CN116020079A - Catalytic hydrodechlorination process - Google Patents
Catalytic hydrodechlorination process Download PDFInfo
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- CN116020079A CN116020079A CN202111258076.0A CN202111258076A CN116020079A CN 116020079 A CN116020079 A CN 116020079A CN 202111258076 A CN202111258076 A CN 202111258076A CN 116020079 A CN116020079 A CN 116020079A
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- nickel
- nickel carbide
- nanocomposite
- oxygen
- catalyst
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- 238000000034 method Methods 0.000 title claims abstract description 60
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 316
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 157
- 239000002114 nanocomposite Substances 0.000 claims abstract description 88
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 47
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- 239000011159 matrix material Substances 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000460 chlorine Substances 0.000 claims abstract description 24
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000011258 core-shell material Substances 0.000 claims abstract description 15
- 238000000026 X-ray photoelectron spectrum Methods 0.000 claims abstract description 12
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 12
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 12
- 238000001228 spectrum Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 29
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 26
- 229910052783 alkali metal Inorganic materials 0.000 claims description 25
- -1 alkali metal salt Chemical class 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 22
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 238000000197 pyrolysis Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 7
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
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- 150000001298 alcohols Chemical class 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 150000003071 polychlorinated biphenyls Chemical group 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 238000007580 dry-mixing Methods 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 claims description 2
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 claims description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 235000011087 fumaric acid Nutrition 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 47
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
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- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalysis, and discloses a catalytic hydrodechlorination method. The method comprises the following steps: in the presence of a catalyst, contacting a chlorine-containing organic compound with hydrogen to perform catalytic hydrogenation dechlorination reaction; the catalyst is nickel carbide nano composite material, and in a C1s X ray photoelectron spectrum of the nickel carbide nano composite material, a spectrum peak exists in a binding energy range of 287eV-290 eV; the nickel carbide nanocomposite comprises a carbon matrix doped with oxygen and nickel carbide nanoparticles loaded on the carbon matrix; and/or the nickel carbide nanocomposite contains a core-shell structure with a shell layer and an inner core, wherein the shell layer is a carbon matrix doped with oxygen, and the inner core is nickel carbide nano particles. The method has high hydrodechlorination performance, can avoid the use of high-cost noble metal catalyst, and does not need to use the pH which is easy to generate extremely toxicity in the preparation process 3 The method is more environment-friendly, and has great industrial value in the field of catalytic hydrogenation dechlorination.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a catalytic hydrodechlorination method.
Background
Chlorinated organic compounds are important chemical raw materials and widely used as intermediates, solvents, pesticides and the like of chemical synthetic products. However, part of chlorinated organic compounds are very stable in the environment and have high toxicity, such as polychlorinated biphenyl (PCD), bis-p-chlorophenyl trichloroethane (DDT), hexachlorocyclohexane (hexahexa-hexa), and the like, and high residues can be detected in water bodies, sediment and organisms until the production is stopped, so that the environmental hazard is high. Therefore, pollution control on chlorinated organic compounds is an important research direction in the field of environmental protection, and is widely paid attention to researchers.
The treatment method of the chlorinated organic compound mainly comprises active carbon adsorption, chemical oxidation, catalytic hydrogenation dechlorination and the like. Wherein, the catalytic hydrodechlorination can convert chlorine substituent groups into hydrogen chloride and absorb the hydrogen chloride by alkali, so that the toxicity of chlorinated organic matters is reduced, and the method is considered as a simple, effective and safe dechlorination method. In addition, halogen can be used as an effective protective functional group in the functional group conversion of organic molecules. For example, double bonds can be generated by reacting after the double bonds are protected by chlorine or bromine simple substance addition, and then removing halogen to regenerate double bonds. Therefore, the development of selective hydrodechlorination catalysts is also of great importance for the synthesis of fine chemicals.
CN103691464a discloses a palladium/phosphoric acid modified alumina catalyst for low-temperature catalytic hydrogenation elimination of chlorophenols in water and a preparation method thereof, and the method has higher cost due to the use of noble metal Pd. In addition, the preparation process of the catalyst uses a surfactant, an acid, an alkali and a reducing agent, and the steps are complicated.
CN105344368A discloses the preparation and use of a transition metal phosphide for hydrodechlorination reaction, although cost is significantly advantageous over noble metal catalysts, such catalysts are prone to highly toxic PH during the preparation process 3 。
Therefore, the catalyst which is simple in preparation, low in cost, easy to amplify and high in hydrodechlorination performance is developed and applied to the field of catalytic hydrodechlorination, and has important significance for pollution control of chlorinated organic compounds and synthesis of fine chemicals.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a catalytic hydrodechlorination method which is low in cost, environment-friendly and good in hydrodechlorination performance.
