CN109942391A - A method of catalysis oxygen solution lignin preparation is containing vanillic aldehyde and syringaldehyde extract liquor - Google Patents
A method of catalysis oxygen solution lignin preparation is containing vanillic aldehyde and syringaldehyde extract liquor Download PDFInfo
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Abstract
The present invention relates to a kind of catalysis oxygen solution lignin to prepare the method containing vanillic aldehyde and syringaldehyde extract liquor, including step 1: by Spruce lignin in NaHCO3It is pre-processed in aqueous solution；Step 2: the pretreated Spruce lignin of step 1 and perovskite type catalyst are placed in a closed reactor, using ethanol/water mixed solution as solvent, are passed through O2It is reacted, reaction solution is cooled to room temperature discharging after reaction；Step 3: the discharging of step 2 being successively filtered, is rotated, is extracted using ethyl acetate, to obtain the extract liquor containing vanillic aldehyde and syringone.Reaction condition of the invention is mild, and no pollution to the environment, can be realized the higher value application to biomass, is of great significance to preserving the ecological environment.
Description
Technical field
The present invention relates to technical field of lignin utilization more particularly to a kind of preparation of catalysis oxygen solution lignin containing vanillic aldehyde and
The method of syringaldehyde extract liquor.
Background technique
It is increasingly depleted with fossil energy, it finds novel renewable extremely urgent to substitute fossil energy, and gives birth to
Substance energy reserve greatly, cleaning and it is non-hazardous, have substitution fossil energy great potential.Biomass is broadly divided into fiber
Element, hemicellulose, lignin three categories, among these, although structure is complicated and unformed for lignin, but phenyl ring is in nature
Unique renewable source in boundary.In China, the meeting huge lignin of generation quantity in paper-making industry and wood hydrolysis industry, due to
The physicochemical characteristics of lignin complexity, 95% or so lignin can not be directly discharged into rivers by higher value application,
Caused by huge environmental pollution.The higher value application of lignin is to realization biomass higher value application, tool of preserving the ecological environment
It is of great importance.
The functional groups such as a large amount of phenyl ring, hydroxyl, methoxyl group, aldehyde radical, the ketone group that contain in the structure of lignin carry out it
Liquid phase oxidation degradation can provide the high values platform chemicals such as aromatic aldehyde, aromatic ketone, have wide Research Prospects.
For the oxidative degradation of lignin under catalytic condition because reaction condition is mild, energy consumption of reaction is low, and selectivity of product is high, is
A kind of depolymerization mode of very promising lignin.Chinese patent application CN108218673 A discloses one kind with M (mpo) n
Complex (M=Fe, co, n=3；M=Ni, n=2) it is catalyst, organosolv lignin, lignosulfonates, alkali lignin are original
Material, in 80 DEG C -200 DEG C, nitrogen atmosphere o.1MPa, aromatic series biology oil yield is 34-71%.Chinese patent application CN
102295547 A are disclosed in alkaline environment, with p-nitrophenyl acid, 3,5- dinitrobenzoic acid, 3-Nitrosalicylic Acid, 5-
Nitro-salicylic acid or 3,5- dinitrosalicylic acid are that catalyst carries out catalytic degradation to lignin, and obtaining purity is respectively 97.3%
With 98.2% Acetovanillone and acetosyringone.But there is also obvious deficiencies: first is that the reaction condition of strong acid and strong base is more
Harshness, easily cause equipment corrode and it is unfriendly to environment；Second is that the low yield of target product.
Summary of the invention
A kind of catalysis oxygen solution lignin preparation is provided it is an object of the invention to overcome the shortcomings of the prior art
Method containing vanillic aldehyde and syringaldehyde extract liquor, reaction condition of the invention is mild, and no pollution to the environment, can be realized to life
The higher value application of substance, is of great significance to preserving the ecological environment.
Method of a kind of catalysis oxygen solution lignin preparation containing vanillic aldehyde and syringaldehyde extract liquor proposed according to the present invention,
It is characterized in that, specific steps include the following:
Step 1: by Spruce lignin in NaHCO3It is pre-processed in aqueous solution；
Step 2: the pretreated Spruce lignin of step 1 and perovskite type catalyst are placed in a confined reaction
In kettle, using ethanol/water mixed solution as solvent, it is passed through O2It is reacted, reaction solution is cooled to room temperature discharging after reaction；
Step 3: the discharging of step 2 being successively filtered, is rotated, is extracted using ethyl acetate, to obtain
Extract liquor containing vanillic aldehyde and syringone.
