CN104610030A - Method for preparing cyclohexanone compounds through catalytic action and vapor phase hydrogenation of phenolic compounds - Google Patents
Method for preparing cyclohexanone compounds through catalytic action and vapor phase hydrogenation of phenolic compounds Download PDFInfo
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- CN104610030A CN104610030A CN201510022808.4A CN201510022808A CN104610030A CN 104610030 A CN104610030 A CN 104610030A CN 201510022808 A CN201510022808 A CN 201510022808A CN 104610030 A CN104610030 A CN 104610030A
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- 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
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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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
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- 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
Abstract
The invention discloses a method for preparing cyclohexanone compounds through catalytic action and vapor phase hydrogenation of phenolic compounds. The phenolic compounds are preheated and vaporized and have a hydrogenation reaction with hydrogen under the action of a catalyst, a product is collected after condensed, and the catalyst is a porous carbon supported Pd (palladium) catalyst and comprises 0.1wt%-20wt% of Pd particles and 80 wt%-99.9 wt% of porous carbon carriers. The porous carbon supported Pd catalyst is adopted for continuous operation and is economical and convenient; with adoption of the method, the phenolic compounds are efficiently catalyzed in a high-selectivity manner to synthesize the corresponding cyclohexanone compounds, the selectivity can be 97.1%-98.1%, the conversion rate can be 99.1%-99.9%, and the yield is higher than the yield produced when an ordinary Pd/C catalyst is used by more than 10%. The porous carbon supported Pd catalyst is stable to water, air and heat and can be continuously used for an experiment for 1,000 hours, the activity of the catalyst is not changed, and the catalytic performance is good.
Description
Technical field
The present invention relates to organic synthesis field, particularly relate to a kind of method that catalysis phenolic compound gas phase hydrogenation prepares cyclohexanone analog compound.
Background technology
Pimelinketone is important Organic Chemicals, mainly for the preparation of monomer hexanolactam and the hexanodioic acid of synthon nylon 6 and nylon66 fiber, simultaneously or the important intermediate of the fine chemicals such as medicine, coating, dyestuff, a small amount of as industrial solvents such as rubber, leather, coating and agricultural chemicals, also can be used as the auxiliary agent of fine chemicals.Because phenol/pimelinketone, phenol/hexalin form azeotrope, so its separation is the commercial run that a cost is very high, based on this, the content of phenol in product should be reduced as far as possible.
Pimelinketone industrial manufacture process mainly contains cyclohexane oxidation process, cyclohexene hydration method and phenol hydrogenation method in the world.Nineteen forty-three, I.G.Fargen company of Germany built up the production equipment of phenol hydrogenation method synthesizing cyclohexanone.Nineteen sixty, BASF Corp. of Germany adopted cyclohexane oxidation process to build up large-scale cyclohexanone production apparatus, cyclohexane oxidation technology is developed rapidly, and causes the extensive development of tynex.Cyclohexane liquid-phase oxidation method has two oxidizing process routes, and one is catalytic oxidation technique, and another kind is non-catalyst oxidation technique.Catalytic oxidation technique mainly adopts cobalt salt, boric acid or metaboric acid to be catalyzer, but this method needs to carry out under higher temperature and pressure, easily multiple oxidized byproduct is produced in catalytic oxidation of cyclohexane process, thus adopt the method for low-conversion (<10%), highly selective (about 80%), and this technological cycle energy consumption is large.Non-catalytic oxidation method has French Phone-Ponlene company first to develop, be characterized in reaction in two steps, the first step is under the condition of 160 ~ 170 DEG C, the direct oxidation by air of hexanaphthene is cyclohexyl hydroperoxide, second under alkaline condition and catalyst action condition, decomposing cyclohexyl hydrogen peroxide is pimelinketone and hexalin, the advantage of this technique is reaction proceed step by step, oxidation stage does not adopt catalyzer, avoid the problem of oxidizing reaction phase slagging scorification, run continuously under the condition that device is allowed at equipment, and the yield of cyclohexyl hydroperoxide can reach more than 95%.Its shortcoming is that the selectivity of hexalin and pimelinketone in decomposing cyclohexyl hydrogen peroxide process is less than 90%, and needs a large amount of alkali.Because this technique hexanaphthene per pass conversion is lower, technical process is increased, causes energy consumption higher.Asahi Chemical Industry of Japan developed cyclohexene hydration and prepared pimelinketone technique the eighties in 20th century, this technique take benzene as raw material, 100 ~ 800 DEG C, 3 ~ 10Mpa, ruthenium catalyst condition under carry out Partial hydrogenation reaction prepare tetrahydrobenzene, the transformation efficiency 50 ~ 60% of benzene, the selectivity of tetrahydrobenzene is 80%, the by product of 20% is hexanaphthene, under supersiliceous zeolite ZSM-5 catalyst action, cyclohexene hydration generates hexalin, hexalin dewaters generation pimelinketone further, the per pass conversion of tetrahydrobenzene is 10% ~ 15%, and the selectivity of hexalin can reach 99%.This technique effectively prevent the waste lye produced in cyclohexane oxidation process, reduces environmental pollution, but complex steps, intermediate product separation difficulty.From phenol one step Hydrogenation for pimelinketone because step is simple, reaction temperature and and enjoy the favor of people.Phenol hydrogenation comprises gas phase and liquid-phase hydrogenatin, and catalyzer used is mainly centered around in the research of load P d type gas phase catalysis.The feature of its uniqueness gives its excellent catalytic activity, selectivity, anti-poisoning performance, also has eco-friendly feature simultaneously, one of efficient and eco-friendly new catalytic material becoming 21 century most DEVELOPMENT PROSPECT.
