CN107602362A - The method that molybdenum oxide catalyst Catalytic lignin prepares single phenols aromatic compound - Google Patents
The method that molybdenum oxide catalyst Catalytic lignin prepares single phenols aromatic compound Download PDFInfo
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Abstract
The present invention discloses a kind of method that Supported molybdenum oxide catalyst lignin hydrodepolymerization prepares single phenols aromatic compound, after lignin, Supported molybdenum oxide catalyst and reaction dissolvent are mixed, heating and stirring reaction after hydrogen are passed through again, solid product and product liquid are obtained after filtering, and single phenols aromatic compound is obtained after gained product liquid drying.It can be realized by using transiting metal oxidation molybdenum catalyst and lignin is converted into by single step reaction by single phenols aromatic compound in high yield, with high selectivity, to realize the recycling of lignin and higher value application.The catalytic degradation high conversion rate of lignin in the present invention, reaction condition is gentle, and is mainly lignin list phenolic compound in product, and selectivity is high, and added value is high, has good prospects for commercial application.
Description
Technical field
The present invention relates to the preparation of aromatic compound, specifically a kind of Supported molybdenum oxide catalyst is wooden
The method that plain hydrodepolymerization prepares single phenols aromatic compound.
Background technology
Aromatic compound is the widely used bulk chemical of the mankind, and critical role is occupied in petroleum chemical industry.
For example benzene, toluene and phenol and its derivatives are the fine chemicals such as production rubber, resin, paint, ink, medicine, polyurethane
Important source material.These bulk chemicals derive from the non-renewable fossil resources such as oil, coal and natural gas at present, however as
Fossil fuel gradually decreases, and energy crisis and environmental problem have become increasingly serious.Therefore renewable life is developed and utilized
Physical resources, which prepare aromatic compound, has important scientific meaning and potential prospects for commercial application.
In tree growth law, the content of lignin is only second to cellulose and hemicellulose, is most abundant in nature
Natural aromatic compounds of group resource, and regenerated with annual 50000000000 tons of speed.In pulp and paper industry, 1 ton of paper is often produced
Slurry then discharges 1.5 tons of black liquor and obtains 0.5 ton of lignin byproduct simultaneously.But so far, the trans-utilization of lignin still lacks
Weary effective way.The industrial lignin of the whole world 1.5~1.8 hundred million tons of discharge every year, the overwhelming majority utilize as combustion value fuel, only
There are the lignosulfonates less than 1% to be reused as Organic chemistry sources, some is then straight in the form of " black liquor " in addition
Run in and put as environmental contaminants.Therefore, rationally energy chemistry product can be prepared for non-fossil sources using Liginon Resource and provided
One new approach, while also have great importance to environmental protection, saving fossil resource.
Lignin mainly has three basic structures unit, i.e. guaiacyl（G types）, lilac base（S types）And p-hydroxyphenyl
（H types）, wherein softwood lignin is mainly G types, and broadleaf lignin is mainly G types and S types, and grass lignin
In addition to G types and S type lignin, also containing H type lignin.In chemical constitution, lignin is by phenyl-propane structure list
Member passes through C-C（Account for 1/4~1/3）With C-O keys（Account for 3/2~3/4）The three-dimensional netted high molecular polymer being formed by connecting.Due to wood
The molecular structure and aggregated structure of quality are extremely complex, it is difficult to are used directly.Therefore, suitably urged by designing and preparing
Agent, by the method for catalytic hydrogenation depolymerization, cut off ehter bond in lignin and to its hydrogenating reduction efficient selective, be system
The key of standby fragrant same clan's compound.
