CN112844319A - Metal organic framework adsorbent with valence-sub metal nodes prepared by steam reduction method, and preparation method and application thereof - Google Patents
Metal organic framework adsorbent with valence-sub metal nodes prepared by steam reduction method, and preparation method and application thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 126
- 239000002184 metal Substances 0.000 title claims abstract description 126
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 98
- 239000003463 adsorbent Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 9
- 230000023556 desulfurization Effects 0.000 claims abstract description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001336 alkenes Chemical class 0.000 claims abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 239000013110 organic ligand Substances 0.000 claims abstract description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 68
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 20
- 239000013206 MIL-53 Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 239000013291 MIL-100 Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000013260 porous coordination network Substances 0.000 claims description 4
- -1 MIL-125 Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- AXNCYYJNXAOOJQ-UHFFFAOYSA-N 1,3,8-trichloronaphthalene Chemical compound ClC1=CC=CC2=CC(Cl)=CC(Cl)=C21 AXNCYYJNXAOOJQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 2
- 239000013177 MIL-101 Substances 0.000 claims description 2
- 239000013216 MIL-68 Substances 0.000 claims description 2
- 239000013259 porous coordination polymer Substances 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 56
- 238000001816 cooling Methods 0.000 description 20
- 238000007789 sealing Methods 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a metal organic framework adsorbent with a valence metal node prepared by a steam reduction method, and a preparation method and application thereof, and the metal organic framework adsorbent is characterized in that: the porous structure is loaded with a three-dimensional network formed by self-assembly of the divalent metal nodes and organic ligands containing carboxylic acid, imidazole, pyrimidine or pyridine. The prepared metal organic framework adsorbent with the divalent metal nodes is directly used for adsorption desulfurization of fuel oil, separation of olefin and alkane and recovery of carbon monoxide, and the metal framework adsorbent provided by the invention has large adsorption capacity and high selectivity and adsorption separation efficiency.
Description
Technical Field
The invention relates to the technical field of chemical separation, in particular to a metal organic framework adsorbent with a valence metal node prepared by a steam reduction method, and a preparation method and application thereof.
Background
The environmental problems associated with the combustion of large quantities of sulfur-containing fuel oils are becoming increasingly serious. Although hydrodesulfurization is widely used to effectively remove mercaptans, sulfides, disulfides and the like in fuel oil, it is not reasonable to remove thiophenic sulfides, and thus it is imperative to remove thiophenic sulfides in oil products. The conditions for separating such mixtures are particularly harsh due to the similar molecular size and volatility of the olefins and alkanes. The industrial separation of ethylene/ethane requires rectification at low temperature and high pressure with a consequent huge energy consumption. Therefore, it is of great interest to develop an efficient and energy-saving olefin/paraffin separation technique. Carbon monoxide is an important raw material in the chemical industry and is used for synthesizing various chemicals such as polymer fibers, plastics, medicines, and the like. Although the carbon monoxide is rich in source, most of the raw material gas is doped with N2、CH4And H2And other impurity gases cannot be directly used for synthesizing chemicals, and further purification treatment is required.
The adsorption separation technology has mild operation conditions, simple process and low cost, and becomes a research hotspot at present. The development of an adsorbent with large adsorption capacity and high adsorption selectivity is still the core of the application of the technology. Due to the fact that the complex acting force formed between the valence-sub metal sites and unsaturated bonds is stronger than Van der Waals force and weaker than chemical acting force, the porous adsorbent with the valence-sub metal nodes is used as a complex adsorbent and shows excellent adsorption performance and regeneration performance in the aspects of deep desulfurization of fuel oil, olefin alkane separation, carbon monoxide recovery and the like. Meanwhile, the metal organic framework material has a developed pore structure and a large number of metal sites, and becomes a hot spot in the field of adsorption application. However, in the prior art, the valence state of the metal site in the metal-organic framework material directly prepared by the reaction of the metal salt and the organic ligand is usually the highest valence state, the adsorption effect with the adsorbate is weak, and the adsorption separation effect is poor.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above-mentioned technical drawbacks.
Therefore, as one aspect of the invention, the invention overcomes the defects in the prior art, and provides a metal organic framework adsorbent with a valence metal node prepared by a steam reduction method, and a preparation method and application thereof.
In order to solve the technical problems, the invention provides the following technical scheme: the metal organic framework adsorbent with the divalent metal nodes prepared by the steam reduction method comprises a metal organic framework, wherein the metal organic framework adsorbent with the divalent metal nodes comprises a metal organic framework, the metal organic framework is loaded with the divalent metal nodes, and the metal organic framework and an organic ligand containing carboxylic acid, imidazole, pyrimidine or pyridine are self-assembled to form a three-dimensional network porous structure.
The invention also aims to provide a preparation method for preparing the metal organic framework adsorption with the valence-sub metal nodes by the steam reduction method.
To solve the above technical problem, according to an aspect of the present invention, the present invention provides the following technical solutions: a preparation method for preparing a metal organic framework adsorbent with a valence metal node by a steam reduction method is characterized by comprising the following steps: the method comprises the following steps: weighing a metal organic framework material, placing the metal organic framework material in a glass bottle, then adding a reducing agent to ensure that the metal oil-valence framework material is not contacted with the reducing agent, placing the glass bottle in a reaction kettle for heating, and taking out the glass bottle after the heating is finished to obtain the metal organic framework adsorbent with the sub-valence metal nodes.
As a preferable embodiment of the method for preparing the metal-organic framework adsorbent having a divalent metal node by the steam reduction method of the present invention, wherein: the reducing agent comprises one or more of formamide, acetamide, N '-dimethylformamide and N, N' -dimethylacetamide.
As a preferable embodiment of the method for preparing the metal-organic framework adsorbent having a divalent metal node by the steam reduction method of the present invention, wherein: the reducing agent is formamide.
As a preferable embodiment of the method for preparing the metal-organic framework adsorbent having a divalent metal node by the steam reduction method of the present invention, wherein: the metal organic framework comprises one or more of PCNs, PCP or Laval-Hill series.
As a preferable embodiment of the method for preparing the metal-organic framework adsorbent having a divalent metal node by the steam reduction method of the present invention, wherein: the PCNs series metal organic framework material comprises one or more of PCN-13, PCN-14, PCN-11, PCN-22 or HKUST-1 metal organic frameworks, and the Laval-Hill series metal organic framework material comprises one or more of MIL-100, MIL-101, MIL-125, MIL-53, MIL-47, MIL-91, MIL-96, MIL-110, MIL-167, MIL-168, MIL-169 or MIL-68.
As a preferable embodiment of the method for preparing the metal-organic framework adsorbent having a divalent metal node by the steam reduction method of the present invention, wherein: the heating temperature is 200-300 ℃.
As a preferable embodiment of the method for preparing the metal-organic framework adsorbent having a divalent metal node by the steam reduction method of the present invention, wherein: the heating temperature for heating was 250 ℃.
As a preferable embodiment of the method for preparing the metal-organic framework adsorbent having a divalent metal node by the steam reduction method of the present invention, wherein: the valence metal node of the obtained metal-organic framework adsorbent with the valence metal node comprises Ti3+、V3+、Cr3+、Fe2+Or Cu+One or more of them, gold of inferior valenceThe content of the subnodes is 0.1-6 mmol/g.
The invention also aims to provide application of the steam reduction method in preparing the metal organic framework adsorption with the valence-sub metal nodes.
To solve the above technical problem, according to an aspect of the present invention, the present invention provides the following technical solutions: a steam reduction method for preparing a metal organic framework adsorbent with a valence metal node comprises the following steps: the application in automobile desulfurization, olefin and alkane separation and the application in carbon monoxide adsorption.
The method utilizes the volatilization of the reducing agent to generate steam which coordinates with the metal nodes of the metal organic framework material, thereby enhancing the oxidation-reduction reaction and reducing the metal nodes to prepare the metal organic framework adsorbent with the valence metal nodes. The synthesized metal organic framework adsorbent with the divalent metal nodes is directly used for adsorption desulfurization of fuel oil, separation of olefin and alkane and recovery of carbon monoxide, and the adsorbent is large in adsorption capacity, high in selectivity and high in adsorption separation efficiency.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
0.1g of metal node is weighed as Fe3+Putting the MIL-100 dry powder into a glass bottle, placing the glass bottle and 2mL of N, N '-dimethylformamide in an isolated manner to ensure that the MIL-100 dry powder and the N, N' -dimethylformamide are not contacted, sealing, placing the glass bottle in an oven at 250 ℃ for 10 hours, and cooling to obtain the Fe-containing powder2+Metal-organic framework adsorbents for metal nodes.
Example 2
0.1g of metal node is weighed as Fe3+Putting the MIL-100 dry powder into a glass bottle, placing the glass bottle and 2mL of formamide in an isolated manner to ensure that the MIL-100 dry powder and the formamide are not contacted, sealing the glass bottle and the formamide, placing the sealed glass bottle in a 250 ℃ oven for 10 hours, and cooling to obtain the Fe-containing powder2+Metal-organic framework adsorbents for metal nodes.
Example 3
0.1g of metal node is weighed as Fe3+The MIL-100 dry powder is put in a glass bottle and is isolated from 2mL of acetamide to ensure that the MIL-100 dry powder and the acetamide are not contacted, the sealed MIL-100 dry powder is put in a 250 ℃ oven for 10 hours, and the sealed MIL-100 dry powder is cooled to obtain the Fe2+Metal-organic framework adsorbents for metal nodes.
Example 4
0.1g of metal node is weighed as Fe3+Putting the MIL-100 dry powder into a glass bottle, placing the glass bottle and 2mL of N, N '-dimethylacetamide in an isolated manner to ensure that the MIL-100 dry powder and the N, N' -dimethylacetamide do not contact with each other, sealing the glass bottle, placing the glass bottle in an oven at 250 ℃ for 10 hours, and cooling the glass bottle to obtain the Fe-containing dry powder2+Metal-organic framework adsorbents for metal nodes.
Example 5
0.1g of metal node is weighed as Fe3+Putting the MIL-100 dry powder into a glass bottle, placing the glass bottle and 2mL of N, N '-dimethylformamide in an isolated manner to ensure that the MIL-100 dry powder and the N, N' -dimethylformamide are not contacted, sealing, placing the glass bottle in an oven at 300 ℃ for 10 hours, and cooling to obtain the Fe-containing powder2+Metal-organic framework adsorbents for metal nodes.
Example 6
0.1g of metal node is weighed as Fe3+The MIL-100 dry powder is placed in a glass bottle and is isolated from 2mL formamide to ensure that the MIL-100 dry powder and the formamide are not contactedSealing, placing in a 300 ℃ oven for 10h, and cooling to obtain Fe2+Metal-organic framework adsorbents for metal nodes.
Example 7
0.1g of metal node is weighed as Fe3+Putting the MIL-100 dry powder into a glass bottle, placing the glass bottle and 2mL of N, N '-dimethylformamide in an isolated manner to ensure that the MIL-100 dry powder and the N, N' -dimethylformamide are not contacted, sealing, placing the glass bottle in an oven at 200 ℃ for 10 hours, and cooling to obtain the Fe-containing powder2+Metal-organic framework adsorbents for metal nodes.
Example 8
0.1g of metal node is weighed as Cr6+Putting the MIL-53 dry powder into a glass bottle, placing the glass bottle and 2mL of N, N '-dimethylformamide in an isolated manner to ensure that the MIL-53 dry powder and the N, N' -dimethylformamide are not contacted, sealing, placing the glass bottle in an oven at 250 ℃ for 10 hours, and cooling to obtain the Cr-containing powder3+Metal-organic framework adsorbents for metal nodes.
Example 9
0.1g of metal node is weighed as Cr6+Putting the MIL-53 dry powder into a glass bottle, placing the glass bottle and 2mL of formamide in an isolated manner to ensure that the MIL-53 dry powder and the formamide are not contacted, sealing the glass bottle and the formamide, placing the sealed glass bottle in a 250 ℃ oven for 10 hours, and cooling the sealed glass bottle to obtain the Cr-containing powder3+Metal-organic framework adsorbents for metal nodes.
Example 10
0.1g of metal node is weighed as Cr6+Putting the MIL-53 dry powder into a glass bottle, placing the glass bottle and 2mL of acetamide in a separated way to ensure that the MIL-53 dry powder and the acetamide are not contacted, sealing the glass bottle and the acetamide, placing the sealed glass bottle in a 250 ℃ oven for 10 hours, and cooling the sealed glass bottle to obtain the Cr-containing powder3+Metal-organic framework adsorbents for metal nodes.
Example 11
0.1g of metal node is weighed as Cr6+Putting the MIL-53 dry powder into a glass bottle, placing the glass bottle and 2mL of N, N '-dimethylacetamide in an isolated manner to ensure that the MIL-53 dry powder and the N, N' -dimethylacetamide are not contacted, sealing the MIL-53 dry powder and the N, N '-dimethylacetamide, placing the MIL-53 dry powder and the N, N' -dimethylacetamide in an oven at 250 ℃ for 10 hours after sealing, and cooling to obtain3+Metal-organic framework adsorbents for metal nodes.
Example 12
0.1g of metal node is weighed as Cr6+MIL-53 dried powder of (4)Placing in a glass bottle, placing in a state of isolation from 2mL of N, N' -dimethylformamide to ensure that the two do not contact, sealing, placing in an oven at 300 ℃ for 10h, and cooling to obtain the product with Cr3+Metal-organic framework adsorbents for metal nodes.
Example 13
0.1g of metal node is weighed as Cr6+Putting the MIL-53 dry powder into a glass bottle, placing the glass bottle and 2mL of formamide in an isolated manner to ensure that the MIL-53 dry powder and the formamide are not contacted, sealing the glass bottle and the formamide, placing the sealed glass bottle in a 300 ℃ oven for 10 hours, and cooling the sealed glass bottle to obtain the Cr-containing powder3+Metal-organic framework adsorbents for metal nodes.
Example 14
0.1g of metal node is weighed as Cr6+Putting the MIL-53 dry powder into a glass bottle, placing the glass bottle and 2mL of N, N '-dimethylformamide in an isolated manner to ensure that the MIL-53 dry powder and the N, N' -dimethylformamide are not contacted, sealing, placing the glass bottle in an oven at 200 ℃ for 10 hours, and cooling to obtain the Cr-containing powder3+Metal-organic framework adsorbents for metal nodes.
Example 15
0.1g of metal node is weighed as Ti4+Putting the MIL-125 dry powder into a glass bottle, placing the glass bottle and 2mL of N, N '-dimethylformamide in a separated manner to ensure that the MIL-125 dry powder and the N, N' -dimethylformamide are not contacted, sealing, placing the glass bottle in a 250 ℃ oven for 6 hours, and cooling to obtain the metal-organic framework adsorbent with the valence metal nodes.
Example 16
0.1g of metal node is weighed as Ti4+The MIL-125 dry powder is placed in a glass bottle and isolated from 2mL of formamide to ensure that the MIL-125 dry powder and the formamide are not contacted, the glass bottle is sealed and then placed in a 250 ℃ oven for 6 hours, and the metal organic framework adsorbent with the valence metal nodes can be obtained after cooling.
Example 17
0.1g of metal node is weighed as Ti4+The MIL-125 dry powder is placed in a glass bottle and is isolated from 2mL of acetamide to ensure that the MIL-125 dry powder and the acetamide are not contacted, the sealed MIL-125 dry powder is placed in a 250 ℃ drying oven for 6 hours, and the metal organic framework adsorbent with the valence metal nodes can be obtained after cooling.
Example 18
Weighing 0.1g of goldThe subordinate node is Ti4+Putting the MIL-125 dry powder into a glass bottle, placing the glass bottle and 2mL of N, N '-dimethylacetamide in an isolated manner to ensure that the MIL-125 dry powder and the N, N' -dimethylacetamide do not contact with each other, sealing, placing the glass bottle in a 250 ℃ oven for 6 hours, and cooling to obtain the metal-organic framework adsorbent with the valence metal nodes.
Example 19
0.1g of metal node is weighed as Ti4+Putting the MIL-125 dry powder into a glass bottle, placing the glass bottle and 2mL of N, N '-dimethylformamide in an isolated manner to ensure that the MIL-125 dry powder and the N, N' -dimethylformamide are not contacted, sealing, placing the glass bottle in an oven at 300 ℃ for 6 hours, and cooling to obtain the metal-organic framework adsorbent with the valence metal nodes.
Example 20
0.1g of metal node is weighed as Ti4+The MIL-125 dry powder is placed in a glass bottle and isolated from 2mL of formamide to ensure that the MIL-125 dry powder and the formamide are not contacted, the glass bottle is sealed and then placed in a 300 ℃ oven for 6 hours, and the metal organic framework adsorbent with the valence metal nodes can be obtained after cooling.
Example 21
0.1g of metal node is weighed as Ti4+Putting the MIL-125 dry powder into a glass bottle, placing the glass bottle and 2mL of N, N '-dimethylformamide in a separated manner to ensure that the MIL-125 dry powder and the N, N' -dimethylformamide are not contacted, sealing, placing the glass bottle in an oven at 200 ℃ for 6 hours, and cooling to obtain the metal-organic framework adsorbent with the valence metal nodes.
Example 22
The content of the divalent metal nodes in the metal-organic framework adsorbent with the divalent metal nodes prepared in examples 1 to 21 was measured, and the obtained data is recorded in table 1, wherein the measuring method of the content of the divalent metal nodes is as follows:
the content of the metal in the material is measured by the obtained metal organic framework with the valence metal nodes by adopting ICP (inductively coupled plasma), the percentage content of the metal with different valence states is measured by XPS (XPS), the content of the valence metal nodes in the material can be obtained by multiplying, and the obtained data is recorded in the table 1.
TABLE 1 content of divalent metal nodes in the metal-organic framework adsorbents having the divalent metal nodes prepared in examples 1 to 19
| Examples | Sub-valent metal node (Fe)2+Or Cr3+Or Ti3+) Content (mmol/g) |
| Example 1 | 0.63 |
| Example 2 | 0.87 |
| Example 3 | 0.91 |
| Example 4 | 1.05 |
| Example 5 | 1.14 |
| Example 6 | 1.21 |
| Example 7 | 0.33 |
| Example 8 | 0.71 |
| Example 9 | 0.42 |
| Example 10 | 0.89 |
| Example 11 | 0.90 |
| Example 12 | 1.02 |
| Example 13 | 1.07 |
| Example 14 | 0.29 |
| Example 15 | 1.15 |
| Example 16 | 0.97 |
| Example 17 | 1.15 |
| Example 18 | 0.74 |
| Example 19 | 0.93 |
| Example 20 | 1.14 |
| Example 21 | 0.37 |
As can be seen from Table 1, the invention provides a processThe metal-organic framework adsorbent having a divalent metal node comprising Fe2+、Cr3+、Ti3+Three divalent metals, the reducing agents adopted by the divalent metals comprise N, N '-dimethylformamide, N' -dimethylacetamide, formamide and acetamide which can be used as the reducing agents of the invention, and the metal organic framework materials can adopt MIL-100, MIL-53, MIL-125 and the like.
The content of the divalent metal nodes of the metal-organic framework adsorbent having the divalent metal nodes obtained in examples 1 to 4 in table 1 was found to be the highest, and N, N '-dimethylacetamide was a preferred reducing agent when N, N' -dimethylacetamide was used as the reducing agent.
The content of the divalent metal nodes of the metal-organic framework adsorbents having the divalent metal nodes obtained in examples 1, 5 and 7 in table 1 was found to be higher, and the higher the heating temperature was, the higher the content of the divalent metal nodes of the metal-organic framework adsorbents having the divalent metal nodes was.
From the content of the divalent metal nodes of the metal-organic framework adsorbent having the divalent metal nodes obtained in example 14 in table 1, when the reducing agent used was N, N' -dimethylacetamide, which is a preferred reducing agent, the content of the divalent metal nodes of the metal-organic framework adsorbent having the divalent metal nodes obtained was significantly increased.
The content of the divalent metal nodes of the metal-organic framework adsorbents having the divalent metal nodes obtained in examples 1, 8 and 15 of table 1 was determined, the content of the divalent metal nodes of the metal-organic framework adsorbents having the divalent metal nodes obtained in example 15 was the highest, the metal-organic framework material was preferably MIL-125, and the divalent metal ion was preferably Ti3+。
Example 23
The metal organic framework adsorbents with the divalent metal nodes prepared in examples 1 to 7 were subjected to desulfurization experiments and gas adsorption experiments, and the measured data are recorded in table 2, where the desulfurization experiments and the gas adsorption experiments are as follows:
desulfurization experiment: and (3) measuring the desulfurization performance of the adsorbent by adopting a dynamic adsorption method. 0.1g of dry metal organic framework adsorbent with a divalent metal node is placed in a glass column, model oil with the sulfur content of 500ppm is introduced at the rate of 3mL/h, the model oil is adsorbed at normal temperature, and the sulfur content of the adsorbed model gasoline is analyzed by using a Walian chromatography VARIANP-3800.
Adsorption gas experiment: 0.05g of dry metal organic framework adsorbent with a divalent metal node is placed on an ASAP2020 full-automatic rapid specific surface area and porosity analyzer for analysis. The pretreatment of the sample is specifically that the sample is placed in a sealed bottle and treated for 6 hours at 150 ℃ under vacuum condition, then the temperature is reduced to room temperature, and nitrogen is filled into the bottle until the pressure is normal.
TABLE 2 adsorption capacities of the metal-organic frameworks having a divalent metal node prepared in examples 1 to 7
As can be seen from Table 2, the adsorption capacity is proportional to the content of the divalent metal nodes contained therein, and the higher the content of the divalent metal nodes is, the higher the adsorption capacity is.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A steam reduction method for preparing a metal organic framework adsorbent with a valence metal node is characterized in that: the metal organic framework adsorbent with the divalent metal nodes comprises a metal organic framework, the metal organic framework is loaded with the divalent metal nodes, and the metal organic framework and an organic ligand containing carboxylic acid, imidazole, pyrimidine or pyridine are self-assembled to form a three-dimensional network porous structure.
2. A steam reduction method for preparing a metal organic framework adsorbent with a valence metal node is characterized in that: the method comprises the following steps: weighing a metal organic framework material, placing the metal organic framework material in a glass bottle, then adding a reducing agent to ensure that the metal organic framework material is not in contact with the reducing agent, placing the glass bottle in a reaction kettle for heating, and taking out the glass bottle after the heating is finished to obtain the metal organic framework adsorbent with the divalent metal nodes.
3. The method for preparing a metal-organic framework adsorbent having a divalent metal node according to claim 2, characterized in that: the reducing agent comprises one or more of formamide, acetamide, N '-dimethylformamide and N, N' -dimethylacetamide.
4. The method for preparing a metal-organic stranded adsorbent having jacquard metal nodes according to claim 2 or 3, wherein: the reducing agent is formamide.
5. The method for preparing a metal-organic framework adsorbent having a divalent metal node according to claim 2, characterized in that: the metal organic framework comprises one or more of PCNs, PCPs or Laval-Hill series.
6. The method for preparing a metal-organic framework adsorbent having a divalent metal node according to claim 5, characterized in that: the PCNs series metal organic framework material comprises one or more of PCN-13, PCN-14, PCN-11, PCN-22 or HKUST-1 metal organic frameworks, and the Laval-Hill series metal organic framework material comprises one or more of MIL-100, MIL-101, MIL-125, MIL-53, MIL-47, MIL-91, MIL-96, MIL-110, MIL-167, MIL-168, MIL-169 or MIL-68.
7. The method for preparing a metal-organic framework adsorbent having a divalent metal node according to claim 2, characterized in that: the heating temperature of the heating is 200-300 ℃.
8. The method for preparing a metal-organic framework adsorbent having jacquard metal nodes according to claim 7, wherein: the heating temperature of the heating is 250 ℃.
9. The method for preparing a metal-organic framework adsorbent having a divalent metal node according to claim 2, characterized in that: the valence metal nodes of the obtained metal organic framework adsorbent with the valence metal nodes comprise Ti3+、V3+、Cr3+、Fe2+Or Cu+One or more of the above, wherein the content of the divalent metal node is 0.1-6 mmol/g.
10. The use of the steam reduction method according to claim 2 for the preparation of a metal-organic framework adsorbent having a divalent metal node, characterized in that: the metal organic framework adsorbent with the divalent metal node comprises one or more of applications in automobile desulfurization, olefin and alkane separation and carbon monoxide adsorption.
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