A kind of method of the catalysis oxygen solution lignin preparation containing vanillic aldehyde and syringaldehyde extract liquor proposed by the present invention is further
Preferred embodiment be:
Pretreated method described in step 1 are as follows:
1.1 by Spruce lignin, is the NaHCO that 1:10 is added that mass fraction is 5% by solid-to-liquid ratio3In aqueous solution,
6h is stirred at room temperature, obtains the sample of Spruce lignin；
1.2 pairs above-mentioned 1.1 of sample filters, and filter residue deionized water is rinsed 3 times；
Gained sample in above-mentioned 1.2 is placed in baking oven and is dried by 1.3, and the drying temperature is 80 DEG C, drying time 12
Hour.
Perovskite type catalyst described in step 2 is CeCoO3、CeCuO3、CeNiO3、CeFeO3One of, titanium ore type
Catalyst the preparation method comprises the following steps:
2.1 take Ce (NO3) 36H2O and 0.01molCo (NO3) 26H2O, Cu (NO3) 33H2O, Ni of 0.01mol
(NO3) citric acid of 26H2O or Fe (NO3) 39H2O and 0.03mol are dissolved in 20ml deionized water, are added 2ml's
Ethylene glycol forms precursor liquid, uses magnetic agitation 8h, whipping temp for 60 DEG C the precursor liquid, until forming colloidal sol；
Gained gel in 2.1 is placed in baking oven and is dried by 2.2, and the drying temperature is 105 DEG C, drying time is 12 small
When, obtain the presoma of perovskite type catalyst；
The presoma of perovskite type catalyst described in 2.2 is placed in Muffle furnace and calcines by 2.3, and calcination atmosphere is sky
Gas, calcination temperature are 600 DEG C, calcination time is 6 hours to get the series for arriving perovskite type catalyst.
O described in step 22Pressure be 0.6MPa；The volume ratio of ethyl alcohol and water in the ethanol/water mixed solvent
For 1:1；It is described to be passed through O2The reaction temperature reacted is 120 DEG C~240 DEG C；It is described to be passed through O2The reaction time reacted
For 10min~120min.
The present invention compared with prior art the advantage is that:
First, the present invention carries out catalysis oxidation to it in ethanol/water mixed solvent using Spruce lignin as raw material
Depolymerization is to prepare the extract liquor of high value single phenolic compounds vanillic aldehyde and syringaldehyde, to the high level protected environment, realize biomass
Change using and is of great significance to preserving the ecological environment.
Second, in NaHCO3Spruce lignin is pre-processed in aqueous solution, fine and close three-dimensional netted of lignin
Structure is destroyed, so that lignin is more readily oxidized depolymerization, Product yields get a promotion.
Third, novel perovskite type catalyst CeBO prepared by the present invention3(B=Co/Cu/Fe/Ni) serial, for wood
Quality carries out liquid phase catalytic oxidation depolymerization, can realize the efficient depolymerization of lignin in a mild condition, belongs to height to be made
It is worth the vanillic aldehyde of fine chemicals and the extract liquor of syringaldehyde, and cheap, hydro-thermal performance is stable and environmentally friendly.
Detailed description of the invention
Fig. 1 is difference perovskite type catalyst CeBO described in embodiment 13To perfume (or spice) under the conditions of (wherein B=Co/Cu/Fe/Ni)
The schematic diagram of oxalaldehyde yield impact.
Fig. 2 is difference perovskite type catalyst CeBO described in embodiment 13To fourth under the conditions of (wherein B=Co/Cu/Fe/Ni)
The schematic diagram of fragrant aldehyde yield impact.
Fig. 3 is the schematic diagram under the condition of different temperatures of embodiment 2~6 to vanillic aldehyde yield impact.
Fig. 4 is the schematic diagram under the condition of different temperatures of embodiment 2~6 to syringaldehyde yield impact.
Fig. 5 is the schematic diagram under the differential responses time conditions of embodiment 7~11 to vanillic aldehyde yield impact.
