CN106748640B - The method that photocatalytic conversion lignin and its derivative aryl oxide prepare aromatic compound - Google Patents
The method that photocatalytic conversion lignin and its derivative aryl oxide prepare aromatic compound Download PDFInfo
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- CN106748640B CN106748640B CN201611249745.7A CN201611249745A CN106748640B CN 106748640 B CN106748640 B CN 106748640B CN 201611249745 A CN201611249745 A CN 201611249745A CN 106748640 B CN106748640 B CN 106748640B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The method that photocatalytic conversion lignin and its derivative aryl oxide prepare aromatic compound, is related to aromatic compound.Light-catalyzed reaction is carried out under conditions of visible light, and lignin and its derivative aryl oxide are converted to aromatic compound.It is after the oxygen in removing system, to open light source in lignin or its solution for deriving aryl oxide and carry out light-catalyzed reaction to get product aromatic compound is arrived that sulfide semiconductor catalyst, which is added to raw material,.Realize that lignin and its derivative aryl oxide prepare aromatic compound under visible light.This method carries out light-catalyzed reaction using visible light, has the characteristics that environmentally protective, reaction condition is mild.Technical process is simple, does not need using sacrifice agent, and reaction carries out under an inert atmosphere, and catalyst activity is high, stability is high, and product aromatic compound is not easy to be excessively oxidated, selectivity is high, low in raw material price and advantages of environment protection.
Description
Technical field
The present invention relates to aromatic compounds, prepare aromatization more particularly, to photocatalytic conversion lignin and its derivative aryl oxide
The method for closing object.
Background technique
Rich reserves, the method for developing conversion of biomass preparation high level chemicals are sustainable to establishing on earth for biomass
The society of development is of great significance.Lignin is the important component of biomass, is most important aroma type in nature
Compound source can be applied to production high added value aromatics chemicals.For example, under proper condition, lignin after depolymerization,
The products such as available vanillic aldehyde, Acetovanillone, isoeugenol, homovanillic acid.Lignin structure is complicated, and depolymerization is more difficult,
It lacks effective trans-utilization approach, and the whole world generates sharp only less than 2% in 1.5~1.8 hundred million tons of industrial lignins every year
With.Therefore the Efficient Conversion utilization ways of exploitation lignin are very necessary.
Photocatalytic method can directly utilize natural light, and reaction condition is mild.There is minority to degrade using light-catalyzed reaction wooden
Element generates the report of a small amount of fragrant monomer product.The report such as Mohamed Ksibi, is dropped under ultraviolet light using nano-titanium dioxide
The lignin extracted in solution black liquor, detection obtains vanillic aldehyde, vanillic acid etc., but the yield of aromatic product from catabolite
It is low, product only with GC-MS do qualitative analysis (Journal of Photochemistry and Photobiology A:
Chemistry 2003,154,211-218).Most researchs all concentrate on carrying out under conditions of ultraviolet light is aerobic at present, photocatalysis
Agent generates the oxygen species of high activity under illumination condition, thus lignin degrading, but be difficult to that product is made to rest on aromatic compound,
Easy excessive oxidation.Although having document report in Pd/ZnIn2S4And TiO2Under the co-catalysis of two kinds of photochemical catalysts, by ultraviolet
The mode of light and visible light switching, may be implemented the scission of link of the derivative aryl oxide of lignin, but cannot achieve the conversion of true lignin
(ACS Catalysis 2016,6,7716-7721).And the research is still necessary to using ultraviolet light and sacrifice agent, and is being had
Photoetch easily occurs for catalyst under the conditions of oxygen.And under visible light, lignin and its derivative virtue are realized using heterogeneous photocatalyst
The research that the highly selective conversion of ether prepares aromatic compound is not reported.
Summary of the invention
The purpose of the present invention is to provide the light with the features such as environmentally protective, reaction condition is mild, and selectivity of product is high
The method that catalyzed conversion lignin and its derivative aryl oxide prepare aromatic compound.
The present invention carries out light-catalyzed reaction using sulfide semiconductor catalyst under conditions of visible light, by lignin and
It derives aryl oxide and is converted to aromatic compound.
The route that the photocatalytic conversion lignin and its derivative aryl oxide prepare aromatic compound is as follows:
The photocatalytic conversion lignin and its derivative aryl oxide prepare the method for aromatic compound, and specific step is as follows:
It is in lignin or its solution for deriving aryl oxide, in the system of removing that sulfide semiconductor catalyst, which is added to raw material,
In oxygen after, open light source carry out light-catalyzed reaction to get arrive product aromatic compound.