Lignin hydrogenolysis is prepared into the method for aromatic compound mainly using noble metals such as Ru, Pd, and with biology at present
Matter is that raw material hydrogenation catalyst degrades to obtain lignin monomer compound.It is that catalyst reacts in 3MPa hydrogen, 250 DEG C such as using Ru/C
Under the conditions of, it is to mainly contain the monomer of the yield 50% with 4- propyl guaiacols and 4- propyl syringols by birch depolymerization
（Energy Environ. Sci., 8, 1748–1763）.In the recent period, the Jeremy S. of Polytechnics of Lausanne, SUI federation
Luterbacher teaches seminar effectively can prevent lignin from being condensed after Science reports addition formaldehyde, and is catalyzed in Ru/C
Under the conditions of agent, the lignin monomer yield of beech reaches 50% or so, and using the white poplar timber after genetic modification as raw material then
Lignin monomer can reach 79%（Science, 2016, 354, 329–333）.Have been reported that in Pd/C be catalyst, add
A certain amount of Zn hydrogenolysis Poplar Powders under 225 DEG C and 3.4MPa Hydrogen Vapor Pressures, obtain with 2,6- dimethoxy-4 's-propylphenol and
2- methoxyl groups -4- propyl group-phenol is the lignin monomer of main yield 54%（Green Chem., 2015, 17, 1492–
1499）.
Using base metal（Mainly W and Ni）The method of hydrogenolysis lignin is also shown in document report, but also main using life
Material is raw material.Ni-W such as using W as main active component2C/AC Catalyzed by Pt/M Bimetallic Nano birch powder, in 235 DEG C and 6MPa
Lignin monomer yield reaches 47% under Hydrogen Vapor Pressure（Energy Environ. Sci., 2012, 5, 6383–6390）.With
Ni/C does catalyst hydrogenolysis birch powder, lignin monomer yield under 200 DEG C and 1MPa argon pressures and reaches 20%（Catal.
Sci. Technol., 2015, 5, 3242–3245）.
Problems be present in the above method：First, use timber in itself rather than lignin, second, used into
This high noble metal, third, lignin monomer yield is relatively low.Finding based on document, at present still without any report
Using script lignin as raw material, using cheap non-zero valence molybdenum-base oxide as catalyst, catalytic degradation is wooden efficiently, with high selectivity
Quality prepares aromatic compound.
The content of the invention
Prepared to solve the above problems, the present invention provides a kind of Supported molybdenum oxide catalyst lignin hydrodepolymerization
The method of single phenols aromatic compound, can be realized by using transiting metal oxidation molybdenum catalyst will be wooden by single step reaction
Element is converted into single phenols aromatic compound in high yield, with high selectivity, to realize the recycling of lignin and high-valued profit
With.
To reach above-mentioned purpose, the present invention is achieved through the following technical solutions：A kind of molybdenum oxide catalyst Catalytic lignin
The method for preparing single phenols aromatic compound, by following each step：
It is 1 by the mass ratio of lignin, Supported molybdenum oxide catalyst and reaction dissolvent:（0.01~10）:（5~200）, by wood
It is closed in addition reactor after quality, Supported molybdenum oxide catalyst and reaction dissolvent mixing, then be warming up to instead after being passed through hydrogen
It is 200~280 DEG C to answer temperature, and 1~5h of stirring reaction, and reaction terminates rear Temperature fall pressure release and drives kettle, consolidated after filtering
Body product and product liquid, gained product liquid obtain single phenols aromatic compound after 110 DEG C of drying.Gained list phenols
Aromatic compound is present with lignin oil form, i.e., the main component of wooden vegetable oil is single phenols aromatic compound（Wood
Lignin monomer compound）.
The lignin includes enzyme acidolysis lignin（enzymatic mild acidolysis lignins）, milled wood lignin
Quality（milled wood lignin）, alkali lignin（alkaline lignin）, organic solvent lignin（organosolv
lignin）, sulfate-reducing conditions（kraft lignin）, sulfonate lignin（lignosulfonate）, lignocellulosic it is former
Material（Softwood, broadleaf and draft class）.
The lignin is natural lignin, industrial lignin, biomass by hydrolyzation residue, the tree growth law containing lignin
In one or more.
The natural lignin is shrub red building lignin, birch lignin, poplar lignin, Eucalyptus lignin, beech
One or more in lignin, pine lignin, Chinese silvergrass lignin, switchgrass lignin or agricultural crop straw lignin.
