that generates be placed in single port flask, add a certain amount of alkali and make reaction regeneration catalyst;
(2), by above-mentioned reactant liquor under agitation, be warming up to 90 degree, isothermal reaction 2 hours, after reaction terminates, the glycidol of higher degree can be obtained, achieve the dispose procedure of carbon dioxide and the regeneration of absorbent/reaction raw materials.
As further improvement, regenerated catalyst of the present invention is NaOH or potash or ethylenediamine or cesium carbonate.
Beneficial effect of the present invention is as follows:
Adopt technique provided by the invention, simple to operate, absorption efficiency is high, and the operating cost of whole piece technique is very low.The catalyst that technical scheme raw material of the present invention is inexpensive, trapping process does not need costliness, zero-emission, process green, the utilization rate of easy operation control simultaneously, absorbent/reaction raw materials is higher, for suitability for industrialized production provides new thinking.Meanwhile, the regeneration technology of absorbent/reaction raw materials is simple, can have effectively achieved the selective enrichment with carbon dioxide that recycles of absorbent/reaction raw materials.Further illustrate specific operation process of the present invention with specific embodiment below, but the actual temp of absorption process, pressure and solvent composition are not restricted to the following examples.
Detailed description of the invention:
Below by specific embodiment, technical scheme of the present invention is described further.Embodiment 1
Absorption process: be in the simple high-voltage still of 500 milliliters at a volume, add 150 milliliters of DMFs successively, 150 milliliters of glycidols, mix; Be filled with carbon dioxide 3MPa.Under stirring condition, be heated to 100 degree, react after 4 hours and stop stirring.Product is used in conjunction qualification through chromatography-mass spectroscopy, is defined as carbonic acid glyceride, and by the Dosage calculation of initial glycidol, the absorption efficiency of carbon dioxide is 38.4 grams of carbon dioxide/mole glycidol.
Regenerative process: in the single port flask that a volume is 500 milliliters, add 200 milliliters of carbonic acid glycerides, 1.08 grams of NaOH, mix, and are heated to 90 degree under stirring condition, reacts after 2 hours and stops stirring.Product is used in conjunction qualification through chromatography-mass spectroscopy, is defined as glycidol, and by the Dosage calculation of initial carbon acid glyceride, the growing amount of glycidol is 0.93 moles/mole carbonic acid glyceride.
Embodiment 2
Absorption process: be in the simple high-voltage still of 500 milliliters at a volume, add 150 milliliters of DMFs successively, 150 milliliters of glycidols, mix; Be filled with carbon dioxide 1MPa.Under stirring condition, be heated to 100 degree, react after 4 hours and stop stirring.Product is used in conjunction qualification through chromatography-mass spectroscopy, and the absorption efficiency of carbon dioxide is 34.3 grams of carbon dioxide/mole glycidol.
Regenerative process: in the single port flask that a volume is 500 milliliters, add 200 milliliters of carbonic acid glycerides, 3.73 grams of potash, mix, and are heated to 90 degree under stirring condition, reacts after 2 hours and stops stirring.Product is used in conjunction qualification through chromatography-mass spectroscopy, and the growing amount of glycidol is 0.82 moles/mole carbonic acid glyceride.
Embodiment 3
Absorption process: be in the simple high-voltage still of 500 milliliters at a volume, add 150 milliliters of DMFs successively, 150 milliliters of glycidols, mix; Be filled with carbon dioxide 0.2MPa.Under stirring condition, be heated to 100 degree, react after 4 hours and stop stirring.Product is used in conjunction qualification through chromatography-mass spectroscopy, and the absorption efficiency of carbon dioxide is 32.1 grams of carbon dioxide/mole glycidol.
Regenerative process: in the single port flask that a volume is 500 milliliters, add 200 milliliters of carbonic acid glycerides, 2.75 grams of triethylamines, mix, and are heated to 90 degree under stirring condition, reacts after 2 hours and stops stirring.Product is used in conjunction qualification through chromatography-mass spectroscopy, and the growing amount of glycidol is 0.75 moles/mole carbonic acid glyceride.
