CN104226358B - Method for preparing alkane by catalyzing phenol compounds through hydrodeoxygenation and catalytic reaction system - Google Patents
Method for preparing alkane by catalyzing phenol compounds through hydrodeoxygenation and catalytic reaction system Download PDFInfo
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- CN104226358B CN104226358B CN201410351466.6A CN201410351466A CN104226358B CN 104226358 B CN104226358 B CN 104226358B CN 201410351466 A CN201410351466 A CN 201410351466A CN 104226358 B CN104226358 B CN 104226358B
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- nickel formate
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Abstract
The invention provides a method for preparing alkane by catalyzing phenol compounds through hydrodeoxygenation. The method is performed in a high-pressure reactor, the phenol compounds serve as raw materials, and alkane solvents are adopted. The method is characterized in that a catalytic reaction system consisting of nickel formate and solid acids is used, metal Ni generated by in-situ decomposition of nickel formate serves as an active ingredient for hydrogenation, and hydrogen generated by decomposition of nickel formate can provide a high-activity hydrogenation hydrogen source. The invention also provides a catalytic reaction system used in a hydrodeoxygenation reaction for catalyzing the phenol compounds. The raw materials used in the catalytic reaction system provided by the invention are readily available, low in price, easy to operate and high in reaction activity. In activity evaluation of the catalytic system, the conversion rate of each phenol compound is close to 100 percent.
Description
Technical field
The present invention provides a kind of phenolic compound catalytic hydrodeoxygenation to prepare method and the catalystic converter system of alkane, especially
It is related to a kind of method and catalysis acting on catalysis phenolic compound hydrogenation deoxidation reaction using original position metallic nickel coupling solid acid
Reaction system.
Technical background
Lignin, as the chief component of living beings, is lignocellulose biomass by hydrolyzation fermentation ethanol industry processed
With the Main By product of paper industry, due to being not fully utilized, become environmental contaminants, bring very big pressure to environment
Power.Lignin is a kind of natural polymerses being made up of phenylpropyl alcohol alkyl structure unit, can be real by catalysis orientation degraded
Now liquefy, obtain product liquid.But contain substantial amounts of phenols oxygenatedchemicals, its calorific value, viscosity, stability in product liquid
The needs of using energy source terminal client can not be met with performance indications such as corrosivity, therefore, phenolic product to liquefying lignin
It is necessary for carrying out efficient catalytic hydrogenation deoxidation PROCESS FOR TREATMENT (hdo).
The sulfuration that prior art document report will be carried on the carriers such as aluminum oxide, activated carbon, silica, alumina silicate
Nimo, como catalyst is applied to partly realize the lifting of bio oil performance indications in the hydrogenation deoxidation technique of bio oil.As special
Profit application wo-2007/141293 describes a kind of hydrodeoxygenation process of the raw material from renewable source, and it is using containing extremely
A kind of few metal selected from viii cluster and the catalyst being in sulphided form of at least one metal selected from vib cluster, its
In one or more metal selected from viii cluster and one or more metal selected from vib cluster mol ratio 0.48-0.97's
In the range of.However, this process must introduce sulfur-containing compound (as h in catalystic converter system2S, thiophene phenol etc.) with stable
Play the metal sulfuration phase of catalytic action.Introduce sulfur-containing compound pollution sources in the bio oil of no sulphur, be the one of this technique
Individual shortcoming.For overcoming this shortcoming, scientific worker starts to explore the noble metal hydrogenation dehydrogenation catalyst with high catalytic activity,
The catalyst such as rh, pt, the pd as solid acid support type, or noble metal couple with inorganic acid composition hdo catalystic converter system.But
Be due to hydrogenation deoxidation during, oxygenatedchemicals is easily polymerized, coking, and catalyst service life is not long, noble metal valency in addition
Lattice are high, inhibit the large-scale application of such catalyst to a certain extent.
Content of the invention
It is an object of the invention to provide a kind of be applied to the method that phenolic compound hydrogenation deoxidation prepares hydrocarbon compound, and
The catalystic converter system using in the reaction.
