CN110538634A - Preparation and application of amino modified metal organic framework material with high CO2/N2O separation performance - Google Patents
Preparation and application of amino modified metal organic framework material with high CO2/N2O separation performance Download PDFInfo
- Publication number
- CN110538634A CN110538634A CN201910755917.5A CN201910755917A CN110538634A CN 110538634 A CN110538634 A CN 110538634A CN 201910755917 A CN201910755917 A CN 201910755917A CN 110538634 A CN110538634 A CN 110538634A
- Authority
- CN
- China
- Prior art keywords
- mil
- organic framework
- framework material
- preparation
- amino
- 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.)
- Granted
Links
Classifications
-
- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- 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
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
-
- 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
Abstract
The invention belongs to the technical field of separation materials, and particularly relates to a preparation method of an amino modified metal organic framework material. The method comprises the following steps: sealing MIL-100V in a glove box, taking out, vacuumizing and activating for a period of time at a certain temperature to avoid contacting air; adding the vacuumized and activated MIL-100V into ethanol under the protection of argon, stirring, adding ethylenediamine, and continuing stirring for 2 hours; transferring the solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for a period of time at a certain temperature, and then activating the ethylene diamine modified material ED-MIL-100V in vacuum at a certain temperature to obtain the amino modified metal organic framework material with high CO2/N2O separation performance. The introduction of amino groups on the ethylenediamine provides a new adsorption site for CO2, and the selectivity of CO2/N2O is greatly improved, so that the high-efficiency separation of CO2/N2O is realized.
Description
Technical Field
The invention belongs to the technical field of separation materials, and particularly relates to a preparation method of an amino modified metal organic framework material. More specifically, ethylene diamine is adopted to modify a metal organic framework material MIL-100V under the protection of argon to prepare a material capable of efficiently separating CO2/N2O, and the separation material can be applied to separation of a mixture of CO2 and N2O in tail gas generated in the industrial production process of nitric acid, adipic acid and the like.
Background
Nitrous oxide (N2O, laughing gas) is the third largest greenhouse gas behind the carbon dioxide (CO 2), methane (CH 4) which is a six-gas relay carbon dioxide (CO 2) regulated by kyoto protocol, causes 298 times of greenhouse effect as carbon dioxide and damages stratospheric ozone. In addition, N2O has important application in the fields of medicine, food and spaceflight. Therefore, the recovery and utilization of N2O have a double meaning. 40% of the N2O emissions are caused by human activity, mainly agriculture, transportation and industry. N2O is often emitted as a by-product in the production of adipic acid and nitric acid. At present, there are two main methods for industrially treating N2O, one of them is that for the low concentration of N2O in the tail gas, N2O can be directly catalytically decomposed into N2 and O2 which are pollution-free to the environment, but the decomposition of N2O requires high temperature and energy consumption, and N2O after decomposition cannot be used as a valuable intermediate for producing other fine chemical products. In another method, for high-concentration N2O, N2O can be used as an oxidant to industrially oxidize benzene to prepare phenol in one step, but the concentration of N2O in tail gas generally does not meet the requirement and needs further enrichment. Therefore, it is necessary to find an economical and efficient method for separating or enriching N2O for other industrial production. Besides N2O, the tail gas from the production of adipic acid and nitric acid also has CO2 which is close to the properties of the tail gas. Although CO2 and N2O are composed of different elements, they have the same relative molecular mass and kinetic diameter, similar liquefaction temperature and polarizability, and therefore, the separation of CO2/N2O is very challenging. Pressure swing adsorption separation (PSA) has received increasing attention in recent years due to its advantages such as low energy consumption and simple operation. The metal organic framework material is a porous material with a three-dimensional periodic grid structure formed by self-assembly of organic ligands and metal ions or metal clusters, and has an important position in the field of gas adsorption separation due to the advantages of high and adjustable porosity, ultrahigh specific surface area, open metal sites, structural composition diversity, chemical modification and the like. And then the synthetic modification is used as an important means for changing the original performance of the material, and has important application in the field of gas adsorption separation.
