CN111375382A - SO (SO)2Adsorbing material and preparation method thereof - Google Patents
SO (SO)2Adsorbing material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000001413 amino acids Chemical class 0.000 claims abstract description 11
- 239000013094 zinc-based metal-organic framework Substances 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000013132 MOF-5 Substances 0.000 claims description 21
- 239000011159 matrix material Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000003546 flue gas Substances 0.000 claims description 11
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 10
- 239000012621 metal-organic framework Substances 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 7
- 239000004475 Arginine Substances 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 5
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 5
- 239000013118 MOF-74-type framework Substances 0.000 claims description 4
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 4
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 abstract description 12
- 150000003751 zinc Chemical class 0.000 abstract description 2
- 239000002184 metal Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 238000001514 detection method Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 235000001014 amino acid Nutrition 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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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
Abstract
The invention relates to a SO2The adsorbing material is prepared with zinc-base metal-organic skeleton material as base material, and through doping amino acid, carbonizing at certain temperature to obtain SO2Adsorbing the material. SO according to the invention2The adsorbing material is prepared by the method. SO of the invention2The adsorbing material is obtained based on modified zinc-based metal organic framework material and has high SO2Adsorption capacity and selectivity, in particular in favor of SO2High-efficiency physical adsorption.
Description
Technical Field
The invention belongs to the field of atmospheric pollution control, and particularly relates to SO2An adsorbing material and a preparation method thereof.
Background
SO2Is one of the main atmospheric pollutants, an important source of acid rain, SO2The emission causes a series of hazards to human life, health and industrial production. As early as in the fifteen program, SO2Becomes one of the main pollutant emission indexes for national key control of emission.
Currently, widely used desulfurization techniques can be classified into wet desulfurization techniques and dry desulfurization techniques. The dry desulfurization technology is mainly used for adsorbing SO in flue gas under the action of an adsorbing material2And after the adsorption is saturated, the adsorbent is desorbed and can be further recycled. The active carbon (coke) material widely used in industry has high specific surface area and pore structure, and the catalytic action of metal active center on the active carbon material can make SO pass through chemical reaction2Conversion to SO3Then further with H2O reaction to produce H2SO4Realizing SO in flue gas after alkaline washing2And (4) removing. But for high concentrations of SO2Flue gases, e.g. SO from S-Zorb flue gases of petroleum refining2Concentration of>1%, SO is more suitable2And desorbing after physical adsorption so as to recycle and utilize the sulfur. Therefore, an adsorbent such as activated carbon (coke) having a chemical reaction adsorbing property is not suitable.
The metal organic framework Materials (MOFs) are macromolecular porous materials which take metal as a central node and are combined with organic ligands through coordination to form an infinite topological structure, and have high specific surface area, uniform pore structure and pore size. However, MOFs contain metal oxides and adsorb SO2While easily generating chemical reaction, is suitable for low-concentration SO2Chemical adsorption of gas is not beneficial to SO2Physical adsorption of (1).
Disclosure of Invention
Aiming at the existing SO2The invention provides SO2An adsorbing material and a preparation method thereof. SO of the invention2The adsorbing material is obtained based on modified zinc-based metal organic framework material and has high SO2Adsorption capacity and selectivity, in particular in favor of SO2High-efficiency physical adsorption.
SO provided by the invention2Preparation method of adsorbing materialThe method comprises the following steps: zinc-based metal organic framework material is taken as a matrix, a certain amount of amino acid is doped, and carbonization is carried out at a certain temperature to obtain SO2Adsorbing the material.
In the invention, the zinc-based metal organic framework material can be selected from at least one of MOF-5, MOF-74, ZIF series and the like, and is preferably MOF-5. The ZIF series material can be at least one of ZIF-8, ZIF-20, ZIF-21 and the like. Furthermore, the specific surface area of the zinc-based metal organic framework material is 1500-1660 m2The pore volume is 1.07-1.15 cm3/g。
In the present invention, the amino acid is a basic amino acid, and may be at least one of lysine, arginine, histidine, and the like, preferably histidine.
In the invention, the dosage of the amino acid is 0.01-5.0% of the mass of the metal organic framework material, and preferably 0.1-2.0%.
In the invention, the carbonization conditions are as follows: in the presence of nitrogen, the carbonization temperature is 900-1150 ℃, and the carbonization time is 5-10 hours.
SO according to the invention2The adsorbing material is prepared by the method. Prepared SO2The specific surface area of the adsorbing material is 1210-2650 m2A pore volume of 0.95 to 3.8cm3Per g, no metal element, SO2Has good physical adsorption effect. Setting the concentration of the adsorption outlet not higher than 50mg/m3The time is the penetration time, and the SO is in the penetration time under 0.1-0.3 MPa2The adsorption capacity of the material is 120-175 mg/g, which is more than 2 times that of commercial activated carbon and more than 1.6 times that of MOFs materials. After multiple times of cyclic adsorption-desorption, the adsorption capacity can still be stabilized to more than 85% of the initial adsorption capacity.
SO according to the invention2Application of adsorbing material in flue gas2Physical adsorption of (2), wherein SO is in flue gas2The content of (b) is more than 0.1%, generally 0.1% to 5% by volume. The adsorption conditions were: the pressure is 0.1-0.3 MPa, the temperature is 5-25 ℃, and the volume space velocity is 100-1000 h-1。
The invention is obtained by modifying based on MOFs materialTo SO2The adsorbing material has high specific surface area and uniform microporous structure, the proportion of the microporous structure is high, the content of the impurity elements except carbon is low, and SO is facilitated2Shows more excellent SO compared with commercial activated carbon2Physical adsorption property, and aims to solve SO in flue gas in petroleum refining industry2Provides a new idea for removal and further recycling. According to the invention, a certain amount of amino acid is doped before the MOFs material is carbonized to modify the MOFs material, SO that SO is favorably realized2High-efficiency physical adsorption.
Drawings
FIG. 1 shows the cyclic adsorption-desorption of SO from the adsorbent prepared in example 12The effect diagram of (1).
Detailed Description
The SO of the present invention is further illustrated by the following examples2An adsorbing material and a preparation method thereof. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
The specific surface area and the pore volume of the material of the invention are N2And (4) analyzing and obtaining an adsorption and desorption curve by an adsorption instrument. The content of the metal element was analyzed by the ICP method. SO in gas2The content was analyzed by an instrument (EmersonX-STREAM). The concentration of the adsorption outlet was set to 50mg/m3Is the penetration time, SO on activated carbon2The adsorption capacity is calculated by the following formula:
in the formula: q is sulfur capacity, mg/g; q is the total flow of the mixed gas at the inlet, mL/min; c0Is an inlet SO2Concentration, mg/L; ciIs the ith sampling outlet SO2Concentration, mg/L; t is the ith sampling time, min; n is the sampling times when the adsorption reaches saturation or within a specified time; m is the loading of the adsorbent material, g.
Example 1
Taking MOF-5 as a matrix, the specific surface area is 1655 m2G, pore volume of 1.13 cm3G, Zn content 31.2%. Doping histidine accounting for 1.0 percent of MOF-5 mass, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 2642 m by detection2G, pore volume of 3.76 cm3(ii)/g, containing no metal element.
Example 2
Taking MOF-5 as a matrix, the specific surface area is 1655 m2G, pore volume of 1.13 cm3G, Zn content 31.2%. Doping lysine accounting for 1.0 percent of the mass of the MOF-5, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 2175 m by detection2G, pore volume of 3.27 cm3(ii)/g, containing no metal element.
Example 3
Taking MOF-5 as a matrix, the specific surface area is 1655 m2G, pore volume of 1.13 cm3G, Zn content 31.2%. Adding arginine accounting for 1.0 percent of the MOF-5 by mass, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 2382m through detection2Per g, pore volume of 3.65 cm3(ii)/g, containing no metal element.
Example 4
ZIF-8 is taken as a substrate, and the specific surface area is 1150 m2Per g, pore volume of 0.82 cm3G, Zn content 30.7%. Doping arginine accounting for 1.0 percent of the mass of ZIF-8, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 1440 m through detection2G, pore volume of 1.52 cm3(ii)/g, containing no metal element.
Example 5
Taking MOF-74 as a matrix and having a specific surface area of 852 m2Per g, pore volume 1.02 cm3G, Zn content 29.2%. Adding arginine accounting for 1.0 percent of the mass of the MOF-74, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 1210 m through detection2G, pore volume of 1.44 cm3(ii)/g, containing no metal element.
Example 6
Taking MOF-5 as a matrix, the specific surface area is 1655 m2G, pore volume of 1.13 cm3G, Zn content 31.2%. Doping histidine accounting for 0.1 percent of MOF-5 mass, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 2471 m by detection2G, pore volume of 3.63 cm3(ii)/g, containing no metal element.
Example 7
Taking MOF-5 as a matrix, the specific surface area is 1655 m2G, pore volume of 1.13 cm3G, Zn content 31.2%. Doping histidine accounting for 2.0% of MOF-5 mass, and carbonizing at 1000 deg.C for 6 hr in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 2519 m by detection2Per g, pore volume of 3.72 cm3(ii)/g, containing no metal element.
Example 8
Taking MOF-5 as a matrix, the specific surface area is 1655 m2G, pore volume of 1.13 cm3G, Zn content 31.2%. Doping histidine accounting for 5.0% of MOF-5 mass, and carbonizing at 1000 deg.C for 6 hr in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 2320 m by detection2G, pore volume of 3.42 cm3(ii)/g, containing no metal element.
Comparative example 1
Taking MOF-5 as a matrix, the specific surface area is 1655 m2G, pore volume of 1.13 cm3G, Zn content 31.2%. Carbonizing at 1000 deg.C for 6 hr in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 2164 m by detection2G, pore volume of 3.22 cm3(ii)/g, containing no metal element.
Comparative example 2
Taking MOF-5 as a matrix, the specific surface area is 1655 m2G, pore volume of 1.13 cm3G, Zn content 31.2%. Doping glutamic acid accounting for 1.0 percent of MOF-5 mass, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 1336 m through detection2G, pore volume of 1.02 cm3(ii)/g, containing no metal element.
Comparative example 3
Taking MOF-5 as a matrix, the specific surface area is 1655 m2G, pore volume of 1.13 cm3G, Zn content 31.2%. Mechanically mixing and doping histidine accounting for 1.0% of MOF-5 mass to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 1202m by detection2Per g, pore volume of 0.85 cm3In terms of a/g, the metal content is 30.8%.
Comparative example 4
Active carbon is taken as a matrix, and the specific surface area is 875 m2Per g, pore volume of 0.51 cm3(ii) in terms of/g. Doping histidine accounting for 1.0 percent of the mass of the activated carbon, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 1025 m by detection2Per g, pore volume of 0.68 cm3/g。
The adsorbing properties of the adsorbing materials prepared in examples 1 to 8 of the present invention and comparative examples 1 to 4 were tested as follows. Wherein, SO in the flue gas2The content of (b) is 5% by volume. The adsorption conditions were: the adsorption temperature is 20 ℃, and the volume space velocity is 500 h-1The adsorption pressure is normal pressure and 0.2MPa, and the concentration of the adsorption outlet is 50mg/m3Time is taken as the breakthrough time. The results are shown in Table 1.
Table 1 examples and comparative examples SO of prepared materials2Adsorption capacity (mg/g)
The adsorption performance of the adsorption material prepared in example 1 of the present invention was tested under different pressure and temperature conditions. Wherein, SO in the flue gas2The volume content of (A) is 2%. The adsorption conditions were: the volume space velocity is 1000h-1At an adsorption outlet concentration of 50mg/m3Time is taken as the breakthrough time. Under the pressurization condition, the adsorption efficiency can be improved by 1.4-3.4 times. Temperature to SO at 5-25 deg.C under the same pressure2The adsorption capacity has no obvious influence. The results are shown in Table 2.
TABLE 2 SO at different temperatures and pressures2Adsorption amount (unit: mg/g)
The material of example 1 was tested for repeatability, with the adsorption conditions: the adsorption temperature is 20 ℃, and the space velocity of the adsorption volume is 400h-1The adsorption pressure is normal pressure and 0.2MPa, and the concentration of the adsorption outlet is 50mg/m3The time is taken as the penetration time, and SO is absorbed and desorbed for 30 times2The adsorption amount was stabilized at 150mg or more, and the results are shown in FIG. 1.
Claims (10)
1. SO (SO)2The preparation method of the adsorbing material is characterized by comprising the following steps: zinc-based metal organic framework material is taken as a matrix, a certain amount of amino acid is doped, and carbonization is carried out at a certain temperature to obtain SO2Adsorbing the material.
2. The method of claim 1, wherein: the zinc-based metal organic framework material is at least one of MOF-5, MOF-74 and ZIF series, and MOF-5 is preferred.
3. The method of claim 2, wherein: the ZIF series material is at least one of ZIF-8, ZIF-20 and ZIF-21.
4. A method according to claim 1, 2 or 3, characterized in that: the specific surface area of the zinc-based metal organic framework material is 1500-1660 m2The pore volume is 1.07-1.15 cm3/g。
5. The method of claim 1, wherein: the amino acid is basic amino acid, and the basic amino acid is at least one of lysine, arginine and histidine, preferably histidine.
6. The method according to claim 1 or 5, characterized in that: the dosage of the amino acid is 0.01-5.0 percent of the mass of the metal organic framework material, and preferably 0.1-2.0 percent.
7. The method of claim 1, wherein: the carbonization conditions are as follows: in the presence of nitrogen, the temperature is 900-1150 ℃, and the carbonization time is 5-10 hours.
8. SO (SO)2An adsorbent material, characterised in that it is prepared by a process according to any one of claims 1 to 7.
9. SO according to claim 82The application of the adsorbing material is characterized in that: for SO in flue gas2Physical adsorption of (2), wherein SO is in flue gas2The volume content of (a) is more than 0.1%, preferably 0.1% to 5%.
10. Use according to claim 9, characterized in that: the adsorption temperature is 5-25 ℃, and the space velocity of the adsorption volume is 100-1000 h-1The adsorption pressure is 0.1-0.3 MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979983A (en) * | 2021-03-03 | 2021-06-18 | 太原理工大学 | Surface-doped porous ZIF-8 flexible MOFs material, preparation method and application |
| CN114015065A (en) * | 2021-11-10 | 2022-02-08 | 中国石油大学(华东) | Fmoc-amino acid-ZIF-8 nano material, and preparation method and application thereof |
| CN114797809A (en) * | 2022-04-22 | 2022-07-29 | 云南师范大学 | Porous liquid gas chromatography chiral column for resolving racemic compound |
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