CN116803505A - Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation - Google Patents
Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation Download PDFInfo
- Publication number
- CN116803505A CN116803505A CN202310702716.5A CN202310702716A CN116803505A CN 116803505 A CN116803505 A CN 116803505A CN 202310702716 A CN202310702716 A CN 202310702716A CN 116803505 A CN116803505 A CN 116803505A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- dehydrogenation
- groups
- diphenylamine
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 81
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- -1 carbazole compound Chemical class 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 150000001716 carbazoles Chemical class 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 239000012018 catalyst precursor Substances 0.000 description 30
- 238000010025 steaming Methods 0.000 description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 238000001035 drying Methods 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 230000018044 dehydration Effects 0.000 description 14
- 238000006297 dehydration reaction Methods 0.000 description 14
- 238000001704 evaporation Methods 0.000 description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010499 C–H functionalization reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- DKLYDESVXZKCFI-UHFFFAOYSA-N n,n-diphenylacetamide Chemical compound C=1C=CC=CC=1N(C(=O)C)C1=CC=CC=C1 DKLYDESVXZKCFI-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- SDFLTYHTFPTIGX-UHFFFAOYSA-N 9-methylcarbazole Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C2=C1 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000006254 arylation reaction Methods 0.000 description 2
- 150000005347 biaryls Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- CADSTRJVECIIAT-UHFFFAOYSA-N 1-carbazol-9-ylethanone Chemical compound C1=CC=C2N(C(=O)C)C3=CC=CC=C3C2=C1 CADSTRJVECIIAT-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229930013930 alkaloid Natural products 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
- 230000000202 analgesic effect Effects 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 230000007131 anti Alzheimer effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000003178 anti-diabetic effect Effects 0.000 description 1
- 230000003556 anti-epileptic effect Effects 0.000 description 1
- 230000036436 anti-hiv Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 229940127219 anticoagulant drug Drugs 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 239000003472 antidiabetic agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- GRJHONXDTNBDTC-UHFFFAOYSA-N phenyl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=CC=C1 GRJHONXDTNBDTC-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the technical field of chemical catalysis, and discloses a dehydrogenation catalyst, a preparation method and application thereof in preparing carbazole by dehydrogenating diphenylamine. The composition of the dehydrogenation catalyst comprises: active component, auxiliary agent and carrier, the active component is Pt, the carrier is ZrO 2 The auxiliary agent is Co, ni and Fe. The catalytic action of the dehydrogenation catalyst provided by the invention is utilized to enable the substituted or unsubstituted diphenylamine to generate intramolecular dehydrogenation ring-closure reaction, so as to prepare the carbazole compound. Compared with the prior art, the preparation method of the carbazole compound not only improves the conversion rate of substituted or unsubstituted diphenylamine, but also improves the selectivity of the carbazole compound, thereby being capable of obtaining a target product with high yield.
Description
Technical Field
The invention relates to the technical fields of organic chemical industry and organic synthesis, in particular to a dehydrogenation catalyst, a preparation method and application thereof in preparing carbazole by dehydrogenating diphenylamine.
Background
Carbazole, also known as 9-aza (hetero) fluorene, consists of two benzene rings fused on either side of a central pyrrole ring, and is one of the important components of coal tar. The pure substance has a melting point of 244.8 ℃ and a boiling point of 355 ℃, has a planar tricyclic skeleton, is colorless monoclinic flaky crystals, has special smell, is easy to sublimate, is slightly soluble in water, and can be dissolved in organic solvents such as ethanol, diethyl ether and the like.
Carbazole structural motifs are prevalent in plant or bacterial sources of natural alkaloids that exhibit potent biological activity in medicine (e.g., anticancer, anti-HIV, antibacterial, anti-Alzheimer's disease, anticoagulant, analgesic, antiepileptic, antidiabetic, antioxidant, etc.). Meanwhile, carbazole is taken as an intermediate of fine chemicals, a pi-expansion system can be provided, and different structures can be adopted for modification to adjust the molecular and optical properties of the carbazole, so that carbazole compounds are also ideal components of advanced materials for optical and thermal electronic application, conductive polymers, liquid crystals or luminescent dye development. The carbazole compound has excellent solubility, so that the carbazole compound is widely used for constructing D-A conjugated polymers and is used for preparing organic photoconductors, nonlinear optical materials, photorefractive materials, efficient blue phosphorescent devices and other materials. In particular, carbazole is of great significance to the dye industry, and can be used for synthesizing carbazole blue dye, azo dye, anthraquinone dye and the like, and the dyes can be used as photosensitive materials for electrophotography. At present, carbazole is mainly obtained from coal tar, the carbazole content is about 1.5%, and the extraction method mainly comprises a crystallization-distillation method and a solvent washing method, but the two methods have the problems of low yield, low purity, serious three wastes and the like. Therefore, the research on the synthesis method of carbazole is of great significance to facilitate industrial production.
