CN111437812A - Noble metal catalyst and preparation method and application thereof - Google Patents
Noble metal catalyst and preparation method and application thereof Download PDFInfo
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- CN111437812A CN111437812A CN201910040271.2A CN201910040271A CN111437812A CN 111437812 A CN111437812 A CN 111437812A CN 201910040271 A CN201910040271 A CN 201910040271A CN 111437812 A CN111437812 A CN 111437812A
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- metal catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 52
- 125000000962 organic group Chemical group 0.000 claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 23
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 41
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 19
- 238000001694 spray drying Methods 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- -1 salt compound Chemical class 0.000 claims description 5
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 claims description 4
- INPHIYULSHLAHR-UHFFFAOYSA-N 1-pentylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCCC INPHIYULSHLAHR-UHFFFAOYSA-N 0.000 claims description 4
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- RKMPHYRYSONWOL-UHFFFAOYSA-N 1-ethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(CC)CCC2 RKMPHYRYSONWOL-UHFFFAOYSA-N 0.000 claims description 2
- LZNGSHFBWBKBFH-UHFFFAOYSA-N 1-pentyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(CCCCC)CCC2 LZNGSHFBWBKBFH-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-M isobutyrate Chemical compound CC(C)C([O-])=O KQNPFQTWMSNSAP-UHFFFAOYSA-M 0.000 claims description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 2
- ZVSLRJWQDNRUDU-UHFFFAOYSA-L palladium(2+);propanoate Chemical compound [Pd+2].CCC([O-])=O.CCC([O-])=O ZVSLRJWQDNRUDU-UHFFFAOYSA-L 0.000 claims description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-M pivalate Chemical compound CC(C)(C)C([O-])=O IUGYQRQAERSCNH-UHFFFAOYSA-M 0.000 claims description 2
- YNGCBAQTERUCJP-UHFFFAOYSA-L platinum(2+);propanoate Chemical compound [Pt+2].CCC([O-])=O.CCC([O-])=O YNGCBAQTERUCJP-UHFFFAOYSA-L 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 7
- 239000012224 working solution Substances 0.000 abstract description 5
- 238000003795 desorption Methods 0.000 abstract description 3
- 230000036571 hydration Effects 0.000 abstract description 3
- 238000006703 hydration reaction Methods 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 12
- 230000002209 hydrophobic effect Effects 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- OTBHDFWQZHPNPU-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CCCC2 OTBHDFWQZHPNPU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012051 hydrophobic carrier Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/23—
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The application discloses a noble metal catalyst, a preparation method and application thereof. The catalyst comprises a carrier and an active component; the active component is loaded on the carrier; the support comprises silica modified with organic groups; the active component comprises an active element; the active element is at least one of Pd and Pt. The hydrogenation catalyst has the advantages that organic groups are introduced into the silicon oxide carrier, the hydrophobicity and the polarity of the carrier are adjusted, the hydration effect of water in the hydrogenation working solution on active components is avoided, the desorption effect of anthraquinone-hydrogenated species-anthrahydroquinone is further improved, and the selectivity and the stability of the hydrogenation catalyst are improved. The catalyst can be used in the process of producing hydrogen peroxide by catalytic hydrogenation of anthraquinone in a slurry bed, and the hydrogenation catalyst shows high hydrogenation selectivity and stability.
Description
Technical Field
The application relates to a noble metal catalyst, a preparation method and application thereof, and belongs to the technical field of chemical production.
Background
The final product decomposed in the using process of the hydrogen peroxide is mainly water, secondary pollutants can not be generated, and the hydrogen peroxide is an environment-friendly chemical. As a green chemical product, the hydrogen peroxide can be used as an oxidant, a bleaching agent, a disinfectant, a polymer initiator and the like, and is widely applied to the industries of chemical synthesis, papermaking, spinning, environmental protection, food, electronics, aerospace and the like.
The anthraquinone process is the main process for producing hydrogen peroxide in the world at present. In the anthraquinone hydrogenation process, the most important step is the hydrogenation process of the anthraquinone, and the solid catalyst has great influence on the energy consumption and the material consumption of an anthraquinone hydrogenation system.