The industrial lignin is the one or more in alkali lignin, sulfonate lignin or lignosulfonate.I.e.
From industry byproduct, such as lignin byproduct in pulp and paper industry.
The lignocellulosic material is shrub red building powder, birch powder, Poplar Powder, Eucalyptus powder, beech powder, pine powder, awns
One or more in grass meal, switchgrass powder or agricultural residues powder.
The reaction dissolvent is methanol, several mixing of the one or any ratio of ethanol, isopropanol, ethylene glycol, water.
The pressure for being passed through hydrogen is 0~8Mpa, and mixing speed is 100~1000rpm.
The preparation method of the Supported molybdenum oxide catalyst, by the following steps：
（1）The preparation of molybdenum dichloride hydrate presoma：By molybdenum pentachloride and molybdenum powder in mass ratio 1:After 2~5 mix, in inertia
With 600~700 DEG C of roasting 5h under gas atmosphere, room temperature is cooled to, is then 40~60 DEG C of 20~30wt% dense with concentration
Hydrochloric acid is washed three times respectively, collects cleaning solution, and cleaning solution stood overnight to obtain the acicular crystal of yellow, is collected after filtering
The crystal and dry obtain molybdenum dichloride hydrate presoma (H3O)2(Mo6Cl8)Cl6·6H2O；
（2）The preparation of Supported molybdenum oxide catalyst：Mass ratio by molybdenum dichloride hydrate presoma and methanol or ethanol is
1:90~110, by step（1）Gained molybdenum dichloride hydrate presoma (H3O)2(Mo6Cl8)Cl6·6H2O is dissolved in methanol or second
In alcohol, it is slowly dropped to after it is completely dissolved in carrier, the mass ratio of molybdenum dichloride hydrate presoma and carrier is 1:2~
15,12h is stood at room temperature, after 40 DEG C of rotary evaporations remove methanol or ethanol, under inert gas atmosphere 400~600
DEG C roasting 6h, be cooled to room temperature, that is, obtain Supported molybdenum oxide catalyst.
The step（2）Carrier be CNT, SBA-15, MCM-41, the one or more in graphene oxide.
The inert gas is nitrogen, argon gas or helium.
The step（2）Methanol or ethanol for it is purchased in market analysis it is pure.
The present invention prepares transition metal catalyst with base of molybdenum in the method for aromatic compound applied to lignin, reaction knot
Shu Hou, product liquid use gas-chromatography after dichloromethane or ethyl acetate extraction（GC）And gas chromatography-mass spectrum（GC-
MS）Carry out qualitative and quantitative analysis and measure.Solid product is determined by tetrahydrofuran qualitative criteria sample, quantitatively using standard
Curve method determines, and weighs to calculate the conversion ratio of lignin.
Lignin conversion rate, wooden vegetable oil yield and monomer yield are calculated using equation below：
Wooden vegetable oil yield（wt%）= wDichloromethane DDGS/ wLignin×100 （1）
Lignin monomer yield（wt%）= wLignin monomer/ wLignin×100 （2）
Unsaturated monomer selectivity of product（%）= wUnsaturated lignin monomer/ wLignin monomer×100 （3）
Wherein, wDichloromethane DDGS representsDichloromethane DDGS, wLigninRepresent the content for adding lignin, wLignin monomerRepresent lignin list
The weight of body.
The present invention is that lignin is in closed height under catalyst with base of molybdenum and with the polar solvent effect of bonding ability is formed
Hydrodepolymerization prepares aromatic compound in pressure reactor；What lignin depolymerization obtained includes phenylol containing aromatic compounds
One or more of mixtures in compound, guaiacol based compound, lilac based compound.
Compared with prior art, the beneficial effects of the present invention are：
1st, the lignin raw material used in the present invention is renewable aromatic compound resource most abundant in nature, and source is wide
It is general, cost is cheap.The method for producing aromatic compound by the Non oil-based route of hydrodepolymerization lignin, can effectively alleviate stone
The anxiety of oily resource, meet the requirement of sustainable development.