Unitary metal sulfide or binary metal sulfide, the unitary gold can be used in the sulfide semiconductor catalyst
Belonging to sulfide can be selected from CdS, CuS, Cu2S、SnS、In2S3、Bi2S3、Ce2S3、Gd2S3、NiS、MoS2, in FeS etc. at least one
Kind, the binary metal sulfide can be selected from ZnxCdyS、CuxInyAt least one of S etc., wherein 0 < x < 1,0 < y < 1；It is described
Light-catalyzed reaction can carry out under conditions of visible light.
The black liquor of Identification of Soluble Organic lignin, alkaline earth lignin or papermaking that the lignin is extracted from biomass；It is described
The derivative aryl oxide of lignin can be selected from least one of diphenyl ether, benzyl phenyl ether, phenyl Phenyl ethers compound etc..
When the raw material is lignin, the product aromatic compound is mainly monocyclic aromatic compounds, contains portion simultaneously
It is divided to the dimer of two phenyl ring and the tripolymer of three phenyl ring；When the raw material is that lignin derives aryl oxide, the product fragrance
Compound is monocyclic aromatic compounds.
The mass ratio of the sulfide semiconductor catalyst and raw material can be 0.002~2, the time of the light-catalyzed reaction
It can be 1~200h.
The light-catalyzed reaction can carry out under conditions of ultraviolet light.
The light source can be used sunlight or simulated solar irradiation, the simulated solar irradiation can be used xenon lamp, mercury lamp, LED light,
One of tungsten halogen lamp etc., the power of the light source can be 10~1500W.
Oxygen in the removing system can be used the method for vacuumizing or being passed through inert gas under stiring and remove system
In oxygen.
The pattern of the sulfide semiconductor catalyst can for nano particle, nanosphere, nanometer rods, nano flower, nano-plates,
One of nanometer sheet, quantum dot etc..
The sulfide semiconductor catalyst can carried metal, metal oxide, metal sulfide, metal nitride, gold
Belong at least one of carbide etc., the load by mass percentage can for sulfide semiconductor catalyst 0.1%~
10%；The metal can be selected from least one of Pt, Pd, Au, Ag, Cu, Rh, Ru, Ir, Ni etc.；The metal oxide can
Selected from FeOx、CoOx、NiOx、CuOx、ZnOx、CrOx、MoOx、WOx、VOx、MnOx、RuOxAt least one of Deng, wherein 0 < x≤
3；The metal sulfide can be selected from NiSy、CoSy、FeSy、MoSy、WSy、CuSy、PdSyAt least one of Deng, wherein 0 < y≤
3；The metal carbides can be selected from least one of CoC, FeC, WC, MoC etc.；The metal nitride can be selected from C3N4、
Ta3N5、TaON、Ti3N4, at least one of GaN etc..
Compared with prior art, the present invention has following technical effect that
1) present invention realizes lignin and its derivative aryl oxide system using the sulfide semiconductor catalyst under visible light
Standby aromatic compound.This method carries out light-catalyzed reaction using visible light, has the characteristics that environmentally protective, reaction condition is mild.
2) ultraviolet light only accounts for about 4% in sunlight, and visible light accounts for about 50%, therefore, heretofore described sulfide half
Conductor catalyst realizes that lignin and its derivative aryl oxide prepare aromatic compound and can significantly improve catalyst pair under visible light
The utilization rate of sunlight has good development prospect.
3) present invention has technical process simple compared with existing synthesis technology, does not need to react using sacrifice agent lazy
Property atmosphere under carry out, catalyst activity is high, stability is high, and product aromatic compound is not easy to be excessively oxidated, selectivity is high, raw material
Cheap and advantages of environment protection.
4) present invention has the characteristics that adaptability to raw materials is wide, and raw material is cheap and easy to get, and raw material can be having for biomass extraction
The solvable lignin of machine, alkaline earth lignin or black liquor of papermaking etc. are also possible to the derivative aryl oxide of lignin comprising diphenyl ether,
Benzyl phenyl ether or phenyl Phenyl ethers compound.
5) light-catalyzed reaction of the present invention is heterogeneous catalytic reaction, and catalyst can recycle again, in addition, reaction item
Part is mild, and the waste of generation is few, energy conservation and environmental protection.
Detailed description of the invention
Fig. 1 is the UV-visible absorption spectrum of CdS nano particle in the embodiment of the present invention 1；
Fig. 2 is the high-efficient liquid phase chromatogram of the reaction product of 2- phenoxy group -1- benzyl carbinol in the embodiment of the present invention 1；
Fig. 3 is the gas chromatography-mass spectrometry chromatogram figure of Identification of Soluble Organic lignin conversion product in the embodiment of the present invention 10.
Specific embodiment
In order to be clearer and more clear technical problems, technical solutions and advantages to be solved, tie below
Embodiment is closed, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention is not intended to limit the present invention.