Drelinkiewicz et al, Bowland scientific institute, propose (Chemical Papers,2013,67(8), 1087-.
Therefore, how to realize a hydrogenation catalyst with high selectivity, high activity and high stability is still a great challenge.
Disclosure of Invention
According to one aspect of the application, the hydrogenation catalyst disclosed by the application is characterized in that organic groups are introduced into a silicon oxide carrier, the hydrophobicity and the polarity of the carrier are adjusted, the hydration effect of water in a hydrogenation working solution on active components is avoided, the desorption effect of anthraquinone-hydrogenated anthraquinone is further improved, and the selectivity and the stability of the hydrogenation catalyst are improved.
According to an aspect of the present application, there is provided a noble metal catalyst comprising a support and an active component; the active component is loaded on the carrier; the support comprises silica modified with organic groups; the active component comprises an active element; the active element is at least one of Pd and Pt.
Aiming at the dispersibility of the noble metal active component of the hydrogenation catalyst and the hydrophobicity of the catalyst carrier in the anthraquinone hydrogenation process, the application provides that the silicon oxide containing organic functional group hydrophobicity is used as the carrier to regulate the type and the quantity of the organic functional group and regulate the hydrophobicity of the silicon oxide carrier, and the activity and the stability of the hydrogenation catalyst are improved through the regulation and control of the physical parameters of the silicon oxide carrier; and after the surface of the silicon oxide is regulated and controlled by organic functional groups, the desorption of anthrahydroquinone species is improved, the selectivity of anthraquinone hydrogenation reaction is improved, and the hydrogenation stability is further improved.
Optionally, the mass content of the active component in the noble metal catalyst is 0.01-2.00 wt%, and the mass content of Pd in the active component is 50-100 wt%; wherein the content of the active component is calculated by the content of active elements; the content of Pd is calculated as the content of Pd element itself.
The upper limit of the mass content of the active component in the noble metal catalyst is selected from 0.4 wt%, 2.00 wt%, and the lower limit of the mass content of the active component in the noble metal catalyst is selected from 0.01 wt%, 0.4 wt%.
The upper limit of the mass content of Pd in the active component is selected from 55 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 100 wt%, and the lower limit of the mass content of Pd in the active component is selected from 50 wt%, 55 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%.
Alternatively, the organic group comprises C1～C18Hydrocarbyl radical, C1～C18At least one of groups formed by substituting at least one carbon atom in the hydrocarbon group with a heteroatom; wherein the heteroatom is selected from at least one of oxygen, nitrogen and sulfur.
Preferably, the organic group comprises C1～C6A hydrocarbon group, and C1～C6At least one of the groups formed by substituting at least one carbon atom of the hydrocarbon group with a heteroatom.
Specifically, the organic group may be methyl, ethyl, propyl, phenyl, phenethyl, benzyl, acetyl, propionyl, fluoroalkyl, pyridyl, or the like.
When the hydrocarbon group contains a heteroatom, atoms such as oxygen, nitrogen, sulfur, etc. should be internal to the organic group, which can adjust the hydrophobicity of the silica support.
Optionally, the noble metal catalyst has a particle size of 20 to 300 μm, an average pore diameter of 10 to 30nm, a pore volume of less than 0.75cc/g, and a specific surface area of 140 to 180m2/g；
The carrier is spherical silicon oxide modified by the organic group;
in the carrier, the mass ratio of the organic group to the spherical silica is 3-20: 100.
according to another aspect of the present application, there is also provided a method for preparing a noble metal catalyst, comprising preparing an oxidation state precursor from a silica sol containing an organic group and a precursor containing an active element, and reducing to obtain the noble metal catalyst; wherein the silica sol containing organic groups refers to SiO modified by organic groups2The sol formed.
