CN101844068B - Method for preparing magnesium oxide modified mesoporous material for adsorbing carbon dioxide - Google Patents
Method for preparing magnesium oxide modified mesoporous material for adsorbing carbon dioxide Download PDFInfo
- Publication number
- CN101844068B CN101844068B CN2010101934744A CN201010193474A CN101844068B CN 101844068 B CN101844068 B CN 101844068B CN 2010101934744 A CN2010101934744 A CN 2010101934744A CN 201010193474 A CN201010193474 A CN 201010193474A CN 101844068 B CN101844068 B CN 101844068B
- Authority
- CN
- China
- Prior art keywords
- mesoporous material
- magnesium oxide
- carbon dioxide
- oxide modified
- modified mesoporous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for preparing a magnesium oxide modified mesoporous material for adsorbing carbon dioxide. The material is prepared by using a one-step synthetic method, namely the method comprises the following steps of: dissolving P123 serving as a template agent and MgCl2.6H2O into hydrochloric solution fully, adding tetraethyl silicate, and drying and calcining the mixture to prepare the MgO modified mesoporous material directly; or the material is prepared by using a later-period immersing method, namely the method comprises the following steps of: dissolving the P123 serving as the template agent into the hydrochloric solution fully, adding the tetraethyl silicate, immersing a mesoporous material prepared by drying and calcination in MgNO3 solution, and calcining the mesoporous material to prepare the MgO modified mesoporous material. The material provided by the invention has the high capability of adsorbing carbon dioxide, and simultaneously, the preparation method is simple and easy to control and avoids equipment corrosion in the process of production and use.
Description
Technical field
The present invention relates to carbon dioxide adsorption technology field, particularly relate to a kind of preparation method who is used for the magnesium oxide modified mesoporous material of carbon dioxide absorption.
Background technology
At present, global warming is the biggest threat to environment for human survival.Global warming is not that simple environment is polluted and ecocatastrophe, and what it destroyed is the weather system of the whole earth, can cause a series of chain reactions, and the consequence that is caused is irreversible.Show as the La Nina phenomenon of large tracts of land low temperature, sleet and freezing disaster, phenomenons such as the severe snows that the whole world is a lot of local are wreaked havoc, floods and drought all have some relations with the overall background of global warming.Academia's research is thought; Carbon dioxide, carbon granules dust that coal, oil, combustion of natural gas etc. produce; And the methane that produces of heap garbage etc., be the main cause that causes global warming, and in the highest flight emission amount of carbon dioxide increase year by year in various greenhouse gases.Show that according to result of study during 2000 to 2004, global CO2 emissions are annual to increase by 3.2%, significantly surpass the growth rate of nineteen ninety to 1999 year average annual 1.1%.Based on this research, global CO2 emissions were about 5,000,000,000 tons in 1980, continue to increase afterwards, to 2004 above 7,300,000,000 tons.Seminar thinks that except that developing country's population increase and economic growth, more and more countries is that the economic output value of keeping certain scale has strengthened greenhouse gas emissions.Seminar warns, " gathering way of CO2 emissions surpasses the prediction of Intergovernmental Panel on Climate Change of the United Nations (IPCC), will further have an immense impact on to global climate ".Scientist's prediction, global CO2 emissions will exceed 40,000,000,000 tons the year two thousand thirty.
Carbon dioxide discharge-reduction has become the major issue of pendulum in face of the national governments, and each state is all in the method for the reduction CO2 emissions of seeking to be fit to oneself.In Copenhagen world climate conference of 7-18 day in December, 2009, Chinese Government is directed against the global climate problem and has proposed the reduction of discharging scheme of oneself, has obtained good international repercussion.The Premier Wen Jiabao held Executive Meeting of the State Council on November 25th, 2009; The CO2 emission of decision the year two thousand twenty per GDP (GDP) descended 40% to 45% than 2005, and it is included in the national economy and social development medium-term and long-term plans as restrictive index.
