CN106753549B - A kind of method that the phenolic product hydrotreating of lignin depolymerization lightweight prepares HC fuel - Google Patents
A kind of method that the phenolic product hydrotreating of lignin depolymerization lightweight prepares HC fuel Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a kind of methods that lignin depolymerization lightweight phenolic product hydrotreating prepares HC fuel, include the following steps：Using the lightweight phenolic product detached in lignin depolymerization product as raw material, pre-hydrotreating reaction is carried out by hydrogenation catalyst of Raney Ni in alcohol solvent, then in Pd/Nb2O5‑SiO2Or Pt/Nb2O5‑SiO2Hydrogenation deoxidation reaction is completed under hydrogenation deoxidation catalyst catalytic action and generates hydrocarbon compound, and hydrocarbon compound is HC fuel.The present invention carries out pre-hydrotreating in a mild condition using more cheap Raney Ni catalyst to the lightweight phenolic product that lignin depolymerization obtains, improve the thermostabilization of lightweight phenolic product, polymerization and the carbon distribution for avoiding subsequent hydrogenation deoxidation reaction process, to extend the service life of follow-up noble metal hydrogenation dehydrogenation catalyst.
Description
Technical field：
The invention belongs to biomass liquid fuel preparing technical fields, and in particular to a kind of lignin depolymerization lightweight phenols production
The method that object hydrotreating prepares HC fuel.
Background technology：
Chief component of the lignin as biomass is lignocellulose biomass by hydrolyzation fermentation ethanol industry processed
Become environmental contaminants due to being not fully utilized with the Main By product of paper industry, very big pressure is brought to environment
Power.Therefore, lignin is efficiently converted into the utilization rate of liquid fuel or chemicals to raising biomass carbon resource, improves biology
Matter utilizes the economy important in inhibiting of technology.Theoretically, mononuclear phenolic platform chemicals are obtained by catalytic degradation, then passed through
Hydrogenation deoxidation obtains carbon number in C6-C10Between hydrocarbon compound, the vapour pressure of this kind of compound, carbon number distribution with gasoline group
Classify seemingly, and its octane number is quite high, is a kind of ideal traffic fuel element.
The catalyst type of phenolic compound hydrogenation deoxidation is more.Wherein study earlier be with molybdenum sulfide is active phase
Bifunctional catalyst is (such as the MoS of load2、NiMoS2、CoMoS2Equal catalyst).But such catalyst needs higher hydrogen pressure
Power is easy coking deactivation in reaction process.In addition, generally need to persistently provide certain density H in the reaction system2S is to maintain
The sulphided state of Mo avoids the loss of catalyst active center.The noble metal catalyst (such as Pt, Pd, Rh, Ru) of load also has
Good hydrogenation deoxidation (HDO) activity, and reaction condition is also more mild.In terms of phenolic compound hydrogenation deoxidation research
Report increased rapidly in recent years, and had relevant technical worker and carry out detailed summary to the work progress in this field
(Chin.J.Catal.2012,33:215；Energy Environ.Sci.,2014,7,103).
However, in the research work reported at present, it is more as the research of object using model compound, and true lignin drop
It is less to solve the research that product is raw material.Although model compound has certain representativeness, the catabolite component of lignin
It is sufficiently complex.Single compound is only used only and is difficult to comprehensively and objectively reflect that the conversion process of true raw material is reacted with catalysis
Mechanism, it is even more impossible to investigate influencing each other between various components.In addition, during the hydrogenation deoxidation of higher temperature, phenol generalization
It closes object and is easy polymerization generation macromolecular organic polymer, so as to cause catalyst surface carbon distribution.In fact, containing in biomass-based
During oxygen compound hydro-upgrading, hydrogenation reaction and the polymerisation of oxygenatedchemicals are parallel competitive relations.However it polymerize
The rate of reaction is generally far larger than the rate of hydrogenation reaction, and therefore, it is existing with coking that hydro-upgrading process is usually associated with polymerization
The generation of elephant, leads to rapid catalyst deactivation.This is that exactly current biomass hydrogenation deoxidation refining is difficult to make a breakthrough
A major reason.Currently, either traditional sulphurized catalyst or noble metal catalyst, without long-play
Test.To overcome this weakness, present invention design to synthesize novel dual-functional hydrogenation dehydrogenation catalyst, and it is pre- using low temperature
Add hydrogen to carry out hydrofinishing to the lightweight phenolic product of lignin depolymerization with the technique that high-temperature hydrogenation deoxidation is combined, is obtained with it
High-grade hydrocarbon fuel oil.