Disclosure of Invention
The technical purpose of the invention is to provide an amino-modified metal organic framework material, which has high CO2/N2O separation performance, can be applied to the technical field of gas separation of CO2 and N2O, and solves the separation problem of CO2/N2O in tail gas generated in the industrial production process of nitric acid, adipic acid and the like.
the invention is realized by the following technical scheme: the preparation of the amino modified metal organic framework material with high CO2/N2O separation performance comprises the following steps:
(1) Sealing MIL-100V in a glove box, taking out, vacuumizing and activating for a period of time at a certain temperature to avoid contacting air;
(2) adding the MIL-100V subjected to vacuum pumping activation in the step (1) into ethanol under the protection of argon, stirring, adding ethylenediamine, and continuing stirring for 2 hours;
(3) and (3) transferring the solution obtained in the step (2) into a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for a period of time at a certain temperature, taking out after reaction, cleaning with ethanol for three times, transferring into a glove box for drying, and then activating the ethylene diamine modified material ED-MIL-100V in vacuum at a certain temperature to obtain the amino modified metal organic framework material with high CO2/N2O separation performance.
According to the invention, a metal organic framework material MIL-100V with empty coordination is selected for full activation, and then ethylene diamine is adopted for modification under the protection of argon gas to prepare an ethylene diamine modified MIL-100V material ED-MIL-100V, so that effective separation of CO2/N2O is realized. The ED-MIL-100V is prepared by adopting a solvothermal method.
Preferably, the activation temperature of MIL-100V in the step (1) can be 150 ℃.
preferably, the activation time of MIL-100V in the step (1) is 10 hours.
Preferably, the mass-to-volume ratio of MIL-100V to ethylenediamine after activation in the step (2) is 0.25:0.4 (g/ml).
Preferably, the reaction temperature in the high-pressure reaction kettle in the step (3) is 85 ℃.
Preferably, the reaction time in the high-pressure reaction kettle in the step (3) is 12 hours.
Preferably, the activation temperature of the modified material ED-MIL-100V in the step (3) is 100 ℃.
preferably, the activation time of the modified material ED-MIL-100V in the step (3) is 5 hours.
In conclusion, the invention has the following beneficial effects:
(1) The MIL-100V material modified by the ethylenediamine realizes the high-efficiency separation of CO 2/N2O. When ethylenediamine is grafted on MIL-100V, the original unsaturated metal adsorption site of the MIL-100V is blocked, and meanwhile, the introduction of the amino group on the ethylenediamine provides a new adsorption site for CO2, so that compared with unmodified MIL-100V, the selectivity of CO2/N2O is greatly improved, and the efficient separation of CO2/N2O is realized.
(2) The modification method of the ethylenediamine modified MIL-100V material is simple, easy for batch production, and has good stability and can be repeatedly used. Has good application prospect, especially can be applied to the separation of CO2/N2O in tail gas generated in the industrial production process of nitric acid, adipic acid and the like, and realizes the effective utilization of N2O.
Drawings
in order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of ED-MIL-100V-0.4 of example 2 of the present invention after modification of MIL-100V with 0.4ml of ethylenediamine, and it can be seen from the figure that the positions and relative intensities of the diffraction peaks of ED-MIL-100V-0.4 of example 2 are identical to those of MIL-100V, demonstrating that the crystal structure of example 2 after modification with ethylenediamine is well maintained and is not destroyed by ethylenediamine.
FIG. 2 is a plot of adsorption-desorption isotherms of ED-MIL-100V-0.4 after modification with ethylenediamine and N2 at-196 ℃ of MIL-100V in example 2 of the present invention, and it can be seen from the plot that the adsorption amount of N2 at-196 ℃ of example 2 after modification with ethylenediamine is reduced because the diffusion of N2 molecules is hindered by the addition of ethylenediamine molecules, resulting in a reduction in the adsorption amount of N2.
FIG. 3 is a graph showing the adsorption isotherms of CO2 and N2O at 25 ℃ of ED-MIL-100V-0.4 modified with MIL-100V and ethylenediamine in example 2 of the present invention, from which we can see that example 2 has a higher adsorption of CO2 and a lower adsorption of N2O.
FIG. 4 is a graph showing adsorption selectivity of MIL-100V to ED-MIL-100V-0.4 modified with ethylenediamine according to ideal solution adsorption theory (IAST) for CO2/N2O (1: 1V/V) mixed gas in example 2 of the present invention. As can be seen from the figure, the example prepared by the method has excellent adsorption selectivity of CO2/N2O, and the adsorption selectivity of CO2/N2O reaches 28 at 298K and 1 bar.