In order to achieve the above object, the present invention provides a catalytic hydrodechlorination process comprising: in the presence of a catalyst, contacting a chlorine-containing organic compound with hydrogen to perform catalytic hydrogenation dechlorination reaction; the catalyst is a nickel carbide nanocomposite, and in a C1s X ray photoelectron spectrum of the nickel carbide nanocomposite, a spectrum peak exists in a binding energy range of 287eV-290 eV;
wherein the nickel carbide nanocomposite comprises an oxygen-doped carbon matrix and nickel carbide nanoparticles supported on the carbon matrix; and/or
The nickel carbide nanocomposite comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a carbon matrix doped with oxygen, and the inner core is nickel carbide nano particles.
According to the technical scheme, the nickel carbide nano composite material is used as a catalyst, and in a C1s X ray photoelectron spectrum of the composite material, a spectrum peak exists in a binding energy range of 287eV-290 eV; the complexThe composite material comprises a carbon matrix doped with oxygen and nickel carbide nano-particles supported on the carbon matrix; and/or the nickel carbide nanocomposite contains a core-shell structure with a shell layer and an inner core, wherein the shell layer is a carbon matrix doped with oxygen, and the inner core is nickel carbide nano particles. The nickel carbide nanocomposite is applied to the catalytic hydrodechlorination reaction of chlorine-containing organic compounds, has higher hydrodechlorination performance, can avoid the use of high-cost noble metal catalysts, and does not need to use highly toxic PH in the preparation process 3 The method provided by the invention is more environment-friendly. In addition, the nickel carbide nanocomposite used by the method provided by the invention is simple in preparation, low in cost and easy to amplify. Has great industrial value in the field of catalytic hydrogenation dechlorination.
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of the nickel carbide nanocomposite obtained in preparation examples 1, 2 and 3;
FIG. 2 is an X-ray photoelectron spectrum of the nickel carbide nanocomposite obtained in preparation examples 1, 2, and 3;
FIG. 3 is a transmission electron microscope image of the nickel carbide nanocomposite obtained in preparation example 1;
FIG. 4 is a transmission electron microscope image of the nickel carbide nanocomposite obtained in preparation example 2.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the term "oxygen" doped with oxygen "refers to an oxygen element, wherein" oxygen content "of the nickel carbide nanocomposite refers to a content of an oxygen element, specifically, an oxygen element in various forms contained in a carbon matrix formed during the preparation of the nickel carbide nanocomposite, and the" oxygen content "is a total content of all forms of oxygen elements.
In the present invention, the term "carbon matrix" means a carbon structure in which a layered structure is clearly observed under a high resolution transmission electron microscope, not an amorphous structure.
In the invention, the term 'core-shell structure' refers to a structure that a shell layer is an oxygen-doped carbon matrix and a core is a nickel carbide nanoparticle, and the core-shell structure formed by coating the oxygen-doped carbon matrix with the nickel carbide nanoparticle is spherical or spheroid.
The invention provides a catalytic hydrodechlorination method, which comprises the following steps: in the presence of a catalyst, contacting a chlorine-containing organic compound with hydrogen to perform catalytic hydrogenation dechlorination reaction; the catalyst is a nickel carbide nanocomposite, and in a C1s X ray photoelectron spectrum of the nickel carbide nanocomposite, a spectrum peak exists in a binding energy range of 287eV-290 eV;
wherein the nickel carbide nanocomposite comprises an oxygen-doped carbon matrix and nickel carbide nanoparticles supported on the carbon matrix; and/or
The nickel carbide nanocomposite comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a carbon matrix doped with oxygen, and the inner core is nickel carbide nano particles.
The inventors of the present invention have found during the course of research that the oxygen doped carbon matrix of the nickel carbide nanocomposite may act synergistically with nickel carbide nanoparticles supported thereon and/or nickel carbide nanoparticles coated therewith. Because the oxygen-doped carbon matrix has carboxyl groups, in the C1s X ray photoelectron spectrum of the nickel carbide nanocomposite, a spectrum peak exists in the binding energy range of 287eV-290eV, and the spectrum peak is different from that of the existing carbon-coated nickel carbide material, so that the nickel carbide nanocomposite is substantially different from other carbon-coated nickel carbide materials in microstructure. In addition, the oxygen-containing functional group can also influence the center electron density of the nickel carbide and the carbon shell layer, thereby facilitating the adsorption of the chloro-functional groupAnd hydrodechlorination reaction. Therefore, the nickel carbide nanocomposite with the specific microstructure is particularly suitable for being used as a catalyst for catalytic hydrodechlorination of chlorine-containing organic compounds, has higher hydrodechlorination performance, can avoid using a high-cost noble metal catalyst, and does not need to use a catalyst which is easy to generate extremely toxic PH in the preparation process 3 The nickel carbide nano composite material is used as a catalyst, so that the metal phosphide catalyst is more environment-friendly. In addition, the nickel carbide nano particles in the nickel carbide nano composite material have reasonable particle size, and the catalytic hydrogenation dechlorination activity of the nickel carbide nano composite material can be further improved by matching with the carbon matrix shell layer doped with oxygen.
