CN106540513A - A kind of silicone solvent and technique for flue gas carbon dioxide eliminating - Google Patents
A kind of silicone solvent and technique for flue gas carbon dioxide eliminating Download PDFInfo
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- CN106540513A CN106540513A CN201510596767.XA CN201510596767A CN106540513A CN 106540513 A CN106540513 A CN 106540513A CN 201510596767 A CN201510596767 A CN 201510596767A CN 106540513 A CN106540513 A CN 106540513A
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- solvent
- flue gas
- carbon dioxide
- silicone
- decarbonization
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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
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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
- 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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Abstract
The invention discloses a kind of silicone solvent and technique for flue gas carbon dioxide eliminating.The silicone solvent has the high CO under low pressure2Absorbability, high thermal stability, high chemical stability, low cost of material, low viscosity, low volatility, low regeneration energy consumption, to equipment low-corrosiveness etc..Possesses the high request for extensive flue gas decarbonization solvent performance completely.
Description
Technical field
The present invention relates to a kind of silicone solvent and technique for flue gas carbon dioxide eliminating, and in particular to a kind of amino silicone class compound and technique.
Background technology
CO2Removing sulfuldioxide is in the fields such as food processing, selexol process commercial applications many decades.Water solublity hydramine technology is always flue gas CO2The technology of the best commercial viability in removing field, but hydramine technology is for extensive stack gas cleaning high cost, the hydramine decarbonization device totle drilling cost ratio that corresponding proportion amplifies will be higher by more than 80% with the cost that midget plant is estimated, therefore typically not take into account that hydramine decarburization technique in extensive flue gas removing field.
High CO higher for the solvent nature requirement that can be used for extensive flue gas decarbonization, such as under low pressure2Absorbability, high thermal stability, high chemical stability, low cost of material, low viscosity, low volatility, low regeneration energy consumption, to equipment low-corrosiveness etc..
But connect each other between many above-mentioned performances, even contradiction is present.It has been, for example, to obtain low volatility, decarbonization solvent typically can all have of a relatively high molecular weight, and high molecular can then cause solvent viscosity to raise, in order to high CO is obtained under lower pressure2Absorbability, then absorb CO2Total reaction heat accordingly raise, will certainly so increase regeneration energy consumption.
Therefore, excellent CO2Trapping solvent should comprehensively include above-mentioned performance as far as possible, while ensure again to interfere between each performance, in addition, to realize commercial applications, the technology must also cost it is relatively low.
The content of the invention
The present invention is providing novel organosilicon series decarbonization solvent and the technique that a kind of energy is adapted to extensive flue gas decarbonization.
For achieving the above object, silicone solvent of the present invention for flue gas carbon dioxide eliminating, it is characterised in that the solvent is structural formula1 With / Or structural formula 2 'sAmino silicone class compound,
Structural formula 1：
Wherein, n >=1, alkyl or aryls of the R for C1 ~ C5；
Structural formula2：
Wherein, n >=1, alkyl or aryls of the R for C1 ~ C5.
Usually, the silicone solvent is structural formula1Or2In one or more.
The silicone solvent is made into decarburization absorption liquid in proportion with water, and solvent is 55 ~ 85%.
There is unshared electron pair due to its N element in amino silicone decarbonization solvent of the present invention, can be combined with proton and be in alkalescence, and which has special odor, water insoluble, and density is less than water, and its boiling point is much larger than 100 DEG C in addition.
The amino-alkyl silicane series decarbonization solvent can absorb rapidly CO2, and obtain thick carbaminate, and its carbaminate for generating can be dissolved in water, easily with the morphological crystal of salt after its absorption CO2, show its higher CO2 absorbability.
For achieving the above object, silicone solvent of the present invention, its preparation technology comprise the steps：
(1) alkylsiloxane that end group contains thiazolinyl is dissolved in CHCl3In, it is incubated at 0 DEG C, is slowly added dropwise the CHCl of metachloroperbenzoic acid afterwards3Solution, stirring reaction overnight, then use 5% Na2CO3Extraction, the anhydrous MgSO of organic layer4It is dried, sucking filtration, concentrating under reduced pressure filtrate, adds hexane, filter off the metachloroperbenzoic acid of residual, filtrate sub-cooled obtains the alkylsiloxane that end group is Oxyranyle；
(2) end group is dissolved in anhydrous tetrahydro furan for the alkylsiloxane of Oxyranyle, and the anhydrous tetrahydrofuran solution of Deca ethylenediamine, reaction solution are cooled to room temperature in 70 DEG C of one nights of insulation reaction, and being concentrated under reduced pressure to give structural formula is1Or2Target product.