2nd, catalyst of the invention uses nature rich reserves, cheap transition metal molybdenum oxide as in activity
The heart, preparation method are simple.Catalyst with base of molybdenum has cheap, easy preparation, catalytic activity high, the features such as can be recycled, realizes
To the high conversion and high selectivity catalytic degradation of lignin.
3rd, the present invention in lignin catalytic degradation high conversion rate, reaction condition is gentle, and predominantly wooden in product
The single phenolic compound of element, selectivity is high, and added value is high, has good prospects for commercial application.
4th, the present invention provides new way for the higher value application of lignin, reduces the dirt caused by the discharge of industrial lignin
Dye.
5th, the present invention is using molybdenum oxide as main activated centre, with wood powder, natural lignin, organic solvent lignin, alkali wood
The industrial lignins such as quality, sodium lignin sulfonate are raw material, by catalytic hydrogenation reaction, are optionally cracked into C6~C9Benzene
The aromatic compound of the derivatives such as phenolic group, guaiacol or lilac base.Lignin monomer yield is up to 52wt%, unsaturated
The selectivity of monomeric products is up to 62.5%.Compared with prior art, the present invention is raw material using renewable biomass, and raw material comes
Source is extensive, cost is cheap.
Brief description of the drawings
Fig. 1 is the product GC spectrograms of shrub red building enzyme acidolysis lignin in methanol solvate, wherein,（a）Add catalyst MoOx/
CNT product GC spectrograms,（b）Be not added with catalyst product GC spectrograms,（c）Add catalyst MoOx/ CNT degrades under a nitrogen atmosphere
Product GC spectrograms.
Fig. 2 is the product GC spectrograms of comparative example 3,4,5, wherein,（a）The GC spectrograms of Ru/C catalytic degradation lignin,（b）
The GC spectrograms of Pd/C catalytic degradation lignin,（c）The GC spectrograms of Raney Ni catalytic degradation lignin.
Fig. 3 is the lignin monomer variation of yield tendency chart of embodiment 3,4,5, wherein,（a）Differential responses temperature depolymerization wood
Lignin monomer variation of yield tendency chart,（b）Differential responses time depolymerization lignin monomer variation of yield tendency chart,（c）Catalyst
Cycle-index catalytic degradation lignin monomer variation of yield tendency chart.
Fig. 4 is the catabolite GC spectrograms of the different enzyme acidolysis lignin raw materials of embodiment 6.
Embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
（1）The preparation of molybdenum dichloride hydrate presoma：By 2g molybdenum pentachlorides MoCl5With 6g powder in mass ratio 1:Turn after 3 mixings
Enter in tube furnace, in a nitrogen atmosphere with 650 DEG C of roasting 5h, room temperature is cooled to, then with 50 that 100ml concentration is 25wt%
DEG C concentrated hydrochloric acid wash respectively three times, collect cleaning solution, and cleaning solution be put in low temperature refrigerator and stands overnight to obtain yellow
Acicular crystal, collects the crystal after filtering and drying obtains molybdenum dichloride hydrate presoma (H3O)2(Mo6Cl8)Cl6·
6H2O；
（2）The preparation of Supported molybdenum oxide catalyst：It is 1 by the mass ratio of molybdenum dichloride hydrate presoma and methanol:100,
By step（1）Gained molybdenum dichloride hydrate presoma (H3O)2(Mo6Cl8)Cl6·6H2O is dissolved in the pure methanol of analysis purchased in market, is treated
It is slowly dropped in multi-walled carbon nanotube after being completely dissolved, and the mass ratio of molybdenum dichloride hydrate presoma and carrier is 1:
11,12h is stood at room temperature, after 40 DEG C of rotary evaporations remove methanol, is placed in tube furnace, 400 DEG C in a nitrogen atmosphere
6h is calcined, room temperature is cooled to, that is, obtains Supported molybdenum oxide catalyst MoOx/ CNT, catalyst loadings 5wt%.