According to some embodiments of the present invention, the nickel carbide nanocomposite may be a nickel carbide nanocomposite known in the art, to which the present invention is not particularly limited. The method of preparing the nickel carbide nanocomposite according to the present invention is not particularly limited, and the nickel carbide nanocomposite may be prepared by any method known in the art. For example, a nickel carbide nanocomposite comprising an oxygen doped carbon matrix and nickel carbide nanoparticles supported on the carbon matrix, with a spectral peak in the binding energy range 287eV-290eV in the C1s X ray photoelectron spectrum, can be prepared as disclosed in CN112705234 a.
According to some embodiments of the invention, the elements of the material surface are detected by X-ray photoelectron spectroscopy (XPS). The X-ray photoelectron spectroscopy analyzer used was an ESCALab220i-XL type radiation electron spectroscopy manufactured by VG scientific company and equipped with Avantage V5.926 software, and the X-ray photoelectron spectroscopy analysis test conditions were: the excitation source is monochromized A1K alpha X-ray with power of 330W and basic vacuum of 3X 10 during analysis and test -9 mbar。
According to some embodiments of the invention, the nickel carbide nanocomposite comprises an oxygen doped carbon matrix and nickel carbide nanoparticles supported on the carbon matrix; and/or the nickel carbide nanocomposite comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a carbon matrix doped with oxygen, and the inner core is nickel carbide nano particles. In order to further improve the catalytic hydrodechlorination performance of the nickel carbide nanocomposite for chlorine-containing organic compounds, preferably, the nickel carbide nanocomposite comprises a core-shell structure having a shell layer and an inner core, wherein the shell layer is an oxygen-doped carbon matrix, and the inner core is nickel carbide nanoparticles.
According to some embodiments of the invention, preferably, the nickel carbide nanocomposite surface has a molar content of carbon of 60-80%, preferably 64-76%, as measured by X-ray photoelectron spectroscopy; the molar content of oxygen is 17-27%, preferably 20-26%; the molar content of nickel is 3-11%, preferably 4-10%.
According to some embodiments of the invention, the nickel carbide nanoparticles preferably have an average particle size of 8-30nm, preferably 10-25nm.
According to some embodiments of the invention, the surface topography of the catalyst is characterized by High Resolution Transmission Electron Microscopy (HRTEM). The model of the adopted high-resolution transmission electron microscope is JEM-2100 (Japanese electronic Co., ltd.) and the testing conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200kV. The average particle size of the nickel carbide nano particles is measured by an electron microscope picture.
In order to further enhance the catalytic hydrodechlorination properties of the nickel carbide nanocomposite with respect to chlorine-containing organic compounds, according to a preferred embodiment of the present disclosure, a method for preparing the nickel carbide nanocomposite comprises the steps of:
(1) Mixing a nickel source, an organic carboxylic acid containing no nitrogen and an alkali metal salt to obtain a precursor;
(2) Pyrolyzing the precursor under inert atmosphere; wherein the pyrolysis temperature is 200-400 ℃.
In early studies, the inventors found that carbon-coated nickel nanocomposites could be obtained by a method of precursor pyrolysis, for example, CN109309213a discloses a carbon-coated nickel nanocomposite and a method of preparing the same, wherein the precursor constant temperature section temperature is 425-800 ℃. In fact, the prior art pyrolysis process for preparing carbon-coated nickel nanoparticles is also typically performed at the aforementioned temperature ranges. However, the inventors of the present invention have surprisingly found during the course of the study that green, simple, low cost preparation of novel oxygen doped nickel carbide nanocomposite materials can be achieved by mixing a nickel source, an organic carboxylic acid free of nitrogen and an alkali metal salt, and pyrolysing the resulting precursor under an inert atmosphere at a temperature of 200-400 ℃. Compared with the prior art, the method does not need to use an organic solvent and a surfactant, and does not need to introduce combustible reducing gases such as hydrogen and the like in the pyrolysis process, so that the preparation of the nickel carbide breaks through the defects of high energy consumption, complex process and the like in the traditional method, and the method brings possibility to industrial mass production and has important significance.
According to some embodiments of the present invention, preferably, the nickel carbide nanocomposite obtained by the method contains a core-shell structure having a shell layer and an inner core, wherein the shell layer is an oxygen-doped carbon matrix, and the inner core is nickel carbide nanoparticles; in the C1s X ray photoelectron spectrum of the nickel carbide nanocomposite, a spectrum peak exists in the binding energy range of 287eV-290 eV.
According to some embodiments of the invention, in step (2), the pyrolysis is carried out at a temperature of 200-400 ℃, preferably 250-350 ℃, more preferably 300-345 ℃, even more preferably 310-340 ℃.
According to some embodiments of the invention, preferably, in step (1), the mixing comprises:
providing a first solution containing the nickel source, a nitrogen-free organic carboxylic acid and an alkali metal salt, and then removing the first solvent from the first solution to obtain a precursor; or (b)
Providing a second solution containing the nickel source and an organic carboxylic acid containing no nitrogen, removing the second solvent in the second solution, and dry-mixing the obtained solid with the alkali metal salt to obtain the precursor.
