CN103694080A - Method for generating cyclohexanol and cyclohexanone by selective oxidation of cyclohexane - Google Patents
Method for generating cyclohexanol and cyclohexanone by selective oxidation of cyclohexane Download PDFInfo
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- CN103694080A CN103694080A CN201210366436.3A CN201210366436A CN103694080A CN 103694080 A CN103694080 A CN 103694080A CN 201210366436 A CN201210366436 A CN 201210366436A CN 103694080 A CN103694080 A CN 103694080A
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- Prior art keywords
- porphyrin
- metal ion
- cyclohexane
- derivatives
- pimelinketone
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 26
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 12
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 41
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011521 glass Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 4
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 3
- 150000003222 pyridines Chemical class 0.000 claims description 11
- 239000004480 active ingredient Substances 0.000 claims description 6
- 150000003009 phosphonic acids Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 10
- JYJVVHFRSFVEJM-UHFFFAOYSA-N iodosobenzene Chemical compound O=IC1=CC=CC=C1 JYJVVHFRSFVEJM-UHFFFAOYSA-N 0.000 abstract description 8
- 150000004033 porphyrin derivatives Chemical class 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- 239000012621 metal-organic framework Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- -1 alcohol ketone Chemical class 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 7
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 description 2
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 102000002004 Cytochrome P-450 Enzyme System Human genes 0.000 description 2
- 101710198130 NADPH-cytochrome P450 reductase Proteins 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- XWVKTOHUMPLABF-UHFFFAOYSA-N thallium(3+) Chemical compound [Tl+3] XWVKTOHUMPLABF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
- C07C27/10—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons
- C07C27/16—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with other oxidising agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/08—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for generating cyclohexanol and cyclohexanone by selective oxidation of cyclohexane; 1.1mL of cyclohexane, 3.3g of PhIO, 15mL of acetonitrile and 1g of catalyst are sequentially added into a glass reactor; after the reaction time at room temperature is 20 hours, centrifuging and filtering the reaction product to obtain cyclohexanol and cyclohexanone; the catalyst is composed of porphyrin or porphyrin derivatives as basic carriers, polypyridine analogues as auxiliary carriers, transition metal ions as active components and metal ions as nodes; the transition metal ion active component is Mn, Fe, V, Pd, Pt or Ru; the basic carrier of porphyrin or porphyrin derivative is porphyrin or derivatives of carboxylic acid, phosphonic acid and sulfonic acid thereof; the polypyridine analogue auxiliary carrier is 4, 4' -bipyridyl or an analogue with two ends being pyridyl; the metal ion node is Fe, Co, Ni, Cu, Zn, Mn or Cd; the method has the cyclohexane conversion rate of 94 percent.
Description
Technical field
The present invention relates to a kind ofly with porphyrin metal-organic framework materials, make catalyzer, selective catalytic oxidation hexanaphthene generates the method for hexalin and pimelinketone.
Background technology
Hexanaphthene selective oxidation generates hexalin and pimelinketone is the focus of producing and studying always.Because not only relate to the activation of saturated carbon hydrogen bond, and hexalin and pimelinketone be important industrial chemicals, is widely used in the industry such as fiber, medicine, industrial coating, synthetic rubber, agricultural chemicals and organic solvent.The traditional technology of producing hexalin and pimelinketone, hexanaphthene turnover ratio is low, alcohol ketone poor selectivity, complex process, seriously polluted, need to be improved, so the research and development of new catalyst become to attach most importance to.