（3）It is 1 by the mass ratio of lignin, Supported molybdenum oxide catalyst and reaction dissolvent:10:10, by shrub red building
Enzyme acidolysis lignin 5mg, Supported molybdenum oxide catalyst MoOxAfter/CNT 50mg and methanol 50mg mixing, add in reactor
It is closed, then it is passed through hydrogen（Pressure is 3MPa）After be warming up to reaction temperature as 240 DEG C, and the stirring reaction under 800rpm rotating speeds
4h, reaction terminate rear Temperature fall pressure release and drive kettle, obtain solid product and product liquid, gained product liquid warp after filtering
Single phenols aromatic compound is obtained after 110 DEG C of drying.On the one hand product liquid claims after dichloromethane extracts, concentrates drying
The wooden vegetable oil yield of re-computation, then through containing target dichloromethane dissolving in n-tetradecane by GC-MS and GC carry out it is qualitative and
Quantitative analysis, and combine lignin monomer standard curve and calculate monomer yield.Catabolite photo and GC spectrograms such as Fig. 1 a institutes
Show.As a result the oily yield and monomer yield for showing shrub red building enzyme acidolysis lignin are respectively 63wt % and 33wt %, and it is not
Saturation monomeric products selectively reach 47%.
Embodiment 2
With embodiment 1, only replacement step（3）Reaction dissolvent methanol.Wooden vegetable oil yield, monomer yield and unsaturated monomer production
Thing selectivity result is as shown in table 1.
MoO in the different solvents of table 1x/ CNT is catalyzed shrub red building enzyme acidolysis lignin hydrodepolymerization result
Embodiment 3
With embodiment 1, only by step（3）Reaction temperature be 240 DEG C to replace with reaction temperature be 260 DEG C.Lignin monomer obtains
Rate is as shown in Figure 3 a.By Fig. 3 a, lignin monomer yield reaches 38.7wt%, unsaturation therein under the conditions of 260 DEG C
Lignin monomer is selectively 56.4%.
Embodiment 4
With embodiment 1, only by step（3）Reaction time 4h replace with 5h.Lignin monomer yield is as shown in Figure 3 b.Pass through figure
3b is understood, then extends the reaction time, and its lignin yield gradually decreases to 21.1wt% by 38.7wt%, and unsaturation therein is wooden
Plain monomer selectivity is to drop to 34.8% by 56.4%.
Embodiment 5
With embodiment 1, only by last reacted catalyst with directly being used after dichloromethane and tetrahydrofuran filtration washing,
Other processes are with embodiment 1, and lignin monomer yield is as shown in Figure 3 c.Pass through Fig. 3 c, MoOx/ CNT catalyst passes through four
Its catalytic degradation lignin yield remains to reach 26.2wt% after secondary circulation, and its unsaturated lignin monomer is selectively 37.4%.
So as to show that the catalyst has higher stability.
Embodiment 6
With embodiment 1, shrub red building enzyme acidolysis lignin is only replaced with into different enzyme acidolysis lignin raw materials, other processes are the same as real
Apply example 1, using two-dimentional nuclear magnetic spectrogram determine enzyme acidolysis lignin β-O- 4 contents（%）With S/G ratios, and it will react front and rear
Lignin passes through gel permeation chromatography after acetylation process（GPC）Chromatographic determination determines its molecular weight（Mw）Size, simultaneously
S/G ratios and unsaturated selectivity of product are calculated according to product（%）.Product GC-MS analysis of spectra is as shown in figure 4, the results are shown in Table
2。
The MoO of table 2x/ CNT is catalyzed different enzyme acidolysis lignin raw material hydrodepolymerization results
Embodiment 7
（1）The preparation of molybdenum dichloride hydrate presoma：By molybdenum pentachloride and molybdenum powder in mass ratio 1:Tube furnace is transferred to after 5 mixings
In, with 700 DEG C of roasting 5h under helium atmosphere, room temperature is cooled to, is then distinguished with 60 DEG C of the concentrated hydrochloric acid that concentration is 20wt%
Washing three times, collects cleaning solution, and cleaning solution is put in the acicular crystal for obtaining yellow is stood overnight in low temperature refrigerator, filtered
After collect the crystal and dry obtain molybdenum dichloride hydrate presoma (H3O)2(Mo6Cl8)Cl6·6H2O；
（2）The preparation of Supported molybdenum oxide catalyst：It is 1 by the mass ratio of molybdenum dichloride hydrate presoma and methanol:110,
By step（1）Gained molybdenum dichloride hydrate presoma (H3O)2(Mo6Cl8)Cl6·6H2O is dissolved in the pure methanol of analysis purchased in market, is treated
It is slowly dropped in mesoporous material SBA-15 after being completely dissolved, and the mass ratio of molybdenum dichloride hydrate presoma and carrier is 1:
15,12h is stood at room temperature, after 40 DEG C of rotary evaporations remove methanol, is placed in tube furnace, 600 DEG C under helium atmosphere
6h is calcined, room temperature is cooled to, that is, obtains Supported molybdenum oxide catalyst MoOx/SBA-15.Change transition metal in maceration extract
The concentration of salt, or by repeatedly impregnating, the catalyst of different loads amount can be obtained.