Invention content：
The purpose of the present invention is to provide a kind of lignin depolymerization lightweight phenolic product hydrotreatings to prepare HC fuel
Method, the method for preparing HC fuel by two step hydrotreatings, using Raney Ni as catalyst, Catalytic lignin depolymerization lightweight
Active unsaturated functional group carries out adding hydrogen in phenolic product, carries out adding hydrogen to the phenyl ring in the phenolic compound of part, to real
The stabilisation of existing lightweight phenolic product, avoids polymerization and the carbon distribution of subsequent hydrogenation deoxidation reaction process, extends making for catalyst
Use the service life.The Pt/Nb proposed in the present invention2O5-SiO2Or Pd/Nb2O5-SiO2Catalyst is used continuously in fixed bed reactors
Catalytic activity is without being decreased obviously after 240h, relative to Pt/Nb2O5、Pd/Nb2O5、Pt/SiO2And Pd/SiO2The catalyst such as catalyst
With apparent advantage.
The object of the present invention is to provide the sides that a kind of lignin depolymerization lightweight phenolic product hydrotreating prepares HC fuel
Method includes the following steps：
(1) lignin progress depolymerization reaction is obtained into lightweight phenolic product, is raw material in anhydrous second using lightweight phenolic product
Pre-hydrotreating reaction is carried out as hydrogenation catalyst using Raney Ni in alcoholic solvent and obtains product liquid, hydrogen in pre-hydrotreating reaction system
Pressure is 2.0~5.0MPa, and reaction temperature is 80 DEG C~180 DEG C, and the reaction time is 1~10h, based on mass fraction, Raney
The quality of Ni catalyst is the 5%~50% of lightweight phenolic product quality, and the quality of lightweight phenolic product is lightweight phenolic product
With the 1%~20% of absolute ethyl alcohol gross mass；
(2) product liquid that step (1) obtains is being filled with Pd/Nb2O5-SiO2Or Pt/Nb2O5-SiO2Hydrogenation deoxidation
Hydrogenation deoxidation reaction is carried out in the fixed bed of catalyst, the temperature of fixed bed is 250 DEG C~360 DEG C, liquid hourly space velocity (LHSV) 0.02
~0.30h-1, Hydrogen Vapor Pressure is 2.0~5.0MPa in reaction system, and hydrogen-oil ratio is 300~1000, the hydrogenated deoxidation of product liquid
Reaction generates hydrocarbon compound, and hydrocarbon compound is HC fuel；
The hydrogenation deoxidation catalyst Pd/Nb2O5-SiO2And Pt/Nb2O5-SiO2Catalyst is using following preparation method
It prepares：
A、Nb2O5-SiO2The preparation of carrier：By Nb:The atomic ratio of Si is 0.5~5:1, weigh the hydration of niobic acid ammonium oxalates
Object is dissolved in distilled water, and ammonium hydroxide is added dropwise under stirring condition, adjusts the pH value of solution to 8；It weighs sodium metasilicate and is dissolved in distilled water
In, ammonium nitrate solution is added dropwise under stirring condition, adjusts the pH value of solution to 8；Then continue to stir after two kinds of suspensions being mixed
2h, after 60 DEG C precipitate aging, are filtered, washed, through dry and roasting, obtained solid is Nb2O5-SiO2Carrier；
B、Pd/Nb2O5-SiO2And Pt/Nb2O5-SiO2The preparation of catalyst：The Nb prepared respectively with step A2O5-SiO2For
Carrier, the ratio for being 0.1%~5% in the mass content of Pt metal in catalyst weigh chloroplatinic acid, Pt/ are prepared by infusion process
Nb2O5-SiO2Catalyst；The ratio for being 0.1%~5% in the mass content of metal Pd in catalyst weighs palladium bichloride, passes through leaching
Stain method prepares Pd/Nb2O5-SiO2Catalyst.In step A it is dry and roast the specific steps are：Dry in 120 DEG C of baking ovens,
500 DEG C of Muffle kiln roastings.
In the prior art, fuel is prepared from lignin by catalytic liquefaction one-step method, and without deoxygenation so that
Oxygen element is still present in fuel, leads to that the calorific value of liquid fuel is low, corrosivity is strong, stability is poor, it is difficult to be directly applied to
Existing on-board engine.Implementation through the invention, lignin can obtain mononuclear phenolic hardware and software platform through catalytic degradation liquefaction
Object is closed, hydrogenated deoxidation is obtained using cycloalkane, alkyl naphthene, benzene and alkylbenzene as main component obtained platform chemicals again
Carbon number in C6-C10Between hydrocarbon compound, vapour pressure, the carbon number distribution of this kind of compound are similar with gasoline component, and
Its octane number is quite high, is a kind of ideal traffic fuel element, existing on-board engine is may be directly applied to, to realize
The Liginon Resource of low value is converted to high-grade traffic fuel.Nb2O5It is a kind of solid acid.It is coordinated unsaturated Nb5+For L acid
Center generates the Lacking oxygen for having extremely strong adsorptivity to the oxygen in phenolic compound.Lacking oxygen and the metal Pd or Pt near it
The active H atom synergistic effect of atomic surface dissociation completes deoxidation hydrogenation reaction so as to efficiently be catalyzed phenolic compound.