In the catalyzed oxidation of alkene and oxidation of alkanes, porphyrin has very important application.Patent CN1915983A, CN 101070310A and CN 1970148A have reported the application of porphyrin in alkene epoxidation, and patent CN 102367709A, CN 1530357A, CN1269343A, CN1850756A, CN1519218A, CN140513A etc. have reported the application of porphyrin in oxidation of alkanes.The alkene of these patent reports and oxidation of alkanes substantially all need higher pressure and higher temperature, equipment and energy consumption are had to very high requirement, improved industrial cost, therefore how olefin oxide and alkane are problem demanding prompt solutions efficiently at normal temperatures and pressures.Porphyrin compound has also caused the great interest of people for simulating the research work of bioprocess, and what wherein have most prospects for commercial application is exactly to utilize the activation oxygen carrier function of metalloporphyrin analog cytochrome P-450 monooxygenase that hydrocarbon polymer is changed into oxygen containing compound.Iodosobenzene (PhIO) is a kind of good oxygenant, and it easily prepares, nontoxic, and chemical property and reactive behavior are similar to the mixture of mercury (II), thallium (III) and plumbous (IV) etc., and there is no problem of environmental pollution.When carrying out alkene, catalytic oxidation alkane with porphyrin compound analog cytochrome P-450 monooxygenase, the metalloporphyrin transfer of Catalytic Oxygen atom from PhIO to saturated hydrocarbon at normal temperatures and pressures and realize the gentleness activation of the hydrocarbon key of inertia.
Summary of the invention
The object of this invention is to provide the method that hexanaphthene selective oxidation generates hexalin and pimelinketone.Utilize porphyrin-organic framework materials at normal temperatures and pressures Catalytic Oxygen atom from PhIO to saturated hydrocarbon, shift and realize the gentleness activation of the hydrocarbon key of inertia, complete hexanaphthene selective oxidation.
Hexanaphthene selective oxidation of the present invention generates the method for hexalin and pimelinketone, adds successively hexanaphthene 1.1mL, PhIO 3.3g, acetonitrile 15mL, catalyzer 1g in glass reactor.After the room temperature reaction time is 20 hours, reaction product through centrifugal, filter after, obtain hexalin and pimelinketone.
Catalyzer is underlying carrier by 1mmol porphyrin or derivatives of porphyrin, and the many pyridine analogs of 1mmol are assistant carrier, and 1mmol transition metal ion is active ingredient, and 2mmol metal ion is that node forms.
Described transition metal ion active ingredient is Mn, Fe, V, Pd, Pt or Ru; Described catalytic active component is positioned at the center of porphyrin.
Described porphyrin or derivatives of porphyrin underlying carrier are the derivative of porphyrin or its carboxylic acid, phosphonic acids, sulfonic acid.
Described many pyridine analogs assistant carrier is the analogue that 4,4'-Bipyridine or two ends are pyridyl.
Described metal ion node is Fe, Co, Ni, Cu, Zn, Mn or Cd.
The preparation method of above-mentioned porphyrin MOF material, comprises the following steps:
(1) by pyrroles, prepare porphyrin or derivatives thereof with corresponding aldehyde reaction.
(2) utilize corresponding metal-salt in DMF solvent, by back flow reaction, to obtain corresponding metalloporphyrin or metal porphyrin derivative with porphyrin or derivatives of porphyrin.
(3) by acid anhydrides, react many pyridine analogs of preparation assistant carrier with P-aminopyridine.
(4), in mixed solvent, porphyrin or derivatives of porphyrin, many pyridine analogs and metal-salt are obtained to dark-brown crystal at 80 ° of C after after a while.Then filter, with DMF, ethanol and ether solvent, wash successively respectively, finally in air, dry, obtain porphyrin MOF material of the present invention.
Further, in described step (4), described mixed solvent is the mixed solvent of DMF, EtOH and nitric acid, hydrochloric acid, acetic acid or perchloric acid; Described metal-salt is nitrate, chlorate, acetate, the perchlorate of Fe, Co, Ni, Cu, Zn, Mn, Cd.
Above-mentioned porphyrin MOF material can be used as the catalyzer of cyclohexane oxidation.
The present invention compares with existing cyclohexane oxidation catalyst, has following technique effect:
1, reaction conditions is gentle, at normal temperature and pressure, just can carry out catalyzed reaction;
2, cost is low, and catalyzer can recycle;
3, transformation efficiency is high, and selectivity is good;
4, environmental friendliness;
5, operation is simple, is easy to realize suitability for industrialized production.