It is to remove in lignin or its derivative aryl oxide solution that sulfide semiconductor catalyst is added to raw material by the present invention
After oxygen in system, opens light source and carry out light-catalyzed reaction to get product aromatic compound is arrived；The sulfide semiconductor is urged
Agent is unitary metal sulfide or binary metal sulfide, and the unitary metal sulfide is selected from CdS, CuS, Cu2S、SnS、
In2S3、Bi2S3、Ce2S3、Gd2S3、NiS、MoS2One or more of with FeS, the binary metal sulfide is selected from
ZnxCdyS and CuxInyOne or more of S, wherein 0 < x < 1,0 < y < 1；The light-catalyzed reaction is in visible light
Under the conditions of carry out；Wherein:
The black liquor of Identification of Soluble Organic lignin, alkaline earth lignin or papermaking that the lignin is extracted from biomass；It is described
The derivative aryl oxide of lignin is selected from one or more of diphenyl ether, benzyl phenyl ether, phenyl Phenyl ethers compound；
When the raw material is lignin, the product aromatic compound is mainly monocyclic aromatic compounds, contains portion simultaneously
It is divided to the dimer of two phenyl ring and the tripolymer of three phenyl ring；When the raw material is that lignin derives aryl oxide, the product fragrance
Compound is monocyclic aromatic compounds；
The sulfide semiconductor catalyst and lignin or its mass ratio for deriving aryl oxide are 0.002~2；The light is urged
The time for changing reaction is 1~200h；
The light-catalyzed reaction can also carry out under conditions of ultraviolet light；The light source be sunlight or simulated solar irradiation,
Simulated solar irradiation can come from xenon lamp, mercury lamp, LED light or tungsten halogen lamp, and power is 10~1500W；
Oxygen in the removing system is utilized in the method for vacuumizing or being passed through inert gas under stirring and removes system
Middle oxygen；
Specifically, the pattern of the sulfide semiconductor catalyst is nano particle, nanosphere, nanometer rods, nano flower, receives
Rice plate, nanometer sheet or quantum dot；
Specifically, the sulfide semiconductor catalyst can load by mass percentage 0.1-10% it is one or two kinds of with
On metal, metal oxide, metal sulfide, metal nitride or metal carbides；Wherein:
In the modification sulfide semiconductor, modify component in metal can be Pt, Pd, Au, Ag, Cu, Rh, Ru, Ir,
One of Ni or a variety of；Metal oxide in modification component can be FeOx、CoOx、NiOx、CuOx、ZnOx、CrOx、
MoOx、WOx、VOx、MnOx、RuOxOne of or it is a variety of, wherein 0 < x≤3；Metal sulfide in modification component can be
NiSy、CoSy、FeSy、MoSy、WSy、CuSyAnd PdSyOne of or it is a variety of, wherein 0 < y≤3；Modify metallic carbide in component
Object can be one of CoC, FeC, WC and MoC or a variety of；The metal nitride modified in component can be with C3N4、Ta3N5、
TaON、Ti3N4, one of GaN or a variety of.
Specific embodiment is as follows: weighing a certain proportion of sulfide semiconductor catalyst, being added to raw material is lignin
Or in its organic solution for deriving aryl oxide, vacuumize or be passed through under stiring inert gas, after the oxygen in removing system, open
The light source for having installed optical filter additional carries out light-catalyzed reaction certain time under visible light conditions.After reaction by centrifugation or
The method staticly settled separates catalyst with solution, then carries out through high performance liquid chromatography and gas chromatography-mass spectrometry chromatogram instrument to product
Analysis.
Embodiment 1
By the Cd (NO of 5mmol3)·4H2The Na of O and 5mmol2S·9H2O is added separately in 80mL water, is sufficiently stirred
30min is to get CdS nano particle.After centrifuge washing 3 times, the dry 12h in 50 DEG C of vacuum ovens.Take CdS made from 10mg
Nano particle and 20mg phenyl phenetole compound (2- phenoxy group -1- benzyl carbinol), being added to 5mL acetonitrile percentage by volume is
Implement reaction (1) in the solution of 50% acetonitrile-water.Vacuumize or be passed through under stiring inert gas, the oxygen in removing system
After gas, the xenon lamp of 300W is opened, carries out light-catalyzed reaction for 24 hours under visible light conditions.After reaction solution filtering, liquid-phase chromatographic analysis
The conversion ratio for showing 2- phenoxy group -1- benzyl carbinol is 88%, and the yield of acetophenone is 81%, and the yield of phenol is 82%.
Fig. 1 provides the UV-visible absorption spectrum of CdS nano particle in the embodiment of the present invention 1.Fig. 2 provides the present invention
The high-efficient liquid phase chromatogram of the reaction product of 2- phenoxy group -1- benzyl carbinol in embodiment 1.