As early as 1872, the synthesis process of carbazole has been studied. In 1908, bucherer (Bucherer H T, seyde F j. Prakt chem.1908,77 (2), 403.) published the preparation of benzocarbazole from naphthol and phenylhydrazine in the presence of sodium sulfite, a new chapter for the synthesis of carbazole and its derivatives, a process also called Bucherer process. The method comprises the steps of (1) synthesizing various functionalized carbazoles by using aniline and phenyl trifluoro methanesulfonate as reaction raw materials and using acetic acid or acetic acid as a solvent and adopting N-arylation-oxidation biaryl coupling, wherein the method can be used for avoiding catalyst poisoning caused by halogen ions by introducing trifluoro methanesulfonate; the reaction is to add acetic acid after the N-arylation is completed, and place the reaction system in oxygen atmosphere, and the yield of carbazole is 69%. The results show that for the reaction of different triflate and aniline under the oxygen condition, the yield of carbazole is reduced due to the fact that the para-position is provided with an electron donating group, the yield of carbazole is improved due to the fact that the para-position is provided with an electron withdrawing group, and the yield of carbazole is reduced during ortho-position substitution. Patent CN103772267A discloses a method for preparing carbazole by a liquid phase method of diphenylamine, wherein diphenylamine, solvent butyric acid or a mixed solution of butyric acid and other acids and catalyst palladium trifluoroacetate are added into an electromagnetic stirring pressurized reaction kettle, oxygen or air is introduced to react for 5 hours at 120 ℃, the conversion rate of diphenylamine is 98.2% when the sample is taken and analyzed, and the carbazole selectivity is 99.9%. However, this method uses a large amount of solvent and noble metal catalyst, and is not suitable for mass industrial production.
Ishida et al (Ishida T, tsunoda R, zhang Z, et al supported palladium hydroxide-catalyzed intramolecular double C-H bond functionalization for synthesis of carbazoles and dibenzofurans. ApplCatal B-Environ,2014, 150:523-531.) studied in Pd (OH) 2 The catalyst is/C, acetic acid is used as a solvent, and diphenylamine is subjected to intramolecular oxidative coupling dehydrogenation to prepare carbazole, wherein the yield is 24%; the method also researches that when acetic acid and toluene, acetic acid and THF are used as mixed solvents, the yield of carbazole is respectively improved by 33% and 30%; when trifluoroacetic acid is added as a cosolvent, the carbazole yield is improved to 30%, and when chloroform or water is added as the cosolvent, the beneficial effect is not achieved. Liegault et al (Liegault B, lee D, huestis M P, et al Intra molecular Pd (II) -catalyzed oxidative biaryl synthesis under air: reaction development and scope. Journal of Organic Chemistry,2008,73 (13): 5022-5028.) uses diphenylamine as a reaction starting material, acetic acid as a solvent, pd (OAc) 2 As catalyst, and adding small amount of K 2 CO 3 Although the reaction under an air atmosphere at 110 ℃ increases the yield, the carbazole yield is still lower, whereas when pivalic acid is used instead of the acetic acid solvent, the carbazole product selectivity is significantly improved, and it is suggested that pivalic acid plays an important role as a cocatalyst in palladium-catalyzed benzene arylation reactions, thus suggesting that pivalic acid promotes C-H bond cleavage. Wang et al (Wang S, mao H, ni Z, et al Pd (I)I) Catalyzed intramolecular C-H activation/C-C cross coupling for the synthesis of carbazoles from diacrylamides tetrahedron Letters 2012,53 (5): 505-508.) palladium catalyzed intramolecular C-H activation/C-C cross-coupling in N, N-diphenylacetamide was studied to form carbazole with different substituents. Firstly synthesizing an intermediate product N, N-diphenyl acetamide through acetanilide and iodobenzene, and then reacting the N, N-diphenyl acetamide in the presence of a palladium catalyst and an oxidant to generate N-acetylcarbazole; at 120℃5% Pd (OAc) was used 2 And Cu (OAc) 2 /Ag 2 O or CsCO 3 /Ag 2 Under the condition that O is a catalyst and acetic acid is a solvent, carbazole yields are 60% and 68% respectively; this document developed an efficient method for producing substituted carbazole by tandem C-H activation. Vlcko et alM,Z, hronec M, et al gas-phase dehydrocyclization of diphenylamine. Applied Catalysis A: general,2007,328 (2): 183-188.) studied the vapor phase dehydrogenation of diphenylamine to carbazole in a fixed bed reactor with platinum and palladium as active components and alumina, magnesia and silica as supports, and the results showed that the palladium catalyst had higher activity but not higher selectivity, while the platinum catalyst had both high activity and selectivity. The most common catalyst for preparing carbazole by dehydrogenating diphenylamine at present is Pt/gamma-Al 2 O 3 The catalyst is unevenly dispersed and has low metal utilization efficiency. The synthesis process in the prior art is gradually eliminated due to the problems of high cost, low product purity, serious pollution and the like. Therefore, it is particularly important to develop a carbazole preparation method with high efficiency, low cost, few byproducts and long catalyst life.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is that the existing diphenylamine dehydrogenation catalyst is uneven in dispersion and low in noble metal utilization rate, and the composition of the catalyst is optimized and improved, so that the dehydrogenation catalyst with even dispersion and high noble metal utilization rate is provided.
The invention also provides a method for preparing the dehydrogenation catalyst, which does not need to directly add metal salt into a reaction system, so that the separation process of the catalyst after the reaction is finished is simpler and more convenient, salt waste is not generated, the purity of the product is improved, and the cost of three-waste treatment is reduced.
Furthermore, the invention also provides application of the dehydrogenation catalyst in preparing carbazole compounds by catalyzing the dehydrogenation of substituted or unsubstituted diphenylamine, and the catalyst can show better catalytic activity and stability under mild reaction conditions, so that the problems of short service life, low purity of reaction products and low yield of the traditional catalyst are solved.
The technical scheme adopted by the invention for achieving the purpose is as follows:
in a first aspect, the present invention provides a dehydrogenation catalyst comprising the composition of: active component, auxiliary agent and carrier, wherein the active component is Pt, and the carrier is ZrO 2 The auxiliary agent is at least one of Co, ni and Fe.
