CN106622325B - Rhenium catalyst and method for catalytically synthesizing 2-methyl-1, 4-naphthoquinone by using rhenium catalyst - Google Patents
Rhenium catalyst and method for catalytically synthesizing 2-methyl-1, 4-naphthoquinone by using rhenium catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 229910052702 rhenium Inorganic materials 0.000 title claims abstract description 57
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 22
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 title abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title abstract description 5
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 12
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 150000003282 rhenium compounds Chemical class 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 47
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 21
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- -1 azoles chloride Chemical class 0.000 claims 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 1
- 150000003716 vitamin K3 derivatives Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- 238000001291 vacuum drying Methods 0.000 description 37
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 239000012299 nitrogen atmosphere Substances 0.000 description 19
- 239000012041 precatalyst Substances 0.000 description 19
- 238000002156 mixing Methods 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZTVIKZXZYLEVOL-DGKWVBSXSA-N 2-hydroxy-2-phenylacetic acid [(1R,5S)-8-methyl-8-azabicyclo[3.2.1]octan-3-yl] ester Chemical group C([C@H]1CC[C@@H](C2)N1C)C2OC(=O)C(O)C1=CC=CC=C1 ZTVIKZXZYLEVOL-DGKWVBSXSA-N 0.000 description 1
- SRJCJJKWVSSELL-UHFFFAOYSA-N 2-methylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(C)=CC=C21 SRJCJJKWVSSELL-UHFFFAOYSA-N 0.000 description 1
- LDASJCNYZISQSR-UHFFFAOYSA-N CC1=CC2=CC=CC=C2C=C1.OO Chemical compound CC1=CC2=CC=CC=C2C=C1.OO LDASJCNYZISQSR-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 208000004880 Polyuria Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000035619 diuresis Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000012711 vitamin K3 Nutrition 0.000 description 1
- 239000011652 vitamin K3 Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a rhenium catalyst and a method for catalyzing and synthesizing 2-methyl-1, 4-naphthoquinone by the rhenium catalyst; the method is characterized in that a rhenium compound is loaded on activated carbon and coated by a carbon-nitrogen material, and then the rhenium compound is calcined in an inert gas atmosphere to obtain the coated supported rhenium catalyst, wherein the supported rhenium accounts for 1-3% of the total mass of the catalyst. The method for synthesizing 2-methyl-1, 4-naphthoquinone by the catalyst comprises the following steps: the method comprises the following specific steps: adding 2-methylnaphthalene, oxidant and catalyst into organic solvent, controlling reaction temperature and time to obtain 2-methyl-1, 4-naphthoquinone. The catalyst has simple preparation method and good stability, is suitable for industrial production, shows good activity and selectivity for the reaction, and is easy to recycle and reuse.
Description
Technical field
The present invention relates to a kind of rhenium catalyst and its methods for catalyzing and synthesizing 2-MNQ, more particularly to one kind
The activated carbon supported rhenium metal nano catalyst and catalysis oxidation of carbon-nitrogen material cladding synthesize 2- methyl-1,4-naphthaquinone.
Background technique
2-MNQ (abbreviation 2-MNQ) is the Vitamin K3 used earliest, and synthesis multivitamin K
Important intermediate.The compound has blood coagulation resisting function, can effectively activate the intracorporal anticoagulin of biology；It can also make
For the additive for promoting domestic animal growth and development feed；It is also most important fat-soluble antioxidant in biosystem, can promotes
Energy-rich compound has the effect of diuresis, enhancing liver detoxification function in the intracorporal metabolism of people.
There are many preparation methods of 2-MNQ, can generally be divided into direct oxidation method and indirect oxidation method.Direct oxidation method
Have with 2- methyl naphthalene (CN105481673A), 2- methyl-1-hydroxyl naphthalene (RSC Advances, 2016,16,12717), 2- first
Base -1- methoxynaphthalene (Tetrohedron Lett, 2005,46,1091；) or 2- methyl-1, EP0247513 4- dimethoxy-naphthalene
(Tetrohedron Lett, 2001,42,6899；) etc. be raw material response path；The report of indirect oxidation method is relatively fewer,
Including methylation reaction (JP2002138063), Diels-Alder reaction (Tur.J.Chem.2002,26,251) etc..