Embodiment 2
By the Cd (NO of 5mmol3)·4H2The Na of O and 5mmol2S·9H2O is added separately in 80mL water, is sufficiently stirred
30min is to get CdS nano particle.After centrifuge washing 3 times, the dry 12h in 50 DEG C of vacuum ovens.It takes made from 0.5g
CdS, is distributed in the methanol-water solution that 100mL methanol volume fraction is 20%, and 5 μ L palladium chlorides are added according to load capacity 0.1%
Solution (0.1g/ml), stirs and vacuumizes.With 300W xenon lamp photo-reduction 0.5h, carried noble metal Pd nano particle is obtained
CdS, i.e. 0.1%Pd/CdS.Centrifuge washing and dry grinding after it is spare.Take 0.1%Pd/CdS nanocatalyst made from 10mg
With 20mg phenyl phenetole compound [2- (4- methylphenoxy) -1- benzyl carbinol], it is added in the acetonitrile solution of 5mL 100%
Implement reaction (2).It vacuumizes or is passed through under stiring inert gas, after the oxygen in removing system, open the halogen tungsten of 1500W
Lamp carries out light-catalyzed reaction 6h under visible light conditions.After reaction solution filtering, liquid-phase chromatographic analysis shows 2- (4- methylenedioxy phenoxy
Base) conversion ratio of -1- benzyl carbinol is 95%, the yield of acetophenone is 89%, and the yield of p-methyl phenol is 91%.
Embodiment 3
By the Cd (CH of 5mmol3COO)2With the Zn (CH of 5mmol3COO)2It is added separately in 80mL water, magnetic agitation
30min adds 20mmol CH3CSNH2, continue to be transferred in the autoclave of 100mL after stirring 30min, with 5 DEG C/min
Rate heating, 180 DEG C at a temperature of keep for 24 hours, obtaining Zn0.5Cd0.5S Nano semiconductor.It takes made from 20mg
Zn0.5Cd0.5S nanocatalyst and 20mg phenyl phenetole compound [2- (2- methoxyphenoxy) -1- benzyl carbinol], are added to
Implement reaction (3) in the solution for the acetonitrile-water that 5mL acetonitrile percentage by volume is 50%.Vacuumize or be passed through under stiring inertia
Gas after the oxygen in removing system, opens the mercury lamp of 500W, light-catalyzed reaction 1h is carried out under visible light conditions.Reaction solution
After filtering, liquid-phase chromatographic analysis shows that the conversion ratio of 2- (2- methoxyphenoxy) -1- benzyl carbinol is 68%, the yield of acetophenone
It is 64%, the yield of o-methoxyphenol is 65%.
Embodiment 4
Cd (the NO of 5mmol is added in 80mL anhydrous ethylenediamine3)2·4H2(the NH of O and 10mmol3)2CS, magnetic agitation
Be transferred in the autoclave of 100mL after uniformly, heated up with the rate of 5 DEG C/min, 160 DEG C at a temperature of keep 48h, i.e.,
Obtain CdS nanometer rods.After centrifuge washing 3 times, 12h is placed in 60 DEG C of baking ovens.Up to CdS Nanorods Catalyst after drying grinding.
Take the catalysis of CdS nanometer rods made from 40mg and 40mg phenyl phenetole compound [2- (2- methoxyphenoxy) -1- (3,4- bis-
Methoxyphenyl) 1,3-PD], it is added in the methanol solution of 5mL 100% and implements reaction (4).It vacuumizes under stiring
Or it is passed through inert gas, after the oxygen in removing system, the xenon lamp of 300W is opened, light-catalyzed reaction is carried out under visible light conditions
24h.After reaction solution filtering, liquid-phase chromatographic analysis shows 2- (2- methoxyphenoxy) -1- (3,4- Dimethoxyphenyl) 1,3-
The conversion ratio of propylene glycol is 30%, and the yield of 3,4- dimethoxy propiophenone alkene is 26%, and the yield of o-methoxyphenol is
27%.
Embodiment 5
Cd (the NO of 10mmol is sequentially added in 80mL anhydrous ethylenediamine3)2·4H2(the NH of O, 20mmol3)2CS and
The Na of 1mmol2MoO6·2H2O is transferred in the autoclave of 100mL after magnetic agitation is uniform, with the rate liter of 5 DEG C/min
Temperature, 200 DEG C at a temperature of keep for 24 hours, obtain load MoS2CdS, both 10%MoS2/CdS.After centrifuge washing 3 times, 60
12h is placed in DEG C baking oven, it is spare after drying grinding.Take 20mg 10%MoS2/ CdS and 20mg benzyl phenyl ether, is added to 5mL
Implement reaction (5) in 100% methanol solution.Vacuumize or be passed through under stiring inert gas, after the oxygen in removing system,
The white LED lamp for opening 10W carries out light-catalyzed reaction 36h under visible light conditions.After reaction solution filtering, liquid-phase chromatographic analysis
The conversion ratio for showing benzyl phenyl ether is 58%, and the yield of methyl benzoate is 36%, and the yield of phenol is 41%.