According to a preferred embodiment of the present invention, in step (1), the mixing comprises:
providing a first solution containing the nickel source, a nitrogen-free organic carboxylic acid and an alkali metal salt, and then removing the first solvent from the first solution to obtain a precursor. The manner of forming the first solution is not particularly limited, and the first solution may be formed by heating, preferably by heating and stirring. The temperature of the heating and the rate of stirring are also not particularly limited as long as the first solution can be formed.
According to some embodiments of the present invention, preferably, the nickel source, the nitrogen-free organic carboxylic acid and the alkali metal salt are dissolved in a first solvent to form the first solution. The type of the first solvent is not particularly limited, provided that the first solution can be formed. Preferably, the first solvent is selected from one or more of water, alcohols and N, N-dimethylformamide, preferably water; the amount of the first solvent is not particularly limited, and the first solvent may be formed. The first solvent in the first solution may be removed by direct evaporation at a temperature and by a process known to those skilled in the art, for example, by heat evaporation.
According to another preferred embodiment of the present invention, in step (1), the mixing includes:
providing a second solution containing the nickel source and an organic carboxylic acid containing no nitrogen, removing the second solvent in the second solution, and dry-mixing the obtained solid with the alkali metal salt to obtain the precursor. The manner of forming the second solution is not particularly limited, and the second solution may be formed by heating, preferably by heating and stirring. The temperature of the heating and the rate of stirring are also not particularly limited as long as the second solution can be formed.
According to some embodiments of the present invention, preferably, a nickel source and an organic carboxylic acid free of nitrogen are dissolved in a second solvent to form the second solution, and after removing the second solvent from the second solution, the resulting solid is dry blended with the alkali metal salt to obtain the precursor. The type of the second solvent is not particularly limited, as long as the second solvent can be formed. Preferably, the second solvent is selected from one or more of water, alcohols and N, N-dimethylformamide, preferably water; the amount of the second solvent is not particularly limited, and the second solvent may be formed. The second solvent in the second solution may be removed by direct evaporation at a temperature and by a process known to those skilled in the art, for example, by heat evaporation.
According to some embodiments of the invention, preferably, in the dry blending step, the molar ratio of nickel to alkali metal salt in the solid is 1:0.01-20, preferably 1:0.02-0.5.
According to some embodiments of the invention, the nickel source is preferably selected from one or more of nickel hydroxide, nickel carbonate, basic nickel carbonate and nickel acetate, preferably basic nickel carbonate.
According to some embodiments of the invention, preferably, the non-nitrogen containing organic carboxylic acid is selected from one or more of citric acid, maleic acid, fumaric acid, succinic acid, tartaric acid, malic acid, gluconic acid and trimesic acid, preferably citric acid.
According to some embodiments of the invention, preferably, the alkali metal salt is selected from one or more of sodium chloride, potassium sulfate, sodium carbonate and potassium carbonate, preferably sodium chloride and/or potassium chloride. It is well known to those skilled in the art that the preparation of nickel carbide is relatively difficult, and generally requires strict requirements on the required reaction conditions, particularly the reaction temperature, and accurate control is required to obtain the nickel carbide. The inventors of the present invention have found that by adding a certain amount of alkali metal salt as a stabilizer, a stable nickel carbide phase is more advantageously formed, and that a nickel carbide nanocomposite can be formed in a relatively wide reaction temperature range.
According to some embodiments of the invention, preferably, the molar ratio of the nickel source, the nitrogen-free organic carboxylic acid and the alkali metal salt is 1, calculated as carboxyl group: 2-8:0.01-20, preferably 1:2.5-7.5:0.02-1, more preferably 1:3-7:0.02 to 0.5, more preferably 1:3-6:0.02 to 0.1, more preferably 1:3-5:0.02-0.05. The inventors of the present invention have surprisingly found during the course of the study that the regulation of the particle size of nickel carbide nanoparticles in nickel carbide nanocomposites can be achieved by regulating the molar ratio of alkali metal salts. By accurately regulating and controlling the proportion of alkali metal salt, the formation of nickel carbide nano particles is ensured, and the particle size is prevented from being too large, so that the catalytic hydrogenation dechlorination activity of the nickel carbide nano composite material is further improved.
According to some embodiments of the invention, preferably, in step (2), the pyrolyzing comprises: heating the precursor to the pyrolysis temperature in an inert atmosphere, and keeping the temperature constant;
preferably, the heating rate is 0.2-20deg.C/min, preferably 0.5-10deg.C/min, more preferably 1-10deg.C/min;
preferably, the pyrolysis temperature is 250-350 ℃, preferably 300-345 ℃, more preferably 310-340 ℃;
preferably, the constant temperature is maintained for a period of 10 to 600 minutes, preferably 20 to 300 minutes, more preferably 50 to 200 minutes.