Embodiment 4
Absorption process: be in the flask of 2000 milliliters at a volume, add 600 milliliters of DMFs successively, 600 milliliters of glycidols, mix; Be heated to 120 degree under stirring condition, and pass into CO with the airflow rate of 25mL/min
2, react after 4 hours and stop stirring.Product is used in conjunction qualification through chromatography-mass spectroscopy, and the absorption efficiency of carbon dioxide is 43.5 grams of carbon dioxide/mole glycidol.
Regenerative process: in the single port flask that a volume is 500 milliliters, add 200 milliliters of carbonic acid glycerides, 8.80 grams of cesium carbonates, stir, and are heated to 90 degree under stirring condition, reacts after 2 hours and stops stirring.Product is used in conjunction qualification through chromatography-mass spectroscopy, and the growing amount of glycidol is 0.94 moles/mole carbonic acid glyceride.
What more than enumerate is only some embodiments of the present invention; obviously; the invention is not restricted to above embodiment; many distortion can also be had; the actual temp of such as absorption process, pressure and solvent composition are not restricted to above embodiment; all distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (2)
1. the capture method of a temperate condition carbon dioxide, it is characterized in that, comprise the absorption process of carbon dioxide, the release of carbon dioxide and the regenerative process of absorbent, the absorption process of described carbon dioxide utilizes glycidol for absorbent and reaction raw materials, glycidol and carbon dioxide are directly reacted under catalyst-free condition and prepares carbonic acid glyceride, the release of described carbon dioxide and the regenerative process of absorbent are decomposed by the carbonic acid glyceride generated to generate glycidol and carbon dioxide, the concrete steps of the absorption process of described carbon dioxide are as follows:
(1), in the reactor, adopt DMF (DMF) to make solvent, add glycidol, control its concentration in 6.5-7.0 mol/L;
(2), in reactor, CO is filled with
2;
(3), by the reactant liquor that mixes under agitation, be warming up to 90 ~ 140 degree, isothermal reaction 2 ~ 8 hours, after reaction, the fluid ester solution that purity is higher can be obtained, achieve the MODEL OF CHEMICAL ABSORPTION PROCESS of carbon dioxide;
The concrete steps of the release of described carbon dioxide and the regenerative process of absorbent are as follows:
(1), get a certain amount of carbon dioxide absorption after the product carbonic acid glyceride that generates be placed in single port flask, add a certain amount of alkali and make reaction regeneration catalyst;
(2), by above-mentioned reactant liquor under agitation, be warming up to 90 degree, isothermal reaction 2 hours, after reaction terminates, the glycidol of higher degree can be obtained, achieve the dispose procedure of carbon dioxide and the regeneration of absorbent/reaction raw materials.
2. the capture method of carbon dioxide according to claim 1, is characterized in that, described regenerated catalyst is NaOH or potash or ethylenediamine or cesium carbonate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310360933.7A CN103463950B (en) | 2013-08-19 | 2013-08-19 | A kind of capture method of temperate condition carbon dioxide |
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| CN201310360933.7A CN103463950B (en) | 2013-08-19 | 2013-08-19 | A kind of capture method of temperate condition carbon dioxide |
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| CN103463950A CN103463950A (en) | 2013-12-25 |
| CN103463950B true CN103463950B (en) | 2015-08-19 |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2760747B1 (en) * | 1997-03-12 | 1999-06-04 | Organisation Nationale Interpr | PROCESS FOR THE MANUFACTURE OF GLYCIDOL OR A GLYCIDYL COMPOUND |
| CN100427477C (en) * | 2006-12-28 | 2008-10-22 | 宁波万华聚氨酯有限公司 | Process of synthesizing cyclic carbonate by epoxy compound with carbon dioxide reaction |
| CN103030622B (en) * | 2013-01-15 | 2014-04-23 | 中国日用化学工业研究院 | Method for preparing glyceride carbonate by using loop reaction device |
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