The apparatus structure that silicone solvent of the present invention is used for flue gas carbon dioxide eliminating is as follows：The bottom on absorption tower is solution collecting tank, circulating pump and heat exchanger are set between the top entry and regenerative response kettle on absorption tower, solution collecting tank outlet at bottom is connected with regenerative response kettle, solution collecting tank top connects circulating pump, upper strata decarbonizing solution is delivered to the absorption tower top down spray by circulating pump, and the regenerative response kettle is pressurization regeneration kettle.
A kind of above-mentioned typical removing process：Amino silicone class compound and water are initially charged in solution collecting tank, and upper strata decarbonization solvent is delivered to absorption tower top down spray by circulating pump, and absorbent uniformly spills down, and flue gas is entered by tower bottom is absorbed, with decarbonization solvent counter current contacting, decarbonization solvent absorption CO2After can become solid forms moment, purified gas are discharged by the top of absorption tower, and while circulating pump is started, lower floor's water Jing regenerative response kettles deliver to absorption tower top down spray by circulating pump Jing heat exchangers, and decarbonization solvent absorbs CO2The carbaminate powder solid for generating afterwards is soluble in the aqueous phase rapidly, aqueous solution is layered into solution collecting tank rapidly with unreacted decarbonization solvent, water is in lower floor, lower floor's water mutually enters regenerative response kettle, regenerative response kettle is by chuck thermal regeneration decarbonization solvent, after regeneration, it is pumped in heat exchanger by circulation and cools to 40 ~ 50
DEG C, absorption tower is entered back into afterwards continues reaction, after decarbonization solvent completes circulation in system, circulation pump.
The regenerative response kettle is pressurization regeneration kettle, and regeneration pressure is 0.2 ~ 0.5 Mpa (absolute pressure).
The suitable ammonia process carbon trapping temperature is 15 ~ 55 DEG C, and resolution temperature is 65 ~ 95
℃。
The amino silicone series of products of present invention laser heating 90 days at 150 DEG C, thermal weight loss loss rate are less than 20%.Bulge test, CO2 absorbances are higher than 90%.
Beneficial effects of the present invention：The silicone decarbonization solvent has the high CO under low pressure2Absorbability, high thermal stability, high chemical stability, low cost of material, low viscosity, low volatility, low regeneration energy consumption, to equipment low-corrosiveness etc. items advantage.The decarbonization solvent can be used for extensive flue gas CO2Trapping.
Description of the drawings
The hot weightless picture that Fig. 1 embodiment of the present invention amino silicone class compounds are incubated 1 month at 150 DEG C.
Fig. 2 embodiments solvent is used for the process flow diagram of flue gas carbon dioxide eliminating.
In figure, 1- absorption towers, 2- solution collecting tanks, 3- circulating pumps, 4- regenerative response kettles, 5- circulating pumps, 6- heat exchangers.
Specific embodiment
The present invention is described in detail in accompanying drawing with reference to embodiments.
Embodiment
1
End divinyl tetramethyl siloxanes (50 g) is dissolved in 200 mL CHCl3, in adding the there-necked flask equipped with magnetic stir bar.Reaction bulb is put in frozen water, and 0 DEG C of insulation, metachloroperbenzoic acid (150 g) are dissolved in 1 L
CHCl3Filter, filtrate is slowly added dropwise into reaction bulb, and 1.5 h of time for adding, reaction solution are stirred overnight.Reactant liquor 2 L, 5% Na2CO3 Extraction, the anhydrous MgSO of organic layer4It is dried, filters afterwards, concentrating under reduced pressure.Hexane is added, the metachloroperbenzoic acid of residual is filtered off, filtrate sub-cooled obtains the tetramethyl siloxanes that end group is bisoxirane base.
End ring oxirane group tetramethyl siloxanes (10 g) is dissolved in 100 mL anhydrous tetrahydro furans, 100 mL anhydrous tetrahydrofuran solutions of Deca ethylenediamine (20 g), 1 h of time for adding, reaction solution flows back one night of insulation reaction in 70 DEG C, room temperature is cooled to, target product is concentrated under reduced pressure to give：
NH2-CH2-CH2-NH-CH2-CH(OH)-Si(Me)2-O-Si(Me)2-CH(OH)-CH2-NH-CH2-CH2-NH2。
Embodiment
2
End-vinyl tetramethyl siloxanes (25 g) is dissolved in 50 mL CHCl3, in adding the there-necked flask equipped with magnetic stir bar.Reaction bulb is put in frozen water, 0 DEG C of insulation, and metachloroperbenzoic acid (excessive 10%) is dissolved in 500 mL CHCl3Filter, filtrate is slowly added dropwise into reaction bulb, and 1 h of time for adding, reaction solution are stirred overnight.2 L of reactant liquor
5% Na2CO3 Extraction, the anhydrous MgSO of organic layer4It is dried, filters afterwards, concentrating under reduced pressure.Hexane is added, the metachloroperbenzoic acid of residual is filtered off, filtrate sub-cooled obtains the tetramethyl siloxanes that end group is Oxyranyle.