More preferably, according to some embodiments of the invention, the pyrolysis comprises: under an inert atmosphere, the temperature is raised to 250-350 ℃ at a rate of 0.2-10 ℃/min, preferably 0.5-5 ℃/min, more preferably 1-5 ℃/min, and then raised to the pyrolysis temperature at a rate of 0.2-10 ℃/min, preferably 0.5-5 ℃/min, more preferably 1-5 ℃/min, and kept constant.
According to some embodiments of the present invention, preferably, the method of preparing the nickel carbide nanocomposite further comprises treating the pyrolyzed product with water to remove soluble substances that may be contained in the product. More preferably, the post-pyrolysis product is treated with a water wash followed by a drying step to remove excess moisture.
According to a particularly preferred embodiment of the present invention, the method for preparing the nickel carbide nanocomposite comprises the steps of:
(S1) mixing a nickel source, an organic carboxylic acid containing no nitrogen and an alkali metal salt to obtain a precursor; wherein the molar ratio of the nickel source, the nitrogen-free organic carboxylic acid and the alkali metal salt is 1, calculated as carboxyl group: 3-7:0.02-0.5;
(S2) pyrolyzing the precursor under an inert atmosphere; wherein the pyrolysis temperature is 200-400 ℃.
The method is particularly beneficial to preparing the nickel carbide nanocomposite which comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a carbon matrix doped with oxygen, the inner core is nickel carbide nano particles, and a spectrum peak exists in a binding energy range of 287eV-290eV in a C1s X ray photoelectron spectrum.
According to some embodiments of the invention, the nickel carbide nanocomposite is prepared by the method, the preparation process is simple, the cost is low, the utilization rate of nickel in the precursor preparation process can reach 100%, and no waste water containing heavy metals is generated.
According to some embodiments of the invention, the catalytic hydrodechlorination process comprises: in the presence of a catalyst, the chlorine-containing organic compound is contacted with hydrogen to carry out catalytic hydrogenation dechlorination reaction. Preferably, the chlorine-containing organic compound is contacted with hydrogen in the presence of a catalyst and a third solvent. The preferred embodiments described above facilitate the adsorption of chlorinated functional groups and the hydrodechlorination reaction.
According to some embodiments of the invention, preferably, the third solvent is selected from one or more of alcohols, ethers, alkanes, and water; more preferably, the third solvent further contains a neutralizing agent, which may be a basic and/or strong alkali weak acid salt conventional in the art, to neutralize HCl product of the hydrodechlorination reaction. Preferably, the neutralizing agent is selected from at least one of triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. Further preferably, the molar ratio of the neutralizing agent to chlorine in the reactant is 1-3:1.
according to some embodiments of the invention, the concentration of the chlorine-containing organic compound is preferably 10-100000mg/L, preferably 20-20000mg/L. Wherein the concentration is the concentration of the chlorine-containing organic compound in the third solvent.
According to some embodiments of the invention, preferably, the chlorine-containing organic compound is selected from one or more of chlorobenzene, dichlorobenzene, trichlorobenzene, chlorophenol, dichlorophenol, trichlorophenol, polychlorinated biphenyl; preferably chlorobenzene and/or p-chlorophenol.
According to some embodiments of the invention, preferably, the mass ratio of the catalyst to the chlorine-containing organic compound is 1:1-100, preferably 1:1-50.
According to some embodiments of the invention, preferably, the conditions of the catalytic hydrodechlorination reaction include: the pressure is 0.5-4MPa, preferably 1-3MPa; the temperature is 60-250deg.C, preferably 80-200deg.C. Wherein the pressure is a hydrogen partial pressure.
According to some embodiments of the invention, the method uses nickel carbide nanocomposite as catalyst, and the composite has a C1s X ray photoelectron spectrum with a spectral peak in the binding energy range of 287eV-290 eV; the composite material comprises a carbon matrix doped with oxygen and nickel carbide nano-particles loaded on the carbon matrix; and/or the nickel carbide nanocomposite contains a core-shell structure with a shell layer and an inner core, wherein the shell layer is a carbon matrix doped with oxygen, and the inner core is nickel carbide nano particles. The nickel carbide nanocomposite is applied to the catalytic hydrodechlorination reaction of chlorine-containing organic compounds, has higher hydrodechlorination performance, can avoid the use of high-cost noble metal catalysts, and does not need to use highly toxic PH in the preparation process 3 Compared with the existing hydrodechlorination method, the method provided by the invention is more environment-friendly. In addition, the nickel carbide nanocomposite used by the method provided by the invention is simple in preparation, low in cost and easy to amplify. Has great industrial value in the field of catalytic hydrogenation dechlorination.
The present invention will be described in detail by examples. In the following examples and comparative examples:
information such as the composition of the material, the structure or morphology of atoms or molecules within the material, and the like is obtained by XRD. The XRD diffractometer is XRD-6000 type X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are as follows: cu target, ka radiation (wavelength λ=0.154 nm), tube voltage 40kV, tube current 200mA, scan speed 10 ° (2θ)/min.