（3）It is 1 by the mass ratio of lignin, Supported molybdenum oxide catalyst and reaction dissolvent:0.01:5, by corncob alkali
Lignin, Supported molybdenum oxide catalyst MoOx/SBA-15（Catalyst loadings are 30wt%）After being mixed with methanol, add anti-
Answer closed in kettle, then be passed through hydrogen（Pressure is 5MPa）After be warming up to reaction temperature as 280 DEG C, and stirring reaction 4h, reaction knot
Kettle is driven in Temperature fall pressure release after beam, obtains solid product and product liquid after filtering, gained product liquid is after 110 DEG C of drying
Obtain single phenols aromatic compound.The oily yield and monomer yield of lignin are respectively 55wt % and 14.8wt %.
Embodiment 8
With embodiment 7, different lignin raw materials is only replaced, other processes the results are shown in Table 3 with embodiment 7.
The MoO of table 3x/ SBA-15 is catalyzed different Wooden Biomass catalytic material Hydrogenations and compared
Embodiment 9
（1）The preparation of molybdenum dichloride hydrate presoma：By molybdenum pentachloride and molybdenum powder in mass ratio 1:Tube furnace is transferred to after 2 mixings
In, with 600 DEG C of roasting 5h under helium atmosphere, room temperature is cooled to, is then distinguished with 40 DEG C of the concentrated hydrochloric acid that concentration is 30wt%
Washing three times, collects cleaning solution, and cleaning solution is put in the acicular crystal for obtaining yellow is stood overnight in low temperature refrigerator, filtered
After collect the crystal and dry obtain molybdenum dichloride hydrate presoma (H3O)2(Mo6Cl8)Cl6·6H2O；
（2）The preparation of Supported molybdenum oxide catalyst：It is 1 by the mass ratio of molybdenum dichloride hydrate presoma and methanol:90, will
Step（1）Gained molybdenum dichloride hydrate presoma (H3O)2(Mo6Cl8)Cl6·6H2O is dissolved in the pure methanol of analysis purchased in market, treats it
It is slowly dropped to after being completely dissolved in Mesoporous silica MCM 41, the mass ratio of molybdenum dichloride hydrate presoma and carrier is 1:
15,12h is stood at room temperature, after 40 DEG C of rotary evaporations remove methanol, is placed in tube furnace, 500 DEG C under helium atmosphere
6h is calcined, room temperature is cooled to, that is, obtains Supported molybdenum oxide catalyst MoOx/MCM-41.Change transition metal in maceration extract
The concentration of salt, or by repeatedly impregnating, the catalyst of different loads amount can be obtained.
（3）It is 1 by the mass ratio of lignin, Supported molybdenum oxide catalyst and reaction dissolvent:5:200, by corncob alkali
Lignin, Supported molybdenum oxide catalyst MoOx/ MCM-41（Catalyst loadings are 30wt%）After being mixed with methanol, add anti-
Answer closed in kettle, then be passed through hydrogen（Pressure is 1MPa）After be warming up to reaction temperature as 200 DEG C, and stirring reaction 4h, reaction knot
Kettle is driven in Temperature fall pressure release after beam, obtains solid product and product liquid after filtering, gained product liquid is after 110 DEG C of drying
Obtain single phenols aromatic compound.The oily yield and monomer yield of lignin are respectively 81wt % and 16.1wt %.
Embodiment 10
With embodiment 9, only by Supported molybdenum oxide catalyst MoOx/ MCM-41 replaces Supported molybdenum oxide catalyst MoOx/
AC, the oily yield and monomer yield of lignin are respectively 50wt % and 16.2wt %.
Embodiment 11
With embodiment 9, catalyst loadings are only replaced, other processes the results are shown in Table 4 with embodiment 9：
The different catalysts load capacity of table 4 catalysis corncob alkali lignin Hydrogenation compares
Embodiment 12
Using different catalyst with base of molybdenum：By 500mg Eucalyptus wood powder, 50mg catalyst（Catalyst loadings are 5wt%）With 15mL first
Alcohol is added in 50mL autoclave, replaces air 3 times in kettle with hydrogen, being then charged with preliminary examination pressure in hydrogen to kettle is
3MPa, 260 °C are warming up to, the stirring reaction 4h under 800rpm rotating speeds, reaction stops stirring and kettle is cooled into room temperature after terminating.
It the results are shown in Table 5：
Wooden Biomass catalytic material hydrogenation reaction compares on 5 different catalyst with base of molybdenum of table
Comparative example 1：The step of with embodiment 1（3）, only it is added without catalyst in course of reaction.Catabolite GC spectrograms such as Fig. 1 b
Shown, wooden vegetable oil yield is 21%, monomer yield 3%, unsaturated monomer selectivity of product are 23%.
Comparative example 2：With embodiment 1, only step（3）Hydrogen replace with nitrogen.Catabolite GC spectrograms as illustrated in figure 1 c,
Wooden vegetable oil yield is 38%, monomer yield 7%, unsaturated monomer selectivity of product are 17%.It is it can be seen that wooden under a nitrogen atmosphere
Quality oil and monomer yield all substantially reduce, and illustrate importance of the hydrogen atmosphere to the catalyst with base of molybdenum catalytic degradation lignin.
Comparative example 3：With embodiment 1, only step（3）Supported molybdenum oxide catalyst MoOx/ CNT replaces with catalysis purchased in market
Agent Ru/C（Catalyst loadings are 5wt%）.As shown in Figure 2 a, wooden vegetable oil yield is that 73%, monomer obtains to catabolite GC spectrograms
Rate is 39%, unsaturated monomer selectivity of product is 0%.It can be seen that although under Ru/C catalysts conditions, shrub red building enzyme acidolysis wood
The oily yield and monomer yield of quality approach with MoOx/CNT catalyst results, but its unsaturated selectivity of product is 0, explanation
Ru/C catalyst obtain be saturation hydrodepolymerization product.
Comparative example 4：With embodiment 1, only step（3）Supported molybdenum oxide catalyst MoOx/ CNT replaces with catalysis purchased in market
Agent Pd/C（Catalyst loadings are 5wt%）.As shown in Figure 2 b, wooden vegetable oil yield is that 76%, monomer obtains to catabolite GC spectrograms
Rate is 34%, unsaturated monomer selectivity of product is 0%.It can be seen that although under Pd/C catalysts conditions, shrub red building enzyme acidolysis wood
The oily yield and monomer yield of quality approach with MoOx/CNT catalyst results, but its unsaturated selectivity of product is 0, explanation
Pd/C catalyst obtain be saturation hydrodepolymerization product.