In addition, niobium oxide is not soluble in water and general acid-base solution, the low mobility of niobium oxide and difficult reproducibility make its height
Temperature is lower to have good structural stability, and hydrothermally stable performance is excellent, this characteristic is to improving the service life of catalyst extremely
Favorably.Water in large quantities is inevitably formed during the hydrogenation deoxidation of ring phenols platform chemicals, this is to catalyst material
The hydrothermal stability of material is clearly a kind of stern challenge.Such as industrial common γ-Al2O3The Mo bases catalyst of load is adding
During hydrogen deoxygenation, often due to γ-Al in thermal and hydric environment2O3Phase transformation make the acid bit quantity and intensity of catalyst
Significantly decline, is reduced so as to cause catalytic activity.Obviously, niobium oxide can be effectively prevented from this defect as carrier material.
Hydrogenation deoxidation catalyst uses composite oxides Nb2O5-SiO2As carrier, single Nb is overcome2O5Metal oxygen
The smaller disadvantage of compound specific surface area, improve metal carrier surface dispersion degree, to further improve active metal
Utilization ratio.
The method that the present invention prepares HC fuel is simple, can be obtained HC fuel without using large scale equipment processing, at
This is low.
Preferably, in step (1) the specific steps are：The quality of Raney Ni catalyst is lightweight phenolic product quality
20%~50%, the quality of lightweight phenolic product is the 10%~20% of lightweight phenolic product and absolute ethyl alcohol gross mass.
Preferably, the lignin carry out depolymerization reaction obtain lightweight phenolic product specific preparation process it is as follows：
A, it is 5 according to the mass ratio of lignin and lye under the Hydrogen Vapor Pressure of 0.5Pa:1, lignin is water-soluble with ethyl alcohol
The solid-to-liquid ratio of liquid is 1:10~1:16g/mL, the volume ratio of ethyl alcohol and water is 3 in ethanol water:1, it is heated under stirring condition
It 260 DEG C~300 DEG C, carries out depolymerization reaction 2h and can be obtained depolymerization product；
B, it after rotary evaporation removes alcohol solvent after the depolymerization product filtering that prepared by step a, is extracted with ethyl acetate,
Ethyl acetate phase contained substance is lignin depolymerization lightweight phenolic product；
C, the ethyl acetate phase that step b is obtained after rotary evaporation removes ethyl acetate to get lightweight phenolic product,.
Further, the lignin is alkali lignin or maize straw hydrolytic residue.
Further, the solid-to-liquid ratio of the lignin and ethanol water is 1:16g/mL is heated under stirring condition
300 DEG C, carry out depolymerization reaction.
Preferably, the mass content of the Pt metal is 1%~5%, the mass content of the metal Pd is 2%~
5%.
Preferably, the HC fuel ingredient include in cycloalkane, alkyl naphthene, benzene and alkylbenzene it is a kind of with
On.
The beneficial effects of the invention are as follows：What the present invention obtained lignin depolymerization using more cheap Raney Ni catalyst
Lightweight phenolic product carries out pre-hydrotreating in a mild condition, improves the thermostabilization of lightweight phenolic product, avoids follow-up
Hydrogenation deoxidation reaction process polymerization and carbon distribution, to extend the service life of follow-up noble metal hydrogenation dehydrogenation catalyst；This
Outside, the present invention devises composite oxides Nb2O5-SiO2Pt, Pd dual-functional hydrogenation dehydrogenation catalyst of load, the catalyst is not
Only there is higher hydrogenation deoxidation catalytic activity, and possess excellent hydrothermal stability, solve traditional γ-Al2O3Deng load
Body material is easy phase transformation in thermal and hydric environment and leads to the problem of catalytic activity decline.
Description of the drawings：
Fig. 1 be embodiment 6 prepare pre-add hydrogen lightweight phenolic product different catalysts effect under hydrogenation deoxidation reaction with
The variation relation of time；
Wherein："-●-" indicates 1%Pt/Nb2O5-SiO2(Nb/Si=3:1) catalyst, "-■-" indicate 2%Pd/
Nb2O5-SiO2(Nb/Si=3:1) catalyst, "-▲-" indicate 1%Pt/Nb2O5Catalyst,Indicate 2%Pd/Nb2O5
Catalyst.
Specific implementation mode：
The following examples are further illustrations of the invention, rather than limiting the invention.
Except special instruction, experiment material and reagent in the present invention are the art regular market purchase product.
A kind of method that the phenolic product hydrotreating of lignin depolymerization lightweight prepares HC fuel, includes the following steps：
(1) lignin progress depolymerization reaction is obtained into lightweight phenolic product, is raw material in anhydrous second using lightweight phenolic product
Pre-hydrotreating reaction is carried out as hydrogenation catalyst using Raney Ni in alcoholic solvent and obtains product liquid, hydrogen in pre-hydrotreating reaction system
Pressure is 2.0~5.0MPa, and reaction temperature is 80 DEG C~180 DEG C, and the reaction time is 1~10h, based on mass fraction, Raney
The quality of Ni catalyst is the 5%~50% of lightweight phenolic product quality, and the quality of lightweight phenolic product is lightweight phenolic product
With the 1%~20% of absolute ethyl alcohol gross mass；
(2) product liquid that step (1) obtains is being filled with Pd/Nb2O5-SiO2Or Pt/Nb2O5-SiO2Hydrogenation deoxidation
Hydrogenation deoxidation reaction is carried out in the fixed bed of catalyst, the temperature of fixed bed is 250 DEG C~360 DEG C, liquid hourly space velocity (LHSV) 0.02
~0.30h-1, Hydrogen Vapor Pressure is 2.0~5.0MPa in reaction system, and hydrogen-oil ratio is 300~1000, the hydrogenated deoxidation of product liquid
Reaction generates hydrocarbon compound, and hydrocarbon compound is HC fuel；
The hydrogenation deoxidation catalyst Pd/Nb2O5-SiO2And Pt/Nb2O5-SiO2Catalyst is using following preparation method
It prepares：
A、Nb2O5-SiO2The preparation of carrier：By Nb:The atomic ratio of Si is 0.5~5:1, weigh the hydration of niobic acid ammonium oxalates
Object is dissolved in distilled water, and ammonium hydroxide is added dropwise under stirring condition, adjusts the pH value of solution to 8；It weighs sodium metasilicate and is dissolved in distilled water
In, ammonium nitrate solution is added dropwise under stirring condition, adjusts the pH value of solution to 8；Then continue to stir after two kinds of suspensions being mixed
2h, after 60 DEG C precipitate aging, are filtered, washed, dry, 500 DEG C of Muffle kiln roastings, obtained solid are in 120 DEG C of baking ovens
For Nb2O5-SiO2Carrier；
B、Pd/Nb2O5-SiO2And Pt/Nb2O5-SiO2The preparation of catalyst：The Nb prepared respectively with step A2O5-SiO2For
Carrier, the ratio for being 0.1%~5% in the mass content of Pt metal in catalyst weigh chloroplatinic acid, Pt/ are prepared by infusion process
Nb2O5-SiO2Catalyst；The ratio for being 0.1%~5% in the mass content of metal Pd in catalyst weighs palladium bichloride, passes through leaching
Stain method prepares Pd/Nb2O5-SiO2Catalyst.
The present invention prepare HC fuel principle be：First, using Raney Ni as catalyst, Catalytic lignin depolymerization lightweight
Active unsaturated functional group carries out adding hydrogen in phenolic product, or even carries out adding hydrogen to the phenyl ring in the phenolic compound of part, from
And realize the stabilisation of lightweight phenolic product, polymerization and the carbon distribution of subsequent hydrogenation deoxidation reaction process are avoided, catalyst is extended
Service life；Secondly, composite oxides Nb is devised2O5-SiO2Pt, Pd dual-functional hydrogenation dehydrogenation catalyst of load, catalysis
By pre-add hydrogen quality depolymerization lightweight phenolic product complete hydrogenation deoxidation reaction, obtain with cycloalkane, alkyl naphthene, benzene and
Alkylbenzene HC fuel as main component；Finally, prepared Nb2O5-SiO2Carrier material has stronger acid and hydro-thermal
Stability solves traditional γ-Al2O3The hydrogenation deoxidation catalyst of load is during the reaction since thermal and hydric environment causes phase
The problem for becoming and catalytic activity being caused to reduce.
Embodiment 1
The preparation of hydrolytic residue depolymerization lightweight phenolic product
Under the Hydrogen Vapor Pressure of 0.5Pa, maize straw hydrolytic residue raw material is added in the autoclave with agitating device
(ethanol/water volume ratio is 75 by 5.0g, NaOH 1.0g, ethanol water 80mL:25) 300 DEG C, are heated under stirring condition, into
Row depolymerization reaction 2h stops heating, and reaction kettle is cooled to room temperature.Reaction kettle is opened, the product liquid in reactor is collected
And it is transferred to Rotary Evaporators.After removing alcohol solvent by rotary evaporation, (ethyl acetate is extracted with 30mL ethyl acetate
It is 1 with depolymerization product volume ratio:1).The ethyl acetate phase of extraction gained is again transferred to Rotary Evaporators, is removed through rotary evaporation
Products therefrom is lignin depolymerization lightweight phenolic product after removing ethyl acetate.It weighs, calculates the production of lignin depolymerization lightweight phenols
The yield of object is 31.5% (being shown in Table 1).
Embodiment 2
The preparation of hydrolytic residue depolymerization lightweight phenolic product
Under the Hydrogen Vapor Pressure of 0.5Pa, alkali lignin raw material 5.0g, NaOH are added in the autoclave with agitating device
(ethanol/water volume ratio is 75 by 1.0g, ethanol water 80mL:25) it, is heated to 260 DEG C under stirring condition, carries out depolymerization reaction
2h stops heating, and reaction kettle is cooled to room temperature.Reaction kettle is opened, the product liquid in reactor is collected and is transferred to rotation
Turn evaporimeter.After removing alcohol solvent by rotary evaporation, (ethyl acetate and depolymerization product are extracted with 30mL ethyl acetate
Volume ratio is 1:1).The ethyl acetate phase of extraction gained is again transferred to Rotary Evaporators, and ethyl acetate is removed through rotary evaporation
Products therefrom is lignin depolymerization lightweight phenolic product afterwards.It weighs, the yield for calculating lignin depolymerization lightweight phenolic product is
18.5% (being shown in Table 1).
Embodiment 3
The preparation of hydrolytic residue depolymerization lightweight phenolic product
Under the Hydrogen Vapor Pressure of 0.5Pa, alkali lignin raw material 5.0g, NaOH are added in the autoclave with agitating device
(ethanol/water volume ratio is 75 by 1.0g, ethanol water 80mL:25) it, is heated to 280 DEG C under stirring condition, carries out depolymerization reaction
2h stops heating, and reaction kettle is cooled to room temperature.Reaction kettle is opened, the product liquid in reactor is collected and is transferred to rotation
Turn evaporimeter.After removing alcohol solvent by rotary evaporation, (ethyl acetate and depolymerization product are extracted with 30mL ethyl acetate
Volume ratio is 1:1).The ethyl acetate phase of extraction gained is again transferred to Rotary Evaporators, and ethyl acetate is removed through rotary evaporation
Products therefrom is lignin depolymerization lightweight phenolic product afterwards.It weighs, the yield for calculating lignin depolymerization lightweight phenolic product is
23.6% (being shown in Table 1).
Embodiment 4
The preparation of hydrolytic residue depolymerization lightweight phenolic product
Under the Hydrogen Vapor Pressure of 0.5Pa, alkali lignin raw material 5.0g, NaOH are added in the autoclave with agitating device
(ethanol/water volume ratio is 75 by 1.0g, ethanol water 50mL:25) it, is heated to 300 DEG C under stirring condition, carries out depolymerization reaction
2h stops heating, and reaction kettle is cooled to room temperature.Reaction kettle is opened, the product liquid in reactor is collected and is transferred to rotation
Turn evaporimeter.After removing alcohol solvent by rotary evaporation, (ethyl acetate and depolymerization product are extracted with 30mL ethyl acetate
Volume ratio is 1:1).The ethyl acetate phase of extraction gained is again transferred to Rotary Evaporators, and ethyl acetate is removed through rotary evaporation
Products therefrom is lignin depolymerization lightweight phenolic product afterwards.It weighs, the yield for calculating lignin depolymerization lightweight phenolic product is
26.1% (being shown in Table 1).
Embodiment 5
The preparation of hydrolytic residue depolymerization lightweight phenolic product
Under the Hydrogen Vapor Pressure of 0.5Pa, alkali lignin raw material 5.0g, NaOH are added in the autoclave with agitating device
(ethanol/water volume ratio is 75 by 1.0g, ethanol water 60mL:25) it, is heated to 280 DEG C under stirring condition, carries out depolymerization reaction
2h stops heating, and reaction kettle is cooled to room temperature.Reaction kettle is opened, the product liquid in reactor is collected and is transferred to rotation
Turn evaporimeter.After removing alcohol solvent by rotary evaporation, (ethyl acetate and depolymerization product are extracted with 30mL ethyl acetate
Volume ratio is 1:1).The ethyl acetate phase of extraction gained is again transferred to Rotary Evaporators, and ethyl acetate is removed through rotary evaporation
Products therefrom is lignin depolymerization lightweight phenolic product afterwards.It weighs, the yield for calculating lignin depolymerization lightweight phenolic product is
26.4% (being shown in Table 1).
The design parameter of Examples 1 to 5 and the yield of lightweight phenolic product are referring to table 1.
Table 1
| Embodiment | Quantity of solvent (mL) | Reaction temperature (DEG C) | Lightweight phenolic product yield (%) |
| Embodiment 1 | 80 | 300 | 33.5 |
| Embodiment 2 | 80 | 260 | 18.5 |
| Embodiment 3 | 80 | 280 | 23.6 |
| Embodiment 4 | 50 | 300 | 26.1 |
| Embodiment 5 | 60 | 300 | 26.4 |
It is obtained by table 1：Reaction temperature is very big on the influence of the yield of lightweight phenolic product, when reaction temperature is 300 DEG C, lightweight
The yield of phenolic product is bigger, wherein reaction temperature is 300 DEG C in embodiment 1, when alcohol solvent is 80mL, lightweight phenols
The yield of product is maximum.
Embodiment 6
The pre-add hydrogen of lignin depolymerization lightweight phenolic product
In the autoclave with agitating device, the lightweight phenolic product 2g that addition embodiment 1 obtains, absolute ethyl alcohol
18g (i.e. the mass fraction of reactant is 10%), Raney Ni catalyst 1g (weight in wet base), with N2In replacement reaction kettle after air,
It is passed through H2To 4.0MPa, heating reaction kettle is to 150 DEG C under stirring condition, reaction time 10h.Liquid production is collected after the completion of reaction
Object is reacted for subsequent hydrogenation deoxidation.
Its pre-hydrotreating reaction step reference implementation example 6 of embodiment 7~12, the difference is that reaction temperature, catalyst are used
Amount, reaction time and reactant concentration, specific response parameter are shown in Table 2.
As shown in table 2：
Table 2
| Embodiment | Reactant concentration (%) | Catalyst amount (%) | Time (h) | Temperature (DEG C) | Hydrogen consumption * (mmol/g) |
| Embodiment 6 | 10 | 50 | 10 | 150 | 12.8 |
| Embodiment 7 | 10 | 50 | 10 | 80 | 5.1 |
| Embodiment 8 | 10 | 5 | 10 | 180 | 1.9 |
| Embodiment 9 | 10 | 20 | 1 | 150 | 0.7 |
| Embodiment 10 | 10 | 20 | 6 | 150 | 6.6 |
| Embodiment 11 | 1 | 20 | 10 | 150 | 8.3 |
| Embodiment 12 | 20 | 20 | 10 | 150 | 7.9 |
* the amounts of hydrogen of every gram of lightweight phenolic product pre-add hydrogen consumption, according to the changing value meter of reactor pressure before and after reaction
It calculates.
It is obtained by table 2：The influence of catalyst amount, reaction temperature to lightweight phenolic product pre-add hydrogen is maximum, reaction temperature
For 150 DEG C, catalyst amount be 20% or more when, add hydrogen effect preferable, wherein in embodiment 6 reaction temperature be 180 DEG C, urge
When agent dosage is 50%, hydrogen consumption maximum, the pre-add hydrogen effect of lightweight phenolic product are best.
Embodiment 13
The preparation of catalyst
Weigh niobic acid ammonium oxalic acid salt hydrate ([(NH4)3NbO(C2O4)3]·4H2O) 19.96g is dissolved in 200mL water,
Ammonium hydroxide is added dropwise under stirring condition until the pH value of solution reaches 8；It weighs sodium metasilicate in proportion to be dissolved in 200mL water, stirring bar
Saturation ammonium nitrate solution is added dropwise under part until the pH value of solution reaches 8；It is then combined with two kinds of suspensions and continues to stir 2h.60℃
It after precipitating aging 6h in water-bath, is filtered, washs successively, dry 12h, 500 DEG C of Muffle kiln roastings in 120 DEG C of baking ovens
4h is to get to atomic ratio Nb/Si=3:1 Nb2O5-SiO2Carrier material.
It weighs that chloroplatinic acid 0.27g is soluble in water, weighs the Nb of above-mentioned preparation2O5-SiO2Carrier material 9.9g is molten in chloroplatinic acid
2h is impregnated in liquid, be then turned on magnetic agitation and is begun to warm up, until moisture is evaporated.Obtained solid is after 120 DEG C of dry 12h
4h is calcined at 450 DEG C again.Obtained solid powder is the Pt/Nb that Pt metal quality contents are 1%2O5-SiO2Catalyst.
Pt/Nb has been prepared with reference to embodiment 13 in the preparation specific steps of 14~24 catalyst of embodiment2O5-SiO2With
Pd/Nb2O5-SiO2Catalyst series, the difference is that the quantity of metal precursor and Nb/Si atomic ratios in type, carrier,
Specific parameter refers to table 3.
As shown in table 3：
Table 3
Embodiment 25
Lightweight phenols phenolic product hydrogenation deoxidation
Catalyst 1%Pt/Nb prepared by embodiment 132O5-SiO2Load the fixed bed reactors for 10mm with internal diameter
In, 400 DEG C and constant temperature 4h are warming up to 2 DEG C/min rates in the hydrogen gas stream before reaction, to complete the reduction of catalyst.Then with
6 pre-add hydrogen lightweight phenolic product of embodiment is passed through in high pressure constant flow pump injection, is carried out hydrogenation deoxidation and is refined, obtains HC fuel, hydrocarbon
The yield of class A fuel A is as shown in table 4.
20~32 lightweight phenolic product hydrogenation deoxidation specific steps of embodiment are with reference to embodiment 19, the difference is that catalysis
Agent parameter, reaction process parameter and hydro carbons yield, as shown in table 4, catalyst used in embodiment 25~44 are embodiment 13
The corresponding catalyst prepared in~24, Nb/Si atomic ratios are 3 wherein in 25~38 catalyst of embodiment:1.
Table 4
Obtain influence that three reactant concentration, reaction temperature, liquid air speed parameters react hydrogenation deoxidation most by table 4
Greatly, wherein preferably process conditions are：Reactant concentration is 10wt%, reaction temperature is 320 DEG C, liquid air speed is 0.1h-1；Phase
Under same process conditions, in catalyst, the mass content of Pt metal is 1%~5% or the mass content of metal Pd is 2%
When~5%, hydro carbons yield is higher.In addition, being obtained by table 4, catalyst 2%Pd/SiO2With 1%Pt/SiO2Hydrogenation deoxidation catalysis is lived
Property is relatively low.
Embodiment 45
The stability of catalyst
Catalyst 1%Pt/Nb prepared by embodiment 132O5-SiO2(Nb/Si=3:1) it is consolidating for 10mm to load with internal diameter
In fixed bed reactor, 400 DEG C and constant temperature 4h are warming up to 2 DEG C/min rates in the hydrogen gas stream before reaction, to complete catalyst
Reduction.Then 6 pre-add hydrogen lightweight phenolic product of embodiment is passed through with high pressure constant flow pump injection, carries out hydrogenation deoxidation and refine, obtains
The yield of the HC fuel trend that changes with time is as shown in Figure 1.
For the implementation process of embodiment 46~48 with reference to embodiment 45, reaction process parameter is 320 DEG C of temperature, Hydrogen Vapor Pressure
4.0MPa, liquid air speed 0.2h-1, reactant concentration 10wt%, hydrogen-oil ratio 500, the difference is that catalyst is respectively 2%
Pd/Nb2O5-SiO2(Nb/Si=3:1), 2%Pd/Nb2O5, 1%Pt/Nb2O5。
As shown in Figure 1, every line segment represents different catalyst with different labels in Fig. 1, by nytron in figure
Object yield changes with time rule it is found that Nb2O5-SiO2(Nb/Si=3:1) Pt loaded and Pd catalyst activities are aobvious
Apparent advantage is shown, catalytic activity is without apparent downward trend after continuous operation 240h, and 2%Pd/Nb2O5Catalyst and 1%
Pt/Nb2O5Catalyst catalytic activity in continuous operation 40h begins to occur significantly declining.
Above to lignin depolymerization lightweight phenolic product hydrotreating provided by the invention prepare HC fuel method into
Go detailed introduction, the explanation of above example is only intended to helping to understand technical scheme of the present invention and its core concept,
It should be pointed out that those of ordinary skill in the art, it without departing from the principle of the present invention, can also be to this hair
Bright some improvement and modification can also be carried out, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (7)
1. a kind of method that lignin depolymerization lightweight phenolic product hydrotreating prepares HC fuel, which is characterized in that including such as
Lower step：
(1) lignin progress depolymerization reaction is obtained into lightweight phenolic product, it is molten in absolute ethyl alcohol by raw material of lightweight phenolic product
Pre-hydrotreating reaction is carried out as hydrogenation catalyst using Raney Ni in agent and obtains product liquid, Hydrogen Vapor Pressure in pre-hydrotreating reaction system
For 2.0~5.0MPa, reaction temperature is 80 DEG C~180 DEG C, and the reaction time is 1~10h, and based on mass fraction, Raney Ni are urged
The quality of agent is the 5%~50% of lightweight phenolic product quality, and the quality of lightweight phenolic product is lightweight phenolic product and nothing
The 1%~20% of water-ethanol gross mass；
(2) product liquid that step (1) obtains is being filled with Pd/Nb2O5-SiO2Or Pt/Nb2O5-SiO2Hydrogenation deoxidation is catalyzed
Hydrogenation deoxidation reaction is carried out in the fixed bed of agent, the temperature of fixed bed is 250 DEG C~360 DEG C, liquid hourly space velocity (LHSV) is 0.02~