The life-span of phenol liquid phase hydrogenating catalyst is restricted, and the catalyzer after reaction needs to filter, and requires higher to catalyst reaction device, and active component palladium solution runs off.The pimelinketone very solution continuation hydrogenation production hexalin that phenol liquid-phase hydrogenatin is produced, the bad control of process.The commercial catalysts Rh/C such as Shirai, Ru/C, Pd/C, Pt/C, have studied supercritical CO
2in phenol hydrogenation, activity is lower.When 55 DEG C, CO
2with H
2pressure be respectively 10Mp condition under, Rh/C catalyst phenol conversion 53%, the selectivity of pimelinketone only has 17%; The transformation efficiency of Pd/C catalyzer only has 3%, the selectivity 54% of pimelinketone.CO
2when pressure is increased to 20Mp, Rh/C catalyst phenol hydrogenation transformation efficiency can reach 87%, and the selectivity of pimelinketone can bring up to 34%.At patent US4,203,923,4,200,553,3,076, disclose in 810 and carry out phenol liquid phase catalytic hydrogenation by the method for Pd/C catalyzer and prepare pimelinketone, the active ingredient of catalyzer is Pd, and gac is as carrier.These reaction process only can provide low selectivity when providing high reactive behavior; Or only can provide low reactive behavior when providing high selectivity.But from angle that is economic and reaction, phenol selectivity Hydrogenation needs high reactive behavior and high selectivity for the reaction process of pimelinketone.Thus obtaining highly purified pimelinketone, this point is to very important during industrial production.
Phenol gas phase hydrogenation one step prepares pimelinketone can realize successive reaction, and Process liquor controls, easy to operate, production safety, environmental nonpollution.Phenol gas phase hydrogenation single stage method prepares the reaction of pimelinketone as shown in Figure 1.
When phenol gas phase selective catalytic hydrogenation prepares pimelinketone, first phenol produce cyclohexenol through catalytic hydrogenation, and the unstable tautomerism of cyclohexenol generates pimelinketone, and pimelinketone continues shortening and produces hexalin.From thermodynamic (al) principle, pimelinketone shortening is more favourable to generation hexalin, and it is difficult that reaction be made to rest on this step of pimelinketone, so must study this reaction from kinetics and catalyzer angle.If catalyzer activity very higher position easily generates hexalin, if the transformation efficiency of the too low phenol of activity is just low, this is conflict.Solve this contradiction, just must study from catalyzer and reaction conditions, namely prepared catalyzer must have higher reactive behavior and very high selectivity.Catalyzed reaction is normally carried out at the internal surface of catalyzer, because much larger than outside surface of internal surface, and phenol is a larger ring molecule, so having in high optionally situation, the aperture of improving catalyzer is conducive to the reactive behavior increasing catalyzer.Improve selectivity then to need to select active ingredient and carrier.For this reason, in the present invention, the catalytic active component of use is selected from periodic table of elements group VIIIB, such as palladium, ruthenium, rhodium, platinum, nickel, preferred palladium, and charge capacity is at 0.1wt ~ 20wt% scope, preferably 5wt%; Require that carrier has larger aperture and specific surface, carrier can adopt gac, activated alumina, SiO
2deng, preferred gac.
The practicable consecutive production of green syt route of phenol gas phase process for selective hydrogenation process simple production process safety environmentally safe, reaction conditions is gentle, and catalyzer is not easily aging, and Pd reclaims convenient, and process easily controls, and produces without waste water and gas.At present, to develop the catalyzer that pimelinketone is prepared in the selective hydrogenation of multiple phenol gas phase.The gas phase hydrogenation catalyzer reported comprises Pd/Al
2o
3, Pd/MgO, Pd/La
2o
3, Pd/CeO
2, Pd/CeO
2-MS, Pd/ZrO
2-MS, Pd/SiO
2, Pd-Yb/SiO
2, Pd/C, Pd/TiO
2, Ru/Al
2o
3, Ni/SiO
2deng.
At document Srinivas ST, Rao PK.Highly selective platinum-chromium/carbon alloy catalysts for single-step vapor phase hydrogenation of phenol togive cyclohexanone [J] .J Chem Soc, Chem Commun.1993 (1): in 33-34., Pt-Cr alloy is as active ingredient, charcoal is as carrier, prepare in pimelinketone reaction at phenol gas phase hydrogenation, selectivity is 100%, but transformation efficiency only has 50 ~ 55%.
At document Smeykal K, Naumann HJ, Schaefer H, Becker K, Veit J, Block A, inventors; In VEB Leuna-Werke " Walter Ulbricht " .assignee.Production of cyclohexanone by the selective hydrogenation of phenol patent GB1063357.1967., Pd is active ingredient, γ-Al
2o
3for carrier, in order to the selectivity of the transformation efficiency and pimelinketone that improve phenol, the method of adding CaO is have employed in the document, containing the pimelinketone of 95% and the hexalin of 2% in the product finally obtained, but still have the phenol that 3% is conversion, because phenol and pimelinketone, hexalin can form azeotrope, this adds difficulty in separation.In patent RU 2528980 C2, when selectivity is 100, transformation efficiency is only 84%.When in patent KR 20091183, transformation efficiency is 99.3, selectivity is 92.9%.In patent NL 7704346 A, when selectivity is 95, transformation efficiency is only 89.9%.