FIG. 5 is a graph showing the breakthrough curves of a mixture of CO2 and N2O (1: 1V/V) after modification of ED-MIL-100V-0.4 with ethylenediamine in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The technical solution of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1:
A preparation method of an amino modified metal organic framework material with high CO2/N2O separation performance comprises the following steps:
(1) Sealing MIL-100V in a glove box, taking out, and vacuumizing and activating at 150 ℃ for 10 hours to avoid air contact;
(2) adding 0.25g of MIL-100V subjected to vacuum pumping activation in the step (1) into 50ml of ethanol under the protection of argon, stirring for 1 hour, adding 0.2 ml of ethylenediamine, and continuing stirring for 2 hours;
(3) Transferring the solution in the step (2) into a 100ml high-pressure reaction kettle with a polytetrafluoroethylene lining, then reacting for 12 hours at 85 ℃, taking out after reaction, washing with ethanol for three times, transferring into a glove box for drying, and then performing vacuum activation for 5 hours at 100 ℃ to obtain ED-MIL-100V-0.2.
example 2:
a preparation method of an amino modified metal organic framework material with high CO2/N2O separation performance comprises the following steps:
(1) Sealing MIL-100V in a glove box, taking out, and vacuumizing and activating at 150 ℃ for 10 hours to avoid air contact;
(2) Adding 0.25g of MIL-100V subjected to vacuum pumping activation in the step (1) into 50ml of ethanol under the protection of argon, stirring for 1 hour, adding 0.4ml of ethylenediamine, and continuing stirring for 2 hours;
(3) And (3) transferring the solution in the step (2) into a 100ml high-pressure reaction kettle with a polytetrafluoroethylene lining, then reacting for 12 hours at 85 ℃, taking out after reaction, washing with ethanol for three times, transferring into a glove box for drying, and then performing vacuum activation for 5 hours at 100 ℃ to obtain ED-MIL-100V-0.4.
Example 3:
a preparation method of an amino modified metal organic framework material with high CO2/N2O separation performance comprises the following steps:
(1) Sealing MIL-100V in a glove box, taking out, and vacuumizing and activating at 150 ℃ for 10 hours to avoid air contact;
(2) Adding 0.25g of MIL-100V subjected to vacuum pumping activation in the step (1) into 50ml of ethanol under the protection of argon, stirring for 1 hour, adding 0.6 ml of ethylenediamine, and continuing stirring for 2 hours;
(3) And (3) transferring the solution in the step (2) into a 100ml high-pressure reaction kettle with a polytetrafluoroethylene lining, then reacting for 12 hours at 85 ℃, taking out after reaction, washing with ethanol for three times, transferring into a glove box for drying, and then performing vacuum activation for 5 hours at 100 ℃ to obtain ED-MIL-100V-0.6.
example 4:
A preparation method of an amino modified metal organic framework material with high CO2/N2O separation performance comprises the following steps:
(1) Sealing MIL-100V in a glove box, taking out, and vacuumizing and activating at 100 ℃ for 5 hours to avoid air contact;
(2) adding 0.25g of MIL-100V subjected to vacuum pumping activation in the step (1) into 50ml of ethanol under the protection of argon, stirring for 1 hour, adding 0.4ml of ethylenediamine, and continuing stirring for 2 hours;
(3) And (3) transferring the solution in the step (2) into a 100ml high-pressure reaction kettle with a polytetrafluoroethylene lining, then reacting for 12 hours at 85 ℃, taking out after reaction, washing with ethanol for three times, transferring into a glove box for drying, and then performing vacuum activation for 5 hours at 100 ℃ to obtain ED-MIL-100V-0.4-1.
the above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. the preparation method of the amino modified metal organic framework material with high CO2/N2O separation performance is characterized by comprising the following steps:
(1) Sealing MIL-100V in a glove box, taking out, vacuumizing and activating for a period of time at a certain temperature to avoid contacting air;
(2) Adding the MIL-100V subjected to vacuum pumping activation in the step (1) into ethanol under the protection of argon, stirring, adding ethylenediamine, and continuing stirring for 2 hours;
(3) And (3) transferring the solution obtained in the step (2) into a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for a period of time at a certain temperature, taking out after reaction, cleaning with ethanol for three times, transferring into a glove box for drying, and then activating the ethylene diamine modified material ED-MIL-100V in vacuum at a certain temperature to obtain the amino modified metal organic framework material with high CO2/N2O separation performance.