0.30h-1, Hydrogen Vapor Pressure is 2.0~5.0MPa in reaction system, and hydrogen-oil ratio is 300~1000, and the hydrogenated deoxidation of product liquid is anti-
Hydrocarbon compound should be generated, hydrocarbon compound is HC fuel；
The hydrogenation deoxidation catalyst Pd/Nb2O5-SiO2And Pt/Nb2O5-SiO2Catalyst is used and is prepared following preparation method：
A、Nb2O5-SiO2The preparation of carrier：By Nb:The atomic ratio of Si is 0.5~5:1, it is molten to weigh niobic acid ammonium oxalic acid salt hydrate
Ammonium hydroxide is added dropwise under stirring condition in distilled water in solution, adjusts the pH value of solution to 8；It weighs sodium metasilicate to be dissolved in distilled water, stir
Ammonium nitrate solution is added dropwise under the conditions of mixing, adjusts the pH value of solution to 8；Then continue to stir 2h, warp after two kinds of suspensions being mixed
60 DEG C of precipitation agings after being filtered, washed, by drying and roast, obtained solid is Nb2O5-SiO2Carrier；
B、Pd/Nb2O5-SiO2And Pt/Nb2O5-SiO2The preparation of catalyst：The Nb prepared respectively with step A2O5-SiO2To carry
Body, the ratio for being 0.1%~5% in the mass content of Pt metal in catalyst weigh chloroplatinic acid, Pt/ are prepared by infusion process
Nb2O5-SiO2Catalyst；The ratio for being 0.1%~5% in the mass content of metal Pd in catalyst weighs palladium bichloride, passes through leaching
Stain method prepares Pd/Nb2O5-SiO2Catalyst.
2. the method that lignin depolymerization lightweight phenolic product hydrotreating according to claim 1 prepares HC fuel,
It is characterized in that：In step (1) the specific steps are：The quality of Raney Ni catalyst be lightweight phenolic product quality 20%~
50%, the quality of lightweight phenolic product is the 10%~20% of lightweight phenolic product and absolute ethyl alcohol gross mass.
3. the method that lignin depolymerization lightweight phenolic product hydrotreating according to claim 1 prepares HC fuel,
It is characterized in that：The specific preparation process that the lignin progress depolymerization reaction obtains lightweight phenolic product is as follows：
A, it is 5 according to the mass ratio of lignin and lye under the Hydrogen Vapor Pressure of 0.5Pa:1, lignin and ethanol water
Solid-to-liquid ratio is 1:10~1:16g/mL, the volume ratio of ethyl alcohol and water is 75 in ethanol water:25, it is heated under stirring condition
It 260 DEG C~300 DEG C, carries out depolymerization reaction 2h and can be obtained depolymerization product；
B, after rotary evaporation removes alcohol solvent after the depolymerization product filtering that prepared by step a, depolymerization product is pressed with ethyl acetate
Volume ratio 1:1 is extracted, and ethyl acetate phase contained substance is lignin depolymerization lightweight phenolic product；
C, the ethyl acetate phase that step b is obtained through rotary evaporation remove ethyl acetate after to get lightweight phenolic product.
4. the method that lignin depolymerization lightweight phenolic product hydrotreating according to claim 3 prepares HC fuel,
It is characterized in that：The lignin is alkali lignin or maize straw hydrolytic residue.
5. the method that lignin depolymerization lightweight phenolic product hydrotreating according to claim 3 prepares HC fuel,
It is characterized in that：The solid-to-liquid ratio of the lignin and ethanol water is 1:16g/mL is heated to 300 DEG C under stirring condition, into
Row depolymerization reaction.
6. the method that lignin depolymerization lightweight phenolic product hydrotreating according to claim 1 or 3 prepares HC fuel,
It is characterized in that：The mass content of the Pt metal is 1%~5%, and the mass content of the metal Pd is 2%~5%.
7. the method that lignin depolymerization lightweight phenolic product hydrotreating according to claim 1 or 3 prepares HC fuel,
It is characterized in that：The HC fuel ingredient includes one or more of cycloalkane, alkyl naphthene, benzene and alkylbenzene.
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| CN112076749B (en) * | 2020-09-28 | 2023-01-17 | 中国科学院广州能源研究所 | Catalyst for preparing liquid fuel by hydrogenating and deoxidizing lignin oil and preparation method and application thereof |
| CN112125784A (en) * | 2020-10-10 | 2020-12-25 | 安徽工业大学 | Method for preparing alkylphenol by using straws |
| CN112552949B (en) * | 2020-12-02 | 2022-10-28 | 中国科学院广州能源研究所 | Method for synthesizing high-density low-freezing-point hydrocarbon component by biomass platform compound |
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| CN113750989B (en) * | 2021-10-11 | 2023-11-17 | 浙江大学 | Catalyst suitable for catalyzing biomass oil phenolic compounds to prepare oxygenated products by hydrogenation, and preparation and application thereof |
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