The dehydrogenation catalyst provided by the invention is prepared from the prior Pt/Al 2 O 3 Co and/or Ni and/or Fe doping is carried out on the basis of the catalyst, and the addition of the auxiliary agents can form an alloy structure with Pt, so that mutual electron transfer occurs, a synergistic effect is generated, and the best catalytic activity is achieved. And the invention also adopts ZrO 2 Substitution of Al 2 O 3 As a carrier, other than Al 2 O 3 Strong acidity of (3), zrO 2 The catalyst is an acid-base two-phase oxide, the acidity provides an active site for the isomerization of the diphenylamine, and the alkalinity is favorable for the desorption of carbazole compounds on the surface of the catalyst, so that the catalytic performance is better exerted.
In an alternative embodiment, the Pt content is 0.1wt% to 5wt% and the adjuvant content is 0.1wt% to 15wt% based on the mass of the support.
In an alternative embodiment, the Pt content is from 0.1wt% to 2wt%, more preferably from 0.8wt% to 1.2wt%.
In an alternative embodiment, the adjuvant is present in an amount of 6wt% to 11wt%.
In an alternative embodiment, the composition of the dehydrogenation catalyst comprises:
0.99wt% of Pt, 4.98wt% of Co and 2.50wt% of Ni; or alternatively, the first and second heat exchangers may be,
1.02wt% of Pt, 4.99wt% of Co and 5.98wt% of Ni; or alternatively, the first and second heat exchangers may be,
0.99wt% of Pt, 5.02wt% of Co and 3.59wt% of Ni; or alternatively, the first and second heat exchangers may be,
pt 1wt%, co 7.01wt%, ni 2.49wt%; or alternatively, the first and second heat exchangers may be,
Pt 1wt％、Co 5.01wt％、Ni 1.21wt％。
in a second aspect, the present invention provides a process for preparing the dehydrogenation catalyst described above, comprising the steps of:
dissolving a platinum source and a salt containing an auxiliary agent in deionized water to obtain a mixed solution, immersing a carrier in the mixed solution for 1-4 hours, removing the solvent, and carrying out first roasting and reduction on the residue.
According to the preparation method, the metal soluble salt can be changed into oxide by removing the solvent and then roasting.
In an alternative embodiment, the solvent is removed by rotary evaporation at a temperature of 70 to 150 ℃ for a period of 1 to 24 hours.
In an alternative embodiment, the first firing temperature is 250 ℃ to 750 ℃ for a period of 0.5h to 10h.
In an alternative embodiment, the molar concentration of platinum in the mixed solution is 0.085mol/L to 0.42mol/L and the molar concentration of the auxiliary is 0.028mol/L to 3.2mol/L.
In an alternative embodiment, the support is subjected to a second calcination prior to impregnation in order to regulate the acidity of the support.
In an alternative embodiment, the second firing temperature is 300 ℃ to 1000 ℃ for a period of 0.5h to 10h.
In an alternative embodiment, the temperature of the rotary evaporation is 100 ℃ to 120 ℃ and the time is 2 hours to 6 hours.
In an alternative embodiment, the first firing temperature is 450 ℃ to 650 ℃ for 3 hours to 6 hours.
In an alternative embodiment, the second firing temperature is 450 ℃ to 650 ℃ for 3 hours to 6 hours.
In an alternative embodiment, the platinum source is selected from at least one of nitrate, oxalate, acetate, chloride.
In an alternative embodiment, the builder-containing salt is selected from at least one of carbonate, nitrate, oxalate, acetate, chloride.
According to the method for preparing the dehydrogenation catalyst, provided by the invention, the metal salt is not required to be directly added into a reaction system, so that the separation process of the catalyst after the reaction is finished is simpler and more convenient, salt waste is not generated, the product purity is improved, and the three-waste treatment cost is reduced.
In a third aspect, the invention provides an application of the dehydrogenation catalyst in preparing carbazole compounds by catalyzing dehydrogenation of substituted or unsubstituted diphenylamine, wherein the substituted diphenylamine is N-alkyl diphenylamine, and the alkyl contains 1-5 carbon atoms.
In a fourth aspect, the invention also provides a preparation method of the carbazole compound, which comprises the following steps:
in the presence of a catalyst and hydrogen, carrying out dehydrogenation reaction on substituted or unsubstituted diphenylamine to obtain carbazole compounds;
the substituted diphenylamine is N-alkyl diphenylamine, and the alkyl contains 1-5 carbon atoms;
the catalyst is the dehydrogenation catalyst provided by the invention or prepared by the preparation method provided by the invention.
In an alternative embodiment, the dehydrogenation reaction is carried out at a temperature of 180℃to 550℃and at a reaction pressure of normal pressure.
In an alternative embodiment, the dehydrogenation reaction is carried out for a period of time ranging from 5 hours to 168 hours.
In an alternative embodiment, the mass ratio of the substituted or unsubstituted diphenylamine to the catalyst is in the range of 1 to 20:1.
in an alternative embodiment, the dehydrogenation reaction is carried out at a temperature of from 250 ℃ to 255 ℃.
In an alternative embodiment, the mass ratio of the substituted or unsubstituted diphenylamine to the catalyst is in the range of 8 to 12:1.
the preparation method of carbazole compounds provided by the invention utilizes the catalysis of the dehydrogenation catalyst provided by the invention to enable the substituted or unsubstituted diphenylamine to generate intramolecular dehydrogenation ring-closure reaction, so as to prepare carbazole compounds. Compared with the prior art, the preparation method of the carbazole compound not only improves the conversion rate of diphenylamine, but also improves the selectivity of the carbazole compound, thereby being capable of obtaining a target product with high yield.
In addition, the preparation method of the carbazole compound provided by the invention can obtain the conversion rate of substituted or unsubstituted diphenylamine of more than 90% and the selectivity of the carbazole compound of more than 90% at a lower reaction temperature and a smaller reaction pressure, and has the advantages of high product yield, less byproducts, long service life and reduced reaction energy consumption.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is an XRD spectrum of the catalysts prepared in examples 1 to 4 and example 7 of the present invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
In order to solve the problems in the related art described above, according to a first aspect of the present invention, there is provided a dehydrogenation catalyst having a composition comprising: active component, auxiliary agent and carrier, wherein the active component is Pt, and the carrier is ZrO 2 The auxiliary agent is at least one of Co, ni and Fe.