It is most simple as the synthetic route of raw material using 2- methyl naphthalene in various preparation methods.Oxidant have Peracetic acid and
Chromic anhybride etc..Oxidizer catalytic oxidation 2- methyl naphthalene (CN103254056A is with substance containing chromium；Med.Chem.Comm, 2014,
5,923；Tetrahedron, 1980,36,123；) yield be 42-65%, but during the reaction, chromate waste water and contain
The generation of chromium solid waste causes serious pollution to environment, makes it unsuitable for industrial application, thus prepare green,
It is stable, reusable catalyst is particularly important to industrial requirement.
Currently, it is relatively fewer using the relevant report of Re catalysis oxidation 2- methyl naphthalene, and it is faced with rhenium content in catalyst
Higher (EP0665209A1, Re:2%) or the irretrievable problem of catalyst (Angew.Chem.Int.Ed.Engl.,
1994,33 (23/24), 2475) etc..
Summary of the invention
A kind of rhenium catalyst is provided the purpose of the invention is to improve the deficiencies in the prior art, another mesh of the invention
There is provided using above-mentioned catalyst synthesis 2- methyl-1,4-naphthaquinone method.The invention is used for existing catalyst
The problem of amount is big, reaction efficiency is low, environmental pollution is serious, provides that a kind of reaction condition is mild, reaction yield is high, catalyst amount
It is low, the environmentally protective new method that 2-MNQ is prepared by 2- methyl Fluidized bed.
The technical solution of the present invention is as follows: a kind of rhenium catalyst, it is characterised in that rhenium compound is carried on active carbon by carbon
Nitrogen material cladding, then calcining obtains the stable Supported rhenium catalyst being wrapped by under atmosphere of inert gases, wherein rhenium
Load quality accounts for the 1%-3% of catalyst gross mass.
Specific step is as follows: be added active carbon in the suitable solvents of metallic compound, suitable solvents be methanol or
One of person's ethyl alcohol, stirs evenly, after addition carbon-nitrogen material continues stirring in 50-60 DEG C of oil bath pan, in rotary evaporation
Instrument is dried overnight to obtain pre-catalyst material at 40-50 DEG C of vacuum oven after being spin-dried for solvent；The material is under indifferent gas atmosphere
The nanocatalyst for the activated carbon supported rhenium metal that carbon-nitrogen material coats is obtained after calcining 2-4h at 600-800 DEG C.
It is preferred that above-mentioned rhenium compound is potassium perrhenate (KReO4) or perrhenic acid (HReO4One of).It is preferred that above-mentioned
Carbon-nitrogen material is obtained by one of 1- methyl -3- cyanogen methylimidazolium chloride, dicyandiamide or 1,10- ferrosin are heated
Carbon-nitrogen material.
It is preferred that above-mentioned inert gas is one of nitrogen or argon gas.The calcining heating rate of preferred catalyst is 5-10
℃/min；Calcination temperature is 600 DEG C -800 DEG C；Calcination time is 2-4h.
It is specific to walk the present invention also provides the method using above-mentioned catalyst synthesis 2-MNQ
Suddenly are as follows: in organic solvent, 2- methyl naphthalene, oxidant and catalyst is added, controls reaction temperature in oil bath pan and the time obtains
Product 2- methyl-1,4-naphthaquinone.Finally, filtration catalytic agent, catalyst is i.e. reusable after washing drying with ether.
It is preferred that above-mentioned solvent is one of acetic acid or acetic anhydride；The oxidant is hydrogen peroxide.It is preferred that aoxidizing
The dosage of agent is 3-10 times of equivalent of substrate 2- methyl naphthalene.
It is preferred that above-mentioned reaction temperature is 70-90 DEG C；Reaction time is 6-12h.
The mole dosage of preferred catalyst is the 0.1%-0.3% of substrate 2- methyl naphthalene mole.
The utility model has the advantages that
Preparation method used in catalyst provided by the invention is simple, and stability is good, activity with higher.The catalyst
Prepared by 2-MNQ with high activity and highly selective for 2- methyl naphthalene, is easily recycled, and react tool
Have the advantages that environmentally protective, is very suitable to industrialized production.