In patent DE 2025726 A, the carrier selected is activated alumina, and active ingredient is Pd, selects the Na of interpolation 3 ~ 10wt%
2cO
3, at 130 DEG C, the content of reactor product cyclohexanone is 92%, and the content of hexalin is 5%, and the content of phenol is 3%.Because phenol gas phase hydrogenation used catalyst reactive behavior is in a mild condition general not high, and pimelinketone easily further hydrogenation generation hexalin.Therefore, in a mild condition efficiently, the catalysis of phenol one-step synthesis pimelinketone of highly selective become the difficult point of this area research, and the key addressed this problem is the design of catalyzer.
Porous carbon material is a class non-silicon porous material, it has larger specific surface area and pore volume, good electroconductibility and the performance superior to most organic solvent inertia etc., and it is easily by calcining removing, in a lot of, there is complementarity with oxide material, therefore, porous carbon material is obtained for and applies widely in catalysis, absorption, separation, Chu Qing, electrochemistry etc.
Application number is that the Chinese patent application of 201110387825.X discloses metal catalyst that a kind of New Type of Mesoporous charcoal supports and preparation method thereof, metal catalyst is made up of metallics 0.01wt% ~ 90wt% and mesoporous carbon carrier 10wt% ~ 99.99wt%, mesoporous carbon carrier is made up of the mesoporous carbon material of Heteroatom doping, the mesoporous carbon material of this Heteroatom doping be with containing heteroatomic ionic liquid for monomer, at room temperature mix with template, then at 400-1000 DEG C, 1-6h is calcined, be cooled to room temperature, finally remove the mesoporous carbon material that template obtains Heteroatom doping, then ultrasonic method is adopted, deposition-precipitation, metal supports on mesoporous carbon material by any one in sol-gel method and Photodeposition, obtain the metal catalyst that described New Type of Mesoporous charcoal supports.
This invention obtains nano-sized metal particles in the deposition of carrier surface with dispersion by the heteroatomic doping regulation and control valence state of metal and metal, thus is conducive to strengthening its catalytic activity.In addition, this catalyst preparing is simple, to water, air and thermally-stabilised.
Application number be 201410796050.5 Chinese patent application disclose a kind of preparation method of multi-stage porous Carbon Materials, the Pd Pd/carbon catalyst that the material utilizing the method to synthesize synthesizes for carrier is to water, air and thermally-stabilised.
Summary of the invention
The invention provides a kind of method that catalysis phenolic compound gas phase hydrogenation prepares cyclohexanone analog compound.The Pd catalyzer that the present invention adopts porous charcoal to support is efficient, the corresponding cyclohexanone analog compound of highly selective catalysis phenolic compound one step hydrogenation synthesis.
Catalysis phenolic compound gas phase hydrogenation prepares a method for cyclohexanone analog compound, vaporization and hydrogen after phenolic compound preheating is carried out hydrogenation reaction in the reactor under catalyst action, collects product after condensation;
Described catalyzer is the Pd catalyzer for porous charcoal supports, and is made up of 0.1wt% ~ 20wt% (weight percent) Pd particle and 80wt% ~ 99.9wt% porous charcoal carrier;
Described phenolic compound structural formula is such as formula shown in (I):
Described cyclohexanone analog structural formula of compound is such as formula shown in (II):
Formula (I) and the middle substituent R of formula (II) are at least one in hydrogen atom, alkyl, alkoxyl group and hydroxyl.
As preferably, described substituent R is hydrogen atom, methyl, methoxyl group or hydroxyl, now the selection rate of cyclohexanone analog compound and transformation efficiency all the highest.
The Pd catalyzer that porous charcoal supports and quartz sand are filled in reactor with the mixing of mass ratio 1:10 ~ 100.
Described phenolic compound is vaporized afterwards and hydrogen successive reaction in the reactor, and phenolic compound mass space velocity (WHSV) is 0.4 ~ 5h
-1, under this mass space velocity condition, the yield that can realize cyclohexanone analog compound is 96.1 ~ 99.1%; The mol ratio of hydrogen and phenolic compound is 2 ~ 20:1, and the present invention fully mixes after phenolic compound vaporization with excess hydrogen, ensures phenolic compound complete reaction.
The temperature of described reaction is 120 DEG C ~ 220 DEG C, and set temperature can make reactant vaporize, and heats up within the specific limits and can improve transformation efficiency.
The pressure of described reaction is 0.5bar ~ 5bar, and certain pressure can promote the carrying out reacted, but hypertonia can cause selectivity to decline.
What described reaction was reacted by gas-chromatography on-line checkingi carries out degree, and the stable reaction time is 0.5h-1h, and substrate is different, stable reaction time slightly difference.
The Pd catalyzer that described porous charcoal supports can adopt application number preparation method disclosed in the patent application of 201110387825.X to obtain.
Preferably, the preparation method of the Pd catalyzer existing porous charcoal supported improves further, and concrete steps are as follows:
(1) biomass material, small molecules nitrogenous compound and template or pore-forming material mixed calcining, cooling, removing template or pore-forming material obtain porous charcoal carrier; (2) porous charcoal carrier and PdCl
2mix ultrasonic after obtain through reduction reaction the Pd catalyzer that porous charcoal supports.
Further preferably, the preparation method of Pd catalyzer porous charcoal in the present invention supported improves, and concrete steps are as follows:
A () nitrogenous carbohydrate derivative mixes with template or pore-forming material, calcine, cool, obtain porous charcoal carrier with water removing pore-forming material;
(b) porous charcoal carrier and PdCl
2mix ultrasonic after obtain through reduction reaction the Pd catalyzer that porous charcoal supports.