The dehydrogenation catalyst provided by the invention is prepared from the prior Pt/Al 2 O 3 Co and/or Ni and/or Fe doping is carried out on the basis of the catalyst, and the addition of the auxiliary agents can form an alloy structure with Pt, so that mutual electron transfer occurs, a synergistic effect is generated, and the best catalytic activity is achieved. And the invention also adopts ZrO 2 Substitution of Al 2 O 3 As a carrier, other than Al 2 O 3 Strong acidity of (3), zrO 2 The catalyst is an acid-base two-phase oxide, the acidity provides an active site for the isomerization of the diphenylamine, and the alkalinity is favorable for the desorption of carbazole compounds on the surface of the catalyst, so that the catalytic performance is better exerted.
In an alternative embodiment, the Pt content is 0.1wt% to 5wt% and the adjuvant content is 0.1wt% to 15wt% based on the mass of the support.
In an alternative embodiment, the Pt content is from 0.1wt% to 2wt%, more preferably from 0.8wt% to 1.2wt%.
In an alternative embodiment, the adjuvant is present in an amount of 6wt% to 11wt%.
In an alternative embodiment, the composition of the dehydrogenation catalyst comprises:
0.99wt% of Pt, 4.98wt% of Co and 2.50wt% of Ni; or alternatively, the first and second heat exchangers may be,
1.02wt% of Pt, 4.99wt% of Co and 5.98wt% of Ni; or alternatively, the first and second heat exchangers may be,
0.99wt% of Pt, 5.02wt% of Co and 3.59wt% of Ni; or alternatively, the first and second heat exchangers may be,
pt 1wt%, co 7.01wt%, ni 2.49wt%; or alternatively, the first and second heat exchangers may be,
Pt 1wt％、Co 5.01wt％、Ni 1.21wt％。
in a second aspect, the present invention provides a process for preparing the dehydrogenation catalyst described above, comprising the steps of:
dissolving a platinum source and a salt containing an auxiliary agent in deionized water to obtain a mixed solution, immersing a carrier in the mixed solution for 1-4 hours, removing the solvent, and carrying out first roasting and reduction on the residue.
According to the preparation method, the metal soluble salt can be changed into oxide by removing the solvent and then roasting.
In an alternative embodiment, the solvent is removed by rotary evaporation at a temperature of 70 to 150 ℃ for a period of 1 to 24 hours.
In an alternative embodiment, the first firing temperature is 250 ℃ to 750 ℃ for a period of 0.5h to 10h.
In an alternative embodiment, the molar concentration of platinum in the mixed solution is 0.085mol/L to 0.42mol/L and the molar concentration of the auxiliary is 0.028mol/L to 3.2mol/L.
In an alternative embodiment, the support is subjected to a second calcination prior to impregnation in order to regulate the acidity of the support.
In an alternative embodiment, the second firing temperature is 300 ℃ to 1000 ℃ for a period of 0.5h to 10h.
In an alternative embodiment, the temperature of the rotary evaporation is 100 ℃ to 120 ℃ and the time is 2 hours to 6 hours.
In an alternative embodiment, the first firing temperature is 450 ℃ to 650 ℃ for 3 hours to 6 hours.
In an alternative embodiment, the second firing temperature is 450 ℃ to 650 ℃ for 3 hours to 6 hours.
In an alternative embodiment, the platinum source is selected from at least one of nitrate, oxalate, acetate, chloride.
In an alternative embodiment, the builder-containing salt is selected from at least one of carbonate, nitrate, oxalate, acetate, chloride.
According to the method for preparing the dehydrogenation catalyst, provided by the invention, the metal salt is not required to be directly added into a reaction system, so that the separation process of the catalyst after the reaction is finished is simpler and more convenient, salt waste is not generated, the product purity is improved, and the three-waste treatment cost is reduced.
In a third aspect, the invention provides an application of the dehydrogenation catalyst in preparing carbazole compounds by catalyzing dehydrogenation of substituted or unsubstituted diphenylamine, wherein the substituted diphenylamine is N-alkyl diphenylamine, and the alkyl contains 1-5 carbon atoms.
In a fourth aspect, the invention also provides a preparation method of the carbazole compound, which comprises the following steps:
in the presence of a catalyst and hydrogen, carrying out dehydrogenation reaction on substituted or unsubstituted diphenylamine to obtain carbazole compounds;
the substituted diphenylamine is N-alkyl diphenylamine, and the alkyl contains 1-5 carbon atoms;
the catalyst is the dehydrogenation catalyst provided by the invention or prepared by the preparation method provided by the invention.
In an alternative embodiment, the dehydrogenation reaction is carried out at a temperature of 180℃to 550℃and at a reaction pressure of normal pressure.
In an alternative embodiment, the dehydrogenation reaction is carried out for a period of time ranging from 5 hours to 168 hours.
In an alternative embodiment, the mass ratio of the substituted or unsubstituted diphenylamine to the catalyst is in the range of 1 to 20:1.
in an alternative embodiment, the dehydrogenation reaction is carried out at a temperature of from 250 ℃ to 255 ℃.
In an alternative embodiment, the mass ratio of the substituted or unsubstituted diphenylamine to the catalyst is in the range of 8 to 12:1.
the invention is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the invention as claimed.
Example 1
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) 10g of ZrO was weighed out 2 Roasting in a muffle furnace at 800 ℃ for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 0.049g of cobalt nitrate and 1.23g of nickel nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, to obtain a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain the catalyst precursor I.