Ethylenediamine (15 g) is dissolved in the water of 100 mL isopropanols and 5 mL, 100 mL aqueous isopropanols of dropping end Oxyranyle tetramethyl siloxanes, reaction solution flows back one night of insulation reaction in 70 DEG C, is cooled to room temperature, is concentrated under reduced pressure to give target product：
Si(Me)3-O-Si(Me)2-CH(OH)-CH2-NH-CH2-CH2-NH2。
Embodiment
3
Bubble absorption CO2Experiment, solvent weightening ratio are shown in Table 1.
1 solvent absorption CO of table2Weightening ratio
--
It is dry：
CO
2
Through exsiccator before reacting with amine
--
It is wet：
CO
2
Through water saturation device before reacting with amine
Embodiment
4
The novel amino siloxane compound of synthesis is incubated into 1 month with MEA at 150 DEG C, the weight-loss ratio of solvent is investigated.Thermal weight loss is tested, and as a result sees accompanying drawing 1.
Application examples
Silicone solvent prepared by above-described embodiment is made into into decarburization absorption liquid in proportion with water, solvent is 55 ~ 85%.Refer to the attached drawing 2, amino silicone class compound and water are initially charged solution collecting tank2It is interior, circulating pump3Upper strata decarbonization solvent is delivered to into absorption tower1Top down is sprayed, and absorbent uniformly spills down, and flue gas is by absorption tower1Bottom enters, with decarbonization solvent counter current contacting, decarbonization solvent absorption CO2After can become solid forms moment, purified gas are discharged by the top of absorption tower, are starting circulating pump3While, lower floor's water Jing regenerative response kettles4, by circulating pump5Jing heat exchangers6Deliver to absorption tower1Top down is sprayed, and decarbonization solvent absorbs CO2The carbaminate powder solid for generating afterwards is soluble in the aqueous phase rapidly, and aqueous solution enters solution collecting tank2It is layered with unreacted decarbonization solvent rapidly, in lower floor, lower floor's water mutually enters regenerative response kettle to water4, regenerative response kettle4By chuck thermal regeneration decarbonization solvent, after regeneration, by circulating pump5It is sent to heat exchanger6In cool to 40 ~ 50 DEG C, enter back into absorption tower afterwards1Continue reaction.After decarbonization solvent completes circulation in system, circulating pump5Can close.
In above-mentioned removing process, regenerative response kettle is pressurization regeneration kettle, and regeneration pressure is 0.2 ~ 0.5 Mpa (absolute pressure).Suitable ammonia process carbon trapping temperature is 15 ~ 55 DEG C, and resolution temperature is 65 ~ 95 DEG C.
Claims (8)
1. a kind of silicone solvent for flue gas carbon dioxide eliminating, it is characterised in that the solvent is the amino silicone class compound of structural formula 1 and/or structural formula 2,
Structural formula 1：
Wherein, n >=1, alkyl or aryls of the R for C1 ~ C5；
Structural formula2：
Wherein, n >=1, alkyl or aryls of the R for C1 ~ C5.
2. the silicone solvent for flue gas carbon dioxide eliminating according to claim 1, it is characterised in that the solvent is structural formula1Or2In one or more.
3. the silicone solvent for flue gas carbon dioxide eliminating according to claim 1, it is characterised in that the solvent is made into decarburization absorption liquid in proportion with water, solvent is 55 ~ 85%.
4. the preparation technology of the silicone solvent of flue gas carbon dioxide eliminating is used for according to claim 1, it is characterised in that comprised the steps：
(1) alkylsiloxane that end group contains thiazolinyl is dissolved in CHCl3In, it is incubated at 0 DEG C, is slowly added dropwise the CHCl of metachloroperbenzoic acid afterwards3Solution, stirring reaction overnight, then use 5% Na2CO3Extraction, the anhydrous MgSO of organic layer4It is dried, sucking filtration, concentrating under reduced pressure filtrate, adds hexane, filter off the metachloroperbenzoic acid of residual, filtrate sub-cooled obtains the alkylsiloxane that end group is Oxyranyle；
(2) end group is dissolved in anhydrous tetrahydro furan for the alkylsiloxane of Oxyranyle, and the anhydrous tetrahydrofuran solution of Deca ethylenediamine, reaction solution are cooled to room temperature in 70 DEG C of one nights of insulation reaction, and being concentrated under reduced pressure to give structural formula is1Or2Target product.