The surface topography of the material was characterized by High Resolution Transmission Electron Microscopy (HRTEM). The model of the adopted high-resolution transmission electron microscope is JEM-2100 (Japanese electronic Co., ltd.) and the testing conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200kV. The particle size of the nano particles in the sample is measured by an electron microscope picture.
The elements of the material surface were detected by X-ray photoelectron spectroscopy (XPS). The X-ray photoelectron spectroscopy analyzer used was an ESCALab220i-XL type radiation electron spectroscopy manufactured by VG scientific company and equipped with Avantage V5.926 software, and the X-ray photoelectron spectroscopy analysis test conditions were: the excitation source is monochromized A1K alpha X-ray with power of 330W and basic vacuum of 3X 10 during analysis and test -9 mbar。
The conversion of the reactants and the selectivity of the desired product were calculated by the following formula:
conversion = (mass of reacted reactant/mass of added reactant) ×100%
Preparation examples 1-3 for illustrating the nickel carbide nanocomposite of the present invention and a method for preparing the same
Preparation example 1
(1) 10.51g (50 mmol) of citric acid monohydrate, 7.28g (50 mmol) of basic nickel carbonate and 0.058g (1 mmol) of sodium chloride are weighed into 100mL of deionized water, the mixture is stirred at 110 ℃ to obtain a uniform solution, the uniform solution is continuously heated and evaporated to dryness, and the obtained solid is ground to obtain a precursor.
(2) And (2) placing 8g of the precursor obtained in the step (1) in a porcelain boat, placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen, heating to 250 ℃ at a speed of 5 ℃/min, heating to 340 ℃ at a speed of 1 ℃/min, keeping the temperature for 150min, stopping heating, and cooling to room temperature under a nitrogen atmosphere to obtain a pyrolysis product.
(3) Transferring the pyrolysis product obtained in the step (2) into a flask, adding 50mL of deionized water, stirring at 70 ℃ for 30min, performing suction filtration, and drying a filter cake at 110 ℃ to obtain the nickel carbide nanocomposite.
Preparation example 2
The procedure of preparation 1 was followed except that in step (1), the amount of sodium chloride added was 0.292g (5 mmol), to obtain a nickel carbide nanocomposite.
Preparation example 3
The procedure of preparation 1 was followed except that in step (1), the amount of sodium chloride added was 1.461g (25 mmol), to obtain a nickel carbide nanocomposite.
Characterization of materials:
fig. 1 (a), 1 (b) and 1 (c) are X-ray diffraction patterns of the nickel carbide nanocomposite materials prepared in preparation examples 1, 2 and 3, respectively. As can be seen from fig. 1, the nickel carbide nanocomposites prepared in preparation examples 1, 2 and 3 all have diffraction peaks at 2θ=39.3°, 41.6 °, 44.7 °, 58.6 °, 71.2 ° and 78.1 °, corresponding to the diffraction peaks of typical nickel carbide materials. The average particle diameters of the nickel carbide nanoparticles in the nickel carbide nanocomposites prepared in preparation examples 1, 2 and 3 were 10.9nm, 15.5nm and 21.1nm, respectively, as calculated according to the scherrer formula. From this, it can be seen that the average particle diameter of the nickel carbide nanoparticles can be effectively controlled by controlling the amount of the alkali metal salt added.
Fig. 2 (a), 2 (b) and 2 (C) are C1-s X ray photoelectron spectra of the nickel carbide nanocomposite materials prepared in preparation examples 1, 2 and 3, respectively. As can be seen from fig. 2, the carbon matrixes of the nickel carbide nanocomposite prepared in preparation examples 1, 2 and 3 have obvious spectrum peaks at the binding energy of 287eV-290eV, which indicates that specific functional groups exist on the carbon of the nickel carbide nanocomposite provided by the invention.
FIG. 3 is a transmission electron microscopic image of the nickel carbide nanocomposite prepared in preparation example 1, and it can be seen from the image that the average particle diameter of the nickel carbide nanoparticles in the composite is about 10nm, which is substantially consistent with the calculation result of the X-ray diffraction pattern. In addition, as can be seen from the figure, the outer layer of the nickel carbide particles also coats the carbon matrix, forming a core-shell structure. As can be seen from the examination by a transmission electron microscope, the outer layers of the nickel carbide particles of the nickel carbide nanocomposite materials prepared in preparation examples 2 and 3 are coated with the carbon matrix similarly to the preparation example 1, so as to form a core-shell structure.
FIG. 4 is a transmission electron microscopic image of the nickel carbide nanocomposite prepared in preparation example 2, from which it can also be seen that the average particle diameter of the nickel carbide nanoparticles is substantially identical to the calculation result of the X-ray diffraction pattern.
