CN116020079B - Catalytic hydrodechlorination process - Google Patents
Catalytic hydrodechlorination process Download PDFInfo
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- CN116020079B CN116020079B CN202111258076.0A CN202111258076A CN116020079B CN 116020079 B CN116020079 B CN 116020079B CN 202111258076 A CN202111258076 A CN 202111258076A CN 116020079 B CN116020079 B CN 116020079B
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- nickel
- nickel carbide
- chlorine
- catalyst
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- 238000000034 method Methods 0.000 title claims abstract description 76
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 326
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 162
- 239000002114 nanocomposite Substances 0.000 claims abstract description 88
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000460 chlorine Substances 0.000 claims abstract description 27
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 27
- 239000011258 core-shell material Substances 0.000 claims abstract description 14
- 238000000026 X-ray photoelectron spectrum Methods 0.000 claims abstract description 12
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 11
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 229910052783 alkali metal Inorganic materials 0.000 claims description 29
- -1 alkali metal salt Chemical class 0.000 claims description 29
- 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000197 pyrolysis Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-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
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 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
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 6
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 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
- 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
- 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
- 229940090668 parachlorophenol Drugs 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 47
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 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
- 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
- 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
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001941 electron spectroscopy Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 230000003595 spectral effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000004429 atom Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229960002809 lindane Drugs 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
Landscapes
- 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 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; 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 higher hydrodechlorination performance, can avoid using a high-cost noble metal catalyst, does not need to use a metal phosphide catalyst which is easy to generate extremely toxic PH 3 in the preparation process, is more environment-friendly, and has higher industrial value in the field of catalytic hydrodechlorination.
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 reactions, which, although having significant advantages over noble metal catalysts, is prone to the formation of extremely toxic PH 3 during the preparation process.
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 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 using a high-cost noble metal catalyst, does not need to use a metal phosphide catalyst which is easy to generate extremely toxic PH 3 in the preparation process, and 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, which is beneficial to the adsorption of the chloro functional group and the 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, does not need to use a metal phosphide catalyst which is easy to generate extremely toxic PH 3 in the preparation process, and is more environment-friendly when being used as a catalyst. 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 including a carbon matrix doped with oxygen and nickel carbide nanoparticles supported on the carbon matrix, and having a spectral peak in the binding energy range of 287eV-290eV in the C1s X ray photoelectron spectrum, may be prepared by the method 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 adopted X-ray photoelectron spectroscopy analyzer is a ESCALab i-XL type ray electron spectroscopy manufactured by VG SCIENTIFC company and provided with AVANTAGE V5.926 software, and the analysis and test conditions of the X-ray photoelectron spectroscopy are as follows: the excitation source was monochromating A1KαX-rays, power 330W, and base vacuum at analytical test was 3X 10 -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 nano composite material as catalyst, and the composite material has a spectral peak in a binding energy range of 287eV-290eV in a C1s X ray photoelectron spectrum; 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, and has higher hydrodechlorination performance, and meanwhile, the nickel carbide nanocomposite can avoid using a high-cost noble metal catalyst, does not need to use a metal phosphide catalyst which is easy to generate extremely toxic PH 3 in the preparation process, and 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 adopted X-ray photoelectron spectroscopy analyzer is a ESCALab i-XL type ray electron spectroscopy manufactured by VG SCIENTIFC company and provided with AVANTAGE V5.926 software, and the analysis and test conditions of the X-ray photoelectron spectroscopy are as follows: the excitation source was monochromating A1KαX-rays, power 330W, and base vacuum at analytical test was 3X 10 -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 C1s 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 evident 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 diffraction peak corresponding to Ni 3 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, H 2 is introduced into the reaction kettle for replacement for 3 times, stirring and heating are carried out under low pressure, the temperature is raised to a preset reaction temperature of 110 ℃, H 2 is introduced again to enable the pressure in the reaction kettle to be 1.0MPa, the reaction is continued for 6 hours, heating is stopped, the pressure is discharged after the reaction kettle is cooled to room temperature, and the reaction kettle is opened to take out a product for chromatographic analysis, so that the chlorobenzene conversion rate is 99.9%.
Example 2
Adding 100mg of the nickel carbide nanocomposite prepared in preparation example 1, 128.5mg of p-chlorophenol and 30mL of ethanol into a reaction kettle, introducing H 2 to replace the reaction kettle for 3 times, stirring at low pressure, heating to a preset reaction temperature of 110 ℃, introducing H 2 again to enable the pressure in the reaction kettle to be 1.0MPa, continuously reacting for 6 hours, stopping heating, cooling to room temperature, discharging pressure, and opening the reaction kettle to take out a product for chromatographic analysis to obtain the p-chlorophenol with the conversion rate of 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, H 2 is introduced into the reaction kettle for replacement for 3 times, stirring and heating are carried out under low pressure, the temperature is raised to a preset reaction temperature of 115 ℃, H 2 is introduced again to enable the pressure in the reaction kettle to be 1.0MPa, the reaction is continued for 6 hours, heating is stopped, the pressure is discharged after the reaction kettle is cooled to room temperature, and the reaction kettle is opened to take out the product for chromatographic analysis, so that 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, H 2 is introduced to replace the reaction kettle for 3 times, H 2 is introduced again to enable the pressure in the reaction kettle to be 1.0MPa, stirring and heating are carried out to a preset reaction temperature of 120 ℃, the reaction is continued for 6 hours, heating is stopped, the temperature is reduced to room temperature, the pressure is discharged, and the reaction kettle is opened to take out a product for chromatographic analysis, so that 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, etc., were the same as in example 1, to obtain a chlorobenzene conversion 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 (27)
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;
the surface of the nickel carbide nano composite material is measured by X-ray photoelectron spectroscopy, and the molar content of carbon is 60-80%; the molar content of oxygen is 17-27%; the molar content of nickel is 3-11%;
The chlorine-containing organic compound is selected from one or more of chlorobenzene, dichlorobenzene, trichlorobenzene, chlorophenol, dichlorophenol, trichlorophenol and polychlorinated biphenyl.