(4) And (3) placing the catalyst precursor I in a tubular furnace at 350 ℃ and reducing for 4 hours in a hydrogen atmosphere to obtain the catalyst I. The composition of the analytical test catalyst I is as follows, based on the mass of the carrier: pt0.9 wt%, co 0.1wt%, ni 2.49wt%.
Example 2
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 0.49g of cobalt nitrate and 1.23g of nickel nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain a catalyst precursor II.
(4) And (3) placing the catalyst precursor II in a tubular furnace at 350 ℃ and reducing for 4 hours in a hydrogen atmosphere to obtain the catalyst II. The composition of the analytical test catalyst II is as follows, based on the mass of the carrier: pt0.99wt%, co0.98wt%, ni 2.51wt%.
Example 3
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 1.58g of cobalt nitrate and 1.23g of nickel nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain a catalyst precursor III.
(4) And (3) placing the catalyst precursor III in a tubular furnace at 350 ℃ and reducing for 4 hours in a hydrogen atmosphere to obtain the catalyst III. The composition of the analytical test catalyst III is as follows, based on the mass of the carrier: pt 1.01wt%, co2.99wt%, ni 2.49wt%.
Example 4
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 2.45g of cobalt nitrate and 1.23g of nickel nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 1h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain the catalyst precursor IV.
(4) And (3) placing the catalyst precursor IV in a tubular furnace at 350 ℃ and reducing for 4 hours in a hydrogen atmosphere to obtain the catalyst IV. The composition of the analysis and test catalyst IV is as follows, based on the mass of the carrier: pt0.99wt%, co4.98wt%, ni 2.50wt%.
Example 5
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 3.43g of cobalt nitrate and 1.23g of nickel nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into an upper rotary steaming bottle, immersing for 4 hours, rotary evaporating for dehydration, drying for 2 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to obtain a catalyst precursor V.
(4) And (3) placing the catalyst precursor V in a 350 ℃ tubular furnace for reduction for 4 hours in a hydrogen atmosphere to obtain the catalyst V. The composition of the analytical test catalyst V is as follows, based on the mass of the support: pt 1wt%, co 7.01wt% and Ni 2.49wt%.
Example 6
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 2.45g of cobalt nitrate and 0.049g of nickel nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2 hours, dehydrating by rotary evaporation, dehydrating and drying for 2 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to obtain the catalyst precursor VI.
(4) And (3) placing the catalyst precursor VI in a tubular furnace at 350 ℃ and reducing for 4 hours in a hydrogen atmosphere to obtain the catalyst VI. The composition of the analytical test catalyst VI is as follows, based on the mass of the support: pt0.99wt%, co4.969wt% and Ni 0.1wt%.
Example 7
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 2.45g of cobalt nitrate and 0.59g of nickel nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain a catalyst precursor VII.
(4) And (3) placing the catalyst precursor VII in a tubular furnace at 350 ℃ for reduction for 4 hours in a hydrogen atmosphere to obtain the catalyst VII. The composition of the analytical test catalyst VII is as follows, based on the mass of the support: pt 1wt%, co 5.01wt% and Ni 1.21wt%.
Example 8
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 2.45g of cobalt nitrate and 1.78g of nickel nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain a catalyst precursor VIII.
(4) And (3) placing the catalyst precursor VIII in a tubular furnace at 350 ℃ and reducing for 4 hours in a hydrogen atmosphere to obtain the catalyst VIII. The composition of the analytical test catalyst VIII, based on the mass of the carrier, is: pt0.99wt%, co5.02wt%, ni 3.59wt%.
Example 9
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 2.45g of cobalt nitrate and 2.94g of nickel nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain a catalyst precursor IX.
(4) And (3) placing the catalyst precursor IX in a tubular furnace at 350 ℃ and reducing for 4 hours in a hydrogen atmosphere to obtain the catalyst IX. The composition of the analytical test catalyst IX is as follows, based on the mass of the support: pt 1.02wt%, co4.99wt%, ni 5.98wt%.
Example 10
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 And 4.93g of cobalt nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain the catalyst precursor X.
(4) And (3) placing the catalyst precursor X in a tubular furnace at 350 ℃ and reducing for 4 hours in a hydrogen atmosphere to obtain the catalyst X. The composition of the analytical test catalyst X, based on the mass of the support, is: pt 1.01wt%, co9.99wt%.
Example 11
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) Weigh 10g commercialZrO 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 And 4.96g of nickel nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain a catalyst precursor XI.
(4) The catalyst precursor XI was reduced in a tube furnace at 350℃under a hydrogen atmosphere for 4 hours to obtain a catalyst XI. The composition of the analytical test catalyst XI, based on the mass of the support, was: pt0.98wt% and Ni9.99wt%.
Example 12
The preparation method of the dehydrogenation catalyst provided by the embodiment comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 And 7.21g of ferric nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain a catalyst precursor XII.
(4) And (3) placing the catalyst precursor XII in a tubular furnace at 350 ℃ and reducing for 4 hours in a hydrogen atmosphere to obtain the catalyst XII. The composition of the analytical test catalyst XII, based on the mass of the support, is: pt 1.01wt% and Fe9.88wt%.
Comparative example 1
The preparation method of the dehydrogenation catalyst provided by the comparative example comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 Dissolve in 5.99mL deionized water and stir at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain a catalyst precursor XIII.
(4) And (3) placing the catalyst precursor XIII in a tubular furnace at 350 ℃ for reduction for 4 hours in a hydrogen atmosphere to obtain the catalyst XIII. The composition of the analytical test catalyst XIII, based on the mass of the support, was: pt 1.02wt%.