Embodiment
The present invention is to provide that to take porphyrin or derivatives of porphyrin be underlying carrier, with many pyridine analogs assistant carrier, take transition metal ion as active ingredient, and the metal ion of take is node from the porphyrin MOF of load material catalyst, can be widely used in alkene and oxidation of alkanes.
Porphyrin MOF material of the present invention is mainly comprised of porphyrin or derivatives of porphyrin underlying carrier, many pyridine analogs assistant carrier, transition metal ion active ingredient and metal ion node.Catalytic active component is transition metal, as: Mn, Fe, V, Pd, Pt, Ru; Catalytic active component is positioned at the center of porphyrin; Porphyrin or derivatives thereof carrier is the derivative of porphyrin or its carboxylic acid, phosphonic acids, sulfonic acid; Node metal is Fe, Co, Ni, Cu, Zn, Mn, Cd.
The preparation method of porphyrin MOF catalyzer of the present invention, comprises the following steps:
(1) by pyrroles, prepare porphyrin or derivatives of porphyrin with corresponding aldehyde reaction.
Described aldehyde is to carboxyl benzaldehyde, a carboxyl benzaldehyde, to phosphonate group phenyl aldehyde, a phosphonate group phenyl aldehyde, p-sulfonic acid benzaldehyde, a sulfonic benzo formaldehyde.
(2) utilize corresponding metal-salt in DMF solvent, by back flow reaction, to obtain corresponding metalloporphyrin or metal porphyrin derivative with porphyrin or derivatives of porphyrin.
Nitrate, acetate, perchlorate, halogenide, vitriol that described metal-salt is Mn, Fe, V, Pd, Pt, Ru are corresponding.
(3) by acid anhydrides, react many pyridine analogs of preparation assistant carrier with P-aminopyridine.
Described acid anhydrides is Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride or pyromellitic dianhydride.
(4), in mixed solvent, metalloporphyrin or metal porphyrin derivative, many pyridine analogs and metal-salt are obtained to dark-brown crystal 80 ° of C reactions after after a while.Then filter, with DMF, ethanol and ether solvent, wash successively respectively, finally in air, dry, obtain porphyrin MOF material of the present invention.
Described mixed solvent is the mixed solvent of DMF, EtOH and nitric acid, hydrochloric acid, acetic acid or perchloric acid; Described metal-salt is nitrate, acetate, perchlorate, halogenide, the vitriol of Mn, Fe, V, Pd, Pt, Ru.
The class zeolite compound that is porous by Advances in crystal X-ray diffraction, PLATON calculating and this MOF material of BET specific surface area calculation specifications.This MOF material has also obtained sign by means such as powder x-ray diffraction, thermal weight loss and IR.
Compare with existing technology, the present invention has high catalytic activity to vinylbenzene, tetrahydrobenzene and cyclohexane oxidation at normal temperatures and pressures, and selectivity is good, and raw material is cheap and easy to get, synthetic simple, catalyzer can recycle, cost is low, particularly can save a large amount of energy consumptions.
Embodiment 1
In the mixed solvent of DMF, EtOH and nitric acid, by the benzoic acid derivative of manganoporphyrin, 1,4,5,8-naphthalenetetracarbacidic acidic acid anhydride reacts preparation many pyridine analogs and zinc nitrate with aminopyridine obtain dark-brown crystal after 80oC places one day, then filter, with DMF, ethanol and ether equal solvent, wash respectively, finally in air, dry.The class zeolite compound that is porous by Advances in crystal X-ray diffraction, PLATON calculating and this MOF material of BET specific surface area calculation specifications.Further by means such as powder x-ray diffraction, thermal weight loss and IR, characterized this MOF material.
Embodiment 1
Catalyst activity evaluation is carried out in the simple reaction glass reaction device with magnetic agitation.In glass reactor, add successively hexanaphthene 1.1mL, PhIO 3.3g, acetonitrile 15mL, catalyzer 1g.After the room temperature reaction time is 20 hours, reaction product through centrifugal, filter after, by gas chromatographic analysis cyclohexane conversion, be 94%, product is hexalin and pimelinketone, hexalin/pimelinketone=40/60.