To achieve these goals, this invention takes technical scheme below:
The present invention is catalyzed the method that phenolic compound hydrogenation deoxidation prepares hydrocarbon product, carries out in autoclave, with
Phenolic compound is raw material, using alkane solvents it is characterised in that: the method is using by urging that nickel formate, solid acid form
Change reaction system, the metal ni that nickel formate decomposition in situ produces is hydrogenation active component, and nickel formate decomposes the hydrogen producing can be provided
Highly active hydrogenation hydrogen source.
Described solid acid is selected from hzsm-5, nb2o5、sio2-zro2.
Described alkane solvent is selected from normal octane, n-dodecane, hexadecane, hexamethylene, decahydronaphthalene.
In described catalystic converter system, the consumption of nickel formate is between the quality 12.1%～41.3% of phenolic compound.
In described catalystic converter system, the mass ratio of nickel formate and solid acid is between 1:0.2～2.
Nickel formate in described catalystic converter system and solid acid are directly added in reaction system.
The reaction temperature of described catalystic converter system controls between 270～340 DEG C.
The initial h of reaction of described catalystic converter system2Stress control is between 2～5mpa.
In described catalystic converter system, phenolic compound and solvent quality are than between 1:1～1:100.
Present invention also offers one kind catalystic converter system used in catalysis phenolic compound hydrogenation deoxidation reaction, its
It is characterised by being made up of nickel formate and solid acid, nickel formate and solid acid are directly added in reaction system, nickel formate is that hydrogenation is lived
Property metal presoma, couple composition with solid acid and there is hydrogenation and the catalystic converter system of deoxidation dual-use function, wherein solid
Acid is selected from hzsm-5, nb2o5、sio2-zro2, between 1:0.2～1:2, nickel formate is in situ for the mass ratio of nickel formate and solid acid
Decomposing the metal ni producing is hydrogenation active component, and nickel formate decomposes the hydrogen producing can provide highly active hydrogenation hydrogen source.
The present invention with phenolic compound (with phenol, guaiacol, vanillic aldehyde, eugenol, anethene, ortho-methyl phenol and
2,4- xylenols etc. be representative) hydrogenation deoxidation prepare alkane be target, formic acid nickel be hydrogenation active metals forerunner
Body, with hzsm-5, nb cheap and easy to get2o5、sio2-zro2Solid acid coupling composition has and is hydrogenated with and the urging of deoxidation dual-use function
Change reaction system.In catalytic hydrodeoxygenation reaction system involved in the present invention, the metal ni that nickel formate decomposition in situ produces is
Hydrogenation active component, nickel formate decomposes the hydrogen producing can provide highly active hydrogenation hydrogen source；Solid acid then can realize phenol generalization
The absorption of adduct molecule and activation, go the functions such as hydroxyls dehydrate, and couple with hydrogenation reaction realize phenolic compound hydrogenation de-
Oxygen.Additionally, with respect to support type bifunctional catalyst, hydrogenation active metals and functional solid acid in the catalyst system and catalyzing of the present invention
Carrier does not almost interact, and breaches the surface two dimension constraint of solid carrier, hydrogenation active metals show preferably urges
Change activity；Active metal will not covering catalyst carrier acid active sites, be conducive to the adsorption activation of phenolic compound and anti-
The hydroxyls dehydrate that goes during answering reacts.
The metal ni that the present invention is produced by nickel formate decomposition in situ and hzsm-5, nb2o5、sio2-zro2Solid acid couples
Constitute hydrogenation deoxidation catalystic converter system, realize the conversion to hydrocarbon compound for the hydrogenated deoxidation of phenolic compound.In the present invention
Raw materials used price is more cheap to be easy to get, and using method is simple, and reactivity is high.In the catalytically active assessment of catalyst system and catalyzing,
The conversion ratio of most of phenolic compound is close to 100%.
Specific implementation method
The present invention will be further illustrated in the examples below, but do not limit the invention.
The invention provides catalysis phenolic compound hydrogenation deoxidation reaction used in catalystic converter system, by formic acid
Nickel and solid acid composition, nickel formate and solid acid are directly added in reaction system, and nickel formate is the presoma of hydrogenation active metals,
Couple composition with solid acid and there is hydrogenation and the catalystic converter system of deoxidation dual-use function, wherein solid acid be selected from hzsm-5,
nb2o5、sio2-zro2, the mass ratio of nickel formate and solid acid between 1:0.2～1:2, nickel formate decomposition in situ produce gold
Genus ni is hydrogenation active component, and nickel formate decomposes the hydrogen producing can provide highly active hydrogenation hydrogen source.
The reaction that catalysis phenolic compound hydrogenation deoxidation prepares alkane is carried out, with phenol generalization in HV XLPE power cables reactor
Compound is raw material, using alkane solvents, adds and is stirred by the catalyst system that nickel formate and solid acid are constituted reacting.Institute
The reaction time having embodiment is all set as 5h, and mixing speed is 800rmp.
The reaction condition of each embodiment, phenols reactant species and reaction result are all listed in Table 1 below.
Table 1
Conversion ratio computing formula is:
Claims (2)
1. a kind of method that catalysis phenolic compound hydrogenation deoxidation prepares hydrocarbon product, is carried out, with phenols in autoclave
Compound is raw material, using alkane solvents it is characterised in that: the method is anti-using the catalysis that is made up of nickel formate, solid acid
Answer system, with the metal ni of nickel formate decomposition in situ generation as hydrogenation active component, nickel formate decomposes the hydrogen producing provides hydrogenation
Hydrogen source；Described solid acid is selected from hzsm-5, nb2o5、sio2-zro2；The mass ratio of nickel formate and solid acid 1:0.2～1:2 it
Between；Described alkane solvent is selected from normal octane, n-dodecane, hexadecane, hexamethylene, decahydronaphthalene；In described catalystic converter system
The consumption of nickel formate is between the 12.1%～41.3% of phenolic compound quality；Reaction temperature is between 270～340 DEG C；Instead
Should initial h2Pressure is between 2～5mpa；Phenolic compound and solvent quality are than between 1:1～1:100.
2. one kind catalystic converter system used in catalysis phenolic compound hydrogenation deoxidation reaction is it is characterised in that by nickel formate
Form with solid acid, nickel formate and solid acid are directly added in reaction system, nickel formate is the presoma of hydrogenation active metals, with
Solid acid coupling composition has the catalystic converter system of hydrogenation and deoxidation dual-use function, and wherein solid acid is selected from hzsm-5, nb2o5、
sio2-zro2, between 1:0.2～1:2, the metal ni that nickel formate decomposition in situ produces is the mass ratio of nickel formate and solid acid
Hydrogenation active component, nickel formate decomposes the hydrogen producing can provide highly active hydrogenation hydrogen source.
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| CN201410351466.6A CN104226358B (en) | 2014-07-22 | 2014-07-22 | Method for preparing alkane by catalyzing phenol compounds through hydrodeoxygenation and catalytic reaction system |
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| CN104862023B (en) * | 2015-05-19 | 2017-11-21 | 中国科学院广州能源研究所 | A kind of method of chemical catalysis production biological fuel gas |
| CN115364867A (en) * | 2021-05-18 | 2022-11-22 | 南京林业大学 | Preparation of bimetallic catalyst and method for applying bimetallic catalyst in catalytic hydrogenation of guaiacol and other phenolic model compounds |
| CN113385204A (en) * | 2021-06-21 | 2021-09-14 | 复旦大学 | Nickel-based metal phosphate catalyst and preparation method and application thereof |
| CN113663682A (en) * | 2021-07-12 | 2021-11-19 | 西南林业大学 | Non-supported mesoporous hydrodeoxygenation catalyst and preparation and application thereof |
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| US20120305836A1 (en) * | 2011-06-01 | 2012-12-06 | Uop Llc | Methods and catalysts for deoxygenating biomass-derived pyrolysis oil |
| CN102430409B (en) * | 2011-08-31 | 2014-04-02 | 中国科学院广州能源研究所 | Catalyst for catalyzing hydrogenation deoxidation reaction of guaiacol and preparation method thereof |
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