Comparative example 2
The preparation method of the dehydrogenation catalyst provided by the comparative example comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 2.45g of cobalt nitrate and 1.38g of palladium nitrate were dissolved in 5.99mL of deionized water, and stirred at room temperature until completely dissolved, designated as a mixed solution.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain a catalyst precursor XIV.
(4) And (3) placing the catalyst precursor XIV in a tubular furnace at 350 ℃ for reduction for 4 hours in a hydrogen atmosphere to obtain the catalyst XIV. The composition of the analytical test catalyst XIV, based on the mass of the support, was: pt0.98wt%, co4.98wt%, pd 2.5wt%.
Comparative example 3
The preparation method of the dehydrogenation catalyst provided by the comparative example comprises the following steps:
(1) 10g of commercial ZrO were weighed out 2 Placing the carrier in a muffle furnace at 800 ℃ for roasting for 4 hours to obtain ZrO 2 A carrier.
(2) Weigh 0.26gH 2 PtCl 6 、0.92g IrCl 3 ·3H 2 O and 1.23g of nickel nitrate were dissolved in 5.99mL of deionized water and stirred at room temperature until completely dissolved, designated as a mixMixing the solutions.
(3) ZrO of step (1) 2 Placing the carrier in a rotary steaming bottle, pouring the mixed solution in the step (2) into the rotary steaming bottle, immersing for 2h, rotary evaporating for dehydration, drying for 2h at 120 ℃, and roasting for 4h at 550 ℃ to obtain a catalyst precursor XV.
(4) And (3) placing the catalyst precursor XV in a tubular furnace at 350 ℃ and reducing for 4 hours in a hydrogen atmosphere to obtain the catalyst XV. The composition of the analytical test catalyst XV, based on the mass of the support, is: pt 1.01wt%, ir 5.01wt%, ni 2.5wt%
Experimental example 1
XRD analysis
XRD tests were carried out on the dehydrogenation catalysts prepared in examples 1 to 4 and example 7, and XRD spectra are shown in FIG. 1. As can be seen from fig. 1, the catalyst prepared by the method has better dispersibility, and only shows characteristic peaks of auxiliary cobalt in XRD, which indicates that cobalt is successfully loaded on the surface of the catalyst; no peak of nickel was detected, probably because the metal of nickel was crystallized to a higher degree and the content was relatively low.
Experimental example 2
1. Evaluation of Activity of catalyst
Crushing the dehydrogenation catalysts prepared in the examples 1 to 12 and the comparative examples 1 to 3, screening out 2g of the catalyst with 20 to 40 meshes, loading the catalyst into a reaction kettle reactor, keeping the temperature at 350 ℃ for 4 hours in a pure hydrogen atmosphere, cooling to the reaction condition, and loading 20g of diphenylamine, thereby carrying out the diphenylamine dehydrogenation performance test. The reaction temperature is 255 ℃, the initial reaction pressure is normal pressure, the reaction time is 5 hours, and after the reaction is stable, the reaction product is condensed and then is analyzed by off-line chromatography. The analysis results are shown in Table 1.
Table 1 reaction results for each catalyst
From the above table, the conversion rate and selectivity of examples 1 to 12 are all above 90%, which indicates that the catalyst prepared by the method has better activity.
2. Catalyst Activity test under different reaction conditions
Taking the catalyst IV as an example, the activity of the catalyst at different temperatures is examined, and the results are shown in Table 2.
TABLE 2 reaction results of the dehydrogenation of diphenylamine under different conditions
From the above table, it can be seen that the catalyst IV shows better activity under different conditions.
3. Catalyst life test
Crushing and screening a dehydrogenation catalyst IV, loading 2g of a 20-40 mesh catalyst into a fixed bed reactor, introducing diphenylamine and hydrogen into the reactor for dehydrogenation reaction, wherein the reaction temperature is 275 ℃, the reaction pressure is 0.1MPa, and the molar ratio of the hydrogen to the diphenylamine is 8:1, liquid hourly space velocity of 0.23 g.gcat -1 ·h -1 The reaction product was condensed and analyzed by gas chromatography, and the analysis results are shown in table 3.
TABLE 3 catalyst IV catalytic diphenylamine dehydrogenation results
| 24h | 48h | 72h | 96h | 120h | 144h | 168h | |
| Conversion/% | 97.38 | 97.12 | 97.17 | 97.15 | 97.13 | 97.14 | 97.17 |
| Selectivity/% | 95.59 | 95.51 | 95.55 | 95.59 | 95.52 | 95.52 | 95.59 |
From the table, the conversion rate and the selectivity are similar at different times, which shows that the auxiliary agent inhibits the deactivation of the carbon deposition of the catalyst, limits the deactivation rate of the catalyst, prolongs the service life of the catalyst, and can keep higher activity under the action of a long time, but the addition of the auxiliary agent can delay the deactivation of the carbon deposition of the catalyst, but cannot avoid the deactivation of the carbon deposition.
4. Dehydrogenation test of N-methyldiphenylamine
Crushing and screening catalyst IV, and loading 2g of 20-40 mesh catalyst into a fixed bed reactorIn the method, N-methyl diphenylamine and hydrogen are introduced into a reactor for dehydrogenation reaction, the reaction temperature is 275 ℃, the reaction pressure is 0.1MPa, and the molar ratio of the hydrogen to the N-methyl diphenylamine is 8:1, liquid hourly space velocity of 0.23 g.gcat -1 ·h -1 The reaction time was 168 hours, the reaction product was condensed and analyzed by chromatography, the conversion of N-methyldiphenylamine was 97.18%, the selectivity of N-methylcarbazole was 97.35%, and the yield of N-methylcarbazole was 94.60%. Therefore, the catalyst prepared by the invention is also suitable for dehydrogenation of the N-alkyl diphenylamine compounds.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst comprises: active component, auxiliary agent and carrier, wherein the active component is Pt, and the carrier is ZrO 2 The auxiliary agent is at least one of Co, ni and Fe.