Embodiment 2
Catalyst activity evaluation is carried out in the simple reaction glass reaction device with magnetic agitation.In glass reactor, add successively hexanaphthene 1.1mL, PhIO 3.3g, acetone 15mL, catalyzer 1g.After the room temperature reaction time is 20 hours, reaction product through centrifugal, filter after, by gas chromatographic analysis cyclohexane conversion, be 41%, product is hexalin and pimelinketone, hexalin/pimelinketone=65/35.
Embodiment 3
Catalyst activity evaluation is carried out in the simple reaction glass reaction device with magnetic agitation.In glass reactor, add successively hexanaphthene 1.1mL, PhIO4.4g, acetonitrile 15mL, catalyzer 1g.After the room temperature reaction time is 20 hours, reaction product through centrifugal, filter after, by gas chromatographic analysis cyclohexane conversion, be 78%, product is hexalin and pimelinketone, hexalin/pimelinketone=55/45.
Embodiment 4
Catalyst activity evaluation is carried out in the simple reaction glass reaction device with magnetic agitation.In glass reactor, add successively hexanaphthene 1.1mL, PhIO2.2g, acetonitrile 15mL, catalyzer 1g.After the room temperature reaction time is 20 hours, reaction product through centrifugal, filter after, by gas chromatographic analysis cyclohexane conversion, be 63%, product is hexalin and pimelinketone, hexalin/pimelinketone=58/42.
Embodiment 5
Reaction and analysis and treatment process and embodiment 12 are identical.After difference is that every secondary response finishes, by centrifugal method by catalyst separating out, after being then dried for several times with acetonitrile washing, be directly used in next catalyzed reaction.Experimental result shows, catalyzer, after 7 times recycle, does not obviously reduce catalytic activity, still keeps higher cyclohexane conversion (79%), and product is hexalin and pimelinketone, hexalin/pimelinketone=67/33.
Claims (1)
1. hexanaphthene selective oxidation generates a method for hexalin and pimelinketone, it is characterized in that: in glass reactor, add successively hexanaphthene 1.1mL, PhIO3.3g, acetonitrile 15mL, catalyzer 1g; After the room temperature reaction time is 20 hours, reaction product through centrifugal, filter after, obtain hexalin and pimelinketone;
Catalyzer is underlying carrier by 1mmol porphyrin or derivatives of porphyrin, and the many pyridine analogs of 1mmol are assistant carrier, and 1mmol transition metal ion is active ingredient, and 2mmol metal ion is that node forms;
Described transition metal ion active ingredient is Mn, Fe, V, Pd, Pt or Ru;
Described porphyrin or derivatives of porphyrin underlying carrier are the derivative of porphyrin or its carboxylic acid, phosphonic acids, sulfonic acid;
Described many pyridine analogs assistant carrier is the analogue that 4,4'-Bipyridine or two ends are pyridyl;
Described metal ion node is Fe, Co, Ni, Cu, Zn, Mn or Cd.
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| CN106565417A (en) * | 2016-09-24 | 2017-04-19 | 上海大学 | Method for synthesizing OH-HBCDs by porphyrin biomimetic catalyst oxidation of HBCDs |
| CN107983397A (en) * | 2017-12-06 | 2018-05-04 | 上海应用技术大学 | A kind of cobalt manganese bimetallic catalyst aoxidized for cyclohexane selectivity, preparation method and application |
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| CN101298054A (en) * | 2008-06-19 | 2008-11-05 | 复旦大学 | Coordination polymer molecular aggregate catalyst material containing metalloporphyrin and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106565417A (en) * | 2016-09-24 | 2017-04-19 | 上海大学 | Method for synthesizing OH-HBCDs by porphyrin biomimetic catalyst oxidation of HBCDs |
| CN106565417B (en) * | 2016-09-24 | 2019-07-23 | 上海大学 | The method that porphyrin bionic catalyst aoxidizes HBCDs synthesis OH-HBCDs |
| CN107983397A (en) * | 2017-12-06 | 2018-05-04 | 上海应用技术大学 | A kind of cobalt manganese bimetallic catalyst aoxidized for cyclohexane selectivity, preparation method and application |
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