Comparative example 5：With embodiment 1, only step（3）Supported molybdenum oxide catalyst MoOx/ CNT replaces with catalysis purchased in market
Agent Raney Ni（Catalyst loadings are 5wt%）.As shown in Figure 2 c, wooden vegetable oil yield is 73% to catabolite GC spectrograms, list
Body yield is 31%, unsaturated monomer selectivity of product is 4%.It can be seen that although under Raney Ni catalysts conditions, shrub red building
The oily yield and monomer yield of enzyme acidolysis lignin approach with MoOx/CNT catalyst results, but its unsaturated selectivity of product
Only 4%, illustrate Raney Ni catalyst obtain be saturation hydrodepolymerization product.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of method that molybdenum oxide catalyst Catalytic lignin prepares single phenols aromatic compound, it is characterised in that under process
Arrange each step：
It is 1 by the mass ratio of lignin, Supported molybdenum oxide catalyst and reaction dissolvent:（0.01~10）:（5~200）, by wood
After quality, Supported molybdenum oxide catalyst and reaction dissolvent mixing, then reaction temperature is warming up to as 200~280 after being passed through hydrogen
DEG C, and 1~5h of stirring reaction, solid product and product liquid are obtained after filtering, and gained product liquid is after 110 DEG C of drying
Obtain single phenols aromatic compound.
2. according to the method for claim 1, it is characterised in that：It is wooden that the lignin includes enzyme acidolysis lignin, ground wood
Element, alkali lignin, organic solvent lignin, sulfate-reducing conditions, sulfonate lignin, lignocellulosic material.
3. according to the method for claim 1, it is characterised in that：The lignin is natural lignin, industrial lignin, life
One or more in Substance P hydrolysis residue, the tree growth law containing lignin.
4. according to the method for claim 3, it is characterised in that：The natural lignin is shrub red building lignin, birch
Lignin, poplar lignin, Eucalyptus lignin, beech lignin, pine lignin, Chinese silvergrass lignin, switchgrass lignin or
One or more in agricultural crop straw lignin.
5. according to the method for claim 2, it is characterised in that：The lignocellulosic material is shrub red building powder, birch
One or more in powder, Poplar Powder, Eucalyptus powder, beech powder, pine powder, Chinese silvergrass powder, switchgrass powder or agricultural residues powder.
6. according to the method for claim 1, it is characterised in that：The reaction dissolvent is methanol, ethanol, isopropanol, second two
Alcohol, water one or any ratio several mixing.
7. according to the method for claim 1, it is characterised in that：The pressure for being passed through hydrogen is 0~8Mpa, mixing speed
For 100~1000rpm.
8. according to the method for claim 1, it is characterised in that：The preparation method of the Supported molybdenum oxide catalyst, warp
Cross the following steps：
（1）The preparation of molybdenum dichloride hydrate presoma：By molybdenum pentachloride and molybdenum powder in mass ratio 1:After 2~5 mix, in inertia
With 600~700 DEG C of roasting 5h under gas atmosphere, room temperature is cooled to, is then 40~60 DEG C of 20~30wt% dense with concentration
Hydrochloric acid is washed three times respectively, collects cleaning solution, and cleaning solution stood overnight to obtain the acicular crystal of yellow, is collected after filtering
The crystal and dry obtain molybdenum dichloride hydrate presoma (H3O)2(Mo6Cl8)Cl6·6H2O；
（2）The preparation of Supported molybdenum oxide catalyst：Mass ratio by molybdenum dichloride hydrate presoma and methanol or ethanol is
1:90~110, by step（1）Gained molybdenum dichloride hydrate presoma (H3O)2(Mo6Cl8)Cl6·6H2O is dissolved in methanol or second
In alcohol, it is slowly dropped to after it is completely dissolved in carrier, the mass ratio of molybdenum dichloride hydrate presoma and carrier is 1:2~
15,12h is stood at room temperature, after 40 DEG C of rotary evaporations remove methanol or ethanol, under inert gas atmosphere 400~600
DEG C roasting 6h, be cooled to room temperature, that is, obtain Supported molybdenum oxide catalyst.
9. according to the method for claim 8, it is characterised in that：The step（2）Carrier for CNT, SBA-15,
One or more in MCM-41, graphene oxide.
10. according to the method for claim 8, it is characterised in that：The inert gas is nitrogen, argon gas or helium.
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