If carbon dioxide capture and storage (CCS) technology can successfully apply to commercial production; People just can catch the great amount of carbon dioxide that produces in the production; It is sealed up for safekeeping and bury in the underground, so just needn't worry the caused greenhouse effects of great amount of carbon dioxide.The main chemiadsorption that adopts of present carbon capture technology as in commercial production, can be isolated carbon dioxide wherein with carbonated waste gas through amine liquid, crosses heating amine liquid at square tube suitably afterwards and carbon dioxide is discharged again.The minority coal-fired plant that carries out commercial carbon capture all uses MEA as carbon-dioxide absorbent now.But MEA corrosivity is strong and evaporation easily, and the main equipment that needs to use is complicated, and only is in slightly to the middle pressure just effective at carbon dioxide.
Porous material is a kind of promising CO
2Absorption and capture material; It has overcome shortcomings such as the evaporation of liquid amine solution, etching apparatus in the liquid amine absorption process; And have that mass transfer rate is fast, equipment is simple to operate, low energy consumption, automaticity advantages of higher, be widely used in synthetic ammonia, methyl alcohol and the hydrogen manufacturing industry.Modal CO is gone up in industry at present
2Sorbing material mainly is inorganic material such as zeolite molecular sieve, active carbon, book clay, metal oxide.Inorganic adsorbing material since alkalescence very a little less than, to CO
2Absorption is main with physical absorption, big limitations its commercial Application.Mesoporous material has caused great concern in fields such as adsoption catalysises; Its structure and performance are between amorphous inorganic porous material (like amorphous aluminosilicate) and have between the inorganic porous material (like zeolite molecular sieve) of crystal structure, and its principal character is: the pore passage structure that 1. has rule; 2. pore-size distribution is narrow, and between 1.5～10nm, can regulate; 3. through optimizing synthesis condition or post processing, can have good heat endurance and certain hydrothermal stability; 4. particle has regular profile, and can in micro-meter scale, keep the duct order of height.These characteristics make mesoporous material have stronger adsorption capacity, and research mainly is silicon-based mesoporous material at present, but the pure silicon based mesoporous material is to CO
2Absorption be main with physical absorption, DeGrain.Based on this, many researchers are being devoted to that silicon-based mesoporous material is carried out modification to improve its absorption property.But to aspect the absorption of carbon dioxide, many needs of work further investigations are arranged still at present at mesoporous silicon based material.
At present, multidigit researcher carries out amino modified to mesoporous silicon based material, increases the basic sites on surface, has improved the carbon dioxide adsorption capacity.Discover that mesoporous material is behind the organic basic base group modification, though adsorption capacity is bigger, hydrothermal stability is difficult to meet the demands.Therefore, synthetic a kind of adsorption capacity is high, to recycle the absorbing carbon dioxide material that performance is good, the regenerative process consumed energy is few most important to the carbon capture technology.
Summary of the invention
Technical problem to be solved by this invention is: a kind of magnesium oxide modified mesoporous material that is used for carbon dioxide absorption is provided, and this material has higher absorbing carbon dioxide ability, can etching apparatus in production and use.This preparation methods also is provided, and this preparation method's technology is simple.
The present invention solves its technical problem and adopts following technical scheme:
The magnesium oxide modified mesoporous material that is used for carbon dioxide absorption provided by the invention; It is processed by the one-step synthesis modified technique; Specifically: with P123 is template; P123 and magnesium source be fully dissolving in hydrochloric acid solution, adds tetraethyl orthosilicate, after drying, calcining, directly prepares described magnesium oxide modified mesoporous material; The quality proportioning of said P123, magnesium source, hydrochloric acid solution and tetraethyl orthosilicate is 1: x: 35.31: 6.51, and x=0.28～0.78.