Embodiment 6
By the Bi (NO of 5mmol3)3·5H2(the NH of O and 10mmol3)280mL H is added in CS2In O, after magnetic agitation is uniform
Be transferred in the autoclave of 100mL, heated up with the rate of 5 DEG C/min, 170 DEG C at a temperature of keep 36h, obtain Bi2S3
Nano semiconductor.After centrifuge washing 3 times, 12h is placed in 60 DEG C of baking ovens, up to Bi after drying grinding2S3Solid powder.It takes
Bi made from 20mg2S3Nanocatalyst and 10mg phenyl phenetole compound (2- phenoxy group -1- benzyl carbinol), are added to 5mL second
Implement reaction (1) in the solution for the acetonitrile-water that nitrile percentage by volume is 50%.Inert gas is vacuumized or is passed through under stiring,
After oxygen in removing system, the xenon lamp of 300W is opened, light-catalyzed reaction 36h is carried out under visible light conditions.Reaction solution filtering
Afterwards, liquid-phase chromatographic analysis shows that the conversion ratio of 2- phenoxy group -1- benzyl carbinol is 66%, and the yield of acetophenone is 59%, phenol
Yield is 56%.
Embodiment 7
By the Cu (NO of 5mmol3)2·5H2(the NH of O and 20mmol3)280mL H is added in CS2In O, after magnetic agitation is uniform
Be transferred in the autoclave of 100mL, heated up with the rate of 5 DEG C/min, 180 DEG C at a temperature of keep for 24 hours, obtaining CuS
Nano particle.After centrifuge washing 3 times, 12h is placed in 60 DEG C of baking ovens, up to CuS solid powder after drying grinding.Take 20mg system
The CuS nanocatalyst and 10mg phenyl phenetole compound (2- phenoxy group -1- benzyl carbinol) obtained, is added to 5mL's 100%
Implement reaction (1) in acetonitrile solution.It vacuumizes or is passed through under stiring inert gas, after the oxygen in removing system, open
The xenon lamp of 500W carries out light-catalyzed reaction 48h under visible light conditions.After reaction solution filtering, liquid-phase chromatographic analysis shows 2- benzene
Oxy-1-benzyl carbinol conversion ratio is 73%, and the yield of acetophenone is 67%, and the yield of phenol is 63%.
Embodiment 8
CdO (0.0256g, 0.2mmol), oleic acid (0.3205g, 1.6mmol) and ODE (4g) are weighed, the three of 25mL are put into
In neck bottle, stirs logical nitrogen and be warming up to 240 DEG C after ten minutes, inject the sulphur solution of 2mL 0.05mol/L, reaction temperature maintains
220 DEG C of hours.Cool down after reaction and 3- mercaptopropionic acid is added and carry out ligand exchange, appropriate amount of acid precipitating is added, centrifugation is washed
It washs, it is dry to get CdS quantum dot catalyst.Take CdS quantum dot made from 10mg and 10mg phenyl phenetole compound (2- benzene
Oxy-1-benzyl carbinol), it is added in the solution for the acetonitrile-water that 5mL acetonitrile percentage by volume is 50% and implements reaction (1).It is stirring
It mixes down and vacuumizes or be passed through inert gas, after the oxygen in removing system, open the xenon lamp of 300W, carried out under visible light conditions
Light-catalyzed reaction 1h.After reaction solution filtering, liquid-phase chromatographic analysis shows that the conversion ratio of 2- phenoxy group -1- benzyl carbinol is 78%, benzene
The yield of ethyl ketone is 74%, and the yield of phenol is 72%.
Embodiment 9
CdO (0.0256g, 0.2mmol), oleic acid (0.3205g, 1.6mmol) and ODE (4g) are weighed, the three of 25mL are put into
In neck bottle, stirs logical nitrogen and be warming up to 240 DEG C after ten minutes, inject the sulphur solution of 2mL 0.05mol/L, reaction temperature maintains
220 DEG C of hours.Cool down after reaction and 3- mercaptopropionic acid is added and carry out ligand exchange, appropriate amount of acid precipitating is added, centrifugation is washed
It washs, it is dry to get CdS quantum dot catalyst.Take CdS quantum dot made from 1mg and 500mg phenyl phenetole compound (2- benzene
Oxy-1-benzyl carbinol), it is added in the solution for the acetonitrile-water that 5mL acetonitrile percentage by volume is 50% and implements reaction (1).It is stirring
It mixes down and vacuumizes or be passed through inert gas, after the oxygen in removing system, open the xenon lamp of 500W, carried out under visible light conditions
Light-catalyzed reaction 200h.After reaction solution filtering, liquid-phase chromatographic analysis shows that the conversion ratio of 2- phenoxy group -1- benzyl carbinol is 85%,
The yield of acetophenone is 79%, and the yield of phenol is 80%.