5. the silicone solvent of flue gas carbon dioxide eliminating is used for according to claim 3, it is characterised in that the apparatus structure of removing flue air carbon dioxide is as follows：The bottom on absorption tower is solution collecting tank, circulating pump and heat exchanger are set between the top entry and regenerative response kettle on absorption tower, solution collecting tank outlet at bottom is connected with regenerative response kettle, solution collecting tank top connects circulating pump, and upper strata decarbonizing solution is delivered to the absorption tower top down spray by circulating pump.
6. the silicone solvent of flue gas carbon dioxide eliminating is used for according to claim 5, it is characterized in that amino silicone class compound and water are initially charged in solution collecting tank, upper strata decarbonization solvent is delivered to absorption tower top down spray by circulating pump, absorbent uniformly spills down, flue gas is entered by tower bottom is absorbed, with decarbonization solvent counter current contacting, decarbonization solvent absorption CO2After can become solid forms moment, purified gas are discharged by the top of absorption tower, and while circulating pump is started, lower floor's water Jing regenerative response kettles deliver to absorption tower top down spray by circulating pump Jing heat exchangers, and decarbonization solvent absorbs CO2The carbaminate powder solid for generating afterwards is soluble in the aqueous phase rapidly, aqueous solution is layered into solution collecting tank rapidly with unreacted decarbonization solvent, water is in lower floor, lower floor's water mutually enter regenerative response kettle, regenerative response kettle by chuck thermal regeneration decarbonization solvent, after regeneration, it is pumped in heat exchanger by circulation and cools to 40 ~ 50 DEG C, absorption tower is entered back into afterwards continues reaction, after decarbonization solvent completes circulation in system, circulation pump.
7. the silicone solvent of flue gas carbon dioxide eliminating is used for according to claim 5 or 6, it is characterised in that the regenerative response kettle to be pressurization regeneration kettle, regeneration pressure is 0.2 ~ 0.5 Mpa (absolute pressure).
8. the silicone solvent of flue gas carbon dioxide eliminating is used for according to claim 5 or 6, it is characterised in that the temperature of ammonia process carbon trapping to be 15 ~ 55 DEG C, resolution temperature is 65 ~ 95 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510596767.XA CN106540513A (en) | 2015-09-18 | 2015-09-18 | A kind of silicone solvent and technique for flue gas carbon dioxide eliminating |
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| CN201510596767.XA CN106540513A (en) | 2015-09-18 | 2015-09-18 | A kind of silicone solvent and technique for flue gas carbon dioxide eliminating |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113477033A (en) * | 2021-07-20 | 2021-10-08 | 金浦新材料股份有限公司 | Self-emulsifiable organic silicon decarbonization solvent |
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| CN102549001A (en) * | 2009-07-30 | 2012-07-04 | 通用电气公司 | Carbon dioxide absorbent and method of using the same |
| CN102665859A (en) * | 2009-10-30 | 2012-09-12 | 通用电气公司 | A spray process for the recovery of CO2 from a gas stream and a related apparatus |
| CN103241738A (en) * | 2012-02-06 | 2013-08-14 | 通用电气公司 | Systems and methods for capturing carbon dioxide |
| WO2016105729A1 (en) * | 2014-12-22 | 2016-06-30 | General Electric Company | Method and system for carbon dioxide desorption in two flash stages |
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2015
- 2015-09-18 CN CN201510596767.XA patent/CN106540513A/en active Pending
Patent Citations (5)
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| CN102549001A (en) * | 2009-07-30 | 2012-07-04 | 通用电气公司 | Carbon dioxide absorbent and method of using the same |
| CN102665859A (en) * | 2009-10-30 | 2012-09-12 | 通用电气公司 | A spray process for the recovery of CO2 from a gas stream and a related apparatus |
| CN102078745A (en) * | 2009-12-01 | 2011-06-01 | 华能集团技术创新中心 | Smoke decarbonizing system and method and regeneration column for smoke decarbonizing system |
| CN103241738A (en) * | 2012-02-06 | 2013-08-14 | 通用电气公司 | Systems and methods for capturing carbon dioxide |
| WO2016105729A1 (en) * | 2014-12-22 | 2016-06-30 | General Electric Company | Method and system for carbon dioxide desorption in two flash stages |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113477033A (en) * | 2021-07-20 | 2021-10-08 | 金浦新材料股份有限公司 | Self-emulsifiable organic silicon decarbonization solvent |
| CN113477033B (en) * | 2021-07-20 | 2023-03-14 | 金浦新材料股份有限公司 | Self-emulsifiable organic silicon decarbonization solvent |
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Application publication date: 20170329 |