Fig. 6 is the schematic diagram under the differential responses time conditions of embodiment 7~11 to syringaldehyde yield impact.
Specific embodiment
A specific embodiment of the invention is described in further detail with reference to the accompanying drawings and examples.
A kind of catalysis oxygen solution lignin proposed by the present invention prepares the method containing vanillic aldehyde and syringaldehyde extract liquor, specific to walk
Suddenly include the following:
Step 1: by Spruce lignin in NaHCO3It is pre-processed in aqueous solution；The pretreated method are as follows:
1.1 by Spruce lignin, is the NaHCO that 1:10 is added that mass fraction is 5% by solid-to-liquid ratio3In aqueous solution,
6h is stirred at room temperature, obtains the sample of Spruce lignin；
1.2 pairs above-mentioned 1.1 of sample filters, and filter residue deionized water is rinsed 3 times；
Gained sample in above-mentioned 1.2 is placed in baking oven and is dried by 1.3, and the drying temperature is 80 DEG C, drying time 12
Hour.
Step 2: the pretreated Spruce lignin of step 1 and perovskite type catalyst are placed in a confined reaction
In kettle, using ethanol/water mixed solution as solvent, it is passed through O2It is reacted, reaction solution is cooled to room temperature discharging after reaction；
Wherein:
The perovskite type catalyst is CeCoO3、CeCuO3、CeNiO3Or CeFeO3One of, the catalysis of titanium ore type
Agent the preparation method comprises the following steps:
2.1 take Ce (NO3) 36H2O and 0.01molCo (NO3) 26H2O, Cu (NO3) 33H2O, Ni of 0.01mol
(NO3) citric acid of 26H2O or Fe (NO3) 39H2O and 0.03mol are dissolved in 20ml deionized water, are added 2ml's
Ethylene glycol forms precursor liquid, uses magnetic agitation 8h, whipping temp for 60 DEG C the precursor liquid, until forming colloidal sol；
Gained gel in 2.1 is placed in baking oven and is dried by 2.2, and the drying temperature is 105 DEG C, drying time is 12 small
When, obtain the presoma of perovskite type catalyst；
The presoma of perovskite type catalyst described in 2.2 is placed in Muffle furnace and calcines by 2.3, and calcination atmosphere is sky
Gas, calcination temperature are 600 DEG C, calcination time is 6 hours to get the series for arriving perovskite type catalyst；
The O2Pressure be 0.6MPa；The volume ratio of ethyl alcohol and water in the ethanol/water mixed solvent is 1:1；
It is described to be passed through O2The reaction temperature reacted is 120 DEG C~210 DEG C；It is described to be passed through O2The reaction time reacted is 10min
~120min；
Step 3: the discharging of step 2 being successively filtered, is rotated, is extracted using ethyl acetate, to obtain
Extract liquor containing vanillic aldehyde and syringone.
Especially it should be noted that: using different reaction conditions it is different to the yield of target product.Such as to select calcium
Titanium ore type catalizer variety (CeCoO3、CeCuO3、CeNiO3Or CeFeO3) for, when use perovskite type catalyst for CeCoO3
When, when reaction temperature is 180 DEG C, the reaction time is 60min, the yield of the extract liquor containing vanillic aldehyde and syringone is higher than other
Catalyst.With CeCoO3For catalyst, reaction time 1h, reaction temperature is 120 DEG C~210 DEG C, to Spruce lignin
Liquefaction oxidative degradation is carried out, when reaction temperature is 210 DEG C, the yield highest of the extract liquor containing vanillic aldehyde and syringone.With
CeCoO3For catalyst, reaction temperature is 210 DEG C, and the reaction time for carrying out liquefaction oxidative degradation to Spruce lignin is
10min~120min, when reacted between be 30min when, the yield of the extract liquor containing vanillic aldehyde and syringone reaches peak value, point
It Wei 7.8%, 4.1%.
A kind of catalysis oxygen solution lignin preparation proposed by the present invention is disclosed further below to extract containing vanillic aldehyde and syringaldehyde
The specific embodiment of the method for liquid.For optimization test condition and comparative effectiveness, following embodiment takes the corn of 0.02g weight
Straw lignin carries out catalysis oxygen solution, but the present invention is described for being catalyzed the Spruce lignin of oxygen solution in practical applications
Weight is not limited.