The contents of the elements on the surfaces of the nickel carbide nanocomposite materials prepared in preparation examples 1, 2 and 3 are shown in table 1 respectively by the analysis of X-ray photoelectron spectroscopy:
TABLE 1
Note that: the raw material molar ratio refers to the molar ratio of the nitrogen-free organic carboxylic acid to the carboxyl group, the nickel source, the nitrogen-free organic carboxylic acid, and the alkali metal salt.
Comparative preparation example 1
The procedure of preparation 1 was followed except that sodium chloride was not added in step (1), to obtain a composite material.
As is apparent from X-ray diffraction (XRD), the composite material has only a diffraction peak corresponding to face-centered cubic (fcc) Ni and a diffraction peak of NiO, and no corresponding Ni 3 Diffraction peak of C. Therefore, in the method provided by the invention, the alkali metal salt is used as the stabilizer to promote the generation of nickel carbide, and when no alkali metal salt exists in the preparation process of the precursor, the nickel carbide nanocomposite can not be prepared.
Examples 1-6 illustrate the method of the present invention for catalyzing hydrodechlorination of chlorine-containing organic compounds using nickel carbide nanocomposites as catalysts
Example 1
100mg of the nickel carbide nanocomposite prepared in preparation example 1, 208. Mu.L of chlorobenzene,420 mu L of triethylamine and 30mL of ethanol are added into a reaction kettle, and H is introduced 2 After the reaction kettle is replaced for 3 times, stirring and heating up under low pressure, heating up to the preset reaction temperature of 110 ℃, and then introducing H again 2 The pressure in the reaction kettle is 1.0MPa, the heating is stopped after the reaction is continued for 6 hours, the pressure is discharged after the temperature is reduced to the room temperature, the reaction kettle is opened, the product is taken out for chromatographic analysis, and the chlorobenzene conversion rate is 99.9%.
Example 2
100mg of the nickel carbide nanocomposite prepared in preparation example 1, 128.5mg of p-chlorophenol and 30mL of ethanol are added into a reaction kettle, and H is introduced 2 3 times of replacement of the reaction kettle, stirring and heating under low pressure, heating to a preset reaction temperature of 110 ℃, and then introducing H 2 The pressure in the reaction kettle is 1.0MPa, the reaction is continued for 6 hours, the heating is stopped, the pressure is discharged after the temperature is reduced to the room temperature, the reaction kettle is opened, the product is taken out for chromatographic analysis, and the conversion rate of the parachlorophenol is 98.3%.
Example 3
100mg of the nickel carbide nanocomposite prepared in preparation example 2, 104 mu L of chlorobenzene, 420 mu L of triethylamine and 30mL of ethanol are added into a reaction kettle, and H is introduced 2 After the reaction kettle is replaced for 3 times, stirring and heating up under low pressure, heating up to the preset reaction temperature of 115 ℃, and then introducing H again 2 The pressure in the reaction kettle is 1.0MPa, the heating is stopped after the reaction is continued for 6 hours, the pressure is discharged after the temperature is reduced to the room temperature, the reaction kettle is opened, the product is taken out for chromatographic analysis, and the chlorobenzene conversion rate is 98.8%.
Example 4
100mg of the nickel carbide nanocomposite prepared in preparation example 3, 104 mu L of chlorobenzene, 420 mu L of triethylamine and 30mL of ethanol are added into a reaction kettle, and H is introduced 2 After 3 times of replacement of the reaction kettle, H is introduced again 2 The pressure in the reaction kettle is 1.0MPa, the temperature is raised to the preset reaction temperature of 120 ℃ by stirring, the heating is stopped after the reaction is continued for 6 hours, the pressure is discharged after the reaction kettle is cooled to the room temperature, the reaction kettle is opened, the product is taken out for chromatographic analysis, and the chlorobenzene conversion rate is 96.5%.
Example 5
According to the method of example 1, except that the catalyst was replaced with the nickel carbide nanocomposite prepared in preparation example 2, and the other conditions, steps and the like were the same as those of example 1, the conversion rate of chlorobenzene was 80.32%, which was lower than that of example 1, and it was found that the composite material having smaller average particle size of the nickel carbide nanoparticles had higher catalytic hydrodechlorination performance.
Example 6
The procedure of example 1 was followed, except that the catalyst was replaced with the nickel carbide nanocomposite prepared in preparation example 3, and the other conditions, steps and the like were the same as in example 1, to obtain a chlorobenzene conversion rate of 75.35%. It can be seen that the composite material with smaller average particle size of the nickel carbide nano particles has higher catalytic hydrodechlorination performance.
Comparative example 1
The procedure of example 1 was followed, except that the catalyst was replaced with the composite material prepared in comparative preparation example 1, and the other conditions, steps and the like were the same as in example 1, to obtain chlorobenzene with a conversion of only 65.53%.