2. The dehydrogenation catalyst of claim 1, wherein the Pt content is 0.1wt% to 5wt% and the promoter content is 0.1wt% to 15wt% based on the mass of the support;
preferably, the Pt content is 0.1wt% to 2wt%, more preferably 0.8wt% to 1.2wt%;
preferably, the content of the auxiliary agent is 6-11 wt%.
3. The dehydrogenation catalyst of claim 1 or 2, wherein the composition of the dehydrogenation catalyst comprises:
0.99wt% of Pt, 4.98wt% of Co and 2.50wt% of Ni; or alternatively, the first and second heat exchangers may be,
1.02wt% of Pt, 4.99wt% of Co and 5.98wt% of Ni; or alternatively, the first and second heat exchangers may be,
0.99wt% of Pt, 5.02wt% of Co and 3.59wt% of Ni; or alternatively, the first and second heat exchangers may be,
pt 1wt%, co 7.01wt%, ni 2.49wt%; or alternatively, the first and second heat exchangers may be,
Pt 1wt％、Co 5.01wt％、Ni 1.21wt％。
4. a process for preparing a dehydrogenation catalyst according to any one of claims 1 to 3, comprising the steps of:
dissolving a platinum source and a salt containing an auxiliary agent in deionized water to obtain a mixed solution, immersing a carrier in the mixed solution for 1-4 hours, removing the solvent, and carrying out first roasting and reduction on the residue.
5. The method according to claim 4, wherein the solvent is removed by rotary evaporation at a temperature of 70 to 150 ℃ for 1 to 24 hours; and/or the number of the groups of groups,
the temperature of the first roasting is 250-750 ℃ and the time is 0.5-10 h; and/or the number of the groups of groups,
the carrier is subjected to second roasting before being impregnated, wherein the second roasting temperature is 300-1000 ℃ and the time is 0.5-10 h;
the molar concentration of platinum in the mixed solution is 0.085 mol/L-0.42 mol/L, and the molar concentration of the auxiliary agent is 0.028 mol/L-3.2 mol/L;
preferably, the temperature of the rotary evaporation is 100-120 ℃ and the time is 2-6 h; and/or the number of the groups of groups,
preferably, the temperature of the first roasting is 450-650 ℃ and the time is 3-6 h; and/or the number of the groups of groups,
preferably, the temperature of the second roasting is 450-650 ℃ and the time is 3-6 h.
6. The method according to claim 4 or 5, wherein the platinum source is at least one selected from the group consisting of nitrate, oxalate, acetate, chloride;
and/or the auxiliary-containing salt is at least one selected from carbonate, nitrate, oxalate, acetate and chloride.
7. Use of the dehydrogenation catalyst according to any one of claims 1 to 3 or prepared by the preparation method according to any one of claims 4 to 6 for the preparation of carbazole compounds by catalytic dehydrogenation of substituted or unsubstituted diphenylamine, said substituted diphenylamine being N-alkyl diphenylamine, said alkyl group containing 1 to 5 carbon atoms.
8. The preparation method of the carbazole compound is characterized by comprising the following steps:
in the presence of a catalyst and hydrogen, carrying out dehydrogenation reaction on substituted or unsubstituted diphenylamine to obtain carbazole compounds;
the substituted diphenylamine is N-alkyl diphenylamine, and the alkyl contains 1-5 carbon atoms;
the catalyst is a dehydrogenation catalyst according to any one of claims 1 to 3 or a dehydrogenation catalyst prepared by the preparation method according to any one of claims 4 to 6.
9. The method for producing carbazole compound according to claim 8, wherein the dehydrogenation reaction is carried out at a temperature of 180 ℃ to 550 ℃ and a reaction pressure of normal pressure; and/or the number of the groups of groups,
the dehydrogenation reaction time is 5-168 hours; and/or the number of the groups of groups,
the mass ratio of the substituted or unsubstituted diphenylamine to the catalyst is 1-20: 1.