Example 1: by the perovskite type catalyst CeCoO of the Spruce lignin of 0.2g and 0.02g3、CeCuO3、
CeFeO3、CeNiO3One of be placed in reaction kettle, the ethanol/water mixed solvent of 20ml, the ethyl alcohol of the in the mixed solvent is added
Volume ratio with water is 1:1；Into reaction kettle, then inflated with nitrogen is vented to 1MPa, completes purge in triplicate；Immediately
Oxygen is passed through into reaction kettle to 0.6MPa；Be arranged reaction temperature be 180 DEG C, reaction time 60min, after reaction,
Reaction kettle is placed in mixture of ice and water and is cooled to room temperature discharging, filters to obtain oxidation residua；Gained filtrate, which rotates to solvent, to be evaporated,
Ethyl acetate is added to be extracted, organic phase is merged and is settled to 10ml, carries out GC-MS detection；With CeCoO3When for catalyst,
Vanillic aldehyde in extract liquor, syringaldehyde yield reach highest, respectively 5.1%, 2%, as shown in Figure 1, 2.
Example 2: by the perovskite type catalyst CeCoO of the Spruce lignin of 0.2g and 0.02g3It is placed in reaction kettle
In, the ethyl alcohol of the in the mixed solvent and the volume ratio of water are 1:1；Into reaction kettle, then inflated with nitrogen is vented, repeats to 1MPa
Purge is completed three times；And then oxygen is passed through into reaction kettle to 0.6MPa；When setting reaction temperature is 120 DEG C, reacts
Between be 60min；Reaction kettle is placed in mixture of ice and water after reaction and is cooled to room temperature discharging, filters to obtain oxidation residua；Institute
Filtrate rotates to solvent and is evaporated, ethyl acetate is added and is extracted, merges organic phase and is settled to 10ml, carry out GC-MS inspection
It surveys；In extract liquor and vanillic aldehyde and syringaldehyde is not detected at this time, as shown in Figure 3,4.
Example 3: by the perovskite type catalyst CeCoO of the Spruce lignin of 0.2g and 0.02g3It is placed in reaction kettle
In, the ethanol/water mixed solvent of 20ml is added, the ethyl alcohol of the in the mixed solvent and the volume ratio of water are 1:1；Into reaction kettle
Then inflated with nitrogen is vented to 1MPa, completes purge in triplicate；And then oxygen is passed through into reaction kettle to 0.6MPa；
Be arranged reaction temperature be 150 DEG C, reaction time 60min, reaction kettle is placed in mixture of ice and water is cooled to after reaction
Room temperature discharging, filters to obtain oxidation residua；Gained filtrate, which rotates to solvent, to be evaporated, and ethyl acetate is added and is extracted, merges organic
Mutually and it is settled to 10ml, carries out GC-MS detection；At this time the vanillic aldehyde in extract liquor, syringaldehyde yield be respectively 0.8%,
0.4%, as shown in Figure 3,4.
Example 4: by the perovskite type catalyst CeCoO of the Spruce lignin of 0.2g and 0.02g3It is placed in reaction kettle
In, the ethanol/water mixed solvent of 20ml is added, the ethyl alcohol of the in the mixed solvent and the volume ratio of water are 1:1；Into reaction kettle
Then inflated with nitrogen is vented to 1MPa, completes purge in triplicate；And then oxygen is passed through into reaction kettle to 0.6MPa；
Be arranged reaction temperature be 180 DEG C, reaction time 60min, reaction kettle is placed in mixture of ice and water is cooled to after reaction
Room temperature discharging, filters to obtain oxidation residua；Gained filtrate, which rotates to solvent, to be evaporated, and ethyl acetate is added and is extracted, merges organic
Mutually and it is settled to 10ml, carries out GC-MS detection；At this time the vanillic aldehyde in extract liquor, syringaldehyde yield be respectively 4.8%,
2.0%, as shown in Figure 3,4.