Optionally, the manner of obtaining the oxidized precursor comprises:
method 1
a1) Forming the silica sol containing organic groups to obtain a silica carrier;
a2) loading the precursor containing the active elements on the silicon oxide carrier, and roasting I to obtain an oxidation state compound I; or
b1) Forming a mixture formed by the precursor containing the active elements and the silica sol containing the organic groups, and roasting II to obtain an oxidation state precursor;
specifically, the method 1 comprises:
1-1) preparing spherical particles from silica sol containing organic groups by a spray drying mode, and then drying to obtain a silicon oxide carrier;
1-2) loading a precursor containing active elements on the silicon oxide carrier obtained in the step 1-1), and drying and roasting I to prepare an oxidation state precursor;
the method 2 comprises the following steps:
2-1) adding the precursor with the active elements into silica sol containing organic groups, then obtaining particles in a spray drying mode, and then drying and roasting II to obtain an oxidation state precursor.
Optionally, the means of shaping comprises spray drying;
the roasting temperature of the roasting I and the roasting II is 200-300 ℃ independently, and the roasting time is 1-5 hours independently.
The method 1 and the method 2 are characterized in that the ball forming is carried out by utilizing a spray drying mode; the forming equipment is selected from centrifugal forming equipment; the dry gas is at least one of nitrogen, helium and carbon dioxide.
Specifically, in the present application, the molding apparatus may be a centrifugal molding apparatus, a pressure type molding apparatus, or a gas-liquid two-phase atomization type molding apparatus.
The upper limit of the roasting temperature of the roasting I and the roasting II is selected from 250 ℃ and 300 ℃, and the lower limit of the roasting temperature of the roasting I and the roasting II is selected from 200 ℃ and 250 ℃.
Optionally, the particle size of the silica sol is 10-100 nm; the solid content of the silica sol is 10-50 wt%. Wherein the solid content of the silica sol is SiO2The mass percentage of the silicon sol.
Specifically, in the present application, the particle size of the silica sol refers to SiO that is not modified with organic groups2The solid content in the silica sol refers to SiO which is not modified by organic groups2Content in silica sol.
Preferably, the particle size of the silica sol containing organic groups is 15-70 nm, and the solid content in the silica sol is 15-40 wt%.
When the solid content of silica is more than 15%, the silica particles are easily formed into spherical particles, and when the solid content of silica is less than 40%, the preparation cost of the hydrophobic silica carrier is reduced.
In the present application, the mass fraction ratio of the solvent of the silica sol to water may be 0.1-12%, and the two solvents are mutually soluble, wherein the solvent may be selected from 1-pentanol (6.8% dissolved water), methyl ethyl ketone (9.9% dissolved water), methyl isopropyl ketone (1.8% dissolved water), cyclohexanone (8% dissolved water), ethyl acetate (2.9% dissolved water), n-butyl ethyl ester (1.9% dissolved water), methyl methacrylate (1.1% dissolved water), diisopropyl ether (0.55% dissolved water), dibutyl ether (0.2% dissolved water), and the like;
optionally, the precursor containing the active element comprises a salt compound containing the active element; the salt compound containing active elements is selected from platinum acetate (Pt (OAc)2) Platinum propionate (Pt (O (C ═ O) CH)2CH3)2) Palladium (II) acetate (Pd (OAc)2) Palladium (II) propionate (Pd (O (C ═ O) CH)2CH3)2) Palladium (II) 2-methylpropionate (Pd (O (C ═ O) CH (CH)3)2)2) Palladium trimethyl acetate (Pd (OPiv))2) At least one of (1).
Optionally, the reducing conditions are: reducing for 5-6 h at 80-100 ℃, wherein the reducing atmosphere is hydrogen.
The application also provides a method for preparing hydrogen peroxide by hydrogenating anthraquinone in a slurry bed, which uses the noble metal catalyst and the noble metal catalyst prepared by the method to catalyze the hydrogenation reaction of anthraquinone.
Optionally, the anthraquinone is selected from at least one of ethylanthraquinone, amylanthraquinone, ethyltetrahydroanthraquinone, amyltetrahydroanthraquinone.