The result shows that the method provided by the invention takes the nickel carbide nanocomposite as a catalyst, is directly applied to the catalytic hydrodechlorination reaction of the chlorine-containing organic compound, has higher hydrodechlorination performance, and has greater industrial value in the field of catalytic hydrodechlorination.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A process for catalytic hydrodechlorination comprising: in the presence of a catalyst, contacting a chlorine-containing organic compound with hydrogen to perform catalytic hydrogenation dechlorination reaction; the catalyst is a nickel carbide nanocomposite, and in a C1s X ray photoelectron spectrum of the nickel carbide nanocomposite, a spectrum peak exists in a binding energy range of 287eV-290 eV;
wherein the nickel carbide nanocomposite comprises an oxygen-doped carbon matrix and nickel carbide nanoparticles supported on the carbon matrix; and/or
The nickel carbide nanocomposite comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a carbon matrix doped with oxygen, and the inner core is nickel carbide nano particles.
2. The method of claim 1, wherein the nickel carbide nanocomposite contains a core-shell structure having a shell layer that is an oxygen-doped carbon matrix and an inner core that is nickel carbide nanoparticles; and/or
The molar content of carbon on the surface of the nickel carbide nano composite material is 60-80%, preferably 64-76% as measured by X-ray photoelectron spectroscopy; the molar content of oxygen is 17-27%, preferably 20-26%; the molar content of nickel is 3-11%, preferably 4-10%; and/or
The average particle diameter of the nickel carbide nano particles is 8-30nm, preferably 10-25nm.
3. The method of claim 1, wherein the method of preparing the nickel carbide nanocomposite comprises the steps of:
(1) Mixing a nickel source, an organic carboxylic acid containing no nitrogen and an alkali metal salt to obtain a precursor;
(2) Pyrolyzing the precursor under inert atmosphere; wherein the pyrolysis temperature is 200-400 ℃, preferably 250-350 ℃, more preferably 300-345 ℃, and even more preferably 310-340 ℃.
4. A process according to claim 3, wherein in step (1) the nickel source is selected from one or more of nickel hydroxide, nickel carbonate, basic nickel carbonate and nickel acetate, preferably basic nickel carbonate;
and/or the non-nitrogen containing organic carboxylic acid is selected from one or more of citric acid, maleic acid, fumaric acid, succinic acid, tartaric acid, malic acid, gluconic acid and trimesic acid, preferably citric acid;
and/or the alkali metal salt is selected from one or more of sodium chloride, potassium sulfate, sodium carbonate and potassium carbonate, preferably sodium chloride and/or potassium chloride;
and/or, the molar ratio of the nickel source, the nitrogen-free organic carboxylic acid and the alkali metal salt is 1, based on the carboxyl group: 2-8:0.01-20, preferably 1:2.5-7.5:0.02-1, more preferably 1:3-7:0.02 to 0.5, more preferably 1:3-6:0.02 to 0.1, more preferably 1:3-5:0.02-0.05.
5. A method according to claim 3, wherein in step (1), the mixing comprises:
providing a first solution containing the nickel source, a nitrogen-free organic carboxylic acid and an alkali metal salt, and then removing the first solvent from the first solution to obtain a precursor; or (b)
Providing a second solution containing the nickel source and an organic carboxylic acid containing no nitrogen, removing the second solvent in the second solution, and dry-mixing the obtained solid with the alkali metal salt to obtain the precursor.
6. The method of claim 4, wherein the first and second solvents are each independently selected from one or more of water, alcohols, and N, N-dimethylformamide.
7. A method according to claim 3, wherein in step (2), the pyrolysis comprises: heating the precursor to the pyrolysis temperature in an inert atmosphere, and keeping the temperature constant;
and/or the heating rate is 0.2-20deg.C/min, preferably 0.5-10deg.C/min, more preferably 1-10deg.C/min; and/or the constant temperature is maintained for 10-600min, preferably 20-300min, more preferably 50-200min;
and/or the method for preparing the nickel carbide nanocomposite further comprises treating the pyrolyzed product with water.
8. The process of any one of claims 1-7, wherein the chlorine-containing organic compound is contacted with hydrogen in the presence of a catalyst and a third solvent; preferably, the third solvent is selected from one or more of alcohols, ethers, alkanes and water; more preferably, the third solvent further contains a neutralizing agent, wherein the neutralizing agent is at least one selected from triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; further preferably, the molar ratio of the neutralizing agent to chlorine in the reactant is 1-3:1, a step of;
and/or the concentration of the chlorine-containing organic compound is 10-100000mg/L, preferably 20-20000mg/L.
9. The method of any one of claims 1-7, wherein the chlorine-containing organic compound is selected from one or more of chlorobenzene, dichlorobenzene, trichlorobenzene, chlorophenol, dichlorophenol, trichlorophenol, polychlorinated biphenyl; preferably chlorobenzene and/or p-chlorophenol.
10. The process of any one of claims 1-7, wherein the mass ratio of catalyst to chlorine-containing organic compound is 1:1-100, preferably 1:1-50; and/or
The conditions of the catalytic hydrodechlorination reaction include: the pressure is 0.5-4MPa, preferably 1-3MPa; the temperature is 60-250deg.C, preferably 80-200deg.C.
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