The preferred value of the quality proportioning of said P123, magnesium source, hydrochloric acid solution and tetraethyl orthosilicate is 1: 0.28: 35.31: 6.51.
Said P123 can adopt triblock polymer; Full name is a polyoxyethylene-poly-oxypropylene polyoxyethylene; English name is that poly (ethylene glycol)-(ethylene glycol, its general formula are EO to block-poly (propylene glycol)-block-poly
20PO
70EO
20
MgCl can be adopted in said magnesium source
26H
2O.
The above-mentioned magnesium oxide modified mesoporous material that is used for carbon dioxide absorption provided by the invention; It is by later stage infusion process modification preparation, and specifically: with P123 is template, fully dissolving in hydrochloric acid solution; Add tetraethyl orthosilicate, the mesoporous material of after calcining dry, the first time, preparing is at MgNO
3Flood in the solution, again through preparing described magnesium oxide modified mesoporous material after the calcining for the second time.
In dry run, its technology can for: baking temperature is 85～110 ℃, and be 12～72 hours drying time.
In calcination process, its technology can for: in first time calcination process, the calcining heat that is adopted is 400～600 ℃, and calcination time is 6～24 hours; In second time calcination process, the calcining heat that is adopted is 400～600 ℃, and calcination time is 5～12 hours.
At MgNO
3In the solution impregnation process, its dip time can be 5～12 hours.
Technique scheme provided by the invention is based on following situation proposition: for mesoporous material, improve the ability of its absorbing carbon dioxide, remove and mesoporous factor own; Outside the Pass having like factors such as specific area, porosity, pore sizes; Also require matrix to have suitable surface nature, bigger adsorption capacity simultaneously also must be reusable; Behind process multiple adsorb-desorption, tangible change does not take place in the structure of material and adsorption capacity.For this reason, need to improve the basic sites on carbon dioxide absorbing material surface, the raising of basic sites helps the raising of carbon dioxide adsorption capacity.
The present invention compared with prior art has following major advantage:
One of which. improve the mesoporous material basic sites owing in mesoporous material, introduce basic anhydride magnesia, therefore have higher absorbing carbon dioxide ability.
They are two years old. owing to have higher absorbing carbon dioxide ability, therefore can catch the great amount of carbon dioxide that produces in the production well, thereby make contributions for reducing emission amount of carbon dioxide.
They are three years old. and synthesis technique is simple, is easy to control and design, and prepared magnesium oxide modified mesoporous material has the adsorption capacity height, and it is good to recycle performance, and the regenerative process consumed energy is few, therefore is beneficial to suitability for industrialized production and promotes the use of.
They are four years old. in production and use, and can etching apparatus.
The specific embodiment
The present invention provides a kind of good carbon dioxide sorbing material for realizing carbon dioxide capture and storage (CCS) technology, and this material adopts one-step synthesis or later stage infusion process modification method to process.
Below in conjunction with specific embodiment the present invention is described further, but does not limit the present invention.
Embodiment 1: utilize the one-step method for synthesizing preparation to be used for the magnesium oxide modified mesoporous material of carbon dioxide absorption
With 2gP123 and 0.56gMgCl
26H
2O is at 9mlHCl and 60mlH
2Fully dissolving adds 14ml tetraethyl orthosilicate (TEOS) in the hydrochloric acid solution that O forms, and 40 ℃ of magnetic agitation 24 hours, forms colloidal sol, and 100 ℃ left standstill 24 hours, and dry back obtains magnesium oxide modified mesoporous material 550 ℃ of calcinings after 6 hours.
Embodiment 2: utilize the one-step method for synthesizing preparation to be used for the magnesium oxide modified mesoporous material of carbon dioxide absorption
With 2gP123 and 1.45gMg (CH
3COO)
2At 9mlHCl and 60mlH
2Fully dissolving adds 14ml tetraethyl orthosilicate (TEOS) in the hydrochloric acid solution that O forms, and 40 ℃ of magnetic agitation 24 hours, forms colloidal sol, and 100 ℃ left standstill 24 hours, and dry back obtains magnesium oxide modified mesoporous material 550 ℃ of calcinings after 6 hours.
The magnesium oxide modified mesoporous material that the foregoing description 1 and 2 obtains, its adsorption capacity reaches 34mg/g.
Embodiment 3: utilize later stage infusion process modification preparation to be used for the magnesium oxide modified mesoporous material of carbon dioxide absorption
With 2gP123 at 9mlHCl and 60mlH
2Fully dissolving adds 14ml tetraethyl orthosilicate (TEOS) in the hydrochloric acid solution that O forms, and 40 ℃ of magnetic agitation 24 hours, 100 ℃ left standstill 24 hours, formed colloidal sol, and dry back was 550 ℃ of calcinings 6 hours.The gained sample is at the MgNO of 1mol/L
380 ℃ flooded 6 hours in the solution, and 500 ℃ of calcinings obtained magnesium oxide modified mesoporous material after 6 hours.
Embodiment 4: utilize later stage infusion process modification preparation to be used for the magnesium oxide modified mesoporous material of carbon dioxide absorption
With 2gP123 at 9mlHCl and 60mlH
2Fully dissolving adds 14ml tetraethyl orthosilicate (TEOS) in the hydrochloric acid solution that O forms, and 40 ℃ of magnetic agitation 24 hours, 100 ℃ left standstill 24 hours, formed colloidal sol, and dry back was 550 ℃ of calcinings 6 hours.The gained sample is at the MgNO of 0.5mol/L
380 ℃ flooded 6 hours in the solution, and 500 ℃ of calcinings obtained magnesium oxide modified mesoporous material after 6 hours.
Embodiment 5: utilize later stage infusion process modification preparation to be used for the magnesium oxide modified mesoporous material of carbon dioxide absorption
With 2gP123 at 9mlHCl and 60mlH
2Fully dissolving adds 14ml tetraethyl orthosilicate (TEOS) in the hydrochloric acid solution that O forms, and 40 ℃ of magnetic agitation 24 hours, 100 ℃ left standstill 24 hours, formed colloidal sol, and dry back was 550 ℃ of calcinings 6 hours.The gained sample is at the MgNO of 1.5mol/L
380 ℃ flooded 6 hours in the solution, and 500 ℃ of calcinings obtained magnesium oxide modified mesoporous material after 6 hours.
Resulting magnesium oxide modified mesoporous material in the foregoing description 3 to 5, because the specific area decline of dipping back, thereby the adsorption capacity of this material reaches 25mg/g.
If do not adopt this method, prepared material is the magnesia mesoporous material that does not have modification, and through detecting, its adsorption capacity is merely 20mg/g.
Claims (8)
1. one kind is used for the magnesium oxide modified mesoporous material that carbon dioxide adsorbs; It is characterized in that this material processed by one-step synthesis, specifically is to be template with P123, and P123 and magnesium source be fully dissolving in hydrochloric acid solution; Add tetraethyl orthosilicate; After drying, calcining, directly prepare described magnesium oxide modified mesoporous material, the quality proportioning of raw materials used P123, magnesium source, hydrochloric acid solution and tetraethyl orthosilicate is 1: x: 35.31: 6.51, and x=0.28～0.78; Perhaps being processed by later stage infusion process modified technique, specifically is to be template with P123, and fully dissolving adds tetraethyl orthosilicate in hydrochloric acid solution, through mesoporous material dry, that prepare after calcining for the first time at Mg (NO
3)
2Flood in the solution, through preparing described magnesium oxide modified mesoporous material after the calcining for the second time, the quality proportioning of raw materials used P123, hydrochloric acid solution and tetraethyl orthosilicate is 1: 35.31: 6.51 again.