2. The method of claim 1, wherein the nickel carbide nanocomposite surface has a carbon molar content of 64-76% as measured by X-ray photoelectron spectroscopy; the molar content of oxygen is 20-26%; the molar content of nickel is 4-10%; and/or
The average particle size of the nickel carbide nano particles is 8-30nm.
3. The method of claim 2, wherein the nickel carbide nanoparticles have an average particle diameter of 10-25nm.
4. 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 ℃.
5. The method of claim 4, wherein in step (2), the pyrolysis temperature is 250-350 ℃.
6. The method of claim 5, wherein in step (2), the pyrolysis is performed at a temperature of 300-345 ℃.
7. The method of claim 6, wherein in step (2), the pyrolysis temperature is 310-340 ℃.
8. The method of claim 4, wherein in step (1), the nickel source is selected from one or more of nickel hydroxide, nickel carbonate, basic nickel carbonate, and nickel acetate;
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;
and/or the alkali metal salt is selected from one or more of sodium chloride, potassium sulfate, sodium carbonate and potassium carbonate;
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.
9. The method of claim 8, wherein in step (1), the molar ratio of the nickel source, the nitrogen-free organic carboxylic acid, and the alkali metal salt, calculated as carboxyl groups, is 1:2.5-7.5:0.02-1.
10. The method of claim 9, wherein the molar ratio of the nickel source, the nitrogen-free organic carboxylic acid, and the alkali metal salt, on a carboxyl group basis, is 1:3-7:0.02-0.5.
11. The method of claim 10, wherein the molar ratio of the nickel source, the nitrogen-free organic carboxylic acid, and the alkali metal salt, on a carboxyl group basis, is 1:3-6:0.02-0.1.
12. The method of claim 11, wherein the molar ratio of the nickel source, the nitrogen-free organic carboxylic acid, and the alkali metal salt, on a carboxyl group basis, is 1:3-5:0.02-0.05.
13. The method of claim 8, 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.
14. The method of claim 13, wherein the first and second solvents are each independently selected from one or more of water, alcohols, and N, N-dimethylformamide.
15. The method of any one of claims 4-7, wherein in step (2), the pyrolyzing comprises: heating the precursor to the pyrolysis temperature in an inert atmosphere, and keeping the temperature constant;
And/or the method for preparing the nickel carbide nanocomposite further comprises treating the pyrolyzed product with water.
16. The method of claim 15, wherein the heating is at a rate of 0.2-20 ℃/min.
17. The method of claim 15, wherein the constant temperature is for a period of 10-600 minutes.
18. The method of claim 15, wherein the heating is at a rate of 0.5-10 ℃/min and the constant temperature is for a period of 20-300min.
19. The method of claim 18, wherein the heating is at a rate of 1-10 ℃/min and the holding time is 50-200min.
20. The process of any one of claims 1-14, wherein the chlorine-containing organic compound is contacted with hydrogen in the presence of a catalyst and a third solvent;
And/or the concentration of the chlorine-containing organic compound is 10-100000 mg/L.
21. The method of claim 20, wherein the third solvent is selected from one or more of alcohols, ethers, alkanes, and water.
22. The method according to claim 20, wherein the third solvent further comprises a neutralizing agent selected from at least one of triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
23. The method of claim 22, wherein the molar ratio of neutralizing agent to chlorine in the reactant is 1-3:1.
24. The process according to claim 20, wherein the concentration of the chlorine-containing organic compound is 20-20000 mg/L.
25. The process of any one of claims 1-14, wherein the chlorine-containing organic compound is a combination of chlorobenzene and parachlorophenol or parachlorophenol.
26. The process of any one of claims 1-14, wherein the mass ratio of catalyst to chlorine-containing organic compound is 1:1-100; and/or
The conditions of the catalytic hydrodechlorination reaction include: the pressure is 0.5-4MPa, and the temperature is 60-250 ℃.
27. The process of claim 26, wherein the mass ratio of catalyst to chlorine-containing organic compound is 1:1-50; and/or
The conditions of the catalytic hydrodechlorination reaction include: the pressure is 1-3MPa; the temperature is 80-200 ℃.
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