Specific embodiment:
Case study on implementation 1:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A1 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 2:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 700 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A2 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 3:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 800 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A3 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 4:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml ethyl alcohol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A4 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 5:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 6h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A5 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 6:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 60 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A6 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 7:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 8h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A7 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 8:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 10h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A8 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 9:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 50 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A9 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 10:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.3152mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A10 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 11:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 8 DEG C/min,
2h is kept at such a temperature.Catalyst A11 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 12:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, obtained pre-catalyst be calcined in tube furnace under nitrogen atmosphere temperature be 600 DEG C, heating rate be 10 DEG C/
Min keeps 2h at such a temperature.Catalyst A12 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 13:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
3h is kept at such a temperature.Catalyst A13 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 14:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
4h is kept at such a temperature.Catalyst A14 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 15:
Measure the perrhenic acid solution containing 0.0200g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A15 is obtained after Temperature fall to room temperature (rhenium load capacity is 2%).
Case study on implementation 16:
Measure the perrhenic acid solution containing 0.0300g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A16 is obtained after Temperature fall to room temperature (rhenium load capacity is 3%).
Case study on implementation 17:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.It stirs
Round-bottomed flask is placed on Rotary Evaporators after mixing and rotates solvent evaporated, then 40 DEG C of vacuum drying in a vacuum drying oven
Overnight, it is 600 DEG C that obtained pre-catalyst is calcined to temperature under argon atmosphere in tube furnace, and heating rate is 5 DEG C/min,
2h is kept at such a temperature.Catalyst A17 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 18:
Weigh 0.0155mgKReO4In a round bottom flask, 20ml methanol is dissolved as solvent, after dissolution into solution
1.0000g active carbon is added, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan, and into round-bottomed flask
0.1576mg 1- methyl -3- cyanogen methylimidazolium chloride is added, 12h is stirred in continuation at such a temperature.By round bottom after stirring
Flask, which is placed on Rotary Evaporators, rotates solvent evaporated, then in a vacuum drying oven 40 DEG C be dried in vacuum overnight, what is obtained is pre-
It is 600 DEG C that catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min, is protected at such a temperature
Hold 2h.Catalyst A18 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 19:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1500mg dicyandiamide is added into round-bottomed flask, 12h is stirred in continuation at such a temperature.Round-bottomed flask is set after stirring
In rotating solvent evaporated on Rotary Evaporators, then in a vacuum drying oven 40 DEG C be dried in vacuum overnight, obtained pre-catalyst
Being calcined to temperature in tube furnace under nitrogen atmosphere is 600 DEG C, and heating rate is 5 DEG C/min, keeps 2h at such a temperature.From
Obtain catalyst A19 after so cooling to room temperature (rhenium load capacity is 1%).
Case study on implementation 20:
Measure the perrhenic acid solution containing 0.0100g rhenium metal in a round bottom flask, 20ml methanol is dilute by its as solvent
It releases, 1.0000g active carbon is then added into solution, 4h is stirred at room temperature.Round-bottomed flask is moved in 50 DEG C of oil bath pan,
And 0.1982mg 1 is added into round-bottomed flask, 12h is stirred in 10- ferrosin, continuation at such a temperature.By round bottom after stirring
Flask, which is placed on Rotary Evaporators, rotates solvent evaporated, then in a vacuum drying oven 40 DEG C be dried in vacuum overnight, what is obtained is pre-
It is 600 DEG C that catalyst is calcined to temperature under nitrogen atmosphere in tube furnace, and heating rate is 5 DEG C/min, is protected at such a temperature
Hold 2h.Catalyst A20 is obtained after Temperature fall to room temperature (rhenium load capacity is 1%).
Case study on implementation 21: the catalyst of preparation is used for the preparation of 2- methyl-1,4-naphthaquinone.