In above-mentioned steps (1), the mass ratio of described biomass material, small molecules nitrogenous compound and template or pore-forming material is 0.5 ~ 20:1 ~ 20:1, and the porous charcoal carrier obtained in this proportional range contains abundant micropore and mesoporous and suitable nitrogen content.
Step (1) described biomass material is at least one in shell, wood chip, Mierocrystalline cellulose, bamboo, glucose and fructose; Described small molecules nitrogenous compound is at least one in trimeric cyanamide, urea, ammonium oxalate and amino acid.Selected biomass material is in the process of charing, and small molecules nitrogenous compound decomposes simultaneously, and nitrogen element can being doped in high-area carbon of original position.
Step (1) and the described template of step (a) are at least one of silicon sol Ludox HS, KIT-6 and SBA-15, and the template adopted with existing preparation method is same or similar.
Described pore-forming material is at least one in saleratus and sodium bicarbonate.
Carbohydrate derivative nitrogenous described in above-mentioned steps (a) and the mass ratio of template are 0.5 ~ 20:1, and the porous charcoal carrier obtained in this proportional range contains abundant micropore and mesoporous.
Described nitrogenous carbohydrate derivative is the one in glucosamine hydrochloride and chitin.
Porous charcoal carrier and PdCl in step (2) and step (b)
2mass ratio be 5 ~ 100:1.
Calcine after biomass material mixes with template or pore-forming material, cool, remove template and obtain porous charcoal carrier.The porous charcoal carrier that this method obtains obtains the Pd catalyzer that porous charcoal supports, and the selection rate of its catalyzed reaction is 90.4% ~ 96.9%, and transformation efficiency is 46.7% ~ 65.2%, and transformation efficiency is lower.
Preferably, biomass material, small molecules nitrogenous compound are calcined after mixing with template or pore-forming material, cool, are removed template or pore-forming material obtains porous charcoal carrier.The porous charcoal carrier that this method obtains obtains the Pd catalyzer that porous charcoal supports, and its catalysis selection rate is 94.2% ~ 97.5%, and transformation efficiency is 82.5% ~ 96.7%, and selection rate and transformation efficiency are all improved.
Preferably, calcine after nitrogenous carbohydrate derivative mixes with template or pore-forming material, cool, remove template and obtain porous charcoal carrier.The porous charcoal carrier that this method obtains obtains the Pd catalyzer that porous charcoal supports, and the selection rate of its catalyzed reaction is 96.8% ~ 97.4%, and transformation efficiency is 98.5% ~ 99.9%, and selection rate and transformation efficiency improve further.
Phenolic compound in feed chute is heated to molten state in initial reaction stage by the inventive method, through standard injection pump delivery, then vaporize through preheating section, vaporization section is entered in the lump afterwards with hydrogen, finally enter superheater with the state of mixed gas, enter reactor after reaching temperature of reaction, successive reaction on the catalyzer that inside is filled, reacted product is collected after condenser condenses.
The phenolic compound that the inventive method adopts is the product that market is sold, for ensureing the purity of cyclohexanone analog compound, phenolic compound purity grade is at least 99wt%, the purity of hydrogen is at least 99wt%, phenolic compound is by standard injection pump delivery, and the flow velocity of hydrogen has mass-flow gas meter to control.
Compared with prior art, the present invention has following beneficial effect:
(1) the transformation efficiency more common Pd/C catalyzer of the Pd catalyst reaction that the porous charcoal that the present invention adopts supports is high by more than 10%.
(2) there is strong interaction between nanometer metal palladium and carrier porous charcoal in the present invention, in conjunction with firmly, limit migration and the reunion of Pd nano particle.The Pd grain diameter 1 ~ 10nm of nano Pd catalyst, is evenly distributed, and good dispersity, catalytic performance is good.
(3) the inventive method adopts the Pd catalyzer that the porous charcoal of high reactivity and highly selective supports, and raw material is cheap and easy to get, energy-conserving and environment-protective, reaction conditions are gentle, operational safety.
(4) the Pd catalyzer that supports of porous charcoal that adopts of the inventive method is to water, air and thermally-stabilised, and carry out experiment in 1000 hours continuously, catalytic activity is constant, can realize operate continuously, economical convenient.Experimental result shows, the catalyst application in the present invention is when pimelinketone is prepared in the selective hydrogenation of phenolic compound gas phase, and the transformation efficiency of phenolic compound can reach more than 99.5%, and the selection rate of pimelinketone can reach more than 97%.
(5) in used catalyst of the present invention, precious metal reclaims conveniently, can directly be obtained by calcination method.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of phenol reduction process.
Fig. 2 is the transmission electron microscope photo of the Pd catalyzer that 5wt% porous charcoal supports.
Fig. 3 is the Pd catalyzer continuity catalytic effect figure that 5wt% porous charcoal supports.
Embodiment
Embodiment 1
By 3.75g template Ludox HS and 4 gram of glucosamine hydrochloride aqueous solution, 1000 DEG C of calcining 3h after evaporate to dryness, remove templated silicas with ammonium bifluoride or NaOH after cool to room temperature, obtain porous carbon material carrier.Get 0.36g porous carbon material to join in 200mL beaker, add 30 ~ 100mL distilled water, ultrasonic vibration 10 ~ 30min, then add the PdCl that 1.5mL concentration is 0.02g/mL
2the aqueous solution, ultrasonic vibration 10 ~ 30min, finally adds 100mgNaBH
4the aqueous solution, ultrasonic vibration 10 ~ 60min, filters, washing, and dry, namely obtain the nano metal Pd catalyzer that 5wt% porous carbon material supports, as shown in Figure 2, the size of Pd particle is within the scope of 1 ~ 20nm.Be heated to 550 DEG C in atmosphere, catalyzer has no obvious decomposition.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.24g catalyzer obtained is in the quartz tube reactor of 5mm, the flow 40mL/min of hydrogen, temperature of reaction is 160 DEG C, pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector, column temperature 260 DEG C, vaporizer 280 DEG C, detector 280 DEG C.By regulating the mass space velocity (WHSV) of phenol, make the yield of product cyclohexanone maximum.Analyze after testing, when pimelinketone yield is maximum, the mass space velocity of phenol is 3.84h
-1, the transformation efficiency of phenol is 99.1 ~ 99.9%, and the selectivity of pimelinketone is 97 ~ 98%, and foreign matter content is less than 0.5%, and through the operation of 1000h, catalyst activity does not reduce, as shown in Figure 3.
Embodiment 2
By 3.75g template KIT-6 and 4 gram of glucosamine hydrochloride aqueous solution, 1000 DEG C of calcining 3h after evaporate to dryness, remove templated silicas with ammonium bifluoride or NaOH after cool to room temperature, obtain porous carbon material carrier.Get 0.36g porous carbon material to join in 200mL beaker, add 30 ~ 100mL distilled water, ultrasonic vibration 10 ~ 30min, then add the PdCl that 1.5mL concentration is 0.02g/mL
2the aqueous solution, ultrasonic vibration 10 ~ 30min, finally adds 100mgNaBH
4the aqueous solution, ultrasonic vibration 10 ~ 60min, filters, washing, and dry, namely obtain the nano metal Pd catalyzer that 5wt% porous carbon material supports, the size of Pd particle is within the scope of 1 ~ 100nm.Be heated to 550 DEG C in atmosphere, catalyzer has no obvious decomposition.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.24g catalyzer obtained is in the quartz tube reactor of 5mm, the flow 40mL/min of hydrogen, temperature of reaction is 160 DEG C, and pressure is normal pressure, and the mass space velocity (WHSV) of phenol is identical with embodiment 1.
Embodiment 3
By 3.75g template SBA-15 and 4 gram of amino acid-glucose hydrochloride aqueous solution, 1000 DEG C of calcining 3h after evaporate to dryness, remove templated silicas with ammonium bifluoride or NaOH after cool to room temperature, obtain porous carbon material carrier.Get 0.36g porous carbon material to join in 200mL beaker, add 30 ~ 100mL distilled water, ultrasonic vibration 10 ~ 30min, then add the PdCl that 1.5mL concentration is 0.02g/mL
2the aqueous solution, ultrasonic vibration 10 ~ 30min, finally adds 100mgNaBH
4the aqueous solution, ultrasonic vibration 10 ~ 60min, filters, washing, and dry, namely obtain the nano metal Pd catalyzer that porous carbon material supports, the size of Pd particle is within the scope of 1 ~ 100nm.Be heated to 550 DEG C in atmosphere, catalyzer has no obvious decomposition.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.24g catalyzer obtained is in the quartz tube reactor of 5mm, the flow 40mL/min of hydrogen, temperature of reaction is 160 DEG C, and pressure is normal pressure, and the mass space velocity (WHSV) of phenol is identical with embodiment 1.
Embodiment 1 ~ 3 has investigated the impact of template on catalyst performance, the character of carrier and to be applied to phenol gas phase selective hydrogenation result as shown in table 1,
Table 1
Embodiment 4
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is glucose unlike charcoal source.
Embodiment 5
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is glucose unlike biomass material used, and small molecules nitrogenous compound is urea.
Embodiment 6
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is fructose unlike charcoal source.
Embodiment 7
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is glucose unlike biomass material, and small molecules nitrogenous compound is trimeric cyanamide.
Embodiment 8
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is glucose unlike biomass material, and small molecules nitrogenous compound is ammonium oxalate.
Different charcoal source has been investigated to the impact of catalyst performance in embodiment Isosorbide-5-Nitrae ~ 8, is applied to phenol gas phase selective hydrogenation result as shown in table 2,
Table 2
| Embodiment | Ketone selection rate Sel.% | Transformation efficiency Conv.% |
| 1 | 97.1～98.1 | 99.1～99.9 |
| 4 | 94.5～95.5 | 56.1～57.5 |
| 5 | 96.5～97.5 | 82.5～83.5 |
| 6 | 95.8～96.9 | 46.7～47.8 |
| 7 | 96.5～97.4 | 85.6～86.6 |
| 8 | 96.1～97.3 | 88.5～89.3 |
Embodiment 9
Mixed with 12g sodium bicarbonate pore-forming material by 6g glucosamine hydrochloride, 800 DEG C of calcining 3h, remove sodium carbonate with water after cool to room temperature, and after filtration, washing, drying obtains porous carbon material carrier.Get 0.36g porous carbon material to join in 200mL beaker, add 30 ~ 100mL distilled water, ultrasonic vibration 10 ~ 30min, then add the PdCl that 1.5mL concentration is 0.02g/mL
2the aqueous solution, ultrasonic vibration 10 ~ 30min, finally adds 100mgNaBH
4the aqueous solution, ultrasonic vibration 10 ~ 60min, filters, and washing is dried, namely obtained the nano metal Pd catalyzer that 5wt% porous carbon material supports.Be heated to 550 DEG C in atmosphere, catalyzer has no obvious decomposition.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.24g catalyzer obtained is in the quartz tube reactor of 5mm, the flow 40mL/min of hydrogen, temperature of reaction is 160 DEG C, and pressure is normal pressure, and the mass space velocity (WHSV) of phenol is identical with embodiment 1.
Embodiment 10
Adopting the method synthetic vectors identical with embodiment 9 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is bamboo unlike biomass material.
Embodiment 11
Adopting the method synthetic vectors identical with embodiment 9 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is chitin unlike nitrogenous carbohydrate derivative.
Embodiment 12
Adopting the method synthetic vectors identical with embodiment 9 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is Mierocrystalline cellulose unlike biomass material.
Embodiment 13
Adopting the method synthetic vectors identical with embodiment 9 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is wood chip unlike biomass material.
Embodiment 14
Adopting the method synthetic vectors identical with embodiment 9 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is Mierocrystalline cellulose unlike biomass material, and small molecules nitrogenous compound is ammonium oxalate.
Embodiment 15
Adopting the method synthetic vectors identical with embodiment 9 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is Mierocrystalline cellulose unlike biomass material, and small molecules nitrogenous compound is urea.
Embodiment 9 ~ 15 reaction result is as shown in table 3,
Table 3
| Embodiment | Ketone selection rate Sel.% | Transformation efficiency Conv.% |
| 9 | 96.8～97.4 | 98.5～99.7 |
| 10 | 96.1～97.2 | 98.2～99.5 |
| 11 | 94.7～96.1 | 96.1～97.4 |
| 12 | 91.3～92.6 | 63.7～65.2 |
| 13 | 90.4～91.5 | 54.7～56.2 |
| 14 | 94.5～96.4 | 96.8～98.1 |
| 15 | 94.2～95.1 | 95.7～96.8 |
Embodiment 16
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition with phenol gas phase hydrogenation reaction, is 2-methylphenol unlike substrate.
Embodiment 17
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition with phenol gas phase hydrogenation reaction, is 3-methylphenol unlike substrate.
Embodiment 18
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition with phenol gas phase hydrogenation reaction, is o-phenol unlike substrate.
Embodiment 19
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition with phenol gas phase hydrogenation reaction, is p methoxy phenol unlike substrate.
Embodiment 1,16 ~ 19 have investigated the impact of differential responses substrate on catalyst performance, under gas phase selective hydrogenation result is as shown in table 4,
Table 4
| Embodiment | Ketone selection rate Sel.% | Transformation efficiency Conv.% |
| 1 | 97.1～98.1 | 99.1～99.9 |
| 16 | 96.1～97.1 | 97.1～99.1 |
| 17 | 95.1～96.1 | 98.3～99.1 |
| 18 | 95.4～97.1 | 97.1～98.5 |
| 19 | 95.8～96.5 | 96.7～97.8 |
Embodiment 20
Adopt carrier and the catalyzer of patent 201110387825.X synthesis, and have identical condition in phenol gas phase hydrogenation, the transformation efficiency of phenol is 93.8 ~ 94.5%, and the selectivity of pimelinketone is 96.1 ~ 97.3%.
Embodiment 21
The carrier adopting patent 201410796050.5 to synthesize and catalyzer, and in phenol gas phase hydrogenation, there is identical condition, the transformation efficiency of phenol is 95.1.8 ~ 96.3%, and the selectivity of pimelinketone is 95.8 ~ 96.9%.
Embodiment 22
Get the business Pd/C catalyzer of certain mass, come from Shaanxi Rui Ke novel material company limited, make to measure identical containing Pd amount with the Pd that contains of catalyzer in embodiment 1,2,3 in catalyzer, when being applied to phenol gas phase hydrogenation reaction condition and embodiment 1,2,3 identical.Reaction result and embodiment 1 compare, as shown in table 5,
Table 5
| Embodiment | Ketone selection rate Sel.% | Transformation efficiency Conv.% |
| 1 | 97.1～98.1 | 99.1～99.9 |
| 22 | 96.8～98.2 | 88.1～89.1 |
Embodiment 23
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 130 DEG C unlike temperature of reaction.
Embodiment 24
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 140 DEG C unlike temperature of reaction.
Embodiment 25
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 150 DEG C unlike temperature of reaction.
Embodiment 26
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 160 DEG C unlike temperature of reaction.
Embodiment 27
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 170 DEG C unlike temperature of reaction.
Embodiment 28
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 180 DEG C unlike temperature of reaction.
Embodiment 29
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 190 DEG C unlike temperature of reaction.
Embodiment 30
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 200 DEG C unlike temperature of reaction.
Embodiment 23 ~ 30 has been investigated differential responses temperature in embodiment 1 and, on the impact of catalyst performance, has been applied to phenol gas phase selective hydrogenation result as shown in table 6,
Table 6
| Embodiment | Ketone selection rate Sel.% | Transformation efficiency Conv.% |
| 23 | 94.8 | 98.9 |
| 24 | 97.8 | 99.5 |
| 25 | 97.2 | 99.6 |
| 26 | 96.3 | 99.7 |
| 27 | 96.1 | 99.7 |
| 28 | 96.0 | 99.8 |
| 29 | 93.2 | 99.7 |
| 30 | 89.8 | 99.7 |
Embodiment 31
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 0.5bar unlike reaction pressure.
Embodiment 32
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 1bar unlike reaction pressure.
Embodiment 33
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 1.5bar unlike reaction pressure.
Embodiment 34
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 2bar unlike reaction pressure.
Embodiment 35
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 2.5bar unlike reaction pressure.
Embodiment 36
Adopting the method synthetic vectors identical with embodiment 1 and catalyzer, and have identical condition in phenol gas phase hydrogenation reaction, is 3bar unlike reaction pressure.
Embodiment 31 ~ 36 has been investigated differential responses pressure in embodiment 1 and, on the impact of catalyst performance, has been applied to phenol gas phase selective hydrogenation result as shown in table 7,
Table 7
| Embodiment | Ketone selection rate Sel.% | Transformation efficiency Conv.% |
| 31 | 99.5 | 68.4 |
| 32 | 97.5 | 99.1 |
| 33 | 96.8 | 99.5 |
| 34 | 94.1 | 99.7 |
| 35 | 88.7 | 99.8 |
| 36 | 79.5 | 99.9 |
Embodiment 37
Adopt the method synthetic vectors identical with embodiment 1 and catalyzer, and in phenol gas phase hydrogenation reaction, there is identical condition, unlike the mass velocity of phenol, make the mol ratio of hydrogen and phenol be 0.5:1.
Embodiment 38
Adopt the method synthetic vectors identical with embodiment 1 and catalyzer, and in phenol gas phase hydrogenation reaction, there is identical condition, unlike the mass velocity of phenol, make the mol ratio of hydrogen and phenol be 1:1.
Embodiment 39
Adopt the method synthetic vectors identical with embodiment 1 and catalyzer, and in phenol gas phase hydrogenation reaction, there is identical condition, unlike the mass velocity of phenol, make the mol ratio of hydrogen and phenol be 2:1.
Embodiment 40
Adopt the method synthetic vectors identical with embodiment 1 and catalyzer, and in phenol gas phase hydrogenation reaction, there is identical condition, unlike the mass velocity of phenol, make the mol ratio of hydrogen and phenol be 3:1.
Embodiment 41
Adopt the method synthetic vectors identical with embodiment 1 and catalyzer, and in phenol gas phase hydrogenation reaction, there is identical condition, unlike the mass velocity of phenol, make the mol ratio of hydrogen and phenol be 4:1.
Embodiment 42
Adopt the method synthetic vectors identical with embodiment 1 and catalyzer, and in phenol gas phase hydrogenation reaction, there is identical condition, unlike the mass velocity of phenol, make the mol ratio of hydrogen and phenol be 5:1.
Embodiment 43
Adopt the method synthetic vectors identical with embodiment 1 and catalyzer, and in phenol gas phase hydrogenation reaction, there is identical condition, unlike the mass velocity of phenol, make the mol ratio of hydrogen and phenol be 6:1.
Embodiment 44
Adopt the method synthetic vectors identical with embodiment 1 and catalyzer, and in phenol gas phase hydrogenation reaction, there is identical condition, unlike the mass velocity of phenol, make the mol ratio of hydrogen and phenol be 7:1.
Embodiment 37 ~ 44 has been investigated different hydrogen and phenol mol ratio in embodiment 1 and, on the impact of catalyst performance, has been applied to phenol gas phase selective hydrogenation result as shown in table 8.
Table 8
| Embodiment | Ketone selection rate Sel.% | Transformation efficiency Conv.% |
| 37 | 99.2 | 28.7 |
| 38 | 98.1 | 56.8 |
| 39 | 97.6 | 83.5 |
| 40 | 97.4 | 99.5 |
| 41 | 97.8 | 99.5 |
| 42 | 96.7 | 99.6 |
| 43 | 95.0 | 99.7 |
| 44 | 92.9 | 99.8 |
Table 8 describes hydrogen and phenol mol ratio when being 4:1, and reaction effect is best.
Claims (10)
1. catalysis phenolic compound gas phase hydrogenation prepares a method for cyclohexanone analog compound, it is characterized in that, vaporization and hydrogen after phenolic compound preheating is passed in reactor and carry out hydrogenation reaction under catalyst action, collect product after condensation;
Described catalyzer is the Pd catalyzer that porous charcoal supports, and be made up of the Pd particle of 0.1wt% ~ 20wt% and the porous charcoal carrier of 80wt% ~ 99.9wt%, Pd mean particle size is 1nm ~ 10nm;
Described phenolic compound structural formula is such as formula shown in (I):
Described cyclohexanone analog structural formula of compound is such as formula shown in (II):
Formula (I) and the middle R of formula (II) are at least one in hydrogen atom, alkyl, alkoxyl group and hydroxyl.
2. catalysis phenolic compound gas phase hydrogenation according to claim 1 prepares the method for cyclohexanone analog compound, it is characterized in that, the Pd catalyzer that porous charcoal supports and quartz sand are filled in reactor with the mixing of mass ratio 1:10 ~ 100.
3. catalysis phenolic compound gas phase hydrogenation according to claim 1 prepares the method for cyclohexanone analog compound, and it is characterized in that, described hydrogenation reaction is carried out in the reactor continuously, and phenolic compound mass space velocity is 0.4 ~ 5h
-1, the mol ratio of hydrogen and phenolic compound is 2 ~ 20:1.
4. the catalysis phenolic compound gas phase hydrogenation according to claim 1 or 3 prepares the method for cyclohexanone analog compound, it is characterized in that, temperature of reaction is 120 DEG C ~ 220 DEG C, and reaction pressure is 0.5bar ~ 5bar.
5. catalysis phenolic compound gas phase hydrogenation according to claim 1 prepares the method for cyclohexanone analog compound, it is characterized in that, the Pd catalyzer that described porous charcoal supports is prepared by following methods:
(1) biomass material, small molecules nitrogenous compound mix with template or pore-forming material, obtain porous charcoal carrier through calcining, cooling, removing template or pore-forming material;
(2) porous charcoal carrier and PdCl
2mix ultrasonic after obtain through reduction reaction the Pd catalyzer that porous charcoal supports.
6. catalysis phenolic compound gas phase hydrogenation according to claim 1 prepares the method for cyclohexanone analog compound, it is characterized in that, the Pd catalyzer that described porous charcoal supports is prepared by following methods:
(1) nitrogenous carbohydrate derivative mixes through calcining, cool with template or pore-forming material, remove template or pore-forming material obtains porous charcoal carrier;
(2) porous charcoal carrier and PdCl
2mix and ultrasonicly obtain through reduction reaction the Pd catalyzer that porous charcoal supports.
7. the catalysis phenolic compound gas phase hydrogenation according to claim 5 or 6 prepares the method for cyclohexanone analog compound, it is characterized in that, described pore-forming material is at least one in saleratus and sodium bicarbonate, and described template is at least one of silicon sol Ludox HS, KIT-6 and SBA-15.
8. catalysis phenolic compound gas phase hydrogenation according to claim 5 prepares the method for cyclohexanone analog compound, it is characterized in that, the mass ratio of biomass material, small molecules nitrogenous compound and template or pore-forming material is 0.5 ~ 20:1 ~ 20:1, described biomass material is at least one in shell, bamboo, wood chip, Mierocrystalline cellulose, fructose and glucose, and described small molecules nitrogenous compound is at least one in trimeric cyanamide, urea, ammonium oxalate and amino acid.
9. catalysis phenolic compound gas phase hydrogenation according to claim 6 prepares the method for cyclohexanone analog compound, it is characterized in that, the mass ratio of nitrogenous carbohydrate derivative and template or pore-forming material is 0.5 ~ 20:1; Described nitrogenous carbohydrate derivative is at least one in glucosamine hydrochloride and chitin.
10. the catalysis phenolic compound gas phase hydrogenation according to claim 5 or 6 prepares the method for cyclohexanone analog compound, it is characterized in that, porous charcoal carrier and PdCl
2mass ratio be 5 ~ 100:1.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622229A (en) * | 2017-01-10 | 2017-05-10 | 湘潭大学 | Preparation method of hydrogenation catalyst and method for preparing cyclohexanone through phenol selective hydrogenation |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1316820A (en) * | 1970-06-05 | 1973-05-16 | Ljubarsky G D Stretlets M M | Method of producing cyclohexanone |
| US4200553A (en) * | 1977-08-23 | 1980-04-29 | Allied Chemical Corporation | Process for producing cyclohexanone |
| US4203923A (en) * | 1974-11-26 | 1980-05-20 | Allied Chemical Corporation | Method for promotion of phenol hydrogenation |
| CN102513099A (en) * | 2011-11-24 | 2012-06-27 | 浙江大学 | Novel metal catalyst loaded by mesoporous carbon and preparation method thereof |
| CN103406096A (en) * | 2013-07-17 | 2013-11-27 | 国家纳米科学中心 | Nitrogen-doped porous carbon material, preparation method and use thereof |
| CN103801705A (en) * | 2014-02-11 | 2014-05-21 | 常州大学 | Method for loading nanocrystalline metal oxide or nanocrystalline metal materials by porous carbon |
-
2015
- 2015-01-16 CN CN201510022808.4A patent/CN104610030A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1316820A (en) * | 1970-06-05 | 1973-05-16 | Ljubarsky G D Stretlets M M | Method of producing cyclohexanone |
| US4203923A (en) * | 1974-11-26 | 1980-05-20 | Allied Chemical Corporation | Method for promotion of phenol hydrogenation |
| US4200553A (en) * | 1977-08-23 | 1980-04-29 | Allied Chemical Corporation | Process for producing cyclohexanone |
| CN102513099A (en) * | 2011-11-24 | 2012-06-27 | 浙江大学 | Novel metal catalyst loaded by mesoporous carbon and preparation method thereof |
| CN103406096A (en) * | 2013-07-17 | 2013-11-27 | 国家纳米科学中心 | Nitrogen-doped porous carbon material, preparation method and use thereof |
| CN103801705A (en) * | 2014-02-11 | 2014-05-21 | 常州大学 | Method for loading nanocrystalline metal oxide or nanocrystalline metal materials by porous carbon |
Non-Patent Citations (1)
| Title |
|---|
| YONG WANG ET AL.: "《Highly Selective Hydrogenation of Phenol and Derivatives over a Pd@Carbon Nitride Catalyst in Aqueous Media》", 《J. AM. CHEM. SOC.》 * |
Cited By (14)
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|---|---|---|---|---|
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| CN106622229B (en) * | 2017-01-10 | 2019-06-28 | 湘潭大学 | The preparation method and phenol selectivity of hydrogenation catalyst add the method for hydrogen preparing cyclohexanone |
| CN108273538A (en) * | 2018-01-30 | 2018-07-13 | 中南民族大学 | A method of reduction N- heteroaryl hydrocarbon compounds prepare N- heterocycle compounds |
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