Embodiment 10
CdO (0.0256g, 0.2mmol), oleic acid (0.3205g, 1.6mmol) and ODE (4g) are weighed, the three of 25mL are put into
In neck bottle, stirs logical nitrogen and be warming up to 240 DEG C after ten minutes, inject the sulphur solution of 2mL 0.05mol/L, reaction temperature maintains
220 DEG C of hours.Cool down after reaction and 3- mercaptopropionic acid is added and carry out ligand exchange, appropriate amount of acid precipitating is added, centrifugation is washed
It washs, it is dry to get CdS quantum dot catalyst.CdS quantum dot catalyst made from 10mg and 20mg Identification of Soluble Organic lignin are taken,
It is added in the methanol solution of 5mL 100% and implements reaction (6).Inert gas is vacuumized or be passed through under stiring, system is removed
In oxygen after, open the xenon lamp of 300W, under visible light conditions carry out light-catalyzed reaction 12h.After reaction solution filtering, through extracting
Weighing, the total recovery for obtaining aromatic compound monomer, dimer and tripolymer is 43%, is analyzed through gas chromatography-mass spectrometry chromatogram instrument, virtue
Aroma compounds monomer total recovery is 19%, and wherein aromatic compound monomer is mainly sinapinic alcohol, coniferyl alcohol etc., institute specific as follows
Show.
Fig. 3 provides the gas chromatography-mass spectrometry chromatogram figure of Identification of Soluble Organic lignin conversion product in the embodiment of the present invention 10.
Embodiment 11
CdO (0.0256g, 0.2mmol), oleic acid (0.3205g, 1.6mmol) and ODE (4g) are weighed, the three of 25mL are put into
In neck bottle, stirs logical nitrogen and be warming up to 240 DEG C after ten minutes, inject the sulphur solution of 2mL 0.05mol/L, reaction temperature maintains
220 DEG C of hours.Cool down after reaction and 3- mercaptopropionic acid is added and carry out ligand exchange, appropriate amount of acid precipitating is added, centrifugation is washed
It washs, it is dry to get CdS quantum dot catalyst.CdS quantum dot catalyst made from 10mg and 10mg Identification of Soluble Organic lignin are taken,
It is added in the acetonitrile solution of 5mL 100% and implements reaction (6).Inert gas is vacuumized or be passed through under stiring, system is removed
In oxygen after, open the xenon lamp of 300W, under visible light conditions carry out light-catalyzed reaction for 24 hours.After reaction solution filtering, through extracting
Weighing, the total recovery for obtaining aromatic compound monomer, dimer and tripolymer is 62%, is analyzed through gas chromatography-mass spectrometry chromatogram instrument, virtue
Aroma compounds monomer total recovery is 32%, and wherein aromatic compound monomer is mainly sinapinic alcohol, coniferyl alcohol etc., institute specific as follows
Show.
Embodiment 12
CdO (0.0256g, 0.2mmol), oleic acid (0.3205g, 1.6mmol) and ODE (4g) are weighed, the three of 25mL are put into
In neck bottle, 240 DEG C are warming up to after stirring logical nitrogen 10min, the sulphur solution of 2mL 0.05mol/L is injected, at 220 DEG C of reaction temperature
Lower maintenance 1h.Cool down after reaction and 3- mercaptopropionic acid is added and carry out ligand exchange, appropriate amount of acid precipitating is added, is centrifuged, washs, does
It is dry to get CdS quantum dot catalyst.CdS quantum dot catalyst made from 20mg and 10mg alkaline earth lignin are taken, 5mL is added to
Implement reaction (6) in 100% methanol solution.Vacuumize or be passed through under stiring inert gas, after the oxygen in removing system,
The xenon lamp for opening 300W carries out light-catalyzed reaction 16h under visible light conditions.It after reaction solution filtering, weighs through extraction, obtains virtue
The total recovery of aroma compounds monomer, dimer and tripolymer is 37%, is analyzed through gas chromatography-mass spectrometry chromatogram instrument, aromatic compound list
Body total recovery is 18%, and wherein aromatic compound monomer is mainly sinapinic alcohol, coniferyl alcohol etc., it is specific as follows shown in.