10. the method for producing carbazole compound according to claim 9, wherein the dehydrogenation reaction is carried out at a temperature of 250 to 255 ℃; and/or the number of the groups of groups,
the mass ratio of the substituted or unsubstituted diphenylamine to the catalyst is 8-12: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310702716.5A CN116803505B (en) | 2023-06-13 | 2023-06-13 | Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310702716.5A CN116803505B (en) | 2023-06-13 | 2023-06-13 | Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116803505A true CN116803505A (en) | 2023-09-26 |
| CN116803505B CN116803505B (en) | 2024-03-26 |
Family
ID=88080289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310702716.5A Active CN116803505B (en) | 2023-06-13 | 2023-06-13 | Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116803505B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117143141A (en) * | 2023-10-30 | 2023-12-01 | 江苏南大光电材料股份有限公司 | Preparation method and preparation system of tri (dimethylamino) silane |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0892213A (en) * | 1994-09-29 | 1996-04-09 | Osaka Gas Co Ltd | Production of carbazole |
| US5760247A (en) * | 1996-05-24 | 1998-06-02 | Bayer Aktiengesellschaft | Process for the preparation of carbazole |
| CN102548966A (en) * | 2009-08-24 | 2012-07-04 | K·H·伽达 | Method for synthesizing N-alkylcarbazoles and derivatives thereof |
| CN104059015A (en) * | 2014-06-30 | 2014-09-24 | 江苏飞亚化学工业有限责任公司 | Method for synthesizing carbazole by fixed bed process |
| CN114100609A (en) * | 2021-12-14 | 2022-03-01 | 中国天辰工程有限公司 | Catalyst for preparing large cyclic olefin through dehydrogenation reaction, and preparation method and application thereof |
| CN114797912A (en) * | 2022-05-30 | 2022-07-29 | 安徽工业大学 | Dehydrogenation catalyst and preparation method thereof |
| CN114797947A (en) * | 2022-05-19 | 2022-07-29 | 兄弟科技股份有限公司 | Efficient dehydrogenation catalyst and application thereof in preparation of pyridine by dehydrogenation of piperidine raw materials |
| CN115739080A (en) * | 2022-11-30 | 2023-03-07 | 中国科学院大连化学物理研究所 | Preparation of Pt-based catalyst and application of Pt-based catalyst in preparation of chloroaniline by selective hydrogenation of chloronitrobenzene |
-
2023
- 2023-06-13 CN CN202310702716.5A patent/CN116803505B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0892213A (en) * | 1994-09-29 | 1996-04-09 | Osaka Gas Co Ltd | Production of carbazole |
| US5760247A (en) * | 1996-05-24 | 1998-06-02 | Bayer Aktiengesellschaft | Process for the preparation of carbazole |
| CN102548966A (en) * | 2009-08-24 | 2012-07-04 | K·H·伽达 | Method for synthesizing N-alkylcarbazoles and derivatives thereof |
| CN104059015A (en) * | 2014-06-30 | 2014-09-24 | 江苏飞亚化学工业有限责任公司 | Method for synthesizing carbazole by fixed bed process |
| CN114100609A (en) * | 2021-12-14 | 2022-03-01 | 中国天辰工程有限公司 | Catalyst for preparing large cyclic olefin through dehydrogenation reaction, and preparation method and application thereof |
| CN114797947A (en) * | 2022-05-19 | 2022-07-29 | 兄弟科技股份有限公司 | Efficient dehydrogenation catalyst and application thereof in preparation of pyridine by dehydrogenation of piperidine raw materials |
| CN114797912A (en) * | 2022-05-30 | 2022-07-29 | 安徽工业大学 | Dehydrogenation catalyst and preparation method thereof |
| CN115739080A (en) * | 2022-11-30 | 2023-03-07 | 中国科学院大连化学物理研究所 | Preparation of Pt-based catalyst and application of Pt-based catalyst in preparation of chloroaniline by selective hydrogenation of chloronitrobenzene |
Non-Patent Citations (1)
| Title |
|---|
| MIROSLAV VLCKO ET AL: "Dehydrocyclization of Diphenylamine to Carbazole over Platinum-Based Bimetallic Catalysts", 《CHINESE JOURNAL OF CATELYSIS》, vol. 31, no. 11, pages 1439 - 1444, XP027565108 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117143141A (en) * | 2023-10-30 | 2023-12-01 | 江苏南大光电材料股份有限公司 | Preparation method and preparation system of tri (dimethylamino) silane |
| CN117143141B (en) * | 2023-10-30 | 2024-01-12 | 江苏南大光电材料股份有限公司 | Preparation method and preparation system of tri (dimethylamino) silane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116803505B (en) | 2024-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN116803505B (en) | Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation | |
| KR20210152882A (en) | Modified organometallic framework and catalyst for hydrogenation reactions comprising the same | |
| WO2014108031A1 (en) | Use of catalyst of subgroup vi element for preparing organic chemical product from lignin | |
| CN104277017A (en) | Method for preparing 2,5-dimethylaminofuran from 2,5-dihydroxymethylfuran | |
| CN114939438B (en) | Method for selective hydrogenation of olefinic unsaturated carbonyl compound and catalyst thereof | |
| CN116920837B (en) | Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation | |
| CN113717038B (en) | Method for synthesizing diaryl ether by nickel/ketone double-catalysis reaction of halogenated aromatic hydrocarbon and aryl phenol | |
| Calcio Gaudino et al. | Batch and Flow Green Microwave‐Assisted Catalytic Conversion Of Levulinic Acid to Pyrrolidones | |
| CN114377718A (en) | Nickel-copper bimetallic catalyst and preparation method and application thereof | |
| WO2018157817A1 (en) | Selective hydrogenation catalyst, preparation method therefor, and evaluation method for catalytic preparation of 2-methylallyl alcohol | |
| Guo et al. | Efficient conversion of furfural to cyclopentanol over lignin activated carbon supported Ni–Co catalyst | |
| CN106608776A (en) | Synthetic method of imine | |
| CN116803498B (en) | Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation | |
| CN110624604A (en) | A kind of modified palladium carbon catalyst, its preparation method and application | |
| CN113083349B (en) | Preparation method and application of SBA-15 modified by nano Cu simple substance | |
| CN114516796A (en) | Method for preparing 5-oxohexanoate | |
| CN108314646B (en) | Method for preparing drug intermediate for urogenital system from high-dispersion bimetal nano material | |
| CN111841587A (en) | Solid base catalyst and preparation method thereof | |
| CN108863905A (en) | A kind of preparation method of indeno succinimide class compound | |
| CN111393338A (en) | A kind of dofetilide-d3 medicine and preparation method thereof | |
| CN117964585A (en) | Method for preparing gamma-butyrolactone by 1, 4-butanediol dehydrogenation coupling succinic acid hydrogenation | |
| CN110028437B (en) | Method for preparing 2-phenyl-3-aldehyde indole compound under microwave promotion | |
| CN114249629B (en) | Method for synthesizing enol by selective catalytic hydrogenation of alkynol | |
| CN111250162B (en) | Solid base catalyst, and preparation method and application thereof | |
| WO2023044884A1 (en) | Method for synthesizing diaryl ether by reacting nickel/ketone double-catalyzed halogenated aromatic hydrocarbon with arylphenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |