CN107935816A - A kind of method for being catalyzed guaiacol hydrogenation deoxidation and preparing cyclohexanol - Google Patents

A kind of method for being catalyzed guaiacol hydrogenation deoxidation and preparing cyclohexanol Download PDF

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CN107935816A
CN107935816A CN201711229788.3A CN201711229788A CN107935816A CN 107935816 A CN107935816 A CN 107935816A CN 201711229788 A CN201711229788 A CN 201711229788A CN 107935816 A CN107935816 A CN 107935816A
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catalyst
guaiacol
cyclohexanol
mno
catalysis
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CN107935816B (en
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刘平乐
龙威
郝芳
熊伟
吕扬
崔海帅
吴生焘
罗和安
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Xiangtan University
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    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen

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  • Engineering & Computer Science (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention discloses a kind of method for being catalyzed guaiacol hydrogenation deoxidation and preparing cyclohexanol.The present invention prepares cyclohexanol with the decahydronaphthalene liquid one-step method hydrogenolysis of loaded catalyst x% Ru y% MnO/g CNTs catalysis guaiacol, catalyst handled using nitration mixture after multi-walled carbon nanotube as carrier, Ru MnO are loaded altogether to be prepared thereon, a step hydrogenolysis guaiacol generates cyclohexanol in neutral liquid phase, the highest selectivity of its principal product cyclohexanol is up to 85.84%, high conversion rate at this time is up to 99.38%, that is high income is up to 85.31%, present invention process route is brief, consersion unit and operating method are simple, reaction condition is gentle, reaction time is shorter, and catalyst is simple and easy to get, cost is low, stability is good, products pure, it is easily isolated and purifies, expected economic benefit is considerable, it is of great significance in industrial application.

Description

A kind of method for being catalyzed guaiacol hydrogenation deoxidation and preparing cyclohexanol
Technical field
The present invention relates to the preparation of cyclohexanol, and in particular to a kind of acid modified carbon nano-tube load Ru and MnO bimetallics are urged The method of agent and direct one step of the hydrogenolysis generation cyclohexanol of catalysis guaiacol.
Background technology
The existence of the mankind be unable to do without the energy, and the new energy for exploring sustainable development is always the emphasis and hot spot of scientific circles. Biomass energy receives the favor of scientific research person in recent years as a kind of green energy resource of sustainable development.Plant Contain substantial amounts of lignin in object, the degraded of lignin can produce substantial amounts of alcohols or aldehydes matter, so as to alleviate The pressure of non-renewable fossil energy, has very big researching value.Guaiacol as lignin degradation products one Kind, its content is up to 60%, and it has typical representativeness.Because not only containing phenyl ring in molecule, but also contain phenolic hydroxyl group, also contain There are the functional groups such as methoxyl group, can be used for liquid-phase hydrogenatin production cyclohexanol in a kettle using it, be emerging hot topic in recent years Scientific and technological route, its core science and technology be concentrated mainly on catalyst preparation and it is modified on.
Cyclohexanol is a kind of very valuable raw material of industry, it can be widely used for preparing resin, paint, ethyl fibre The techniques such as element, rubber are tieed up, it can be used for synthectic detergents, rubber reinforcing agent, Insecticides (tech) ＆ Herbicides (tech), plasticizer, acid dye again Material and textile auxiliary etc..Cyclohexanol molecule contains the six-membered carbon ring of uniqueness and the structure of alcoholic extract hydroxyl group, can be used as in extensive raw Produce the basic material of adipic acid, caprolactam, nylon66 fiber etc..At present, it in fields such as chemical industry, daily use chemicals, building material industries Unique advantage is given play to.
The existing method for preparing cyclohexanol mainly has two kinds of a phenol hydrogenation and cyclohexane oxidation, and the former cost of material Height, there is the drawback such as reaction is complicated, accessory substance is more, yield is low by the latter.Lignin is being concentrated as a kind of renewable resource In purification process, substantial amounts of aldehydes matter can be produced, and directly can just be obtained using this cheap aldehydes matter hydrogenation Valuable raw material of industry cyclohexanol, is a process with great scientific value, is at home and abroad in the research wave of hot topic In tide.Its process relate to biology, environmental protection, the multinomial core technology of chemical field, also be the fusion of multidisciplinary technology, at present also Preferable solution route is not obtained.
The cracking process of lignin is more complicated, its specific research starting is than later：2008, the big fluidization of the Chinese Academy of Sciences Learn the Xu Jie of physics Institute【CN 101768052A】Other metal co-catalysis natural woods are adulterated with regard to having invented nickel-base catalyst Quality or industrial lignin highly effective hydrogenation can generate the aromatic compounds such as phenylol, guaiaci lignum phenolic group and lilac, Liang Zhehan The sum of amount accounts for more than the 90% of whole products, but reaction must be 200 DEG C in temperature, Hydrogen Vapor Pressure is 5.0 MPa, successive reaction 6 Small to carry out at present, its conversion ratio is only capable of reaching 53%.2010, the Zhang Tao of Dalian Inst of Chemicophysics, Chinese Academy of Sciences【CN 102476980A】Hydro-thermal bar can also be passed through efficient for the hydro-conversion of natural lignin by having invented a kind of tungsten-based catalyst Aldehydes matter is hydrogenated under part, its yield is only up to 55.6%, and condition is that temperature is that Hydrogen Vapor Pressure is arranged at 235 DEG C 6.0 MPa and 4 h of successive reaction.Equally, Zhang Tao exists【CN 102746117A】In also successfully pass through bimetallic catalyst realization The hydro-conversion of jerusalem artichoke, be prepared for more content with the hexahydroxylic alcohols such as mannitol as cyclohexanol kind or sorbierite, catalyst Ru/AC is selected, temperature is 80 DEG C, Hydrogen Vapor Pressure is 6.0 MPa successive reactions, 12 h.2012, the Fu Jie of Zhejiang University 【CN 103073395A】In have also discovered microwave method can promote lignin carry out continuous degradation generation small molecule phenols material, Catalyst choice Pd/C, temperature is 160 DEG C, hydrogen is 40 min of successive reaction under normal pressure, is coordinated repeatedly alkaline under microwave action Degraded；2013, external G C Kang Pulin professors existed【CN103620002A】In be found that lignocellulose-like biomass can To generate small-molecule substance by hydro-thermal hydrogenation catalyst, its condition is controlled in 5.2 ~ 7.0 scopes for pH, reaction temperature for 150 ~ 300 DEG C, catalyst is the CoNiMo after vulcanization；2014, the Zhou Jiancheng of Southeast China University existed【CN 104326875A】In also attempt Use catalytic component based on vanadium to be hydrogenated with lignin under liquid-phase condition to degrade, form more phenolic compound, reaction temperature It is 3.0 MPa successive reactions, 60 min for 290 DEG C, hydrogen, its conversion ratio is up to 85.14%；2016, Chinese Academy of Sciences Guangzhou The Zhang Xinghua of Energy Research Institute exists【CN 106495974A】In disclose and a kind of contain MoO3Catalyst, be catalyzed mononuclear phenolic The hydrogenolysis fracture of C-O keys, improves intramolecular deoxidation effectiveness, obtains more aromatic product, reaction temperature is in compound 340 DEG C, Hydrogen Vapor Pressure be 0.2 MPa and 360 min of successive reaction.Therefore, it is pyrolyzed to aldehydes matter from lignin and still compares Readily, suitable active catalyst is selected, its Hydrogen Vapor Pressure and temperature can select appropriate condition to reach higher decomposition And yield.
Guaiacol is the Typical Representative of aldehydes matter in lignin thermal decomposition product, and molecular structure wood the simplest Quality cracking phenolic product represent, while it is poisonous should not preserve for a long time, therefore, the hydro-conversion of guaiacol utilizes process Possesses obvious importance and representativeness.The experimental exploring that its direct step is hydrogenated with is started late both at home and abroad, but it always by To the concern and exploration of domestic and foreign scholars.
The Zhang Ying of China Science ＆ Technology University【CN 102875335A】Selection SBA-15 is carrier, CeO2For auxiliary agent, probe into The noble metals such as Pd, Pt, Ru are the catalyst of active component, and at 170 DEG C, Hydrogen Vapor Pressure is 4.0 MPa, continuously with 1000 Rpm speed stirring reaction 8 it is small when after, mixed phenols（Phenol：Eugenol：Guaiacol=1:1:1）Conversion ratio be 100%, product is mostly alcohols material, but product species are various, is unfavorable for that major product is effectively separated.
Chinese Academy of Sciences's Guangzhou energy Ma Longlong【CN 102430409A】Select ZrO2-SiO2Binary composite oxides For carrier, the bimetallic of infusion process introducing Ni and Cu is utilized（The content of Ni is that the ratio between amount of 10%, Ni and Cu materials is 1:0.5） For the new catalyst of active component, in the case where temperature is 300 DEG C, Hydrogen Vapor Pressure is 5.0 MPa, using normal octane as solvent, confront Measure the guaiacol solution that concentration is 10% and carry out autoclave hydrogenation, its conversion ratio may be up to 100%, and product is mainly alkane, highest Yield is up to 62.7%.
The Wang Yanqin of East China University of Science【CN 104744204A】Ruthenium, platinum, palladium, iridium, iron, cobalt, nickel, the one of copper are probed into Kind or several metal active constituents, are supported on formation on the oxide of transition metal niobium, tantalum, zirconium, molybdenum, tungsten, rhenium etc. and possess The catalyst in acid site is mixed, for Hydrogenation Experiment of the guaiacol in the case where water is solvent, reaction temperature is 250 DEG C, hydrogen pressure Power is 1.0 MPa, and 24 h of successive reaction under with 1000 revs/min of mixing speed, its primary product is aromatic hydrocarbon, and yield is only For 10%, illustrate that water does the hydrogenation deoxidation conversion that solvent is not too much adapted to guaiacol.
2015, the Zhang Qi of Guangzhou Energy Resource Inst., Chinese Academy of Sciences【CN 10104923233A】Then successfully it is prepared for A kind of SiO2Wrap up the catalyst with core-casing structure Ni@SiO of active metal Ni2It is prepared by the selective hydrogenation deoxidation for guaiacol Cyclohexanol.In the decahydronaphthalene solution for the guaiacol that mass fraction is 1%, reaction temperature is 120 DEG C, Hydrogen Vapor Pressure 2.0 After MPa, 2 h of successive reaction, the conversion ratio of reactant and the selection performance of cyclohexanol reach 100%, and this high selectivity attribution In unique pore structure of nucleocapsid, this result is although superior, but the mass fraction of its used guaiacol is only 1%, concentration It is very low, as cost, to have great accordance with tolerance to the measurer of solvent using substantial amounts of solvent decahydronaphthalene, holding is tested every time and is cured The situation that the mass fraction of the wooden phenol of wound is extremely low will waste substantial amounts of solvent, the industrialization cost of the technology is increased severely, therefore even if Preferable selectivity can be obtained, and the separation costs of product are very high, even if the selection performance of cyclohexanol is stably protected 100% is held, content of the product cyclohexanol in reaction solution is still extremely low（About 1%）, this makes to further separation and collection Into larger obstruction, processing cost is more likely to the purification of the product not high higher than purity, therefore economic benefit is unsatisfactory.2016 Year, the Boonyasuwat in the U.S. was taught（Catal Letter,2013,143:783-791）Taught with the Ishikawa of Japan (Applied Catalysis B: Environmental, 2016,182:193-203) propose for moderate concentration （10%~40%）The catalytically-active metals that are most suitable for of Hydrogenation Experiment of guaiacol be Ru rather than Ni, and accessory substance is therewith not It can avoid, the highest yield of its improved technology can not also break through 76% so far.
Zhejiang Polytechnical University in phoenix text【CN 105001902A】Then find to mix guaiacol and alcohol, in HZSM-5 Under the catalytic action of molecular sieve, at 500 ~ 600 DEG C inject fixed bed reactors and keep the temperature 1 it is small when, to its product constantly into Row condensation abstraction recycles, the conversion ratio of its guaiacol can reach 100%, and product is based on hydrocarbons, and yield is only 20.68%.Recently, the Zhang Zongchao of Dalian Inst of Chemicophysics, Chinese Academy of Sciences【CN 106554257A】One kind has been invented again Ag/TiO2Catalyst, in the case where positive flow silane and normal heptane are as solvent condition, mass fraction is 7.5% guaiacol solution 400 DEG C, Hydrogen Vapor Pressure 0.25 h of successive reaction under 3.0 MPa, 700 revs/min of stirring, the highest that can reach guaiacol turns Rate is 81.53%.The Xu Xiwei of Agricultural University Of South China【CN 105461498A】A kind of Fe-Ni bimetallic catalysts are then invented The gas phase hydrogenation experiment for the guaiacol being used on molecular sieve in fixed bed is carried on, is 250 ~ 400 DEG C of areas in normal pressure and temperature Between obtained product BTX（Benzene,toluene,xylene）The sum of yield reach as high as 19.83%, this approach reduces carbon atom Loss and hydrogen consumption, but its yield is too low and required reaction temperature is too high.
In conclusion the hydrogenation of guaiacol can carry out in gas phase and liquid phase, the primary product of gas phase hydrogenation is hydrocarbon Class, the primary product of liquid-phase hydrogenatin is phenols or alcohols.The hydrogenation process of guaiacol depends on the catalyst of high activity, reaction Temperature is usually above 160 DEG C, and Hydrogen Vapor Pressure is 0 ~ 5 MPa, and carrier and active metal, auxiliary agent can influence the species of product and divide Cloth, but the product of excessive hydrogenation is undoubtedly hexamethylene.The hydrogenation process industrialization of guaiacol needs to take into full account answering for instrument Polygamy, the severe of reaction condition and security, the cost of catalyst are low with difficulty or ease, the high income of product is prepared etc..
Recently, scientific circles find that the high activity of noble metal Ru is very suitable for the hydrogenation process of guaiacol, and decahydronaphthalene is made The solvent being hydrogenated with for that can consume hydrogen is very beneficial for the hydrogenation of guaiacol, with the use of lower temperature and compared with low hydrogen Liquid-phase hydrogenatin process under atmospheric pressure is easy to implement, becomes the hot spot of biomass hydro-conversion research.Either phenols, still Hydro carbons or alcohols, the purity level of product determine the scientific value of this hydrogenation process, and the selectivity of principal product improves can be effective Ground promotes the process of industrialization of guaiacol hydrogenation.Strive under mild conditions, can be achieved with more creating using simple instrument The hydrogenation process of wooden phenol, obtains the principal product of high-purity, is very beneficial for industrial production.
The hydrogenation new method of guaiacol, one is pursuing reaction in lower temperature and the temperate condition of lower pressure；Its Reduced second, pursuing accessory substance, to reach the high selectivity of principal product or yield；The third is reduce the cost and solvent of catalyst Usage amount, avoid poisonous and harmful solvent from using as far as possible, realize that green non-pollution, product are easily separated, energy-efficient.
The content of the invention
The above problem of the catalysis process of cyclohexanol, the purpose of the present invention are prepared for existing guaiacol one-step method hydrogenolysis It is to provide a kind of new catalyst of x%-Ru-y%-MnO/g-CNTs, has reached the efficient hydrogenolysis of guaiacol under neutral environment The requirement of reaction.
The present invention also aims to provide a reaction condition compared with it is gentle, technological process is brief, cost of material is low, catalysis Agent is simple and easy to get, environmental-friendly, principal product high income, the method that the environmentally protective guaiacol hydrogenolysis of technique prepares cyclohexanol.
The purpose of the present invention can reach by following technical solution：
A kind of method for being catalyzed guaiacol hydrogenation deoxidation and preparing cyclohexanol, with the double gold of sour modified carbon nano-tube load Ru and MnO Belong to（Abbreviation supported Ru catalysts, be denoted as x%-Ru-y%-MnO/g-CNTs, and x%, y% represent Ru, MnO in the catalyst respectively Quality accounting）For catalyst, under conditions of decahydronaphthalene is solvent, one step of guaiacol hydrogenation deoxidation produces to obtain cyclohexanol, The decahydronaphthalene solution of guaiacol（Abbreviation guaiacol solution）Mass fraction be 10 ~ 25%.
Further, the catalyst is made of the raw material components being calculated in mass percent as follows：
Active component Ru 3~8%
Adulterate auxiliary agent MnO 5~10%
Sour modified carbon nano-tube (g-CNTs) 82~92%
Wherein：
Metal active constituent Ru derives from RuCl3Or Ru (NO) (NO3)3Hydrate；
Decomposition of the MnO from manganese acetate or manganese nitrate.
Further, the mass ratio of catalyst and reaction solution is 0.05 ~ 0.15:6.
Further, the hydrogenation deoxidation of guaiacol, reaction temperature is preferably at 160~220 DEG C, and the reaction time is preferably 30 ~240 min, reaction pressure is preferably in 0.5 ~ 2.5MPa.
Further, the mass fraction of guaiacol is 20%.
In the catalyst that the present invention uses, the modified carbon nanotubes of acid is supported on using the Ru-MnO of different quality ratio and is carried All there is catalytic effect, 6%-Ru-8%-MnO/g-CNTs, i.e. metal Ru in catalytic effect most preferably loaded catalyst on body The quality of quality 6.0%, the MnO that accounts for whole catalyst quality account for the 8% of whole catalyst quality, corresponding guaiacol turns Rate is up to 99.38%, and up to 85.84%, the yield of principal product cyclohexanol can be up to the high selectivity of principal product cyclohexanol 85.31%, and the concentration in reaction solution is also higher, and easy to the Separation ＆ Purification of product, the industrialization for being conducive to the technology pushes away Wide and production.The reaction solution referred in the present invention makees solvent with decahydronaphthalene, and the optimal mass fraction of guaiacol is 20%, relatively The catalyst quality that should be used is less, of low cost, good economy performance.
Be conducive to improve the high selectivity of principal product cyclohexanol and the stabilization of catalyst present invention preferably uses auxiliary agent MnO Property, TEM show auxiliary agent MnO be conducive to metal active constituent Ru be supported on carrier disperse must be more uniformly distributed, meanwhile, auxiliary agent MnO can substantially suppress the appearance of accessory substance.
The beneficial effects of the present invention are：
1st, the present invention is using loaded catalyst x%-Ru-y%-MnO/g-CNTs as catalyst, in the liquid phase with relatively mild condition Under, one step hydrogenolysis of guaiacol is generated into cyclohexanol, higher guaiacol conversion ratio and cyclohexanol selectivity can be obtained.
2nd, reactant feed and catalyst cost of the invention are relatively low and are easy to get, used catalyst stability and circulation Performance is all fine.
3rd, reaction condition is gentleer, short flow, easy to operate, meets industrialization production requirements.
4th, pollution-free, high income, product purity height is easily separated, and building-up process environmental protection, meets green chemistry process requirement.
Brief description of the drawings
Fig. 1 be the present invention 6%-Ru-8%-MnO/g-CNTs catalyst TEM phenograms, its fully show metal Ru with And MnO is evenly dispersed on sour modified carbon nano-tube carrier.
Embodiment
Following embodiments are intended to further illustrate present invention, which is also to belong to protect the claims in the present invention Scope.
The preparation of catalyst and method of hydrotreating：
1. the pretreatment of carrier：Carbon nanotubes needs to carry out acid activation processing.Method is：It is 30.0% first to prepare mass fraction Dilute sulfuric acid and the dust technology mixed liquor that mass fraction is 40%, with 20:1 liquid consolidates mass ratio, and mixed acid solution is added and is placed in three mouthfuls 6 h are continuously roasted at 700 DEG C in bottle（Remove impurity）Multi-wall carbon nano-tube pipe powder in, be placed on 95 DEG C of oil 6 h of Continuous Heat reflux, take out after cooling, are washed with distilled water 5 times, filter after in 110 DEG C of baking ovens continuous drying 12 in bath Hour, taking-up is ground into fine powder, by the way that its powder is placed in the tube furnace under nitrogen protection after 160 mesh sieve, in 400 DEG C 3 h of lower continuous roasting, are subsequently cooled to room temperature and form the modified carbon nano-tube support powder handled well.Test and obtain through BET, place The specific surface area of carbon nanotube carrier before reason is only 195.49 m2/ g, sulfuric acid are carried with the carbon nanotubes after nitric acid mixed processing Surface area per unit volume product increases to 236.57 m2/ g, color compared with before processing blackening some, in fine and smooth powdered, its XRD characterization is shown Main characteristic peak in carrier only containing two carbon nanotubes, purity are very high.Purpose with nitration mixture processing carbon nanotubes is a side Face makes carrier material microcosmic surface form many defects, increase its specific surface area；On the other hand it is to make carrier material show to produce Many microcosmic absorption hydroxyls, strengthen its activity, its carrier handled well is known as g-CNTs.
2. infusion process prepares x%-Ru/g-CNTs loaded catalysts：Three chloride hydrate rutheniums of the certain mass weighed (RuCl3•3H2O) it is dissolved in the high purity deionized water of 20.00 mL, stirring 10 min at room temperature makes it all dissolve, to be formed equal First, after the dark solution stablized, the g-CNTs powder of acid activation processing is carefully added into, it is small to continuously stir lower dipping 8 at room temperature When be in pulpous state, be aged 2 h after 30 min of microwave ultrasound after taking-up, it is drying over night at a temperature of 110 DEG C, be ground into after taking-up Fine powder, crosses 100 mesh sieve, is sent into the tube furnace under nitrogen protection, 3 h are continuously roasted at 400 DEG C, then turn hydrogen environment Lower 3 h, allow its catalyst to turn to be cooled to room temperature under nitrogen after fully reducing.If catalyst placement is more long, just it is put again When using hydrogen reducing 3 small in the tube furnace at 400 DEG C, catalyst A, B, C, D, E, F are formd, corresponding Ru's is negative Mounted mass fraction is 3%, 4%, 5%, 6%, 7% and 8%, and closed isolation air preserves.
3. the experiment that guaiacol hydrogenolysis is carried out under pair different catalyst and different reaction conditions is as follows：
Embodiment 1：Hydrogenation plant is 20 milliliters of stainless steel high pressure electrothermal reaction kettle, is added first in the decahydronaphthalene of 4.8 g The guaiacol of 1.2 g, stirs 30 min using magnetite and forms the guaiacol solution that uniform mass fraction is 20%, then adds Enter the catalyst A of 0.1 g, close autoclave rapidly, and air 3-4 times in kettle is replaced with hydrogen, start stirring, adjust what is be passed through Hydrogen Vapor Pressure is warming up to 200 DEG C, at this temperature 200 min postcoolings of successive reaction to room temperature, careful release of pressure to 2.0 MPa Afterwards and product weighing is taken out, and take supernatant liquid to be detected after centrifuging using gas chromatogram fixative, ethylo benzene is internal standard compound, is calculated The conversion ratio and selective data for obtaining relative species are shown in Table 1.
Embodiment 2：Selecting catalyst B, reaction feeds intake and hydrogenolysis condition is with embodiment 1, and relative species are calculated Conversion ratio and selective data be shown in Table 1.
Embodiment 3：Selecting catalyst C, reaction feeds intake and hydrogenolysis condition is with embodiment 1, and relative species are calculated Conversion ratio and selective data be shown in Table 1.
Embodiment 4：Selecting catalyst D, reaction feeds intake and hydrogenolysis condition is with embodiment 1, and relative species are calculated Conversion ratio and selective data be shown in Table 1.
Embodiment 5：Selecting catalyst E, reaction feeds intake and hydrogenolysis condition is with embodiment 1, and relative species are calculated Conversion ratio and selective data be shown in Table 1.
Embodiment 6：Selecting catalyst F, reaction feeds intake and hydrogenolysis condition is with embodiment 1, and relative species are calculated Conversion ratio and selective data be shown in Table 1.
Table 1
Analysis contrasts six groups of data and understands, when the content of transition metal Ru is less than 6%, the conversion ratio of guaiacol is with metal Ru Load capacity increase and increase, but the selectivity of each product is basically unchanged；When the content of transition metal Ru is higher than 6%, its turn Rate is basically unchanged with the increase of the load capacity of metal Ru, and the selectivity of hexamethylene increased, the choosing of other each products Selecting property is held essentially constant.So the selectivity height of principal product cyclohexanol is not to rely on the load capacity of transition metal Ru, and In order to cost-effective, during the modification of subsequent catalyst is probed into, the load capacity that we have selected transition metal Ru is 6%.
Embodiment 7：Total immersion method prepares x%-Ru-y%-MnO/g-CNTs loaded catalysts：Weigh certain mass RuCl3•3H2O is dissolved in the high purity deionized water of 20.00 mL, and stirring 10 min at room temperature makes it all dissolve, to be formed equal First, the dark solution stablized.The careful manganese acetate Mn (CH for weighing certain mass3COO)2•4H2O solids are added in beaker, room temperature It is lower to continue to stir to the liquid of stable homogeneous, the g-CNTs carriers of the certain mass of acid activation processing are added, are continuously stirred It is lower dipping 8 it is small when, after taking-up after 30 min of ultrasound be aged 2 it is small when, by its at a temperature of 110 DEG C it is drying over night, taking-up is ground into Fine powder, is sent into the tube furnace under nitrogen protection after crossing 100 mesh sieve, 3 h is continuously roasted at 400 DEG C, then turn hydrogen ring Continue 3 h under border, allow its catalyst to turn to be cooled to room temperature under nitrogen after fully reducing.If catalyst placement is more long, just by it It is again placed in using 3 h of hydrogen reducing in the tube furnace at 400 DEG C, forms catalyst G, the load quality of corresponding Ru and MnO Fraction is respectively 6% and 5%, and closed isolation air is kept.The quality that feeds intake and hydrogenolysis condition are calculated with embodiment 1 The conversion ratio and selective data of relative species are shown in Table 2.
Embodiment 8：With the method for preparing catalyst of embodiment 7, it is 6%-Ru-6%-MnO/g- that catalyst H, which is prepared, CNTs, obtains the conversion ratio of relative species under the conditions of same feed intake quality and hydrogenolysis and selective data is shown in Table 2.
Embodiment 9：With the method for preparing catalyst of embodiment 7, it is 6%-Ru-7%-MnO/g- that catalyst I, which is prepared, CNTs, obtains the conversion ratio of relative species under the conditions of same feed intake quality and hydrogenolysis and selective data is shown in Table 2.
Embodiment 10：With the method for preparing catalyst of embodiment 7, it is 6%-Ru-8%-MnO/g- that catalyst J, which is prepared, CNTs, obtains the conversion ratio of relative species under the conditions of same feed intake quality and hydrogenolysis and selective data is shown in Table 2.
Embodiment 11：With the method for preparing catalyst of embodiment 7, it is 6%-Ru-9%-MnO/g- that catalyst K, which is prepared, CNTs, obtains the conversion ratio of relative species under the conditions of same feed intake quality and hydrogenolysis and selective data is shown in Table 2.
Embodiment 12：With the method for preparing catalyst of embodiment 7, it is 6%-Ru-10%-MnO/g- that catalyst L, which is prepared, CNTs, obtains the conversion ratio of relative species under the conditions of same feed intake quality and hydrogenolysis and selective data is shown in Table 2.
Table 2
It is above-mentioned test result indicates that：When quality accountings of the metal Ru in total catalyst of load is 6%, auxiliary agent MnO is catalyzed always When mass ratio in agent is 8%, the conversion ratio of guaiacol and the selectivity of principal product cyclohexanol reach highest.By XRD and XPS characterizations find that Mn is existing in the form of MnO in catalyst, and TEM shows that high dispersive occurs in Ru, illustrates MnO Introducing can be effectively facilitated the scattered of transition metal Ru, so as to promote the performance of hydrogenation activity, while it can also suppress hexamethylene The generation of the accessory substance such as ketone and benzene, greatly improves the selectivity of principal product cyclohexanol.
Embodiment 13：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, reaction temperature are at 160 DEG C, and the quality that feeds intake and other conditions obtain relative species with described in embodiment 1 by experiment Conversion ratio and selective data are shown in Table 3.
Embodiment 14：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, reaction temperature are at 180 DEG C, and the quality that feeds intake and other conditions obtain relative species with described in embodiment 1 by experiment Conversion ratio and selective data are shown in Table 3.
Embodiment 15：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, reaction temperature are 220 DEG C, and the quality that feeds intake and other conditions obtain turning for relative species with described in embodiment 1 by experiment Rate and selective data are shown in Table 3.
Table 3
The data contrasted under different reaction temperatures are understood：Temperature is too low, and the conversion ratio of guaiacol is undesirable, during required reaction Between it is too long, the content of in-between product is also higher, causes the selectivity of principal product cyclohexanol undesirable；Temperature is too high, although turning Rate can be lifted, but cyclohexanol can cause the selection of principal product cyclohexanol to the direction transition of hexamethylene in this hydrogenation process Property be not so good as 200 DEG C when obtained high selectivity（Corresponding to the data of embodiment 10）, the selectivity of hexamethylene has appropriate increase, Therefore, it is comparatively ideal that reaction temperature, which selects 200 DEG C,.
Embodiment 16：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, the pressure for being passed through hydrogen are 0.5 MPa, the quality that feeds intake and other conditions with described in embodiment 1, and correlation is obtained by experiment The conversion ratio and selective data of species are shown in Table 4.
Embodiment 17：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, the pressure for being passed through hydrogen are 1.0 MPa, the quality that feeds intake and other conditions with described in embodiment 1, and correlation is obtained by experiment The conversion ratio and selective data of species are shown in Table 4.
Embodiment 18：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, the pressure for being passed through hydrogen are 1.5 MPa, the quality that feeds intake and other conditions with described in embodiment 1, and correlation is obtained by experiment The conversion ratio and selective data of species are shown in Table 4.
Embodiment 19：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, the pressure for being passed through hydrogen are 2.5 MPa, the quality that feeds intake and other conditions with described in embodiment 1, and correlation is obtained by experiment The conversion ratio and selective data of species are shown in Table 4.
Table 4
The response data contrasted under different hydrogen pressure is understood：The hydrogenation process of guaiacol needs certain Hydrogen Vapor Pressure, such as Fruit is passed through that Hydrogen Vapor Pressure is too small, its conversion ratio and principal product are selectively unsatisfactory, and logical Hydrogen Vapor Pressure is excessive outside, can also lead Cyclohexanol is caused to be converted to hexamethylene, therefore suitable Hydrogen Vapor Pressure is 2 MPa（Corresponding to the data of embodiment 10）.
Embodiment 20：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, reaction time are arranged to 30 min, and the quality that feeds intake and other conditions obtain correlative with described in embodiment 1 by experiment The conversion ratio and selective data of kind are shown in Table 5.
Embodiment 21：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, reaction time are arranged to 60 min, and the quality that feeds intake and other conditions obtain correlative with described in embodiment 1 by experiment The conversion ratio and selective data of kind are shown in Table 5.
Embodiment 22：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, reaction time are arranged to 90 min, and the quality that feeds intake and other conditions obtain correlative with described in embodiment 1 by experiment The conversion ratio and selective data of kind are shown in Table 5.
Embodiment 23：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, reaction time are arranged to 120 min, and the quality that feeds intake and other conditions obtain correlative with described in embodiment 1 by experiment The conversion ratio and selective data of kind are shown in Table 5.
Embodiment 24：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, reaction time are arranged to 150 min, and the quality that feeds intake and other conditions obtain correlative with described in embodiment 1 by experiment The conversion ratio and selective data of kind are shown in Table 5.
Embodiment 25：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, reaction time are arranged to 180 min, and the quality that feeds intake and other conditions obtain correlative with described in embodiment 1 by experiment The conversion ratio and selective data of kind are shown in Table 5.
Embodiment 26：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, reaction time are arranged to 240 min, and the quality that feeds intake and other conditions obtain correlative with described in embodiment 1 by experiment The conversion ratio and selective data of kind are shown in Table 5.
Table 5
By the multi-group data of comparative example 20 ~ 26, we are it is seen that the optimal reaction time is 200 min（Corresponding to reality Apply the data of example 7）, hydrogenation time is long, and the content of by-product cyclic hexane can be caused to increase, and the reaction time is too short, in accessory substance Cyclohexanone can also be contained, other intermediates contents can also increase.
In order to analyze and probe into the influence of catalyst reduction temperature, we have also been made the experiment of relevant comparative's property：
Embodiment 27：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalyst is prepared for, The temperature of calcined catalyst and hydrogen reducing is 200 DEG C in tube furnace, other steps are as before, the quality that feeds intake and other are anti- Condition is answered to obtain the conversion ratio of relative species with described in embodiment 1 by experiment and selective data is shown in Table 6.
Embodiment 28：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, the temperature of calcined catalyst and hydrogen reducing is 300 DEG C in tube furnace, other steps are as before, the quality that feeds intake and its His reaction condition obtains the conversion ratio of relative species by experiment and selective data is shown in Table 6 with described in embodiment 1.
Embodiment 29：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-MnO/g-CNTs catalysis is prepared for Agent, the temperature of calcined catalyst and hydrogen reducing is 500 DEG C in tube furnace, other steps are as before, the quality that feeds intake and its His reaction condition obtains the conversion ratio of relative species by experiment and selective data is shown in Table 6 with described in embodiment 1.
Table 6
The hydrogen reducing temperature of calcination temperature and catalyst has a great influence catalyst, manganese acetate hydrogen at different temperature It is different to reduce obtained species containing manganese（Consist predominantly of Mn3O4、Mn2O3, tetra- kinds of MnO, Mn）.The species reduced at 200 DEG C Mn3O4, the incorporation of species Mn that reduces at 500 DEG C influence little, the selectivity of principal product cyclohexanol is undesirable, and at 300 DEG C also Former species contain Mn at the same time3O4、Mn2O3, MnO, the species reduced at 400 DEG C are mainly MnO.With reference to XRD and XPS to catalysis The characterization of agent, can clearly recognize the form of the auxiliary agent containing Mn, it has been found that the addition of MnO is just most effective for improving catalysis The activity of agent and the selectivity of principal product, its optimal roasting and hydrogen reducing temperature are 400 DEG C（Corresponding to the number of embodiment 10 According to）.
In order to contrast the influence of other metal promoters, we have selected part bimetallic catalyst by substantial amounts of experiment, Its catalytic performance of comparative analysis.
Embodiment 30：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-Ni/g-CNTs catalysis is prepared for Agent（The nickel acetate of certain mass is selected to add）, the temperature of calcined catalyst and hydrogen reducing is 400 DEG C in tube furnace, other are anti- Condition is answered to obtain the conversion ratio of relative species with described in embodiment 1 by experiment and selective data is shown in Table 7.
Embodiment 31：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-Ag/g-CNTs catalysis is prepared for Agent（The silver nitrate of certain mass is selected to add）, the temperature of calcined catalyst and hydrogen reducing is 400 DEG C in tube furnace, other are anti- Condition is answered to obtain the conversion ratio of relative species with described in embodiment 1 by experiment and selective data is shown in Table 7.
Embodiment 32：With the method for preparing catalyst of embodiment 10, a kind of 6%-Ru-8%-Zn/g-CNTs catalysis is prepared for Agent（The zinc acetate of certain mass is selected to add）, the temperature of calcined catalyst and hydrogen reducing is 400 DEG C in tube furnace, other are anti- Condition is answered to obtain the conversion ratio of relative species with described in embodiment 1 by experiment and selective data is shown in Table 7.
Table 7
Compare the above results explanation：The 6%-Ru-8%-MnO/g-CNTs novel supported catalysts that we invent（The quality of Ru point The mass fraction that number is 6%, MnO is 8%）, prepared by cyclohexanol compared with Ni to the decahydronaphthalene liquid hydrogen solution of guaiacol, Ag's, Zn adds Add, possess more preferably catalytic effect.
By the 6%-Ru-8%-MnO/g-CNTs catalyst reactions prepared once after, be collected by centrifugation and drying over night, then It is positioned in tube furnace persistently to roast to be transferred in atmosphere of hydrogen after 3 h in 400 DEG C under nitrogen protection and reduces 3 h, then is transferred to nitrogen It is cooled to room temperature under gas shielded, for continuing Hydrogenation Experiment to probe into the stability of its catalyst, 5 realities is repeated Test, for other reaction conditions with described in embodiment 1, obtained experimental data is as shown in table 8.
Table 8
Same catalyst Hydrogenation Experiment data after contrast circulates 5 times are understood：The stabilization of 6%-Ru-8%-MnO/g-CNTs catalyst Property it is very good, after continuously 4 uses of circulation, its catalytic effect does not reduce substantially, when only circulating the 5th, because catalysis is anti- The loss of Some Species just causes active reduction in answering, therefore it has possessed the potential quality promoted the use of for new industrialization.Catalysis The stability of agent and can be recycled be catalyst superior function embodiment, the catalyst that designs simply is returning in the present invention Receive, is dry, after roasting and activation, embodying very superior recyclable and efficient utility.
In order to probe into influential effect of the mass fraction of guaiacol to the technology, we have selected 6%-Ru-8%- MnO/g-CNTs catalyst has carried out same experiment under different guaiacol concentration, other reaction conditions are the same as embodiment 1 Described, obtained experimental data is as shown in table 9.
Table 9
When the concentration of guaiacol is too low, deficiency in economic performance, commercial Application is seriously restricted, and the present invention, which is investigated from concentration, is Start when 10%.When the reactant concentration of guaiacol reaches 25%, by-product cyclic hexanone occurs, and the reactant for creating wooden phenol is dense When degree reaches 30%, accessory substance benzene also occurs, and shows that reactant concentration increase will cause by-product species to increase, is not easy to The purification of product；When the reactant concentration of the wooden phenol of wound reaches 100%（Decahydronaphthalene is not added）, conversion ratio is relatively low, and principal product ring Hexanol selectivity is not high, and intermediate product 1, the content of 2- cyclohexanediols is up to 24.56%, shows that the extent of reaction is incomplete, and by-product Thing is numerous, less effective.Therefore, control the initial mass concentration of reactant guaiacol ideal for 20%, and its solvent It is essential.
In order to probe into influential effect of the species of more solvent to the technology, we have selected 6%-Ru-8%-MnO/g-CNTs Catalyst is under common different kinds of liquid solvents（The mass fraction of guaiacol remains 20%）Same experiment has been carried out, For other reaction conditions with described in embodiment 1, obtained experimental data is as shown in table 10.
Table 10
Contrasting same catalyst Hydrogenation Experiment performance of guaiacol under different kinds of liquid solvents can find, the polarity of solvent Distribution to reaction product has a certain impact, but the catalytic performance under 8 kinds of solvents done not as good as decahydronaphthalene solvent effect it is good.
In conclusion the multi-walled carbon nanotube after the present invention is handled using nitration mixture loads prepare thereon altogether as carrier, Ru-MnO Bimetallic catalyst, a step hydrogenolysis guaiacol generates cyclohexanol, the highest selection of its principal product cyclohexanol in neutral liquid phase Property is up to 85.84%, and up to 99.38%, the yield of principal product cyclohexanol can be up to 85.31% for high conversion rate at this time, catalyst into This is low, and process conditions are suitable, it is contemplated that economic benefit it is considerable, be of great significance in industrial application. This method process route is brief, and consersion unit and operating method are simple, and reaction condition is gentle, and the reaction time is shorter, and is catalyzed Agent is simple and easy to get, and stability is good, products pure, is easily isolated and purifies, environmental-friendly, is adapted to commercial introduction.

Claims (6)

  1. A kind of 1. method for being catalyzed guaiacol hydrogenation deoxidation and preparing cyclohexanol, it is characterised in that born with sour modified carbon nano-tube It is catalyst to carry Ru and MnO bimetallics, the catalyst, that is, supported Ru catalysts, is denoted as x%-Ru-y%-MnO/g-CNTs, x%, Y% represents the quality accounting of Ru, MnO in the catalyst respectively, under conditions of decahydronaphthalene is solvent, guaiacol hydrogenation deoxidation One step produces to obtain cyclohexanol, and the mass fraction of the decahydronaphthalene solution of guaiacol is 10 ~ 25%.
  2. 2. the method that catalysis guaiacol hydrogenation deoxidation according to claim 1 prepares cyclohexanol, it is characterised in that described Catalyst be made of the raw material components being calculated in mass percent as follows：
    Active component Ru 3~8%
    Adulterate auxiliary agent MnO 5~10%
    Sour modified carbon nano-tube, that is, g-CNTs 82~92%.
  3. 3. the method that catalysis guaiacol hydrogenation deoxidation according to claim 2 prepares cyclohexanol, it is characterised in that activity Component Ru derives from RuCl3Or Ru (NO) (NO3)3Hydrate, decomposition of the MnO from manganese acetate or manganese nitrate.
  4. 4. the method that catalysis guaiacol hydrogenation deoxidation according to claim 1 prepares cyclohexanol, it is characterised in that catalysis The mass ratio of agent and reaction solution is 0.05 ~ 0.15:6.
  5. 5. the method that catalysis guaiacol hydrogenation deoxidation according to claim 1 prepares cyclohexanol, it is characterised in that more create The hydrogenation deoxidation of wooden phenol, reaction temperature are 160~220 DEG C, and the reaction time is 30~240 min, and reaction pressure is 0.5 ~ 2.5 MPa。
  6. 6. the method that catalysis guaiacol hydrogenation deoxidation according to claim 1 prepares cyclohexanol, it is characterised in that more create The mass fraction of wooden phenol is 20%.
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CN115672377A (en) * 2022-11-18 2023-02-03 常州大学 Application of nitrogen-doped carbon-supported cobalt catalyst in guaiacol hydrodeoxygenation reaction

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CN110152672A (en) * 2019-04-08 2019-08-23 浙江师范大学 A kind of nickel-base catalyst prepares the purposes of the catalyst of phenol and cyclohexanol as guaiacol
CN111253216A (en) * 2020-02-14 2020-06-09 河北工业大学 Synthetic method of cyclohexanol derivative 1-methyl-1, 2-cyclohexanediol
CN111253216B (en) * 2020-02-14 2022-08-30 河北工业大学 Synthetic method of cyclohexanol derivative 1-methyl-1, 2-cyclohexanediol
CN112341312A (en) * 2020-11-13 2021-02-09 华南理工大学 Method for preparing cyclohexanol and derivative thereof by selective hydrogenolysis of lignin
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CN114870853A (en) * 2022-06-23 2022-08-09 广东石油化工学院 Core-shell catalyst for preparing cyclohexanol by catalyzing selective hydrogenation and deoxidation of guaiacol
CN114870853B (en) * 2022-06-23 2023-09-26 广东石油化工学院 Core-shell catalyst for preparing cyclohexanol by catalyzing guaiacol to be subjected to selective hydrodeoxygenation
CN115672377A (en) * 2022-11-18 2023-02-03 常州大学 Application of nitrogen-doped carbon-supported cobalt catalyst in guaiacol hydrodeoxygenation reaction
CN115672377B (en) * 2022-11-18 2024-01-26 常州大学 Application of nitrogen-doped carbon-supported cobalt catalyst in guaiacol hydrodeoxygenation reaction

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