Example 5: by the perovskite type catalyst CeCoO of the Spruce lignin of 0.2g and 0.02g3It is placed in reaction kettle
In, the ethanol/water mixed solvent of 20ml is added, the ethyl alcohol of the in the mixed solvent and the volume ratio of water are 1:1；Into reaction kettle
Then inflated with nitrogen is vented to 1MPa, completes purge in triplicate；And then oxygen is passed through into reaction kettle to 0.6MPa；
Be arranged reaction temperature be 210 DEG C, reaction time 60min；Reaction kettle is placed in mixture of ice and water after reaction and is cooled to
Room temperature discharging, filters to obtain oxidation residua；Gained filtrate, which rotates to solvent, to be evaporated, and ethyl acetate is added and is extracted, merges organic
Mutually and it is settled to 10ml, carries out GC-MS detection；At this time the vanillic aldehyde in extract liquor, syringaldehyde yield be respectively 5.0%,
3.6%, as shown in Figure 3,4.
Example 6: by the perovskite type catalyst CeCoO of the Spruce lignin of 0.2g and 0.02g3It is placed in reaction kettle
In, the ethanol/water mixed solvent of 20ml is added, the ethyl alcohol of the in the mixed solvent and the volume ratio of water are 1:1；Into reaction kettle
Then inflated with nitrogen is vented to 1MPa, completes purge in triplicate；And then oxygen is passed through into reaction kettle to 0.6MPa；
Be arranged reaction temperature be 240 DEG C, reaction time 60min, reaction kettle is placed in mixture of ice and water is cooled to after reaction
Room temperature discharging, filters to obtain oxidation residua；Gained filtrate, which rotates to solvent, to be evaporated, and ethyl acetate is added and is extracted, merges organic
Mutually and it is settled to 10ml, carries out GC-MS detection；At this time the vanillic aldehyde in extract liquor, syringaldehyde yield be respectively 4.2%,
3.2%, as shown in Figure 3,4.
Example 7: by the perovskite type catalyst CeCoO of the Spruce lignin of 0.2g and 0.02g3It is placed in reaction kettle
In, the ethanol/water mixed solvent of 20ml is added, the ethyl alcohol of the in the mixed solvent and the volume ratio of water are 1:1；Into reaction kettle
Then inflated with nitrogen is vented to 1MPa, completes purge in triplicate；And then oxygen is passed through into reaction kettle to 0.6MPa；
Be arranged reaction temperature be 210 DEG C, reaction time 10min, reaction kettle is placed in mixture of ice and water is cooled to after reaction
Room temperature discharging, filters to obtain oxidation residua；Gained filtrate, which rotates to solvent, to be evaporated, and ethyl acetate is added and is extracted, merges organic
Mutually and it is settled to 10ml, carries out GC-MS detection；At this time the vanillic aldehyde in extract liquor, syringaldehyde yield be respectively 5.1%,
3.1%, as shown in Figure 5,6.
Example 8: the perovskite type catalyst CeCoO3 of the Spruce lignin of 0.2g and 0.02g are placed in reaction kettle
In, the ethanol/water mixed solvent of 20ml is added, the ethyl alcohol of the in the mixed solvent and the volume ratio of water are 1:1；Into reaction kettle
Then inflated with nitrogen is vented to 1MPa, completes purge in triplicate；And then oxygen is passed through into reaction kettle to 0.6MPa；
Be arranged reaction temperature be 210 DEG C, reaction time 30min, reaction kettle is placed in mixture of ice and water is cooled to after reaction
Room temperature discharging, filters to obtain oxidation residua；Gained filtrate, which rotates to solvent, to be evaporated, and ethyl acetate is added and is extracted, merges organic
Mutually and it is settled to 10ml, carries out GC-MS detection；At this time the vanillic aldehyde in extract liquor, syringaldehyde yield reach highest, respectively
It is 7.8%, 4.1%, as shown in Figure 5,6.
Example 9: the perovskite type catalyst CeCoO3 of the Spruce lignin of 0.2g and 0.02g are placed in reaction kettle
In, the ethanol/water mixed solvent of 20ml is added, the ethyl alcohol of the in the mixed solvent and the volume ratio of water are 1:1；Into reaction kettle
Then inflated with nitrogen is vented to 1MPa, completes purge in triplicate.And then oxygen is passed through into reaction kettle to 0.6MPa；
Be arranged reaction temperature be 210 DEG C, reaction time 60min, reaction kettle is placed in mixture of ice and water is cooled to after reaction
Room temperature discharging, filters to obtain oxidation residua；Gained filtrate, which rotates to solvent, to be evaporated, and ethyl acetate is added and is extracted, merges organic
Mutually and it is settled to 10ml, carries out GC-MS detection；At this time the vanillic aldehyde in extract liquor, syringaldehyde yield be respectively 5.08%,
3.6%, as shown in Figure 5,6.