In the present application, "C1～C18"all refer to the number of carbon atoms contained in a group.
The beneficial effects that this application can produce include:
1) the application provides a hydrophobic supported catalyst for producing hydrogen peroxide by anthraquinone hydrogenation and a preparation method thereof, which mainly improve the once-through hydrogen efficiency and the effective selectivity of anthraquinone, further improve the hydrogenation stability of the catalyst, and prevent the loss and inactivation of noble metals. According to the high-hydrophobicity supported slurry bed hydrogenation catalyst prepared in the application, the silicon oxide carrier containing the organic functional group has hydrophobicity, so that the interaction between water in a working solution and Pd particles in the catalyst is avoided, the hydrolysis resistance of active components of the catalyst can be improved, and the hydrogenation stability of the catalyst is improved; in addition, the silicon oxide carrier containing organic functional groups reduces the polarity of the surface of the catalyst, so that hydrogenated intermediate species generated by hydrogenation are easy to desorb from the inside of the catalyst, and the anthraquinone hydrogenation reaction is a complex reaction integrating series and parallel reactions, and the one-step hydrogenation reaction is an effective reaction for effective anthraquinone and tetrahydroanthraquinone, so that the anthrahydroquinone species can be easy to desorb by introducing the organic groups, the hydrogenation selectivity can be further improved, a large amount of byproducts are effectively avoided, the stability of the hydrogenation catalyst is improved, and the energy consumption of the reaction is reduced.
2) The catalyst can be used in the process of producing hydrogen peroxide by anthraquinone catalytic hydrogenation in a slurry bed, and has the reaction temperature of 40-60 ℃, the pressure of 0.05-0.3MPa and the liquid space velocity of 60-300h-1Under the condition, the hydrogenation catalyst shows high hydrogenation selectivity and stability.
Drawings
FIG. 1 is an apparent topography of sample # 1;
FIG. 2 is a graph of the hydrogenation valence results for the examples of sample # 1, sample # 2, and sample # 6.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
In the present application, silica sols containing organic groups are purchased from Fuso, Grace.
Precursors containing active elements were purchased from the national pharmaceutical companies.
Example 1
1) Preparation method of hydrophobic silicon oxide carrier
The spherical silicon oxide powder is prepared by the way of centrifugal spray drying of the organic silica sol with the solid content of 20 percent. Wherein the average particle size of the nano silicon oxide in the organic silica sol is 30nm, the surface of the nano silicon oxide particle is mainly methyl group, and the selected solvent is methyl ethyl ketone. The specific control parameters of the centrifugal spray drying are as follows:
a. the drying gas for spray drying is selected to be nitrogen;
b. controlling the rotation speed of spray drying to 10000 r/min;
c. the inlet temperature of the spray drying is 160 ℃ and the outlet temperature is maintained between 90 ℃ and 100 ℃.
2) Preparation of hydrophobic catalysts
And taking 5g of spherical silicon oxide powder with the particle size of 120-400 meshes, adding 6.5g of palladium acetate organic solution with the concentration of 3mg/ml dissolved by methanol, standing for 2h, drying at 80 ℃ for 6h, and roasting at 300 ℃ for I2 h to obtain the oxidized precursor.
3) Reduction treatment
And (3) putting the oxidation state compound I into a tubular furnace, introducing hydrogen with the volume flow of 30ml/min, and reducing at the temperature of 80 ℃ for 5 hours to obtain the required noble metal catalyst which is marked as sample No. 1.
In sample # 1, the mass content of palladium in the noble metal catalyst was 0.4 wt%.
Example 2
1) Preparation method of hydrophobic catalyst
50g of an organosilicon sol having a solids content of 20% was weighed. Wherein the average grain size of the nano silicon oxide of the organic silica sol is 30nm, the surface of the nano silicon oxide particle is mainly methyl group, and the selected solvent is methyl ethyl ketone. 13.0g of palladium acetate organic solution with the concentration of 3mg/ml is added into the organic silica sol, wherein the solvent of the palladium acetate is methanol solution, and then the mixture is stirred for 30min at normal temperature.