It is carved in pipe in the quartz of 25ml, 0.5mmol 2- methyl naphthalene, 7mmol hydrogen peroxide, 2ml acetic acid and catalyst is added
A1, and the amount of catalyst is 9.3mg, covers tightly quartz and carves pipe pipe close.It is placed in heating reaction 8h in 80 DEG C of oil bath pan, wait react knot
Shu Hou, taking-up high-voltage tube is placed in from oil bath pan cools to room temperature at room temperature, is extracted with ether, gas chromatographic detection 2- methyl naphthalene
Conversion ratio and 2- methyl-1,4-naphthaquinone selectivity.Finally filtering ether washing catalyst, can repeat after dry makes
With.Reaction equation is as follows:
Using catalyst A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17,
The technique of A18, A19, A20 and the process flow of A1 are consistent, and reaction result is listed in the following table respectively:
Except for the following differences, remaining is identical as case study on implementation 21, solvent according to the form below:
| Solvent | 2- methyl naphthalene conversion ratio | 2- methyl-1,4-naphthaquinone selectivity |
| Acetic anhydride | 66% | 75% |
| Acetic acid | 94% | 75% |
Except for the following differences, remaining is identical as case study on implementation 21, reaction temperature according to the form below:
| Temperature | 2- methyl naphthalene conversion ratio | 2- methyl-1,4-naphthaquinone selectivity |
| 70℃ | 80% | 76% |
| 80℃ | 94% | 75% |
| 90℃ | 74% | 75% |
Except for the following differences, remaining is identical as case study on implementation 21, reaction time according to the form below:
| Time | 2- methyl naphthalene conversion ratio | 2- methyl-1,4-naphthaquinone selectivity |
| 6 | 86% | 75% |
| 8 | 94% | 75% |
| 10 | 88% | 75% |
| 12 | 82% | 74% |
Except for the following differences, remaining is identical as case study on implementation 21, amount of hydrogen peroxide according to the form below:
| Amount of hydrogen peroxide | 2- methyl naphthalene conversion ratio | 2- methyl-1,4-naphthaquinone selectivity |
| 5mmol | 24% | 76% |
| 7mmol | 94% | 75% |
Except for the following differences, remaining is identical as case study on implementation 21, mole of metal Re and 2- methyl naphthalene (MNL) in catalyst
Than according to the form below:
| Re:MNL | 2- methyl naphthalene conversion ratio | 2- methyl-1,4-naphthaquinone selectivity |
| 1:1000 | 94% | 75% |
| 2:1000 | 95% | 75% |
| 3:1000 | 95% | 76% |
The recycling service condition of catalyst A1 is as follows:
| Recovered frequency | 2- methyl naphthalene conversion ratio | 2- methyl-1,4-naphthaquinone selectivity |
| 1 | 94% | 75% |
| 2 | 94% | 76% |
| 3 | 93% | 75% |
| 4 | 94% | 76% |
| 5 | 93% | 76% |
| 6 | 93% | 76% |
Claims (7)
1. a kind of rhenium catalyst, it is characterised in that rhenium compound is carried on active carbon and is coated by carbon-nitrogen material, then in inertia
The Supported rhenium catalyst being wrapped by is calcined under atmosphere, wherein the load quality of rhenium accounts for the 1% of catalyst gross mass；
Wherein the calcining heating rate of catalyst is 5-10 DEG C/min；Calcination temperature is 600 DEG C -800 DEG C；Calcination time is 2-4h；Institute
The rhenium compound stated is perrhenic acid.
2. catalyst according to claim 1, it is characterised in that the carbon-nitrogen material is by 1- methyl -3- cyanogen methyl miaow
The heated obtained carbon-nitrogen material of one of azoles chloride, dicyandiamide or 1,10- ferrosin.
3. a kind of method using catalyst as described in claim 1 synthesis 2-MNQ, specific steps
Are as follows: in organic solvent, 2- methyl naphthalene, oxidant and catalyst is added, controls reaction temperature and the time obtains product 2- methyl-
1,4- naphthoquinones.
4. according to the method described in claim 3, it is characterized in that the solvent is one of acetic acid or acetic anhydride；It is described
Oxidant be hydrogen peroxide.
5. according to the method described in claim 3, it is characterized in that the dosage of oxidant is 3-10 times of substrate 2- methyl naphthalene works as
Amount.
6. according to the method described in claim 3, it is characterized in that the reaction temperature is 70-90 DEG C；Reaction time is 6-
12h。
7. according to the method described in claim 3, it is characterized in that the mole dosage of catalyst is substrate 2- methyl naphthalene mole
0.1%-0.3%.
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| CN113171798B (en) * | 2021-05-07 | 2023-07-07 | 南京工业大学 | Heterogeneous iron catalyst, preparation method thereof and process for preparing 2-methyl-1, 4-naphthoquinone by catalysis |
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