2. magnesium oxide modified mesoporous material according to claim 1, the quality proportioning that it is characterized in that said P123, magnesium source, hydrochloric acid solution and tetraethyl orthosilicate is 1: 0.28: 35.31: 6.51.
3. magnesium oxide modified mesoporous material according to claim 1 is characterized in that said magnesium source is MgCl
26H
2O.
4. the magnesium oxide modified mesoporous material that is used for carbon dioxide absorption according to claim 1, when it is characterized in that adopting one-step synthesis, in dry run, the baking temperature that is adopted is 85～110 ℃, be 12～72 hours drying time.
5. the magnesium oxide modified mesoporous material that is used for carbon dioxide absorption according to claim 1, when it is characterized in that adopting one-step synthesis, in calcination process, the calcining heat that is adopted is 400～600 ℃, calcination time is 6～24 hours.
6. the magnesium oxide modified mesoporous material that is used for carbon dioxide absorption according to claim 1 is characterized in that adopting the later stage during infusion process modified technique, and in dry run, the baking temperature that is adopted is 85～110 ℃, and be 12～72 hours drying time.
7. the magnesium oxide modified mesoporous material that is used for carbon dioxide absorption according to claim 1; It is characterized in that adopting the later stage during infusion process modified technique; In calcination process, the calcining heat that calcining is for the first time adopted is 400～600 ℃, and calcination time is 6～24 hours; The calcining heat that calcining is for the second time adopted is 400～600 ℃, and calcination time is 5～12 hours.
8. the magnesium oxide modified mesoporous material that is used for carbon dioxide absorption according to claim 1 is characterized in that the (NO at Mg
3)
2The solution impregnation time is 5～12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101934744A CN101844068B (en) | 2010-06-07 | 2010-06-07 | Method for preparing magnesium oxide modified mesoporous material for adsorbing carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101934744A CN101844068B (en) | 2010-06-07 | 2010-06-07 | Method for preparing magnesium oxide modified mesoporous material for adsorbing carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101844068A CN101844068A (en) | 2010-09-29 |
| CN101844068B true CN101844068B (en) | 2012-03-07 |
Family
ID=42768996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101934744A Expired - Fee Related CN101844068B (en) | 2010-06-07 | 2010-06-07 | Method for preparing magnesium oxide modified mesoporous material for adsorbing carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101844068B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130101936A (en) * | 2012-03-06 | 2013-09-16 | 삼성전자주식회사 | Adsorbent for carbon dioxide, method preparing the same and capture module for carbon dioxide |
| CN102658080A (en) * | 2012-04-13 | 2012-09-12 | 武汉理工大学 | Preparation method of highly-dispersed meso pore gamma-Al2O3 base alkali (soil) metal composite adsorbent |
| KR102092940B1 (en) * | 2013-04-15 | 2020-03-24 | 삼성전자주식회사 | Carbon dioxide gas adsorbents and production methods thereof, carbon dioxide capture modules comprising the same, and methods for separating carbon dioxide using the same |
| CN103301801B (en) * | 2013-06-07 | 2015-04-08 | 中国科学技术大学 | Mesoporous carbon supported nanometer magnesia and preparation method thereof |
| CN103894152A (en) * | 2014-04-17 | 2014-07-02 | 上海锅炉厂有限公司 | Middle-high-temperature carbon dioxide adsorbent and preparation method thereof |
| CN104014302B (en) * | 2014-07-11 | 2016-06-29 | 上海大学 | The preparation method of magnesium oxide-mesoporous carbon composite material |
| CN105617978B (en) * | 2016-01-04 | 2018-07-17 | 武汉理工大学 | Room temperature CO absorption2Support type MgO/ γ-Al2O3The preparation method of adsorbent |