The above-mentioned organic silica sol mixed with active component was prepared into spherical catalyst particles by a centrifugal spray-drying method, the control parameters of which were as described in example 1.
Roasting the sample subjected to centrifugal spray drying at 300 ℃ for II 2h to obtain an oxidation state compound II;
2) reduction treatment
And putting the oxidation state compound II into a tubular furnace, introducing hydrogen with the volume flow of 30ml/min, and reducing at the temperature of 80 ℃ for 5 hours to obtain the required hydrogenation noble metal catalyst which is recorded as sample No. 2.
In sample 2#, the mass content of palladium in the noble metal catalyst was 0.4 wt%.
Example 3
Preparation of samples # 3 to # 5
The preparation method of sample # 3 is different from the preparation method of sample # 1 in that: the solid content of the organic silica sol is 15 wt%, the average particle size of the nano silica in the organic silica sol is 65nm, the surface of the nano silica particles is mainly phenyl group, 15mg/ml of 2-methyl palladium (II) propionate is prepared by dissolving methanol, 6.5g of 2-methyl palladium (II) propionate organic solution is prepared, the temperature of sintering I is 200 ℃, and the sample is marked as # 3. In sample # 3, the mass content of palladium in the noble metal catalyst was 1.9 wt%.
The preparation method of sample # 4 is different from the preparation method of sample # 1 in that: the solid content of the organic silica sol is 38 wt%, the average particle size of the nano silica in the organic silica sol is 20nm, the surfaces of the nano silica particles are mainly acetyl groups, the organic solution of palladium acetate with the concentration of 0.08mg/ml prepared by dissolving methanol is 6.5g, the temperature of sintering I is 250 ℃, and the sample is marked as # 4. In sample 4#, the mass content of palladium in the catalyst was 0.011 wt%.
The preparation method of sample # 5 is different from the preparation method of sample # 1 in that: 3mg/ml of palladium acetate organic solution is prepared by dissolving methanol, 3mg/ml of platinum acetate organic solution is prepared by dissolving methanol, and 3.2g of each of the palladium acetate organic solution and the platinum acetate organic solution is taken. In sample No. 5, the mass contents of palladium and platinum in the catalyst were 0.4 wt%.
Example 4
Preparation of silica hydrogenation catalyst
Carrying out spray drying on inorganic silica sol with the average particle size of 25nm to obtain a silica carrier, wherein the mass concentration of the inorganic silica sol is 30%, a stabilizer of the sol is sodium ions, and the pH value is 10.02; the control parameters for spray drying were the same as in example 1. The preparation of the hydrogenation catalyst using silica as a carrier is similar to the method for supporting the active component in the above-mentioned example 1. Specifically, 20ml of 2mg/ml palladium nitrate aqueous solution is prepared, 2g of spherical silica powder with the particle size of 120-400 meshes is weighed, 4ml of the palladium nitrate solution with the prepared concentration is added into the silica powder, and then the mixture is dried at 120 ℃ and roasted at 350 ℃ for 3 hours to obtain an oxidized palladium catalyst; putting the oxidized palladium catalyst into a tubular furnace, introducing hydrogen with the volume flow of 30ml/min, and reducing at the temperature of 80 ℃ for 5 hours to obtain the hydrogenated palladium catalyst which is marked as 6 #. In sample 6#, the mass content of palladium in the catalyst was 0.4 wt%.
Example 5
The samples 1# to 5# are respectively subjected to morphology testing, and the testing instrument is JEO L JSM-7800F Scanning Electron Microscope (SEM).
The test result shows that the grain size of the sample No. 1-5 is 20-300 μm.
Taking sample No. 1 as a typical representative, it can be seen from FIG. 1 that the particle size of sample No. 1 is 40 to 150 μm.
Example 6
The specific surface area, pore size and pore size distribution of samples # 1 to # 5, sample # 1 and comparative example # 1 were measured using a NOVA2200e model specific surface-pore size distributor from Quanta corporation, USA, respectively.