Comparative example 1
Take the TiO of 10mg commodity2(P25) nano particle and 20mg phenyl phenetole compound (2- phenoxy group -1- benzene second
Alcohol), it is added in the solution for the acetonitrile-water that 5mL acetonitrile percentage by volume is 50% and implements reaction (1).It vacuumizes under stiring
Or it is passed through inert gas, after the oxygen in removing system, the xenon lamp of 300W is opened, light-catalyzed reaction is carried out under ultraviolet light conditions
24h.After reaction solution filtering, liquid-phase chromatographic analysis shows that the conversion ratio of 2- phenoxy group -1- benzyl carbinol is 8%, the yield of benzaldehyde
It is 6%, the yield of acetophenone is 1%, and the yield of phenol is 2%.
Comparative example 2
Take the TiO of 10mg commodity2(P25) nano particle and 20mg phenyl phenetole compound (2- phenoxy group -1- benzene second
Alcohol), it is added in the solution for the acetonitrile-water that 5mL acetonitrile percentage by volume is 50% and implements reaction (1).Oxygen is filled in system
After gas, the xenon lamp of 300W is opened, carries out light-catalyzed reaction for 24 hours under ultraviolet light conditions.After reaction solution filtering, liquid-phase chromatographic analysis
The conversion ratio for showing 2- phenoxy group -1- benzyl carbinol is 25%, and the yield of benzaldehyde is 1%, and the yield of acetophenone is 0%, phenol
Yield be 2%.
Comparative example 3
Take the TiO of 10mg commodity2(P25) nano particle and 20mg phenyl phenetole compound (2- phenoxy group -1- benzene second
Alcohol), it is added in the solution for the acetonitrile-water that 5mL acetonitrile percentage by volume is 50% and implements reaction (1).It vacuumizes under stiring
Or it is passed through inert gas, after the oxygen in removing system, the xenon lamp of 300W is opened, light-catalyzed reaction is carried out under visible light conditions
24h.After reaction solution filtering, liquid-phase chromatographic analysis shows that the conversion ratio of 2- phenoxy group -1- benzyl carbinol is 0%, the yield of benzaldehyde
It is 0%, the yield of acetophenone is 0%, and the yield of phenol is 0%.
Comparative example 4
Take the TiO of 10mg commodity2(P25) nano particle and 20mg Identification of Soluble Organic lignin, are added to the first of 5mL 100%
Implement reaction (6) in alcoholic solution.It vacuumizes or is passed through under stiring inert gas, after the oxygen in removing system, open 300W
Xenon lamp, under ultraviolet light conditions carry out light-catalyzed reaction 12h.It after reaction solution filtering, weighs through extraction, obtains aromatic compound
The total recovery of monomer, dimer and tripolymer is analyzed less than 1% through gas chromatography-mass spectrometry chromatogram instrument, and the predominantly a small amount of degradation of product is opened
The organic acid of ring.
Comparative example 5
Take the TiO of 10mg commodity2(P25) nano particle and 20mg Identification of Soluble Organic lignin, are added to the first of 5mL 100%
Implement reaction (6) in alcoholic solution.It vacuumizes or is passed through under stiring inert gas, after the oxygen in removing system, open 300W
Xenon lamp, under visible light conditions carry out light-catalyzed reaction 12h.After reaction solution filtering, analyzed through gas chromatography-mass spectrometry chromatogram instrument, instead
Object is answered not convert.
Compared by the experimental data of above embodiments and comparative example, it is known that, using method of the invention, lignin and its
The selectivity of aromatic compound and yield increase significantly in the conversion ratio and product of derivative aryl oxide.And TiO2In ultraviolet light
Under conditions of inert atmosphere, activity is lower, and the selectivity of aromatic compound is also relatively low；In ultraviolet light and there is oxygen atmosphere
Under conditions of, activity increases, but still lower, and especially the selectivity of aromatic compound is extremely low in product.In addition,
TiO2The no any effect of reaction of aromatic compound is prepared to lignin and its derivative aryl oxide under visible light.
The present invention realizes lignin and its derivative aryl oxide preparation fragrance using sulfide semiconductor catalyst under visible light
Compound, it is seen that the wavelength of light is 400~700nm, and ultraviolet wavelength is less than 400nm, therefore compared to the condition of ultraviolet light,
The light-catalyzed reaction of visible light has more environmentally protective, the milder feature of reaction condition.The present invention is lazy using anaerobic
Property atmosphere reacted, the selectivity of product aromatic compound can be effectively improved, and have using improve catalyst stability.This
Invention has technical process simple compared with existing synthesis technology, and reactivity is high, and selectivity of product is high, low in raw material price with
And advantages of environment protection.Sulfide semiconductor catalyst of the present invention, when the gold of load 0.1%~0% on a catalyst
After category, metal oxide, metal sulfide, metal nitride or metal carbides, photocatalytic conversion lignin and its derivative
The performance of aryl oxide aromatic compound can be improved.Light-catalyzed reaction of the present invention is heterogeneous catalytic reaction, catalyst
It can recycle again, in addition, the catalyst reaction mild condition, the waste of generation is few, energy conservation and environmental protection.