2. the preparation of amino-modified metal-organic framework material with high CO2/N2O separation performance as claimed in claim 1, wherein the activation temperature of MIL-100V in step (1) is 150 ℃.
3. the preparation of amino-modified metal-organic framework material with high CO2/N2O separation performance as claimed in claim 1, wherein the activation time of MIL-100V in step (1) is 10 hours.
4. The preparation of amino-modified metal-organic framework material with high CO2/N2O separation performance of claim 1, wherein the mass-to-volume ratio of MIL-100V to ethylenediamine after activation in step (2) is 0.25: 0.4.
5. The preparation of amino-modified metal-organic framework material with high CO2/N2O separation performance as claimed in claim 1, wherein the reaction temperature in the autoclave in step (3) is 85 ℃.
6. the preparation of amino-modified metal-organic framework material with high CO2/N2O separation performance as claimed in claim 1, wherein the reaction time in the autoclave in step (3) is 12 hours.
7. The preparation of amino-modified metal-organic framework material with high CO2/N2O separation performance as claimed in claim 1, wherein the activation temperature of the modified material ED-MIL-100V in step (3) is 100 ℃.
8. the preparation of amino-modified metal-organic framework material with high CO2/N2O separation performance as claimed in claim 1, wherein the activation time of the modified material ED-MIL-100V in step (3) is 5 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910755917.5A CN110538634B (en) | 2019-08-16 | 2019-08-16 | High CO2/N2Preparation and application of amino modified metal organic framework material with O separation performance |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910755917.5A CN110538634B (en) | 2019-08-16 | 2019-08-16 | High CO2/N2Preparation and application of amino modified metal organic framework material with O separation performance |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110538634A true CN110538634A (en) | 2019-12-06 |
CN110538634B CN110538634B (en) | 2022-03-18 |
Family
ID=68711475
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910755917.5A Active CN110538634B (en) | 2019-08-16 | 2019-08-16 | High CO2/N2Preparation and application of amino modified metal organic framework material with O separation performance |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110538634B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112675811A (en) * | 2020-12-18 | 2021-04-20 | 太原理工大学 | High-efficiency separation N2O/CO2Silver exchange molecular sieve adsorbent and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2784599A1 (en) * | 1998-10-20 | 2000-04-21 | Air Liquide | PROCESS FOR PURIFYING A GAS STREAM IN ITS N2O IMPURITIES |
CN103203159A (en) * | 2013-04-08 | 2013-07-17 | 浙江师范大学 | Method for separating nitrous oxide and carbon dioxide by using zeolite-like molecular sieve skeleton material |
CN103285827A (en) * | 2013-05-09 | 2013-09-11 | 中国科学院宁波材料技术与工程研究所 | Carbon dioxide capture material as well as preparation method and applications thereof |
CN105061482A (en) * | 2015-08-17 | 2015-11-18 | 太原理工大学 | Method for directly compounding metal-organic framework material MIL-100A1 by using trimesic acid |
CN107573516A (en) * | 2017-09-11 | 2018-01-12 | 东北石油大学 | A kind of preparation method of vanadium modified metal organic framework material |
CN109513421A (en) * | 2018-10-24 | 2019-03-26 | 浙江省化工研究院有限公司 | CO in a kind of gas2Adsorption method |
-
2019
- 2019-08-16 CN CN201910755917.5A patent/CN110538634B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2784599A1 (en) * | 1998-10-20 | 2000-04-21 | Air Liquide | PROCESS FOR PURIFYING A GAS STREAM IN ITS N2O IMPURITIES |
CN103203159A (en) * | 2013-04-08 | 2013-07-17 | 浙江师范大学 | Method for separating nitrous oxide and carbon dioxide by using zeolite-like molecular sieve skeleton material |
CN103285827A (en) * | 2013-05-09 | 2013-09-11 | 中国科学院宁波材料技术与工程研究所 | Carbon dioxide capture material as well as preparation method and applications thereof |
CN105061482A (en) * | 2015-08-17 | 2015-11-18 | 太原理工大学 | Method for directly compounding metal-organic framework material MIL-100A1 by using trimesic acid |
CN107573516A (en) * | 2017-09-11 | 2018-01-12 | 东北石油大学 | A kind of preparation method of vanadium modified metal organic framework material |