The test results are shown in Table 1, with sample # as representative.
Table 1 physical parameter comparison of hydrophobic support and catalyst
As can be seen from table 1, the ratio and pore volume of the catalyst of example 1 (sample # 1) are smaller than those of the non-supported active component carrier, which is mainly caused by the active component supported on the carrier occupying part of the pore size, but the pore size distribution is not significantly changed, so that the hydrophobic carrier can be impregnated with the organic palladium liquid of methanol. Compared with example 1, example 2 (sample 2#) can also obtain a hydrophobic noble metal catalyst by directly adding the active component into hydrophobic silica gel and then performing spray drying and molding, but the method can reduce partial specific surface area and pore volume, mainly because in the presence of the active component Pd, the spray drying can cause the growth of partial silicon oxide primary particles, so that relatively large pore diameter is formed, and the specific surface area and pore volume of the catalyst are reduced. In addition, as can be seen from table 1, the characteristics of the specific surface area, pore volume and pore diameter of the silica sample of example 4 (sample # 6) are not greatly different from those of the hydrophobic silica samples of examples 1 and 2, and therefore, it can be seen that the performance of the hydrogenation catalyst is obviously changed after the surface of the silica carrier is hydrophobically modified.
Example 7
Evaluation method of catalyst:
the hydrogenation catalyst was evaluated mainly in a continuous mixed slurry bed reactor. In the experiment, the working solution adopted for evaluation is a mixture of amylanthraquinone and ethylanthraquinone, and the solvent is a mixture of heavy arene and diisobutylcarbinol, wherein the mass ratio of amylanthraquinone to ethylanthraquinone to heavy arene to diisobutylcarbinol is 3: 1: 15: 10. adding 2ml hydrogenation catalyst into the reactor, regulating stirring speed to 1200r/min, controlling hydrogen flow rate to 20ml/min, controlling flow rate of working liquid to 120ml/hr, controlling operation pressure of system to 0.05MPa (gauge pressure), and controlling hydrogenation reaction temperature to 40 deg.C.
Oxidizing the hydrogenated liquid with oxygen, extracting with distilled water, and adding KMnO4The hydrogen peroxide produced was determined by titration and the hydrogenation efficiency was calculated. The hydrogenated liquid herein refers to a working liquid after the hydrogenation reaction.
Wherein:
b-hydrogenation efficiency (g/L);
C—KMnO4the concentration (mol-L)；
V0—KMnO4Volume of solution (m L);
M—H2O2molar mass (g/mol);
v is the volume of the hydrogenation solution (mol/L).
The hydrogenation evaluations were carried out for samples # 1 to # 5 and # 6, respectively. Taking samples # 1 and # 2 as representative examples, the evaluation results are shown in fig. 2, and it can be seen from the above examples that the hydrogenation catalysts (sample # 1 and sample # 2) with hydrophobic silica carrier have higher hydrogenation activity and higher stability than the pure silica hydrogenation catalyst (sample # 6) under the condition of the same palladium content as the active component. The main reason is that the organic groups of the carrier of the silicon oxide bonded with the organic functional groups are increased, so that polar substances such as water and the like in the working solution are difficult to contact with the active component Pd of the catalyst, thereby inhibiting the hydration of the hydrogenation catalyst and improving the stability. In addition, the polarity of the anthrahydroquinone after the hydrogenation of the anthraquinone is higher, and the polarity of the surface of the hydrogenation catalyst bonded with the organic functional group is reduced, so that the anthrahydroquinone as the hydrogenated intermediate species is easy to desorb from the surface of the catalyst, the selectivity of the hydrogenation of the anthraquinone is improved, and the stability of the hydrogenation catalyst of the anthraquinone is improved.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A noble metal catalyst comprising a support and an active component;
the active component is loaded on the carrier;
the support comprises silica modified with organic groups;
the active component comprises an active element;
the active element is at least one of Pd and Pt.