Example 10: the perovskite type catalyst CeCoO3 of the Spruce lignin of 0.2g and 0.02g are placed in reaction kettle
In, the ethanol/water mixed solvent of 20ml is added, the ethyl alcohol of the in the mixed solvent and the volume ratio of water are 1:1；Into reaction kettle
Then inflated with nitrogen is vented to 1MPa, completes purge in triplicate；And then oxygen is passed through into reaction kettle to 0.6MPa；
Be arranged reaction temperature be 210 DEG C, reaction time 90min, reaction kettle is placed in mixture of ice and water is cooled to after reaction
Room temperature discharging, filters to obtain oxidation residua；Gained filtrate, which rotates to solvent, to be evaporated, and ethyl acetate is added and is extracted, merges organic
Mutually and it is settled to 10ml, carries out GC-MS detection；At this time the vanillic aldehyde in extract liquor, syringaldehyde yield be respectively 5.1%,
3.4%, as shown in Figure 5,6.
Example 11: the perovskite type catalyst CeCoO3 of the Spruce lignin of 0.2g and 0.02g are placed in reaction kettle
In, the ethanol/water mixed solvent of 20ml is added, the ethyl alcohol of the in the mixed solvent and the volume ratio of water are 1:1；Into reaction kettle
Then inflated with nitrogen is vented to 1MPa, completes purge in triplicate；And then oxygen is passed through into reaction kettle to 0.6MPa；
Be arranged reaction temperature be 210 DEG C, reaction time 120min, reaction kettle is placed in mixture of ice and water is cooled to after reaction
Room temperature discharging, filters to obtain oxidation residua.Gained filtrate, which rotates to solvent, to be evaporated, and ethyl acetate is added and is extracted, merges organic
Mutually and it is settled to 10ml, carries out GC-MS detection；At this time the vanillic aldehyde in extract liquor, syringaldehyde yield be respectively 4.3%,
3.2%, as shown in Figure 5,6.
The explanation being not directed in a specific embodiment of the invention belongs to technology well known in the art, can refer to well-known technique
It is implemented.
The present invention achieves satisfied trial effect through validation trial.
The above specific embodiment and embodiment are to a kind of catalysis oxygen solution lignin preparation proposed by the present invention containing vanilla
The specific support of the method and technology thought of aldehyde and syringaldehyde extract liquor, this does not limit the scope of protection of the present invention, all to press
According to technical idea proposed by the present invention, any equivalent variations or equivalent change done on the basis of the technical program, still
Belong to the range of technical solution of the present invention protection.
Claims (9)
1. a kind of catalysis oxygen solution lignin prepares the method containing vanillic aldehyde and syringaldehyde extract liquor, which is characterized in that specific steps
Include the following:
Step 1: by Spruce lignin in NaHCO3It is pre-processed in aqueous solution；
Step 2: the pretreated Spruce lignin of step 1 and perovskite type catalyst are placed in a closed reactor
In, using ethanol/water mixed solution as solvent, it is passed through O2It is reacted, reaction solution is cooled to room temperature discharging after reaction；
Step 3: the discharging of step 2 being successively filtered, is rotated, is extracted using ethyl acetate, to obtain containing perfume
The extract liquor of oxalaldehyde and syringone.
2. a kind of catalysis oxygen solution lignin according to claim 1 prepares the method containing vanillic aldehyde and syringaldehyde extract liquor,
It is characterized in that, pretreated method described in step 1 are as follows:
1.1 by Spruce lignin, is the NaHCO that 1:10 is added that mass fraction is 5% by solid-to-liquid ratio3In aqueous solution, in room
Temperature is lower to stir 6h, obtains the sample of Spruce lignin；
1.2 pairs above-mentioned 1.1 of sample filters, and filter residue deionized water is rinsed 3 times；
Gained sample in above-mentioned 1.2 is placed in baking oven and is dried by 1.3, and the drying temperature is 80 DEG C, drying time is 12 small
When.