| KR102376491B1 (en) * | 2020-02-27 | 2022-03-17 | 삼성전자주식회사 | Adsorbent for carbon dioxide, method preparing the same and capture module for carbon dioxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457153A (en) * | 2007-12-14 | 2009-06-17 | 中国石油化工股份有限公司 | Hydrocarbon oil conversion method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002282685A (en) * | 2001-03-28 | 2002-10-02 | Toshiba Corp | Carbon dioxide absorbent and combustion apparatus |
| WO2010054427A1 (en) * | 2008-11-11 | 2010-05-20 | The University Of Queensland | A method for producing sorbents for co2 capture under high temperatures |
-
2010
- 2010-06-07 CN CN2010101934744A patent/CN101844068B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457153A (en) * | 2007-12-14 | 2009-06-17 | 中国石油化工股份有限公司 | Hydrocarbon oil conversion method |
Non-Patent Citations (4)
| Title |
|---|
| JP特开2002-282685A 2002.10.02 |
| Karl O. Albrecht et.al..Development of a CaO-Based CO2 Sorbent with Improved Cyclic Stability.《Ind. Eng. Chem. Res.》.2008,第47卷(第20期),7841-7848. * |
| Shiying Lin et.al..CO2 separation during hydrocarbon gasification.《Energy》.2005,第30卷2186-2193. * |
| 李俊宁 等.介孔气体吸附剂.《化学进展》.2008,第20卷(第6期),851-857页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101844068A (en) | 2010-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101844068B (en) | Method for preparing magnesium oxide modified mesoporous material for adsorbing carbon dioxide | |
| Fu et al. | Research progress on CO2 capture and utilization technology | |
| CN104475062A (en) | Amidine modified mesoporous foam material used for carbon dioxide adsorption and preparation method of amidine modified mesoporous foam material | |
| Anwar et al. | CO2 capture and storage: A way forward for sustainable environment | |
| Sahoo et al. | Metal–organic frameworks for CO2 separation from flue and biogas mixtures | |
| CN102614832B (en) | Halloysite carbon dioxide adsorbent and preparation method thereof | |
| Manovic et al. | CO2 looping cycles with CaO-based sorbent pretreated in CO2 at high temperature | |
| Zhao et al. | Liquid-solid phase-change absorption of acidic gas by polyamine in nonaqueous organic solvent | |
| Creamer et al. | Carbon dioxide capture: an effective way to combat global warming | |
| Freire et al. | Potential applications for geopolymers in carbon capture and storage | |
| CN103381330B (en) | A kind of for trapping or the absorbent of separating carbon dioxide and application thereof | |
| Zeng et al. | Porous adsorption materials for carbon dioxide capture in industrial flue gas | |
| CN104261427B (en) | A kind of preparation method of " plug-in card " type multi-stage porous ZSM-5 molecular sieve | |
| CN103894160B (en) | A kind of carbon dioxide solid absorbent and preparation method thereof | |
| WO2006128326A1 (en) | Comprehensive coal burning boiler smoke and ash slag treating process with no pollution emission | |
| Vatalis et al. | Intermediate technologies towards low-carbon economy. The Greek zeolite CCS outlook into the EU commitments | |
| CN105817197A (en) | Preparation method of fly ash based adsorbent for efficiently separating CO2 | |
| CN104941586A (en) | Modified meso-porous silicon material, and preparation method and application thereof | |
| Wang et al. | Adsorption of CO2 by a novel zeolite doped amine modified ternary aerogels | |
| CN105214450B (en) | A kind of selective absorbing SO2Absorbent and absorb SO2Process | |
| CN102674382A (en) | Synthetic process of lithium orthosilicate material | |
| Chu et al. | Integration of carbon emission reduction policies and technologies: Research progress on carbon capture, utilization and storage technologies | |
| CN103230783B (en) | Compound type carbon dioxide adsorbent | |
| CN105477979A (en) | Method for separating CO2 with high-viscosity absorbent based on salting-out effect | |
| Lee et al. | Facile synthesis of nitrogen-enriched mesoporous carbon for carbon dioxide capture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120307 Termination date: 20130607 |