CN109513421A (en) * | 2018-10-24 | 2019-03-26 | 浙江省化工研究院有限公司 | CO in a kind of gas2Adsorption method |
Non-Patent Citations (7)
Title |
---|
JIANGFENG YANG等: "MIL-100Cr with open Cr sites for a record N2O capture", 《CHEM. COMMUN.》 * |
JIANGFENG YANG等: "Protection of open-metal V(III) sites and their associated CO2/CH4/N2/O2/H2O adsorption properties in mesoporous V-MOFs", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
LI WANG等: "Ethylenediamine-functionalized metal organic frameworks MIL-100(Cr) for efficient CO2/N2O separation", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
张飞飞: "基于MIL-100系列材料的生物沼气中CO2/CH4分离性能研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 * |
张飞飞等: "乙二胺改性轻金属铝-金属有机骨架材料用于CO_2/CH_4分离", 《无机化学学报》 * |
梁方方等: "乙二胺改性金属有机骨架材料MIL-101(Cr)常压下吸附CO", 《过程工程学报》 * |
郭政等: "功能化多孔材料对CO_2的吸附分离研究进展", 《环境工程》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112675811A (en) * | 2020-12-18 | 2021-04-20 | 太原理工大学 | High-efficiency separation N2O/CO2Silver exchange molecular sieve adsorbent and preparation method thereof |
CN112675811B (en) * | 2020-12-18 | 2022-06-21 | 太原理工大学 | High-efficiency separation N2O/CO2Silver exchange molecular sieve adsorbent and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN110538634B (en) | 2022-03-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhang et al. | Insights into deNOx processing over Ce-modified Cu-BTC catalysts for the CO-SCR reaction at low temperature by in situ DRIFTS | |
Mei et al. | Morphology-dependent properties of Co3O4/CeO2 catalysts for low temperature dibromomethane (CH2Br2) oxidation | |
CN105944680B (en) | A kind of method of adsorbing separation propylene propine | |
Chang et al. | Methane-trapping metal–organic frameworks with an aliphatic ligand for efficient CH 4/N 2 separation | |
Tang et al. | Design and synthesis of porous non-noble metal oxides for catalytic removal of VOCs | |
CN105013322A (en) | Use of manganite catalyst in catalytic oxidation of formaldehyde | |
JP2021186802A (en) | Porous carbon composite titanium oxide-halogen oxide photocatalyst and method for producing the same | |
CN109293467A (en) | A kind of method of adsorbing separation propylene, propine, propane and allene | |
CN101870455B (en) | Chain type hydrogen and oxygen production integrated method and device | |
CN104492375A (en) | Adsorbent for recovering CO from industrial exhaust gas as well as preparation method and application of adsorbent | |
Ao et al. | Simultaneous catalytic oxidation of NO and Hg0 over LaBO3 (B= Co, Mn, Ni, and Cu) perovskites | |
CN103785389A (en) | High-activity oxygen carrier and preparation method and application thereof | |
CN103691398A (en) | Carbon dioxide adsorbent and preparation method thereof | |
CN112537783A (en) | W18O49Modified g-C3N4Application of material in photocatalysis nitrogen fixation | |
CN104941620B (en) | A kind of application for the method and the carrier of oxygen preparing the carrier of oxygen with vanadium titano-magnetite | |
CN110538634B (en) | High CO2/N2Preparation and application of amino modified metal organic framework material with O separation performance | |
Wang et al. | The efficient separation of N 2 O/CO 2 using unsaturated Fe 2+ sites in MIL-100Fe | |
CN102872473A (en) | Environment-friendly air purifying preparation and method for manufacturing same | |
CN113975946A (en) | Method for converting carbon dioxide by synergy of plasma and photocatalyst | |
CN108948366B (en) | Preparation of Fe-MOF catalyst with rich Lewis acid sites and desulfurization application thereof | |
Que et al. | Novel synthesis of reed flower-like SmMnOx catalyst with enhanced low-temperature activity and SO2 resistance for NH3-SCR | |
CN113457644A (en) | Preparation method of surface modified metal organic framework structure adsorption material | |
CN111318251B (en) | Dual-functional mesoporous adsorbent for adsorbing and catalyzing VOCs (volatile organic compounds), and preparation method and application thereof | |
CN112316902A (en) | Composite MgO adsorbent and preparation method and application thereof | |
Shaya et al. | Introductory Chapter: An Outline of Carbon Dioxide Chemistry, Uses and Technology |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |