CN115124676B - Preparation method and application of halogen-modified covalent organic framework material - Google Patents
Preparation method and application of halogen-modified covalent organic framework material Download PDFInfo
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- CN115124676B CN115124676B CN202210866202.9A CN202210866202A CN115124676B CN 115124676 B CN115124676 B CN 115124676B CN 202210866202 A CN202210866202 A CN 202210866202A CN 115124676 B CN115124676 B CN 115124676B
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 35
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 19
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 diamine salt Chemical class 0.000 claims abstract description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- FXFTWEVIIHVHDS-UHFFFAOYSA-N 2-fluorobenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(F)=C1 FXFTWEVIIHVHDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- NGULVTOQNLILMZ-UHFFFAOYSA-N 2-bromobenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(Br)=C1 NGULVTOQNLILMZ-UHFFFAOYSA-N 0.000 claims description 2
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 claims description 2
- CAAOWHHLKPUWHW-UHFFFAOYSA-N 2-iodobenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(I)=C1 CAAOWHHLKPUWHW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 24
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005120 petroleum cracking Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 11
- 239000011148 porous material Substances 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005384 cross polarization magic-angle spinning Methods 0.000 description 1
- XYVDNBKDAAXMPG-UHFFFAOYSA-M decyl 2-(1-heptylazepan-1-ium-1-yl)acetate;hydroxide Chemical compound [OH-].CCCCCCCCCCOC(=O)C[N+]1(CCCCCCC)CCCCCC1 XYVDNBKDAAXMPG-UHFFFAOYSA-M 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000279 solid-state nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- 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
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
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- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a method for efficiently preparing a halogen-modified covalent organic framework material by using a grinding method and application thereof, belonging to the technical field of new material preparation and gas adsorption separation. Firstly, reacting halogen-containing p-phenylenediamine with p-toluenesulfonic acid to obtain diamine salt, and then reacting with 2,4, 6-trihydroxy-1, 3, 5-benzene trimethylaldehyde by a grinding method to prepare the halogen-modified covalent organic framework material. The method has simple process, short synthesis period, no need of isolating air, economy and environmental protection, and can expand production. The material has good selectivity of acetylene adsorption and separation, and has higher application potential in the fields of petroleum cracking and acetylene production.
Description
Technical Field
The invention belongs to the technical fields of preparation of new materials and gas adsorption separation, and particularly relates to a method for preparing a halogen-modified covalent organic framework material by using a grinding method and application of the covalent organic framework material.
Background
The covalent organic framework materials (COFs) have the characteristics of high specific surface area, easy structure regulation and control, uniform pore diameter, rich active adsorption sites, good chemical stability and thermal stability and the like, and have wide application in the fields of heterogeneous catalysis, gas separation, electric energy storage and the like. In recent years, the structure of COFs is highly controllable, so that the COFs becomes one of hot spot materials in the aspects of gas capture and separation, and functional modification of the framework of the COFs by using different substituent groups is a main method for controlling the structure of the COFs. Halogen has stronger electronegativity, is a widely applied functional group, has the functions of stabilizing chemical property, regulating charge, anchoring guest molecules or providing substitution sites, regulating hydrophobicity and the like, can be used for regulating the electronic structure and aperture size of COFs, and realizes the efficient adsorption separation of gas.
Currently, metal organic framework Materials (MOFs) containing highly active metal adsorption sites are a porous nanomaterial with excellent acetylene selectivity and adsorption capacity. However, MOFs are easy to hydrolyze and have the defects of insufficient stability and the like, so that the MOFs still have great difficulty in application under industrial production conditions such as petroleum cracking, acetylene preparation and the like. Compared with MOFs, the COFs is composed of light elements such as light element C, N, O, H, B, does not contain heavy metal elements, and has higher stability due to the fact that the framework structure is connected through strong covalent bonds. In addition, the structure and the pores can be orderly regulated and controlled, and the functional groups are introduced according to the target requirements to synthesize and modify the structure and the pores. However, the traditional method for synthesizing the COFs by solvent heat has the defects of harsh preparation conditions (air isolation), low synthesis efficiency (long period), poor repeatability and the like, so that the COFs material has less application in the field of acetylene adsorption separation. Therefore, a multi-strategy synthesis method which has simple process, short synthesis period, economy and environmental protection and can carry out large-scale and large-scale production is sought, and the method is an effective way for using COFs in the industrial field.
The COFs is synthesized by a solvothermal method, namely, different types of precursors and required solvents are added into a reaction container, a reaction system is converted into a vacuum environment, and then the reaction is carried out at a certain temperature and pressure, so that the required COFs product is finally obtained. The method has harsh experimental conditions, needs to ensure the vacuum environment of a reaction system, has long reaction period, generally needs to be carried out for 72 hours, and needs to regulate and control the solvent proportion, so that the experimental result has poor repeatability and has great influence on the final synthesis efficiency. In contrast, the COFs is synthesized by mechanical grinding, so that the precursors are fully and uniformly mixed, and a large amount of solvent is not needed. Therefore, the grinding method has the advantages of simple operation, economy, environmental protection, short reaction period and the like, and provides a new thought and a new method for the synthesis of COFs.
The halogen atom modified COFs synthesized by the grinding method has good adsorption selectivity and adsorption quantity to acetylene, and provides an important preparation thought for industrial application of the COFs in the field of acetylene adsorption.
Disclosure of Invention
The invention aims to provide a novel halogen-containing covalent organic framework material.
Another object of the invention is to provide a simple, fast, economical and environment-friendly preparation method of the covalent organic framework material.
It is also an object of the present invention to provide a gas adsorption application of the covalent organic framework material.
The invention adopts the following technical scheme that on the one hand, the invention provides a grinding preparation method of a covalent organic framework gas adsorption material, which is characterized by comprising the following steps of: the method comprises the following steps:
(1) Reacting the halogen-containing p-phenylenediamine with p-toluenesulfonic acid to form diamine salt crystals;
(2) Uniformly mixing diamine salt crystals and 2,4, 6-trihydroxy-1, 3, 5-benzene trimethyl aldehyde, grinding, dripping a trace of deionized water in the grinding process to obtain a mud-like substance, and heating at 80-100 ℃ to obtain red powder;
(3) And after the reaction is finished, washing the product by adopting a Soxhlet extraction method, and then carrying out vacuum drying to obtain the covalent organic framework material modified by halogen atoms.
In a preferred embodiment, the halogen-containing p-phenylenediamine is one of 2-fluoro-1, 4-phenylenediamine, 2-chloro-1, 4-phenylenediamine, 2-bromo-1, 4-phenylenediamine, 2-iodo-1, 4-phenylenediamine.
In a preferred technical embodiment, the 2,4, 6-trihydroxy-1, 3, 5-benzene tricaldehyde in the step (2) is used in an amount of 63mg to 1000mg, and the molar ratio of the 2,4, 6-trihydroxy-1, 3, 5-benzene tricaldehyde to the halogen-containing p-phenylenediamine to the p-toluenesulfonic acid is 1:1.5:5 to 10; the ratio of the 2,4, 6-trihydroxy-1, 3, 5-benzaldehyde to the dropwise added deionized water is 63mg: 50-100 mu L.
In a preferred embodiment, the grinding time in step (2) is 20-30 min, and grinding is continued for 10-20 min after adding the liquid.
In a preferred embodiment, the solvent used in the washing in step (3) is deionized water, N-dimethylformamide, acetone and methanol, and the number of washing times is 3 to 5.
In a preferred technical embodiment, the process parameters of the vacuum drying in the step (3) are that the drying temperature is 100-150 ℃ and the time is 12-48 h.
In another aspect, the present invention provides a covalent organic framework material (designated as TpPa-F) synthesized by milling 2,4, 6-trihydroxy-1, 3, 5-benzenetricaldehyde after formation of diamine salt crystals from 2-fluoro-1, 4-benzenediamine reacted with p-toluenesulfonic acid.
In yet another aspect, the covalent organic framework material of the present invention is used for the adsorptive separation of acetylene gas.
The preparation and application of the covalent organic framework material TpPa-F for gas adsorption provided by the invention have the following advantages:
(1) The method for synthesizing the COFs by utilizing the grinding method is simple and quick, has a short synthesis period compared with a solvothermal method, does not need to add any organic solvent, and is economical and environment-friendly.
(2) The COFs prepared by the method is mainly used for adsorbing acetylene gas, and halogen atoms are introduced into the COFs to increase active sites for adsorbing acetylene, so that the selectivity and the adsorption quantity for acetylene are enhanced.
(3) The COFs prepared by the method has higher stability, provides a new material for industrial application of adsorption separation of acetylene gas, and has higher application potential in the fields of petroleum cracking and acetylene production.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a schematic representation of the synthesis of a covalent organic framework material of the present invention;
FIG. 2 is an XRD spectrum of a covalent organic framework material of the present invention;
FIG. 3 is an SEM image of a covalent organic framework material of the present invention;
FIG. 4 is a solid state nuclear magnetic resonance spectrum of a covalent organic framework material of the present invention;
FIG. 5 is an N-gram of a covalent organic framework material of the present invention 2 Adsorption-desorption curve and pore size distribution curve;
FIG. 6 is an acetylene adsorption curve for a covalent organic framework material of the present invention.
Detailed Description
The invention is further illustrated below in connection with specific examples, but the invention is not limited to these examples only.
Example 1: the preparation of the covalent organic framework material TpPa-F
This example is the preparation of covalent organic framework material TpPa-F, as shown in FIG. 1, and the specific preparation method is as follows:
reacting 2-fluoro-1, 4-phenylenediamine with p-toluenesulfonic acid to form diamine salt crystals; grinding diamine salt crystal for 20min, adding 2,4, 6-trihydroxy-1, 3, 5-benzene trimethyl aldehyde, grinding for 20min, dripping 100 mu L deionized water in the grinding process to obtain mud, and heating at 90 ℃ to obtain red powder; after the reaction is finished, a Soxhlet extraction method is adopted, deionized water, N-dimethylformamide, acetone and methanol are used for washing the product, and the product is placed into a vacuum oven for vacuum drying at 120 ℃ for 24 hours, so that the covalent organic framework material TpPa-F modified by fluorine atoms is obtained.
Example 2: structural characterization of covalent organic framework material TpPa-F of the invention
This example is a structural characterization of the covalent organic framework material TpPa-F, and is specifically as follows:
XRD spectrum
The X-ray diffraction (XRD) pattern of the covalent organic framework material TpPa-F is shown in figure 2, the scanning range is from 3 DEG to 40 DEG, and the scanning speed is 5 DEG min -1 The covalent organic framework material TpPa-F has diffraction characteristic peaks at 2 theta of 4.68 degrees, 8.06 degrees, 9.30 degrees, 12.30 degrees and 26.50 degrees, and is basically similar to the report of the literature, thus indicating that the TpPa-F is successfully synthesized.
Sem image of
Analyzing the morphology and structure of the covalent organic framework material TpPa-F by adopting a scanning electron microscope: as can be seen from fig. 3, the covalent organic framework material TpPa-F exhibits a block-like structure of clusters.
3. Solid nuclear magnetic resonance spectrogram
Covalent organic framework materials TpPa-F 13 The C cross-polarized magic angle spinning (CP/MAS) nmr spectrum is shown in fig. 4, further confirming the presence of c=n, indicating covalent organic framework material TpPSuccessful synthesis of a-F.
Example 3: the invention relates to a gas adsorption performance test of a covalent organic framework material TpPa-F
1.N 2 Adsorption-desorption curve and pore size distribution curve
The specific surface area and pore volume of the covalent organic framework material TpPa-F were determined using a nitrogen adsorption BET specific surface area determinator. The measured results were: the covalent organic framework material TpPa-F has a specific surface area of 1048 (m 2 g -1 ) The pore size isN of which is 2 The adsorption-desorption curves are shown in fig. 5, demonstrating the microporous structure of the material.
2. Acetylene adsorption curve
The adsorption curve of the covalent organic framework material TpPa-F to acetylene is shown in FIG. 6, and is combined with CO 2 Compared with the method, at two different temperatures of 273K and 298K, the adsorption quantity of TpPa-F to acetylene is obviously increased, which shows that TpPa-F has good adsorption selectivity and adsorption quantity to acetylene.
Claims (7)
1. A method for preparing a halogen-modified covalent organic framework material, which is characterized in that: the method specifically comprises the following steps:
(1) Reacting the halogen-containing p-phenylenediamine with p-toluenesulfonic acid to form diamine salt crystals;
(2) Uniformly mixing diamine salt crystals and 2,4, 6-trihydroxy-1, 3, 5-benzene trimethyl aldehyde, grinding, dripping a trace of deionized water in the grinding process to obtain a mud-like substance, and heating at 80-100 ℃ to obtain red powder;
(3) After the reaction is finished, washing the product by adopting a Soxhlet extraction method, and then carrying out vacuum drying to obtain the covalent organic framework material modified by halogen atoms.
2. The method according to claim 1, wherein the halogen-containing paraphenylenediamine is one of 2-fluoro-1, 4-phenylenediamine, 2-chloro-1, 4-phenylenediamine, 2-bromo-1, 4-phenylenediamine, and 2-iodo-1, 4-phenylenediamine.
3. The preparation method according to claim 1, wherein the 2,4, 6-trihydroxy-1, 3, 5-benzene tricaldehyde is used in the step (2) in an amount of 63mg to 1000mg, and the molar ratio of the 2,4, 6-trihydroxy-1, 3, 5-benzene tricaldehyde to the halogen-containing p-phenylenediamine to the p-toluene sulfonic acid is 1:1.5:5 to 10; the ratio of the 2,4, 6-trihydroxy-1, 3, 5-benzaldehyde to the dropwise added deionized water is 63mg: 50-100 mu L.
4. The method according to claim 1, wherein the grinding time in the step (2) is 20 to 30 minutes, and the grinding is continued for 10 to 20 minutes after the liquid is added.
5. The method according to claim 1, wherein the solvent used for the washing in the step (3) is deionized water, N-dimethylformamide, acetone, and methanol, and the number of washing times is 3 to 5.
6. The method of claim 1, wherein the vacuum drying process parameters in step (3) are: the drying temperature is 100-150 ℃ and the drying time is 12-48 h.
7. Use of a halogen-containing covalent organic framework material according to any one of claims 1-2 for the capture and separation of acetylene gas.
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