Certainly, light-catalyzed reaction of the present invention is under conditions of visible light in addition to carrying out, can also be in sunlight or ultraviolet
It is carried out under conditions of light.
Claims (7)
1. the route that photocatalytic conversion lignin and its derivative aryl oxide prepare aromatic compound, it is characterised in that under inert atmosphere,
The route is as follows:
The sulfide semiconductor catalyst uses unitary metal sulfide or binary metal sulfide；The unitary metal vulcanization
Object is selected from CdS, CuS, Cu2S、SnS、In2S3、Bi2S3、Ce2S3、Gd2S3、NiS、MoS2, at least one of FeS；The binary
Metal sulfide is selected from ZnxCdyS、CuxInyAt least one of S, wherein 0 < x < 1,0 < y < 1；The light-catalyzed reaction can be can
It is carried out under conditions of light-exposed.
2. the method that photocatalytic conversion lignin and its derivative aryl oxide prepare aromatic compound, it is characterised in that its specific steps is such as
Under:
It is in lignin or its solution for deriving aryl oxide, in removing system that sulfide semiconductor catalyst, which is added to raw material,
After oxygen, opens light source and carry out light-catalyzed reaction to get product aromatic compound is arrived；The sulfide semiconductor catalyst uses
Unitary metal sulfide or binary metal sulfide；The unitary metal sulfide is selected from CdS, CuS, Cu2S、SnS、In2S3、
Bi2S3、Ce2S3、Gd2S3、NiS、MoS2, at least one of FeS；The binary metal sulfide is selected from ZnxCdyS、CuxInyS
At least one of, wherein 0 < x < 1,0 < y < 1；The light-catalyzed reaction can carry out under conditions of visible light.
3. the method that photocatalytic conversion lignin as claimed in claim 2 and its derivative aryl oxide prepare aromatic compound, feature
It is the black liquor for Identification of Soluble Organic lignin, alkaline earth lignin or the papermaking that the lignin is extracted from biomass；It is described wooden
The derivative aryl oxide of element is selected from least one of diphenyl ether, benzyl phenyl ether, phenyl Phenyl ethers compound.
4. the method that photocatalytic conversion lignin as claimed in claim 2 and its derivative aryl oxide prepare aromatic compound, feature
The mass ratio for being the sulfide semiconductor catalyst and raw material is 0.002~2, and the time of the light-catalyzed reaction can be 1
~200h.
5. the method that photocatalytic conversion lignin as claimed in claim 2 and its derivative aryl oxide prepare aromatic compound, feature
It is the light source using sunlight or simulated solar irradiation, xenon lamp, mercury lamp, LED light, tungsten halogen lamp can be used in the simulated solar irradiation
One of, the power of the light source can be 10~1500W.
6. the method that photocatalytic conversion lignin as claimed in claim 2 and its derivative aryl oxide prepare aromatic compound, feature
It is that the oxygen in the removing system is utilized in the method removing system for vacuumizing or being passed through inert gas under stirring
Oxygen；
The pattern of the sulfide semiconductor catalyst can be nano particle, nanosphere, nanometer rods, nano flower, nano-plates, nanometer
One of piece, quantum dot.
7. the method that photocatalytic conversion lignin as claimed in claim 2 and its derivative aryl oxide prepare aromatic compound, feature
It is the sulfide semiconductor catalyst carried metal, metal oxide, metal sulfide, metal nitride, metallic carbide
At least one of object, the load can be the 0.1%~10% of sulfide semiconductor catalyst by mass percentage；The gold
Category can be selected from least one of Pt, Pd, Au, Ag, Cu, Rh, Ru, Ir, Ni；The metal oxide can be selected from FeOx、CoOx、
NiOx、CuOx、ZnOx、CrOx、MoOx、WOx、VOx、MnOx、RuOxAt least one of, wherein 0 < x≤3；The metal sulfide
It can be selected from NiSy、CoSy、FeSy、MoSy、WSy、CuSy、PdSyAt least one of, wherein 0 < y≤3；The metal carbides can
Selected from least one of CoC, FeC, WC, MoC；The metal nitride can be selected from C3N4、Ta3N5、TaON、Ti3N4, in GaN
At least one.
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