3. a kind of catalysis oxygen solution lignin according to claim 1 prepares the method containing vanillic aldehyde and syringaldehyde, feature
It is, perovskite type catalyst described in step 2 is CeCoO3、CeCuO3、CeNiO3、CeFeO3One of, titanium ore type is urged
Agent the preparation method comprises the following steps:
2.1 take the Ce (NO of 0.01mol3)3·6H2O and 0.01molCo (NO3)2·6H2O、Cu(NO3)3·3H2O、Ni
(NO3)2·6H2O or Fe (NO3)3·9H2The citric acid of O and 0.03mol is dissolved in 20ml deionized water, and the second of 2ml is added
Glycol forms precursor liquid, uses magnetic agitation 8h, whipping temp for 60 DEG C the precursor liquid, until forming colloidal sol；
Gained gel in 2.1 is placed in baking oven and is dried by 2.2, and the drying temperature is 105 DEG C, drying time is 12 hours, is obtained
To the presoma of perovskite type catalyst；
The presoma of perovskite type catalyst described in 2.2 is placed in Muffle furnace and calcines by 2.3, and calcination atmosphere is air, forges
Burning temperature is 600 DEG C, calcination time is 6 hours to get the series for arriving perovskite type catalyst.
4. a kind of catalysis oxygen solution lignin according to claim 1 prepares the method containing vanillic aldehyde and syringaldehyde extract liquor,
It is characterized in that, O described in step 22Pressure be 0.6MPa.
5. a kind of catalysis oxygen solution lignin according to claim 1 prepares the method containing vanillic aldehyde and syringaldehyde extract liquor,
It is characterized in that, the volume ratio ratio 1:1 of ethyl alcohol and water in ethanol/water mixed solvent described in step 2.
6. a kind of catalysis oxygen solution lignin according to claim 1 prepares the method containing vanillic aldehyde and syringaldehyde extract liquor,
It is characterized in that, being passed through O described in step 22The reaction temperature reacted is 120 DEG C~240 DEG C.
7. according to right want 6 described in a kind of method of the catalysis oxygen solution lignin preparation containing vanillic aldehyde and syringaldehyde extract liquor,
It is characterized in that, O is passed through described in step 22The reaction temperature reacted is 210 DEG C.
8. a kind of catalysis oxygen solution lignin according to claim 1 prepares the method containing vanillic aldehyde and syringaldehyde extract liquor,
It is characterized in that, being passed through O described in step 22The reaction time reacted is 10min~120min.
9. a kind of catalysis oxygen solution lignin according to claim 8 prepares the method containing vanillic aldehyde and syringaldehyde extract liquor,
It is characterized in that, being passed through O described in step 22The reaction time reacted is 30min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898355A (en) * | 2021-01-22 | 2021-06-04 | 北华大学 | Method for preventing lignin degradation intermediate product from polycondensation |
| CN114635304A (en) * | 2022-03-04 | 2022-06-17 | 昆明理工大学 | Method for directly preparing micro-nano cellulose from grass fiber material |
| CN114700081A (en) * | 2022-03-18 | 2022-07-05 | 南京大学 | Preparation and application of perovskite type cerium metal salt with transition metal ion regulation and control performance |
-
2019
- 2019-03-14 CN CN201910194593.2A patent/CN109942391B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| HAIBO DENG等: "Activity and Stability of Perovskite-Type Oxide LaCoO3 Catalyst in Lignin Catalytic Wet Oxidation to Aromatic Aldehydes Process", 《 ENERGY & FUELS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112898355A (en) * | 2021-01-22 | 2021-06-04 | 北华大学 | Method for preventing lignin degradation intermediate product from polycondensation |
| CN112898355B (en) * | 2021-01-22 | 2023-01-06 | 北华大学 | Method for preventing lignin degradation intermediate product from polycondensation |
| CN114635304A (en) * | 2022-03-04 | 2022-06-17 | 昆明理工大学 | Method for directly preparing micro-nano cellulose from grass fiber material |
| CN114700081A (en) * | 2022-03-18 | 2022-07-05 | 南京大学 | Preparation and application of perovskite type cerium metal salt with transition metal ion regulation and control performance |
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