2. The noble metal catalyst according to claim 1, wherein the mass content of the active component in the noble metal catalyst is 0.01 to 2.00 wt%, and the mass content of Pd in the active component is 50 to 100 wt%;
wherein the content of the active component is calculated by the content of active elements;
the content of Pd is calculated as the content of Pd element itself.
3. The noble metal catalyst of claim 1 wherein the organic group comprises C1～C18Hydrocarbyl radical, C1～C18At least one of groups formed by substituting at least one carbon atom in the hydrocarbon group with a heteroatom;
wherein the heteroatom is selected from at least one of oxygen, nitrogen and sulfur.
4. The noble metal catalyst according to claim 1, wherein the noble metal catalyst has a particle size of 20 to 300 μm, an average pore diameter of 10 to 30nm, a pore volume of less than 0.75cc/g, and a specific surface area of 140 to 180m2/g；
The carrier is spherical silicon oxide modified by the organic group;
in the carrier, the mass ratio of the organic group to the spherical silica is 3-20: 100.
5. the method for producing a noble metal catalyst according to any one of claims 1 to 4, wherein an oxidized precursor is prepared from a silica sol containing an organic group and a precursor containing an active element, and the oxidized precursor is reduced to obtain the noble metal catalyst;
wherein the silica sol containing organic groups refers to SiO modified by organic groups2The sol formed.
6. The method of claim 5, wherein the oxidized form precursor is obtained by:
method 1
a1) Forming the silica sol containing organic groups to obtain a silica carrier;
a2) loading the precursor containing the active elements on the silicon oxide carrier, and roasting I to obtain the oxidation state precursor; or
Method 2
b1) Forming a mixture formed by the precursor containing the active elements and the silica sol containing the organic groups, and roasting II to obtain the oxidation state precursor;
preferably, the means of shaping comprises spray drying;
preferably, the roasting temperature of the roasting I and the roasting II is 200-300 ℃ independently, and the roasting time is 1-5 hours independently.
7. The preparation method according to claim 5, wherein the silica sol has a particle size of 10 to 100nm, and a solid content of 10 to 50 wt%;
wherein the solid content of the silica sol is SiO2The mass percentage of the silicon sol;
preferably, the particle size of the silica sol is 15-70 nm, and the solid content of the silica sol is 15-40 wt%.
8. The production method according to claim 5, wherein the precursor containing an active element includes a salt compound containing an active element;
the salt compound containing the active element is at least one selected from platinum acetate, platinum propionate, palladium (II) acetate, palladium (II) propionate, palladium (II) 2-methyl propionate and palladium trimethyl acetate.
9. The method of claim 5, wherein the reducing conditions are: reducing for 5-6 h at 80-100 ℃, wherein the reducing atmosphere is hydrogen.
10. A method for preparing hydrogen peroxide by anthraquinone hydrogenation in a slurry bed is characterized in that a noble metal catalyst according to any one of claims 1 to 4 and a noble metal catalyst prepared by the method according to any one of claims 5 to 9 are used for catalyzing the hydrogenation reaction of anthraquinone;
preferably, the anthraquinone is selected from at least one of ethylanthraquinone, amylanthraquinone, ethyltetrahydroanthraquinone, amyltetrahydroanthraquinone.
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| CN112973677A (en) * | 2019-12-13 | 2021-06-18 | 山西潞安矿业(集团)有限责任公司 | Preparation method and application of hydrophobic noble metal catalyst |
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| CN115672315A (en) * | 2021-07-29 | 2023-02-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
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| CN114618486A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Platinum-palladium-silver compound catalyst, and preparation method and application thereof |
| CN114618486B (en) * | 2020-12-11 | 2023-10-10 | 中国科学院大连化学物理研究所 | Platinum-palladium-silver compound catalyst and preparation method and application thereof |
| CN115672315A (en) * | 2021-07-29 | 2023-02-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN114029053A (en) * | 2021-11-22 | 2022-02-11 | 中国科学院大连化学物理研究所 | Preparation method of supported catalyst and application of supported catalyst in preparation of methyl glycolate from ethylene glycol |
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